Note: Descriptions are shown in the official language in which they were submitted.
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WATER-DISPERSIBLE ARTICLE INCLUDING
WATER-DISPERSIBLE CORE CONSTRUCTION
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No.
63/185,632, filed
May 7, 2021, which application is expressly incorporated by reference herein
in its entirety.
FIELD
[0002] The present disclosure relates generally to water-dispersible and/or
water-soluble unit
dose articles including water-dispersible and/or water-soluble core
constructions. More
particularly, the disclosure relates to water-dispersible articles including
water-dispersible
substrates, such as nonwoven substrates, configured to contain a cleaning
formulation, for
example, for handwashing an object.
BACKGROUND
[0003] Water-soluble packaging materials, such as water-soluble film packaging
materials, are
commonly used to simplify dispersing, pouring, dissolving, and dosing of a
material to be
delivered. Pouches made from conventional water-soluble films are commonly
used to package
formulations, such as laundry detergents, dish detergents, or personal care
formulations. A
consumer can directly add the water-soluble film pouch that contains a dish
detergent
formulation into an automatic dishwashing unit before starting the dishwasher
cleaning cycle.
Advantageously, this provides for accurate dosing while eliminating the need
for the consumer to
measure the formulation. However, this single unit dose concept has not been
extended to
handwashing to facilitate the dish washing process of a consumer choosing to
wash dishes
manually rather than using an automatic dishwashing unit. Instead, consumers
choosing manual
handwashing must rely on chemical and mechanical means of cleaning their
dishes across
multiple brands, products, and forms, e.g., bulk dish detergents or powders
and a sponge, brush,
cloth, or towel to provide a scrubbing action that present hygiene concerns if
not frequently
replaced.
[0004] Thus, there exists a need in the art for unit dose articles, such as
single unit dose
articles or multiple unit dose articles, having a construction that is easily
manufacturable and
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provides an abrasive surface suitable for dry-cleaning debris from cookware
and tableware, e.g.,
pots, pans, dishes, cooking utensils, eating utensils, glasses, and/or cups,
while also being
dissolvable or soluble when contacted with water at a suitable temperature to
deliver a cleaning
formulation, e g , introduced into a sink containing a volume of water to
deliver a suitable
sanitizing and/or cleaning formulation in which the cookware and tableware can
soak. After
soaking in the water containing the sanitizing and/or cleaning formulation,
the cookware and
tableware can be easily cleaned, if necessary, rinsed, and dried.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIGS. 1-4 are schematic sectional views of example articles containing
an active
cleaning formulation and optionally a carrier solvent, according to example
embodiments; and
[0006] FIG. 5 illustrates an example method for making an article, according
to an example
embodiment.
DETAILED DESCRIPTION
[0007] In example embodiments described herein, an article for cleaning or
hand-washing an
object is provided. Example articles, such as unit dose articles, e.g., single
unit dose (SUD)
articles or multiple unit dose (MUD) articles, include one or more water-
dispersible and/or
water-soluble core substrates, e.g., one or more water-dispersible and/or
water-soluble
nonwoven, foam, or film substrates, having precision dosing to deliver a
carrier solvent with one
or more active cleaning formulations, e.g., one or more cleaning agents, for
cleaning soiled
cookware and tableware including, without limitation, pots, pans, dishes,
plates, cooking
utensils, eating utensils, forks, spoons, knives, glasses, and/or cups. The
core substrates may be
water-dispersible at a temperature, for example, from about 10 C to about 40
C, and water-
soluble after multiple uses at such a temperature or at a higher temperature.
In example
embodiments, the article includes a water-dispersible core substrate
comprising a water-
dispersible resin. The core substrate has one or more abrasive surfaces having
a relatively fibrous
appearance and/or profile and one or more smooth surfaces having a relatively
smooth
appearance and/or profile. The core substrate is configured to contain an
active cleaning
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formulation, e.g., a sanitizing and/or a cleaning formulation. A carrier
solvent is optionally
included.
[0008] Contacting an abrasive surface of the article to a dry or wet surface
of a soiled or dirty
pan, for example, a consumer simply applies pressure against the surface of
the soiled or dirty
pan such that the abrasive surface removes the baked or dried soiling on the
pan surface. Once
the soiling is removed from the pan surface, the article may be contacted with
water at a suitable
temperature, for example, to release the active cleaning formulation for
chemical and/or
mechanical cleaning action. Alternatively, the consumer may place the article
in a sink or vessel
containing a suitable volume of water such that, as the core substrate is
dispersible or eventually
soluble, the active cleaning formulation is released. Once released, the
active cleaning
formulation will disperse, dissolve, and/or biodegrade during the hand wash
cleaning process
without leaving undesired residue.
[0009] In example embodiments, when the core substrate is contacted with water
having a
temperature greater than 40 C, or having a temperature greater than 80 C, the
water-soluble core
substrate is soluble to release the active cleaning formulation. In example
embodiments, the core
substrate includes a water-dispersible or water-soluble polymer, such as
polyvinyl alcohol
(PVOH) polymer, starch derivatives, or blends thereof, for example, with
otherwise water
dispersible polymers that have a high degree of biodegradation activity or can
be composted or
recycled
[0010] The article and, more specifically, in example embodiments, the core
substrate, is
configured to contain one or more active cleaning formulations, such as a
sanitizing formulation
and/or a cleaning detergent formulation. As an example, the active cleaning
formulation may
include, without limitation, a sanitizer and/or a dish detergent, soap, or
cleaner. Other examples
include a detergent, soap or cleaner, a fabric softener, a bleaching agent, a
laundry booster, a
stain remover, an optical brightener, a water softener, a shampoo, a
conditioner, a body wash, a
face wash, a skin lotion, a skin treatment, a body oil, fragrance, a hair
treatment, a bath salt, an
essential oil, a bath bomb, or an enzyme, or any suitable combination thereof.
In example
embodiments, suitable carrier solvents include solvents having a desired
polarity and coat weight
to facilitate incorporation of the active cleaning formulation into the
polymer matrix of the
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water-soluble core substrate including, without limitation, water, polyols,
such as glycerol, DPG
(dipropylene glycol), and other polar carrier solvents or any combination
thereof In example
embodiments, the carrier solvent with the active cleaning formulation is
disposed on or coats one
or more surfaces of the core substrate or is embedded in and/or adhered to the
water-soluble core
substrate. The core substrate may include a single layer, for example, a
single layer nonwoven
core substrate, or may include a plurality of layers, for example, a sheet of
nonwoven core
substrate folded in a serpentine arrangement or cut and plied to form layers
with the carrier
solvent with the active cleaning formulation disposed between adjacent layers
of the water-
soluble nonwoven core substrate, for example.
[0011] As used herein and unless specified otherwise, the term "water-
dispersible" refers to
any nonwoven substrate (or nonwoven web), foam substrate, film, or laminate
wherein upon
submersion in water at a specified temperature, the nonwoven substrate, foam
substrate, film, or
laminate physically disassociates into smaller constituent pieces. The smaller
pieces may or may
not be visible to the naked eye, may or may not remain suspended in the water,
and may or may
not ultimately dissolve. In example embodiments wherein a dispersion
temperature is not
specified, the nonwoven substrate, foam substrate, film, or laminate will
disintegrate in 300
seconds or less at a temperature of about 100 C or less, according to MSTM-
205. For example,
the disintegration time optionally can be 200 seconds or less, 100 seconds or
less, 60 seconds or
less, or 30 seconds or less at a temperature of about 80 C, about 70 C, about
60 C, about 50 C,
about 40 C, about 20 C, or about 10 C, according to MSTM-205. For example,
such dispersion
parameters can be characteristic of a nonwoven substrate, foam substrate,
film, or laminate
structure having a thickness of 6 mil (about 152 [tm). In example embodiments,
the water-
dispersible core substrate has a dispersion time of 300 seconds or less.
[0012] As used herein and unless specified otherwise, the term "water-soluble"
refers to any
nonwoven substrate (or nonwoven web), foam substrate, film, or laminate having
a dissolution
time of 300 seconds or less at a specified temperature as determined according
to MSTM-205 as
set forth herein. For example, the dissolution time of the nonwoven substrate,
foam substrate,
film, or laminate optionally can be 200 seconds or less, 100 seconds or less,
60 seconds or less,
or 30 seconds or less at a temperature of about 80 C, about 70 C, about 60 C,
about 50 C, about
40 C, about 20 C, or about 10 C according to MSTM-205. In example embodiments
wherein
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the dissolution temperature is not specified, the water-soluble nonwoven
substrate, foam
substrate, film, or laminate has a dissolution time of 300 seconds or less at
a temperature no
greater than about 80 C. In example embodiments, "water-soluble nonwoven
substrate" or
"water-soluble nonwoven web" means that at a thickness of 1.5 mil (about 38
pm), the
nonwoven substrate dissolves in 300 seconds or less at a temperature no
greater than 80 C
according to MSTM-205. For example, a 1.5 mil (about 38 lam) thick water-
soluble nonwoven
substrate can have a dissolution time of 300 seconds or less, 200 seconds or
less, 100 seconds or
less, 60 seconds or less, or 30 seconds or less at a temperature of about 70
C, about 60 C, about
50 C, about 40 C, about 30 C, about 20 C, or about 10 C according to MSTM-205.
In example
embodiments, the water-soluble core substrate has a dissolution time of 300
seconds or less.
[0013] As used herein and unless specified otherwise, the term "hot water-
soluble" refers to
any water-soluble nonwoven substrate, foam substrate, film, or laminate having
a dissolution
time of 300 seconds or less at a temperature of at least 40 C, for example, in
a range of about
40 C to about 100 C, as determined according to MSTM-205. For example, the
dissolution time
of a hot water-soluble nonwoven substrate, foam substrate, film, or laminate
optionally can be
200 seconds or less, 100 seconds or less, 60 seconds or less, or 30 seconds at
a temperature
greater than about 40 C according to MSTM-205, for example, in a range of
about 41 C to about
80 C, about 40 C to about 100 C, about 40 C to about 60 C, about 50 C to about
60 C, about
60 C to about 80 C, or about 60 C to about 90 C. In example embodiments, "hot
water-soluble
nonwoven substrate" or "hot water-soluble nonwoven web" means that at a
thickness of 1.5 mil
(about 38 p.m), the nonwoven substrate dissolves in 300 seconds or less at a
temperature no less
than about 21 C according to MSTM-205. For example, a 1.5 mil (about 38 [tm)
thick water-
soluble nonwoven substrate can have a dissolution time of 300 seconds or less,
200 seconds or
less, 100 seconds or less, 60 seconds or less, or 30 seconds or less at a
temperature of about
80 C, 70 C, about 60 C, about 50 C, or about 40 Caccording to MSTM-205. In
example
embodiments, a hot water-soluble substrate, such as a "hot water-soluble
nonwoven substrate" or
a -hot water-soluble nonwoven web," remains stable, e.g., does not dissolve,
when contacted
with water having a temperature less than its hot water-soluble temperature
but is soluble, e.g.,
dissolves, when contacted with water having a temperature equal to its hot
water-soluble
temperature for a suitable dissolution time, e.g., at least 300 seconds to
between 300 seconds and
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600 seconds. For example, in example embodiments, a hot water-soluble nonwoven
substrate
contacted with water having a temperature of 40 C for at least 300 seconds,
e.g., for 300 seconds
to 600 seconds, is soluble according to MSTM-205; however, the hot water-
soluble nonwoven
substrate is stable when contacted with water having a temperature less than
40 C or contacted
with water having a temperature of 40 C for less than 300 seconds.
[0014] As used herein and unless specified otherwise, the term "nonwoven web"
refers to a
web or sheet comprising, consisting of, or consisting essentially of fibers
arranged (e.g., by a
carding process) and bonded to each other. Thus, the term "nonwoven web" can
be considered
short hand for nonwoven fiber-based webs. Further, as used herein, -nonwoven
web" includes
any structure including a nonwoven web or sheet, including, for example, a
nonwoven web or
sheet having a film laminated to a surface thereof. Methods of preparing
nonwoven webs from
fibers are well known in the art, for example, as described in Nonwoven
Fabrics Handbook,
prepared by Ian Butler, edited by Subhash Batra et al., Printing by Design,
1999, herein
incorporated by reference in its entirety. As used herein and unless specified
otherwise, the term
"film" refers to a continuous film or sheet, e.g., prepared by a casting or
extrusion process.
[0015] As used herein, a "plurality of fibers" can include a sole fiber type
or can include two
or more different fiber types. In example embodiments wherein the plurality of
fibers comprise
two or more different fiber types, each fiber type can be generally included
in any amount, for
example, from about 0.5 wt.% to about 99.5 wt.% of the total weight of the
plurality of fibers. In
example embodiments wherein the plurality of fibers consists of a sole fiber
type, the plurality of
fibers is substantially free of a second or more fiber types. A plurality of
fibers is substantially
free of a second or more fiber types when the plurality of fibers comprise
less than about 0.5
wt.% of the second or more fiber types. In general, the difference between
fiber types can be a
difference in fiber length to diameter ratio (LID), tenacity, shape,
rigidness, elasticity, solubility,
melting point, glass transition temperature (Tg), chemical composition, color,
or a combination
thereof.
[0016] As used herein, the terms "resin(s)" and "polymer(s)" should be
considered
interchangeable. In certain embodiments, the terms resin(s) and polymer(s),
respectively, are
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used to refer to a polymer optionally combined with one or more additional
polymers, and to a
single type of polymer, e.g., a resin can comprise more than one polymer.
[0017] As used herein and unless specified otherwise, the terms "wt.%" and
"wt%" are
intended to refer to the composition of the identified element in "dry" (non-
water) parts by
weight of the entire water-soluble film, for example, including residual
moisture in the water-
soluble film, or parts by weight of the entire composition, depending on
context.
[0018] As used herein and unless specified otherwise, the term "PHR" ("phr")
is intended to
refer to the composition of the identified element in parts per one hundred
parts water-soluble
polymer resin(s) (whether PVOH or other polymer resins, unless specified
otherwise) in the
water-soluble nonwoven substrate, foam substrate, or film, or a solution used
to make the water-
soluble nonwoven substrate, foam substrate, or film.
[0019] As used herein and unless specified otherwise, the term "comprising"
means that
various components, ingredients, or steps can be conjointly employed in
practicing the present
disclosure. Accordingly, the term "comprising" encompasses the more
restrictive terms
"consisting essentially of' and "consisting of" The present compositions can
comprise, consist
essentially of, or consist of any of the required and optional elements
disclosed herein. The
disclosure illustratively disclosed herein suitably may be practiced in the
absence of any element
or step which is not specifically disclosed herein.
[0020] When values are expressed as approximations, by use of the antecedent
"about," it will
be understood that the particular value forms another embodiment. As used
herein, "about X"
(where X is a numerical value) in example embodiments refers to 10% (for
example, 5%) of
the recited value, inclusive.
[0021] The articles, the water-dispersible and/or water-soluble nonwoven
materials, the water-
dispersible and/or water-soluble foam materials, and the water-dispersible
and/or water-soluble
film materials, and related methods of making and using the articles, the
water-dispersible and/or
water-soluble nonwoven materials, the water-dispersible and/or water-soluble
foam materials,
and the water-dispersible and/or water-soluble film materials are contemplated
to include
embodiments including any combination of one or more of the additional
optional elements,
features, and steps further described below, unless stated otherwise.
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[0022] In example embodiments, the article includes a water-dispersible and/or
water-soluble
core substrate including a water-dispersible and/or water-soluble resin. In
example embodiments,
the core substrates and the resin may be water-dispersible at a temperature,
for example, from
about 10 C to about 40 C, and water-soluble after multiple uses at such a
temperature or at a
higher temperature such as 40 C or above. The highest safe hot water
temperature for domestic
use is about 48 C. In example embodiments, the core substrate includes one of
more water-
dispersible nonwoven core substrates. The core substrate contains an active
cleaning
formulation, wherein, when the core substrate is contacted with water having a
temperature
greater than 20 C, or water having a temperature greater than 40 C, or water
having a
temperature greater than 80 C, the core substrate is dispersible or soluble to
release the active
cleaning formulation. In example embodiments, the active cleaning formulation
is in the form of
at least one of a solid, e.g., a powder or plurality of granules or particles,
a gel, a liquid, or a
slurry form, or any suitable combination thereof In certain embodiments, the
core substrate is
saturated with the carrier solvent with the active cleaning formulation. In
other embodiments, the
carrier solvent with the active cleaning formulation is embedded in, disposed
on, applied to,
coated on, and/or adhered to the water-soluble core substrate, e.g., the
carrier solvent with the
active cleaning formulation is disposed on a surface of the water-soluble core
substrate. In
example embodiments, the water-soluble core substrate is at least one of
coated with the carrier
solvent with the active cleaning formulation or impregnated with the carrier
solvent with the
active cleaning formulation. In example embodiments, the carrier solvent with
the active
cleaning formulation is present in the core substrate, e.g., present in the
fiber-forming
composition, the foam-forming composition, or the film-forming composition.
The carrier
solvent is optional.
[0023] Referring to the Figures and, initially, to FIGS. 1-4, an article, such
as a single unit
dose article 20, includes a water-dispersible and/or water-soluble nonwoven
substrate 22
comprising a plurality of fibers including a water-dispersible and/or water-
soluble resin. In
example embodiments, nonwoven substrate 22 includes any suitable fiber
chemistry including,
without limitation, PVOH fibers as described herein or PVOH fibers blended
with up to 90 wt.%
cellulose-type fibers, or PVOH fibers blended with fibers made of other
polymers. In some
embodiments, the nonwoven substrate is made of water-dispersible fibers.
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[0024] In example embodiments, nonwoven substrate 22 has a basis weight of 15
gsm to 150
gsm (grams per square meter); a fiber length of 10.0 mm to 150 mm; and a
suitable fiber
diameter of 5 microns to 100 microns. In other example embodiments, water-
soluble nonwoven
substrate 22 has any suitable basis weight, fiber length, and/or fiber
diameter. For example, in
example embodiments, the fiber diameter is less than 5 microns or greater than
100 microns. The
fibers of nonwoven substrate 22 may be formed using any suitable methods
including, without
limitation, a carded process or any suitable process for making water-soluble
nonwoven fibers.
Further, the fibers of nonwoven substrate 22 are bonded together using any
suitable bonding
process or method including, without limitation, a heat, thermal, chemical,
water, and/or solution
bonding method or any suitable bonding method known in the art of nonwoven
fiber bonding. As
described below and shown in FIGS. 1-4, nonwoven substrate 22 may include any
suitable
number of layers or plies, for example, 1 layer or ply to 50 layers or plies,
or more in certain
embodiments Nonwoven substrate 22 may be porous or non-porous and cold water-
soluble,
warm water-soluble, or hot water-soluble. In alternative example embodiments,
the nonwoven
substrate may be cold water-dispersible, warm water-dispersible, or hot water-
dispersible.
Water-soluble nonwoven substrate 22 may be formed using any suitable
manufacturing process
known in the nonwoven manufacturing art including, without limitation, a
carded process. The
construction of water-soluble nonwoven substrate 22 may include, for example,
folded layers or
plies, stacked layers or plies, and/or rolled layers or plies.
[0025] In example embodiments, nonwoven substrate 22 contains an active
cleaning
formulation 26 and optionally a carrier solvent 25. In example embodiments,
nonwoven substrate
22 has a moisture content less than 15 wt.%, and, more particularly, less than
10 wt.%, and, even
more particularly, between 2 wt.% and 10 wt.% before contact with carrier
solvent 25 with active
cleaning formulation 26. In example embodiments as described herein, upon
contact of carrier
solvent 25 with at least one fiber of the plurality of fibers, the at least
one fiber exhibits a degree
of shrinkage of 0.5% to 65%. In example embodiments, active cleaning
formulation 26 is a
liquid formulation.
[0026] In example embodiments, when nonwoven substrate 22 is contacted with
water having
a temperature in a range of 10 C to 40 C, the nonwoven substrate 22 is
dispersible to release the
active cleaning formulation 26. When the nonwoven substrate 22 is contacted
with water having
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a temperature greater than 40 C, or a temperature greater than 80 C, water-
soluble nonwoven
substrate 22 is soluble, i.e., dissolves. Further, in example embodiments,
when nonwoven
substrate 22 is contacted with water having a temperature greater than 20 C,
or a temperature
greater than 40 Cfor not more than 300 seconds, active cleaning formulation 26
is substantially
released from water-soluble nonwoven substrate 22. In example embodiments,
nonwoven
substrate 22 has a dissolution time of at least 300 seconds according to MSTM-
205 at a
temperature, for example, above 40 C such as 60-100 C. In example embodiments,
the core
substrate dissolves completely in application, and can be assessed by being
able to completely
dissolve under MSTM 205 testing in under 300 seconds. In an example
application test, there is
no residue remaining when the water-soluble core substrate is dissolved in 40
C to 100 C in less
than 600 seconds with undefined agitation.
[0027] Suitable carrier solvents 25 include, without limitation,
water, polyols, such as
glycerol, DPG, etc., and other polar solvents having a desired polarity and
coat weight to
facilitate incorporation of active cleaning formulation 26 into the polymer
matrix of water-
soluble nonwoven substrate 22. Active cleaning formulation 26 may be in the
form of a solid,
e.g., a powder or a plurality of granules or particles, a gel, a liquid, or a
slurry formulation, or
any suitable combination of a solid, a gel, a liquid, or a slurry formulation,
for example. In
example embodiments, active cleaning formulation 26 is in any suitable phase
including, for
example, a solid phase, a liquid phase, a slurry phase (a liquid containing
solids and multiple
phases), or any suitable combination of phases. For example, active cleaning
formulation 26 may
include fine powder particles or granules, gels, one or more liquids, or a
slurry, or multiple
phases. Active cleaning formulation 26 may include, without limitation, one or
more of the
following: sanitizers, sanitizing agents, detergents, surfactants,
emulsifiers, chelants, dirt
suspenders, stain releasers, enzymes, pH adjusters, builders, soil release
polymers, structurants,
free fragrance, encapsulated fragrance, preservatives, solvent, minerals,
oxidizers, a foam
builder, an TILB adjuster, or a degreaser, and/or any ingredients suitable for
including in a
sanitizer and/or dish detergent (or personal care, laundry detergent, and/or
home surface cleaners
or cleansers). In example embodiments, active cleaning formulation 26 may
include a sanitizer
or a sanitizing agent or water-soluble nonwoven substrate 22 may include the
sanitizer or the
sanitizing agent as an auxiliary agent. In example embodiments, article 20
includes active
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cleaning formulation 26 having a mass of 0.5 gram (g) to 250 grams, and a
volume of 1.0
milliliter (m1) to 250 ml. In example embodiments wherein active cleaning
formulation 26 is a
solid phase, the particles or granules may have a size of 1 micron to 100
microns, for example, or
may be in tablet form
[0028] In example embodiments, active cleaning formulation 26 is contained in
or by
nonwoven substrate 22, for example, by saturating nonwoven substrate 22 with
carrier solvent 25
with active cleaning formulation 26, by disposing, e.g., applying or coating,
carrier solvent 25
with active cleaning formulation 26 on one or more surfaces, e.g., a first
surface 28 and/or a
second surface 30, of nonwoven substrate 22, as shown in FIGS. 1 and 3, by
embedding carrier
solvent 25 with active cleaning formulation 26 in a matrix 32 of nonwoven
substrate 22, as
shown in FIGS. 2 and 4, e.g., in one or more layers of nonwoven substrate 22,
and/or by
disposing, e.g., applying or coating, carrier solvent 25 with active cleaning
formulation 26
between different layers, e.g., adjacent layers, of nonwoven substrate 22,
e.g., coating one or
more surfaces of one or more layers, for example, with carrier solvent 25 with
active cleaning
formulation 26. Carrier solvent 25 with active cleaning formulation 26 may be
adsorbed in
and/or adhered to or bonded to a surface of nonwoven substrate 22, for
example. In example
embodiments, carrier solvent 25 with one or more active cleaning formulations
26 is suspended
in a water-soluble polymer system or resin, such as a PVOH resin as described
herein, or
disposed on, e.g., coated on, one or more surfaces of water-soluble nonwoven
substrate 22. The
various morphologies as described herein allow for control over a release
and/or a delivery of
active cleaning formulation 26 and a solubility of article 20. In example
embodiments, active
cleaning formulation 26 is released at a specific or determined water
temperature and/or over a
specific or determined amount of time dictated by thermodynamics and capillary
pressure. The
carrier solvent 25 is optional. In some embodiments, the article 20 contains
no carrier solvent 25.
[0029] In example embodiments, one or more first surfaces 28 includes an
abrasive material
34 forming a rough area or region of water-soluble nonwoven substrate 22,
e.g., an abrasive
portion or region, having a fibrous appearance and/or profile. In example
embodiments, abrasive
material 34 includes, without limitation, at least one of the following: the
plurality of fibers
described herein, the active cleaning formulation in solid form as described
herein, silicon
dioxide or silica (SiO2), diatomaceous earth, one or more clays, minerals,
jute, or a plurality of
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natural insoluble fibers, or combinations thereof, for providing first surface
28 with a desired
abrasiveness suitable for scrubbing or scouring dry or wet soiled cookware and
tableware
without damaging the surface finish of the cookware or the tableware. In
example embodiments,
the plurality of fibers in the nonwoven substrate 22 and the active cleaning
formulation 26 in
solid form as the abrasive material 34 provide the first surface 28 with a
desired abrasiveness.
Other suitable abrasive materials 34 may also be used, alone or in
combination, to provide first
surface 28 with the desired abrasiveness. Generally, in example embodiments
abrasion is defined
by a change in Ra (gloss) values before and after a metallic surface has been
cleaned, with
defined parameters in an X-direction and a rotational direction. In example
embodiments, the
one or more abrasive materials 34 are contained within water-soluble nonwoven
substrate 22.
For example, abrasive material 34 is embedded in, disposed on, applied to,
coated on, and/or
adhered to first surface 28 and/or embedded in nonwoven substrate 22, e.g.,
abrasive material 34
is disposed in matrix 32 of nonwoven substrate 22. In example embodiments, the
abrasive
material has a surface finish Ra value for a carbon steel substrate of about 8
uin (0.2 itm) to
about 16 uin (0.4 um) (XY Auto); 11 uin (0.275 um) to about 22 uin (0.55 pm)
(Off Hand
Short); and about 13 uin (0.325 p.m) to about 21 uin (0.525 itm) (Off Hand
Long). In example
embodiments, the abrasive material has a surface finish Ra value for an
aluminum substrate of
about 29 uin (0.725 nm) to about 57 uin (1.425 nm) (XY Auto); and about 33 uin
(0.825 nm) to
about 60 uin (1.5 nm) (Off Hand Short).
[0030] In example embodiments, nonwoven substrate 22 includes one or more
relatively
smooth second surfaces 30, i.e., each second surface 30 has a relatively
smooth appearance
and/or profile compared to the relatively fibrous appearance and/or profile of
first surface 28. For
example, second surface 30 may be coated with water and/or heated to create a
continuous
smooth surface.
