Note: Descriptions are shown in the official language in which they were submitted.
CA 02904373 2015-11-19
WATER-SOLUBLE FILM FOR DELAYED RELEASE
Field of the Disclosure
[0002] This disclosure relates generally to water-soluble films. More
particularly, this
disclosure relates to water-soluble film pouches or packets for the delayed
release of an active
agent from the water-soluble pouch or packet.
Background
[0003] Water-soluble polymeric films are commonly used as packaging materials
to simplify
dispersing, pouring, dissolving and dosing of a material to be delivered. For
example, packets
made from water-soluble film are commonly used to package household care
compositions, e.g.,
a pouch containing a laundry or dish detergent. A consumer can directly add
the pouch to a
mixing vessel, such as a bucket, sink or washing machine. Advantageously, this
provides for
accurate dosing while eliminating the need for the consumer to measure the
composition. The
pouch may also reduce mess that would be associated with dispensing a similar
composition
from a vessel, such as pouring a liquid laundry detergent from a bottle. The
pouch also insulates
the composition therein from contact with the user's hands. In sum, soluble
polymeric film
packets containing pre-measured agents provide for convenience of consumer use
in a variety of
applications.
[0004] The efficacy of certain laundry actives (e.g. enzymes) can be increased
if alkaline
actives (e.g. bleach additives) are introduced at a secondary stage that is
delayed, for example by
15 to 20 minutes. To achieve the delayed release of alkaline actives in a wash
cycle, a water-
soluble film packet must be slow dissolving and remain substantially intact
for the 15-20 minutes
at nominally 40 C. The components of the unit dose packet system must also be
made to be
chemically compatible with each other or chemically isolated from one another
as to prevent any
chemical or physical changes to the packaged materials.
1
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0005] Some water-soluble polymeric films that are used to make packets will
incompletely
dissolve during such a laundry wash cycle, leaving film residue on items
within the wash, or will
dissolve prematurely resulting in a decreased efficacy of certain laundry
additives (e.g.,
enzymes) that may become unstable in the presence of other active agents.
[0006] Water-soluble polymeric films based on PVOH can be subject to changes
in solubility
characteristics. The acetate group in the co-poly(vinyl acetate vinyl alcohol)
polymer is known
by those skilled in the art to be hydrolysable by either acid or alkaline
hydrolysis. This is an
inherent weakness in the application of films based on just the vinyl
acetate/alcohol co-polymer
typified by commercial PVOH resins. In the presence of a strong base such as a
laundry
bleaching additive PVOH resins with pendant carboxyl groups such as vinyl
alcohol/hydrolyzed
methyl acrylate sodium salt resins will deteriorate over the course of several
weeks at relatively
warm (ambient) and high humidity conditions.
[0007] Thus, it is believed that such a film can become more soluble due to
chemical
interactions between the film and an alkaline composition inside the pouch
during storage.
Consequently, as they age, the packets may become increasingly prone to
premature dissolution
during a hot wash cycle (nominally 40 C), and may in turn decrease the
efficacy of certain
laundry actives due to the presence of the bleaching agent.
[0008] The current state of the art in water-soluble/reactive/dispersible
pouches and packets
for delivering bleach with a delay relative to a laundry detergent includes
the use of a multi-
compartment water-soluble pouch made from polyvinyl alcohol (PVOH) film,
wherein the
second pouch, containing a solid, dissolves slower than the first as is
described in U.S. Patent
No. 6,727,215, and U.S. Patent Publication Nos. 2009/0011970 and 2010/0192086.
Further,
various different chemical coatings applied to powders of bleach or bleach
activator as a means
to delay release are described in U.S. Patent Nos. 4,725,378; 5,965,505; and
5,755,992.
[0009] There remains a need for packets comprising water-soluble films having
the desired
characteristics of delayed release in hot water, sufficient solubility as to
not leave any film
residue on the wash load once the wash cycle is complete, chemical and
physical compatibility
with laundry detergent, and mechanical properties including good
processability.
2
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
Summary
[0010] The present disclosure provides a water-soluble pouch or packet
including a first sealed
compartment containing a first composition, the first sealed compartment
including a water-
soluble film, the water-soluble film including a polyvinyl alcohol (PVOH) and
an acrylate resin
(e.g., methyl acrylate) and the first composition including an alkaline agent.
Optionally, the
water-soluble film remains intact for at least 3 minutes when submerged in
water heated to a
temperature of about 40 C, as determined by Bleach Compatibility Method A
(described herein),
and thereafter fully dissolves. Optionally, the alkaline agent can include a
bleach composition.
Further optionally, the bleach composition can be coated with a coating. The
packet or pouch
can optionally include two or more compartments.
[0011] In a related aspect, the disclosure provides a method of making a film
for delayed
solubility in hot water according to the steps of selecting a water-soluble
resin comprising PVOH
and methyl acrylate; wherein the water-soluble resin comprises about 5 mol%
methyl acrylate
and preparing a water-soluble film having a thickness of about 3 mil to about
6 mil (about 0.076
mm to about 0.15 mm).
[0012] In one embodiment, the packet includes a first and a second sealed
compartment. The
second compartment is in a generally superposed relationship with the first
sealed compartment
such that the second sealed compartment and the first sealed compartment share
a partitioning
wall interior to the pouch.
[0013] In one embodiment, the packet including a first and a second
compartment further
includes a third sealed compartment. The third sealed compartment is in a
generally superposed
relationship with the first sealed compartment such that the third sealed
compartment and the
first sealed compartment share a partitioning wall interior to the pouch.
[0014] In some embodiments, the first composition and the second composition
are
individually selected from liquids, and powders. For example, the embodiments
can include the
following combinations: liquid, liquid; liquid, powder; powder, powder; and
powder, liquid.
[0015] In some embodiments, the first, second and third compositions
individually are
individually selected from liquids, and powders. For example, the embodiments
can include the
following combinations: solid, liquid, liquid; solid, solid, liquid; and
liquid, liquid, liquid.
3
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0016] In any of the embodiments, the single compartment or plurality of
sealed
compartments contains a composition. The plurality of compartments may each
contain the
same or a different composition. The composition is selected from a liquid,
solid or combination
thereof As used herein, "liquid" includes pastes, liquids, gels, foams or
mousse. Non-limiting
examples of liquids include light duty and heavy duty liquid detergent
compositions, fabric
enhancers, detergent gels commonly used for laundry, bleach and laundry
additives. Gases, e.g.,
suspended bubbles or solids e.g. particles, may be included within the
liquids. A "solid" as used
herein includes powders, agglomerates or mixtures thereof Non-limiting
examples of solids
include: micro-capsules; beads; noodles; and pearlised balls. Solids, e.g.,
solid composition(s),
may provide a technical benefit including, but not limited to, through-the-
wash benefits, pre-
treatment benefits, and/or aesthetic effects.
[0017] In any of the embodiments, the composition may be selected from the
group of liquid
light duty and liquid heavy duty liquid detergent compositions, powdered
detergent
compositions, fabric enhancers, detergent gels commonly used for laundry, and
bleach and
laundry additives.
[0018] Further aspects and advantages will be apparent to those of ordinary
skill in the art
from a review of the following detailed description, taken in conjunction with
the drawings.
While the compositions, films, pouches, and packets described herein are
susceptible to
embodiments in various forms, the description hereafter includes specific
embodiments with the
understanding that the disclosure is illustrative, and is not intended to
limit the invention to the
specific embodiments described herein.
[0019] Optional features, such as specific components, compositional ranges
thereof,
substituents, conditions, and method steps, can be selected from the various
examples provided
herein.
Brief Description of the Drawings
[0020] For further facilitating the understanding of the present disclosure,
four drawing figures
are appended hereto, wherein:
[0021] Figure 1 is a perspective view of a test apparatus used to determine
the water
disintegration and dissolution times of film samples according to MSTM 205
described herein;
4
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0022] Figure 2 is a perspective view of the test apparatus and test set-up
illustrating the
procedure for determining the water-solubility of film samples according to
MSTM 205
described herein;
[0023] Figure 3 is a top view of the test set-up of Figure 2; and
[0024] Figure 4 is a plot of the pH vs. time for a tablet of 10 g compressed
tablet of sodium
carbonate and sodium percarbonate (1:1 wt.%), a 10 g compressed tablet of
sodium carbonate
and sodium percarbonate (1:1 wt.%) coated with polyethylene glycol (PEG MW
6,000), a 10 g
compressed tablet of sodium carbonate and sodium percarbonate (1:1 wt.%)
contained within a
water-soluble film pouch according to the disclosure, and a 10 g compressed
tablet of sodium
carbonate and sodium percarbonate (1:1 wt.%) coated with PEG (MW 6,000) and
contained
within a water-soluble film pouch according to the disclosure.
Detailed Description
[0025] The present disclosure provides a water-soluble pouch or packet
including a first sealed
compartment containing a first composition, the first sealed compartment
including a wall of a
water-soluble film, the water-soluble film including a polyvinyl alcohol
(PVOH) and acrylate
resin and the first composition including an alkaline agent. Preferably, the
film is a monolayer
film. The compartment can have its entire wall structure provided by the PVOH-
based film. In
any type of embodiment described herein, the acrylate resin can be a methyl
acrylate. As an
alternative, in any type of embodiment described herein, the acryalte resin
can be a methyl
acrylate or a methyl methacrylate. Optionally, the water-soluble film remains
intact for at least 3
minutes when submerged in water heated to a temperature of about 40 C, as
determined by
Bleach Compatibility Method A (described herein), and thereafter fully
dissolves. Optionally,
the alkaline agent can include a bleach composition. Further optionally, the
bleach composition
can be coated with a coating. The packet or pouch can optionally include two
or more
compartments. In addition or in the alternative, the water-soluble film
including polyvinyl
alcohol (PVOH) and methyl acrylate resin remains intact for at least 9 minutes
in a washing
machine at 40 C, as determined by Bleach Compatibility Method B (described
herein), and
thereafter fully dissolves. Advantageously, the water soluble film of the
disclosure can be used
to delay the release of an alkaline bleaching agent into a wash cycle, thereby
delaying
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
basification of the wash water and reducing loss of functionality from
alkaline sensitive materials
present in laundry detergents.
[0026] The articles and methods are contemplated to include embodiments
including any
combination of one or more of the additional optional elements, features, and
steps further
described below (including those shown in the figures), unless stated
otherwise.
[0027] As used herein, the term "comprising" indicates the potential inclusion
of other agents,
elements, steps, or features, in addition to those specified.
[0028] Advantageously, when a bleach component is coated as described herein
and enclosed
within a pouch comprising the water-soluble film of the present disclosure,
the water-soluble
film remains intact for at least 8 minutes when submerged in water heated to a
temperature of
about 40 C, as determined by Bleach Compatibility Method A, corresponding to
at least 15
minutes in a washing machine, as determined by Bleach Compatibility Method B.
Thus, the
water-soluble film/bleach coating of the disclosure can be used to delay the
release of an alkaline
bleaching agent into a wash cycle for at least 15 minutes, thereby delaying
basification of the
water and preventing loss of functionality from alkaline sensitive materials
(such as enzymes)
present in laundry detergents.
[0029] In a related aspect, the disclosure provides a method of making a film
for delayed
solubility in hot water according to the steps of selecting a water-soluble
resin comprising PVOH
and methyl acrylate; wherein the water-soluble resin comprises about 5 mol%
methyl acrylate
and preparing a water-soluble film having a thickness of about 3 mil to about
6 mil (about 0.076
mm to about 0.15 mm).
[0030] In one embodiment, the packet includes first and second sealed
compartments. The
second compartment can be in a generally superposed relationship with the
first sealed
compartment such that the second sealed compartment and the first sealed
compartment share a
partitioning wall interior to the pouch.
