Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02649407 2011-01-20
62301-2770
COMPOSITION FOR VISIBILITY AND IMPACT OF SUSPENDED MATERIALS
BACKGROUND OF THE INVENTION
[00021 Structured liquids are known in the art for suspending materials such
as beads in
liquid cleaning compositions. The methods of providing structure to the liquid
includes using
particular surfactants to structure the liquid, or by the addition of
structuring agents such as
polymers, natural guns and clays which enable the liquid to suspend materials
therein for
long periods of time. These suspended materials can be functional, aesthetic
or both. By
aesthetic it is meant that the suspended materials impart a certain visual
appearance that is
pleasing or eye catching. By functional it is meant that the suspended
materials contribute to
the action of the composition in cleaning, fragrance release, shine
enhancement, or other
intended action of the composition.
[00031 The suspension of materials, however, in a structured cleaning liquid
composition
by the aforementioned use of surfactants, polymers, natural gums and clays has
characteristics
that consumers often do not associate with acceptable liquid dish detergents.
Conventional
structured liquids are often opaque or turbid thereby obscuring the visual
appeal to the
consumer of the suspended materials which are shown to best advantage in a
nearly
transparent or clear liquid.
[0004] Further, a by-product of structuring a liquid to suspend materials
causes a
significant increase in liquid viscosity and a corresponding decrease in
liquid pourability and
ease of dissolution in water. Both properties are generally not considered
consumer
acceptable, particularly, in liquid cleaning products like hand dishwashing
liquid. Still further,
the structured liquid with suspended materials must be able to provide good
cleaning and
manifest the- foaming and rinsing properties which consumers today expect from
a
commercial liquid detergent. Finally, the dissolution rate of the structured
liquid in water is
desired to be rapid so that foam generation is not delayed. Foam is a signal
to consumers that
the detergent is high quality. Pourability and dissolution are in part linked
to liquid viscosity.
[0005] Even further, adding materials such as beads and structure to an
otherwise un-
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beaded un-structured product adds cost. Therefore, it would be desirable to
enhance the
visual impact of such materials in a liquid detergent product. The visual
impact can include
both the liquid composition and the packaging.
[0006] The liquid detergent by necessity must be distributed to the consumer
in a labeled
container. Labeling can obscure the viewability of the product in the bottle.
It would be
desirable to produce a liquid detergent with suspended material to provide an
acceptable
visual impact.
BRIEF SUMMARY OF THE INVENTION
[0007] A composition comprising suspended material and a liquid portion
comprising at
least one surfactant, wherein
a) the surfactant is present in the composition in an amount that is at least
15% by weight
of the composition based on active weight of the surfactant;
b) the composition has a viscosity less than 10,000 -Pas as measured at 25 C;
c) the liquid portion has a transmittance, as measured by visible
spectroscopy, of at least
15%; and
d) the suspended material has a particle size of 100 to 2500 microns.
DETAILED DESCRIPTION OF THE INVENTION
[0008] As used throughout, ranges are used as shorthand for describing each
and every
value that is within the range. Any value within the range can be selected as
the terminus of
the range.
[0009] Unless otherwise stated, references to weight % in this specification
are on an
active basis in the total composition.
[0010] This invention teaches how to enhance the aesthetic benefits of
surfactant
containing compositions with suspended materials. These materials are defined
as water
insoluble visible particles. They can be functional or non-functional, i.e.
functional materials
have components that augment the performance capabilities of the product and
non-functional
materials are present solely for aesthetic purposes. Functionality can often
be provided by
encapsulating materials that deliver functional benefits or by providing a
tactile benefit (e.g.
scrubbing). Functional materials, however, may also have aesthetic purposes.
It has been
found that it is desirable to take the entire product (package and the liquid
composition) into
consideration to enhance the appearance (visual impact) of materials. Since
suspended
materials add cost to normally un-beaded detergent liquid, maximizing their
appearance is
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important to success in the market place.
[0011] The composition comprises at least one surfactant in a liquid portion
and
suspended material. The liquid portion refers to the part of the composition
that is not the
suspended material. The combination of the suspended material in the
composition provides a
desired aesthetic appearance. The composition is formulated to provide for the
following
combination of properties, the ability to suspend materials, desired clarity,
a pourable
viscosity, and enhanced visible impact.
[0012] The suspended material can be density matched to the liquid portion if
very low
viscosity is desired. Density matched means that the density of the suspended
material is
close to the density of the liquid portion so that the suspended material
remains suspended. In
one embodiment, the density of the suspended material has a density that is
97% to 103% of
the density value of the liquid portion.
[0013] The composition can be formulated to be any type of detergent
composition. The
composition can be used as a light duty liquid (LDL) dish detergent, hand
soap, body wash, or
a laundry detergent. One embodiment described below will be for a dish
detergent.
LIQUID CLARITY
[0014] The composition has a clarity that provides for at least 15%
transmittance as
measured by the test described below. In other embodiments, the transmittance
is >50%,
>90%, or up to 100%. The transmittance is measured in the liquid portion.
Transmittance is
usually decreased by the addition of coloring material (pigments or dyes) to
the formula. The
addition of any coloring agent to the liquid portion must not decrease the
transmittance below
the minimum 15% specified. It is unlikely that a colored composition would
have a 100%
transmittance, although a very pale color in a detergent composition of high
clarity can
approach this limit.
COLOR
[0015] The liquid portion, the suspended material, the container, and the
label can each
individually be colored or uncolored as long as the suspended material is
visually detectable
to an observer. Color can be measured by the L* a* b* system established by
the
Commission Internationale d'Eclairage (CIE). (See for example, McClelland, D.,
Macworld Photoshop 4 Bible, IDG Books Worldwide, Inc. 1997, pp. 157-184.)
