Note: Descriptions are shown in the official language in which they were submitted.
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W O96/18717 PCTrUS95/15920
MICROEMULSION LIGHlr DU~Y LIQUID CLEANING COMPOSITIONS
Field of Invention
This invention relates to a iight duty liquid cleaning composition which imparts5 mildness to the skin and is in the form of a microemulsion designed in particular for
cleaning hard surfaces and which is effective in removing grease soil and/or bath soil
and in leaving unrinsed surfaces with a shiny appearance.
B~ckground of the Invention
In recent years all-purpose liquid detergents have become widely accepted for
10 cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls,
bathtubs, linoleum or tile floors, washable wall paper, etc.. Such all-purpose liquids
comprise clear and opaque aqueous mixtures of water-soluble organic detergents and
water-soluble detergent builder salts. In order to achieve comparable cleaning
efficiency with granular or powdered all-purpose cleaning compositions, use of water-
15 soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids.
For example, such early phosphate-containing compositions are described in U.S.
Patent Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No. 1,223,739.
In view of the environmentalist's efforts to reduce phosphate levels in ground
water, improved all-purpose liquids containing reduced concentrations of inorganic
20 phosphate builder salts or non-phosphate builder salts have appeared. A particularly
useful self-opacified liquid of the latter type is described in U.S. Patent No. 4,244,840.
However, these prior art all-purpose liquid detergents containing detergent
builder salts or other equivalent tend to leave films, spots or streaks on cleaned
unrinsed surfaces, particularly shiny surfaces. Thus, such liquids require thorough
25 rinsing of the cleaned surfaces which is a time-consuming chore for the user.In order to overcome the foregoing disadvantage of the prior art all-purpose
liquid, U.S. Patent No. 4,017,409 teaches that a mixture of paraffin sulfonate and a
reduced concentration of inorganic phosphate builder salt should be employed.
However, such compositions are not completely acceptable from an environmental
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point of view based upon the phosphate content. On the other hand, another
alternative to achieving phosphate-free all-purpose liquids has been to use a major
proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol
ether solvent and organic amine as shown in U.S. Patent NO. 3,935,130. Again, this
approach has not been completely satisfactory and the high levels of organic
detergents necessary to achieve cleaning cause foaming which, in turn, leads to the
need for thorough rinsing which has been found to be undesirable to today's
consumers.
Another approach to formulating hard surface or all-purpose liquid detergent
10 composition where product homogeneity and clarity are important considerations
involves the formation of oil-in-water (o/w) microemulsions which contain one or more
surface-active detergent compounds, a water-immiscible solvent (typically a
hydrocarbon solvent), water and a "cosurfactant" compound which provides productstability. By definition, an o/w microemulsion is a spontaneously forming colloidal
15 dispersion of "oil" phase particles having a particle size in the range of about 25 to
about 800 A in a continuous aqueous phase.
In view of the extremely fine particle size of the dispersed oil phase particles,
microemulsions are transparent to light and are clear and usually highly stable against
phase separation.
Patent disclosures relating to use of grease-removal solvents in o/w
microemulsions include, for example, European Patent Applications EP 0137615 andEP 0137616 - Herbots et al; European Patent Application EP 0160762 - Johnston et al;
and U.S. Patent No. 4,561,991 - Herbots et al. Each of these patent disclosures also
teaches using at least 5% by weight of grease-removal solvent.
It also is known from British Patent Application GB 21 44763A to Herbots et al,
published March 13, 1985, that magnesium salts enhance grease-removal performance
of organic grease-removal solvents, such as the terpenes, in o/w microemulsion liquid
detergent compositions. The compositions of this invention described by Herbots et al.
require at least 5% of the mixture of grease-removal solvent and magnesium salt and
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preferably at least 5O/o of solvent (which may be a mixture of water-immiscible non-polar
solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium
salt.
However, since the amount of water immiscible and sparingly soluble
5 components which can be present in an o/w microemulsion, with low total activeingredients without impairing the stability of the microemulsion is rather limited (for
example, up to about 18% by weight of the aqueous phase), the presence of such high
quantities of grease-removal solvent tend to reduce the total amount of greasy or oily
soils which can be taken up by and into the microemulsion without causing phase
10 separation.
The following representative prior art patents also relate to liquid detergent
cleaning compositions in the form of o/w microemulsions: U.S. Patents Nos.. 4,472,291
- Rosario; 4,540,448 - Gauteer et al; 3,723,330 - Sheflin; etc.