[0031] Abrasive material 34 may be applied to first surface 28 using any
suitable application
method known to those skilled in the art including, for example, adhesive or
heat applications. In
example embodiments, a suitable adhesive is applied to first surface 28 to
adhere abrasive
material 34 to first surface 28 or first surface 28 is heated and abrasive
material 34 is applied to
first surface 28 using a suitable spraying application or placing first
surface 28 on a suitable
abrasive material 34 contained within a bed or container, for example. In
other example
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embodiments, nonwoven substrate 22 is impregnated with abrasive material 34.
In example
embodiments, abrasive material 34 is present in the nonwoven substrate 22,
e.g., present in the
fiber-forming composition.
[0032] In other example embodiments, one or more abrasive materials 34 are
embedded in,
disposed on, applied to, coated on, and/or adhered to second surface 30 and/or
embedded in
water-soluble nonwoven substrate 22 to form a rough area or region of water-
soluble nonwoven
substrate 22, e.g., an abrasive portion or region, on second surface 30 having
a fibrous
appearance and/or profile. In example embodiments, abrasive material 34 may be
disposed
throughout a thickness of water-soluble nonwoven substrate 22 such that an
abrasive gradient is
formed, wherein first surface 28 has a first degree of abrasiveness and
opposing second surface
30 has a second degree of abrasiveness less than or greater than the first
degree of abrasiveness.
In example embodiments, first surface 28 has a relatively rougher appearance
and/or a rougher
profile when compared to the appearance and/or the profile of second surfaces
30. Conversely,
second surface 30 has a relatively smoother appearance and/or a smoother
profile when
compared to the appearance and/or the profile of first surfaces 28.
[0033] In example embodiments such as shown in FIG. 1, article 20 includes one
or more
layers of nonwoven substrate 22 forming a nonwoven sheet 36 and carrier
solvent 25 with active
cleaning formulation 26 in a solid phase disposed on first surface 28 and/or
opposing second
surface 30 of nonwoven substrate 22 In example embodiments, such as shown in
FIG 2, article
20 includes one or more layers of nonwoven substrate 22 forming a nonwoven
sheet 36
containing carrier solvent 25 with active cleaning formulation 26 in a solid
phase embedded
within matrix 32 of nonwoven substrate 22. In example embodiments such as
shown in FIG. 3,
article 20 includes a plurality of sheets 36 (for example, 3611, 36n+i, 36n-2,
36n+3, 36n+4, 36n+5,
as shown in FIGS. 3 and 4) of nonwoven substrate 22 coupled together to form a
sphere or
spheroid and carrier solvent 25 with active cleaning formulation 26 in a solid
phase disposed on
one or more surfaces of one or more sheets 36, e.g., first surface 28 and/or
opposing second
surface 30 of sheet 36. The plurality of sheets 36 may be coupled together
along a center line 38
of each sheet 36, as shown in FIGS. 3 and 4, collectively defining a center
point 40 of article 20
and forming a sphere-shaped article 20 or spheroid-shaped article 20. In other
example
embodiments, one or more sheets 36 may be coupled along an edge of each sheet
36, for
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example, collectively defining center point 40 of article 20 and forming the
sphere-shaped article
20 or spheroid-shaped article 20. In example embodiments, such as shown in
FIG. 3, one or more
sheets 36 of nonwoven substrate 22 contain carrier solvent 25 with active
cleaning formulation
26 in a solid phase disposed on first surface 2g and/or opposing second
surface 30 of sheet 36 Tn
example embodiments, such as shown in FIG. 4, article 20 includes one or more
sheets 36 of
nonwoven substrate 22 containing carrier solvent 25 with active cleaning
formulation 26 in a
solid phase embedded within matrix 32 of nonwoven substrate 22.
[0034] Referring further to FIGS. 1-4, in example embodiments, nonwoven
substrate 22
includes a plurality of fibers as described herein but not explicitly shown in
FIGS. 1-4. In
example embodiments, one or more fibers of the plurality of fibers is
saturated with or
impregnated with carrier solvent 25 with active cleaning formulation 26.
Carrier solvent 25 with
active cleaning formulation 26 may be embedded in one or more of fibers of the
plurality of
fibers or between one or more adjacent fibers of the plurality of fibers, or
carrier solvent 25 with
active cleaning formulation may be disposed on, e.g., applied to or coated on,
a surface of one or
more fibers of the plurality of fibers.
[0035] In example embodiments, an example water dispersible and/or water-
soluble article 20,
e.g., a water-dispersible and/or water-soluble nonwoven towel, sheet, wipe,
loofa, pad, strip, or
sponge, is provided that allows the consumer to initially scrub or scour the
soiled or dirty
cookware and dinnerware. Article 20 is configured in example embodiments to
provide one or
more abrasive surfaces to facilitate cleaning wet or dry debris and food
stuffs from surfaces of
the cookware and dinnerware and deliver a suitable amount of active cleaning
formulation 26 for
cleaning a single load of hand-washed cookware and dinnerware, for example. A
consumer may
scrub dishes when the dishes are dry. Once a desired amount of debris and food
stuffs are
removed using article 20, article 20 can be dissolved in a sink (or in a
soaking tub) to deliver a
sanitizing and/or cleaning formulation for further removal of debris and food
stuffs from the
dishes and sanitize the dishes. As another example, a consumer may apply cold
water (e.g., water
having a temperature not greater than 20 C) to the dishes as the consumer
scrubs the dishes, and
article 20 dissolves progressively or slowly during use. Once the dishes are
cleaned, water may
be squeezed out of article 20, which may be reused. After single or multiple
uses, the consumer
can apply hot water (e.g., water having a temperature of at least 40 C,
preferably 60-70 C or
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above) to article 20 to substantially or completely dissolve article 20 and
release a sanitizing
agent into the hot water contained in the sink. When the water temperature is
close to 40 C,
article 20 starts to dissolve while dissolving much faster at a temperature of
60-70 C or above.
As another example, article 20 does not dissolve as the dishes are washed with
hot water (e g ,
water having a temperature of at least 40 C). During the washing process,
carrier solvent 25 with
active cleaning formulation 26 is substantially continuously released from
article 20. Once the
manual dish washing process is complete, article 20 can be introduced into an
automatic dish
washer where article 20 dissolves during the washing cycle to aid in dish
washing. Alternatively,
because article 20 exhibits a suitable biodegradation profile, article 20 may
be disposed of in the
trash or placed in a paper recycle bin.
[0036] Referring now to FIG. 5, in example embodiments, a method 100 for
making an article
20, such as a single unit dose article, containing an active cleaning
formulation and optionally
carrier solvent includes step 102 or steps 102 and 104. At step 102, a core
substrate comprising a
plurality of fibers including a water-dispersible and/or water-soluble resin
is formed. In example
embodiments, one or more layers of the core substrate or substrates containing
a carrier solvent
with an active cleaning formulation are formed. In example embodiments, the
core substrate,
e.g., nonwoven substrate 22, is configured to contain the carrier solvent with
the one or more
active cleaning formulation, such as described herein. In example embodiments,
carrier solvent
25 with active cleaning formulation 26 is contained in or by nonwoven
substrate 22, for example,
by saturating nonwoven substrate 22 with carrier solvent 25 with active
cleaning formulation 26,
by disposing, e.g., applying or coating, carrier solvent 25 with active
cleaning formulation 26 on
one or more surfaces, e.g., a first surface 28 and/or a second surface 30, of
nonwoven substrate
22, as shown in FIGS. 1 and 3, by embedding carrier solvent 25 with active
cleaning formulation
26 in a matrix 32 of nonwoven substrate 22, as shown in FIGS. 2 and 4, e.g.,
in one or more
layers of nonwoven substrate 22, and/or by disposing carrier solvent 25 with
active cleaning
formulation 26 between different layers, e.g., adjacent layers, of nonwoven
substrate 22, e.g.,
coating one or more surfaces of one or more layers, for example, with carrier
solvent 25 with
active cleaning formulation 26. Active cleaning formulation 26 may be adsorbed
in and/or
adhered to or bonded to a surface of nonwoven substrate 22, for example. When
at least one fiber
of the plurality of fibers forming nonwoven substrate 22 is contacted with a
suitable amount of
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carrier solvent 25, the at least one fiber exhibits a degree of shrinkage of
0.5% to 65%. In
example embodiments, method 100 includes contacting the carrier solvent with
the nonwoven
substrate 22, wherein upon contact with the carrier solvent, the at least one
fiber exhibits a
degree of shrinkage of 0.5% to 65% Tn example embodiments, when nonwoven
substrate 221s
contacted with water having a temperature greater than 20 C, or water having a
temperature
greater than 40 C, or water having a temperature greater than 80 C, nonwoven
substrate 22 is
dispersible or soluble to release the active cleaning formulation. The carrier
solvent 25 is
optional in the article 20. If carrier solvent 25 is used, it may be dried off
in the article 20.
[0037] In example embodiments, method 100 includes step 104. At step 104, an
abrasive
surface is formed on the water-soluble nonwoven substrate 22. For example, one
or more
surfaces of nonwoven substrate 22 are formed having a rough or abrasive area
or region. In
example embodiments, one or more abrasive materials 34 are formed on, disposed
in, or adhered
to one or more first surfaces 28 of nonwoven substrate 22 forming a rough area
or region of
nonwoven substrate 22, e.g., an abrasive area or region, having a fibrous
appearance and/or
profile, for example. Suitable abrasive materials 34, as described herein, may
be used, alone or in
combination, to provide first surface 28 with the desired abrasiveness. In
example embodiments,
the one or more abrasive materials 34 are contained within nonwoven substrate
22. For example,
abrasive material 34 is embedded in, disposed on, applied to, coated on,
and/or adhered to first
surface 28 and/or embedded in nonwoven substrate 22, e.g., abrasive material
34 is disposed in
matrix 32 of nonwoven substrate 22.
[0038] In example embodiments, method 100 includes forming one or more
abrasive materials
34 on first surface 28 or applying one or more abrasive materials 34 to first
surface 28 using any
suitable application method known to those skilled in the art including, for
example, adhesive or
heat applications. In example embodiments, a suitable adhesive is applied to
first surface 28 to
adhere abrasive material 34 to first surface 28 or first surface 28 is heated
and abrasive material
34 is applied to first surface 28 using a suitable spraying application or
placing first surface 28
on a suitable abrasive material 34 contained within a bed or container, for
example. In other
example embodiments, first surface 28 is at least partially dissolved and
abrasive material 34 is
applied to at least partially dissolved first surface 28 or nonwoven substrate
22 is impregnated
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with abrasive material 34. In example embodiments, abrasive material 34 is
present in the
nonwoven substrate 22, e.g., present in the fiber-forming composition or
resin.
[0039] In example embodiments, method 100 includes forming one or more
surfaces of water-
soluble nonwoven substrate 22 having a relatively smooth area or region having
a smooth
appearance and/or profile. For example, water-soluble nonwoven substrate 22
may include one
or more relatively smooth second surfaces 30, i.e., each second surface 30 has
a relatively
smooth appearance and/or profile compared to the relatively fibrous appearance
and/or profile of
first surface 28. In example embodiments, second surface 30 may be coated with
water and/or
heated to create a continuous smooth surface. In other example embodiments,
method 100
includes forming one or more abrasive areas or regions on second surfaces 30.
For example, one
or more abrasive materials 34 are embedded in, disposed on, applied to, coated
on, and/or
adhered to second surface 30 and/or embedded in nonwoven substrate 22 to form
a rough area or
region of nonwoven substrate 22, e.g., an abrasive area or region, on second
surface 30 having a
fibrous appearance and/or profile.
[0040] In other example embodiments, method 100 includes forming an abrasive
gradient
throughout a thickness of nonwoven substrate 22. For example, abrasive
material 34 may be
disposed throughout a thickness of nonwoven substrate 22 such that an abrasive
gradient is
formed, wherein first surface 28 has a first degree of abrasiveness and
opposing second surface
30 has a second degree of abrasiveness less than or greater than the first
degree of abrasiveness
In example embodiments, first surface 28 has a relatively rougher appearance
and/or rougher
profile when compared to the appearance and/or profile of second surfaces 30.
Conversely,
second surface 30 has a relatively smoother appearance and/or smoother profile
when compared
to the appearance and/or profile of first surfaces 28.
Water-Soluble Film and Fiber-Forming Materials
[0041] Water-soluble polymers for use in the water-soluble fibers, water-
soluble nonwoven
substrates, water-soluble foam substrates, and water-soluble films include,
but are not limited to,
a polyvinyl alcohol (PVOH) polymer, polyacrylate, water-soluble acrylate
copolymer, polyvinyl
pyrrolidone, polyethyleneimine, pullulan, water-soluble natural polymers
including, but not
limited to, guar gum, gum Acacia, xanthan gum, carrageenan, and starch, water-
soluble polymer
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derivatives including, but not limited to, modified starches, ethoxylated
starch, and
hydroxypropylated starch, copolymers of the forgoing and combinations of any
of the foregoing.
Other water-soluble polymers can include polyalkylene oxides, polyacrylamides,
polyacrylic
acids and salts thereof, celluloses, cellulose ethers, cellulose esters,
cellulose amides, polyvinyl
acetates, polycarboxylic acids and salts thereof, polyaminoacids, polyamides,
gelatines,
methylcelluloses, carboxymethylcelluloses and salts thereof, dextrins,
ethylcelluloses,
hydroxyethyl celluloses, hydroxypropyl methylcelluloses, maltodextrins,
polymethacrylates, and
combinations of any of the foregoing. Such water-soluble polymers, whether
PVOH or
otherwise, are commercially available from a variety of sources.
[0042] In general, the fibers, foams, and films as described herein include
polyvinyl alcohol.
Polyvinyl alcohol is a synthetic polymer generally prepared by the
alcoholysis, usually termed
"hydrolysis" or "saponification," of polyvinyl acetate. Fully hydrolyzed PVOH,
where virtually
all the acetate groups have been converted to alcohol groups, is a strongly
hydrogen-bonded,
highly crystalline polymer which dissolves only in hot water, e.g., water
having a temperature
greater than about 140 F (about 60 C). If a sufficient number of acetate
groups are allowed to
remain after the hydrolysis of polyvinyl acetate, that is the PVOH polymer is
partially
hydrolyzed, then the polymer is more weakly hydrogen-bonded, less crystalline,
and is generally
soluble in cold water, e.g., water having a temperature less than about 50 F
(about 10 C). As
such, the partially hydrolyzed polymer is a vinyl alcohol-vinyl acetate
copolymer that is a PVOH
copolymer, but is commonly referred to as PVOH.
[0043] In some embodiments, suitable examples of such a polymer include,
without limitation,
a polyvinyl alcohol homopolymer, a polyvinyl alcohol copolymer, a modified
polyvinyl alcohol
copolymer, and combinations thereof. For example, the polyvinyl alcohol
copolymer is a
copolymer of vinyl acetate and vinyl alcohol in some embodiments. For example,
in some
embodiments, the modified polyvinyl alcohol copolymer comprises an anionically
modified
copolymer, which may be a copolymer of vinyl acetate and vinyl alcohol further
comprising
additional groups such as a carboxylate, a sulfonate, or combinations thereof.
As such, the
partially hydrolyzed polymer is a vinyl alcohol-vinyl acetate copolymer that
is a PVOH
copolymer, but is commonly referred to as "polyvinyl alcohol (PVOH)" or "the
PVOH
polymer." For brevity, the term "PVOH polymer" used herein is understood to
encompass a
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homopolymer, a copolymer, and a modified copolymer comprising vinyl alcohol
moieties, for
example, 50% or higher of vinyl alcohol moieties. The term "PVOH fiber" used
herein refers to
fiber comprising a PVOH polymer.
[0044] The fibers, foams, and/or films described herein can include one or
more polyvinyl
alcohol (PVOH) homopolymers, one or more polyvinyl alcohol copolymers, one or
more
modified polyvinyl alcohol copolymers, or a combination thereof. As used
herein, the term
"homopolymer- generally includes polymers having a single type of monomeric
repeating unit
(e.g., a polymeric chain consisting of or consisting essentially of a single
monomeric repeating
unit). For the particular case of PVOH, the term "PVOH polymer"further
includes copolymers
consisting of a distribution of vinyl alcohol monomer units and vinyl acetate
monomer units,
depending on the degree of hydrolysis (e.g., a polymeric chain consisting of
or consisting
essentially of vinyl alcohol and vinyl acetate monomer units). In the limiting
case of 100%
hydrolysis, a PVOH homopolymer can include a true homopolymer having only
vinyl alcohol
units. In some embodiments, the fibers, foams, and/or films of the disclosure
include polyvinyl
alcohol copolymers. In some embodiments, the fibers, foams, and/or films of
the disclosure
include cold-water soluble or hot water-soluble polyvinyl alcohol copolymers.
[0045] Unless expressly indicated otherwise, the term "degree of hydrolysis"
is understood as
a percentage (e.g., a molar percentage) of hydrolyzed moieties among all
hydrolyzable moieties a
polymer initially has For example, for a polymer comprising at least one of a
vinyl acetate
moiety or a vinyl alcohol moiety, partial replacement of an ester group in
vinyl acetate moieties
with a hydroxyl group occurs during hydrolysis, and a vinyl acetate moiety
becomes a vinyl
alcohol moiety. The degree of hydrolysis of a polyvinyl acetate homopolymer is
considered as
zero, while the degree of hydrolysis of a polyvinyl alcohol homopolymer is
considered as 100%.
The degree of hydrolysis of a copolymer of vinyl acetate and vinyl alcohol is
equal to a
percentage of vinyl alcohol moieties among a total of vinyl acetate and vinyl
alcohol moieties,
and is between zero and 100%.
[0046] In some embodiments, the polyvinyl alcohol polymer includes a modified
polyvinyl
alcohol, for example, a copolymer. The modified polyvinyl alcohol can include
a co-polymer or
higher polymer (e.g., ter-polymer) including one or more monomers in addition
to the vinyl
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acetate/vinyl alcohol groups. Optionally, the modification is neutral, e.g.,
provided by an
ethylene, propylene, N-vinylpyrrolidone or other non-charged monomer species.
Optionally, the
modification is a cationic modification, e.g., provided by a positively
charged monomer species.
Optionally, the modification is an anionic modification Thus, in some
embodiments, the
polyvinyl alcohol includes an anionic modified polyvinyl alcohol.
[0047] An anionic modified polyvinyl alcohol can include a partially or fully
hydrolyzed
PVOH copolymer that includes an anionic monomer unit, a vinyl alcohol monomer
unit, and
optionally a vinyl acetate monomer unit (i.e., when not completely
hydrolyzed). In some
embodiments, the modified PVOH copolymer can include two or more types of
anionic
monomer units. General classes of anionic monomer units which can be used for
the PVOH
copolymer include the vinyl polymerization units corresponding to sulfonic
acid vinyl monomers
and their esters, monocarboxylic acid vinyl monomers, their esters and
anhydrides, dicarboxylic
monomers having a polymerizable double bond, their esters and anhydrides, and
alkali metal
salts of any of the foregoing. Examples of suitable anionic monomer units
include the vinyl
polymerization units corresponding to vinyl anionic monomers including vinyl
acetic acid,
maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, fumaric
acid, monoalkyl
fumarate, dialkyl fumarate, itaconic acid, monoalkyl itaconate, dialkyl
itaconate, citraconic acid,
monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic
acid, monoalkyl
mesaconate, dialkyl mesaconate, glutaconic acid, monoalkyl glutaconate,
dialkyl glutaconate,
alkyl acrylates, alkyl alkacrylates, vinyl sulfonic acid, allyl sulfonic acid,
ethylene sulfonic acid,
2-acrylamido-1-methyl propane sulfonic acid, 2-acrylamide-2-
methylpropanesulfonic acid, 2-
methylacrylamido-2-methylpropanesulfonic acid (AMPS), 2-sulfoethyl acrylate,
alkali metal
salts of the foregoing (e.g., sodium, potassium, or other alkali metal salts),
esters of the foregoing
(e.g., methyl, ethyl, or other CI-C4 or C6 alkyl esters), and combinations of
the foregoing (e.g.,
multiple types of anionic monomers or equivalent forms of the same anionic
monomer). In some
embodiments, the PVOH copolymer can include two or more types of monomer units
selected
from neutral, anionic, and cationic monomer units.
[0048] The level of incorporation of the one or more anionic monomer units in
the PVOH
copolymers is not particularly limited. In certain embodiments, the one or
more anionic
monomer units are present in the PVOH copolymer in an amount in a range of
about 1 mol.% or
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2 mol.% to about 6 mol.% or 10 mol.% (e.g., at least 1.0, 1.5, 2.0, 2.5, 3.0,
3.5, or 4.0 mol.%
and/or up to about 3.0, 4.0, 4.5, 5.0, 6.0, 8.0, or 10 mol.% in various
embodiments).
[0049] Polyvinyl alcohols can be subject to changes in solubility
characteristics. The acetate
group in the co-poly(vinyl acetate vinyl alcohol) polymer (PVOH copolymer) is
known by those
skilled in the art to be hydrolysable by either acid or alkaline hydrolysis.
As the degree of
hydrolysis increases, a polymer composition made from the PVOH copolymer will
have
increased mechanical strength but reduced solubility at lower temperatures
(e.g., requiring hot
water temperatures for complete dissolution). Accordingly, exposure of a PVOH
homopolymer
to an alkaline environment (e.g., resulting from a laundry bleaching additive)
can transform the
polymer from one which dissolves rapidly and entirely in a given aqueous
environment (e.g., a
cold-water medium) to one which dissolves slowly and/or incompletely in the
aqueous
environment, potentially resulting in undissolved polymeric residue.
[0050] The degree of hydrolysis (DH) of the PVOH homopolymers and PVOH
copolymers
(including modified PVOH copolymers) included in the water-soluble fibers,
foams, and films of
the present disclosure can be in a range of about 75% to about 99.9% (e.g.,
about 79% to about
92%, about 75% to about 89%, about 80% to about 90%, about 88% to 92%, about
86.5% to
about 89%, or about 88%, 90% or 92% such as for cold-water-soluble
compositions; about 90%
to about 99.9%, about 90% to about 99% about 92% to about 99%, about 95% to
about 99%,
about 98% to about 99%, about 98% to about 999%, about 96%, about 98%, about
99%, or
greater than 99%). As the degree of hydrolysis is reduced, a fiber, foam, or
film made from the
polymer will have reduced mechanical strength but faster solubility at
temperatures below about
20 C. As the degree of hydrolysis increases, a fiber, foam, or film made from
the polymer will
tend to be mechanically stronger and the thermoformability will tend to
decrease. The degree of
hydrolysis of the PVOH can be chosen such that the water-solubility of the
polymer is
temperature dependent, and thus the solubility of a film, foam, or fiber made
from the polymer
and additional ingredients is also influenced. In certain embodiments, the
film, foam, and/or
fibers are cold water-soluble. For a co-poly(vinyl acetate vinyl alcohol)
polymer that does not
include any other monomers (e.g., a homopolymer not copolymerized with an
anionic monomer)
a cold water-soluble fiber, foam, or film, soluble in water at a temperature
of less than 10 C, can
include PVOH with a degree of hydrolysis in a range of about 75% to about 90%,
about 75% to
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about 89%, or in a range of about 80% to about 90%, or in a range of about 85%
to about 90%.
In another embodiment, the fiber, foam, or film is hot water-soluble. For a co-
poly(vinyl acetate
vinyl alcohol) polymer that does not include any other monomers (e.g., a
copolymer not
copolymerized with an anionic monomer) a hot water-soluble fiber, foam, or
film that is soluble
in water at a temperature of at least about 60 C, can include PVOH with a
degree of hydrolysis
of at least about 98%. In example embodiments, one of more of the plurality of
fibers comprise a
polyvinyl alcohol polymer having a degree of hydrolysis in a range of about
75% to about
99.9%. In example embodiments, one or more of the plurality of fibers comprise
a polyvinyl
alcohol polymer having a degree of hydrolysis in a range of about 75% to about
98%. In example
embodiments, one of more of the plurality of fibers comprise a polyvinyl
alcohol polymer having
a degree of hydrolysis in a range of about 75% to about 89%. In example
embodiments, one of
more of the plurality of fibers comprise a polyvinyl alcohol polymer having a
degree of
hydrolysis in a range of about 90% to about 99.9%. In example embodiments, the
water-soluble
film comprises a polyvinyl alcohol homopolymer or a PVOH copolymer having a
degree of
hydrolysis in a range of about 75% to about 99.9%. In example embodiments, the
water-soluble
film comprises a polyvinyl alcohol copolymer or a modified polyvinyl alcohol
copolymer having
a degree of hydrolysis in a range of about 75% to about 98%.
[0051] The degree of hydrolysis of a polymer blend can also be characterized
by the
arithmetic weighted, average degree of hydrolysis (H ). For example, H for a
PVOH
polymer that includes two or more PVOH polymers is calculated by the formula
H = E(T/V, = Hi) where W, is the molar percentage of the respective PVOH
polymer and H, is
the respective degrees of hydrolysis. When a polymer is referred to as having
(or not having) a
specific degree of hydrolysis, the polymer can be a single polyvinyl alcohol
polymer having the
specified degree of hydrolysis or a blend of polyvinyl alcohol polymers having
an average
degree of hydrolysis as specified.
[0052] The viscosity of a PVOH polymer ( ) is determined by measuring a
freshly made
solution using a Brookfield LV type viscometer with UL adapter as described in
British Standard
EN ISO 15023-2:2006 Annex E Brookfield Test method. It is international
practice to state the
viscosity of 4% aqueous polyvinyl alcohol solutions at 20 C. All viscosities
specified herein in
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Centipoise (cP) should be understood to refer to the viscosity of 4% aqueous
polyvinyl alcohol
solution at 20 C, unless specified otherwise. Similarly, when a polymer is
described as having
(or not having) a particular viscosity, unless specified otherwise, it is
intended that the specified
viscosity is the average viscosity for the polymer, which inherently has a
corresponding
molecular weight distribution, i.e., the weighted natural log average
viscosity. It is well known in
the art that the viscosity of PVOH polymers is correlated with the weight
average molecular
weight (w) of the PVOH polymer, and often the viscosity is used as a proxy for
the
[0053] In example embodiments, the PVOH resin may have a viscosity of about
1.0 to about
50.0 cP, about 1.0 to about 40.0 cP, or about 1.0 to about 30.0 cP, for
example, about 4 cP, 8 cP,
15 cP, 18 cP, 23 cP, or 26 cP. In example embodiments, the PVOH homopolymers
and/or
copolymers may have a viscosity of about 1.0 to about 40.0 cP, or about 5 cP
to about 23 cP, for
example, about 1 cP, 1.5 cP, 2 cP, 2.5 cP, 3 cP, 3.5 cP, 4 cP, 4.5 cP, 5 cP,
5.5 cP, 6 cP, 6.5 cP, 7
cP, 7.5 cP, 8 cP, 8.5 cP, 9 cP, 9.5 cP, 10 cP, 11 cP, 12 cP, 13 cP, 14 cP, 15
cP, 17.5 cP, 18 cP, 19
cP, 20 cP, 21 cP, 22 cP, 23 cP, 24 cP, 25 cP, 26 cP, 27 cP, 28 cP, 29 cP, 30
cP, 31 cP, 32 cP, 33
cP, 34 cP, 35 cP, or 40 cP. In example embodiments, the PVOH homopolymers
and/or
copolymers may have a viscosity of about 21 cP to 26 cP. In example
embodiments, the PVOH
homopolymers and/or copolymers can have a viscosity of about 5 cP to about 14
cP. In example
embodiments, the PVOH homopolymers and/or copolymers can have a viscosity of
about 5 cP to
about 23 cP.