Color can
also be measured by the L*C*h system also established by Commission
Internationale
d'Eclairage (CIE). This system is very comparable to how human subjects
describe colors,
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representing the terms "lightness", "chroma", and "hue". L* refers to the
lighness/darkness of
a color. C*, chroma, refers to the intensity of the color, for instance how
intensely red the red
is. Hue, h , refers to what people generally refer to as "color" - red, blue,
green, orange and is
given as an angle. Unlike the L*a*b* system which operates on a standard
Cartesian system,
L*C*h operates on a polar coordinate system. Color differences that are
significant can be
specified by the LECMC tolerancing system based on CIELCH and devised by the
Color
Measurement Committee of the Society of Dyers and Colourists in Great Britain.
By this
system, it can be seen that there minimum distances between colors for the
colors to be seen
as different, and these differences vary with hue and chroma.
[0016] In one embodiment, it is desired to have a liquid portion hue or
container hue that
is not complementary to at least a portion of the suspended material hue, that
is having a
liquid portion hue or container hue that is not 180 degrees away from the
suspended material
hue on a standard color wheel, or any color visually indistinguishable from
the oppositional
color. In other embodiments, the liquid portion hue and/or container hue is
not
complementary to more than 50%, more than 60%, more than 70%, more than 80%,
more
than 90%, more than 95%, or more than 99% of the suspended material hue. The
color of the
suspended material can be altered by viewing it through the liquid portion and
the package if
the color of those items is not completely colorless. When viewed through and
surrounded by
a complementary color, the color of the suspended material tends to have a
strong gray cast, in
which the brightness and impact of the suspended material color is less than
it could be, which
may not be a desired affect. If multiple suspended material colors are used,
the liquid portion
hue or container hue preferably should not be complementary to any of the
suspended
material colors. If the liquid portion or container hue is complementary to
the suspended
color (whether single or multiple suspended material color), then the liquid
portion or
container color should have the lowest chroma possible. The appearance of the
suspended
material is more impactful if the chroma of the liquid portion or container is
different from the
chroma of the suspended material color.
[0017] In one embodiment, it is desired that the visual intensity, or chroma,
of the colors
of the liquid portion and the container are coordinated. The overall
transmittance of the liquid
porition and container are selected to allow the suspended material to be
visible. The
transmittance of the liquid portion and that of the container are due to its
clarity and its color.
It is also desirable to provide visual contrast between the suspended
material, the liquid
portion, and the container. The chroma of the liquid portion and container can
thus be chosen
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to be different from the chroma of at least a portion of the suspended
material. In other
embodiments, the chroma of the liquid portion and/or container are different
from more than
50%, more than 60%, more than 70%, more than 80%, more than 90%, more than
95%, or
more than 99% of the suspended material chroma. This differentiation by chroma
can be used
if the hue of the suspended material is close to that of the hue of the liquid
portion or container
so that the suspended material is visually detectable. The clarity of the
liquid portion and the
clarity of the container should also be maximized so that the maximum light is
passed to
illuminate the suspended material.
[0018] The chroma and hue of the liquid portion and that of the container can
match or be
different depending on the aesthetic effect desired. In one embodiment, the
chromas of the
liquid portion and the container can be the same as long as the transmittance
through the
container and the liquid portion meet the stated limits for transmittance. In
another
embodiment, the hue of the container and the hue of the liquid portion should
not be 180
degrees apart from each other on a standard color wheel or any color that is
visually
indistinguishable from the oppositional color.
SUSPENDED MATERIALS
[0019] At least a portion of the suspended material is of any size that is
viewable by a
person. By viewable it is meant that the suspended material can be seen by a
non-color blind
person with an unaided eye at 20/20 or corrected to 20/20 with glasses or
contact lenses at a
distance of 30 cm from the composition under incandescent light, florescent
light, or sunlight.
In other embodiments, at least 50%, at least 60%, at least 70%, at least 80%,
at least 90%, at
least 95%, or at least 99% of the particles are viewable by a person. In one
embodiment, the
particle size is 100 to 2500 microns in a longest dimension of the suspended
material. In
another embodiment, the particle size is 250 to 2250 microns. In another
embodiment, the
particle size is 500 to 1500 microns. In another embodiment, the particle size
is 700 to 1000
microns. In another embodiment, a combination of more than one particle sizes
can be used.
In another embodiment, there is a combination of five particle sizes.
[0020] The suspended material can have any shape. Examples of shapes include,
but are
not limited to, spherical, polyhedral, cubic, box, tetrahedral, irregular
three dimensional
shapes, flat polygons, triangles, rectangles, squares, pentagons, hexagons,
octagons, stars,
characters, animals, plants, objects, cars, or any other desired shape.
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[0021] The suspended material can be present in any amount in the composition
that
allows the suspended material to remain suspended. In one embodiment, the
suspended
material is present in an amount of 0.01 and 10% by weight of the total
composition.
[0022] The suspended material can be selected to be of one size and one shape,
one size
and a combination of shapes, a combination of sizes and one shape, or a
combination of sizes
and a combination of shapes. Also, the color of the suspended material can be
varied along
with the size and/or shape. Mixtures of suspended materials that vary by size,
shape, and/or
color can be used to communicate different attributes that the product can
deliver to a
consumer.
[0023] The suspended material can be functional, non-functional, or a
combination of
both. They can be made from a variety of materials such as the following non-
limiting
examples: gelatin, cellulose, agar, waxes, polyethylene, and insoluble
inorganic materials like
silica and calcium carbonate. The material may also have an encapsulate core
containing
hydrophobic compounds and mixtures such as these non-limiting examples: aloe,
vitamins,
essential oils, natural oils, solvents, esters, or any fragrance ingredient.