[0031] In one embodiment, the packet including a first and a second
compartment further
includes a third sealed compartment. The third sealed compartment can be in a
generally
superposed relationship with the first sealed compartment such that the third
sealed compartment
and the first sealed compartment share a partitioning wall interior to the
pouch.
6
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0032] In some embodiments, the first composition and the second composition
are
individually selected from liquids, and powders. For example, the embodiments
can include the
following combinations: liquid, liquid; liquid, powder; powder, powder; and
powder, liquid.
[0033] In some embodiments, the first, second and third compositions
individually are
individually selected from liquids and solids. For example, the embodiments
can include the
following combinations: solid, liquid, liquid; solid, solid, liquid; and
liquid, liquid, liquid.
[0034] In any of the embodiments, the single compartment or plurality of
sealed
compartments contains a composition. The plurality of compartments may each
contain the
same or a different composition. The composition can be selected from a
liquid, solid or
combination thereof. As used herein, "liquid" includes free-flowing liquids,
as well as pastes,
gels, foams and mousses. Non-limiting examples of liquids include light duty
and heavy duty
liquid detergent compositions, fabric enhancers, detergent gels commonly used
for laundry,
bleach and laundry additives. Gases, e.g., suspended bubbles, or solids, e.g.
particles, may be
included within the liquids. A "solid" as used herein includes, but is not
limited to, powders,
agglomerates, and mixtures thereof. Non-limiting examples of solids include:
micro-capsules;
beads; noodles; and pearlised balls. Solid compositions, may provide a
technical benefit
including, but not limited to, through-the-wash benefits, pre-treatment
benefits, and/or aesthetic
effects.
[0035] In any of the laundry-centric embodiments, the composition may be
selected from the
group of liquid light duty and liquid heavy duty liquid detergent
compositions, powdered
detergent compositions, fabric enhancers, detergent gels commonly used for
laundry, and bleach
and laundry additives, for example.
[0036] As used herein, the term "comprising" indicates the potential inclusion
of other agents,
elements, steps, or features, in addition to those specified.
[0037] As used herein and unless specified otherwise all measurements of PVOH
viscosity in
centipoise (cP) are of a 4% (w/v) solution in water at 20 C, and unless
specified otherwise all
measurements of carboxymethyl cellulose viscosity are of a 2% (w/v) solution
in water at 25 0 C.
[0038] 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
7
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
weight of the entire film (when applicable) or parts by weight of the entire
composition enclosed
within a pouch (when applicable). As used herein and unless specified
otherwise, the term "phr"
is intended to refer to the composition of the identified element in parts per
one hundred parts
water-soluble PVOH resins.
[0039] As used herein and unless specified otherwise, the term
"disintegration" refers to the
point at a water soluble pouch releases the entire contents of the pouch
without dissolution of the
film.
[0040] As used herein and unless specified otherwise, the term "dissolution"
refers to the point
at which a film and any of its fragmented remains are completely dissolved and
are in solution.
[0041] As used herein and unless specified otherwise, the term "inadequate
solubility" refers
to a film that does not completely dissolve in water heated to a temperature
of 40 C in 55
minutes or less.
[0042] As used herein and unless specified otherwise, the term "Point A Time"
refers to the
point at which the pH of the solution begins to climb at a rate greater than
or equal to 0.1 pH
units per minute in Bleach Compatibility Method A.
[0043] The water-soluble film according to the disclosure includes polyvinyl
alcohol (PVOH).
PVOH is a synthetic resin generally prepared by the alcoholysis, usually
termed hydrolysis or
saponification, of polyvinyl acetate. Fully hydrolyzed PVOH, wherein 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 -- greater than about 140 F (60
C). If a sufficient
number of acetate groups are allowed to remain after the hydrolysis of
polyvinyl acetate, the
PVOH polymer then being known as partially hydrolyzed, it is more weakly
hydrogen-bonded
and less crystalline and is soluble in cold water -- less than about 50 F (10
C). An intermediate
cold/hot water soluble film can include, for example, intermediate partially-
hydrolyzed PVOH
(e.g., with degrees of hydrolysis of about 94% to about 98%), and is readily
soluble only in
warm water¨ e.g., rapid dissolution at temperatures of about 40 C and
greater. Both fully and
partially hydrolyzed PVOH types are commonly referred to as PVOH homopolymers
although
the partially hydrolyzed type is technically a vinyl alcohol-vinyl acetate
copolymer.
Accordingly, a copolymer with an acrylate can be a vinyl alcohol-vinyl acetate
terpolymer.
8
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0044] It is well known in the art that the viscosity of a resin is correlated
with the weight
average molecular weight (Mw) of the same resin, and often the viscosity is
used as a proxy for
_
Mw. The viscosity of a PVOH resin 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.
[0045] As mentioned above, the acetate group in the co-poly(vinyl acetate
vinyl alcohol)
polymer is hydrolyzable by either acid or alkaline hydrolysis. As a result,
the solubility
characteristics of packets formed with PVOH can, under appropriate
circumstances, degrade
over time and thus the packets may prematurely dissolve.
[0046] It has been found, as demonstrated in the examples, that the solubility
of films
comprising fully hydrolyzed PVOH (i.e. a degree of hydrolysis of 98-100%)
homopolymers in
40 C water is dependent on the molecular weight of the PVOH. For example,
films comprising
low molecular weight, fully hydrolyzed PVOH homopolymers, wherein the
viscosity is about 4
cPs or less, are fully soluble at 40 C. Films comprising fully hydrolyzed
PVOH homopolymers
characterized by a viscosity greater than 10 cPs are not soluble at 40 C and
films comprising
fully hydrolyzed PVOH homopolymers characterized by viscosities of about 5-6
cPs
demonstrate inconsistent solubility at 40 C. It was further found that the
fully hydrolyzed
PVOH homopolymers that were soluble at 40 C (i.e., characterized by lower
viscosities and thus
having lower molecular weights) were difficult to process and the resulting
films had poor
mechanical properties.
[0047] It has been further found, as demonstrated in the examples, that the
solubility of films
comprising partially hydrolyzed PVOH homopolymers in 40 C water is dependent
upon the pH
of the water. At neutral pH, films comprising partially hydrolyzed PVOH
homopolymers were
fully soluble in water at 40 C. However, when tested in contact with an
alkaline agent (e.g.,
with sodium carbonate and percarbonate) the films became insoluble in water at
40 C. Without
intending to be bound by theory, it is believed that the sodium carbonate
further hydrolyzes the
resin, resulting in a fully hydrolyzed homopolymer, which has been shown to be
insoluble in
water at 40 C. This interaction makes partially hydrolyzed PVOH homopolymers
unsuitable for
use by themselves in films for package alkaline components, including bleach
components such
as sodium carbonate or percarbonate, for dissolution release into a wash water
system at 40 C.
9
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0048] The PVOH resins of the disclosure demonstrate good processability
characteristics,
and films comprising the PVOH resin of the disclosure are soluble at 40 C,
even while in
contact with a 1:1 mixture of sodium carbonate and percarbonate. The PVOH
resin of the
disclosure is a copolymer including PVOH and an acrylate.
[0049] The PVOH included in the copolymer used in the water-soluble films of
the present
disclosure can be fully hydrolyzed (i.e., the degree of hydrolysis is about
98% to about 100%),
having very little residual acetate groups. As the degree of hydrolysis is
reduced below fully
hydrolyzed, a film made from the resin will have reduced mechanical strength
but faster
solubility. Of course, as known in the art, below a degree of hydrolysis of
about 60% the PVOH
resins and films made therefrom will no long be water soluble
[0050] The copolymer of the invention can comprise about 5 mol% of an
acrylate, for
example methyl acrylate and/or methyl methacrylate. Without intending to be
bound by theory it
is believed that the pendant carboxyl groups from the acrylate undergo
methanolysis to form
lactone rings. It is believed that because the closed lactone rings do not
undergo hydrolysis to
form fully hydrolyzed PVOH, the resin remains soluble at 40 C, even in the
presence of sodium
carbonate. As shown in the examples, as the mol% of acrylate, for example
methyl
methylacrylate, in the copolymer decreases below 5%, the solubility of the
PVOH copolymer
resin in water heated to a temperature of about 40 C decreases. It is
believed that the decrease
in solubility is due to the resin more closely resembling a fully hydrolyzed
PVOH polymer
because of the increased amount of PVOH in the copolymer. Further, it is
believed that as the
mol% of acrylate in the copolymer increases above 5 mol%, the solubility of
the PVOH
copolymer resin in water heated to a temperature of about 40 C decreases as
the polymer
becomes only soluble in increasingly hot water.
[0051] The amount of acrylate resin in an acrylate-PVOH copolymer can be used
to effect the
solubility, and therefore the delayed release characteristics, of a water-
soluble film comprising
the acrylate-PVOH copolymer and packets made from the water-soluble film. For
example, a
packet comprising a water-soluble film including greater than about 5 mol%
acrylate in the
water-soluble resin would demonstrate a similar length of delayed release of
the contents
enclosed in the packet as a at a lower temperature than a packet comprising a
water-soluble film
including about 5 mol% acrylate in the water-soluble resin. Further, a packet
comprising a
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
water-soluble film including less than about 5 mol% acrylate in the water-
soluble resin would
demonstrate a similar length of delayed release of the contents enclosed in
the packet at a higher
temperature than a packet comprising a water-soluble film including about 5
mol% acrylate in
the water-soluble resin. The amount of acrylate included in the water-soluble
PVOH copolymer
can be between about 2 mol% and about 10 mol%, about 2 mol% and about 8 mol%,
about 2
mol% and about 6 mol%, about 3 mol% to about 6mol%, about 4 mol% and about 6
mol%,
and/or about 5 mol%.
[0052] The water-soluble resin can be included in the water-soluble film in
any suitable
amount, for example an amount in a range of about 35 wt% to about 90 wt%, or
about 40 wt% to
about 90 wt%, or about 45 wt% to about 90 wt%, or about 50 wt% to about 90
wt%, or about 55
wt% to about 90 wt%, or about 60 wt% to about 90 wt%, or about 65 wt% to about
90 wt%, or
about 70 wt% to about 90 wt%, or about 75 wt% to about 85 wt%, or about 80
wt%.
[0053] Water-soluble PVOH resins for use in the films described herein can be
characterized
by any suitable viscosity for the desired film properties, optionally a
viscosity in a range of about
8.0 to about 40.0 cP, or about 10.0 cP to about 30 cP, or about 13 cP to about
27 cP.
[0054] The water-soluble films according to the present disclosure may include
other optional
additive ingredients including, but not limited to, plasticizers, surfactants,
emulsifiers, fillers,
extenders, antiblocking agents, detackifying agents, antifoams, film formers
and other functional
ingredients, for example in amounts suitable for their intended purpose.
[0055] Water is recognized as a very efficient plasticizer for PVOH and other
polymers;
however, the volatility of water makes its utility limited since polymer films
need to have at least
some resistance (robustness) to a variety of ambient conditions including low
and high relative
humidity. Glycerin is much less volatile than water and has been well
established as an effective
plasticizer for PVOH and other polymers. Glycerin or other such liquid
plasticizers by
themselves can cause surface "sweating" and greasiness if the level used in
the film formulation
is too high. This can lead to problems in a film such as unacceptable feel to
the hand of the
consumer and even blocking of the film on the roll or in stacks of sheets if
the sweating is not
mitigated in some manner, such as powdering of the surface. This could be
characterized as over
plasticization. However, if too little plasticizer is added to the film the
film may lack sufficient
11
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
ductility and flexibility for many end uses, for example to be converted into
a final use format
such as packets.