The water-soluble polymers, whether polyvinyl alcohol polymers or otherwise,
can be blended.
When the polymer blend includes a blend of polyvinyl alcohol polymers, the
PVOH polymer
blend can include a first PVOH polymer (-first PVOH polymer") which can
include a PVOH
copolymer or a modified PVOH copolymer including one or more types of anionic
monomer
units (e.g., a PVOH ter- (or higher co-) polymer) and a second PVOH polymer
("second PVOH
polymer") which can include a PVOH copolymer or a modified PVOH copolymer
including one
or more types of anionic monomer units (e.g., a PVOH ter- (or higher co-)
polymer). In some
embodiments, the PVOH polymer blend includes only the first PVOH polymer and
the second
PVOH polymer (e.g., a binary blend of the two polymers). Alternatively, or
additionally, the
PVOH polymer blend or a fiber, foam, or film made therefrom can be
characterized as being free
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or substantially free from other polymers (e.g., other water-soluble polymers
generally, other
PVOH-based polymers specifically, or both). As used herein, "substantially
free" means that the
first PVOH polymer and the second PVOH polymer make up at least 95 wt.%, at
least 97 wt.%,
or at least 99 wt .% of the total amount of water-soluble polymers in the
water-soluble fiber,
foam, or film. In other embodiments, the water-soluble fiber, foam, or film
can include one or
more additional water-soluble polymers. For example, the PVOH polymer blend
can include a
third PVOH polymer, a fourth PVOH polymer, a fifth PVOH polymer, etc. (e.g.,
one or more
additional PVOH copolymers or modified PVOH copolymers, with or without
anionic monomer
units). For example, the water-soluble fiber or film can include at least a
third (or fourth, fifth,
etc.) water-soluble polymer which is other than a PVOH polymer (e.g., other
than PVOH
copolymers or modified PVOH copolymers, with or without anionic monomer
units). A PVOH
homopolymer may also be included in each blend.
Biodegradability
[0054] Polyvinyl alcohol polymers are generally biodegradable as they
decompose in the
presence of water and enzymes under aerobic, anaerobic, soil, and compost
conditions. In
general, as the degree of hydrolysis of a polyvinyl alcohol polymer increases
up to about 80%,
the biodegradation activity of the polyvinyl alcohol polymer increases.
Without intending to be
bound by theory, it is believed that increasing the degree of hydrolysis above
80% does not
appreciably affect biodegradability. Additionally, the stereoregularity of the
hydroxyl groups of
polyvinyl alcohol polymers has a large effect on the biodegradability activity
level and the more
isotactic the hydroxyl groups of the polymer sequence, the higher the
degradation activity
becomes. Without intending to be bound by theory, for soil and/or compost
biodegradation, it is
believed that a nonwoven substrate or nonwoven web prepared from a polyvinyl
alcohol fiber
will have higher biodegradation activity levels relative to a water-soluble
film prepared from a
similar polyvinyl alcohol polymer, due to the increase in the polymer surface
area provided by
the nonwoven substrate or nonwoven web relative to a film. Further, without
intending to be
bound by theory, it is believed that while the degree of polymerization of the
polyvinyl alcohol
polymer has little to no effect on the biodegradability of a film, foam, or
nonwoven substrate or
web prepared with the polymer, the polymerization temperature may have an
effect on the
biodegradability of a film, foam substrate, or nonwoven substrate because the
polymerization
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temperature can affect the crystallinity and aggregating status of a polymer.
As the crystallinity
decreases, the polymer chain hydroxyl groups become less aligned in the
polymer structure and
the polymer chains become more disordered allowing for chains to accumulate as
amorphous
aggregates, thereby decreasing availability of ordered polymer structures such
that the
biodegradation activity is expected to decrease for soil and/or compost
biodegradation
mechanisms wherein the polymer is not dissolved. Without intending to be bound
by theory, it is
believed that because the stereoregularity of the hydroxyl groups of polyvinyl
alcohol polymers
has a large effect on biodegradability activity levels, the substitution of
functionalities other than
hydroxyl groups (e.g., anionic AMPS functional groups, carboxylate groups, or
lactone groups)
is expected to decrease the biodegradability activity level, relative to a
polyvinyl alcohol
copolymer having the same degree of hydrolysis, unless the functional group
itself is also
biodegradable, in which case biodegradability of the polymer can be increased
with substitution.
Further, it is believed that while the biodegradability activity level of a
substituted polyvinyl
alcohol can be less than that of the corresponding homopolymer or copolymer,
the substituted
polyvinyl alcohol will still exhibit biodegradability.
[0055] Methods of determining biodegradation activity are known in the art,
for example, as
described in Chiellini et al., Progress in Polymer Science, Volume 28, Issue
6, 2003, pp. 963-
1014, which is incorporated herein by reference in its entirety. Further
methods and standards
can be found in ECHA's Annex XV Restriction Report ¨ Microplastics, Version
number 1,
January 11, 2019, which is incorporated herein by reference in its entirety.
Suitable standards
include OECD 301B (ready biodegradation), OECD 301B (enhanced biodegradation),
OECD
302B (inherent biodegradation), OECD 311(anaerobic), and ASTM D5988 (soil).
[0056] In example embodiments, the fibers described herein can be of the
standard ready
biodegradation or enhanced degradation. As used herein, the term "ready
biodegradation" refers
to a standard that is met if the material (e.g., a fiber) reached 60%
biodegradation
(mineralization) within 28 days of the beginning of the test, according to the
OECD 301B test as
described in the ECHA's Annex XV. As used herein, the term "enhanced
biodegradation" refers
to a standard that is met if the material (e.g., a fiber) reaches 60%
biodegradation within 60 days
from the beginning of the test, according to the OECD 301B test as described
in the ECHA's
Annex XV. In example embodiments, the fibers meet the standards of ready
biodegradation.
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Carrier Solvent
[0057] In example embodiments, the carrier solvent comprises a polar solvent.
In example
embodiments, the solvent comprises octanol, heptanol, hexanol, pentanol,
butanol, propanol,
tetrahydrofuran, dichloromethane, acetone, ethanol, N-methylpyrrolidone,
methanol, acetonitrile,
ethylene glycol, /V,N-dimethylformamide, glycerol, dimethyl sulfoxide, formic
acid, water, or a
combination thereof. In example embodiments, the carrier solvent comprises n-
octanol, ii-
heptanol, n-hexanol, n-pentanol, n-butanol, isobutanol, sec-butanol, tert-
butanol, n-propanol,
isopropanol, acetone, ethanol, N-methylpyrrolidone, methanol, acetonitrile,
IV,N-
dimethylformamide, dimethyl sulfoxide, formic acid, water, or a combination
thereof In
example embodiments, the carrier solvent comprises n-propanol, acetone,
ethanol, N-
methylpyrroli done, methanol, acetonitrile, N,N-dimethylformami de, dimethyl
sulfoxide, formic
acid, water, or a combination thereof. In example embodiments, the carrier
solvent comprises an
alcohol that is a liquid under the admixing conditions. In example
embodiments, the carrier
solvent comprises methanol. In example embodiments, the carrier solvent
comprises methanol
and at least one additional solvent. In embodiments, the carrier solvent
comprises methanol and
water. In example embodiments, the carrier solvent comprises at least one of
butanol, pentanol,
hexanol, heptanol, and octanol in combination with water. In example
embodiments, the carrier
solvent comprises DMSO and water. In example embodiments, the carrier solvent
comprises
DMSO and water and the DMSO and water are provided in a weight ratio of about
40/60 to
80/20. Without intending to be bound by theory, it is believed that as the
amount of water
increases above 60% or the amount of DMSO increases above about 80%, the
interaction of the
respective solvents with polyvinyl alcohol increases, resulting in increased
swelling and gelling
of the polymer.
[0058] In example embodiments, the carrier solvent comprises a nonpolar
solvent. In example
embodiments, the carrier solvent comprises hexanes, cyclohexane,
methylpentane, pentane,
cyclopropane, dioxane, benzene, pyridine, xylene, toluene, diethyl ether,
chloroform, or a
combination thereof.
[0059] In example embodiments, the carrier solvent comprises a mixture of a
first carrier
solvent and a second carrier solvent. In example embodiments, the first
carrier solvent comprises
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a polar solvent and the second carrier solvent comprises a nonpolar solvent.
In example
embodiments, the first carrier solvent has a first dielectric constant and the
second carrier solvent
has a second dielectric constant and the dielectric constant of the first
carrier solvent is different
from, e g , higher than, the dielectric constant of the second carrier solvent
In example
embodiments, the first dielectric constant is 5 or less, 4 or less, 3 or less,
or 2 or less. In example
embodiments, the second dielectric constant is greater than 5, greater than
7.5, greater than 10,
greater than 15, greater than 18, greater than 20, greater than 25, or greater
than 30. In example
embodiments, the difference between the first dielectric constant and the
second dielectric
constant is at least 3, at least 5, at least 8, or at least 10. In example
embodiments, wherein the
carrier solvent comprises a mixture of a first carrier solvent and a second
carrier solvent, the first
carrier solvent and the second carrier solvent can be provided in any ratio
provided the fiber is
not soluble in the mixture prior to treatment, during treatment, and after
treatment. In example
embodiments, the first carrier solvent and the second carrier solvent can be
provided in a weight
ratio of about 99/1 to about 1/99, about 95/5 to about 5/95, about 90/10 to
10/90, about 85/15 to
about 15/85, about 80/20 to about 20/80, about 75/25 to about 25/75, about
70/30 to about 30/70,
about 65/35 to about 35/65, about 60/40 to about 40/60, about 55/45 to about
45/55, or about
50/50.
Active Cleaning Formulations
[0060] In example embodiments, the article and, more specifically, the water-
dispersible
and/or water-soluble core substrate, is configured to contain a carrier
solvent with one or more
active cleaning formulations, such as a dish wash detergent formulation. In
example
embodiments, the carrier solvent with the active cleaning formulation is
disposed on, e.g.,
applied to or coated on, one or more surfaces of the core substrate or is
embedded in and/or
adhered to the core substrate. The core substrate may include a single layer,
for example, a single
layer nonwoven core substrate, or may include a plurality of layers, for
example, a sheet of
nonwoven core substrate folded in a serpentine arrangement or plied to form
layers with the
carrier solvent with the active cleaning formulation disposed between adjacent
layers of the
nonwoven core substrate, for example. As an example, the active cleaning
formulation may
include, without limitation, an active, a sanitizing agent and/or a dish
detergent, soap or cleaner.
Other examples include a laundry detergent, a soap, a fabric softener, a
bleaching agent, a
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laundry booster, a stain remover, an optical brightener, or a water softener,
a shampoo, a
conditioner, a body wash, a face wash, a skin lotion, a skin treatment, a body
oil, fragrance, a
hair treatment, a bath salt, an essential oil, a bath bomb, or an enzyme.
Auxiliary Agents
[0061] In general, along with the film-forming, foam-forming, and/or fiber-
forming material,
the fibers, nonwoven substrates or webs, foam substrates, and/or water-soluble
films of the
disclosure can include auxiliary agents such as, but not limited to,
sanitizers or sanitizing agents,
plasticizers, plasticizer compatibilizers, surfactants, lubricants, release
agents, fillers, extenders,
cross-linking agents, antiblocking agents, antioxidants, detackifying agents,
antifoams,
nanoparticles such as layered silicate-type nanoclays (e.g., sodium
montmorillonite), bleaching
agents (e.g., sodium metabisulfite, sodium bisulfite or others), aversive
agents such as bitterants
(e.g., denatonium salts such as denatonium benzoate, denatonium saccharide,
and denatonium
chloride; sucrose octaacetate; quinine; flavonoids such as quercetin and
naringen; and
quassinoids such as quassin and brucine) and pungents (e.g., capsaicin,
piperine, allyl
isothiocyanate, and resinferatoxin), and other functional ingredients, in
amounts suitable for their
intended purposes. Suitable sanitizing agents include, without limitation, one
or more of the
following sanitizing agents: Quaternary Ammonium Compounds (QACs), halogenated
oxidizers,
hypochlorous acid generating compounds, hypochlorite generating compounds, 1-
Bromo-3-
chloro-5,5-dimethylhydantoin, dichloroisocyanuric acid, alcohols including,
without limitation,
methanol, ethanol, isopropyl alcohol, and/or other longer chain alcohols,
oxygen radical
generators, hydrogen peroxide (H202), sulfate generating compounds,
Methylisothiazolinone
(MIT), Benzisothiazolinone (BIT), or sodium metabisulfite. As used herein and
unless specified
otherwise, "auxiliary agents" include secondary additives, processing agents,
and active agents.
Specific such auxiliary agents can be selected from those suitable for use in
water-soluble fibers,
non-water-soluble fibers, nonwoven webs, foams, or those suitable for use in
water-soluble
films.
[0062] In example embodiments, the fibers, foams, and/or films can be free of
auxiliary
agents. As used herein and unless specified otherwise, "free of auxiliary
agents" with respect to
the fiber means that the fiber includes less than about 0.01 wt.%, less than
about 0.005 wt.%, or
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less than about 0.001 wt.% of auxiliary agents, based on the total weight of
the fiber. As used
herein and unless specified otherwise, "free of auxiliary agents" with respect
to the nonwoven
substrate or web means that the nonwoven substrate or web includes less than
about 0.01 wt.%,
less than about 0.005 wt.%, or less than about 0.001 wt.% of auxiliary agents,
based on the total
weight of the nonwoven substrate or web. In example embodiments, the water-
soluble fibers
comprise a plasticizer. In example embodiments, the water-soluble fibers
comprise a surfactant.
In example embodiments, the non-water-soluble fibers comprise a plasticizer.
In example
embodiments, the non-water-soluble fibers comprise a surfactant. In example
embodiments, the
nonwoven substrate or web includes a plasticizer. In example embodiments, the
nonwoven
substrate or web includes a surfactant.
[0063] A plasticizer is a liquid, solid, or semi-solid that is added
to a material (usually a resin
or elastomer) making that material softer, more flexible (by decreasing the
glass-transition
temperature of the polymer), and easier to process. A polymer can
alternatively be internally
plasticized by chemically modifying the polymer or monomer. In addition, or in
the alternative, a
polymer can be externally plasticized by the addition of a suitable
plasticizing agent. Water is
recognized as a very efficient plasticizer for PVOH polymer and other polymers
including, but
not limited to, water-soluble polymers; however, the volatility of water makes
its utility limited
because polymer films need to have at least some resistance (robustness) to a
variety of ambient
conditions including low and high relative humidity.
[0064] The plasticizer can include, without limitation, glycerin,
diglycerin, sorbitol, xylitol,
maltitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene
glycol, tetraethylene
glycol, propylene glycol, polyethylene glycols up to 1000 MW, neopentyl
glycol,
trimethylolpropane, polyether polyols, sorbitol, 2-methyl-1,3-propanediol
(MPDioh1D),
ethanolamines, and a mixture thereof.
[0065] Surfactants for use in films are well known in the art and can suitably
be used in the
fibers, foam, films, and/or compositions of the disclosure. Optionally,
surfactants are included to
aid in the dispersion of the fibers during carding. Optionally, surfactants
are included as cleaning
aids. Suitable surfactants can include the nonionic, cationic, anionic and
zwitterionic classes.
Suitable surfactants include, but are not limited to, propylene glycols,
diethylene glycols,
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monoethanolamine, polyoxyethylenated polyoxypropylene glycols, alcohol
ethoxylates,
alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides
(nonionics),
polyoxyethylenated amines, quaternary ammonium salts and quaternized
polyoxyethylenated
amines (cationics), alkali metal salts of higher fatty acids containing about
S to 24 carbon atoms,
alkyl sulfates, alkyl polyethoxylate sulfates and alkylbenzene sulfonates
(anionics), and amine
oxides, N-alkylbetaines and sulfobetaines (zwitterionics). Other suitable
surfactants include
dioctyl sodium sulfosuccinate, lactylated fatty acid esters of glycerin and
propylene glycol,
lactylic esters of fatty acids, sodium alkyl sulfates, polysorbate 20,
polysorbate 60, polysorbate
65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerin and
propylene glycol, and
odium lauryl sulfate, acetylated esters of fatty acids, myristyl dimethylamine
oxide, trimethyl
tallow alkyl ammonium chloride, quaternary ammonium compounds, alkali metal
salts of higher
fatty acids containing about 8 to 24 carbon atoms, alkyl sulfates, alkyl
polyethoxylate sulfates,
alkylbenzene sulfonates, monoethanolamine, lauryl alcohol ethoxylate,
propylene glycol,
diethylene glycol, sodium cocoyl isethionate, sodium lauryl sulfate,
glucotain, phoenamids, cola
lipid, cocamides, such as cocamide ethanolamines, ethylene oxide based
surfactants, saponified
oils of avocado and palm, salts thereof and combinations of any of the
foregoing. In example
embodiments, the surfactant comprises a cocamide. Without intending to be
bound by theory, it
is believed that a cocamide can aid in foam formation, enhancing the foaming
experience of an
article comprising a personal care composition. In various embodiments, the
amount of
surfactant in the fiber is in a range of about 0.01 wt.% to about 10 wt.%,
about 0.1 wt.% to about
wt.%, about 1.0 wt.% to about 2.5 wt.%, about 0.01 wt.% to about 1.5 wt.%,
about 0.1 wt.% to
about 1 wt.%, about 0.01 wt.% to 0.25 wt.%, or about 0.10 wt.% to 0.20 wt.%.
[0066] In example embodiments, the nonwoven substrates or webs, foam, and/or
films of the
disclosure can further comprise auxiliary agents such as one or more auxiliary
agents in the
group of: an exfoliant (chemical exfoliants and mechanical exfoliants), a
fragrance and/or
perfume microcapsule, an aversive agent, a surfactant, a colorant, an enzyme,
a skin conditioner,
a de-oiling agent, and a cosmetic agent.
[0067] In example embodiments, an auxiliary agent is provided in or on one or
more of the
nonwoven web, the foam, the plurality of fibers, and the water-soluble film.
In example
embodiments, an active cleaning formulation is provided on or in one or more
of the group of the
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nonwoven web, the plurality of fibers, and the water-soluble film. In example
embodiments, one
or more auxiliary agents can be provided on the surface of the nonwoven web.
In example
embodiments, one or more auxiliary agents can be dispersed among the fibers of
the nonwoven
web Tn example embodiments, one or more auxiliary agents can be dispersed on a
face of the
nonwoven web. In example embodiments, one or more auxiliary agents can be
dispersed in the
fibers. In example embodiments, one or more auxiliary agents can be dispersed
on the fibers. In
example embodiments, one or more auxiliary agents can be provided on a face of
the water-
soluble film.
[0068] The chemical exfoliants, mechanical exfoliants, fragrances and/or
perfume
microcapsules, aversive agents, surfactants, colorants, proteins, peptides,
enzymes, skin
conditioners, de-oiling agents, cosmetic agents, or a combination thereof,
when present, can be
provided in an amount of at least about 1 wt.%, or in a range of about 1 wt.%
to about 99 wt.%
based on the weight of the polymeric mixture (e.g., fiber forming material or
film forming
material). In example embodiments, the chemical exfoliants, mechanical
exfoliants, fragrances
and/or perfume microcapsules, aversive agents, surfactants, colorants,
enzymes, skin
conditioners, de-oiling agents, and/or cosmetic agents can be provided in an
amount sufficient to
provide additional functionality to the fiber and/or film, such as exfoliation
of human skin. The
chemical exfoliants, mechanical exfoliants, fragrances and/or perfume
microcapsules, aversive
agents, surfactants, colorants, enzymes, skin conditioners, de-oiling agents,
cosmetic agents, or a
combination thereof, can take any desired form, including as a solid (e.g.,
powder, granulate,
crystal, flake, or ribbon), a liquid, a mull, a paste, a gas, etc., and
optionally can be encapsulated,
such as microcapsules.
[0069] In certain embodiments, the nonwoven substrate or web, foam, and/or
film can
comprise an enzyme. Suitable enzymes include enzymes categorized in any one of
the six
conventional Enzyme Commission (EC) categories, i.e., the oxidoreductases of
EC 1 (which
catalyze oxidation/reduction reactions), the transferases of EC 2 (which
transfer a functional
group, e.g., a methyl or phosphate group), the hydrolases of EC 3 (which
catalyze the hydrolysis
of various bonds), the lyases of EC 4 (which cleave various bonds by means
other than
hydrolysis and oxidation), the isomerases of EC 5 (which catalyze
isomerization changes within
a molecule) and the ligases of EC 6 (which join two molecules with covalent
bonds). Examples
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of such enzymes include dehydrogenases and oxidases in EC 1, transaminases and
kinases in EC
2, lipases, cellulases, amylases, mannanases, and peptidases (a.k.a. proteases
or proteolytic
enzymes) in EC 3, decarboxylases in EC 4, isomerases and mutases in EC 5 and
synthetases and
synthases of EC 6 Suitable enzymes from each category are described in, for
example, U.S
Patent No. 9,394,092, the entire disclosure of which is herein incorporated by
reference. In
certain embodiments, enzymes can include bromeline (pineapple extract), papain
(papaya), ficin
(fig), actinidin (kiwi), hyaluronidase, lipase, peroxidase, superoxide
dismutase, tyrosinase,
alkaline phosphatase, or a combination thereof. In example embodiments, the
enzyme can be
encapsulated in the form of, for example, nanoemulsions, nanocapsules,
granules or a
combination thereof.
[0070] Enzymes for use in laundry and dishwashing applications can include one
or more of
protease, amylase, lipase, dehydrogenase, transaminase, kinase, cellulase,
mannanase, peptidase,
decarboxylase, isomerase, mutase, synthetase, synthase, and oxido-reductase
enzymes, including
oxido-reductase enzymes that catalyze the formation of bleaching agents.
[0071] It is contemplated that an enzyme for use herein can come from any
suitable source or
combination of sources, for example, bacterial, fungal, plant, or animal
sources. In one
embodiment, a mixture of two or more enzymes will come from at least two
different types of
sources. For example, a mixture of protease and lipase can come from a
bacterial (protease) and
fungal (lipase) sources.
[0072] Optionally, an enzyme for use herein, including but not limited to any
enzyme class or
member described herein, is one which works in alkaline pH conditions, e.g., a
pH in a range of
about 8 to about 11. Optionally, an enzyme for use herein, including but not
limited to any
enzyme class or member described herein, is one which works in a temperature
in a range of
about 5 C to about 45 C.
[0073] In example embodiments, the nonwoven substrate or web, foam, and/or
film can
comprise a protein and/or peptide. Suitable proteins and/or peptides can
include, but are not
limited to, collagen and/or collagen peptides, or amino acids, for example,
aspartic acid, glutamic
acid, serine, histidine, glycine, threonine, arginine, alanine, tyrosine,
cysteine, valine,
methionine, phenylalanine, isoleucine, leucine, lysine, hydroxyproline, or
proline.
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[0074] In example embodiments, the nonwoven substrate or web, foam, and/or
film can
comprise a colorant. Suitable colorants can include an indicator dye, such as
a pH indicator (e.g.,
thymol blue, bromothymol, thymolphthalein, and thymolphthalein), a
moisture/water indicator
(e g , hydrochromic inks orleuco dyes), or a thermochromic ink, wherein the
ink changes color
when temperature increases and/or decreases. Suitable colorants include, but
are not limited to a
triphenylmethane dye, an azo dye, an anthraquinone dye, a perylene dye, an
indigoid dye, a food,
drug and cosmetic (FD&C) colorant, an organic pigment, an inorganic pigment,
or a combination
thereof. Examples of colorants include, but are not limited to, FD&C Red #40;
Red #3; FD&C
Black #3; Black #2; Mica-based pearlescent pigment; FD&C Yellow #6; Green #3;
Blue #1;
Blue #2; titanium dioxide (food grade); brilliant black; and a combination
thereof. Other
examples of suitable colorants can be found in U.S. Patent No. 5,002,789,
hereby incorporated
by reference in its entirety.
[0075] Other embodiments can include one or more fragrances in the nonwoven
substrate or
webs, foams, and/or films of the disclosure. As used herein, the term
"fragrance" refers to any
applicable material that is sufficiently volatile to produce a scent.
Embodiments including
fragrances can include fragrances that are scents pleasurable to humans, or
alternatively
fragrances that are scents repellant to humans, animals, and/or insects.
Suitable fragrances
include, but are not limited to, fruits including, but not limited to, lemon,
apple, cherry, grape,
pear, pineapple, orange, strawberry, raspberry, musk, and flower scents
including, but not limited
to, lavender-like, rose-like, iris-like and carnation-like. Optionally, the
fragrance is one which is
not also a flavoring. Other fragrances include herbal scents including, but
not limited to,
rosemary, thyme, and sage; and woodland scents derived from pine, spruce, and
other forest
smells. Fragrances may also be derived from various oils, including, but not
limited to, essential
oils, or from plant materials including, but not limited to, peppermint,
spearmint, and the like or
any combination thereof. Suitable fragrant oils can be found in U.S. Patent
No. 6,458,754,
hereby incorporated by reference in its entirety. Suitable fragrant oils
include, but are not limited
to, 4-(2,2,6-trimethylcyclohex-1-eny1)-2-en-4-one, acetaldehyde phenylethyl
propyl acetal,
2,6,10-trimethy1-9-undecenal, hexanoic acid 2-propenyl ester, 1-octen-3-ol,
trans-anethole, iso
butyl (z)-2-methyl-2-butenoate, anisaldehyde diethyl acetal, 3-methy1-5-propyl-
cyclohezen-1-
one, 2,4-dimethy1-3-cyclohexene-1-carbaldehyde, trans-4-decenal, decanal, 2-
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pentylcyclopentanone, ethyl anthranilate, eugenol, 3-(3-
isopropylphenyl)butanal, methyl 2-
octynoate, isoeugenol, cis-3-hexenyl methyl carbonate, linalool, methyl-2-
nonynonate, benzoic
acid 2-hydroxymethyl ester, nonal, octanal, 2-nonennitrile, 4-nonanolide, 9-
decen-1 -ol, and 10-
undecen-l-al . Applicable fragrances can also be found in U.S. Patent Nos.
4,534,981; 5,112,688;
5,145,842; 6,844,302; and Perfumes Cosmetics and Soaps, Second Edition, edited
by W. A.
Poucher, 1959, all hereby incorporated by reference in their entireties. These
fragrances include
acacia, cassie, chypre, cyclamen, fern, gardenia, hawthorn, heliotrope,
honeysuckle, hyacinth,
jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cut hay, orange
blossom, orchids,
reseda, sweet pea, trefle, tuberose, vanilla, violet, wallflower, and the like
or any combination
thereof.