These materials may
be density matched by encapsulating oils or other materials that help make the
density of the
suspended material equal to that of the bulk composition. Alternatively, they
may be made
porous in a way that allows the liquid portion to diffuse into the suspended
material in a
manner that is self density matching. Density matching produces compositions
that can
suspend material at a viscosity less than 1500 mPas. Also, the particles may
be non-density
matched, that is being either less or more dense than the composition. In
these compositions,
the liquid portion can be designed to have a yield stress to aid in the
stabilization of suspended
material.
[0024] While the composition can be formulated to suspend material without the
need of a
suspending agent, suspending agents can be added to increase the stability of
the suspended
material to keep the material suspended. The composition can be stored in
warehouses
anywhere in the world. Temperatures can range from very cold to very hot. As
temperatures
change, the density of the liquid may be different from the density of the
suspended material.
The composition can be formulated to keep the suspended matter suspended at
both
temperature extremes.
SUSPENDING AGENTS
[0025] Suspending agents are any material that increases the ability of the
composition to
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suspend material. Examples of suspending agents include, but are not limited
to, gellan gum,
polymeric gums, polysaccharides, pectine, alginate, arabinogalactan,
carageenan, xanthum
gum, guar gum, rhamsan gum, furcellaran gum, and other natural gum. A
synthetic
structuring agent in one embodiment is a polyacrylate. One acrylate aqueous
solution used to
form a stable suspension of the solid particles is manufactured by Noveon as
CARBOPOLTM
Aqua 30. The CARBOPOLTM resins, also known as CARBOMERTM, are hydrophilic high
molecular weight, crosslinked acrylic acid polymers having an average
equivalent weight of
76, and the general structure illustrated by the following formula has a
molecular weight of
about 1,250,000; CARBOPOLTM 940 with a molecular weight of approximately
4,000,000
and CARBOPOLTM 934 with a molecular weight of approximately 3,000,000. The
CARBOPOLTM resins can be crosslinked with polyalkenyl polyether, e.g. about 1%
of a
polyalkyl ether of sucrose having an average of about 5,8 alkyl groups for
each molecule of
sucrose.
[0026] The suspending agents can be used alone or in combination. The amount
of
suspending agent can be any amount that provides for a desired level of
suspending ability. In
one embodiment, the suspending agent is present in an amount from about 0.01
to 10% by
weight of the composition. In one embodiment, gellan gum is included in the
composition.
STABILITY OF SUSPENDED PARTICLES
[0027] The composition can keep the suspended materials suspended for at least
2 weeks
at room temperature (23-25 C). By suspended it is meant that at least 90%, or
at least 95%, or
at least 97%, or at least 99% of the suspended material remains suspended in
the composition
without settling out to the bottom of the liquid portion. This is measured by
counting the
number of particles that remain suspended in the liquid portion after the
elapse of time as
compared to the number of particles in the liquid portion initially. In other
embodiments, the
suspended material can be suspended for at least two months, at least six
months, or at least
one year at room temperature (23-25 C). In other embodiments, the composition
can keep the
suspended materials suspended for at least 18 weeks at 40.5 C (105 F). In
another
embodiment, the composition can keep the suspended material suspended for at
least 2 weeks
at -10 C. In another embodiment, the composition can keep the suspended
material
suspended for at least 3 weeks at 4.5 C. While factors such as the amount of
surfactant, the
size of the suspended materials, and the amount of suspending agent can affect
stability,
amounts for each of these factors can be selected so that the above stability
tests are met.
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LIQUID VISCOSITY
[0028] The composition has a viscosity that allows the composition to be
pourable, which
is usually below 10,000 niPas. Viscosity is measured using a Brookfield RVT
Viscometer
using spindle 21 at 20 RPM at 25 C. In one embodiment, the viscosity is less
than 5,000
mPas. In other embodiments, the viscosity is less than 1,500 mPas, less than
1,000 mPas, less
than 750 mPas, or less than 500 mPas.
LIQUID PORTION
[0029] The composition contains at least one surfactant that is present in an
amount that is
at least 15% by weight of the composition based on the active amount of the
surfactant. In
other embodiments, the amount of surfactant is at least 20%, at least 25%, at
least 30 %, at
least 35%, or at least 40% by weight. In another embodiment, the amount of
surfactant ranges
from 15% to 45% by weight. The surfactant can be any surfactant or any
combination of
surfactants. Examples of surfactants include anionic, nonionic, cationic,
amphoteric, or
zwitterionic.
[0030] Anionic surfactants include, but are not limited to, those surface-
active or
detergent compounds that contain an organic hydrophobic group containing
generally 8 to 26
carbon atoms or generally 10 to 18 carbon atoms in their molecular structure
and at least one
water-solubilizing group selected from sulfonate, sulfate, and carboxylate so
as to form a
water-soluble detergent. Usually, the hydrophobic group will comprise a C8-C22
alkyl, or
acyl group. Such surfactants are employed in the form of water-soluble salts
and the salt-
forming cation usually is selected from sodium, potassium, ammonium, magnesium
and
mono-, di- or tri-C2-C3 alkanolammonium, with the sodium, magnesium and
ammonium
cations again being the usual ones chosen.
[0031] The anionic surfactants that are used in the composition of this
invention are water
soluble and include, but are not limited to, the sodium, potassium, ammonium,
and
ethanolammonium salts of linear C8-C16 alkyl benzene sulfonates, alkyl ether
carboxylates,
C10-C20 paraffin sulfonates, C8-C25 alpha olefin sulfonates, C8-C18 alkyl
sulfates, alkyl
ether sulfates and mixtures thereof.
[0032] The paraffin sulfonates (also known as secondary alkane sulfonates) may
be
monosulfonates or di-sulfonates and usually are mixtures thereof, obtained by
sulfonating
paraffins of 10 to 20 carbon atoms. Commonly used paraffin sulfonates are
those of C12-18
carbon atoms chains, and more commonly they are of C14-17 chains. Paraffin
sulfonates that
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have the sulfonate group(s) distributed along the paraffin chain are described
in U.S. Patent
Nos. 2,503,280; 2,507,088; 3,260,744; and 3,372,188; and also in German Patent
735,096.