Liquid detergent compositions which include terpenes, such as d-limonene, or
other grease-removal solvent, although not disclosed to be in the form of o/w
microemulsions, are the subject matter of the following representative patent
documents: European Patent Application 0080749; British Patent Specification
1,603,047; 4,414,128; and 4,540,505. For example, U.S. Patent No. 4,414,128 broadly
discloses an aqueous liquid detergent composition characterized by, by weight:
(a) from about 1% to about 20% of a synthetic anionic, nonionic, amphoteric
or zwitterionic surfactant or mixture thereof;
(b) from about 0.5% to about 10% of a mono- or sesquiterpene or mixture
thereof, at a weight ratio of (a):(b) Iying in the range of 5:1 to 1:3; and
(c ) from about 0.5% about 10% of a polar solvent having a solubility in water
at 1 5~C in the range of from about 0.2% to about 10%. Other ingredients present in the
formulations disclosed in this patent include from about 0.05% to about 2% by weight of
an alkali metal, ammonium or alkanolammonium soap of a C1 3-C24 fatty acid; a
calcium sequestrant from about 0.5% to about 13% by weight; non-aqueous solvent,e.g., alcohols and glycol ethers, up to about 10% by weight; and hydrotropes, e.g.,
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urea, ethanolamines, salts of lower alkylaryl sulfonates, up to about 10% by weight. All
of the formulations shown in the Examples of this patent include relatively large
amounts of detergent builder salts which are detrimental to surface shine.
U.S. Patent 5,082,584 discloses a microemulsion composition having an anionic
5 surfactant, a cosurfactant, nonionic surfactant, perfume and water; however, these
compositions are not light duty liquid compositions.
The present invention relates to novel microemulsion light duty liquid detergentcompositions with high foaming properties, containing a nonionic surfactant, a sulfonate
surfactant, a betaine surfactant, and an ethoxylated alkyl ether sulfate surfactant.
Nonionic surfactants are in general chemically inert and stable toward pH
change and are therefore well suited for mixing and formulation with other materials.
The superior performance of nonionic surfactants on the removal of oily soil is well
recognized. Nonionic surfactants are also known to be mild to human skin. However,
as a class, nonionic surfactants are known to be low or moderate foamers.
15 Consequently, for detergents which require copious and stable foam, the application of
nonionic surfactants is limited. There have been substantial interest and efforts to
develop a high foaming detergent with nonionic surfactants as the major active
ingredient. Yet, little has been achieved.
The prior art is replete with light duty liquid detergent compositions containing
20 nonionic surfactants in combination with anionic and/or betaine surfactants wherein the
nonionic detergent is not the major active surfactant, as shown in U.S. Patent No.
3,658,985 wherein an anionic based shampoo contains a minor amount of a fatty acid
alkanolamide. U.S. Patent No. 3,769,398 discloses a betaine-based shampoo
containing minor amounts of nonionic surfactants. This patent states that the low
25 foaming properties of nonionic detergents renders its use in shampoo compositions
non-preferred. U.S. Patent No. 4,329,335 also discloses a shampoo containing a
betaine surfactant as the major ingredierlt and minor amounts of a nonionic surfactant
and of a fatty acid mono- or di-ethanolamide. U.S. Patent No. 4,259,204 discloses a
shampoo comprising 0.8-20% by weight of an anionic phosphoric acid ester and one
. .. .. .. . . ..
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additional surfactant which may be either anionic, amphoteric, or nonionic. U.S. Patent
No. 4,329,334 discloses an anionic-amphoteric based shampoo containing a major
amount of anionic surfactant and lesser amounts of a betaine and nonionic surfactants.
U.S. Patent No. 3,935,129 discloses a liquid cleaning composition based on the
5 alkali metal silicate content and containing five basic ingredients, namely, urea,
glycerin, triethanolamine, an anionic detergent and a nonionic detergent. The silicate
content determines the amount of anionic and/or nonionic detergent in the liquidcleaning composition. However, the foaming property of these detergent compositions
is not discussed therein.
U.S. Patent No. 4,129,515 discloses a heavy duty liquid detergent for launderingfabrics comprising a mixture of substantially equal amounts of anionic and nonionic
surfactants, alkanolamines and magnesium salts, and, optionally, zwitterionic
surfactants as suds modifiers.