[0056] Plasticizers for use in water-soluble films of the present disclosure
include, but are not
limited to, sorbitol, glycerol, diglycerol, propylene glycol, ethylene glycol,
diethyleneglycol,
triethylene glycol, tetraethyleneglycol, polyethylene glycols up to MW 400, 2
methyl 1, 3
propane diol, lactic acid, monoacetin, triacetin, triethyl citrate, 1,3-
butanediol,
trimethylolpropane (TMP), polyether triol, and combinations thereof. As less
plasticizer is used,
the film can become more brittle, whereas as more plasticizer is used the film
can lose tensile
strength. Plasticizers can be included in the water-soluble films in an amount
in a range of about
phr to about 50 phr, or from about 10 phr to about 40 phr, or from about 15
phr to about 30
phr, for example.
[0057] Surfactants for use in water-soluble films are well known in the art.
Optionally,
surfactants are included to aid in the dispersion of the resin solution upon
casting. Suitable
surfactants for water-soluble films of the present disclosure include, but are
not limited to,
dialkyl sulfosuccinates, lactylated fatty acid esters of glycerol and
propylene glycol, lactylic
esters of fatty acids, sodium alkyl sulfates, polysorbate 20, polysorbate 60,
polysorbate 65,
polysorbate 80, alkyl polyethylene glycol ethers, lecithin, acetylated fatty
acid esters of glycerol
and propylene glycol, sodium lauryl sulfate, acetylated esters of fatty acids,
myristyl
dimethylamine oxide, trimethyl tallow alkyl ammonium chloride, quaternary
ammonium
compounds, salts thereof and combinations of any of the forgoing. Too little
surfactant can
sometimes result in a film having holes, whereas too much surfactant can
result in the film
having a greasy or oily feel from excess surfactant present on the surface of
the film. Thus,
surfactants can be included in the water-soluble films in an amount of less
than about 2 phr, for
example less than about 1 phr, or less than about 0.5 phr, for example.
[0058] One type of secondary component contemplated for use in the film-
forming
composition is a defoamer. Defoamers can aid in coalescing of foam bubbles.
Suitable
defoamers for use in water-soluble films according to the present disclosure
include, but are not
limited to, hydrophobic silicas, for example silicon dioxide or fumed silica
in fine particle sizes,
including Foam Blast defoamers available from Emerald Performance Materials,
including
Foam Blast 327, Foam Blast UVD, Foam Blast 163, Foam Blast 269, Foam Blast
338,
12
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
Foam Blast 290, Foam Blast 332, Foam Blast 349, Foam Blast 550 and Foam
Blast
339, which are proprietary, non-mineral oil defoamers. In embodiments,
defoamers can be used
in an amount of 0.7 phr, or less, for example, 0.5 phr, 0.05 phr, 0.04 phr,
0.03 phr, 0.02 phr, or
0.01 phr.
[0059] Suitable lubricants/release agents can include, but are not limited to,
fatty acids and
their salts, fatty alcohols, fatty esters, fatty amines, fatty amine acetates
and fatty amides.
Preferred lubricants/release agents are fatty acids, fatty acid salts, and
fatty amine acetates. In
embodiments, lubricant/release agents can be used in an amount of about 0.02
wt% to about 1.5
wt%, optionally about 0.1 wt% to about 1 wt%, for example.
[0060] Suitable fillers/extenders/antiblocking agents/detackifying agents
include, but are not
limited to, starches, modified starches, crosslinked polyvinylpyrrolidone,
crosslinked cellulose,
microcrystalline cellulose, silica, metallic oxides, calcium carbonate, talc
and mica. Preferred
materials are starches, modified starches and silica. In one type of
embodiment, the amount of
filler/extender/antiblocking agent/detackifying agent in the water-soluble
film is 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.%,
for example.
[0061] During preparation of PVOH resin solutions a browning effect can occur.
Whereas, in
most applications, clear and colorless water-soluble films are desirable, a
suitable bleaching
agent can be added to the PVOH resin solution. The use of sodium metabisulfite
has been found
to substantially maintain the solution clarity and colorlessness during
preparation when used in
the composition in an amount in the range of about 0.05 wt.% to about 1.0
wt.%, or about 0.05
wt.% to about 0.7 wt.%, or about 0.1 wt.% to about 0.5 wt.%, or about 0.1 wt.%
to about 0.3
wt.%, or about 0.2 wt.%.
[0062] The thickness of the water-soluble film can also be used to effect the
solubility and
delayed-release characteristics of the water-soluble films and packets made
from the water-
soluble films. As the thickness of the water-soluble film increases, the
dissolution time of the
water-soluble film increases. Water-soluble films of the disclosure can have a
thickness of about
3 mil to about 6 mil (about 0.076 mm to about 0.15 mm), for example, about 3.5
mil to about 6
mil (about 0.09 mm to about 0.15 mm), or about .4 mil to about 5.5 mil (about
0.10 mm to about
0.14 mm), or about 4.5 mil to about 5.5 mil (0.11 mm to about 0.14 mm), or
about 5 mil (0.13).
13
CA 02904373 2016-05-27
[0063] The water-soluble films of the disclosure are advantageous in that they
can remain
intact for at least about 3 minutes, as determined by Bleach Compatibility
Method A, or at least 9
minutes as determined by Bleach Compatibility Method B, after submersion in
water heated to a
temperature of 40 C, when in contact with a 1:1 mixture of sodium carbonate
and percarbonate.
[0064] Bleach Compatibility Method A is a laboratory test that can be used to
determine if a
water-soluble film is chemically compatible with an alkaline agent, such as a
bleach. The test
sample for Method A is a small, 2 x 2 inches (5.08 x 5.08 cm), nominal 5 mil
(127 inn), water-
soluble film pouch filled with either 5.8 g of 1:1 (wt%) sodium carbonate and
sodium
percarbonate mixed powder or a 10 g compressed tablet of the same material,
and then heat
sealed. The bleach tablets can comprise stearic acid as a binding agent and
are made with
compression techniques well known to those skilled in the art. The bleach
powder materials are
available from Solvay Chemicals. The pouch is secured using a vinyl coated 0.5
inch (1.3 cm)
metal mesh cage and is submerged into a 600 ml beaker containing 500 ml of 40
C deionized
water, and stirred. The water is stabilized to pH 7 before submerging the
metal mesh cage
containing the pouch. After the pouch is submerged, the pH of the water is
monitored using a
pH probe and recorded every minute until a pH of 9.5 or higher is reached, or
until 20 minutes
has elapsed. The integrity and dissolution behavior of the pouch is observed
and recorded.
[0065] Ideal dissolution behavior of a water-soluble film in contact with an
alkaline bleach in
40 C water is marked by a sudden increase in pH through the release of the
active materials
from the pouch in a range of about 9 to about12 minutes from the start of the
test. This ideal
behavior corresponds to an active release delay of about 15-20 minutes within
a commercially-
available laundry machine cycle at nominally 40 C wash water (Bleach
Compatibility Method
B).
[0066] Bleach Compatibility Method B tests the dissolution behavior of
water-soluble packets
prepared from water-soluble film that enclose a bleaching agent in a
commercially-available
laundry machine. The test samples are prepared as described above for Method
A. The samples
are tested in a SIEMENS brand SI 6-79 washing machine using the program
Koch/Bunt
(cotton/colored), or an equivalent. The SIEMENS' brand S16-79 automatic
washing machine
has a 65 liter drum capacity and variable temperature selection. The
temperature of the wash water
was either 20 C, 40 C, or 60 C. In the tests reported herein, the water
hardness was
14
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
determined to be 250 ppm CaCO3 (14 d, German hardness degrees). The wash load
is 3 kg,
consisting of 2 bed sheets (1.5 x 1.5 m ISO 2267), 4 pillow cases (0.8 x 0.8 m
ISO 2267), and 3
huckaback towels cotton bleached. The dissolution time for Method B
corresponds to the time at
which a pH of 9.5 or higher is reached, as measured by a pH probe. In one type
of embodiment,
the desired behavior is marked by a sudden increase in pH through the release
of the active
materials from the pouch at about 15 to 20 minutes within a commercially-
available automatic
laundry machine cycle using nominally 40 C wash water.
[0067] A contemplated class of embodiments is characterized by good
thermoformability of
the water-soluble film made as described herein. A thermoformable film is one
that can be
shaped through the application of heat and a force.
[0068] Thermoforming a film is the process of heating the film, shaping it,
for example in a
mold, and then allowing the film to cool, whereupon the film will hold the
formed shape, e.g. the
shape of the mold. The heat may be applied using any suitable means. For
example, the film
may be heated directly by passing it under a heating element or through hot
air, prior to feeding
it onto a surface or once on a surface. Alternatively, it may be heated
indirectly, for example by
heating the surface or applying a hot item onto the film. In some embodiments,
the film is
heated using an infrared light. The film may be heated to a temperature in a
range of about 50
C to about 150 C, about 50 C to about 120 C, about 60 C to about 130 C,
about 70 C to
about 120 C, or about 60 C to about 90 C. Thermoforming can be performed by
any one or
more of the following processes, for example: the manual draping of a
thermally softened film
over a mold, or the pressure induced shaping of a softened film to a mold
(e.g., vacuum
forming), or the automatic high-speed indexing of a freshly extruded sheet
having an accurately
known temperature into a forming and trimming station, or the automatic
placement, plug and/or
pneumatic stretching and pressuring forming of a film. The extent of the film
stretch is defined
by the areal draw ratio which is the pocket (or cavity) surface area divided
by the film surface
area before thermoforming. The areal draw ratio (also called areal depth of
draw) can be
calculated according to the method described in Technology of Thermoforming,
James L.
Throne, Hanser publisher, (1996) Chapter 7.4, pg 488-494 (ISBN 3-446-17812-0).
Herein for
thermoformed films, the areal draw ratio can be in a range of 1.05 to 2.7; or
in a range of 1.2 to
2.3; or in a range of 1.3 to 2Ø
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0069] In the alternative to or in addition to heating, the film can be wetted
by any suitable
means, for example directly by spraying a wetting agent (including water, a
solution of the film
composition, a plasticizer for the film composition, or any combination of the
foregoing) onto
the film, prior to feeding it onto the surface or once on the surface, or
indirectly by wetting the
surface or by applying a wet item onto the film.
[0070] Once a film has been heated and/or wetted, it may be drawn into an
appropriate mold,
preferably using a vacuum. The filling of the molded film can be accomplished
by utilizing any
suitable means. In some embodiments, the most preferred method will depend on
the product
form and required speed of filling. In some embodiments, the molded film is
filled by in-line
filling techniques. The filled, open packets are then closed forming the
pouches, using a second
film, by any suitable method. This may be accomplished while in horizontal
position and in
continuous, constant motion. The closing may be accomplished by continuously
feeding a
second film, preferably water-soluble film, over and onto the open packets and
then preferably
sealing the first and second film together, typically in the area between the
molds and thus
between the packets. Such package forming and sealing methods are already
known in the art.
[0071] Any suitable method of sealing the packet and/or the individual
compartments thereof
may be utilized. Non-limiting examples of such means include heat sealing,
solvent welding,
solvent or wet sealing, and combinations thereof Typically, only the area
which is to form the
seal is treated with heat or solvent. The heat or solvent can be applied by
any method, typically
on the closing material, and typically only on the areas which are to form the
seal. If solvent or
wet sealing or welding is used, it may be preferred that heat is also applied.
Preferred wet or
solvent sealing/welding methods include selectively applying solvent onto the
area between the
molds, or on the closing material, by for example, spraying or printing this
onto these areas, and
then applying pressure onto these areas, to form the seal. Sealing rolls and
belts as described
above (optionally also providing heat) can be used, for example.
[0072] The formed pouches may then be cut by a cutting device. Cutting can be
accomplished
using any known method. It may be preferred that the cutting is also done in
continuous manner,
and preferably with constant speed and preferably while in horizontal
position. The cutting
device can, for example, be a sharp item, or a hot item, or a laser, whereby
in the latter cases, the
hot item or laser 'burns' through the film/ sealing area.