[0076] Fragrances can include perfumes. The perfume may comprise neat perfume,
encapsulated perfume, or mixtures thereof. In example embodiments, the perfume
includes neat
perfume. A portion of the perfume may be encapsulated in a core-shell
encapsulate. In other
embodiments, the perfume will not be encapsulated in a core/shell encapsulate.
[0077] As used herein, the term "perfume" encompasses the perfume raw
materials (PRMs)
and perfume accords. The term "perfume raw material" as used herein refers to
compounds
having a molecular weight of at least about 100 g/mol and which are useful in
imparting an odor,
fragrance, essence or scent, either alone or with other perfume raw materials.
As used herein, the
terms "perfume ingredient" and "perfume raw material" are interchangeable. The
term "accord"
as used herein refers to a mixture of two or more PRMs. In example
embodiments, any of the
perfume accords, perfume raw materials, or fragrances can be encompassed in a
microcapsule,
termed "perfume microcapsules" as used herein.
[0078] Typical PRM comprise inter alia alcohols, ketones, aldehydes, esters,
ethers, nitrites,
and alkenes, such as terpene. A listing of common PRMs can be found in various
reference
sources, for example, "Perfume and Flavor Chemicals," Vols. I and II; Steffen
Arctander Allured
Pub. Co. (1994) and "Perfumes: Art, Science and Technology," Miller, P. M. and
Lamparsky,
D., Blackie Academic and Professional (1994). The PRMs are characterized by
their boiling
points (B.P.) measured at the normal pressure (760 mm Hg), and their
octanol/water partitioning
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coefficient (P). Based on these characteristics, the PRMS may be categorized
as Quadrant I,
Quadrant II, Quadrant III, or Quadrant IV perfumes.
[0079] In example embodiments, the nonwoven web, foam, and/or film can include
an
exfoliant. In example embodiments, the exfoliant can comprise a chemical
exfoliant or a
mechanical exfoliant. Suitable mechanical exfoliants for use herein can
include, but are not
limited to, apricot shells, sugar, oatmeal, salt, silica, diatomaceous earth,
clay, aluminum
hydrates, PVOH microbeads, pumice, or a combination thereof. Suitable chemical
exfoliants for
use herein can include, but are not limited to, alpha hydroxyl acid, beta
hydroxyl acid, enzyme,
salicylic acid, glycolic acid, citric acid, malic acid, or a combination
thereof.
[0080] In certain embodiments, the aversive agents, surfactants, colorants,
enzymes, skin
conditioners, de-oiling agents, cosmetic agents, or a combination thereof, are
encapsulated,
allowing for controlled release. Suitable microcapsules can include or be made
from one or more
of melamine formaldehyde, polyurethane, urea formaldehyde, chitosan,
polymethyl
methacrylate, polystyrene, polysulfone, poly tetrahydrofuran, gelatin, gum
arabic, starch,
polyvinyl pyrrolidone, carboxymethylcellulose, hydroxyethylcellulose,
methylcellulose,
arabinogalactan, polyvinyl alcohol, polyacrylic acid, ethylcellulose,
polyethylene,
polymethacrylate, polyamide, poly (ethylenevinyl acetate), cellulose nitrate,
silicones,
poly(lactideco-glycolide), paraffin, carnauba, spermaceti, beeswax, stearic
acid, stearyl alcohol,
glyceryl stearates, shellac, cellulose acetate phthalate, zein, and
combinations thereof In one
type of embodiment, the microcapsule is characterized by a mean particle size
(e.g., Dv50) of at
least about 0.1 micron, or in a range of about 0.1 micron to about 200
microns, for example. In
alternate embodiments, the microcapsules can form agglomerates of individual
particles, for
example wherein the individual particles have a mean particle size of at least
about 0.1 micron,
or in a range of about 0.1 micron to about 200 microns.
Water-dispersible and/or Water-Soluble Fibers
[0081] As described, fibers used for making a core substrate are water-
dispersible and/or
water-soluble. The fibers may be dispersible at a lower temperature (e.g., 10-
40 C) and soluble
in water at a higher temperature (e.g., above 40 C). Such fibers are referred
as water-soluble
fibers for the conciseness of the description. Water-soluble fibers include
fibers and/or fiber
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forming materials made of any material that, when provided as the sole resin
in a film or foam,
or sole fiber forming material in a nonwoven, the film, foam, or nonwoven
dissolves in 300
seconds or less at temperatures of 80 C or less, as determined by MSTM-205.
The water-soluble
fibers can include a single water-soluble polymer or a blend of water-soluble
polymers. Suitable
water-soluble polymers include, but are not limited to, polyvinyl alcohol
homopolymer,
polyvinyl alcohol copolymer, modified polyvinyl alcohol copolymer,
polyacrylate, water-soluble
acrylate copolymer, polyvinyl pyrrolidone, polyethyleneimine, pullul an, water-
soluble natural
polymer including, but not limited to, guar gum, gum Acacia, xanthan gum,
carrageenan, and
starch, water-soluble polymer derivatives including, but not limited to,
modified starches,
ethoxylated starch, and hydroxypropylated starch, copolymers of the forgoing
and combinations
of any of the foregoing. Yet other water-soluble fibers can include
polyalkylene oxides,
polyacrylamides, polyacrylic acids and salts thereof, celluloses, cellulose
ethers, cellulose esters,
cellulose amides, polyvinyl acetates, polycarboxylic acids and salts thereof,
polyaminoacids,
polyamides, gelatines, methylcelluloses, carboxymethylcelluloses and salts
thereof, dextrins,
ethylcelluloses, hydroxyethyl celluloses, hydroxypropyl methylcelluloses,
maltodextrins,
polymethacrylates, and combinations of any of the foregoing. In example
embodiments, the
water-soluble fibers can include a PVOH copolymer fiber forming material,
modified PVOH
copolymer fiber forming material, or a combination thereof. In example
embodiments, the water-
soluble fibers can comprise a sole PVOH homopolymer fiber forming material or
a blend of
PVOH copolymer fiber forming materials. In example embodiments, the water-
soluble fibers can
comprise a hot water-soluble PVOH homopolymer fiber forming material. In
further
embodiments, the water-soluble fibers can comprise a PVOH copolymer fiber
forming material
with a viscosity in a range of 5 cP to 23 cP and a degree of hydrolysis in a
range of 86% to 92%.
[0082] In example embodiments, the water-soluble fibers can include an
auxiliary agent as
described above. In example embodiments, the water-soluble fibers can be
substantially free of
auxiliary agents as described above. In example embodiments, the water-soluble
fibers can
include a plasticizer as described above. The total amount of the non-water
plasticizer provided
in the water-soluble fiber can be in a range of about 1 wt.% to about 45 wt.%,
or about 5 wt.% to
about 45 wt.%, or about 10 wt.% to about 40 wt.%, or about 20 wt.% to about 30
wt.%, about 1
wt.% to about 4 wt.%, or about 1.5 wt.% to about 3.5 wt.%, or about 2.0 wt.%
to about 3.0 wt.%,
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for example about 1 wt.%, about 2.5 wt.%, about 5 wt.%, about 10 wt.%, about
15 wt.%, about
20 wt.%, about 25 wt.%, about 30 wt.%, about 35 wt.%, or about 40 wt.%, based
on total fiber
weight. In example embodiments, the water-soluble fibers comprise glycerin,
sorbitol, or a
combination thereof. Tn example embodiments, the water-soluble fibers comprise
glycerin. Tn
example embodiments, the water-soluble fibers comprise sorbitol. In certain
embodiments, the
water-soluble fibers can include glycerin, for example, in about 10 wt.% based
on total fiber
weight, and sorbitol, for example, in about 5 wt.% based on the total fiber
weight.
[0083] In example embodiments, the water-soluble fibers can include a
surfactant as described
above. In various embodiments, the amount of surfactant in the water-soluble
fiber is in a range
of about 0.01 wt.%, to about 2.5 wt.%, about 0.1 wt.% to about 2.5 wt.%, about
1.0 wt.% to
about 2.0 wt.%, about 0.01 wt.% to 0.25 wt.%, or about 0.10 wt.% to 0.20 wt.%.
[0084] In example embodiments, any of the auxiliary agents disclosed herein
can be added to
the fibers of the disclosure. In refinements of the forgoing embodiment, the
auxiliary agents can
be added to the fiber forming material prior to formation of the fiber such
that the auxiliary
agents are dispersed in the fiber. In addition, and/or in the alternative,
auxiliary agents can be
added to the surface of a fiber after fiber formation (e.g., dispersed on the
fibers).
[0085] When included in the water-soluble fiber, a colorant can be provided in
an amount of
0.01% to 25% by weight of the polymer mixture, such as, 0.02%, 0.05%, 0.1%,
0.5%, 1%, 2%,
3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%,
20%,
21%, 22%, 23%, and 24% by weight of the polymer mixture.
Non-Water-Soluble Fibers
[0086] Non-water-soluble fibers generally include fibers and/or fiber forming
materials made
of any material that, when provided in a film as the sole film forming
material or provided in a
nonwoven web or foam as the sole fiber forming material, the film, the
nonwoven web, or the
foam does not dissolve in 300 seconds or less at temperatures of 80 C or less,
as determined by
MSTM-205. The non-water-soluble fibers can include a sole non-water-soluble
polymer fiber
forming material or a blend of non-water-soluble polymer fiber forming
materials. Suitable non-
water-soluble fibers and/or non-water-soluble fiber forming materials include,
but are not limited
to, cotton, polyester, polyethylene (e.g., high density polyethylene and low
density
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polyethylene), polypropylene, wood pulp, fluff pulp, abaca, viscose,
polylactic acid, polyester,
nylon 6, insoluble cellulose, insoluble starch, hemp, jute, flax, ramie,
sisal, bagasse, banana fiber,
lacebark, silk, sinew, catgut, wool, sea silk, mohair, angora, cashmere,
collagen, actin, nylon,
dacron, rayon, bamboo fiber, modal, dia.cetate fiber, tri acetate fiber, and
combinations thereof. Tn
example embodiments, the non-water-soluble fiber forming material and/or non-
water-soluble
fibers comprise one or more of the group of: cotton, hemp, jute, flax, ramie,
sisal, bagasse,
banana, lacebark, silk, sinew, catgut, wool, sea silk, mohair, angora,
cashmere, collagen, actin,
nylon, dacron, rayon, bamboo, modal, diacetate fiber, triacetate fiberõ or a
combination thereof.
[0087] In example embodiments, the non-water-soluble fibers can include an
auxiliary agent
as described above. In example embodiments, the non-water-soluble fibers can
be substantially
free of auxiliary agents as described above. In example embodiments, the non-
water-soluble
fibers can include a plasticizer as described above. The total amount of the
non-water plasticizer
provided in the non-water-soluble fiber can be in a range of about 1 wt.% to
about 45 wt.%, or
about 5 wt.% to about 45 wt.%, or about 10 wt.% to about 40 wt.%, or about 20
wt.% to about 30
wt.%, about 1 wt.% to about 4 wt.%, or about 1.5 wt.% to about 3.5 wt.%, or
about 2.0 wt.% to
about 3.0 wt.%, for example, about 1 wt.%, about 2.5 wt %, about 5 wt.%, about
10 wt.%, about
15 wt.%, about 20 wt.%, about 25 wt.%, about 30 wt.%, about 35 wt.%, or about
40 wt.%, based
on total fiber weight. In example embodiments, the non-water-soluble fibers
comprise glycerin,
sorbitol, or a combination thereof. In example embodiments, the non-water-
soluble fibers
comprise glycerin. In example embodiments, the non-water-soluble fibers
comprise sorbitol. In
certain embodiments, the non-water-soluble fibers can include a plasticizer
such as glycerin, for
example in about 10 wt% based on total fiber weight, and sorbitol, for example
in about 5 wt%
based on the total fiber weight.
[0088] In example embodiments, the non-water-soluble fibers can include a
surfactant as
described above. In various embodiments, the amount of surfactant in the water-
soluble fiber is
in a range of about 0.01 wt.%, to about 2.5 wt.%, about 0.1 wt.% to about 2.5
wt.%, about 1.0
wt.% to about 2.0 wt.%, about 0.01 wt.% to 0.25 wt.%, or about 0.10 wt.% to
0.20 wt.%.
[0089] In example embodiments, any of the auxiliary agents disclosed herein
can be added to
the fibers of the disclosure. In refinements of the forgoing embodiment can be
added to the fiber
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forming material prior to formation of the fiber such that the auxiliary
agents can be added to the
surface of a fiber after fiber formation. In refinements of the foregoing
embodiments, the
auxiliary agents can be added to a surface of the fiber after fiber formation.
[0090] When included in the non-water-soluble fiber, the colorant can be
provided in an
amount of 0.01% to 25% by weight of the polymer mixture, such as, 0.02%,
0.05%, 0.1%, 0.5%,
1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%,
18%,
19%, 20%, 21%, 22%, 23%, and 24% by weight of the polymer mixture.
Nonwoven Webs or Nonwoven Substrates
[0091] The nonwoven web or nonwoven substrates of the disclosure can be water-
soluble (or
water dispersible), non-water-soluble, or at least partially non-water-
soluble. The article of the
disclosure can include a nonwoven web, wherein at least a portion of the
nonwoven web is
soluble in water at a temperature in a range of about 0 C to about 20 C
according to MSTM-205,
or at least a portion of the nonwoven web is not soluble in water at a
temperature of 20 C or less
according to MSTM-205, or the nonwoven web is not soluble in water at a
temperature of 20 C
or less according to MSTM-205, or the nonwoven web is soluble in water at a
temperature in a
range of about 0 C to about 20 C according to MSTM-205. It will be understood
that "at least a
portion" of a nonwoven web is soluble (or not soluble) at a given temperature
if the nonwoven
web includes in the plurality of the fibers, a fiber type which when provided
in a nonwoven as
the sole fiber type, the nonwoven web consisting of that fiber type is soluble
(or not soluble) at
the given temperature, according to MSTM-205.
[0092] The nonwoven web of the disclosure includes a plurality of fibers. A
nonwoven web
refers to an arrangement of fibers bonded to one another, wherein the fibers
are neither woven
nor knitted. The plurality of fibers can be arranged in any orientation. In
example embodiments,
the plurality of fibers are arranged randomly (i.e., do not have an
orientation). In example
embodiments, the plurality of fibers are arranged in a unidirectional
orientation. In example
embodiments, the plurality of fibers are arranged in a bidirectional
orientation. In some
embodiments, the plurality of fibers are multi-directional, having different
arrangements in
different areas of the nonwoven web.
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[0093] The plurality of fibers in any given nonwoven web can include any fiber-
forming
materials disclosed herein. The nonwoven web can include (1) a single fiber
type including a
single fiber forming material, (2) a single fiber type including a blend of
fiber forming materials,
(3) a blend of fiber types, each fiber type including a single fiber forming
material, (4) a blend of
fiber types, each fiber type including a blend of fiber forming materials, or
(5) a blend of fiber
types, each fiber type including a single fiber forming material or a blend of
fiber forming
materials. In example embodiments including a blend of fiber types, the
different fiber types can
have a difference in one or more of the group of length to diameter ratio
(LID), tenacity, shape,
rigidness, elasticity, solubility, melting point, glass transition temperature
(TO, fiber forming
material chemistries, and color. In certain embodiments, the plurality of
fibers can comprise two
or more types of water-soluble fibers. In example embodiments, the plurality
of fibers can
comprise at least one fiber type comprising at least one type of water-soluble
fiber forming
materials and at least one fiber type comprising at least type of one non-
water-soluble fiber. In
example embodiments, the plurality of fibers can comprise two or more fiber
types comprising at
least one type of non-water-soluble fiber forming material.
[0094] In example embodiments, the nonwoven web can further comprise any
carrier solvent
with any suitable active cleaning formulation and/or any auxiliary agents as
disclosed herein for
fibers and/or films. In example embodiments, the carrier solvent, the active
cleaning formulation,
and/or the auxiliary agents can be added to the fiber itself, to the nonwoven
web during carding
of the nonwoven web, to the nonwoven web prior to bonding (e.g., after
carding), to the
nonwoven web after bonding, or a combination thereof. The carrier solvent,
active cleaning
formulation, and/or auxiliary agents added to the fibers during carding can be
distributed
throughout the nonwoven web. The carrier solvent, active cleaning formulation,
and/or auxiliary
agents added to the nonwoven web after carding but prior to bonding can be
selectively added to
one or both faces of the nonwoven web.
[0095] The carrier solvent, active cleaning formulation, and/or auxiliary
agents can be applied
to one or more faces of a nonwoven web or to an article containing same, e.g.,
a packet, by any
suitable means. In example embodiments, the carrier solvent, active cleaning
formulation, and/or
auxiliary agents are in powder form. In refinements of the foregoing
embodiment, one or more
stationary powder spray guns are used to direct the powder stream towards the
web or a packet,
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from one or more than one direction, while the web or packet is transported
through the coating
zone by means of a belt conveyor. In example embodiments, a web or packet is
conveyed
through a suspension of the powder in air. In example embodiments, the webs or
packets are
tumble-mixed with the powder in a trough-like apparatus Tn example
embodiments, which can
be combined with any other embodiment, electrostatic forces are employed to
enhance the
attraction between the powder and the packet or web. This type of process may
be based on
negatively charging the powder particles and directing these charged particles
to the grounded
packets or webs. In other alternative embodiments, the powder is applied to
the web or packet by
a secondary transferring tool including, but not limited to, rotating brushes
which are in contact
with the powder or by powdered gloves which can transfer the powder from a
container to the
web or packet. In yet another embodiment, the powder is applied by dissolving
or suspending the
powder in a non-aqueous solvent or carrier which is then atomized and sprayed
onto the web or
packet. In one embodiment, the solvent or carrier subsequently evaporates,
leaving the active
agent powder behind. In certain embodiments, the powder is applied to the web
or packet in an
accurate dose. These embodiments utilize closed-system dry lubricant
application machinery,
such as PekuTECH's powder applicator PM 700 D. In this process, the powder,
optionally batch-
wise or continuously, is fed to a feed trough of application machinery. The
webs or packets are
transferred from the output belt of a standard rotary drum pouch machine onto
a conveyor belt of
the powder application machine, wherein a controlled dosage of the powder is
applied to the web
or packet The web or packet can thereafter be conveyed to a suitable secondary
packaging
process.
[0096] In example embodiments wherein the carrier solvent, active cleaning
formulation,
and/or auxiliary agents are in liquid form or in a solution, the foregoing can
be dispersed among
the fibers, dispersed on a face of the nonwoven web, or a combination thereof,
for example, by
spin casting, spraying a solution such as an aerosolized solution, roll
coating, flow coating,
curtain coating, extrusion, knife coating, and combinations thereof.
[0097] The auxiliary agents, such as chemical exfoliants, mechanical
exfoliants, fragrances
and/or perfume microcapsules, aversive agents, surfactants, colorants,
enzymes, skin
conditioners, de-oiling agents, cosmetic agents, or a combination thereof,
when present in the
nonwoven web, are in an amount of at least about 1 wt.%, or in a range of
about 1 wt.% to about
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99 wt.%, provides additional functionality to the nonwoven web. The chemical
exfoliants,
mechanical exfoliants, fragrances and/or perfume microcapsules, aversive
agents, surfactants,
colorants, enzymes, skin conditioners, de-oiling agents, cosmetic agents, or a
combination
thereof, can take any desired form, including as a solid (e.g., powder,
granulate, crystal, flake, or
ribbon), a liquid, a mull, a paste, a gas, etc., and optionally can be
encapsulated.
[0098] In example embodiments, the nonwoven web can be colored, pigmented,
and/or dyed
to provide an improved aesthetic effect relative to water-soluble films.
Suitable colorants for use
in the nonwoven web can include an indicator dye, such as a pH indicator
(e.g., thymol blue,
bromothymol, thymolphthalein, and thymolphthalein), a moisture/water indicator
(e.g.,
hydrochromic inks or leuco dyes), or a thermochromic ink, wherein the ink
changes color when
temperature increases and/or decreases. Suitable colorants include, but are
not limited to, a
triphenylmethane dye, an azo dye, an anthraquinone dye, a perylene dye, an
indigoid dye, a food,
drug and cosmetic (FD&C) colorant, an organic pigment, an inorganic pigment,
or a combination
thereof. Examples of colorants include, but are not limited to, FD&C Red #40,
Red #3, FD&C
Black #3; Black #2; Mica-based pearlescent pigment; FD&C Yellow #6; Green #3;
Blue #1;
Blue #2; titanium dioxide (food grade); brilliant black; and a combination
thereof.
[0099] In example embodiments, the nonwoven web can include any of the
surfactants
disclosed herein. In example embodiments, the nonwoven web can comprise one or
more of the
group of: sodium cocoyl isethionate, glucotain, phoenamids, cola lipid,
cocamides, such as
cocamide ethanolamines, ethylene oxide-based surfactants, and saponified oils
of avocado and
palm.
[0100] The nonwoven webs of the disclosure can generally have any thickness.
Suitable
thicknesses can include, but are not limited to, about 5 microns (um) to about
10,000 um (1 cm),
about 5 um to about 5,000 p.m, about 5 pm to about 1,000 p.m, about 5 um to
about 500 um,
about 200 um to about 500 p.m, about 5 um to about 200 p.m, about 20 p.m to
about 100 um, or
about 40 um to about 90 um, or about 50 um to 80 um, or about or about 60 pm
to 65 um, for
example, 50 um, 65 um, 76 um, or 88 p.m. The nonwoven webs of the disclosure
can be
characterized as high loft or low loft. In general, loft refers to the ratio
of thickness to mass per
unit area (i.e., basis weight). High loft nonwoven webs can be characterized
by a high ratio of
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thickness to mass per unit area. As used herein, -high loft" refers to a
nonwoven web of the
disclosure having a basis weight as defined herein and a thickness exceeding
200 p.m. The
thickness of the nonwoven web can be determined according to ASTM D5729-97,
ASTM
D5736, and/or ISO 9073-2.1995 and can include, for example, subjecting the
nonwoven web to a
load of 2 N and measuring the thickness. High loft materials can be used
according to known
methods in the art, for example, cross-lapping, which uses a cross-lapper to
fold the unbonded
web over onto itself to build loft and basis weight. Without intending to be
bound by theory, in
contrast to water-soluble films wherein the solubility of the film can be
dependent on the
thickness of the film, the solubility of a nonwoven web is not believed to be
dependent on the
thickness of the web. In this regard, it is believed that because the
individual fibers provide a
higher surface area than a water-soluble film, regardless of the thickness of
the nonwoven web,
the parameter that limits approach of water to the fibers and, thereby,
dissolution of the fibers is
the basis weight (i.e., fiber density in the nonwoven).
[0101] In general, the coefficient of dynamic friction and the ratio of the
coefficient of static
friction to the coefficient of dynamic friction for a nonwoven web of the
disclosure will be lower
than the coefficient of dynamic friction and the ratio of the coefficient of
static friction to the
coefficient of dynamic friction for a water-soluble film due to the increased
surface roughness of
the nonwoven web relative to a water-soluble film, which provides decreased
surface contact to
the nonwoven web. Advantageously, this surface roughness can provide an
improved feel to the
consumer (i.e., a cloth-like hand-feel instead of a rubbery hand-feel),
improved aesthetics (i.e.,
less glossy than a water-soluble film), and/or facilitate processability in
preparing thermoformed,
and/or vertical formed, filled, and sealed, and/or multichamber packets which
require drawing
the web along a surface of the processing equipment/mold. Accordingly, the
water-soluble fibers
and/or non-water-soluble fibers should be sufficiently coarse to provide a
surface roughness to
the resulting nonwoven web without being so coarse as to produce drag.
[0102] The solubility in water of the nonwoven webs of the disclosure is
generally a function
of the type of fiber(s) used to prepare the web as well as the basis weight of
the web. Without
intending to be bound by theory, it is believed that the solubility profile of
a nonwoven web
follows the same solubility profile of the fiber(s) used to prepare the
nonwoven web, and the
solubility profile of the fiber generally follows the same solubility profile
of the polymer(s) from
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which the fiber is prepared. For example, for nonwoven webs comprising PVOH
fibers, the
degree of hydrolysis of the PVOH polymer can be chosen such that the water-
solubility of the
nonwoven web is also influenced. In general, at a given temperature, as the
degree of hydrolysis
of the PVOH polymer increases from partially hydrolyzed (88% DH) to fully
hydrolyzed (>98%
DH), water solubility of the polymer generally decreases. Thus, in example
embodiments, the
nonwoven web can be cold water-soluble. For a co-poly(vinyl acetate vinyl
alcohol) polymer
that does not include any other monomers (e.g., not copolymerized with an
anionic monomer) a
cold water-soluble web, soluble in water at a temperature of less than 10 C,
can include fibers of
PVOH with a degree of hydrolysis in a range of about 75% to about 90%, or in a
range of about
75% to about 89%, or in a range of about 80% to about 90%, or in a range of
about 85% to about
90%, or in a range of about 90% to about 99.5%. In other example embodiments,
the nonwoven
web can be hot water-soluble. For example, a co-poly(vinyl acetate vinyl
alcohol) polymer that
does not include any other monomers (e.g., not copolymerized with an anionic
monomer), a hot
water-soluble web can be soluble in water at a temperature of at least about
60 C, by including
fibers of PVOH with a degree of hydrolysis of at least about 98%.
[0103] Modification of PVOH generally increases the solubility of the PVOH
polymer. Thus,
it is expected that at a given temperature the solubility of a nonwoven web or
film prepared from
a PVOH copolymer would be higher than that of a nonwoven web or film prepared
from a
PVOH homopolymer having the same degree of hydrolysis as the PVOH copolymer.
Following
these trends, a nonwoven web having specific solubility characteristics can be
designed by
blending polymers within the fibers and/or blending fibers within the nonwoven
web. Further, as
described herein, the nonwoven web includes a plurality of fibers that may, in
some cases,
include two or more fiber types that differ in solubility.
[0104] Inclusion of non-water-soluble fiber and/or non-water-soluble fiber
forming material in
the plurality of fibers of a nonwoven web can also be used to design a
nonwoven web having
specific solubility and/or prolonged release properties. Without intending to
be bound by theory,
it is believed that as the weight percent of non-water-soluble fiber included
in a nonwoven web is
increased (based on the total weight of the nonwoven web), the solubility of
the nonwoven web
generally decreases and the prolonged release properties of a pouch comprising
a nonwoven web
generally increases. Upon contact with water at a temperature at or above the
solubility
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temperature of the water-soluble fiber, a nonwoven web comprising water-
soluble fiber and non-
water-soluble fiber will begin to disperse as the water-soluble fiber
dissolves, thereby breaking
down the web structure and/or increasing the pore size of the pores of the
nonwoven web. In
general, the larger the break-down of the web structure or increase in the
pore size, the faster the
water can access the contents of the pouch and the faster the contents of the
pouch will be
released. Similarly, prolonged release of the contents of a pouch comprising
the nonwoven web
of the disclosure can be achieved by using a blend of water-soluble fibers
having different
solubility properties and/or different solubility temperatures. Once the
faster dissolving fiber has
dissolved, thereby breaking up the web, the less soluble fibers will have a
larger surface area
exposed, facilitating dissolution of the less soluble fibers and release of
the pouch contents. In
example embodiments wherein the nonwoven web includes water-soluble fibers and
non-water-
soluble fibers, the ratio of soluble fibers to non-water-soluble fibers is not
particularly limited.