U.S. Patent No. 4,224,195 discloses an aqueous detergent composition for
laundering socks or stockings comprising a specific group of nonionic detergents,
namely, an ethylene oxide of a secondary alcohol, a specific group of anionic
detergents, namely, a sulfuric ester salt of an ethylene oxide adduct of a secondary
alcohol, and an amphoteric surfactant which may be a betaine, wherein either theanionic or nonionic surfactant may be the major ingredient.
I he prior art also discloses detergent compositions containing all nonionic
surfactants as shown in U.S. Patent Nos. 4,154,706 and 4,329,336 wherein the
shampoo compositions contain a plurality of particular nonionic surfactants in order to
effect desirable foaming and detersive properties despite the fact that nonionicsurfactants are usually deficient in such properties.
U.S. Patent No. 4,013,787 discloses a piperazine based polymer in conditioning
and shampoo compositions which may contain all nonionic surfactant or all anionic
surfactant.
U.S. Patent 4,671,895 teaches a liquid detergent composition containing an
alcohol sulfate surfactant, a nonionic surfactant, a paraffin sulfonate surfactant, an alkyl
CA 02207683 1997-06-13
ether sulfate surfactant and water but fails to disclose an alkyl polysaccharidesurfactant. U.S. Patent No. 4,450,091 discloses high viscosity shampoo compositions
containing a blend of an amphoteric betaine surfactant, a polyoxybutylene
polyoxyethylene nonionic detergent, an anionic surfactant, a fatty acid alkanolamide
and a polyoxyalkylene glycol fatty ester. But, none of the exemplified compositions
contains an active ingredient mixture wherein the nonionic detergent is present in
major proportion, probably due to the low foaming properties of the polyoxybutylene
polyoxyethylene nonionic detergent. U.S. Patent No. 4,~95,526 describes a
composition comprisin~ a nonionic surfactant, a betaine surfactant, an anionic
surfactant and a C12-C14 fatty acid monethanolamide foam stabilizer. U.S. Patent5,082,584 teaches a low foaming microemulsion used to clean hard surfaces.
However, none of the above-cited patents discloses a microemulsion foaming, liquid
detergent composition containing a nonionic surfactant, a supplementary high
foaming anionic sulfonate surfactant, a betaine surfactant, and an ethoxylated alkyl
ether sulfate surfactant and a water insoluble hydrocarbon or perfume as the essential
ingredients and optionally an alkyl monoalkanol amide such as an alkanol
monoethanol amide (LMMEA), and the composition does not contain any abrasives,
silicas, alkaline earth metal carbonates, alkyl glycine surfactant, cyclic imidinium
surfactant, alkali metal carbonates or more than 3 wt. % of a fatty acid or its salt
thereof.
Summary of the Invention
It has now been found that a microemulsion light duty liquid detergent can be
formulated with a nonionic surfactant which has desirable cleaning properties,
mildness to the human skin. An object of this invention is to provide a novel
microemulsion light duty liquid detergent composition containing a nonionic
surfactant, a betaine surfactant, a sulfate or sulfonate anionic surfactant and an
ethoxylated alkyl ether sulfate surfactant and optionally an alkyl monoalkanol amide,
wherein the composition does not contain any silicas, abrasives, alkali metal
carbonates, alkaline earth metal carbonates, alkyl glycine
AMENDED S~!EET
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surfactant, cyclic imidinium surfactant, or more than 3 wt. % of a fatty acid or salt
thereof.
Another object of this invention is to provide a novel microemulsion light duty
liquid detergent with desirable high foaming and cleaning properties which is mild to the
5 human skin.
Additional objects, advantages and novel features of the invention will be set
forth in part in the description which follows, and in part will become apparent to those
skilled in the art upon examination of the following or may be learned by practice of the
invention. The objects and advantages of the invention may be realized and attained
10 by means of the instrumentalities and combinations particularly pointed out in the
appended claims.
To achieve the foregoing and other objects and in accordance with the purpose ofthe present invention, as embodied and broadly described herein the novel, high foaming
microemulsion light duty liquid detergent of this invention comprises four essential
15 surfactants: a water soluble, ethoxylated, nonionic surfactant, a betaine surfactant, an
ethoxylated alkyl ether sulfate surfactant and a sulfonate anionic surfactant as well as a
cosurfactant, a hydrocarbon and water, wherein the composition does not contain any
amine oxide, HEDTA, fatty acid alkanolamides, silicas, abrasives, alkali metal carbonates,
alkaline earth metal carbonates, alkyl glycine surfactant, cyclic imidinium surfactant or
20 more than 3 wt. % of a fatty acid or salt thereof.