Such compounds may be made to specifications and desirably the content of
paraffin
sulfonates outside the C14-17 range will be minor and will be minimized, as
will be any
contents of di- or poly-sulfonates. Examples of paraffin sulfonates include,
but are not limited
to HOSTAPURTM SAS30, SAS 60, SAS 93 secondary alkane sulfonates from Clariant,
and
BIO-TERGETM surfactants from Stepan, and CAS No. 68037-49-0.
[0033] Pareth sulfate surfactants can also be included in the composition. The
pareth
sulfate surfactant is a salt of an ethoxylated C10-C16 pareth sulfate
surfactant having 1 to 30
moles of ethylene oxide. In some embodiments, the amount of ethylene oxide is
1 to 6 moles,
and in other embodiments it is 2 to 3 moles, and in another embodiment it is 2
moles. In one
embodiment, the pareth sulfate is a C12-C13 pareth sulfate with 2 moles of
ethylene oxide. An
example of a pareth sulfate surfactant is STEOLTM 23-2S/70 from Stepan, or
(CAS No.
68585-34-2).
[0034] Examples of suitable other sulfonated anionic detergents are the well
known higher
alkyl mononuclear aromatic sulfonates, such as the higher alkylbenzene
sulfonates containing
9 to 18 or preferably 9 to 16 carbon atoms in the higher alkyl group in a
straight or branched
chain, or C8-15 alkyl toluene sulfonates. In one embodiment, the alkylbenzene
sulfonate is a
linear alkylbenzene sulfonate having a higher content of 3-phenyl (or higher)
isomers and a
correspondingly lower content (well below 50%) of 2-phenyl (or lower) isomers,
such as
those sulfonates wherein the benzene ring is attached mostly at the 3 or
higher (for example 4,
5, 6 or 7) position of the alkyl group and the content of the isomers in which
the benzene ring
is attached in the 2 or 1 position is correspondingly low. Materials that can
be used are found
in U.S. Patent 3,320,174, especially those in which the alkyls are of 10 to 13
carbon atoms.
[0035] Other suitable anionic surfactants are the olefin sulfonates, including
long-chain
alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene
sulfonates and
hydroxyalkane sulfonates. These olefin sulfonate detergents may be prepared in
a known
manner by the reaction of sulfur trioxide (S03) with long-chain olefins
containing 8 to 25,
preferably 12 to 21 carbon atoms and having the formula RCH=CHR1 where R is a
higher
alkyl group of 6 to 23 carbons and R1 is an alkyl group of 1 to 17 carbons or
hydrogen to
form a mixture of sultones and alkene sulfonic acids which is then treated to
convert the
sultones to sulfonates. In one embodiment, olefin sulfonates contain from 14
to 16 carbon
atoms in the R alkyl group and are obtained by sulfonating an a-olefin.
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[0036] Examples of satisfactory anionic sulfate surfactants are the alkyl
sulfate salts and
the and the alkyl ether polyethenoxy sulfate salts having the formula
R(OC2H4)n OSO3M
wherein n is 1 to 12, or 1 to 5, and R is an alkyl group having about 8 to
about 18 carbon
atoms, or 12 to 15 and natural cuts, for example, C12-14 or C12-16 and M is a
solubilizing
cation selected from sodium, potassium, ammonium, magnesium and mono-, di- and
triethanol ammonium ions. The alkyl sulfates may be obtained by sulfating the
alcohols
obtained by reducing glycerides of coconut oil or tallow or mixtures thereof
and neutralizing
the resultant product.
[0037] The ethoxylated alkyl ether sulfate may be made by sulfating the
condensation
product of ethylene oxide and C8_18 alkanol, and neutralizing the resultant
product. The
ethoxylated alkyl ether sulfates differ from one another in the number of
carbon atoms in the
alcohols and in the number of moles of ethylene oxide reacted with one mole of
such alcohol.
In one embodiment, alkyl ether sulfates contain 12 to 15 carbon atoms in the
alcohols and in
the alkyl groups thereof, e.g., sodium myristyl (3 EO) sulfate.
[0038] Ethoxylated C8_18 alkylphenyl ether sulfates containing from 2 to 6
moles of
ethylene oxide in the molecule are also suitable for use in the invention
compositions. These
detergents can be prepared' by reacting an alkyl phenol with 2 to 6 moles of
ethylene oxide
and sulfating and neutralizing the resultant ethoxylated alkylphenol.
[0039] Other suitable anionic detergents are the C9-C15 alkyl ether
polyethenoxyl
carboxylates having the structural formula R(OC2H4)nOX COOH wherein n is a
number
from 4 to 12, preferably 6 to 11 and X is selected from the group consisting
of CH2, C(O)R1
and
O 11
C
wherein R1 is a C1-C3 alkylene group. Types of these compounds include, but
are not
limited to, C9-C11 alkyl ether polyethenoxy (7-9) C(O) CH2CH2COOH, C13-C15
alkyl ether
polyethenoxy (7-9)
0 a COOH
and C10-C12 alkyl ether polyethenoxy (5-7) CH2COOH. These compounds may be
prepared
by condensing ethylene oxide with appropriate alkanol and reacting this
reaction product with
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chloracetic acid to make the ether carboxylic acids as shown in U.S. Pat. No.
3,741,911 or
with succinic anhydride or phtalic anhydride.
[0040] The amine oxide is depicted by the formula:
R2
R1 (C2H4O)n-N, 0
R3
wherein Rl is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-
hydroxypropyl radical
in which the alkyl and alkoxy, respectively, contain from about 8 to about 18
carbon atoms;
R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-
hydroxypropyl, or 3-
hydroxypropyl; and n is from 0 to about 10. In one embodiment, the amine
oxides are of the
formula:
R2
R1 I - " O
R3
wherein R1 is a C12-18 alkyl and R2 and R3 are methyl or ethyl. The above
ethylene oxide
condensates, amides, and amine oxides are more fully described in U.S. Patent
No, 4,316,824.