The water-soluble fibers can comprise about 1% to about 99%, about 20% to
about 80%, about
40% to about 90%, about 50% to about 90%, or about 60% to about 90% by weight,
of the total
weight of the plurality of fibers, and the non-water-soluble fibers can
comprise about 1% to
about 99%, about 20% to about 80%, about 10% to about 60%, about 10% to about
50%, or
about 10% to about 40% by weight, of the total weight of the fibers. In
example embodiments,
the plurality of fibers comprise about 10% to about 80% water-soluble fibers
by weight, based on
the total weight of the fibers and the balance being non-water-soluble fibers.
[0105] In example embodiments, the nonwoven web, the plurality of fibers, the
foam, the
water-soluble film, or a combination thereof, disclosed herein can comprises a
biodegradable
polymer. In certain embodiments, the plurality of fibers can comprise non-
water-soluble fiber
forming materials that are biodegradable. In example embodiments, the
plurality of fibers can
comprise first fibers that are non-water-soluble biodegradable fibers, and
second fibers that are
soluble in water at a temperature of about 10 C to about 20 C according to
MSTM-205 or not
soluble in water at a temperature of about 30 C or less according to MSTM-205,
according to
MSTM-205. In example embodiments, the nonwoven web is non-water-soluble and
biodegradable.
[0106] In example embodiments, the nonwoven web is biodegradable. As used
herein, when
the nonwoven web is said to be biodegradable, at least 50% of the nonwoven web
is
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biodegradable, for example, at least 60%, at least 70%, at least 80%, at least
90%, or 100%, of
the nonwoven web is biodegradable.
[0107] The nonwoven web as disclosed herein can comprise the plurality of
fibers comprising
a first fiber type and a second fiber type, wherein the first and second fiber
types have a
difference in diameter, length, tenacity, shape, rigidness, elasticity,
solubility, melting point,
glass transition temperature (Tg), chemical composition, color, or a
combination thereof. In
example embodiments, the first fiber type can comprise a PVOH homopolymer
fiber forming
material, a PVOH copolymer fiber forming material, or a combination thereof.
In example
embodiments, the first fiber type can comprise two or more PVOH homopolymer
fiber forming
materials, two or more PVOH copolymer fiber forming materials, or a
combination thereof. In
example embodiments, the second fiber type can comprise a PVOH homopolymer
fiber forming
material, a PVOH copolymer fiber forming material, or a combination thereof.
In example
embodiments, the second fiber type can comprise two or more PVOH homopolymer
fiber
forming materials, two or more PVOH copolymer fiber forming materials, or a
combination
thereof. In example embodiments, the first fiber type and/or the second fiber
type are non-water-
soluble fiber forming material. In example embodiments, the first fiber type
can comprise a non-
water-soluble polymer fiber forming material and the second fiber type can
comprise a polyvinyl
alcohol fiber forming material that, when provided as the sole fiber forming
material of a
nonwoven web or as a film, the resulting web or film is soluble in water at a
temperature in a
range of about 0 C to about 20 C according to MSTM-205. In example
embodiments, the first
fiber type can comprise a non-water-soluble polymer fiber forming material and
the second fiber
type can comprise a PVOH homopolymer or copolymer fiber forming material that,
when
provided as the sole fiber forming material of a nonwoven web or as a film,
the resulting web or
film is not soluble in water at a temperature of 20 C or less according to
MSTM-205. in example
embodiments, the first fiber type comprises two or more polyvinyl alcohol
homopolymer fiber
forming materials, two or more polyvinyl alcohol copolymer fiber forming
materials, or a
combination of polyvinyl alcohol homopolymer fiber forming materials and
polyvinyl alcohol
copolymer fiber forming materials. In example embodiments, the second fiber
type comprises
two or more polyvinyl alcohol homopolymer fiber forming materials, two or more
polyvinyl
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alcohol copolymer fiber forming materials, or a combination of polyvinyl
alcohol homopolymer
fiber forming materials and polyvinyl alcohol copolymer fiber forming
materials.
[0108] The plurality of fibers comprised in the nonwoven webs of the
disclosure can generally
have any tenacity. The tenacity of the fiber correlates to the coarseness of
the fiber. As the
tenacity of the fiber decreases the coarseness of the fiber increases. Fibers
used to prepare the
nonwoven webs of the disclosure can have a tenacity in a range of about 1 to
about 100 cN/dtex,
or about 1 to about 75 cN/dtex, or about 1 to about 50 cN/dtex, or about 1 to
about 45 cN/dtex, or
about 1 to about 40 cN/dtex, or about 1 to about 35 cN/dtex, or about 1 to
about 30 cN/dtex, or
about 1 to about 25 cN/dtex, or about 1 to about 20 cN/dtex, or about 1 to
about 15 cN/dtex, or
about 1 to about 10 cN/dtex, or about 3 to about 8 cN/dtex, or about 4 to
about 8 cN/dtex, or
about 6 to about 8 cN/dtex, or about 4 to about 7 cN/dtex, or about 10 to
about 20, or about 10 to
about 18, or about 10 to about 16, or about 1 cN/dtex, about 2 cN/dtex, about
3 cN/dtex, about 4
cN/dtex, about 5 cN/dtex, about 6 cN/dtex, about 7 cN/dtex, about 8 cN/dtex,
about 9 cN/dtex,
about 10 cN/dtex, about 11 cN/dtex, about 12 cN/dtex, about 13 cN/dtex, about
14 cN/dtex, or
about 15 cN/dtex. In example embodiments, the plurality of fibers can have a
tenacity in a range
of about 3 cN/dtex to about 15 cN/dtex, or about 5 cN/dtex to about 12
cN/dtex, or about 5
cN/dtex to about 10 cN/dtex.
[0109] The tenacity of the nonwoven web can be the same or different from the
tenacity of the
plurality of fibers used to prepare the web Without intending to be bound by
theory, it is
believed that the tenacity of the nonwoven web is related to the strength of
the nonwoven web,
wherein a higher tenacity provides a higher strength to the nonwoven web. In
general, the
tenacity of the nonwoven web can be modified by using fibers having different
tenacities. The
tenacity of the nonwoven web may also be affected by processing. In general,
the nonwoven
webs of the disclosure have relatively high tenacities, i.e., the nonwoven web
is a self-supporting
web that can be used as the sole material for preparing an article and/or
pouch. In contrast,
nonwoven webs prepared according to melt blown, electro-spinning, and/or
rotary spinning
processes have low tenacities and may not be self-supporting or capable of
being used as a sole
web for forming an article or pouch.
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[0110] The fibers used to prepare the nonwoven webs of the disclosure can
generally have any
fineness. The fineness of the fiber correlates to how many fibers are present
in a cross-section of
a yarn of a given thickness. The fineness of a fiber can be measured by the
linear mass density, a
measure of the ratio of fiber mass per unit length The main physical unit of
linear mass density
is 1 tex, which is equal to 1000 m of fiber weighing 1 g. The unit dtex is
used, representing 1
g/10,000 m of fiber. The linear mass density can be selected to provide a
nonwoven web having
suitable stiffness/hand-feel of the nonwoven web, torsional rigidity,
reflection and interaction
with light, absorption of dye and/or other actives/additives, ease of fiber
spinning in the
manufacturing process, and uniformity of the finished article. In general, as
the linear mass
density of the fibers increases the nonwovens resulting therefrom demonstrate
higher uniformity,
improved tensile strengths, extensibility, and luster. Additionally, without
intending to be bound
by theory it is believed that finer fibers will lead to slower dissolution
times as compared to
larger fibers based on density. Further, without intending to be bound by
theory, when a blend of
fiber types is used, the average linear mass density can be determined using a
weighted average
of the individual fiber types. Fibers can be characterized as very fine (dtex
< 1.22), fine (1.22<
dtex < 1.54), medium (1.54< dtex < 1.93), slightly coarse (1.93< dtex < 2.32),
and coarse (dtex
>2.32). The nonwoven web of the disclosure can include fibers that are very
fine, fine, medium,
slightly coarse, or a combination thereof. In example embodiments, the
nonwoven web has an
average linear mass density in a range of about 1 dtex to about 5 dtex, or
about 1 dtex to about 3
dtex, or about 1.5 dtex to about 2.5 dtex. In example embodiments, the
nonwoven web comprises
a blend of fibers wherein first fiber comprises 1.7 dtex average linear mass
density and second
fiber comprises 2.2 dtex average linear mass density.
[0111] The plurality of fibers used to prepare the nonwoven webs of the
disclosure have a
diameter in a range of about 10 microns to 300 microns, for example, at least
10 microns, at least
25 microns, at least 50 microns, at least 100 microns, or at least 125 microns
and up to about 300
microns, up to about 275 microns, up to about 250 microns, up to about 225
microns, or up to
about 200 microns. In example embodiments, the plurality of fibers used to
prepare the
nonwoven webs of the disclosure can have a diameter greater than 100 microns
to about 300
microns. In example embodiments, the diameters of the plurality of fibers used
to prepare the
nonwoven webs of the disclosure have diameters that are substantially uniform.
In example
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embodiments, the one or more fiber types can have a mean diameter in a range
of about 10
microns to about 300 microns, or about 50 microns to 200 microns, or about 50
microns to about
100 microns.
[0112] The plurality of fibers used to prepare the nonwoven webs of the
disclosure can
generally be of any length. In example embodiments, the length of the
plurality of fibers can be
in a range of about 10 millimeters (mm) to about 100 mm, about 10 mm to about
60 mm, or
about 30 mm to about 60 mm, for example, at least about 30 mm, at least about
35 mm, at least
about 40 mm, at least about 45 mm, or at least about 50 mm, and up to about
100 mm, up to
about 95 mm, up to about 90 mm, up to about 80 mm, up to about 70 mm, or up to
about 60 mm.
In example embodiments, the length of the plurality of fibers can be less than
about 30 mm or in
a range of about 0.25 mm to less than about 30 mm, for example, at least about
0.25 mm, at least
about 0.5 mm, at least about 0.75 mm, at least about 1 mm, at least about 2.5
mm, at least about
mm, at least about 7.5 mm, or at least about 10 mm and up to about 29 mm, up
to about 28
mm, up to about 27 mm, up to about 26 mm, up to about 25 mm, up to about 20
mm, or up to
about 15 mm. In example embodiments, the fibers have an average length of
about 30 mm to
about 100 mm, or about 30 mm to about 60 mm. In example embodiments, the
nonwoven web
comprises a blend of fiber types wherein first fiber type comprises a length
of about 38 mm and
second fiber type comprises a length of about 54 mm.
[0113] The plurality of fibers used to prepare the nonwoven webs of the
disclosure can
generally have any length to diameter (L/D) ratio. Advantageously, the
tactility of a nonwoven
web of the disclosure can be controlled using the L/D ratio of the fibers and
the respective
amounts of fibers having various L/D ratios in the nonwoven composition. In
general, as the L/D
of the fiber decreases, the stiffness and resistance to bending increases,
providing a rougher hand
feel. The fibers of the disclosure generally impart a rough feel to a nonwoven
web including
same, when the fibers have a low L/D ratio in a range of about 0.5 to about
15, or about 0.5 to
about 25, or about 1 to about 5. Such low L/D fibers can be provided in a
nonwoven web in an
amount in a range of about 0 to about 50 % by weight, based on the total
weight of the fibers in
the nonwoven web, for example, in a range of about 0.5 wt.% to about 25 wt.%,
or about 1 wt.%
to about 15 wt.%. If the amount of low L/D fibers in a nonwoven web is not
known, the amount
can be estimated by visual inspection of a micrograph of a nonwoven web. In
example
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embodiments wherein a first fiber includes a blend of fiber forming materials
including a first
polyvinyl alcohol fiber forming material, at least a portion of the first
fibers can have a LID ratio
of about 0.5 to about 25, or about 0.5 to about 15, or about 1 to about 5.
[0114] Pore sizes can be determined using high magnification and ordered
surface analysis
techniques including, but not limited to Brunauer-Emmett-Teller theory (BET),
small angle X-
ray scattering (SAXS), and molecular adsorption.
[0115] Nonwoven webs can be characterized by basis weight. The basis weight of
a nonwoven
web is the mass per unit area of the nonwoven web. Basis weight can be
modified by varying
manufacturing conditions, as is known in the art. A nonwoven web can have the
same basis
weight prior to and after bonding. Alternatively, the bonding method can
change the basis weight
of the nonwoven web. For example, wherein bonding occurs through the
application of heat and
pressure, the thickness of the nonwoven (and, thus, the area of the nonwoven)
can be decreased,
thereby increasing the basis weight. Accordingly, as used herein and unless
specified otherwise,
the basis weight of a nonwoven refers to the basis weight of the nonwoven
after bonding.
[0116] The nonwoven webs of the disclosure can generally have any basis weight
in a range of
about 0.1 g/m2 to about 700 g/m2, about 0.5 g/m2 to about 600 g/m2, about 1
g/m2 to about 500
g/m2, about 1 g/m2 to about 400 g/m2, about 1 g/m2 to about 300 g/m2, about 1
g/m2 to about 200
g/m2, about 1 g/m2 to about 100 g/m2, about 30 g/m2 to about 100 g/m2, about
20 g/m2 to about
100 g/m2, about 20 g/m2 to about 80 g/m2, or about 25 g/m2 to about 70 g/m2.
[0117] Further, as the basis weight of the web increases the rate of
dissolution of the web
decreases, provided the fiber composition and web thickness remain constant,
as there is more
material to be dissolved. For example, at a given temperature, a water-soluble
web prepared from
fibers comprising PVOH polymer(s) and having a basis weight of, e.g., 40 g/m2,
is expected to
dissolve slower than an otherwise-identical water-soluble web having a basis
weight of, e.g., 30
g/m2. Accordingly, basis weight can also be used to modify the solubility
characteristics of the
nonwoven web. The nonwoven web can generally have any basis weight in a range
of about 1
g/m2 to about 700 g/m2, about 1 g/m2 to about 600 g/m2, about 1 g/m2 to about
500 g/m2, about 1
g/m2 to about 400 g/m2, about 1 g/m2 to about 300 g/m2, about 1 g/m2 to about
200 g/m2, about
g/m2 to about 100 g/m2, about 30 g/m2 to about 100 g/m2, about 20 g/m2 to
about 100 g/m2,
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about 20 g/m2 to about 80 g/m2, about 25 g/m2 to about 70 g/m2, or about 40
g/m2 to about 60
g/m2.
[0118] The nonwoven web of the disclosure can be used as a single layer or can
be layered
with other nonwoven webs or can be in the form of a laminate with a water-
soluble film. In some
embodiments, the nonwoven web includes a single layer of nonwoven web. In some
embodiments, the nonwoven web is a multilayer nonwoven web comprising two or
more layers
of nonwoven webs. The two or more layers can be laminated to each other. In
refinements of the
foregoing embodiment, the two or more layers can be the same (e.g., be
prepared from the same
fibers and basis weight). In refinements of the foregoing embodiment, the two
or more layers can
be different (e.g., be prepared from different types of fibers, fiber
chemistries, and/or have
different basis weights).
[0119] In general, a multilayer nonwoven web can have a basis weight that is
the sum of the
basis weights of the individual layers. Accordingly, a multilayer nonwoven web
will take longer
to dissolve than any of the individual layers provided as a single layer.
Water-Soluble Foams
[0120] In example embodiments, a suitable water-soluble foam includes any
suitable resin
chemistry, such as a homopolymer, MA modified PVOH, MMM Modified PVOH, AMPS
Modified PVOH, cellulose and cellulose derivatives, PVP, proteins, casein,
soy, or any water-
dispersible or water-soluble resin. In certain embodiments, the water-soluble
foam substrate has
a thickness of 3 microns to 3000 microns and can be formed using any suitable
manufacturing
process known in the foam manufacturing art including, without limitation, a
cast, extruded, melt
processed, coated, chemically blown, mechanically aerated, air injected,
turbulent extrusion
process. The water-soluble foam substrate may be porous or non-porous and cold
water-soluble
or hot water-soluble. The construction of the water-soluble foam substrate may
include, for
example, folded layers or plies, stacked layers or plies, or rolled layers or
plies.
[0121] In example embodiments, the water-soluble foam substrate can further
comprise any
auxiliary agents as disclosed herein for nonwoven webs, fibers and/or films.
The auxiliary agents
can be applied to one or more faces of a water-soluble foam substrate or to an
article containing
same, e.g., a packet, by any suitable means. In example embodiments, the
auxiliary agents are in
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powder form. In refinements of the foregoing embodiment, one or more
stationary powder spray
guns are used to direct the powder stream towards the water-soluble foam
substrate or a packet,
from one or more than one direction, while the water-soluble foam substrate or
packet is
transported through the coating zone by means of a belt conveyor. Tn example
embodiments, a
water-soluble foam substrate or packet is conveyed through a suspension of the
powder in air. In
example embodiments, the water-soluble foam substrate or packets are tumble-
mixed with the
powder in a trough-like apparatus. In example embodiments, which can be
combined with any
other embodiment, electrostatic forces are employed to enhance the attraction
between the
powder and the packet or water-soluble foam substrate. This type of process
may be based on
negatively charging the powder particles and directing these charged particles
to the grounded
packets or water-soluble foam substrates. In other alternative embodiments,
the powder is
applied to the water-soluble foam substrate or packet by a secondary
transferring tool including,
but not limited to, rotating brushes, which are in contact with the powder or
by powdered gloves,
which can transfer the powder from a container to the water-soluble foam
substrate or the packet.
In yet another embodiment, the powder is applied by dissolving or suspending
the powder in a
non-aqueous solvent or carrier, which is then atomized and sprayed onto the
water-soluble foam
substrate or packet. In one embodiment, the solvent or carrier subsequently
evaporates, leaving
the active agent powder behind. In certain embodiments, the powder is applied
to the water-
soluble foam substrate or packet in an accurate dose. These embodiments
utilize closed-system
dry lubricant application machinery, such as PekuTECH's powder applicator PM
700 D. In this
process, the powder, optionally batch-wise or continuously, is fed to a feed
trough of application
machinery. The water-soluble foam substrates or packets are transferred from
the output belt of a
standard rotary drum pouch machine onto a conveyor belt of the powder
application machine,
wherein a controlled dosage of the powder is applied to the water-soluble foam
substrate or
packet. The water-soluble foam substrate or packet can thereafter be conveyed
to a suitable
secondary packaging process.
[0122] In example embodiments wherein the auxiliary agents are in liquid form
or in a
solution, the foregoing can be dispersed in the water-soluble foam substrate,
dispersed on a face
of the water-soluble foam substrate, or a combination thereof, for example, by
spin casting,
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spraying a solution such as an aerosolized solution, roll coating, flow
coating, curtain coating,
extrusion, knife coating, and combinations thereof.
[0123] The auxiliary agents, such as chemical exfoliants, mechanical
exfoliants, fragrances
and/or perfume microcapsules, aversive agents, surfactants, colorants,
enzymes, skin
conditioners, de-oiling agents, cosmetic agents, or a combination thereof,
when present in the
water-soluble foam substrate, are in an amount of at least about 1 wt.%, or in
a range of about 1
wt.% to about 99 wt.%, provides additional functionality to the water-soluble
foam substrate.
The chemical exfoliants, mechanical exfoliants, fragrances and/or perfume
microcapsules,
aversive agents, surfactants, colorants, enzymes, skin conditioners, de-oiling
agents, cosmetic
agents, or a combination thereof, can take any desired form, including as a
solid (e.g., powder,
granulate, crystal, flake, or ribbon), a liquid, a mull, a paste, a gas, etc.,
and optionally can be
encapsulated.
[0124] In example embodiments, the water-soluble foam substrate can be
colored, pigmented,
and/or dyed to provide an improved aesthetic effect relative to water-soluble
films. Suitable
colorants for use in the water-soluble foam substrate can include an indicator
dye, such as a pH
indicator (e.g., thymol blue, bromothymol, thymolphthalein, and
thymolphthalein), a
moisture/water indicator (e.g., hydrochromic inks or leuco dyes), or a
thermochromic ink,
wherein the ink changes color when temperature increases and/or decreases.
Suitable colorants
include, but are not limited to, a triphenylmethane dye, an azo dye, an
anthraquinone dye, a
perylene dye, an indigoid dye, a food, drug and cosmetic (FD&C) colorant, an
organic pigment,
an inorganic pigment, or a combination thereof Examples of colorants include,
but are not
limited to, FD&C Red #40; Red #3; FD&C Black #3; Black #2; Mica-based
pearlescent
pigment; FD&C Yellow #6; Green #3; Blue #1; Blue #2; titanium dioxide (food
grade); brilliant
black; and a combination thereof.
[0125] In example embodiments, the water-soluble foam substrate can include
any of the
surfactants disclosed herein. In example embodiments, the water-soluble foam
substrate can
comprise one or more of the group of: sodium cocoyl isethionate, glucotain,
phoenamids, cola
lipid, cocamides, such as cocamide ethanolamines, ethylene oxide-based
surfactants, and
saponified oils of avocado and palm.
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[0126] The water-soluble foam substrate of the disclosure can have any
thickness. Suitable
thicknesses can include, but are not limited to, about 5 microns ([im) to
about 10,000 p.m (1 cm),
about 3 lam to about 5,000 lam, about 5 lam to about 1,000 [tm, about 5 lam to
about 500 lam,
about 200 [im to about 500 [im, about 5 [im to about 200 [im, about 20 [im to
about 100 [im, or
about 40 lam to about 90 lam, or about 50 lam to 80 pm, or about or about 60
1M1 to 65 lam, for
example, 50 lam, 65 lam, 76 lam, or 88 lam. The water-soluble foam substrate
of the disclosure
can be characterized as high loft or low loft. Loft refers to the ratio of
thickness to mass per unit
area (i.e., basis weight). High loft water-soluble foam substrates can be
characterized by a high
ratio of thickness to mass per unit area. As used herein, "high loft" refers
to a water-soluble foam
substrate of the disclosure having a basis weight as defined herein and a
thickness exceeding 200
p.m. The thickness of the water-soluble foam substrate can be determined
according to ASTM
D5729-97, ASTM D5736, and/or ISO 9073-2:1995 and can include, for example,
subjecting the
water-soluble foam substrate to a load of 2 N and measuring the thickness.
High loft materials
can be used according to known methods in the art, for example, cross-lapping,
which uses a
cross-lapper to fold the unbonded web over onto itself to build loft and basis
weight.
[0127] In general, the coefficient of dynamic friction and the ratio of the
coefficient of static
friction to the coefficient of dynamic friction for a water-soluble foam
substrate of the disclosure
will be lower than the coefficient of dynamic friction and the ratio of the
coefficient of static
friction to the coefficient of dynamic friction for a water-soluble film due
to the increased
surface roughness of the water-soluble foam substrate relative to a water-
soluble film, which
provides decreased surface contact to the water-soluble foam substrate.
Advantageously, this
surface roughness can provide an improved feel to the consumer (i.e., a cloth-
like hand-feel
instead of a rubbery hand-feel), improved aesthetics (i.e., less glossy than a
water-soluble film),
and/or facilitate processability in preparing thermoformed, and/or vertical
formed, filled, and
sealed, and/or multichamber packets which require drawing the water-soluble
foam substrate
along a surface of the processing equipment/mold. Accordingly, the water-
soluble fibers and/or
non-water-soluble fibers should be sufficiently coarse to provide a surface
roughness to the
resulting water-soluble foam substrate without being so coarse as to produce
drag.
[0128] The solubility in water of the soluble foam substrate closure is a
function of the type of
fiber(s) used to prepare the water-soluble foam substrate as well as the basis
weight of the water-
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soluble foam substrate. Without intending to be bound by theory, it is
believed that the solubility
profile of a water-soluble foam substrate follows the same solubility profile
of the fiber(s) used
to prepare the water-soluble foam substrate, and the solubility profile of the
fiber generally
follows the same solubility profile of the polymer(s) from which the fiber is
prepared For
example, for the water-soluble foam substrates comprising PVOH fibers, the
degree of
hydrolysis of the PVOH polymer can be chosen such that the water-solubility of
the water-
soluble foam substrate is also influenced. At a given temperature, as the
degree of hydrolysis of
the PVOH polymer increases from partially hydrolyzed (88% DH) to fully
hydrolyzed (>98%
DH), water solubility of the polymer generally decreases. Thus, in example
embodiments, the
water-soluble foam substrate can be cold water-soluble. For a co-poly(vinyl
acetate vinyl
alcohol) polymer that does not include any other monomers (e.g., not
copolymerized with an
anionic monomer) a cold water-soluble web, soluble in water at a temperature
of less than 10 C,
can include fibers of PVOH with a degree of hydrolysis in a range of about 75%
to about 90%,
or in a range of about 75% to about 89%, or in a range of about 80% to about
90%, or in a range
of about 85% to about 90%, or in a range of about 90% to about 99.5%. In other
example
embodiments, the water-soluble foam substrate can be hot water-soluble. For
example, a co-
poly(vinyl acetate vinyl alcohol) polymer that does not include any other
monomers (e.g., not
copolymerized with an anionic monomer), a hot water-soluble foam substrate can
be soluble in
water at a temperature of at least about 60 C, by including fibers of PVOH
with a degree of
hydrolysis of at least about 98%.
[0129] Modification of a PVOH polymer increases the solubility of the PVOH
polymer. Thus,
it is expected that at a given temperature the solubility of a water-soluble
foam substrate
prepared from a modified PVOH copolymer would be higher than that of a water-
soluble foam
substrate prepared from a PVOH copolymer having the same degree of hydrolysis
as the
modified PVOH copolymer. Following these trends, a water-soluble foam
substrate having
specific solubility characteristics can be designed by blending polymers
within the fibers and/or
blending fibers within the water-soluble foam substrate. Further, as described
herein, the water-
soluble foam substrate includes a plurality of fibers that may, in some cases,
include two or more
fiber types that differ in solubility.