Detailed Description of the Invention
The microemulsion light duty liquid compositions of the instant invention
comprise approximately by weight:
(a) 14% to 24% of an alkali metal salt of a C12 18 paraffin sulfonate;
(b) 2% to 6% of an alkali metal salt of a Cg 1 8 ethoxylated alkyl ether sulfate;
(c) 2% to 8% of a betaine surfactant;
(d) 4% to 12% of a nonionic surfactant;
(e) 1% to 10% of at least one solubilizing agent;
ff) 1% to 14% of at least one cosurfactant;
_ _ _ _
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(g) 0 to 10% of a supplemental solubilizing aGent
(h) 1% to 8% of a water insoluble saturated or unsaturated organic
compound having 4 to 20 carbon atoms;
(i) 0 to 5%, more preferably 0.5% to 4.5% of an alkyl monoalkanol; and
(J) the balance being water.
The nonionic surfactant is present in amounts of about 4 to 12%, preferàbly 4%
to 10% by weight of the composition and provides superior performance in the
removal of oily soil and mildness to human skin.
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 PLURAFACSrM (BASF) and
condensates of ethylene oxide with sorbitan fatty acid esters such as the TWEENSrM
(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 acarboxy, 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. The nonionic detergent 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
AM~NDED S~IEET
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per mole of alcohol and tallow alcohol ethoxylates conta;nin~ 6 .~0 to 11 EO pet mole
of alcohol.
A preferred group of the foregoing nonionic surfactants are the NEODOLrM
ethoxylates (Shell Co.), which are higher aliphatic, primary alcohol containing about
9-15 carbon atoms, such as Cg-C1 1 alkanol condensed with 7 to 10 moles of
ethylene oxide (NEODOLlM 91-8), C12 13 alkanol condensed with 6.5 moles ethyleneoxide (NEODOLTM 23-6.5), C12 15 alkanol condensed with 12 moles ethylene oxide
(NEODOLrM 25-12), C14 15 alkanol condensed with 13 moles ethylene oxide
(NeodolrM 45-13), and the like. Such ethoxamers have an HLB (hydrophobic
lipophilic balance) value of about 8 to 15 and give good O/W emulsification, whereas
ethoxamers with HLB values below 8 contain less than 5 ethyleneoxide groups and
tend to be poor emulsifiers and poor detergents.
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 C1 1 -C1s secondary alkanol condensed with either 9 EO
(TERGITOLrM 1 5-S-9) or 12 EO (TERGITOLTM 1 5-S-12) marketed by Union Carbide.
Other suitable nonionic detergents 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 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 includeIGEPAL'M C0-630 (nonyl phenol ethoxylate) marketed by GAF Corporation. Also
among the satisfactory nonionic detergents are the water-soluble condensation
products of a Cg-C20 alkanol with a heteric mixture of ethylene oxide and propylene
oxide wherein the weight ratio of ethylene oxide to propylene oxide is from
AME~!DED SHE-~T
~ CA 02207683 1997-06-13
2.5:1 to 4:1, preferably 2.8:1 to 3.3:1, with the total of th~ ett~léne oxidG a~d propyle.,e
oxide (including the terminal ethanol or propanol group) being from 60-85%,
preferably 70-80%, by weight. Such detergents are commercially available from
BASF-Wyandotte and a particularly preferred detergent is a C10-C16 alkanol
condensate with ethylene oxide and propylene oxide, the weight ratio of ethyleneoxide to propylene oxide being 3:1 and the total alkoxy content being about 75~/O by
weight. Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-
C1 0-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 suffactants are
well known and are available from Imperial Chemical Industries under the Tween
trade name. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate,
polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate
and polyoxyethylene (20) sorbitan tristearate.
Other suitable water-soluble nonionic detergents are marketed under the trade
name "Pluronics." 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. The anionic
sulfonate surfactants used in the detergent of this invention are water soluble and
include the sodium, potassium, ammonium and ethanolammonium salts of linear Cg-
C16 alkyl benzene sulfonates; C10-c2o paraffin sulfonates, alpha olefin sulfonates
containing about 10-24 carbon atoms. The preferred anionic sulfonate surfactant is a
C12 18 paraffin sulfonate
AMEND~D SHEET
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W O96/18717 PCTrUS95115920
present in the composition at a concentration of about 14% to 24 wt. %, more preferably
15% to 22%.