In another embodiment, the amine oxide is depicted by the formula:
0
I I H 12
R1 C N (CH2)3-N I ~ 0
R3
wherein Rl is a saturated or unsaturated alkyl group having about 6 to about
24 carbon atoms,
R2 is a methyl group, and R3 is a methyl or ethyl group. The preferred amine
oxide is
cocoamidopropyl-dimethylamine oxide.
[0041] The water soluble nonionic surfactants utilized in this invention are
commercially
well known and include the primary aliphatic alcohol ethoxylates, secondary
aliphatic alcohol
ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide
condensates on
primary alkanols, such a PLURAFACTM surfactants (BASF) and condensates of
ethylene
oxide with sorbitan fatty acid esters such as the TWEENTM surfactants (ICI).
The nonionic
synthetic organic detergents generally are the condensation products of an
organic aliphatic or
alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups.
Practically
any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with
a free
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hydrogen attached to the nitrogen can be condensed with ethylene oxide or with
the
polyhydration product thereof, polyethylene glycol, to form a water-soluble
nonionic
detergent. Further, the length of the polyethenoxy chain can be adjusted to
achieve the
desired balance between the hydrophobic and hydrophilic elements.
[0042] The nonionic surfactant class includes the condensation products of a
higher
alcohol (e.g., an alkanol containing about 8 to 18 carbon atoms in a straight
or branched chain
configuration) condensed with about 5 to 30 moles of ethylene oxide, for
example, lauryl or
myristyl alcohol condensed with about 16 moles of ethylene oxide (EO),
tridecanol condensed
with about 6 to moles of EO, myristyl alcohol condensed with about 10 moles of
EO per mole
of myristyl alcohol, the condensation product of EO with a cut of coconut
fatty alcohol
containing a mixture of fatty alcohols with alkyl chains varying from 10 to
about 14 carbon
atoms in length and wherein the condensate contains either about 6 moles of EO
per mole of
total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol
ethoxylates
containing 6 EO to 11 EO per mole of alcohol.
[0043] In one embodiment, the nonionic surfactants are the NEODOLTM
ethoxylates
(Shell Co.), which are higher aliphatic, primary alcohol containing about 9-15
carbon atoms,
such as C9-C11 alkanol condensed with 2.5 to 10 moles of ethylene oxide
(NEODOLTM 91-
2.5 OR -5 OR -6 OR -8), C12-13 alkanol condensed with 6.5 moles ethylene oxide
(NEODOLTM 23-6.5), C12-15 alkanol condensed with 12 moles ethylene oxide
(NEODOLTM
25-12), C14-15 alkanol condensed with 13 moles ethylene oxide (NEODOLTM 45-
13), and the
like.
[0044] Additional satisfactory water soluble alcohol ethylene oxide
condensates are the
condensation products of a secondary aliphatic alcohol containing 8 to 18
carbon atoms in a
straight or branched chain configuration condensed with 5 to 30 moles of
ethylene oxide.
Examples of commercially available nonionic detergents of the foregoing type
are C 11 -C 15
secondary alkanol condensed with either 9 EO (TERGITOLTM 15-S-9) or 12 EO
(TERGITOLTM 15-S-12) marketed by Union Carbide.
[0045] Other suitable nonionic surfactants include the polyethylene oxide
condensates of
one mole of alkyl phenol containing from about 8 to 18 carbon atoms in a
straight- or
branched chain alkyl group with about 5 to 30 moles of ethylene oxide.
Specific examples of
alkyl phenol ethoxylates include, but are not limited to, nonyl phenol
condensed with about
9.5 moles of EO per mole of nonyl phenol, dinonyl phenol condensed with about
12 moles of
EO per mole of phenol, dinonyl phenol condensed with about 15 moles of EO per
mole of
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phenol and di-isoctylphenol condensed with about 15 moles of EO per mole of
phenol.
Commercially available nonionic surfactants of this type include IGEPALTM CO-
630 (nonyl
phenol ethoxylate) marketed by GAF Corporation.
[0046] Also among the satisfactory nonionic surfactants are the water-soluble
condensation products of a C8-C20 alkanol with a heteric mixture of ethylene
oxide and
propylene oxide wherein the weight ratio of ethylene oxide to propylene oxide
is from 2.5:1 to
4:1, preferably 2.8:1 to 3.3:1, with the total of the ethylene oxide and
propylene oxide
(including the terminal ethanol or propanol group) being from 60-85%,
preferably 70-80%, by
weight. Such detergents are commercially available from BASF and a
particularly preferred
detergent is a CIO-C16 alkanol condensate with ethylene oxide and propylene
oxide, the
weight ratio of ethylene oxide to propylene oxide being 3:1 and the total
alkoxy content being
about 75% by weight.
[0047] Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and
tri-C10-
C20 alkanoic acid esters having a HLB of 8 to 15 also may be employed as the
nonionic
detergent ingredient in the described composition. These surfactants are well
known and are
available from Imperial Chemical Industries under the TWEENTM trade name.
Suitable
surfactants include, but are not limited to, polyoxyethylene (4) sorbitan
monolaurate,
polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan
trioleate and
polyoxyethylene (20) sorbitan tristearate.
[0048] Other suitable water-soluble nonionic surfactants are marketed under
the trade
name PLURONICTM. The compounds are formed by condensing ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide with propylene
glycol. The
molecular weight of the hydrophobic portion of the molecule is of the order of
950 to 4000
and preferably 200 to 2,500. The addition of polyoxyethylene radicals to the
hydrophobic
portion tends to increase the solubility of the molecule as a whole so as to
make the surfactant
water-soluble. The molecular weight of the block polymers varies from 1,000 to
15,000 and
the polyethylene oxide content may comprise 20% to 80% by weight. Preferably,
these
surfactants will be in liquid form and satisfactory surfactants are available
as grades L 62 and
L 64.