16
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0073] The different compartments of a multi-compartment pouches may be made
together in
a side-by-side style wherein the resulting, cojoined pouches may or may not be
separated by
cutting. Alternatively, the compartments can be made separately.
[0074] In embodiments, pouches may be made according to a process comprising
the steps of:
a) forming a first compartment (e.g., as described above);
b) forming a recess within some or all of the closed compartment formed in
step (a),
to generate a second molded compartment superposed above the first
compartment;
c) filling and closing the second compartments by means of a third film;
d) sealing the first, second and third films; and
e) cutting the films to produce a multi-compartment pouch.
[0075] The recess formed in step (b) may be achieved by applying a vacuum to
the
compartment prepared in step (a).
[0076] In some embodiments, second, and/or third compartment(s) can be made in
a separate
step and then combined with the first compartment as described in European
Patent Application
Number 08101442.5 or WO 2009/152031 (filed June 13, 2008 and assigned to the
Procter &
Gamble Company).
[0077] In some embodiments, pouches may be made according to a process
comprising the
steps of:
a) forming a first compartment, optionally using heat and/or vacuum, using
a first
film on a first forming machine;
b) filling the first compartment with a first composition;
c) on a second forming machine, deforming a second film, optionally using
heat and
vacuum, to make a second and optionally third molded compartment;
d) filling the second and optionally third compartments;
e) sealing the second and optionally third compartment using a third film;
0 placing the sealed second and optionally third compartments onto
the first
compartment;
g) sealing the first, second and optionally third compartments; and
h) cutting the films to produce a multi-compartment pouch.
[0078] The first and second forming machines may be selected based on their
suitability to
perform the above process. In some embodiments, the first forming machine is a
horizontal
17
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
forming machine, and the second forming machine is a rotary drum forming
machine, for
example located above the first forming machine.
[0079] It should be understood that by the use of appropriate feed stations,
it may be possible
to manufacture multi-compartment pouches incorporating a number of different
or distinctive
compositions and/or different or distinctive liquid, gel or paste
compositions.
[0080] The present pouches may contain various compositions. A multi-
compartment pouch
may contain the same or different compositions in each separate compartment.
[0081] As described above, the film and pouch of the disclosure are
particularly advantageous
for packaging (e.g., in direct contact with) alkaline materials.
[0082] This feature of the disclosure may be utilized to keep compositions
containing
incompatible ingredients (e.g., bleach and enzymes) physically separated or
partitioned from
each other. It is believed that such partitioning may expand the useful life
and/or decrease
physical instability of such ingredients. Additionally or alternatively, such
partitioning may
provide aesthetic benefits as described in European Patent Application Number
09161692.0
(filed June 2, 2009 and assigned to the Procter & Gamble Company).
[0083] Pouches made of films according to the disclosure advantageously delay
the release of
alkaline agents, such as sodium carbonate or percarbonate bleaching agents,
for at least 3
minutes, as determined by Bleach Compatibility Method A, or at least 9 minutes
as determined
by Bleach Compatibility Method B, after submersion in water heated to a
temperature of 40 C,
when in contact with a 1:1 mixture of sodium carbonate and percarbonate,
followed by full
dissolution of the film.
[0084] Pouches may comprise one or more alkaline agents, including an
inorganic bleach.
Without intending to be bound by theory, it is believed that the inorganic
bleaching agents,
including sodium carbonate and/or percarbonate in the presence of water or
high humidity will
deteriorate PVOH film, thereby increasing the solubility of PVOH film. In
films according to
the disclosure, however, it is believed that the film is more resistant to the
deteriorating effects of
sodium carbonate and/or percarbonate than a homopolymer of PVOH due to the
presence of the
lactone rings present in the resin from the about 5 mol% of methyl acrylate.
As other alkaline
agents, such as other inorganic bleaches, would deteriorate PVOH film in the
same way as
sodium carbonate and/or percarbonate, the film according to the disclosure
will be effective in
18
CA 02904373 2016-05-27
delaying the release of such alkaline agents while still fully dissolving for
the same reasons the
film is effective in delaying the release of sodium carbonate and/or
percarbonate.
[0085] Suitable inorganic bleaches for use with the delayed release films
include salts of
carbonate, borate, phosphate, sulfate and silicate, as well as perhydrate
salts such as perborate,
percarbonate, perphosphate, persulfate and persilicate salts. The inorganic
bleaches are normally
the alkali metal salts. The inorganic bleaches may be included as the
crystalline solid without
additional protection, e.g. without physical protection such as a coating on
the solid particles or
around an agglomerated mass of solid. Alternatively, the inorganic bleach can
be coated or
otherwise encapsulated as described herein.
[0086] In some embodiments of the disclosure, the inorganic bleach is in a
coated form. One
of the functions of the coating material is to prevent chemical interaction of
the bleach with the
water-soluble film that makes up the pouch that encloses the bleach, thereby
enhancing the
delayed release of the bleach by extending the amount of time the water-
soluble film will remain
intact after submersion in 40 C water, relative to a water-soluble film pouch
enclosing a bleach
agent without a coating.
[0087] It has been found, as demonstrated in the examples, that coating the
water-soluble film
with a laminate material or an additional PVOH inner layer, rather than
coating the bleach agent,
does not prevent the interaction of the caustic active with the exterior film
and, therefore, does
not provide an enhanced delayed release, relative to a pouch or packet of the
water-soluble film
of the invention at a thickness eaual to the thickness of the pouch or packet
plus laminate.
[0088] It has further been found, as demonstrated in the examples, that a
bleach coating
consisting of polyethylene oxide, such as DuPont's N-80 PolyOxTM, was not
fully effective at
preventing chemical interaction of the caustic active with the water-soluble
film. Further,
carboxymethylcellulose coatings were found to be not fully soluble in water at
40 C and
therefore are not an ideal coating material for the intended purpose.
[0089] In embodiments wherein the inorganic bleach is coated with a suitable
coating of the
disclosure herein and enclosed in a water-soluble pouch and/or packet
comprising a water-
soluble film of the disclosure herein, the packets achieve a delayed release
of the inorganic
bleach of at least about 8 minutes, as determined by Bleach Compatibility
Method A, or at least
about 15 minutes, as determined by Bleach Compatibility Method B. Bleach
coating materials
19
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
can include polyethylene glycol (PEG) coatings. Suitable polyethylene glycols
for coating
materials according to the disclosure can be any polyethylene glycol having a
molecular weight
(in Daltons) in a range of about 1000 to about 20, 000, or about 1000 to about
18000, or about
1000 to about 15000, or about 1000 to about 11,000, or about 2000 to about
10000, or about
3000 to about 9000, or about 4000 to about 8000, or about 5000 to about 7000,
or about 6000.
PEG coatings according to the disclosure can have a thickness in a range of
about 20 mil to about
150 mil (about 0.5 mm to about 3.8 mm), about 20 mil to about 100 mil (about
0.5 mm to about
2.5 mm), about 20 mil to about 80 mil (about 0.5 mm to about 2.0 mm), or about
40 mil to about
60 mil (about 1.0 mm to about 1.5 mm).
[0090] PEG can be coated to compressed bleach tablets prior to the tablet
being enclosed in
the water-soluble pouch or packet. The PEG coating can be applied by
sequentially dipping
alternating sides of the compressed bleach tablet into molten PEG at a
temperature in a range of
about 65 C to about 67 C, for example. The tablets are then cooled
immediately by dipping the
coated tablet into liquid nitrogen for a few seconds. The process of dipping
the tablet into
molten PEG followed by dipping the tablet into liquid nitrogen is repeated
until the desired
uniform coating thickness is achieved.
[0091] Alternatively, a first water-soluble packet or pouch comprising an
inorganic bleach can
be coated with a hard crystalline sugar coating, and the entire coated first
pouch can be placed
inside a second water-soluble packet or pouch comprising the delayed release
water-soluble film
of the disclosure. The hard crystalline sugar coating preferably is not
applied directly to a bleach
tablet or composition due to the increased reactivity of oxidizing agents
within the bleach
materials at the elevated temperatures used with molten sugar. Suitable hard
crystalline sugar
coatings of the disclosure can include a mixture of granulated sugar, corn
syrup, and water. Hard
crystalline sugar coatings can include a weight ratio of granulated sugar to
corn syrup in a range
of about 5:1 to about 1:5, about 1:4 to about 4:1, about 1:3 to about 3:1,
about 1:2 to about 2:1,
about 1:1, about 1:0.5, and/or about 1:0.1. In some embodiments, the coating
mixture may be
made free of corn syrup. The hard crystalline sugar coating can be applied by
mixing a solution
of granulated sugar, corn syrup, and water and then heating the solution to
150 C, followed by
dipping of the water-soluble pouch or packet enclosing the bleach into the
molten sugar solution,
for example.
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0092] As described above, pouches can be multi-compartment. The pouches of
the
disclosure can be used in combination with secondary pouches or compartments
that comprise
useful compositions including, but not limited to, light duty and heavy duty
liquid detergent
compositions, detergent gels commonly used for laundry, and other laundry
additives.
Secondary pouches or compartments can be made from any film comprising a
polymer resin that
is readily soluble in water at 40 C and, therefore, able to release the pouch
or compartment
component prior to the pouch or compartment comprising the delayed release
film releasing the
component enclosed therein. Suitable resins for water-soluble films of the
secondary pouches or
compartments include, but are not limited to, modified polyvinyl alcohols,
polyacrylates, water-
soluble acrylate copolymers, polyaminopropyl sulfonic acid and salts thereof
polyitaconic acid
and salts thereof, polyacryamides, polyvinyl pyrrolidone, pullulan,
cellulosics, including but not
limited to carboxymethyl cellulose and hydroxypropyl methyl cellulose, water-
soluble natural
polymers including, but not limited to, guar gum, xanthan gum, carrageenan,
and starch, water-
soluble polymer derivatives including, but not limited to, modified starches,
including
ethoxylated starch and hydroxypropylated starch, poly(sodium acrylamido-2-
methylpropane
sulfonate), polymonomethylmaleate and salts thereof copolymers thereof and
combinations of
any of the foregoing with each other and/or with PVOH. Of course, the water-
soluble films that
make up secondary pouches or components can include other optional additive
ingredients
including, but not limited to, plasticizers, surfactants, emulsifiers,
fillers, extenders, antiblocking
agents, detackifying agents, antifoams, film formers and other functional
ingredients, for
example in amounts suitable for their intended purpose, as described herein in
connection with
the delayed release film.
[0093] Compositions for use in the present pouches may take the form of a
liquid, solid or a
powder. Liquid compositions may comprise a solid. Solids may include powder or
agglomerates, such as micro-capsules, beads, noodles or one or more pearlized
balls or mixtures
thereof Such a solid element may provide a technical benefit, through the wash
or as a pre-treat,
delayed or sequential release component; additionally or alternatively, it may
provide an
aesthetic effect.
[0094] In pouches comprising laundry, laundry additive and/or fabric enhancer
compositions,
the compositions may comprise one or more of the following non-limiting list
of ingredients:
fabric care benefit agent; detersive enzyme; deposition aid; rheology
modifier; builder; organic
21
CA 02904373 2015-11-19
bleach; bleach precursor; bleach booster; bleach catalyst; perfume and/or
perfume microcapsules
(see for example US 5,137,646); perfume loaded zeolite; starch encapsulated
accord;
polyglycerol esters; whitening agent; pearlescent agent; enzyme stabilizing
systems; scavenging
agents including fixing agents for anionic dyes, complexing agents for anionic
surfactants, and
mixtures thereof; optical brighteners or fluorescers; polymer including but
not limited to soil
release polymer and/or soil suspension polymer; dispersants; antifoam agents;
non-aqueous
solvent; fatty acid; suds suppressors, e.g., silicone suds suppressors (see:
U.S. Publication No.