The paraffin sulfonates may be monosulfonates or di-sulfonates and usually are
mixtures thereof, obtained by sulfonating paraffins of 10 to 20 carbon atoms. Preferred
paraffin sulfonates are those of C12-18 carbon atoms chains, and more preferably they
are of C1 4-17 chains. Paraffin sulfonates that have the sulfonate group(s) distributed
along the paraffin chain are described in U.S. Patents 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 C1 4-1 7 range
10 will be minor and will be minimized, as will be any contents of di- or poly-sulfonates.
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 Cg 15 alkyl toluene sulfonates. A preferred
15 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
20 position is correspondingly low. Preferred materials are set forth in U.S. Patent
3,320,174, especially those in which the alkyls are of 10 to 13 carbon atoms.
The Cg 1 8 ethoxylated alkyl ether sulfate surfactants have the structure
+
R-(OCHCH2)nOS03M
wherein n is about 1 to about 22 more preferably 1 to 3 and R is an alkyl group having
about 8 to about 18 carbon atoms, more preferably 12 to 15 and natural cuts, for
example, C12-14; C12-15 and M is an ammonium cation or a metal cation, most
preferably sodium. The ethoxylated alkyl ether sulfate is present in the composition at a
concentration of about 2.0 to about 5.0 wt. %, more preferably about 2.5% to 4.5 wt. %.
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12
The ethoxylated alkyl ether sulfate may be made by sulfating the condensation
product of ethylene oxide and Cg 1 o 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
5 mole of such alcohol. Preferred ethoxylated alkyl ether polyethenoxy sulfates contain
12 to 15 carbon atoms in the alcohols and in the alkyl groups thereof, e.g., sodium
myristyl (3 EO) sulfate.
Ethoxylated Cg 1 8 alkylphenyl ether sulfates containing from 2 to 6 moles of
ethylene oxide in the molecule are also suitable for use in the invention compositions.
10 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. The
concentration of the ethoxylated alkyl ether sulfate surfactant is about 1 to about 8 wt.
%.
The water-soluble zwitterionic surfactant (betaine), which is also an essential
15 ingredient of present microemulsion light duty liquid detergent composition, constitutes
about 2% to 8%, preferably 3% to 6%, by weight and provides good foaming proper~es
and mildness to the present nonionic based liquid detergent. The zwitterionic surfactant
is a water soluble betaine having the general formula:
R2
+
R1 - N - R4X
R3
wherein X~ is selected from the group consisting of SO3- and CO2- and R1 is an alkyl
group having 10 to about 20 carbon atoms, preferably 12 to 16 carbon atoms, or the
amido radical:
O H
R -C - N - (CH2)a ~
wherein R is an alkyl group having about 9 to 19 carbon atoms and a 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,
CA 02207683 1997-06-13
13 , ,
optionally, one hydroxyl group. Typical alkyldimethyl betaines ir~ de der:yl 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 dimethylbetaine, lauryl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine, etc.
The amidobetaines similarly include cocoamidoethylbetaine, cocoamidopropyl
dimethyl betaine and the like. A preferred betaine is coco (~g-C18) amidopropyl
dimethyl betaine.
The role of the water insoluble hydrocarbon in the instant microemulsion light
duty liquid formula is performed by an aliphatic hydrocarbon having 8 to 20 carbon
atoms, terpineol, d or limonene, dipentene, an essential oil or a perfume and mixtures
thereof at a concentration range of about 1.0 wt. % to about 8.0 wt. %, more preferably
about 2.0 wt. % to about 7.0 wt. %.
Suitable essential oils are selected from the group consisting of:
Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam
(Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose
(Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic
technical, Cananga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil
(China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove
leaf, Coriander (Russia), Coumarin 69~C (China), Cyclamen Aldehyde, Diphenyl
oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil,
Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit pil, Guaiacwood oil,
Gurjun balsam, Heliotropin, Isobornyl acetate, Isolongifolene, Juniper berry oil, L-
methyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oil distilled, Litsea
Cubeba oil, Longifolene, Menthol crystals, Methyl cedryl ketone, Methyl chavicol,
Methyl salicylate, Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil,
Patchouli oil, Peppermint oil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil,
Rosalin, Sandalwood oil, Sandenol, Sage oil, Clary sage, Sassafras oil, Spearmint
oil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java), Wintergreen.