[0049] The alkyl polysaccharides surfactants, which can be used in the instant
composition, have a hydrophobic group containing from about 8 to about 20
carbon atoms,
preferably from about 10 to about 16 carbon atoms, or from about 12 to about
14 carbon
atoms, and polysaccharide hydrophilic group containing from about 1.5 to about
10, or from
13
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about 1.5 to about 4, or from about 1.6 to about 2.7 saccharide units (e.g.,
galactoside,
glucoside, fructoside, glucosyl, fructosyl; and/or galactosyl units). Mixtures
of saccharide
moieties may be used in the alkyl polysaccharide surfactants. The number x
indicates the
number of saccharide units in a particular alkyl polysaccharide surfactant.
For a particular
alkyl polysaccharide molecule x can only assume integral values. In any
physical sample of
alkyl polysaccharide surfactants there will be in general molecules having
different x values.
The physical sample can be characterized by the average value of x and this
average value can
assume non-integral values. In this specification the values of x are to be
understood to be
average values. The hydrophobic group (R) can be attached at the 2-, 3-, or 4-
positions rather
than at the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed
to a glucoside or
galactoside). However, attachment through the 1- position, i.e., glucosides,
galactoside,
fructosides, etc., is preferred. In one embodiment, the additional saccharide
units are
predominately attached to the previous saccharide unit's 2-position.
Attachment through the
3-, 4-, and 6- positions can also occur. Optionally and less desirably there
can be a
polyalkoxide chain joining the hydrophobic moiety (R) and the polysaccharide
chain. The
preferred alkoxide moiety is ethoxide.
[0050] Typical hydrophobic groups include alkyl groups, either saturated or
unsaturated,
branched or unbranched containing from about 8 to about 20, preferably from
about 10 to
about 18 carbon atoms. In one embodiment, the alkyl group is a straight chain
saturated alkyl
group. The alkyl group can contain up to 3 hydroxy groups and/or the
polyalkoxide chain can
contain up to about 30, preferably less than about 10, alkoxide moieties.
[0051] Suitable alkyl polysaccharides include, but are not limited to, decyl,
dodecyl,
tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta-,
and hexaglucosides,
galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or
galactosyls and
mixtures thereof.
[0052] The alkyl monosaccharides are relatively less soluble in water than the
higher alkyl
polysaccharides. When used in admixture with alkyl polysaccharides, the alkyl
monosaccharides are solubilized to some extent. The use of alkyl
monosaccharides in
admixture with alkyl polysaccharides is a preferred mode of carrying out the
invention.
Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and
pentaglucosides and tallow alkyl
tetra-, penta-, and hexaglucosides.
[0053] In one embodiment, the alkyl polysaccharides are alkyl polyglucosides
having the
formula
14
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WO 2007/123566 PCT/US2006/035923
R20(CnH2n0)r(Z)x
wherein Z is derived from glucose, R is a hydrophobic group selected from
alkyl, alkylphenyl,
hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain
from about 10 to
about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, r is
from 0 to 10; and
x is from 1.5 to 8, or from 1.5 to 4, or from 1.6 to 2.7. To prepare these
compounds a long
chain alcohol (R2OH) can be reacted with glucose, in the presence of an acid
catalyst to form
the desired glucoside. Alternatively the alkyl polyglucosides can be prepared
by a two step
procedure in which a short chain alcohol (R1OH) can be reacted with glucose,
in the presence
of an acid catalyst to form the desired glucoside. Alternatively the alkyl
polyglucosides can
be prepared by a two step procedure in which a short chain alcohol (C1-6) is
reacted with
glucose or a polyglucoside (x=2 to 4) to yield a short chain alkyl glucoside
(x=1 to 4) which
can in turn be reacted with a longer chain alcohol (R2OH) to displace the
short chain alcohol
and obtain the desired alkyl polyglucoside. If this two step procedure is
used, the short chain
alkylglucosde content of the final alkyl polyglucoside material should be less
than 50%,
preferably less than 10%, more preferably less than about 5%, most preferably
0% of the alkyl
polyglucoside.
[0054] The amount of unreacted alcohol (the free fatty alcohol content) in the
desired
alkyl polysaccharide surfactant is generally less than about 2%, or less than
about 0.5% by
weight of the total of the alkyl polysaccharide. For some uses it is desirable
to have the alkyl
monosaccharide content less than about 10%.
[0055] "Alkyl polysaccharide surfactant" is intended to represent both the
glucose and
galactose derived surfactants and the alkyl polysaccharide surfactants.
Throughout this
specification, "alkyl polyglucoside" is used to include alkyl polyglycosides
because the
stereochemistry of the saccharide moiety is changed during the preparation
reaction.
[0056] In one embodiment, APG glycoside surfactant is APG 625 glycoside
manufactured
by the Henkel Corporation of Ambler, PA. APG25 is a nonionic alkyl
polyglycoside
characterized by the formula:
CnH2n+iO(C6H1OOs)XH
wherein n=10 (2%); n=122 (65%); n=14 (21-28%); n=16 (4-8%) and n=18 (0.5%) and
x
(degree of polymerization) = 1.6. APG 625 has: a pH of 6 to 10 (10% of APG 625
in
distilled water); a specific gravity at 25 C of 1.1 g/ml; a density at 25 C of
9.1 lbs/gallon; a
calculated HLB of 12.1 and a Brookfield viscosity at 35 C, 21 spindle, 5-10
RPM of 3,000 to
7,000 cps.