2003/0060390 Al, If 65-77); cationic starches (see: US 2004/0204337 Al and US
2007/0219111
Al); scum dispersants (see: US 2003/0126282 A1, 1189 ¨ 90); dyes; colorants;
opacifier;
antioxidant; hydrotropes such as toluenesulfonates, cumenesulfonates and
naphthalenesulfonates;
color speckles; colored beads, spheres or extrudates; clay softening agents.
Any one or more of
these ingredients is further described in described in European Patent
Application Number
09161692.0 (filed June 2, 2009), U.S. Publication Number 2003/0139312 Al
(filed May 11,
2000) and U.S. Publication Number 2011/0023240 Al (filed July 7, 2010), each
of which are
assigned to the Procter & Gamble Company. Additionally or alternatively, the
compositions
may comprise surfactants and/or solvent systems, each of which is described
below.
[0095] The detergent compositions can comprise from about 1% to 80% by weight
of a
surfactant, for example. Detersive surfactants utilized can be of the anionic,
nonionic,
zwitterionic, ampholytic or cationic type or can comprise compatible mixtures
of these types. In
one type of embodiment, surfactants are selected from the group consisting of
anionic, nonionic,
and cationic surfactants, and mixtures thereof The compositions can be
substantially free of
betaine surfactants. Examples of detergent surfactants useful herein are
described in U.S.
Patents 3,664,961; 3,919,678; 4,222,905; and 4,239,659. In another type of
embodiment
surfactants are selected from the group consisting of anionic surfactants,
nonionic surfactants,
and combinations thereof.
[0096] Useful anionic surfactants can themselves be of several different
types. For example,
water-soluble salts of the higher fatty acids, i.e., "soaps", are useful
anionic surfactants in the
compositions herein. This includes alkali metal soaps such as the sodium,
potassium,
ammonium, and alkyl ammonium salts of higher fatty acids containing from about
8 to about 24
carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can
be made by
direct saponification of fats and oils or by the neutralization of free fatty
acids. Particularly
22
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
useful are the sodium and potassium salts of the mixtures of fatty acids
derived from coconut oil
and tallow, i.e., sodium or potassium tallow and coconut soap.
[0097] Additional non-soap anionic surfactants which are suitable for use
herein include the
water-soluble salts, preferably the alkali metal, and ammonium salts, of
organic sulfuric reaction
products having in their molecular structure an alkyl group containing from
about 10 to about 20
carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in
the term "alkyl" is the
alkyl portion of acyl groups.) Examples of this group of synthetic surfactants
include: a) the
sodium, potassium and ammonium alkyl sulfates, especially those obtained by
sulfating the
higher alcohols (C8-Ci8) such as those produced by reducing the glycerides of
tallow or coconut
oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates,
particularly those in
which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon
atoms, and
wherein the polyethoxylate chain contains from 1 to 15, preferably 1 to 6
ethoxylate moieties;
and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl
group contains from
about 9 to about 15 carbon atoms, in straight chain or branched chain
configuration, e.g., those of
the type described in U.S. Patents 2,220,099 and 2,477,383. Especially
valuable are linear
straight chain alkylbenzene sulfonates in which the average number of carbon
atoms in the alkyl
group is from about 11 to 13, abbreviated as C11-C13 LAS.
[0098] Nonionic surfactants can be selected from one or more of those of the
formula
Ri(0C2H4)110H, wherein R1 is a C10-C16 alkyl group or a C8-C12 alkyl phenyl
group, and n is
from 3 to about 80. Condensation products of C 12-C 15 alcohols with from
about 5 to about 20
moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed
with about 6.5
moles of ethylene oxide per mole of alcohol, are specifically contemplated.
[0099] The solvent system in the present compositions can be a solvent system
containing
water alone or mixtures of organic solvents with water. Organic solvents can
include 1,2-
propanediol, ethanol, glycerol, dipropylene glycol, methyl propane diol and
mixtures thereof
Other lower alcohols, C1-C4 alkanolamines such as monoethanolamine and
triethanolamine, can
also be used. Solvent systems can be absent, for example from anhydrous solid
embodiments of
the disclosure, but more typically are present at levels in the range of from
about 0.1% to about
98%, preferably at least about 1% to about 50%, more usually from about 5% to
about 25%.
23
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[00100] Organic bleaches can include organic peroxyacids including diacyl and
tetraacylperoxides, especially diperoxydodecanedioc acid,
diperoxytetradecanedioc acid, and
diperoxyhexadecanedioc acid. The organic peroxyacid can be dibenzoyl peroxide.
The diacyl
peroxide, especially dibenzoyl peroxide, can be present in the form of
particles having a weight
average diameter of from about 0.1 to about 100 microns, preferably from about
0.5 to about 30
microns, more preferably from about 1 to about 10 microns, for example. In
embodiments, at
least about 25% to 100%, or at least about 50%, or at least about 75%, or at
least about 90%, of
the particles are smaller than 10 microns, optionally smaller than 6 microns.
[0100] Other organic bleaches include the peroxy acids, particular examples
being the
alkylperoxy acids and the arylperoxy acids. Representatives include: (a)
peroxybenzoic acid and
its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also
peroxy-a-naphthoic
acid and magnesium monoperphthalate; (b) the aliphatic or substituted
aliphatic peroxy acids,
such as peroxylauric acid, peroxystearic acid, 8-phthalimidoperoxycaproic
acid[phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic
acid, N-
nonenylamidoperadipic acid and N-nonenylamidopersuccinates; and (c) aliphatic
and araliphatic
peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-
diperoxyazelaic acid,
diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-
decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyldi(6-aminopercaproic
acid).
[0101] Bleach activators can include organic peracid precursors that enhance
the bleaching
action in the course of cleaning at temperatures of 60 C and below. Bleach
activators suitable
for use herein include compounds which, under perhydrolysis conditions, give
aliphatic
peroxoycarboxylic acids having preferably from 1 to 10 carbon atoms, in
particular from 2 to 4
carbon atoms, and/or optionally substituted perbenzoic acid. Suitable
substances bear 0-acyl
and/or N-acyl groups of the number of carbon atoms specified and/or optionally
substituted
benzoyl groups. Preference is given to polyacylated alkylenediamines, in
particular
tetraacetylethylenediamine (TAED), acylated triazine derivatives, in
particular 1,5-diacety1-2,4-
dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular
tetraacetylglycoluril
(TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated
phenolsulfonates,
in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS),
carboxylic
anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in
particular triacetin,
24
CA 02904373 2016-05-27
ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and also
triethylacetyl citrate
(TEAC).
[0102] Bleach catalysts for use in the detergent composition herein include
the manganese
triazacyclononane and related complexes (US-4,246,612, US-A-5,227,084); Co,
Cu, Mn and Fe
bispyridylamine and related complexes (US-5,114,611); and pentamine acetate
cobalt(III) and
related complexes (US-4,810,410). Another description of bleach catalysts
suitable for use
herein can be found in U.S. Pat. No. 6,599,871, which may be referred to for
details.
[0103] Builders suitable for use in the detergent composition described herein
include water-
soluble builders, including citrates, carbonates, silicate and polyphosphates,
e.g. sodium
tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium
tripolyphosphate and
mixed sodium and potassium tripolyphosphate salts.
[0104] Enzymes suitable for use in the detergent composition described herein
include
bacterial and fungal cellulases including CAREZYME"and CELLUZYME" (Novo
NordiskA/S);
peroxidases; lipases including AMANO-P' (Amano Pharmaceutical Co.), MI LIPASE
and
LIPOMAX" (Gist-Brocades) and LIPOLASE'and LIPOLASE ULTRA'"(Novo); cutinases;
proteases including ESPERASETM, ALCALASETM, DURAZYM' and SAVINASE"(Novo) and
MAXATASET", MAXACALTM, PROPERASET"and MAXAPEM"(Gist-Brocades); a and p
amylases including PURAFECT OX AM"(Genencor) and TERMAMYL', BANTM,
FUNGAMYLT", DURAMYL', and NATALASE"(Novo); pectinases; and mixtures thereof.
Enzymes can be added herein as prills, granulates, or cogranulates at levels
typically in the range
from about 0.0001% to about 2% pure enzyme by weight of the cleaning
composition.
[0105] Suds suppressers suitable for use in the detergent composition
described herein include
nonionic surfactants having a low cloud point. "Cloud point" as used herein,
is a well known
property of nonionic surfactants which is the result of the surfactant
becoming less soluble with
increasing temperature, the temperature at which the appearance of a second
phase is observable is
referred to as the "cloud point" (See Van Nostrand's Scientific Encyclopedia,
4th Ed., p. 366,
(1968)). As used herein, a "low cloud point" nonionic surfactant is defined as
a nonionic surfactant
system ingredient having a cloud point of less than 30 C, preferably less
than about 20 C, and
even more preferably less than about 10 C, and most preferably less than
about 7.5 C. Low cloud
point nonionic surfactants can include nonionic alkoxylated surfactants,
CA 02904373 2016-05-27
especially ethoxylates derived from primary alcohol, and
polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/E0/P0) reverse block
polymers.
Also, such low cloud point nonionic surfactants can include, for example,
ethoxylated-
propoxylated alcohol (e.g., BASF Poly-Tergent SLF18) and epoxy-capped
poly(oxyalkylated)
alcohols (e.g., BASF Poly-Tergent SLF18B series of nonionics, as described,
for example, in
US-A-5,576,281).
[0106] Other suitable components for use in the detergent composition
described herein include
cleaning polymers having anti-redeposition, soil release or other detergency
properties. Anti-
redeposition polymers for use herein include acrylic acid containing polymers
such as
SOKALANTM PA30, PA20, PAIS, PA10 and SOKALANTM CP 10 (BASF GmbH), ACUSOLTM
45N, 480N, 460N (Rohm and Haas), acrylic acid/maleic acid copolymers such as
SOKALANTM
CP5 and acrylic/methacrylic copolymers. Soil release polymers for use herein
include alkyl and
hydroxyalkyl celluloses (US-A-4,000,093), polyoxyethylenes, polyoxypropylenes
and copolymers
thereof, and nonionic and anionic polymers based on terephthalate esters of
ethylene glycol,
propylene glycol and mixtures thereof.
[0107] Heavy metal sequestrants and crystal growth inhibitors are also
suitable for use in the
detergent, for example diethylenetriamine penta(methylene phosphonate),
ethylenediamine
tetra(methylene phosphonate) hexamethylenediamine tetra(methylene
phosphonate), ethylene
diphosphonate, hydroxy-ethylene-1,1-diphosphonate, nitrilotriacetate,
ethylenediaminotetracetate, ethylenediamine-N,N'-disuccinate in their salt and
free acid forms.
[0108] Suitable for use in the detergent composition described herein is also
a corrosion
inhibitor, for example organic silver coating agents (especially paraffins
such as WINOG 70 sold
by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor
compounds (for
example benzotriazole and benzimadazole - see GB-A-1137741) and Mn(II)
compounds,
particularly Mn(II) salts of organic ligands.
[0109] Other suitable components for use in the detergent composition herein
include enzyme
stabilizers, for example calcium ion, boric acid and propylene glycol.