The instant compositions contain about 1 wt. % to about 10 wt. %, more
preferably about 1 wt. % to about 8 wt. %, of at least one solubilizing agent which is a
A~lENDED SHEET
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W O96/18717 PCTrUS95/15920
14
C2 4 mono or dihydroxy alkanols such as ethanol, isopropanol and propylene glycol
and mixtures thereof. The solubilizing agents are included in order to control low
temperature cloud clear properties. Urea can be optionally employed in the instant
composition as a supplemental solubilizing agent at a concentration of 0 to about 10 wt.
5 %, more preferably about 0.5 wt. % to about 8 wt. %.
The cosurfactant may play an essential role in the formation of the dilute o/w
microemulsion and the concentrated microemulsion compositions. Very briefly, in the
absence of the cosurfactant the water, detergent(s) and hydrocarbon (e.g., perfume)
will, when mixed in appropriate proportions form either a micellar solution (low10 concentration) or form an oil-in-water emulsion in the first aspect of the invention. With
the cosurfactant added to this system, the interfacial tension at the interface between
the emulsion droplets and aqueous phase is reduced to a very low value. This
reduction of the interfacial tension results in spontaneous break-up of the emulsion
droplets to consecutively smaller aggregates until the state of a transparent colloidal
15 sized emulsion. e.g., a microemulsion, is formed. In the state of a microemulsion,
thermodynamic factors come into balance with varying degrees of stability related to the
total free energy of the microemulsion. Some of the thermodynamic factors involved in
determining the total free energy of the system are (1 ) particle-particle potential; (2)
interfacial tension or free energy (stretching and bendlng); (3) droplet dispersion
20 entropy; and (4) chemical potential changes upon formation. A thermodynamically
stable system is achieved when (2) interfacial tension or free energy is minimized and
(3) droplet dispersion entropy is maximized.
Thus, the role of cosurfactant in formation of a stable o/w microemulsion is to (a)
decrease interfacial tension (2); and (b) modify the microemulsion structure and25 increase the number of possible configurations (3). Also, the cosurfactant will (c)
decrease the rigidity. Generally, an increase in cosurfactant concentration results in a
wider temperature range of the stability of the product.
The major class of compounds found to provide highly suitable cosurfactants for
the microemulsion over temperature ranges extending from 5~C to 43~C for instance
CA 02207683 1997-06-13
are glycerol, ethylene glycol, water-soluble polyethylene glyoolc having a nolecular
weight of 300 to 1000, polypropylene glycol of the formula HO(CH3CHCH2O)nH
wherein n is a number from 2 to 18, mixtures of polyethylene glycol and polypropylene
glycol (SYNALOX)TM and mono and di C1-c6 alkyl ethers and esters of ethylene
glycol and propylene glycol having the structural formulas R(X)nOH, R1 (X)nOH,
R(X)nOR and R1 (X)nOR1wherein R is C1-C6 alkyl group, R1 is C2-C4 acyl group, X is
(OCH2CH2) or (OCH2(CH3)CH) and n is a number from 1 to 4, diethylene glycol,
triethylene glycol, an alkyl lactate, wherein the alkyl group has 1 to 6 carbon atoms,
1 methoxy-2 propanol, 1 methoxy-3-propanol, and 1 methoxy 2-, 3- or 4-butanol.
Representative members of the polypropylene glycol include dipropylene
glycol and polypropylene glycol having a molecular weight of 150 to 1000, e.g.,
polypropylene glycol 400. Other satisfactory glycol ethers are ethylene glycol
monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol),
triethylene glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether,
tetraethylene glycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether,
propylene glycol monomethyl ether, ethylene glycol monohexyl ether, diethylene
glycol monohexyl ether, propylene glycol tertiary butyl ether, ethylene glycol
monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl
ether, ethylene glycol monopentyl ether, diethylene glycol monomethyl ether,
diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene
glycol monopentyl ether, triethylene glycol monomethyl ether, triethylene glycolmonoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monopentyl
ether, triethylene glycol monohexyl ether, mono, di, tripropylene glycol monoethyl
ether, mono, di tripropylene glycol monopropyl ether, mono, di, tripropylene glycol
monopentyl ether, mono, di, tripropylene glycol monohexyl ether, mono, di, tributylene
glycol mono methyl ether, mono, di, tributylene glycol monoethyl ether, mono, di,
tributylene glycol monopropyl ether, mono, di, tributylene glycol monobutyl ether,
mono, di, tributylene glycol monopentyl ether and mono, di, tributylene glycol
monohexyl ether, ethylene glycol monoacetate and dipropylene glycol propionate.