CA 02649407 2008-10-15
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[0057] The zwitterionic surfactant can be any zwitterionic surfactant. In one
embodiment,
the zwitterionic surfactant is a water soluble betaine having the general
formula
R2
R1 N R4+-X -
R3
wherein X- is selected from COO- and SOY and RI is an alkyl group having 10 to
about 20
carbon atoms, or 12 to 16 carbon atoms, or the amido radical:
117
R -C N (CH2)õ-
wherein R is an alkyl group having about 9 to 19 carbon atoms and n is the
integer 1 to 4; R2
and R3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R4
is an alkylene
or hydroxyalkylene group having from 1 to 4 carbon atoms and, optionally, one
hydroxyl
group. Typical alkyldimethyl betaines include, but are not limited to, decyl
dimethyl betaine
or 2-(N-decyl-N, N-dimethyl-ammonia) acetate, coco dimethyl betaine or 2-(N-
coco N, N-
dimethylammonia) acetate, myristyl dimethyl betaine, palmityl dimethyl
betaine, lauryl
dimethyl betaine, cetyl dim ethyl betaine, stearyl dimethyl betaine, etc. The
amidobetaines
similarly include, but are not limited to, cocoamidoethylbetaine,
cocoamidopropyl betaine and
the like. The amidosulfobetaines include, but are not limited to,
cocoamidoethylsulfobetaine,
cocoamidopropyl sulfobetaine and the like. In one embodiment, the betaine is
coco (C8-C18)
amidopropyl dimethyl betaine. Three examples of betaine surfactants that can
be used are
EMPIGENTM BS/CA from Albright and Wilson, REWOTERICTM AMB 13 and Goldschmidt
Betaine U.
[0058] The composition may also contain solvents or salts to modify the
cleaning,
stability and rheological properties of the composition.
[0059] Solvents can include any water soluble solvents. Water soluble solvents
include,
but are not limited to, C2_4 mono, dihydroxy, or polyhydroxy alkanols and/or
an ether or
diether, such as ethanol, isopropanol, diethylene glycol monobutyl ether,
dipropylene glycol
methyl ether, diproyleneglycol monobutyl ether, propylene glycol n-butyl
ether, propylene
glycol, and hexylene glycol, and alkali metal cumene, alkali metal toluene, or
alkali metal
xylene sulfonates such as sodium cumene sulfonate and sodium xylene sulfonate.
In some
embodiment, the solvents include ethanol and diethylene glycol monobutyl
ether, both of
16
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WO 2007/123566 PCT/US2006/035923
which are miscible with water. Urea can be optionally used at a concentration
of 0.1 % to 7
weight%.
[0060] Salts can include any desirable salt. Examples of salts include, but
are not limited
to, sodium chloride and magnesium sulfate.
[0061] Additional optional ingredients may be included to provide added effect
or to
make the product more attractive. Such ingredients include, but are not
limited to, perfumes,
fragrances, abrasive agents, disinfectants, radical scavengers, bleaches,
chelating agents,
antibacterial agents/preservatives, optical brighteners, hydrotropes, or
combinations thereof.
[0062] In some embodiments, preservatives can be used in the composition at a
concentration of 0 wt. % to 3 wt. %, more preferably 0.01 wt. % to 2.5 wt. %.
Examples of
preservatives include, but are not limited to, benzalkonium chloride;
benzethonium chloride,5-
bromo-5-nitro-1,3dioxane; 2-bromo-2-nitropropane-1,3-diol; alkyl trimethyl
ammonium
bromide; N-(hydroxymethyl)-N-(1,3-dihydroxy methyl-2,5-dioxo-4-imidaxolidinyl-
N'-
(hydroxy methyl) urea; 1-3-dimethyol-5,5-dimethyl hydantoin; formaldehyde;
iodopropynl
butyl carbamate, butyl paraben; ethyl paraben; methyl paraben; propyl paraben,
mixture of
methyl isothiazolinone/methyl-chloroisothiazoline in a 1:3 wt. ratio; mixture
of
phenoxythanol/butyl paraben/methyl parabenlpropylparaben; 2-phenoxyethanol;
tris-
hydroxyethyl-hexahydrotriaz- ine; methylisothiazolinone; 5-chloro-2-methyl-4-
isothiazolin-3-
one; 1,2-dibromo-2, 4-dicyanobutane; 1-(3-chloroalkyl)-3,5,7-triaza-azoniaadam-
antane
chloride; and sodium benzoate.
[0063] Generally, water is included in the composition. The amount of water is
variable
depending on the amounts of other materials added to the composition.
[0064] The compositions can be made by simple mixing methods from readily
available
components which, on storage, do not adversely affect the entire composition.
Mixing can be
done by any mixer that forms the composition. Examples of mixers include, but
are not
limited to, static mixers and in-line mixers. Solubilizing agents such as a C1-
C3 alkyl
substituted benzene sulfonate such as sodium cumene or sodium xylene sulfonate
and
mixtures thereof can be used at a concentration of 0.5 wt. % to 10 wt. % to
assist in
solubilizing the surfactants.
17
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CONTAINER
[0065] The composition can be provided in any type of container that is
compatible with
the composition. Non-limiting examples of containers are made from plastic or
glass. For
consumer convenience, plastic may be chosen. The plastic can be any type of
plastic.
Examples of plastic include, but are not limited to, polyethylene tetra
phthalate (PET),
polyethylene, polypropylene, or polyvinyl chloride. The plastic bottle
preferably does not
overly affect the visual impact of the materials. Container properties, such
as clarity, gloss,
color, and shape can be selected to provide a desired aesthetic effect.
[0066] In one embodiment, the container has clarity of at least 15%
transmittance as
measured by the transmittance test described below. In another embodiment, the
transmittance is >50%. and in another embodiment the transmittance is > 90%
transmittance.
The transmittance can be up to 100%.