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[0130] Inclusion of non-water-soluble fiber and/or non-water-soluble fiber
forming material in
the plurality of fibers of a water-soluble foam substrate can also be used to
design a water-
soluble foam substrate having specific solubility and/or prolonged release
properties. Without
intending to be bound by theory, it is believed that as the weight percent of
non-water-soluble
fiber included in a water-soluble foam substrate is increased (based on the
total weight of the
water-soluble foam substrate), the solubility of the water-soluble foam
substrate generally
decreases and the prolonged release properties of a pouch comprising a water-
soluble foam
substrate generally increases. Upon contact with water at a temperature at or
above the solubility
temperature of the water-soluble fiber, a water-soluble foam substrate
comprising water-soluble
fiber and non-water-soluble fiber will begin to disperse as the water-soluble
fiber dissolves,
thereby breaking down the foam structure and/or increasing the pore size of
the pores of the
water-soluble foam substrate. The larger the break-down of the foam structure
or increase in the
pore size, the faster the water can access the contents of the pouch and the
faster the contents of
the pouch will be released. Similarly, prolonged release of the contents of a
pouch comprising
the water-soluble foam substrate of the disclosure can be achieved by using a
blend of water-
soluble fibers having different solubility properties and/or different
solubility temperatures. Once
the faster dissolving fiber has dissolved, thereby breaking up the foam, the
less soluble fibers
will have a larger surface area exposed, facilitating dissolution of the less
soluble fibers and
release of the pouch contents. In example embodiments wherein the foam
substrate includes
water-soluble fibers and non-water-soluble fibers, the ratio of soluble fibers
to non-water-soluble
fibers is not particularly limited. The water-soluble fibers can comprise
about 1% to about 99%,
about 20% to about 80%, about 40% to about 90%, about 50% to about 90%, or
about 60% to
about 90% by weight, of the total weight of the plurality of fibers, and the
non-water-soluble
fibers can comprise about 1% to about 99%, about 20% to about 80%, about 10%
to about 60%,
about 10% to about 50%, or about 10% to about 40% by weight, of the total
weight of the fibers.
In example embodiments, the plurality of fibers comprise about 10% to about
80% water-soluble
fibers by weight, based on the total weight of the fibers and the balance
being non-water-soluble
fibers.
[0131] In example embodiments, the nonwoven web, the plurality of fibers, the
foam, the
water-soluble film, or a combination thereof, disclosed herein can comprises a
biodegradable
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polymer. In certain embodiments, the plurality of fibers can comprise non-
water-soluble fiber
forming materials that are biodegradable. In example embodiments, the
plurality of fibers can
comprise first fibers that are non-water-soluble biodegradable fibers, and
second fibers that are
soluble in water at a temperature of about 10 C to about 20 C according to
MSTM-205 or not
soluble in water at a temperature of about 30 C or less according to MSTM-205,
according to
MSTM-205. In example embodiments, the nonwoven web is non-water-soluble and
biodegradable.
[0132] In example embodiments, the foam substrate is biodegradable. As used
herein, when
the foam substrate is said to be biodegradable, at least 50% of the foam
substrate is
biodegradable, for example, at least 60%, at least 70%, at least 80%, at least
90%, or 100%, of
the foam substrate is biodegradable.
[0133] The foam substrate as disclosed herein can comprise the plurality of
fibers comprising
a first fiber type and a second fiber type, wherein the first and second fiber
types have a
difference in diameter, length, tenacity, shape, rigidness, elasticity,
solubility, melting point,
glass transition temperature (TO, chemical composition, color, or a
combination thereof. In
example embodiments, the first fiber type can comprise a PVOH homopolymer
fiber forming
material, a modified PVOH copolymer fiber forming material, a PVOH copolymer
fiber forming
material, or a combination thereof. In example embodiments, the first fiber
type can comprise
two or more PVOH homopolymer fiber forming materials, two or more PVOH
copolymer fiber
forming materials, two or more modified PVOH copolymer fiber forming
materials, or a
combination thereof. In example embodiments, the second fiber type can
comprise a PVOH
homopolymer fiber forming material, a PVOH copolymer fiber forming material, a
more
modified PVOH copolymer fiber forming material, or a combination thereof. In
example
embodiments, the second fiber type can comprise two or more PVOH homopolymer
fiber
forming materials, two or more PVOH copolymer fiber forming materials, two or
more modified
PVOH copolymer fiber forming materials, or a combination thereof. In example
embodiments,
the first fiber type and/or the second fiber type are non-water-soluble fiber
forming material. In
example embodiments, the first fiber type can comprise a non-water-soluble
polymer fiber
forming material and the second fiber type can comprise a polyvinyl alcohol
fiber forming
material that, when provided as the sole fiber forming material of a nonwoven
web or as a film,
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the resulting web or film is soluble in water at a temperature in a range of
about 0 C to about
20 C according to MSTM-205. In example embodiments, the first fiber type can
comprise a non-
water-soluble polymer fiber forming material and the second fiber type can
comprise a PVOH
homopolymer or copolymer fiber forming material that, when provided as the
sole fiber forming
material of a water-soluble foam substrate, the resulting water-soluble foam
substrate is not
soluble in water at a temperature of 20 C or less according to MSTM-205. In
example
embodiments, the first fiber type comprises two or more PVOH copolymer fiber
forming
materials, two or more modified PVOH copolymer fiber forming materials, or a
combination of
PVOH copolymer fiber forming materials and modified PVOH copolymer fiber
forming
materials. In example embodiments, the second fiber type comprises two or more
PVOH
copolymer fiber forming materials, two or more modified PVOH copolymer fiber
forming
materials, or a combination of PVOH copolymer fiber forming materials and
modified PVOH
copolymer fiber forming materials.
[0134] The plurality of fibers comprised in the water-soluble foam substrate
of the disclosure
can have any tenacity. The tenacity of the fiber correlates to the coarseness
of the fiber. As the
tenacity of the fiber decreases the coarseness of the fiber increases. Fibers
used to prepare the
nonwoven webs of the disclosure can have a tenacity in a range of about 1 to
about 100 cN/dtex,
or about 1 to about 75 cN/dtex, or about 1 to about 50 cN/dtex, or about 1 to
about 45 cN/dtex, or
about 1 to about 40 cN/dtex, or about 1 to about 35 cN/dtex, or about 1 to
about 30 cN/dtex, or
about 1 to about 25 cN/dtex, or about 1 to about 20 cN/dtex, or about 1 to
about 15 cN/dtex, or
about 1 to about 10 cN/dtex, or about 3 to about 8 cN/dtex, or about 4 to
about 8 cN/dtex, or
about 6 to about 8 cN/dtex, or about 4 to about 7 cN/dtex, or about 10 to
about 20, or about 10 to
about 18, or about 10 to about 16, or about 1 cN/dtex, about 2 cN/dtex, about
3 cN/dtex, about 4
cN/dtex, about 5 cN/dtex, about 6 cN/dtex, about 7 cN/dtex, about 8 cN/dtex,
about 9 cN/dtex,
about 10 cN/dtex, about 11 cN/dtex, about 12 cN/dtex, about 13 cN/dtex, about
14 cN/dtex, or
about 15 cN/dtex. In example embodiments, the plurality of fibers can have a
tenacity in a range
of about 3 cN/dtex to about 15 cN/dtex, or about 5 cN/dtex to about 12
cN/dtex, or about 5
cN/dtex to about 10 cN/dtex.
[0135] The tenacity of the water-soluble foam substrate can be the same or
different from the
tenacity of the plurality of fibers used to prepare the web. Without intending
to be bound by
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theory, it is believed that the tenacity of the water-soluble foam substrate
is related to the
strength of the nonwoven web, wherein a higher tenacity provides a higher
strength to the
nonwoven web. The tenacity of the water-soluble foam substrate can be modified
by using fibers
having different tenacities The tenacity of the water-soluble foam substrate
may also be affected
by processing. The water-soluble foam substrate of the disclosure has
relatively high tenacities,
i.e., the water-soluble foam substrate is a self-supporting substrate that can
be used as the sole
material for preparing an article and/or pouch. In contrast, water-soluble
foam substrate prepared
according to melt blown, electro-spinning, and/or rotary spinning processes
have low tenacities
and may not be self-supporting or capable of being used as a sole substrate
for forming an article
or pouch.
[0136] Water-soluble foam substrates can be characterized by basis weight. The
basis weight
of a water-soluble foam substrate is the mass per unit area of the water-
soluble foam substrate.
Basis weight can be modified by varying manufacturing conditions, as is known
in the art. A
water-soluble foam substrate can have the same basis weight prior to and after
bonding.
Alternatively, the bonding method can change the basis weight of the water-
soluble foam
substrate. For example, wherein bonding occurs through the application of heat
and pressure, the
thickness of the water-soluble foam substrate (and, thus, the area of the
water-soluble foam
substrate) can be decreased, thereby increasing the basis weight. Accordingly,
as used herein and
unless specified otherwise, the basis weight of a water-soluble foam substrate
refers to the basis
weight of the water-soluble foam substrate after bonding.
[0137] The water-soluble foam substrate of the disclosure can have any basis
weight in a
range of about 0.1 g/m2 to about 700 g/m2, about 0.5 g/m2 to about 600 g/m2,
about 1 g/m2 to
about 500 g/m2, about 1 g/m2 to about 400 g/m2, about 1 g/m2 to about 300
g/m2, about 1 g/m2 to
about 200 g/m2, about 1 g/m2 to about 100 g/m2, about 30 g/m2 to about 100
g/m2, about 20 g/m2
to about 100 g/m2, about 20 g/m2 to about 80 g/m2, or about 25 g/m2 to about
70 g/m2.
[0138] Further, as the basis weight of the water-soluble foam substrate
increases the rate of
dissolution of the water-soluble foam substrate decreases, provided the fiber
composition and
web thickness remain constant, as there is more material to be dissolved. For
example, at a given
temperature, a water-soluble foam substrate prepared from fibers comprising
PVOH polymer(s)
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and having a basis weight of, e.g., 40 g/m2, is expected to dissolve slower
than an otherwise-
identical water-soluble web having a basis weight of, e.g., 30 g/m2.
Accordingly, basis weight
can also be used to modify the solubility characteristics of the water-soluble
foam substrate. The
water-soluble foam substrate can generally have any basis weight in a range of
about 1 g/m2 to
about 700 g/m2, about 1 g/m2 to about 600 g/m2, about 1 g/m2 to about 500
g/m2, about 1 g/m2 to
about 400 g/m2, about 1 g/m2 to about 300 g/m2, about 1 g/m2 to about 200
g/m2, about 10 g/m2
to about 100 g/m2, about 30 g/m2 to about 100 g/m2, about 20 g/m2 to about 100
g/m2, about 20
g/m2 to about 80 g/m2, about 25 g/m2 to about 70 g/m2, or about 40 g/m2 to
about 60 g/m2.
[0139] The water-dispersible or water-soluble foam substrate of the disclosure
can be used as
a single layer or can be layered with other water-soluble foam substrates or
can be in the form of
a laminate with a water-soluble film. In some embodiments, the foam substrate
includes a single
layer. In some embodiments, the foam substrate is a multilayer foam substrate
comprising two or
more layers. The two or more layers can be laminated to each other. In
refinements of the
foregoing embodiment, the two or more layers can be the same (e.g., be
prepared from the same
fibers and basis weight). In refinements of the foregoing embodiment, the two
or more layers can
be different (e.g., be prepared from different types of fibers, fiber
chemistries, and/or have
different basis weights).
[0140] A multilayer foam substrate can have a basis weight that is the sum of
the basis
weights of the individual layers. Accordingly, a multilayer water-soluble foam
substrate will take
longer to dissolve than any of the individual layers provided as a single
layer.
Water-Soluble Films
[0141] The water-dispersible and/or water-soluble film described herein
generally comprises
any of the water-dispersible and/or water-soluble polymers disclosed herein.
In example
embodiments, the film of the disclosure comprises a polyvinyl alcohol (PVOH)
resin, a modified
polyvinyl alcohol resin, or combinations thereof. In example embodiments, the
water-soluble
film includes a PVOH resin selected from the group consisting of a PVOH
homopolymer, a
PVOH copolymer, a PVOH copolymer having an anionic modification, and
combinations of the
foregoing. In example embodiments, the film can comprise a single PVOH polymer
or a blend of
PVOH polymer. In example embodiments, the film comprises a PVOH copolymer. In
example
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embodiments, the film comprises a hot water-soluble PVOH copolymer. In example
embodiments wherein the nonwoven web includes a surfactant and/or an
exfoliant, the film can
comprise a modified PVOH copolymer having an anionic modification. In example
embodiments, the -film can comprise a water-soluble polyvinyl alcohol
copolymer or modified
copolymer that, when provided in a film as the sole film forming material, the
film is soluble in
water at a temperature in a range of about 0 C to about 20 C according to MSTM-
205. In
example embodiments, the film can comprise a water-soluble polyvinyl alcohol
copolymer or
modified copolymer that, when provided in a film as the sole film forming
material, the film is
not water-soluble at a water temperature of 20 C or less according to MSTM-
205.
[0142] The water-soluble film can include other film forming polymers
including, but not
limited to, polyvinyl alcohols, water-soluble acrylate copolymers,
polyethyleneimine, pullulan,
water-soluble natural polymers including, but not limited to, guar gum, gum
Acacia, xanthan
gum, carrageenan, and starch, water-soluble polymer modified starches,
copolymers of the
foregoing, or a combination of any of the foregoing. Other water-soluble
polymers can include
polyalkylene oxides, polyacrylamides, celluloses, cellulose ethers, cellulose
esters, cellulose
amides, polyvinyl acetates, polycarboxylic acids and salts thereof,
polyaminoacids, polyamides,
gelatines, methylcelluloses, carboxymethylcelluloses and salts thereof,
dextrins, ethylcelluloses,
hydroxyethyl celluloses, hydroxypropyl methylcelluloses, maltodextrins,
polymethacrylates, or a
combination of any of the foregoing. Such water-soluble polymers are
commercially available
from a variety of sources. In example embodiments, the water-soluble film can
include a PVOH
homopolymer, PVOH copolymer, modified PVOH copolymer, or a combination
thereof. In
example embodiments, the water-soluble film comprises a single PVOH copolymer
or a blend of
PVOH copolymers. In further embodiments, the water-soluble film comprises a
PVOH
copolymer with a viscosity in a range of 5 cP to 23 cP and a degree of
hydrolysis in a range of
86% to 92%.
[0143] The film can have any suitable thickness, and a film thickness of about
76 microns
(pm) is typical and particularly contemplated. Other values and ranges
contemplated include
values in a range of about 5 tm to about 200 m, or in a range of about 20 tm
to about 100 pm,
or about 40 p.m to about 90 pm, or about 50 p.m to 80 pm, or about or about 60
p.m to 65 p.m, for
example, 65 p.m, 76 p.m, or 88 pm.
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[0144] In example embodiments, the water-dispersible and/or water-soluble
films can include
an auxiliary agent as described above. In example embodiments, the films can
be substantially
free of auxiliary agents as described above. In example embodiments, the water-
soluble films
can include a plasticizer as described above. The total amount of the non-
water plasticizer
provided in the water-soluble film can be in a range of about 1 wt.% to about
45 wt.%, or about 5
wt.% to about 45 wt.%, or about 10 wt.% to about 40 wt.%, or about 20 wt.% to
about 30 wt.%,
about 1 wt.% to about 4 wt.%, or about 1.5 wt.% to about 3.5 wt.%, or about
2.0 wt.% to about
3.0 wt.%, for example, about 1 wt.%, about 2.5 wt.%, about 5 wt.%, about 10
wt.%, about 15
wt.%, about 20 wt.%, about 25 wt.%, about 30 wt.%, about 35 wt.%, or about 40
wt.%, based on
total film weight. In example embodiments, the film comprises one or more of
propylene glycol,
glycerol, diglycerol, sorbitol, xylitol, maltitol, trimethylol propane (TMP),
and polyethylene
glycol (100-1000 molecular weight).
[0145] In example embodiments, the films can include a surfactant as described
above. In
various embodiments, the amount of surfactant in the film is in a range of
about 0.01 wt.%, to
about 2.5 wt.%, about 0.1 wt.% to about 2.5 wt.%, about 1.0 wt.% to about 2.0
wt.%, about 0.01
wt.% to 0.25 wt.%, or about 0.10 wt.% to 0.20 wt %. In example embodiments,
the film
comprises one or more of polysorbate 80, lecithin from various plant sources,
and sodium lauryl
sulfate (SLS) and the like.
[0146] In example embodiments, the auxiliary agents of the film can include
fillers/extenders/antiblocking agents/detackifying agents. Suitable
fillers/extenders/antiblocking
agents/detackifying agents include, but are not limited to, crosslinked
polyvinylpyrrolidone,
crosslinked cellulose, microcrystalline cellulose, silica, metallic oxides,
calcium carbonate, talc,
mica, stearic acid, and metal salts thereof, for example, magnesium stearate.
Optionally, an
additional unmodified starch or modified starch can be included the water-
soluble in addition to
one of the specific starch components described above, for example,
hydroxypropylated starch
present in an amount in a range of about 5 phr to about 30 phr, or modified
starch having a
degree of modification of greater than about 2% and is present in an amount in
a range of about
2.5 phr to about 30 phr, or an unmodified starch having an amylose content in
a range of about
20% to about 80%, or a hydroxypropyl modified starch having an amylose content
in a range of
about 23% to about 95% when the polyvinyl alcohol comprises an unmodified
polyvinyl alcohol
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or an anionic modified polyvinyl alcohol copolymer with the proviso that the
anionic modifier is
not an acrylate. Preferred materials are starches, modified starches, and
silica. In one
embodiment, the amount of filler/extender/antiblocking agent/detackifying
agent in the water-
soluble film can be in a range of about 1 wt % to about 6 wt %, or about 1 wt
% to about 4 wt %,
or about 2 wt.% to about 4 wt.%, or about 1 phr to about 6 phr, or about 1 phr
to about 4 phr, or
about 2 phr to about 4 phr, for example. In example embodiments, when a starch
or modified
starch is included in the water-soluble film in addition to one of the
specific starch components
described above, the additional starch component will be provided in an amount
of less than
about 50 wt.%, based on the total weight of all starches included in the film.
Without intending
to be bound by theory, it is believed that any benefit provided to the films
of the disclosure from
the inclusion of the starch component described above is not affected by
including an additional
starch component that provides a lesser benefit to the water-soluble film or
no benefit to the
water-soluble film.
[0147] The film can further have a residual moisture content of at least 4
wt.%, for example, in
a range of about 4 wt.% to about 10 wt.%, as measured by Karl Fischer
titration.
Methods of Preparing Fibers
[0148] Wet Cooled Gel Spinning
[0149] In example embodiments, the plurality of water-soluble fibers can
include water-
soluble fibers prepared according to a wet cooled gel spinning process, the
wet cooled gel
spinning process including the steps of:
(a) dissolving the water-soluble polymer (or polymers) in solution to form a
polymer mixture,
the polymer mixture optionally including auxiliary agents;
(b) extruding the polymer mixture through a spinneret nozzle to a
solidification bath to form an
extruded polymer mixture;
(c) passing the extruded polymer mixture through a solvent exchange bath;
(d) optionally wet drawing the extruded polymer mixture; and
(e) finishing the extruded polymer mixture to provide the water-soluble
fibers.
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[0150] The solvent in which the water-soluble polymer is dissolved can
suitably be any
solvent in which the water-soluble polymer is soluble. In example embodiments,
the solvent in
which the water-soluble polymer is dissolved includes a polar aprotic solvent.
In example
embodiments, the solvent in which the water-soluble polymer is dissolved
includes dimethyl
sulfoxide (DMSO).
[0151] The solidification bath includes a cooled solvent for gelling
the extruded polymer
mixture. The solidification bath can generally be at any temperature that
facilitates solidification
of the extruded polymer mixture. The solidification bath can be a mixture
including a solvent in
which the polymer is soluble and a solvent in which the polymer is not
soluble. The solvent in
which the polymer is not soluble is generally the primary solvent, wherein the
solvent in which
the polymer is not soluble makes up greater than 50% of the mixture by volume.
[0152] After passing through the solidification bath, the extruded polymer
mixture gel can be
passed through one or more solvent replacement baths. The solvent replacement
baths are
provided to replace the solvent in which the water-soluble polymer is soluble
with the solvent in
which the water-soluble polymer is not soluble to further solidify the
extruded polymer mixture
and, further, to replace the solvent in which the water-soluble polymer is
soluble with a solvent
that will more readily evaporate, thereby reducing the drying time. Solvent
replacement baths
can include a series of solvent replacement baths having a gradient of solvent
in which the water-
soluble polymer is soluble with the solvent in which the water-soluble polymer
is not soluble, a
series of solvent replacement baths having only the solvent in which the water-
soluble polymer is
not soluble, or a single solvent replacement bath having only the solvent in
which the water-
soluble polymer is not soluble. In example embodiments, at least one solvent
replacement bath
can consist essentially of a solvent in which the water-soluble polymer is not
soluble.
[0153] Finished fibers are sometimes referred to as staple fibers, shortcut
fibers, or pulp. In
example embodiments, finishing includes drying the extruded polymer mixture.
In example
embodiments, finishing includes cutting or crimping the extruded polymer
mixture to form
individual fibers. Wet drawing of the extruded polymer mixture can provide a
substantially
uniform diameter to the extruded polymer mixture and, thus, the fibers cut
therefrom. Drawing is
distinct from extruding, as is well known in the art. In particular,
"extruding" refers to the act of
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making fibers by forcing the resin mixture through the spinneret head whereas
drawing refers to
mechanically pulling the fibers in the machine direction to promote polymer
chain orientation
and crystallinity for increased fiber strength and tenacity.
[0154] In example embodiments wherein the water-soluble fibers are prepared
from a wet
cooled gel spinning process, the water-soluble polymer can be generally any
water-soluble
polymer or blend thereof, e.g., two or more different polymers, as generally
described herein. In
refinements of the foregoing embodiment, the polymer(s) can have any degree of
polymerization
(DP), for example, in a range of 10 to 10,000,000, for example, at least 10,
at least 20, at least
50, at least 100, at least 200, at least 300, at least 400, at least 500, at
least 750, or at least 1000
and up to 10,000,000, up to 5,000,000, up to 2,500,00, up to 1,000,000, up to
900,000, up to
750,000, up to 500,000, up to 250,000, up to 100,000, up to 90,000, up to
75,000, up to 50,000,
up to 25,000, up to 12,000, up to 10,000, up to 5,000, or up to 2,500, for
example in a range of
1000 to about 50,000, 1000 to about 25,000, 1000 to about 12,000, 1000 to
about 5,000, 1000 to
about 2,500, about 50 to about 12,000, about 50 to about 10,000, about 50 to
about 5,000, about
50 to about 2,500, about 50 to about 1000, about 50 to about 900, about 100 to
about 800, about
150 to about 700, about 200 to about 600, or about 250 to about 500. In
example embodiments,
the DP is at least 1,000. Auxiliary agents, as described above, can be added
to the fibers
themselves or to the nonwoven web during the carding and/or bonding process.
[0155] Thermoplastic Fiber Spinning
[0156] Thermoplastic fiber spinning is well known in the art. Briefly,
thermoplastic fiber
spinning includes the steps of:
(a) preparing a polymer mixture including the fiber forming polymer optionally
including
auxiliary agents;
(b) extruding the polymer mixture through a spinneret nozzle to form an
extruded polymer
mixture;
(c) optionally drawing the extruded polymer mixture; and
(d) finishing the extruded polymer mixture to provide the fibers.
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[0157] The finished staple fibers of the thermoplastic fiber spinning process
can be finished by
drying, cutting, and/or crimping to form individual fibers. Drawing of the
extruded polymer
mixture mechanically pulls the fibers in the machine direction, promoting
polymer chain
orientation and crystallinity for increased fiber strength and tenacity.
Preparing the polymer
mixture for thermoplastic fiber spinning can include (a) preparing a solution
of a fiber-forming
material and a readily volatile solvent such that after extruding the solution
through the spinneret
when the solution is contacted with a stream of hot air, the solvent readily
evaporates leaving
solid fibers behind or (b) melting the polymer such that after extruding the
hot polymer through
the spinneret, the polymer solidifies by quenching with cool air. The
thermoplastic fiber spinning
method is distinct from the wet cooled gel spun method at least in that (a) in
the thermoplastic
fiber spinning method the extruded fibers are solidified by evaporation of the
solvent or by
quenching hot solid fibers with cool air, rather than by use of a
solidification bath; and (b) in the
wet-cool gel spun method, the optional drawing is performed while the fibers
are in a gel state
rather than a solid state.
[0158] Fiber forming materials for preparing fibers from a thermoplastic fiber
spinning
process can be be any fiber forming polymer or blend thereof, e.g., two or
more different
polymers, provided that the polymer or blend thereof has suitable solubility
in a readily volatile
solvent and/or have a melting point lower than and distinct from their
degradation temperature.
Further, when a blend of fiber forming polymers are used to make a fiber, the
fiber forming
materials must have similar solubility in a readily volatile solvent and/or
have similar heat
profiles such that the two or more fiber forming materials will melt at
similar temperatures. In
contrast, the fiber forming materials for preparing fibers from the wet cooled
gel spinning
process are not as limited and fibers can be prepared from a blend of any two
or more polymers
that are soluble in the same solvent system, and the solvent system need not
be a single solvent
or even a volatile solvent.
[0159] The fiber forming polymer(s) for preparing thermoplastic fiber spun
fibers can have a
degree of polymerization (DP), for example, in a range of 10 to 10,000 for
example, at least 10,
at least 20, at least 50, at least 100, at least 200, at least 300, at least
400, at least 500, at least
750, or at least 1000 and up to 10,000, up to 5,000, up to 2,500, up to 1,000,
up to 900, up to 750,
up to 500, or up to 250. In example embodiments, the DP is less than 1,000.
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[0160] Melt Spinning
[0161] Melt spinning is well known in the art and is understood to refer to
both spun bond
processes and melt blown processes. Melt spinning is a continuous process
which directly
prepares a nonwoven web in-line with fiber formation. As such, the melt-spun
formed fibers are
not finished and cut to any consistent length (e.g., staple fibers are not
prepared by these
processes). Additionally, melt spinning does not include a drawing step and,
therefore, the only
control over the diameter of the resulting melt-spun fibers is the size of the
holes through which
the fiber forming materials are extruded, and the polymer chains are not
oriented in any specific
direction.
[0162] In certain embodiments, melt spinning includes the steps of:
(a) preparing a polymer mixture including the fiber forming polymer optionally
including
auxiliary agents;
(b) extruding the polymer mixture into a die assembly to form an extruded
polymer mixture;
(c) quenching the extruded polymer mixture;
(d) depositing the quenched, extruded polymer mixture on a belt to form a
nonwoven web; and
(e) bonding the nonwoven web.
[0163] In the spun bond process, the extruded polymer mixture is pumped into
the die
assembly as molten polymer and quenched with cold air once passed through the
die assembly.
