BACKGROUND OF THE INVENTION
[0001] 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 gums 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.
[0002] 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.
[0003] 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.
[0004] Even further, adding materials such as beads and structure to an otherwise un-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.
[0005] 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.
[0006] US-B-6,362,156 discloses a pourable transparent/translucent liquid detergent composition with suspended
particles.
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 mPas as measured at 25°C;
- c) the liquid portion has a transmittance, as measured by visible spectroscopy, of
at least 15%;
- d) the suspended material has a particle size of 100 to 2500 microns;
- e) the liquid portion has a hue that is not a complementary hue to more than 50% of
the suspended material; and
- f) the liquid portion has a chroma that is different from more than 50% of the suspended
material.
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 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, 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 ΔECMC 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] The liquid portion has a hue that is not a complementary hue to more than 50% of
the suspended material and, in one embodiment, it is desired to have a 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 to be different from the chroma
of at least a portion of the suspended material. In the present invention, the liquid
portion has a chroma that is different from more than 50% 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.
[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 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 CARBOPOL™ Aqua 30. The CARBOPOL™ resins, also known as CARBOMER™, 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; CARBOPOL™ 940 with a molecular weight of approximately
4,000,000 and CARBOPOL™ 934 with a molecular weight of approximately 3,000,000. The
CARBOPOL™ 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.
LIQUID VISCOSITY
[0028] The composition has a viscosity that allows the composition to be pourable, which
is usually below 10,000 mPas. 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 C
8-C
22 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-C
2-C
3 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 C
8-C
16 alkyl benzene sulfonates, alkyl ether carboxylates, C
10-C
20 paraffin sulfonates, C
8-C
25 alpha olefin sulfonates, C
8-C
18 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
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 HOSTAPUR™ SAS30, SAS 60, SAS 93 secondary alkane sulfonates from
Clariant, and BIO-TERGE™ 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 C
10-C
16 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 C
12-C
13 pareth sulfate with 2 moles of ethylene oxide. An example of a pareth sulfate surfactant
is STEOL™ 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 C
8-15 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 (SO
3) with long-chain olefins containing 8 to 25, preferably 12 to 21 carbon atoms and
having the formula RCH=CHR
1 where R is a higher alkyl group of 6 to 23 carbons and R
1 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.
[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(OC
2H
4)
n OSO
3M 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, C
12-14 or C
12-16 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 C
8-18 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 C
8-18 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 C
9-C
15 alkyl ether polyethenoxyl carboxylates having the structural formula R(OC
2H
4)
nOX COOH wherein n is a number from 4 to 12, preferably 6 to 11 and X is selected from
the group consisting of CH
2, C(O)R
1 and

wherein R
1 is a C
1-C
3 alkylene group. Types of these compounds includes but are not limited to, C
9-C
11 alkyl ether polyethenoxy (7-9) C(O) CH
2CH
2COOH, C
13-C
15 alkyl ether polyethenoxy (7-9)

and C
10-C
12 alkyl ether polyethenoxy (5-7) CH
2COOH. These compounds may be prepared by condensing ethylene oxide with appropriate
alkanol and reacting this reaction product with
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:

wherein R
1 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; R
2 and R
3 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:

wherein R
1 is a C
12-18 alkyl and R
2 and R
3 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:

wherein R
1 is a saturated or unsaturated alkyl group having about 6 to about 24 carbon atoms,
R
2 is a methyl group, and R
3 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 PLURAFAC™ surfactants (BASF) and condensates of ethylene
oxide with sorbitan fatty acid esters such as the TWEEN™ 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 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 NEODOL™ ethoxylates (Shell Co.),
which are higher aliphatic, primary alcohol containing about 9-15 carbon atoms, such
as C
9-C
11 alkanol condensed with 2.5 to 10 moles of ethylene oxide (NEODOL™ 91-2.5 OR -5 OR
-6 OR -8), C
12-13 alkanol condensed with 6.5 moles ethylene oxide (NEODOL™ 23-6.5), C
12-15 alkanol condensed with 12 moles ethylene oxide (NEODOL™ 25-12), C
14-15 alkanol condensed with 13 moles ethylene oxide (NEODOL™ 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 (TERGITOL™ 15-S-9) or 12 EO (TERGITOL™
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 phenol and di-isoctylphenol condensed with about 15 moles
of EO per mole of phenol. Commercially available nonionic surfactants of this type
include IGEPAL™ CO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.
[0046] Also among the satisfactory nonionic surfactants are the water-soluble condensation
products of a C
8-C
20 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 C
10-C
16 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-C
10-C
20 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 TWEEN™ 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
PLURONIC™. 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
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
R
2O(C
nH
2nO)
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 (R
2OH) 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 (R
1OH) 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 (C
1-6) 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 (R
2OH) 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:
C
nH
2n+1O(C
6H
10O
5)
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.
[0057] The zwitterionic surfactant can be any zwitterionic surfactant. In one embodiment,
the zwitterionic surfactant is a water soluble betaine having the general formula

wherein X- is selected from COO- and SO
3- and R
1 is an alkyl, group having 10 to about 20 carbon atoms, or 12 to 16 carbon atoms,
or the amido radical:

wherein R is an alkyl group having about 9 to 19 carbon atoms and n is the integer
1 to 4; R
2 and R
3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R
4 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 dimethyl 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 (C
8-C
18) amidopropyl dimethyl betaine. Three examples of betaine surfactants that can be
used are EMPIGEN™ BS/CA from Albright and Wilson, REWOTERIC™ AMB 13 and Goldschmidt
Betaine L7.
[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, C
2-4 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 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 paraben/propylparaben;
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 C
1-C
3 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.
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 10 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, mm |
Min, mm |
| Side to Side |
250 |
30 |
| Front to Back |
160 |
30 |
| Height |
350 |
60 |
[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 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.
[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.
[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, Starna
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.
Table 1
| Material |
wt/wt % |
| Water |
QS |
| C12-15 Alcohol EO 1.3:1 Ammonium Sulfate |
12.2 |
| Mg Dodecyl Benzene Sulfonate |
9.3 |
| Lauramidopropyldimethylamine oxide |
4.3 |
| Na Dodecyl Benzene Sulfonate |
3.9 |
| Ethanol |
3.5 |
| Sodium Xylene Sulfonate (40%) |
2.0 |
| Myristamidopropylamine oxide |
1.4 |
| Fragrance |
0.5 |
| FD&C Green No. 3, CI42053 Dye |
0.02 |
| Gellan Gum |
0.125 |
| Pentasodium Pentetate |
0.13 |
| DMDM Hydantoin |
0.12 |
| LIPOSHERE™ 0258 spheres (blue) |
0.5 |
| TOTAL |
100 |
| % Transmittance |
at least 15% |
1. Zusammensetzung, die suspendiertes Material und einen flüssigen Anteil umfasst, der
mindestens ein Tensid umfasst, wobei
(a) das Tensid in der Zusammensetzung in einer Menge vorhanden ist, die mindestens
15 Gew.% der Zusammensetzung beträgt, bezogen auf das Wirkstoffgewicht des Tensids,
(b) die Zusammensetzung eine Viskosität von weniger als 10.000 mPas besitzt, gemessen
bei 25°C,
(c) der flüssige Anteil eine Lichtdurchlässigkeit, gemessen durch Vis-Spektroskopie,
von mindestens 15 % besitzt,
(d) das suspendierte Material eine Partikelgröße von 100 bis 2500 Mikrometer besitzt,
(e) der flüssige Anteil eine Farbe besitzt, die keine Komplementärfarbe für mehr als
50 % des suspendierten Materials ist, und
(f) der flüssige Anteil eine Farbart besitzt, die sich von der Farbart von mehr als
50 % des suspendierten Materials unterscheidet.
2. Zusammensetzung nach Anspruch 1, wobei der flüssige Anteil, mindestens ein Teil des
suspendierten Materials, oder beide eine Färbung besitzen.
3. Zusammensetzung nach Anspruch 1 oder Anspruch 2, wobei das suspendierte Material suspendiertes
Material mit mehr als einer Färbung und/oder mehr als einer Form und/oder mehr als
einer Größe umfasst.
4. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das suspendierte Material
eine Form ausgewählt aus kugelförmig, polyedrisch, würfelförmig, kastenförmig, tetraedrisch,
unregelmäßigen dreidimensionalen Formen, flachen Polygonen, Dreiecken, Rechtecken,
Quadraten, Fünfecken, Sechsecken, Achtecken, Sternen, Buchstaben, Tieren, Pflanzen,
Objekten und Autos besitzt.
5. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei mindestens ein Teil
des suspendierten Materials von einer Person visuell beobachtbar ist und gegebenenfalls
mehr als 50 % des suspendierten Materials von einer Person visuell beobachtbar sind.
6. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das suspendierte Material
in einer Menge von 0,01 bis 10 Gew.-% der Gesamtzusammensetzung vorhanden ist.
7. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei der flüssige Anteil
eine Lichtdurchlässigkeit von mindestens 95 % besitzt.
8. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei die Zusammensetzung
90 % des suspendierten Materials (a) mindestens ein Jahr bei Raumtemperatur und/oder
(b) mindestens 18 Wochen bei 40,5°C und/oder (c) mindestens 2 Wochen bei -10°C und/oder
(d) mindestens 3 Wochen bei 4,5°C suspendiert hält.
9. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei sich die Zusammensetzung
in einem Behälter befindet.
10. Zusammensetzung nach Anspruch 9, wobei der Behälter eine Farbe hat, die keine Komplementärfarbe
für mehr als 50 % des suspendierten Materials ist.
11. Zusammensetzung nach Anspruch 9 oder Anspruch 10, wobei der Behälter und der flüssige
Anteil jeweils eine Farbe haben, die keine Komplementärfarbe für mehr als 50 % des
suspendierten Materials ist.
12. Zusammensetzung nach einem der Ansprüche 9 bis 11, wobei der Behälter eine Farbart
besitzt, die sich von mehr als 50 % des suspendierten Materials unterscheidet.
13. Zusammensetzung nach einem der Ansprüche 9 bis 12, wobei der Behälter und der flüssige
Anteil jeweils eine Farbart haben, die sich von mehr als 50 % des suspendierten Masterials
unterscheidet.
14. Zusammensetzung nach einem der Ansprüche 9 bis 13, wobei der Behälter einen Glanz
von 10 bis 500 Glanzeinheiten besitzt, gemessen bei 60 Grad.