[0110] Suitable rinse additives are known in the art. Commercial rinse aids
for dishwashing
typically are mixtures of low-foaming fatty alcohol polyethylene/polypropylene
glycol ethers,
solubilizers (for example cumene sulfonate), organic acids (for example citric
acid) and solvents
26
CA 02904373 2016-05-27
(for example ethanol). The function of such rinse aids is to influence the
interfacial tension of
the water in such a way that it is able to drain from the rinsed surfaces in
the form of a thin
coherent film, so that no water droplets, streaks, or films are left after the
subsequent drying
process. A review of the composition of rinse aids and methods for testing
their performance is
presented by W. Schirmer et al. in Tens. Surf. Det. 28, 313 (1991). European
Patent 0 197 434
B1 to Henkel describes rinse aids which contain mixed ethers as surfactants.
Rinse additives
such as fabric softeners and the like are also contemplated and suitable for
encapsulation in a
film according to the disclosure herein.
[0111] In one embodiment, a pouch or packet can comprise two or more
components wherein
a first pouch or compartment comprising the water-soluble film of the
disclosure comprises an
alkaline agent and a second pouch or compartment can comprise a liquid laundry
detergent.
Non-limiting examples of liquid laundry detergents can include the ingredients
presented in
Table 1 below.
Table 1
A
Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Glycerol 3 5 3 0.6 5 5.3
1,2 Propanediol 16 14 16 12 10
Citric acid 1 1 0.5 0.5
isopropanol 7.7
NaOH 0.5 3.5 1
MarliparC12-14E07 22 22 14 20.1
C13.15E09 1 15 1
C9-11E09 72
Linear alkyl benzene
16 25 16 23 24.6
sulfonic acidl
C12.18 Fatty acid 16 5 16 6 16.4
C12.14 alkyl
9
ethoxy 3 sulfate
Enzymes 2.5 1.5 2.5 2.0 1.5 2.0
Polyethyleneimine
ethoxylate 2 2 3.0
PEI 600 E20
Diethylenetriamine
0.9 1
Pentaacetic Acid
Dequest 2010 1.5 1.5 1 1.1
Optical brightening agent 1 1.2 1 0.5 0.2
Mg Cl2 0.2
Potassium sulfite 0.35 0.2
Structurant 0.21 0.15
Silicone softening agent 2.5
27
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
(PDMS)
Water 8 10 8 6 9
Miscellaneous (dyes,
To 100 To 100 To 100 To 100 To 100
aesthetics, perfume etc)
Monoethanol amine To pH To pH 7.5 To pH 7.4 To pH 7.6
To pH 7.6 To pH 7.6
7.6
Suitable LAS also comprise an alkyl group comprising from about 9 to about 15
carbon atoms,
in straight chain configuration.
[0112] Additional embodiments are described in the following numbered
paragraphs.
[0113] 1. A water-soluble packet comprising a first sealed compartment
containing a first
composition, the first sealed compartment comprising a wall of water-soluble
film, the water-
soluble film comprising a polyvinyl alcohol (PVOH) and acrylate resin and the
first composition
comprising an alkaline agent.
[0114] 2. The water-soluble packet of paragraph 1, wherein the polyvinyl
alcohol and
acrylate resin is a copolymer of polyvinyl alcohol and methyl acrylate.
[0115] 3. The water-soluble packet of paragraph 2, wherein the methyl acrylate
comprises
from about 2 mol% to about 10 mol% of the copolymer.
[0116] 4. The water-soluble packet of paragraph 2, wherein the methyl acrylate
comprises
about 5 mol% of the copolymer.
[0117] 5. The water-soluble packet of any one of paragraphs 2 to 4, wherein
the copolymer
has a suitable viscosity and the water-soluble film has a suitable thickness
to provide a desired
delay in solubility of the film in water having a selected temperature prior
to full dissolution of
the film of the film in the water of the selected temperature.
[0118] 6. The water-soluble packet of any one of the preceding paragraphs,
wherein the
water-soluble film remains intact for at least 3 minutes when submerged in
water heated to a
temperature of about 40 C, as determined by Bleach Compatibility Method A, and
thereafter
fully dissolves within 55 minutes.
[0119] 7. The water-soluble packet of any of the preceding paragraphs, wherein
the
thickness of the water soluble film is in a range of about 3 mil to about 6
mil (about 0.076 mm to
about 0.15 mm).
28
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0120] 8. The water-soluble packet of any of the preceding paragraphs, wherein
the PVOH
copolymer viscosity is in a range of about 8 cPs to about 40 cPs.
[0121] 9. The water-soluble packet of any of the preceding paragraphs, wherein
the PVOH
and methyl acrylate resin comprises about 35 to about 90 wt.% of the film,
based on the total
weight of the film.
[0122] 10. The water-soluble packet of any of the preceding paragraphs,
further comprising
about 10 to about 50 phr of plasticizer, per 100 parts PVOH copolymer resin.
[0123] 11. The water-soluble packet of paragraph 10, wherein the plasticizer
comprises a
material selected from the group consisting of sorbitol, glycerol, diglycerol,
propylene glycol,
ethylene glycol, diethyleneglycol, triethylene glycol, tetraethyleneglycol,
polyethylene glycols
up to MW 400, 2 methyl 1, 3 propane diol, lactic acid, monoacetin, triacetin,
triethyl citrate, 1,3-
butanediol, trimethylolpropane (TMP), polyether triol, and combinations
thereof
[0124] 12. The water-soluble packet of any of the preceding paragraphs,
further comprising
less than about 2 phr of surfactant, per 100 parts PVOH copolymer resin.
[0125] 13. The water-soluble packet of paragraph 12, wherein the surfactant
comprises a
material selected from the group consisting of dialkyl sulfosuccinates,
lactylated fatty acid esters
of glycerol and propylene glycol, lactylic esters of fatty acids, sodium alkyl
sulfates, polysorbate
20, polysorbate 60, polysorbate 65, polysorbate 80, alkyl polyethylene glycol
ethers, lecithin,
acetylated fatty acid esters of glycerol and propylene glycol, sodium lauryl
sulfate, acetylated
esters of fatty acids, myristyl dimethylamine oxide, trimethyl tallow alkyl
ammonium chloride,
quaternary ammonium compounds, salts thereof and combinations of any of the
forgoing.
[0126] 14. The water-soluble packet of any of the preceding paragraphs,
further comprising a
second sealed compartment, the second sealed compartment containing a second
composition,
wherein the first sealed compartment and the second sealed compartment are
optionally
conjoined about a partitioning wall.
[0127] 15. The water-soluble packet of any of the preceding paragraphs,
wherein the first
composition and the second composition are combinations of compositions
selected from the
group consisting of: liquid, liquid; liquid, powder; and powder, powder.
29
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0128] 16. The water-soluble packet of any of the preceding paragraphs,
wherein the alkaline
agent comprises an inorganic bleach.
[0129] 17. The water-soluble packet of paragraph 16, wherein the inorganic
bleach
comprises sodium carbonate, percarbonate, or a combination thereof
[0130] 18. The water-soluble packet of paragraph any one of the preceding
paragraphs,
wherein the alkaline agent is coated with a coating material comprising
polyethylene glycol.
[0131] 19. The water-soluble packet of paragraph 18, wherein the coating has a
thickness in
a range of about 20 mil to about 150 mil (about 0.5 mm to about 3.8 mm).
[0132] 20. The water-soluble packet of paragraph 18 or paragraph 19, wherein
the first
sealed compartment remains intact for at least 8 minutes when submerged in
water heated to a
temperature of about 40 C, as measured by Bleach Compatibility Method A.
[0133] 21. The water-soluble packet of any one of paragraphs 1-17, wherein the
alkaline
agent is enclosed in a second packet, and the second packet is coated with a
hard crystalline
sugar coating.
[0134] 22. The water-soluble packet of paragraph 21, wherein the hard
crystalline sugar
coating comprises a mixture of granulated sugar and corn syrup/
[0135] 23. The water-soluble packet of paragraph 21 or paragraph 22, wherein
the hard
crystalline sugar coating comprises granulated sugar and corn syrup in a
weight ratio in a range
of about 5:1 to about 1:5.
[0136] 24. A method of making a packet for delayed solubility and delayed
release of an
alkaline component therein in hot water of a selected temperature, comprising:
preparing a packet comprising a sealed compartment containing an alkaline
composition,
the sealed compartment made from a water-soluble film comprising a copolymer
of polyvinyl
alcohol (PVOH) and methyl acrylate;
selecting the mol % methyl acrylate in the copolymer, the viscosity of the
copolymer, and
the thickness of the film to provide a desired delay in solubility of the film
in hot water of the
selected temperature prior to full dissolution of the film of the film in the
hot water of the
selected temperature.
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0137] 25. A water-soluble packet, comprising: a first sealed compartment
containing a first
composition comprising an alkaline agent comprising a mixture of sodium
carbonate and
percarbonate, the first sealed compartment comprising a water-soluble film
comprising a
polyvinyl alcohol (PVOH) and methyl acrylate resin comprising about 5 mol%
methyl acrylate
and having a thickness of about 3 mil to about 6 mil (about 0.076 mm to about
0.15 mm), and the
packet further comprising a second sealed compartment containing a second
composition,
wherein the first sealed compartment and the second sealed compartment are
optionally
conjoined about a portioning wall, wherein the second composition comprises a
laundry additive
and wherein the first sealed compartment releases the first composition at
least 3 minutes after
being submerged in water-heated to about 40 C, as measured by Bleach
Compatibility Method
A, and the water-soluble film of the first sealed component fully dissolves
within 55 minutes.
Examples
DETERMINATION OF BLEACH COMPATIBILITY METHOD A (METHOD A)
[0138] A small, nominal 5 mil (127 m), water-soluble film pouch is filled
with either 5.8 g of
1:1 (wt%) sodium carbonate and sodium percarbonate mixed powder or a 10 g
compressed tablet
of the same material, and heat sealed. The compressed bleach tablets can
comprise stearic acid
as a binding agent and are made with compression techniques well known to
those skilled in the
art. . The bleach powder materials are available from Solvay Chemicals. The
pouch is secured
using a vinyl coated 0.5 inch metal mesh cage and submerged into a 600 ml
beaker containing
500 ml of 40 C deionized water, with stirring. The water is stabilized to pH
7 before
submerging the metal mesh cage containing the pouch. After the pouch is
submerged, the pH of
the water was monitored using a pH probe and recorded every minute until a pH
of 9.5 or higher
is reached, or until 20 minutes have elapsed. The integrity and dissolution
behavior of the pouch
is observed and recorded. Ideal behavior in 40 C water is marked by a sudden
increase in pH
through the release of the active materials from the pouch at about 9 to 12
minutes from the start
of the test (submerging of the pouch). This ideal behavior corresponds to an
active release delay
of about 15 to 20 minutes within a commercially-available automatic laundry
machine cycle
using nominally 40 C wash water.
DETERMINATION OF BLEACH COMPATIBILITY METHOD B (METHOD B)
[0139] The bleach compatibility of water-soluble packets prepared from water-
soluble film are
tested in a Siemens S16-79 washing machine using the program Koch/Bunt
(cotton/colored), or
31
CA 02904373 2016-05-27
an equivalent. The SIEMENS brand S16-79 automatic washing machine has a 65
liter drum
capacity and variable temperature selection. The test samples are prepared as
described above
for Bleach Compatibility Method A. The temperature of the wash water is either
20 C, 40 C,
or 60 C. The water hardness is 250 ppm CaCO3 (14 d, German degrees
hardness). The wash
load is 3 kg, consisting of 2 bed sheets (1.5 x 1.5 m ISO 2267), 4 pillow
cases (0.8 x 0.8 m ISO
2267), and 3 huckaback towels, cotton bleached. The dissolution time for
Method B corresponds
to the time at which a pH of 9.5 or higher is reached, as measured by a pH
probe. Ideal behavior
is marked by a sudden increase in pH through the release of the active
materials from the pouch
at about 15 to 20 minutes within a commercially-available automatic laundry
machine cycle
using nominally 40 C wash water.