In the melt blown process, the extruded polymer mixture is pumped into a die
assembly having
hot air blown through it and is quenched upon exiting the die assembly and
coming into contact
with ambient temperature air. In both processes, the fibers are continuously
dropped onto a belt
or dnim, usually facilitated by pulling a vacuum under the belt or dmm
[0164] The diameter of melt-spun fibers are in a range of about 0.1 to about
50 micron, for
example, at least about 0.1 micron, at least about 1 micron, at least about 2
micron, at least about
micron, at least about 10 micron, at least about 15 micron, or at least about
20 micron and up to
about 50 micron, up to about 40 micron, up to about 30 micron, up to about 25
micron, up to
about 20 micron, up to about 15 micron, up to about 10 micron, about 0.1
micron to about 50
micron, about 0.1 micron to about 40 micron, about 0.1 micron to about 30
micron, about 0.1
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micron to about 25 micron, about 0.1 micron to about 20 micron, about 0.1
micron to about 15
micron, about 0.1 micron to about 10 micron, about 0.1 micron to about 9
micron, about 0.1
micron to about 8 micron, about 0.1 micron to about 7 micron, about 0.1 micron
to about 6
micron, about 0 1 micron to about 6 micron, about 5 micron to about 35 micron,
about 5 micron
to about 30 micron, about 7.5 micron to about 25 micron, about 10 micron to
about 25 micron, or
about 15 micron to about 25 micron. It is well known in the art that melt
blown processes can
provide micro-fine fibers having an average diameter in a range of about 1-10
micron, however,
the melt blown process has very high variation in fiber-to-fiber diameter,
e.g., 100-300%
variation. Further, it is well known in the art that spun bond fibers can have
larger average fiber
diameters, e.g., about 15 to about 25 micron, but improved uniformity between
fibers, e.g., about
10% variation.
[0165] The fiber forming material for heat extruded processes (e.g., melt-
spun, thermoplastic
fiber spinning) is more limited than for the wet-cooled gel spun process. For
example, the degree
of polymerization for heat extruding processes is limited to a range of about
200 to about 500. As
the degree of polymerization decreases below 200, the viscosity of the fiber
forming material is
too low and the individual fibers prepared by pumping the material through the
die assembly do
not maintain adequate separation after exiting the die assembly. Similarly, as
the degree of
polymerization increases above 500, the viscosity is too high to efficiently
pump the material
through sufficiently small holes in the die assembly to run the process at
high speeds, thus losing
process efficiency and fiber and/or nonwoven uniformity. Further, processes
requiring heating of
the fiber forming material, are unsuitable for polyvinyl alcohol homopolymers
as the
homopolymers generally do not have the thermal stability required.
[0166] The wet cooled gel spinning process advantageously provides one or more
benefits
such as providing a fiber that includes a blend of water-soluble polymers,
providing control over
the diameter of the fibers, providing relatively large diameter fibers,
providing control over the
length of the fibers, providing control over the tenacity of the fibers,
providing high tenacity
fibers, providing fibers from polymers having a large degree of
polymerization, and/or providing
fibers which can be used to provide a self-supporting nonwoven web. Continuous
processes such
as spun bond, melt blown, electro-spinning and rotary spinning generally do
not allow for
blending of water-soluble polymers (e.g., due to difficulties matching the
melt index of various
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polymers), forming large diameter (e.g., greater than 50 micron) fibers,
controlling the length of
the fibers, providing high tenacity fibers, and the use of polymers having a
high degree of
polymerization. Further, the wet cooled gel spinning process advantageously is
not limited to
polymers that are only melt processable and, therefore, can access fibers made
from fiber
forming materials having very high molecular weights, high melting points, low
melt flow index,
or a combination thereof, providing fibers having stronger physical properties
and different
chemical functionalities compared to fibers prepared by a heat extrusion
process. Further still,
advantageously, the wet cooled gel spinning process is not limited by the
viscosity of the
polymer. In contrast, it is known in the art that processes that require
melting of the fiber forming
material are limited to fiber forming materials having viscosities of 5 cP or
less. Thus, fibers
including polymers, including polyvinyl alcohol homopolymers and copolymers,
having a
viscosity of greater than 5 cP are only accessible by wet cooled gel spinning.
Methods of Preparing Nonwoven Webs
[0167] The nonwoven webs of the disclosure are sheet-like structures having
two exterior
surfaces, the nonwoven webs including a plurality of fibers. The nonwoven webs
of the
disclosures can be prepared from fibers using any known methods in the art. As
is known in the
art, when fibers are spun bond or melt blown, the fibers are continuously laid
down to form the
nonwoven web, followed by bonding of the fibers.
[0168] Staple fibers can be carded or airlaid and bonded to provide a nonwoven
web. Methods
of carding and airlaying are well known in the art.
[0169] Methods of bonding nonwoven webs are well known in the art_ For
example, bonding
can include thermal, mechanical, and/or chemical bonding. Thermal bonding can
include, but is
not limited to calendering, embossing, air-through, and ultra-sound.
Mechanical bonding can
include, but is not limited to, hydro-entangling (spunlace), needle-punching,
and stitch-bonding.
Chemical bonding can include, but is not limited to, solvent bonding and resin
bonding.
[0170] Thermal bonding is achieved by applying heat and pressure, and
maintains the pore
size, shape, and alignment produced by the carding process. The conditions for
thermal bonding
can be readily determined by one of ordinary skill in the art. If the heat
and/or pressure applied is
too low, the fibers will not sufficiently bind to form a free-standing web and
if the heat and/or
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pressure is too high, the fibers will begin to meld together. The fiber
chemistry dictates the upper
and lower limits of heat and/or pressure for thermal bonding. Without
intending to be bound by
theory, it is believed that at temperatures above 235 C, polyvinyl alcohol-
based fibers degrade.
Methods of embossment for thermal bonding of fibers are known The embossing
can be a one-
sided embossing or a double-sided embossing. Embossing of water-soluble fibers
includes one-
sided embossing using a single embossing roll consisting of an ordered
circular array and a steel
roll with a plain surface. As embossing is increased (e.g., as surface
features are imparted to the
web), the surface area of the web is increased. Without intending to be bound
by theory it is
expected that as the surface are of the web is increased, the solubility of
the web is increased.
Accordingly, the solubility properties of the nonwoven web can be
advantageously tuned by
changing the surface area through embossing.
[0171] Air-through bonding requires a high thermoplastic content in the
nonwoven web and
two different melting point materials. In air-through bonding, the nonbonded
nonwoven web is
circulated around a drum while hot air flows from the outside of the drum
toward the center of
the drum. Air-through bonding can provide nonwovens having low density and
higher basis
weight (e.g., greater than 20 to about 2000 g/m2). Nonwovens bonded by air-
bonding is very
soft.
[0172] Chemical bonding includes solvent bonding and resin bonding. In
particular, chemical
bonding may use a binder solution of a solvent and a resin (e.g., latex or the
waste polymer left
over from preparing the fibers). The nonwoven can be coated with the binder
solution and heat
and pressure applied to cure the binder and bond the nonwoven. The binder
solution can be
applied by immersing the nonwoven in a bath of binder solution, spraying the
binder solution
onto the nonwoven, extruding the binder solution onto the web (foam bonding),
and/or applying
the binder solution as a print or gravure.
[0173] Chemical bonding can result in smaller, less ordered pores relative to
the pores as
carded/melt-spun. Without intending to be bound by theory, it is believed that
if the resin
solution used for chemical bonding is sufficiently concentrated and/or
sufficient pressure is
applied, a nonporous nonwoven web can be formed. The solvent used in chemical
bonding
induces partial solubilization of the existing fibers in the web to weld and
bond the fibers
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together. Thus, the solvent for chemical bonding can be any solvent that can
at least partially
solubilize one or more fiber forming materials of the fibers of the nonwoven.
In example
embodiments, the solvent is selected from the group consisting of water,
ethanol, methanol,
DMSO, glycerin, and a combination thereof. In example embodiments, the solvent
is selected
from the group consisting of water, glycerin, and a combination thereof. In
example
embodiments, the binder solution comprises a solvent selected from the group
consisting of
water, ethanol, methanol, DMSO, glycerin, and a combination thereof and
further comprises a
resin selected from the group consisting of polyvinyl alcohol, latex, and
polyvinylpyrrolidone.
The binder provided in the solution assists in the welding process to provide
a more
mechanically robust web. The temperature of the polymer solution is not
particularly limited and
can be provided at room temperature (about 23 C).
[0174] In some embodiments, a second layer of fibers can be used to bond the
nonwoven web.
In example embodiments, the nonwoven layer can be bonded using thermal,
mechanical, or
chemical bonding, alone or in addition to bonding using an additional layer of
nonwoven
web/fibers.
Methods of Laminating Films to Nonwoven Webs or Foam Substrates
[0175] Methods of preparing a laminate (e.g., water-soluble film and a
nonwoven) can
include, but is not limited to, calender lamination (thermal with pressure) or
melt adhesion.
[0176] Calender lamination is achieved by applying heat and pressure. The
conditions for
calender lamination can be readily determined by one of ordinary skill in the
art. If the heat
and/or pressure applied is too low, the fibers will not sufficiently bind to
the water-soluble film
to form a laminate and if the heat and/or pressure is too high, the fibers
will begin to meld
together with each other and the film. The fiber chemistry and film chemistry
dictates the upper
and lower limits of heat and/or pressure for calender lamination. Without
intending to be bound
by theory, it is believed that at temperatures above 235 C, polyvinyl alcohol-
based fibers
degrade. In example embodiments, the heat added to the overlaid nonwoven and
water-soluble
film is about 50 C to about 200 C, for example, about 100 C to about 200 C,
about 110 C to
about 190 C, about 120 C to about 180 C, or about 130 C to about 160 C. In
example
embodiments, the pressure applied to the overlaid nonwoven and water-soluble
film is about 5
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psi to about 50 psi, such as, about 10 psi to about 40 psi, about 15 psi to
about 30 psi, or about 20
psi to about 30 psi. In example embodiments, the heat added to the overlaid
nonwoven and
water-soluble film is about 150 C and the pressure applied is about 25 psi. In
example
embodiments, the heat and pressure are applied for about 2-4 seconds Methods
of embossment
for calender lamination of fibers and/or the film are contemplated. The
embossing can be a one-
sided embossing or a double-sided embossing. Embossing of water-soluble fibers
and/or water-
soluble films includes one-sided embossing using a single embossing roll
consisting of an
ordered circular array and a steel roll with a plain surface. As embossing is
increased (e.g.,
increased amounts of surface features are imparted to the web and/or the
film), the surface area
of the laminate is increased. Without intending to be bound by theory it is
believed that as the
surface of the article is decreased, the solubility of the web and/or film is
decreased.
Accordingly, the solubility properties of the nonwoven web and/or water-
soluble film can be
advantageously tuned by changing the surface area through embossing. Without
intending to be
bound by theory, it is believed that as the degree of lamination of the unit
dose article is
increased, the surface area of the laminate decreases and the bonding between
the water-soluble
film and nonwoven increases, resulting in the solubility decreasing and the
liquid release time
increasing.
[0177] Melt adhesion lamination is achieved by applying an adhesive directly
to the water-
soluble film and the nonwoven web is then laid on top of the water-soluble
film with the applied
adhesive and is subjected to cold lamination for adhesion of the nonwoven web
and the water-
soluble film. As used herein, the term "cold lamination" refers to a
lamination process that
involves pressure but does not involve added heat. The adhesive can be any
suitable adhesive to
one of ordinary skill in the art. In example embodiments, the adhesive is a
Henkel National
Adhesive. The application of the adhesive directly to the water-soluble film
can be applied by
any suitable method to one of ordinary skill in the art, such as, a hot melt-
spray process. In
example embodiments, the melt adhesion lamination process can include a hot
melt spray
process at 160 C, followed by cold lamination at a pressure of 94 N/mm2.
[0178] The laminate of the disclosure may include a water-soluble film and a
nonwoven web.
In example embodiments, the laminates can have a degree of lamination of about
1% to about
100%, for example, the degree of lamination can be in a range of about 1% to
about 90%, or
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about 25% to about 75%, or about 1% to about 50%, or about 5% to about 25%, or
about 25% to
about 100%, or about 50% to about 100%. As used herein, the term "degree of
lamination" refers
to the amount of total area of the water-soluble film that is bonded to the
nonwoven web. For
example, a laminate having a degree of lamination of about 25% or less means
that about 25% or
less of the water-soluble film's area is bonded to the nonwoven web, e.g.,
lamination at the seals
only. For example, a laminate having a degree of lamination of about 100%
means that about
100% of the area of the water-soluble film is bonded to the nonwoven web. In
example
embodiments wherein the degree of lamination is about 25% or less, the
laminate can be
achieved during the heat seal process wherein the lamination occurs at each
seal of the unit dose
article. In example embodiments wherein the laminate has a degree of
lamination of about 25%
or less, this low degree of lamination can be advantageous as there is an
interior void volume
where the water-soluble film and the nonwoven web are not laminated providing
physical
separation for components having non-compatible chemistries, as well as
providing an
opportunity for a 2-step delivery system of compositions in a unit dose
article. In example
embodiments, the degree of lamination is in a range of about 5% to about 25%.
In example
embodiments, the degree of lamination is in a range of about 50% to about
100%.
Dissolution and Disintegration Test (Modified MSTM-205)
[0179] A nonwoven web, water-soluble film, or laminate structure can be
characterized by or
tested for Dissolution Time and Disintegration Time according to the MonoSol
Test Method 205
(MSTM 205), a method known in the art. See, for example, U.S. Patent No.
7,022,656. The
description provided below refers to a nonwoven web, while it is equally
applicable to a water-
soluble film or laminate structure.
[0180] Apparatus and Materials:
600 mL Beaker
Magnetic Stirrer (Labline Model No. 1250 or equivalent)
Magnetic Stirring Rod (5 cm)
Thermometer (0 to 100 C 1 C)
Template, Stainless Steel (3.8 cm x 3.2 cm)
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Timer (0 ¨ 300 seconds, accurate to the nearest second)
Polaroid 35 mm slide Mount (or equivalent)
MonoSol 35 mm Slide Mount Holder (or equivalent)
Distilled water
[0181] For each nonwoven web to be tested, three test specimens are cut from a
nonwoven
web sample that is a 3.8 cm x 3.2 cm specimen. Specimens should be cut from
areas of web
evenly spaced along the traverse direction of the web. Each test specimen is
then analyzed using
the following procedure.
Lock each specimen in a separate 35 mm slide mount.
Fill beaker with 500 mL of distilled water. Measure water temperature with
thermometer
and, if necessary, heat or cool water to maintain the temperature at the
temperature for which
dissolution is being determined, e.g., 20 C (about 68 F).
Mark height of column of water. Place magnetic stirrer on base of holder.
Place beaker
on magnetic stirrer, add magnetic stirring rod to beaker, turn on stirrer, and
adjust stir speed until
a vortex develops which is approximately one-fifth the height of the water
column. Mark depth
of vortex.
Secure the 35 mm slide mount in the alligator clamp of the 35 mm slide mount
holder
such that the long end of the slide mount is parallel to the water surface.
The depth adjuster of
the holder should be set so that when dropped, the end of the clamp will be
0.6 cm below the
surface of the water. One of the short sides of the slide mount should be next
to the side of the
beaker with the other positioned directly over the center of the stirring rod
such that the
nonwoven web surface is perpendicular to the fl ow of the water.
In one motion, drop the secured slide and clamp into the water and start the
timer.
Rupture occurs when the sample has become compromised within the slide, for
example, when a
hole is created. Disintegration occurs when the nonwoven web breaks apart and
no sample
material is left in the slide. When all visible nonwoven web is released from
the slide mount,
raise the slide out of the water while continuing to monitor the solution for
undissolved
nonwoven web fragments. Dissolution occurs when all nonwoven web fragments are
no longer
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visible and the solution becomes clear. Rupture and dissolution can happen
concurrently for
nonwoven samples wherein the fibers are prepared from polyvinyl alcohol
polymer having a low
degree of hydrolysis (e.g., about 65-88%). Dissolution times are recorded
independently of
rupture times when there is a 5 second or greater difference between rupture
and di ssoluti on
[0182] Thinning time can also be determined using MSTM-205. Thinning of a
nonwoven web
occurs when some of the fibers making up the nonwoven web dissolve, while
other fibers remain
intact. The thinning of the web occurs prior to disintegration of the web.
Thinning is
characterized by a decrease in opacity, or increase in transparency, of the
nonwoven web. The
change from opaque to increasingly transparent and can be visually observed.
During MSTM-
205, after the secured slide and clamp have been dropped into the water the
opacity/transparency
of the nonwoven web is monitored. At the time point wherein no change in
opacity/transparency
is observed (i.e., the web does not become any less opaque or more
transparent), the time is
recorded as the thinning time.
[0183] The results should include the following: complete sample
identification; individual
and average disintegration and dissolution times; and water temperature at
which the samples
were tested.
'corrected ¨ 'measured X (reference thickness/measured thickness)1-93 [1]
Scon-ected = Smeasured X (reference thickness/measured thickness)'' [2]
Method for Determining Single Fiber Solubility
[0184] The solubility of a single fiber can be characterized by the water
breaking temperature.
The fiber breaking temperature can be determined as follows. A load of 2
mg/dtex is put on a
fiber having a fixed length of 100 mm. Water temperature starts at 1.5 C and
is then raised by
1.5 C increments every 2 minutes until the fiber breaks. The temperature at
which the fiber
breaks is denoted as the water breaking temperature.
[0185] The solubility of a single fiber can also be characterized by the
temperature of
complete dissolution. The temperature of complete dissolution can be
determined as follows. 0.2
g of fibers having a fixed length of 2 mm are added to 100 mL of water. Water
temperature starts
at 1.5 C and is then raised by 1.5 C increments every 2 minutes until the
fiber completely
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dissolves. The sample is agitated at each temperature. The temperature at
which the fiber
completely dissolves in less than 30 seconds is denoted as the complete
dissolution temperature.
Diameter Test Method
[0186] The diameter of a discrete fiber or a fiber within a nonwoven web is
determined by
using a scanning electron microscope (SEM) or an optical microscope and an
image analysis
software. A magnification of 200 to 10,000 times is chosen such that the
fibers are suitably
enlarged for measurement. When using the SEM, the samples are sputtered with
gold or a
palladium compound to avoid electric charging and vibrations of the fiber in
the electron beam.
A manual procedure for determining the fiber diameters is used from the image
(on monitor
screen) taken with the SEM or the optical microscope. Using a mouse and a
cursor tool, the edge
of a randomly selected fiber is sought and then measured across its width
(i.e., perpendicular to
the fiber direction at that point) to the other edge of the fiber. A scaled
and calibrated image
analysis tool provides the scaling to get an actual reading in microns. For
fibers within a
nonwoven web, several fibers are randomly selected across the sample of
nonwoven web using
the SEM or the optical microscope. At least two portions of the nonwoven web
material are cut
and tested in this manner. Altogether at least 100 such measurements are made
and then all data
are recorded for statistical analysis. The recorded data are used to calculate
average (mean) of the
fibers, standard deviation of the fibers, and median fiber diameters.
Tensile Strength, Modulus, and Elongation Test
A nonwoven web, water-soluble film, or laminate structure characterized by or
to be tested for
tensile strength according to the Tensile Strength (TS) Test, modulus (or
tensile stress) according
to the Modulus (MOD) Test, and elongation according to the Elongation Test is
analyzed as
follows. The description provided below refers to a nonwoven web, while it is
equally applicable
to a water-soluble film or laminate structure. The procedure includes the
determination of tensile
strength and the determination of modulus at 10% elongation according to ASTM
D 882
("Standard Test Method for Tensile Properties of Thin Plastic Sheeting") or
equivalent. An
INSTRON tensile testing apparatus (Model 5544 Tensile Tester or equivalent) is
used for the
collection of nonwoven web data. A minimum of three test specimens, each cut
with reliable
cutting tools to ensure dimensional stability and reproducibility, are tested
in the machine
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direction (MD) (where applicable) for each measurement. Tests are conducted in
the standard
laboratory atmosphere of 23 + 2.0 C and 35 + 5 % relative humidity. For
tensile strength or
modulus determination, 1"-wide (2.54 cm) samples of a nonwoven web are
prepared. The
sample is then transferred to the TNSTRON tensile testing machine to proceed
with testing while
minimizing exposure in the 35% relative humidity environment. The tensile
testing machine is
prepared according to manufacturer instructions, equipped with a 500 N load
cell, and calibrated.
The correct grips and faces are fitted (INSTRON grips having model number 2702-
032 faces,
which are rubber coated and 25 mm wide, or equivalent). The samples are
mounted into the
tensile testing machine and analyzed to determine the 100% modulus (i.e.,
stress required to
achieve 100% film elongation), tensile strength (i.e., stress required to
break film), and
elongation % (sample length at break relative to the initial sample length).
In general, the higher
the elongation % for a sample, the better the processability characteristics
for the nonwoven web
(e.g., increased formability into packets or pouches).
Abrasion Test
[0187] Off Hand Test:
[0188] 3" diameter discs are fitted with RolocTM attachment. A carbon steel
test panel as well
as an aluminum test panel are abraded with a coated abrasive belt
corresponding to any Example
on hackstand to impose a linear grain on the test piece. The average Ra is 75
pin on carbon steel
and 150 pin on aluminum test panels. The panel and disc are then weighed
before testing.
[0189] Off Hand Short Test:
[0190] For one minute, working in the direction of the grain of the respective
panel, scratches
were removed from half of the panel with the nonwoven disc according to any
Example. For a
second one-minute period, working in the direction of the grain, the scratches
are removed from
the second half of the panel. The disc and workpiece are then cleaned and
weighed. The Ra of
the panel is also measured in 5 discreet areas and recorded.
[0191] Off Hand Long Test:
[0192] For one minute, working in the direction of the grain of the respective
panels, scratches
are removed from half of the panel with the nonwoven disc according to any
Example. For a
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second one-minute period, working in the direction of the grain, the scratches
are removed from
the second half of the panel.
[0193] The panel is weighed before and after the 2-minute period to determine
the mass loss
of the panel.
[0194] A new panel is used for another 2 minutes with the methodology used
above.
[0195] This process is continued for 4 panels - 8 minutes of total off hand
grinding time for
each disc. The surface finish is measured on the first panel and the fourth
panel in 5 discreet
areas per panel. The highest and lowest surface finish numbers are discarded
and the middle 3 Ra
numbers are averaged. The average surface finish from panel 1 and panel 4 are
averaged to give
the final surface finish number.
[0196] XY Auto Test:
[0197] 3" diameter discs are fitted with RO1OCTM attachment. The XY tests the
disc for 8
cycles. Each cycle is 1 minute long in which the disc abraded a flat test
panel. During the testing
a robotic arm moves in the X and Y directions abrading the surface of the
panel. The Ra that the
disc leaves behind is checked after the first cycle and after cycle #8 in 5
discreet areas. The panel
and disc are weighed before cycle 1 and after cycle 8 to determine the
substrate and disc mass
loss.
[0198] Force and RPM used when abrading carbon steel is either 5 pounds (lbs.)
and 9000
RPM or 10 lbs. and 11,000 RPM. Force used when abrading aluminum is either 5
lbs. and 9,000
RPM or 5 lbs. and 11,0000 RPM.
Fiber Shrinkage Percent Test (MSTM)
[0199] A percent shrinkage of a fiber when contacted with a suitable amount of
a carrier
solvent can be determined according to a Fiber Shrinkage Percent Test under
MonoSol Standard
Operating Procedure.
[0200] Apparatus and Materials:
1. Fiber samples (approx. 3 grams)
2. 500 mL beaker
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3. Chilled deionized water (located in refrigerator)
4. Deionized water
5. Paper clip
6. Alligator clamp (solubility stand)
7. Stir plate
8. Timer
[0201] Samples are prepared as follows:
1. Obtain a small bundle of fibers that isn't entangled. Enough to ensure
it will hold
in the paper clip and the alligator clamp, approximate weight of fiber bundle
is 0.013 gram (g) to
0.015 g.
2. Take a paper clip and pull an end of the fiber through the cross
sections of the
paper clip.
3. Do this so each unique fiber to be tested has a replicate of N=3 for
each testing
temperature, 23 C and 10 C.
[0202] Apparatus set-up:
1. Fill 500 ml beaker with 400 ml of respective temperature water. Make
sure to
check the water temperature with a temperature probe before and during
testing.
2. Tape a ruler to the top of the alligator clamp so the ruler hangs
parallel to the
clamp.
3. Place the beaker on a stir plate and place the solubility stand next to
the stir plate,
submerging ruler into beaker so then you can read the length.
[0203] Testing procedure:
1. Attach the free end of the paper clipped fiber in the alligator clamp.
2. Submerge the test sample into the beaker so that the test sample is
aligned next to
the ruler.
3. Start the timer and record the initial length of the fiber. The test
sample fiber
length is from the end of alligator clip to the top of the paper clip.
4. After two minutes, record the final length of the fiber.
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5. Lift the clamp out of the water and remove the sample from
the clamp. Be sure to
thoroughly dry off the outside of the clamp and the inside of clamp between
each test.
[0204] Calculating Shrinkage Percent:
Shrinked length = initial length - final length [3]
Fiber Shrinkage (%) = (shrinked length/initial length) x 100% [4]
Uses of Articles
[0205] The articles of the disclosure are suitable for a variety of commercial
applications.
Suitable commercial applications for the article such as the single unit dose
articles of the
disclosure include delivering active cleaning formulations including, without
limitation, a
laundry detergent, a soap, a fabric softener, a bleaching agent, a laundry
booster, a stain remover,
an optical brightener, or a water softener. In example embodiments, the active
cleaning
formulation may include, without limitation, actives, detergents, surfactants,
emulsifiers,
chelants, dirt suspenders, stain releasers, enzymes, pH adjusters, builders,
soil release polymers,
structurants, free fragrance, encapsulated fragrance, preservatives, solvent,
minerals, and/or any
ingredients suitable in personal care, laundry detergent, dish detergent,
and/or home surface
cleaners or cleansers. Other examples include a dish detergent, soap or
cleaner, a shampoo, a
conditioner, a body wash, a face wash, a skin lotion, a skin treatment, a body
oil, fragrance, a
hair treatment, a bath salt, an essential oil, a bath bomb, or an enzyme. The
active cleaning
formulation may be in the form of a solid, e.g., a powder or a plurality of
granules or particles, a
gel, a liquid, or a slurry formulation, or any suitable combination of a
powder, a solid, a gel, a
liquid, or a slurry formulation, for example
[0206] Additional applications for the unit dose articles of the
disclosure can include
delivering personal care products such as exfoliating materials, shampoo,
conditioner, body
wash, face wash, skin lotion, skin treatment, hair treatment, bath salts,
essential oil, or a
combination thereof. Additional contemplated applications include those that
can involve a
constant flow of water, for example, automotive cleaning applications and/or
dish cleaning
applications. Advantageously, in such applications, before and/or once at
least a portion of the
composition is released from the article, the nonwoven web can be used to
facilitate foaming
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and/or scrubbing hard to remove grime without damaging the surface being
cleaned, for
example, the paint on a car or a non-stick cooking surface.
EXAMPLES
[0207] As described herein, the unit dose article may include one of the
following
constructions, wherein a first surface or a first side of the nonwoven
substrate is fibrous in
appearance and a second surface or a second side of the nonwoven substrate is
generally smooth
or coated with water to create a continuous layer using a heat and/or water
application:
(a) a single use cold water-dispersible nonwoven cleaning article, such as a
towel or pad,
having no moisture or a low moisture dish wash detergent and an abrasive
material on one or
more surfaces of the nonwoven towel for cleaning dry dishes; the water-soluble
nonwoven towel
is dissolved when contacted with cold water and delivers a sanitizer for
soaking the dishes to be
cleaned, once the dishes are cleaned, the dishes can be rinsed and dried on a
rack, for example;
or
(b) a hot water-soluble (>40 C) nonwoven cleaning article, such as a towel or
pad,
having a dish wash detergent and an abrasive material for cleaning dishes, the
water-soluble
nonwoven towel is dissolved when contacted with hot water and delivers a
sanitizer for soaking
the dishes to be cleaned, once the dishes are cleaned, the dishes can be
rinsed and dried on a
rack. The cleaning article can be for single use or multiple uses. The
cleaning article may
comprises a single layer or multiple layers of nonwoven sheets.