[0067] In one embodiment, the combined transmittance of the container and the
liquid
portion is at least 15%. In other embodiments, the transmittance can be >50%,
>90%, or up to
100%. The transmittance is measured along a longest horizontal path from the
front of the
container to the rear of the container.
[0068] In one embodiment, the container has a gloss of 10 to 500 gloss units
as measured
at 60 degrees according to the test described below. In another embodiment,
the gloss is from
to 100 as measured at 60 degrees.
[0069] The container can be any color or uncolored. The container can be
opaque, but it
is preferred that the container is transparent or translucent. In one
embodiment, the container
is transparent and uncolored. In another embodiment, the container is
transparent and
colored. In one embodiment, the color intensity is not more than 20 chroma
units as measured
by the test described below.
[0070] The container can be of any desired shape. Types of shapes include, but
are not
limited to, round, triangular, cylindrical, oval, asymmetrical, or waisted
(having defined
shoulders and hips). In one embodiment, the container has a shape as the
defined by the side
to side, front to back and height dimensions below:
Max, Min,
mm mm
Side to Side 250 30
Front to Back 160 30
Height 350 60
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[0071] In one embodiment, the greatest side to side dimension of the container
is greater
than the greatest front to back dimension of the container. In another
embodiment, the height
of the container is greater than the greatest front to back dimension and the
greatest side to
side dimension of the container.
LABEL
[0072] The composition is intended to be distributed to a consumer in a
container with a
label. The label identifies the brand, manufacturer, and type of product, and
it can include any
safety or regulatory information, usage instructions, or other useful
information. Generally,
extensive information must be contained in a limited amount of space. Labels
can be opaque,
translucent (clear), or have a transmittance between opaque and clear. In one
embodiment,
the label has transparency of at least 15% transmittance. In other
embodiments, the
transmittance is >50%, >90%, or up to 100% in areas not covered by printing.
The printing
on the label can be designed with the same level of transmittance as long as
the printing can
be read. In one embodiment, the combined transmittance of the label, the
container, and the
liquid portion is at least 15% in areas not covered by printing. In other
embodiments, the
transmittance is >50%, >90%, or up to 100% in areas not covered by printing.
[0073] The label can be adhered to the container by any desired method.
Examples
include, but are not limited to, permanent, peel-off, or peel off leaving a
residual but smaller
portion of the overall label. The label can be textured, contain any desired
graphics including
a hologram, 3D effects, light reflection, or plain printing.
CLOSURE
[0074] The composition can be distributed to the consumer in a container with
a closure to
prevent spillage and evaporation, and it can aid in dispensing. Any type of
closure can be
used with the container that allows for the dispensing of the composition.
Examples of
closures include, but are not limited to, push pull, flip top, spout, valve,
or pump type. These
allow for easy dispensing. These types can provide for a flow rate of at least
1 ml/sec. (as
measured by volume dispensed over time). The closure opening diameter can be
adjusted as
desired for product viscosity.
[0075] Transmittance refers to the amount of light that can be transmitted.
through an
object as a fraction of the incident light. The longer the path length, the
more the light
intensity detectable on the side opposite the incident light is attenuated.
Transmittance can be
19
CA 02649407 2011-01-20
62301-2770
TM
measured using a Shimadzu UV-160U instrument according to the manufacturer's
instructions. A sample to be measured is placed in a 1 cm cuvette and placed
in the machine.
The wavelength of light used is 720 nm. Transmittance is read directly from
the instrument as
% transmittance.
TM
[0076] Surface gloss is measured by using a Gardner Micro TRI Gloss Meter by
following
the instructions given for operating the instrument at 60 . For transparent or
translucent
surfaces a nonreflective black backing is placed under the sample so that
transmitted light
does not contribute to the gloss measurement.
TM
[0077] Measurements of lightness, chroma, and hue angle are done with an X-
Rite SP60
Sphere Spectrophotometer with 4 mm aperture. For transparent or translucent
liquids, the
instrument is placed in its stand fitted with a holder for a rectangular,
10mm, Stama glass
colorimeter cell. The Starna cell is filled with the sample, the cap placed on
top and the cell
placed in the holder. The sphere spectrophotometer is triggered to initiate
the measurement.
Although this method does not give the same results as transmission color
measurements, the
measurements are correct relative to other measures done by this method so
that comparisons
of chroma, hue angle and lightness can be done. Therefore, to measure solid
samples (such as
packaging materials) a sample of the material is cut to fit in the Starna cell
and the
measurement is done in the same way after placing the sample in the cell.
Measurements are
done under conditions of the 10 observer and fluorescent light. Optionally,
other light
sources, such as incandescent or sunlight, can be used if it is desired to
optimize the viewing
of the composition under those light sources. For standardized measurements,
fluorescent
lighting is used.
[0078] The following example illustrates a composition of the invention.
Unless
otherwise specified, all percentages are by weight. The exemplified
composition is
illustrative only and does no limit the scope of the invention. Unless
otherwise specified, the
proportions in the examples and elsewhere in the specification are by active
weight. The
active weight of a material is the weight of the material itself excluding
water or other
materials that may be present in the supplied form of the material.
CA 02649407 2008-10-15
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Table 1
Material wt/wt %
Water QS
C12-15 Alcohol EO 1.3:1 Ammonium Sulfate 12.2
Mg Dodecyl Benzene Sulfonate 9.3
Lauramido ro yldimethylamine oxide 4.3
Na Dodecyl Benzene Sulfonate 3.9
Ethanol 3.5
Sodium Xylene Sulfonate (40%) 2.0
Myristainido ro ylamine oxide 1.4
Fragrance 0.5
FD&C Green No. 3, C142053 Dye 0.02
Gellan Gum 0.125
Pentasodium Pentetate 0.13
DMDM Hydantoin 0.12
LIPOSHERETM 0258 spheres (blue) 0.5
TOTAL 100
% Transmittance at least 15%
21