DETERMINATION OF FILM SOLUBILITY CHARACTERISTICS (MSTM 205)
[0140] Film solubility can be measured by MONOSOL Test Method 205 (MSTM 205),
which
is disclosed with reference to Figures 1-3 herein.
[0141] MSTM 205
[0142] Apparatus and Materials:
600 mL Beaker 12
Magnetic Stirrer 14 (Labline Model No. 1250 or equivalent)
Magnetic Stirring Rod 16 (5 cm)
Thermometer (0 to 100 C., +1 C.)
Template, Stainless Steel (3.8 cm x3.2 cm)
Timer, (0-300 seconds, accurate to the nearest second)
Po1aroid'35 mm Slide Mount 20 (or equivalent)
MONOSOL"35 mm Slide Mount Holder 25 (or equivalent, see Figure 1)
Distilled Water
[0143] Test Specimen:
32
CA 02904373 2015-09-04
WO 2014/151718
PCT/US2014/026305
[0144] 1.
Cut three test specimens from film sample using stainless steel template
(i.e., 3.8
cmx3.2 cm specimen). If cut from a film web, specimens should be cut from
areas of web evenly
spaced along the transverse direction of the web.
[0145] 2. Lock each specimen in a separate 35 mm slide mount 20.
[0146] 3. Fill beaker 12 with 500 mL of distilled water. Measure water
temperature with
thermometer and, if necessary, heat or cool water to maintain temperature at
40 C (about 104
F).
[0147] 4. Mark height of column of water. Place magnetic stirrer 14 on base 27
of holder 25.
Place beaker 12 on magnetic stirrer 14, add magnetic stirring rod 16 to beaker
12, turn on stirrer
14, and adjust stir speed until a vortex develops which is approximately one-
fifth the height of
the water column. Mark depth of vortex.
[0148] 5. Secure the 35 mm slide mount 20 in the alligator clamp 26 of the
MONOSOL 35
mm slide mount holder 25 (Figure 1) such that the long end 21 of the slide
mount 20 is parallel
to the water surface, as illustrated in Figure 2. The depth adjuster 28 of the
holder 25 should be
set so that when dropped, the end of the clamp 26 will be 0.6 cm below the
surface of the water.
One of the short sides 23 of the slide mount 20 should be next to the side of
the beaker 12 with
the other positioned directly over the center of the stirring rod 16 such that
the film surface is
perpendicular to the flow of the water, as illustrated in Figure 3.
[0149] 6. In one motion, drop the secured slide and clamp into the water and
start the timer.
Disintegration occurs when the film breaks apart. When all visible film is
released from the slide
mount, raise the slide out of the water while continuing to monitor the
solution for undissolved
film fragments. Dissolution occurs when all film fragments are no longer
visible and the solution
becomes clear.
[0150] Data Recording:
[0151] The results should include the following:
[0152] complete sample identification;
[0153] individual and average disintegration and dissolution times; and
[0154] water temperature at which the samples were tested.
33
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0155] The time for complete dissolution (in seconds) is obtained.
EXAMPLE 1: BLEACH COMPATIBILITY
Component Description 1
PVOH 18 cPs, DH 98-99 100
Copolymer (5 mol%
methyl acrylate))
Sorbitol (70% Plasticizer 18.37
active), MP Diol,
Glycerin
Process Aids surfactant 2.03
Lubricant/release 0.12
agent
Starch 2.57
Clarity stabilizer 0.21
Dissolution Time at 1:20
40 C(minutes)
[0156] A water-soluble film was prepared with the ingredients identified in
the table above in
the amounts shown (phr). 5 mil (127 gm) thick water-soluble films were cast
according to
formula 1, and were tested for solubility characteristics according to MSTM
205 as described
above. Films were then formed into pouches and 5.8 g of a 1:1 (wt.%) mixture
of sodium
carbonate and percarbonate was enclosed within the pouches and the pouches
were heat sealed.
The bleach compatibility of the pouches were determined according to Bleach
Compatibility
Method A and Bleach Compatibility Method B. The film according to Example 1
demonstrated
a release of the bleach component in after having been submerged in water
heated to a
temperature of 40 C for 3 min, as determined by Method A, and after 9
minutes, as determined
by Method B.
[0157] Example 1 demonstrates a film according to the disclosure that is fully
soluble in water
heated to a temperature of 40 C. Example 1 further demonstrates that a pouch
made of a film of
the disclosure can provide a delayed release of alkaline contents of 3 minutes
as determined by
Method A, that corresponds to 9 minutes in a washing machine, as determined by
Method B.
34
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
COMPARATIVE EXAMPLE 2: DISSOLUTION BEHAVIOR OF FULLY HYDROLYZED PVOH
HOMOPOLYMERS
Component Description 1 2 3 4
PVOH 18 cPs, 98- 100
Copolymer (5 99% DH
mol% methyl
acrylate))
PVOH 6 cPs, 98% 100
DH
PVOH 10 cPs, 98% 100
DH
PVOH 30 cPs, 98% 100
DH
Sorbitol (70% Plasticizer 18.37 18.37 18.37
18.37
active), MP
Diol, Glycerin
Process Aids surfactant 2.03 2.03 2.03 2.03
Lubricant/rel 0.12 0.12 0.12 0.12
ease agent
Starch 2.57 2.57 2.57 2.57
Clarity 0.21 0.21 0.21 0.21
stabilizer
Time to pH Method A 8.25 2.98 not 16.01
9.5 applicable,
will not be
soluble
Solubility Desired Dissolves Will be Does not
behavior at 40 delayed faster than insoluble
fully dissolve
C solubility acceptable after
releasing
packet
content
[0158] Water-soluble films were prepared with the ingredients identified in
the table above in
the amounts shown (phr). 5 mil (127 gm) thick water-soluble films were cast
according to
formulae 1, 2 and 4, formed into pouches and 5.8 g of a 1:1 (wt.%) mixture of
sodium carbonate
and percarbonate was enclosed within the pouches and the pouches were heat
sealed. The
pouches were tested for pH delay according to Method A as described above.
[0159] Comparative Example 2 demonstrates that PVOH homopolymers are
unsuitable for
applications that require both good film processability and complete
dissolution at 40 C. Low
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
viscosity (6 cPs) films, cast from film formula 2, demonstrated faster than
desired solubility at 40
C but with considerable variability indicating that the PVOH resin is in a
transition region.
Films have varying molecular weight averages depending on the manufacturer
(and, therefore
varying viscosity) resulting in varying solubility properties. Thus, in the
observed transition
region (about 6 cPs) the PVOH resin may exhibit a solubility that is too fast
or too slow based on
minor manufacturer processing variations. As the viscosity of the water-
soluble resin increased,
for example films cast from film formula 4 (30 cPs), the resulting films
demonstrated insolubility
at 40 C. A film cast from film formula 3, having a viscosity of 10 cPs will
also be insoluble and
therefore will not exhibit a delayed release in water heated to a temperature
of 40 C.
36
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
COMPARATIVE EXAMPLE 3: DISSOLUTION BEHAVIOR OF ALTERNATE RESINS
Component Description 1 5 6 7 8 9 10
PVOH 18 cPs, 98- 100
Copolymer (5 99% DH
mol% methyl
acrylate))
PVOH 17 cPs, 92% 100
DH
PVOH 29 cPs, 96% 100
DH
PVOH/ 5 28 cPs, fully 100
mol% methyl hydrolyzed
methacrylate
copolymer
PVOH/ 5 17 cPs, fully 100
mol% methyl hydrolyzed
methacrylate
copolymer
PVOH 6 cPs, 98% 100
homopolymer DH
PVOH 30 cPs, 98% 100
homopolymer DH
Sorbitol (70% Plasticizer 18.37 18.37 18.37 18.37
18.37 18.37 18.37
active), MP
Diol, Glycerin
Process Aids surfactant 2.03 2.03 2.03 2.03 2.03
2.03 2.03
Lubricant/ 0.12 0.12 0.12 0.12 0.12 0.12
0.12
release agent
Starch 2.57 2.57 2.57 2.57 2.57 2.57 2.57
Clarity 0.21 0.21 0.21 0.21 0.21 0.21 0.21
stabilizer
Time to pH Method A
9.5 (packet
releases
content)
Solubility Method A Fully Inadequate
Inadequate Inadequate Inadequate Too Inadequate
behavior at 40 Soluble solubility solubility
solubility solubility soluble solubility
C - will not - did not -
did not - did not - did not
fully dissolve dissolve
fully dissolve
dissolve dissolve
Point A Time at Method A 3:30 N/A 16:18 N/A 13:12
3:06 with N/A
40 C in pouch did
disintegration pouch did
presence of not release
not release
carbonate
(minutes)
37
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
[0160] Water-soluble film was prepared with the ingredients identified in the
table above in
the amounts shown (phr). 5 mil (127 gm) thick water-soluble films were cast
according to
formulae 6-10. Films were then formed into pouches, 5.8 g of a 1:1 (wt. %)
mixture of sodium
carbonate and percarbonate was enclosed within each pouch, and the pouches
were heat sealed.
The pouches were then tested for bleach compatibility according to Method A.
[0161] Comparative Example 3 demonstrates the bleach compatibility of PVOH
homopolymers with a moderate degree of hydrolysis (5 and 6), fully hydrolyzed
PVOH
homopolymers having a viscosity less than 5 cPs (9), fully hydrolyzed PVOH
homopolymers
having a viscosity greater than 5 cPs (10), and modified PVOH resins
comprising methyl
acrylate in amounts less than 5 mol% (7 and 8). Comparative Example 3 shows
that PVOH
homopolymer with a moderate degree of hydrolysis (6) display inadequate
solubility and did not
fully dissolve in 55 minutes or less, as would be required for a washing
machine application.
Films cast from formula 5 containing a PVOH homopolymer with a moderate degree
of
hydrolysis (5) will also display inadequate solubility and will not fully
dissolve in 55 minutes or
less, as would be required for a washing machine application. Comparative
Example 3 further
shows that, as expected based on the solubility data from MSTM 205, fully
hydrolyzed PVOH
homopolymers having a viscosity less than 5 cPs (9), are too readily soluble
and disintegrate in
water heated to a temperature of 40 C, releasing the contents of the pouch.
Similarly, as
expected from the solubility testing using MSTM 205, fully hydrolyzed PVOH
homopolymers
having a viscosity greater than 5 cPs (10) display inadequate solubility and
do not even release
the pouch contents into the water heated to a temperature of 40 C. Finally,
Comparative
Example 3 further demonstrates that films comprising modified PVOH resins
comprising methyl
acrylate in amounts less than 5 mol% do not display adequate solubility and do
not fully dissolve
in 55 minutes or less (7 and 8). Further, the pouch made from film formula 7
also did not even
release the pouch contents into the water heated to a temperature of 40 C.
38
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
EXAMPLE 4: COATINGS LAMINATE MATERIAL OR AN ADDITIONAL PVOH INNER LAYER,
POLYETHYLENE OXIDE, CARBOXYMETHYLCELLULOSE COATINGS, PEG, SUGAR.