[0208] The nonwoven article, such as a towel or pad, can be water-dispersible
at a temperature
below 40 C, for example, in a range of from about 10 C to about 40 C, and
water-soluble at a
temperature of 40 C and above, for example, in a range of from about 50 C to
about 100 C, or
from about 60 C to about 70 C. In certain embodiments, a plurality of
particles of an active
cleaning formulation can be bonded to the core substrate, such as a nonwoven
substrate, to form
the abrasive surface as described herein. A consumer uses a single-use
nonwoven towel to scrub
dishes. The towel delivers the necessary cleaning for a suitable load of hand-
washed dishes, as
well as an abrasive, for cleansing the physical food stuffs from the cookware,
e.g., a pot, a pan, a
plate, dinnerware, and/or cutlery. In example embodiments, the cookware is
scrubbed when the
cookware is dry. Once a suitable amount of the food stuffs are removed using
the towel, the
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towel can be dissolved in a sink, for example, or in a soaking tub to deliver
sanitizers or dish
cleaning soap for further removal of debris and sanitization of cookware. In
other example
embodiments, cold water is applied to the cookware as the cookware is
scrubbed, and the towel
dissolves progressively or slowly during use Once the cookware is washed, hot
water is applied
and the towel dissolves completely or substantially completely to deliver the
sanitizing agent. In
other example embodiments, the towel does not dissolve during use and the
cookware is washed
with hot water. An active cleaning formulation is continuously released and
the towel does not
dissolve during use. In certain embodiments, the cleaning article can be used
multiple times. The
cleaning article, such as towel or pad, can be disposed of in the dishwasher
where the core
substrate fully or substantially dissolves and aids in dish washing, or the
towel is placed in the
trash where the single use towel has an improved biodegradation profile, or
the towel is recycled.
[0209] In the Examples, a nonwoven substrate including an active cleaning
formulation is
described as one example of the core substrate for illustration purposes. The
core substrate and
the active cleaning formulation can have any composition and/or form as
described herein. For
example, the core substrate can be a water-dispersible and/or water-soluble
nonwoven, foam,
film, or any combination thereof. Such core substrate may include one or more
PVOH polymers
such as vinyl alcohol-vinyl acetate copolymers. For example, in certain
embodiments, the core
substrate includes at least one nonwoven web or sheet comprising the plurality
of fibers. The
plurality of fibers comprise a first type of fiber comprising a polyvinyl
alcohol copolymer having
a degree of hydrolysis in a range of about 75% to about 89.9 % (e.g., 80%-
89.9%), and a second
type of fiber comprising a polyvinyl alcohol copolymer having a degree of
hydrolysis in a range
of about 90% to about 99.9 % (e.g., 95%-98%). A suitable ratio of the first
type of fiber to the
second type of fiber is, for example, in a range of from about 5:95 to about
25:75 by weight. In
certain embodiments, the first type of fiber and the second type of fiber are
mixed together in the
at least one nonwoven web or sheet. In certain embodiments, the at least one
nonwoven web or
sheet comprises a first type of nonwoven made of the first type of fiber and a
second type of
nonwoven made of the second type of fiber. The two types of fibers may be in
different
nonwoven webs or sheets. In certain example embodiments, the cleaning article
may include
PVOH polymer-based fibers blended with non-PVOH polymer fibers, such as
polyester,
polylactic acid, and/or cellulose-based fibers.
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Fibers Used
[0210] As shown in Table 1, several types of fibers, i.e., Fiber 1 ("Fl"),
Fiber 2 ("F2"), Fiber
3 ("F3"), and Fiber 4 ("F4") which comprise a copolymer of vinyl acetate and
vinyl alcohol
having a degree of hydrolysis of 88%, 96%, 98%, and 99.99%, respectively, were
used as the
starting materials. These fibers have uniform composition, and have additional
properties shown
in Table 1. In the Examples described herein, Fibers Fl and F2 each had a
fineness-length of 2.2
dpf-51 mm. Fiber F3 includes two types of fibers: a first fiber type having a
fineness-length of
1.7 dtex-38 mm, and a second fiber type having a fineness of 2.2 dtex-51 mm.
Fiber F4 had a
fineness-length of 1.7 dtex-38 mm. The units of fineness dtex and dpf are
similar to each other
and can be converted using a coefficient (dtex =dpf /0.9). In the Examples, a
polymer comprising
vinyl alcohol moieties is referred as -a polyvinyl alcohol polymer" and a
fiber comprising such a
polymer is referred as "a polyvinyl alcohol fiber."
[0211] Table 1
Viscosity
DH Fineness Solubility Tenacity
Elongation
Fiber (4%
solution) (mol%) (dtex) Temp ( C) (cN/dtex)
(A)
Fl 22-23 88 2.2 20 5
20
F2 22-23 96 2.2 40 7
15
F3 22-23 98 1.7, 2.2 70 7
12
F4 22-23 99.99 1.7 95 9
10
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[0212] As shown in Table 2, under different bonding conditions, the four types
of fibers were
used to make nonwoven core substrates. In certain examples, the two type of
fibers were also
mixed to make one type of nonwoven core substrate (called a "blended
nonwoven").
[0213] Table 2
Composition Calender
Bonding
Fiber Fiber
Fiber Fl - F2- Fiber F3 F3 Fiber F4
Calendar Calender Calender
2.2dpf x 2.2dpf 1.7dtex 2.2dtex
1.7dtex x
Sample 51mm Speed Pressure
Temperature
x x 38mm x 38mm
(FPM) (PSI)
( C)
(A) 51mm (%) 51mm (A)
(A) (A)
Ex. 1 100 1 40 180
Ex. 2 100 1 50 180
Ex. 3 100 1 50 190
Ex 4 100 1 40 190
Ex 5 50 50 2 40 180
Ex. 6 50 50 2 40 190
Ex. 7 50 50 2 40 180
Ex. 8 50 50 2 40 190
Ex. 9 50 50 2 40 180
Ex. 10 50 50 2 40
190
Ex. 11 25 75 2 40
180
Ex. 12 25 75 2 40
180
Ex. 13 75 25 2 40
180
Ex. 14 75 25 2 40
180
Ex. 15 50 50 2 40
180
Ex. 16 50 50 2 40
180
Ex. 17 50 50 2 40
180
[0214] The properties for Examples 1-17 are shown in Tables 3 and 4. These
properties
include solubility data, such as rupture time and disintegration time, tensile
strength, softness
rating, and surface roughness. These nonwoven (NW) samples were also applied
to a testing
substrate made of acrylic polymer on aluminum. The gloss of the testing
substrate before and
after the applications were recorded. The Ra values were measured using an SPI
Roughness
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Tester II, which had measurement limit of 250 pin. The gloss measurement were
performed
using a BYK micro-TRI-gloss. All gloss measurements were recorded at 20 .
[0215] Table 3
Solubility 80 C Solubility 90 C Tensile Softness
Rating
1 - softest,
Disintegration Rupture Disintegration Max Load
5 -
Sample Rupture (s)
(s) (s) (s) (N) extremely
rough
Ex. 1 3.33 7.67 6,99
3
Ex. 2 2.67 9.00 3.58
2
Ex. 3 4.33 10.33 9.33
3
Ex. 4 7.67 15.67 6.13
3
Ex. 5 2.67 21.33 7.37
2
Ex. 6 4.67 21.00 7.24
3
Ex. 7 5.33 13.33 1.59
2
Ex. 8 23.33 74.00 2.49
3
Ex. 9 4.33 10.33 7.75
2
Ex. 10 13.67 41.00 10.08
3
Ex. 11 10.07
5
Ex. 12 3.33 8.33 7.64
3
Ex. 13 61.10
5
Ex. 14 4.33 13.00 5.31
3
Ex. 15 10.33 32.00 29.81
5
Ex. 16 5.00 10.00 2.86
3
Ex. 17 8.00 21.67 7.46
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[0216] Table 4
. Gloss (Acrylic
Gloss (Acrylic
Surface on Aluminum
on Aluminum
Roughness Sheet) Post
Sheet)
NW
Average Ra
Sample Average GU Average GU
(min)
Ex. 1 159.33 254.5 249.5
Ex. 2 160.33 250.5 255.5
Ex. 3 173 254.5 249.5
Ex. 4 154.67 254.5 253
Ex. 5 197.00 252.5 249.5
Ex. 6 216.67 250.5 250.5
Ex. 7 175.33 251.5 257
Ex. 8 189.33 249.5 255.5
Ex. 9 214.33 255 233
Ex. 10 169.67 253.5 250.5
Ex. 11 241.67 250.5 248.5
Ex. 12 207.67 248.5 250
Ex. 13 249.67 251.5 249.5
Ex. 14 208.00 251 250
Ex. 15 250.67 254.5 253.5
Ex. 16 205.33 249 255
Ex. 17 225 253 254.5
[0217] Based on the compositions and the property data shown in Tables 2-4, in
example
embodiments at least one nonwoven (as the core substrate) comprises a
plurality of fibers made
of a PVOH copolymer having a degree of hydrolysis in a range of 90-99.99%,
more particularly
in a range of 90% to 98%. For example, nonwoven substrates made of one or two
fibers, such as
Fiber F3 (D.H. of 98%) or a combination of Fiber F3 and Fiber F2 (D. H. of
96%), for example,
Samples Exs. 1, 5, and 16, provide a short disintegration time in hot water
(e.g., at 80 C) and
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good softness. Fiber Fl (D.H. 88%) can be also combined with Fiber F3 or F2,
but the content of
Fiber Flin example embodiments is less than 50% or equal to or less than 25%
of a total weight
of the fibers. The introduction of Fl (e.g., Sample Exs. 11, 13, and 15) tends
to decrease the
softness and increase disintegration time of the nonwoven samples. Most of the
samples were
calendered at 180 C. Fiber Fl is more heat sensitive and susceptible to heat
degradation when
compared to Fiber F2 and Fiber F3 resulting in stiffer nonwoven samples. With
an increasing
amount of Fiber F4, the disintegration time of a resulting nonwoven sample in
hot water tends to
increase. As shown in Table 4, the stiffer fibers had a higher Ra value, but
there was no
observable difference in gloss measurements to assess or distinguish the
abrasiveness of
Experimental Samples 1-17.
[0218] As shown in Table 5, Experimental Samples 18-23 were made from blends
of Fiber F2
with other fiber chemistries of varying denier, including TREVIRAT" polyester
fibers, polylactic
acid (PLA) fibers, Rayon Viscose (cellulose) fibers, polyethylene
terephthalate (PET) fibers,
VESTERATm cellulose fibers, and LENZING LYOCELLTm cellulose fibers. The
property data
of these samples are shown in Table 6. Blends of nonwovens with fibers of
higher denier, are
expected to be less soft comparted to lower denier blends.
[0219] Table 5
Composition
Polylatic
TREVIRA Rayon
Round Lenzing
Fiber F2 - acid
polyester Viscose PET Vestera
Lyocell
Sample 2.2dpf x (PL A)
298 1.5dpf x 5dpf x 20dpf 1.8dtex
x 1.5dpf x
51mm (%) 6c x
38 mm (%) 60mmlpf(%) 76mm (%) 51mm (%)
38mm (%)
Ex. 18 50 50
Ex. 19 50 50
Ex. 20 50 50
Ex. 21 75 25
Ex. 22 50
50
Ex. 23 50 50
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[0220] Table 6
Calendar Bonding Basis Solubility Solubility T ensile
Softness Surface
Settings Weight 23 C 40 C Rating
Roughness
1-
Calender Calender Max
Target Rupture Rupture
softest Average
Sample Pressure Temperature Load
(PSI) ( C)
(GSM) (s) (s) (N) 5 -
Ra (pin)
rough
Ex. 18 40 140 50 3.95 2
187
Ex. 19 40 140 50 5.24 4
220.33
Ex. 20 40 140 50 130.67 11.67 4.89 2
215.00
Ex. 21 40 140 50 123.33 8.67 10.94 4
222.00
Ex. 22 40 140 50 144.67 24.00 5.70 3
138.33
Ex. 23 40 140 134.33 14.67 1.88 2
160.00
[0221] As shown in Tables 7 and 8, Experimental Samples 24-25 were nonwoven
samples (70
gsm) made of 100% Fibers F3 with different bonding pattern. These nonwoven
samples are
water-dispersible and eventually water-soluble in hot water. These samples
were evaluated both
with and without abrasive powder dishwasher detergent adhered to the surface.
The abrasive
powder was Cascade Complete and the detergent powder was adhered to the
surface of the
WSNW using Elmer's Multi-Purpose Spray Adhesive. Each of Experimental Samples
24-25 are
two samples:a first sample without the detergent powder and a second sample
with the detergent
powder. The detergent powder has dual functions as both the active cleaning
formulation and the
abrasive powder. Compared to the point bonding pattern, the daisy bonding
pattern has a higher
bonding density. The daisy bonded water-soluble nonwoven showed a higher Ra
value than the
point bonded material. This increase in Ra corresponded to the nonwoven's
rougher subjective
feel. Both nonwovens without any abrasive powders were rubbed on an aluminum
surface and an
acrylic surfaces resulting in no changes to the gloss of those surfaces. The
nonwoven samples
with abrasive powders, however, did scratch both the acrylic surface and the
aluminum surface
with rubbing, resulting in a significant decrease in gloss.
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[0222] Table 7
Surface
Fiber F3 Fiber F3 Surface
Bonding Basis
Roughness (NW
1.7dtex x 2.2dtex x
Roughness
Pattern Weight
+Abrasive
Sample 38mm 51mm (NW
only)
powder)
Daisy or Average
(%) (%) (gsm)
Average Ra ( in)
Point Ra (On)
Ex. 24 50 50 Daisy 70 245
250+
Ex. 25 50 50 Point 70 150.33
250+
[0223] Table 8
Gloss
Gloss (Acrylic
Gloss (Acrylic Gloss (Aluminum
on Aluminum
on Aluminum (Aluminum Sheet) -with Softness
Sheet) -with NW
Sheet)-with Sheet)- with NW
Rating
Sample NW only +Abrasive
NW only +Abrasive
Powder
Powder
1-soft, 5-
Average GU Average GU Average GU Average GU
rough
Ex. 24 250.67 148.33 133.50 99.10
4
Ex. 25 250.00 160.00 134.00 102.50
2
[0224] Example embodiments of the disclosure are described in the following
numbered
paragraphs. These example embodiments are intended to be illustrative in
nature and not
intended to be limiting.
[0225] The following paragraphs describe further aspects of the disclosure:
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1. An article for hand-washing an object, comprising:
a core substrate comprising a plurality of fibers including a resin, the core
substrate
having an abrasive surface and containing an active cleaning formulation,
wherein the core substrate is water-dispersible upon contact with water having
a
temperature of 40 C or lower according to Testing Method MSTM-205 to release
the active
cleaning formulation from the core substrate.
2. The article according to clause 1, wherein the core substrate has a
dispersion time
of 300 seconds or less.
3. The article according to clause 1 or 2, wherein the core substrate is
water-soluble
upon contact with water having a temperature of greater than 40 C according to
Testing Method
MSTM-205.
4. The article according to any of clauses 1-3, wherein the core substrate
has a
moisture content of less than 10 wt.%.
5. The article according to any of clauses 1-4, wherein the abrasive
surface has an
Ra value of 8 uin (0.2 gm) to 60 uin (1.5 gm).
6. The article according to any of clauses 1-5, wherein the active cleaning
formulation is in the form of at least one of the following: a solid, a
liquid, a gel, or a slurry
form.
7. The article according to any of clauses 1-6, wherein the active cleaning
formulation comprises one or more of the following: a sanitizer or sanitizing
agent, a detergent, a
surfactant, an emulsifier, a chel ants, a dirt suspender, a stain lifter or
releaser, an enzyme, a pH
adjuster, a builder, a soil release agent, a structurant, a free fragrance an
encapsulated fragrance,
a preservative, a solvent, a mineral, a foam builder, an HLB adjuster, or a
degreaser, or a
combination thereof.
8. The article according to any of clauses 1-7, wherein the active cleaning
formulation is at least one of disposed on a surface of the core substrate or
embedded in a matrix
of the core substrate.
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9. The article according to any of clauses 1-8, wherein the core substrate
is at least
one of saturated with the active cleaning formulation, coated with the active
cleaning formulation
or impregnated with the active cleaning formulation.
10. The article according to any of clauses 1-9, wherein the active
cleaning
formulation is present in the core substrate.
11. The article according to any of clauses 1-10, wherein the active
cleaning
formulation comprises a carrier solvent.
12. The article according to any of clauses 1-11, wherein each fiber of the
plurality of
fibers having a length of 10 mm to 100 mm.
13. The article according to any of clauses 1-12, wherein each fiber of the
plurality of
fibers having a length to diameter (LID) ratio of 0.5 to 25.
14. The article according to any of clauses 1-13, wherein the core
substrate comprises
a nonwoven substrate in the form of a nonwoven sheet, a plurality of nonwoven
sheets bonded to
form a nonwoven block substrate, or a plurality of nonwoven sheets coupled to
form a sphere or
spheroid.
15. The article according to any of clauses 1-14, wherein the active
cleaning
formulation comprises one or more of the following sanitizing agents:
quaternary ammonium
compounds (QACs), halogenated oxidizers, hypochlorous acid generating
compounds,
hypochlorite generating compounds, 1-bromo-3-chloro-5,5-dimethylhydantoin,
dichloroisocyanuric acid, alcohols, oxygen radical generators, hydrogen
peroxide (1+02), sulfate
generating compounds, methylisothiazolinone (MIT), benzisothiazolinone (13IT),
or sodium
metabisulfite.
16. The article according to any of clauses 1-15, wherein the core
substrate comprises
at least one nonwoven sheet comprising a plurality of fibers made of the
resin.
17. The article according to clause 16, wherein the plurality of fibers is
saturated with
the active cleaning formulation.
18. The article according to clause 16 or 17, wherein the active cleaning
formulation
is one of disposed on a surface of the plurality of fibers or embedded in the
plurality of fibers.
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19. The article according to any of clauses 16-18, wherein the core
substrate includes
a plurality of nonwoven layers, and the active cleaning formulation is
disposed between adjacent
layers of the plurality of layers.
20. The article according to any of clauses 16-19, wherein the resin is a
polymer
comprising a vinyl alcohol moiety.
21. The article according to clause 20, wherein the polymer comprising a
vinyl
alcohol moiety including a polyvinyl alcohol homopolymer, a polyvinyl alcohol
copolymer, or a
combination thereof.
22. The article according to clause 21, wherein the polyvinyl alcohol
copolymer is a
copolymer of vinyl acetate and vinyl alcohol or an anionically modified
copolymer.
23. The article according to clause 22, wherein the anionically modified
copolymer
comprises a carboxylate, a sulfonate, or combinations thereof.
24. The article according to any of clauses 16-23, wherein the plurality of
fibers
comprise a polyvinyl alcohol copolymer having a degree of hydrolysis in a
range of about 95 %
to about 98 %.
25. The article according to any of clauses 16-23, wherein the plurality of
fibers
comprise a first type of fiber comprising a polyvinyl alcohol copolymer having
a degree of
hydrolysis in a range of about 75% to about 89.9%, and a second type of fiber
comprising a
polyvinyl alcohol copolymer having a degree of hydrolysis in a range of about
90% to about
9999%
26. The article according to clause 25, wherein a ratio of the first type
of fiber to the
second type of fiber is in a range of from about 5:95 to about 25:75 by
weight.
27. The article according to clause 25 or 26, wherein the first type of
fiber comprises
a polyvinyl alcohol copolymer having a degree of hydrolysis in a range of
about 80% to about
89%, and the second type of fiber comprises a polyvinyl alcohol copolymer
having a degree of
hydrolysis in a range of about 95% to about 98%.
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28. The article according to any of clauses 25-27, wherein the core
substrate
comprises at least one nonwoven sheet including a mixture of the first type of
fiber and the
second type of fiber.
29. The article according to any of clauses 20-28, wherein the core
substrate
comprises fibers made of a polymer, which is not a polymer comprising a vinyl
alcohol moiety.
30. The article according to any of clauses 1-29, wherein the core
substrate comprises
a plurality of layers, the plurality of layers selected from a nonwoven sheet,
a foam layer, a film,
or any combination thereof.
31 The article according to clause 30, wherein the plurality
of layers includes
separate sheets in a plied construction or a continuous sheet folded in a
serpentine construction.
32. The article according to any of clauses 1-31, wherein the abrasive
surface
comprises a plurality of particles comprising the active cleaning formulation
bonded onto the
core substrate.
33. The article according to any of clauses 1-31, wherein the resin is
biodegradable.
34. A method for making an article for hand-washing an object, the method
comprising:
forming a nonwoven substrate comprising a plurality of fibers including a
resin, the
nonwoven substrate containing an active cleaning formulation,; and
forming an abrasive surface of the nonwoven substrate.
35. The method according to clause 34, wherein forming a nonwoven substrate
comprising a plurality of fibers including a resin, the nonwoven substrate
containing an active
cleaning formulation, comprises at least one of saturating the nonwoven
substrate with the active
cleaning formulation, disposing the active cleaning formulation on a surface
of the water-soluble
nonwoven substrate, coating a surface of the substrate with the active
cleaning formulation,
embedding the active cleaning formulation in the nonwoven substrate, or
impregnating the
nonwoven substrate with the active cleaning formulation.
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36. The method according to clause 35 or 36, wherein the active cleaning
formulation
includes a carrier solvent.
37. The method according to clause 36, wherein the nonwoven substrate is
water-
dispersible upon contact with water having a temperature of 40 C or lower, and
is water-soluble
upon contact with water having a temperature greater than 40 C according to
Testing Method
MSTM-205.
38. The method according to any of clauses 34-37, wherein forming an
abrasive
surface of the nonwoven substrate comprises forming an abrasive material on,
disposing an
abrasive material on, embedding an abrasive material in, coating an abrasive
material on, or
adhering an abrasive material to a first surface of the nonwoven substrate.
39. The method according to any of clauses 34-38, wherein forming an
abrasive
surface of the nonwoven substrate comprises adhesively bonding the abrasive
material to a first
surface of the nonwoven substrate.
40. The method according to clause 39, wherein the abrasive material
comprises a
plurality of particles made of the active cleaning formulation.
41. The method according to any of clauses 34-40, wherein forming an
abrasive
surface of the nonwoven substrate comprises heating a first surface of the
substrate to adhere an
abrasive material to the first surface.
42. The method according to any of clauses 34-41, wherein forming an
abrasive
surface of the nonwoven substrate comprises disposing an abrasive material in
a matrix of the
nonwoven substrate.
43. The method according to any of clauses 34-42, wherein forming an
abrasive
surface of the nonwoven substrate comprises at least partially dissolving a
first surface of the
nonwoven substrate and applying an abrasive material to the first surface.
44. The method according to any of clauses 34-43, further comprising
forming a
substantially smooth surface of the nonwoven substrate.
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45. The method according to clause 44, comprising coating a second surface
of the
nonwoven substrate with water or heating the second surface to create a
continuous smooth
second surface.
46. The method according to any of clauses 34-45, wherein forming an
abrasive
surface of the nonwoven substrate comprises forming an abrasive gradient
through a thickness of
the nonwoven substrate.
[0226] All percentages, parts and ratios referred to herein are based upon the
total dry weight
of the fiber composition, film composition, or total weight of the packaging
material composition
of the present disclosure, as the case may be, and all measurements made are
at about 25 C,
unless otherwise specified. All percentages, parts and ratios referred to
herein for liquid
formulations are based upon the total weight of the liquid formulation. All
such weights as they
pertain to listed ingredients are based on the active level and therefore do
not include carriers or
by-products that may be included in commercially available materials, unless
otherwise
specified.
[0227] All ranges set forth herein include all possible subsets of ranges and
any combinations
of such subset ranges. By default, ranges are inclusive of the stated
endpoints, unless stated
otherwise. Where a range of values is provided, it is understood that each
intervening value
between the upper and lower limit of that range and any other stated or
intervening value in that
stated range, is encompassed within the disclosure. The upper and lower limits
of these smaller
ranges may independently be included in the smaller ranges, and are also
encompassed within
the disclosure, subject to any specifically excluded limit in the stated
range. Where the stated
range includes one or both of the limits, ranges excluding either or both of
those included limits
are also contemplated to be part of the disclosure.
[0228] It is expressly contemplated that for any number value described
herein, e.g., as a
parameter of the subject matter described or part of a range associated with
the subject matter
described, an alternative which forms part of the description is a
functionally equivalent range
surrounding the specific numerical value (e.g., for a dimension disclosed as
"40 millimeters
(mm)" an alternative embodiment contemplated is -about 40 mm").
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[0229] Reference throughout this specification to -example embodiment" or "an
embodiment"
may mean that a particular feature, structure, or characteristic described in
connection with a
particular embodiment may be included in at least one embodiment of claimed
subject matter.
Thus, appearances of the phrase "example embodiments" or "an example
embodiment" in
various places throughout this specification is not necessarily intended to
refer to the same
embodiment or to any one particular embodiment described. Further, it is to be
understood that
particular features, structures, or characteristics described may be combined
in various ways in
one or more embodiments. In general, of course, these and other issues may
vary with the
particular context of usage. Therefore, the particular context of the
description or the usage of
these terms may provide helpful guidance regarding inferences to be drawn for
that context.
[0230] Although the subject matter has been described in language specific to
structural
features and/or methodological acts, it is to be understood that the subject
matter defined in the
appended claims is not necessarily limited to the specific features or acts
described. Rather, the
specific features and acts are disclosed as illustrative forms of implementing
the claims.
[0231] One skilled in the art will realize that a virtually unlimited number
of variations to the
above descriptions are possible, and that the examples and the accompanying
figures are merely
to illustrate one or more examples of implementations.
[0232] It will be understood by those skilled in the art that various other
modifications may be
made, and equivalents may be substituted, without departing from claimed
subject matter.
Additionally, many modifications may be made to adapt a particular situation
to the teachings of
claimed subject matter without departing from the central concept described
herein. Therefore, it
is intended that claimed subject matter is not limited to the particular
embodiments disclosed, but
that such claimed subject matter may also include all embodiments falling
within the scope of
the appended claims, and equivalents thereof.
[0233] In the detailed description above, numerous specific details are set
forth to provide a
thorough understanding of claimed subject matter. However, it will be
understood by those
skilled in the art that claimed subject matter may be practiced without these
specific details. In
other instances, methods, apparatuses, or systems that would be known by one
of ordinary skill
have not been described in detail so as not to obscure claimed subject matter.
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