Coating 11: Laminate 12: 13:PV0H 14: Poly 15: 16:
Material ¨ 3 mil of Laminate coating ¨ Ox CMC Sugar
film ¨ 3 mil 3 mil of Coating coating
Coating
according to film film
film formula formula according
1 12 to film
formula 6
Point A 8 min 5 min Did not 8 min CMC
11:54
Time dissolve did not
dissolve
[0162] Water soluble films were prepared according to the formulations
described above for
film formulation 1. A 5 mil (127 gm) water-soluble film was cast according to
film formula 1
and was laminated with either 3 mil (76 gm) of a film according to film
formula 1 (11) or 3 mil
(76 gm) of formula 12 (12) and formed into a pouch. The laminate film
according to formula 12
(12) having a thickness of 3 mil (76 gm) was cast from a water-soluble mixture
comprising 100
phr of a PVOH resin comprising 4 mol% sodium aminopropyl sulfonate with a
viscosity of 12
cPs and a degree of hydrolysis of greater than 95%, 26.24 phr plasticizers,
0.53 phr surfactants,
0.03 phr defoamer, 1.33 phr filler, 2.67 phr starch, 0.67 phr
lubricant/release agent, and 0.27 phr
of a stabilizer. The pouches were filled with 5.8 g of a 1:1 (wt.%) mixture of
sodium carbonate
and percarbonate, heat sealed, and tested according to Method A. The control
pouch (11) had a
Point A Time of about 8 minutes. The pouch of formula 12 (12) had a Point A
Time of about 5
minutes. Thus, pouches (11) and (12) of Example 4 demonstrate that laminating
a pouch of the
invention with a more ionic film, such as a film of formula 12, does not
result in an improvement
of the delayed release of the pouch contents. Pouch (11) of Example 4 further
demonstrates that
an increase in the thickness of the water-soluble film results in an increase
in the dissolution time
and, therefore, the delayed release of the pouch contents. Pouch (11)
(nominally 8 mils thick)
had a Point A Time of about 8 minutes whereas a pouch of the same film having
a thickness of 5
mils (Example 2, formula 1) had a Point A Time of about 3.5 minutes.
[0163] A 5 mil (127 gm) water-soluble film of the disclosure, according to
film formula 1,
was coated with 3 mil (76 gm) of a PVOH resin of an intermediately hydrolyzed
PVOH
homopolymer having a viscosity of 29 cPs, according to film formula 6 in
Example 2 and
39
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
formed into a pouch (13). The pouch was filled with 5.8 g of a 1:1 (wt.%)
mixture of sodium
carbonate and percarbonate, heat sealed and tested according to Method A. The
water-soluble
film did not fully dissolve in 55 minutes or less, thereby demonstrating that
coating the water-
soluble film of the invention with a PVOH homopolymer resin is unsuitable for
delayed release
laundry applications.
[0164] A wetted lOg compressed tablet of a 1:1 (wt.%) mixture of sodium
carbonate and
percarbonate with stearic acid as a binding agent was powder coated with Dow's
N-80 Poly0x
material (nonionic, high molecular weight water-soluble poly (ethylene oxide)
polymer, viscosity
range of 65 to 115 mPA. s for a 5% solution at 25 C). The coating was allowed
to dry and the
tablet was then heat sealed into a 5 mil (127 gm) thick water-soluble pouch
according to film
formula 1 (14). The pouch was then tested according to Method A. The Poly0x
coating was
found to be ineffective at providing enhanced compatibility and reducing
premature basification
of the was water. The tablets coated with Poly0x demonstrated inconsistent
results due to the
powdered nature of the Poly0x coating. Because Poly0x is not melt-processable
the tablets
were first wetted to improve adhesion of the Poly0x coating. Such a wetting
process is not
desirable because it initiates activation of the bleach compounds. The
activated bleach causes in
pin-hole formation in the water-soluble of the water-soluble pouch containing
it during storage
(i.e. while on a store shelf before purchase). Pin-hole formation leads to a
decrease in the
delayed release properties of the film. Further, the powdered nature of the
Poly0x resulted in
poor storage integrity (the powdered coating can chip/be rubbed off of the
bleach tablet) which
further resulted in inconsistent delayed release properties.
[0165] A wetted lOg compressed tablet of a 1:1 (wt.%) mixture of sodium
carbonate and
percarbonate with stearic acid as a binding agent was powder coated with Cekol
300
carboxymethyl cellulose (CMC). Cekol 300 has a viscosity of 200 ¨ 400 cPs and
a degree of
substitution between 0.60 to 0.95. The coating was allowed to dry and the
tablet was then heat
sealed into a 5 mil (127 gm) thick water-soluble pouch according to film
formula 1 (15). The
pouch was then tested according to Method A. The CMC coating was found to be
not soluble
enough for this application.
[0166] A water-soluble film having a thickness of 3 mil (76 gm) was cast from
a water-
soluble mixture comprising 100 phr of a PVOH resin comprising 5 mol% methyl
acrylate with a
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
viscosity of 18 cPs and a degree of hydrolysis of greater than 99% (i.e. fully
hydrolyzed), 48.78
phr plasticizers, 6.02 phr surfactants, 0.7 phr defoamer, 3.7 phr filler, 3.41
phr starch, and 0.2 phr
of a stabilizer. The film was formed into a pouch, filled with 5.8 g of a 1:1
(wt. %) mixture of
sodium carbonate and percarbonate and heat sealed. The pouch was then dipped
into a molten
sugar mixture comprising granulated sugar, corn syrup and water heated to 150
C. The ratio of
granulated sugar to corn syrup was about 3:1. The molten sugar was allowed to
cool. The pouch
was then encapsulated in a 5 mil (127 um) thick water-soluble pouch according
to film formula 1
(16) and the bleach compatibility was measured according to Method A. The
hard, crystalline,
sugar coated bleach pouch (16) had demonstrated good delay release properties
with a point A
time of about 12 minutes and good dissolution properties.
EXAMPLE 5: DISSOLUTION OF ALKALINE BLEACH TABLETS
A: Tablet, no B:Tablet no coating C: Tablet D:
Tablet
pouch in pouch of film
coating PEG coated with
formula 1 6000 Peg 6000 in
pouch of
film
formula 1
Point A 0 3:12 min 1 min 8:40 min
Time
(min)
[0167] Four variations of a 10 g alkaline bleach tablet were tested for
dissolution time. The
tablets tested were lOg compressed tablets of a 1:1 (wt.%) mixture of sodium
carbonate and
percarbonate, with stearic acid as a binding agent. The four variations that
were tested were A)
an uncoated tablet not enclosed in a pouch, B) an uncoated tablet enclosed in
a pouch comprising
the water-soluble film of film formulation 1, C) a tablet coated with 65 mil
(1.65 mm) of PEG
(MW = 6000) and D) a tablet coated with 65 mil (1.65 mm) of PEG 6000 enclosed
in a pouch
comprising the water-soluble film of film formulation 1. The pouches had a
water-soluble film
thickness of about 4.75 mil (120 um). The tablets and pouches enclosing the
tablets were tested
according to Method A. The results are shown in the above table and Figure 4.
Figure 4 shows
that the uncoated tablet not enclosed in a pouch (A) dissolves in less than 1
minute after being
placed in water at a temperature of 40 C. Figure 4 further shows that the
same tablet, when
41
CA 02904373 2015-09-04
WO 2014/151718 PCT/US2014/026305
enclosed in a water-soluble pouch of the invention (C), begins to be released
about 3 minutes
after submerging the pouch in water heated to a temperature of 40 C. Further,
Figure 4 shows
that a tablet coated with PEG 6000 not enclosed in a pouch (B) begins to
dissolve about 1 minute
after being submerged in water heated to a temperature of 40 C and that a
tablet coated with
PEG 6000 and enclosed in a water-soluble pouch of the invention (D) does not
begin to basify
the water heated to a temperature of 40 C until at least 8 minutes after the
pouch has been
submerged in the water. These results show that although the PEG 6000 coating
does provide a
small delayed release feature to the tablet (about 1 minute; tablet A vs.
table C), the enhanced
delayed release time demonstrated by the pouch enclosing the coated tablet (D,
8 minutes vs. 3
minutes for the pouch enclosing the uncoated tablet B), is a result of the
enhanced chemical
stability of the pouch when the pouch is not in contact with the alkaline
material of the bleach
tablet.
EXAMPLE 6: STORAGE STABILITY
Description/Aging time 0 Weeks 2 Weeks 4 Weeks 6
Weeks
Pouch of film formulation 1 with Point A time:
Point A time: Point A time: Point A time:
uncoated tablet enclosed 3:12 min 3:02 min 2:46 min 3:00
min
Ambient Conditions
Pouch of film formulation 1 with N/A Point A time:
Point A time: Point A time:
uncoated tablet enclosed 2:25 min 2:09 min 2:16
min
38 C, 80% Relative Humidity
Pouch of film formulation 1 with Point A time:
Point A time: Point A time: Point A time:
PEG 6000 table enclosed 8:40 min 9:27 min 8:42 min
10:33 min
Ambient Conditions
Pouch of film formulation 1 with N/A Point A time:
Point A time: Point A time:
PEG 6000 tablet enclosed 11:27 min 9:01 min 7:57
min
38 C, 80% Relative Humidity
[0168] Water-soluble film was prepared according to film formulation 1. 5 mil
(127 m)
thick water-soluble films were cast according to formula 1, formed into
pouches and a 10 g tablet
of a 1:1 (wt.%) mixture of sodium carbonate and percarbonate, with stearic
acid as a binding
agent (uncoated, or coated with a 65 mil coating of PEG 6000) were enclosed
within the pouches
and the pouches were heat sealed. The bleach compatibility of the pouches were
determined
according to Bleach Compatibility Method A. Pouches were stored up to 6 weeks
under either
42
CA 02904373 2015-11-19
ambient conditions (23 C and 35 RH) or at 38 C and 80% relative humidity.
Example 6
demonstrates that the water-soluble films of the disclosures maintain an
acceptable delayed
release profile over 6 weeks when stored under ambient conditions or at a
temperature of 38 C
and 80% relative humidity. It is believed that in the case of the uncoated
bleach, hydrolysis of
the lactone rings by moisture in the bleach would increase the solubility of
the water-soluble
films (L e., the films resemble a partially hydrolyzed PVOH), however the
bleach component
reacts with the film in the presence of moisture to hydrolyze the film resin
which leads to a
decrease in solubility and thus, the effects counter-act one another. As a
result, the moisture
from the air does not significantly affect the solubility of the film and the
dissolution time
remains relatively stable over time. It is further believed that in the case
of the coated bleach
tablets, any moisture from the bleach tablet cannot interact with the water-
soluble resin and
therefore the water-soluble film demonstrates enhanced initial solubility.
Further, the film with
the coated bleach table is more susceptible to moisture from the atmosphere
during storage
because there is no counter-acting effect from the bleach tablet. Thus, the
solubility of the water-
soluble film with the coated bleach tablet increases more significantly over
storage. However,
even with the increase in solubility, the water-soluble films with coated
bleach tablets still
maintain an acceptable delayed release profile.
[0169] The foregoing description is given for clearness of understanding only,
and no
unnecessary limitations should be understood therefrom, as modifications
within the scope of the
invention defined by the claims may be apparent to those having ordinary skill
in the art.
[0170] Throughout this specification and the claims which follow, unless the
context requires
otherwise, the word "comprise" and variations such as "comprises" and
"comprising" will be
understood to imply the inclusion of a stated integer or step or group of
integers or steps but not
the exclusion of any other integer or step or group of integers or steps.
[0171] Throughout the specification, where compositions are described as
including
components or materials, it is contemplated that the compositions can also
consist essentially of,
or consist of, any combination of the recited components or materials, unless
described
otherwise. Likewise, where methods are described as including particular
steps, it is
contemplated that the methods can also consist essentially of, or consist of,
any combination of
the recited steps, unless described otherwise. The invention illustratively
disclosed herein
43
CA 02904373 2015-11-19
suitably may be practiced in the absence of any element or step which is not
specifically
disclosed herein.
101721 The practice of a method disclosed herein, and individual steps
thereof, can be
performed manually and/or with the aid of or automation provided by electronic
equipment.
Although processes have been described with reference to particular
embodiments, a person of
ordinary skill in the art will readily appreciate that other ways of
performing the acts associated
with the methods may be used. For example, the order of various steps may be
changed without
departing from the scope of the method defined by the appended claims. In
addition, some of the
individual steps can be combined, omitted, or further subdivided into
additional steps.
44