When these glycol type cosurfactants are at a concentartion of about 1.0 to
Al\IENDED SHEET
CA 022076X3 l997-06-l3
16
about 14 weight %, more preferably about 2.0 weight % io aoout: 1 G weight % ir.combination with a water insoluble hydrocarbon which is at a concentration of at least
0.5 weight %, more preferably 1.5 weight % one can form a microemulsion
composition.
While all of the aforementioned glycol ether compounds provide the described
stability, the most preferred cosurfactant compounds of each type, on the basis of cost
and cosmetic appearance (particularly odor), are dipropylene glycol monomethyl
ether and diethylene glycol monobutyl ether.
The amount of cosurfactant required to stabilize the microemulsion
compositions will, of course, depend on such factors as the surface tension
characteristics of the cosurfactant, the type and amounts of the primary surfactants and
water insoluble hydrocarbon, and the type and amounts of any other additional
ingredients which may be present in the composition and which have an influence on
the thermodynamic factors enumerated above. Amounts of cosurfactant in the rangeof from 1% to 14%, preferably from about 2 wt. % to 10 wt. % provide stable dilute o/w
microemulsions for the above-described levels of primary surfactants and water
insoluble hydrocarbon and any other additional ingredients as described below.
The ability to formulate mild, acid or neutral products without builders which
have grease removal capacities is a feature of the present invention because the prior
art o/w microemulsion formulations most usually are highly alkaline or highly built or
both.
The instant microemulsion formulas explicitly exclude alkali metal silicates andalkali metal builders such as alkali metal polyphosphates, alkali metal carbonates,
alkali metal phosphonates and alkali metal citrates because these materials, if used in
the instant composition, would cause the composition to have a high pH as well as
leaving residue on the surface being cleaned.
The final essential ingredient in the inventive microemulsion compositions
having improved interfacial tension properties is water. The proportion of water in the
microemulsion compositions generally is in the range of 35% to 65%, preferably 40%
to 60% by weight of the usual diluted o/w microemulsion composition.
A~lE~DED SltEET
CA 02207683 1997-06-13
17
. .
In final form, the instant compositions exhibit sta~ility ~t r~c~uce~ ann increase~
temperatures. More specifically, such compositions remain clear and stable in the
range of 5~C to 50~C, especially 10~C to 43~C. Such compositions exhibit a pH of 5 to
8. The liquid microemulsion compositions are readily pourable and exhibit a viscosity
in the range of 6 to 300 milliPascal . second (mPas.) as measured at 25~C. with a
Brookfield RVT Viscometer using a #1 spindle rotating at 20 RPM. Preferably, theviscosity is maintained in the range of 10 to 200 mPas.
The following examples illustrate liquid cleaning compositions of the described
invention. Unless otherwise specified, all percentages are by weight. The
exemplified compositions are illustrative only and do not limit the scope of theinvention. Unless otherwise specified, the proportions in the examples and elsewhere
in the specification are by weight.
Example 1
The following compositions in ~t. % were prepared by simple mixing
procedure:
A B C D E F G H
C1416Paraffirsulfonatesodiumsalt 14 14 14 14 14 14 14 14
C13 14 AEOS 2:1 EO 3 3 3 3 3 3 3 3
C 1 2 1 4 A kyl be-aine - - - - - - - -
Cocoamico propyl dimethyl betaine 5 5 5 5 5 5 5
NonionicCg 11 7.5-8 EO 12 12 1~ 12 12 12 12 12
Ethanol 3.3 3 ~ 4.~ ,. 3 3 3 ~ 3 3 3 9
Urea 2.4 2.~ 2.~ 2.4 2.4 2.~ 2.4 2.4
Terpineol 5 - 8 6 8 8 8 8
_imonene - 5
-;opropanol - - - - 2 - 4 2
-~EGI~/ BE
EG ~00
~PM 6 6 6 7 6 6 6
Propylene ~Iycol
Minors 1 1 - 1 -
Water 4 .3 4 .3 4~.3 45.6 43.3 4 .3 41.3 4 .7
Appearance @ RT t'K O ~ C ~ O ~ O ~ C ~ OK OK
Appearaloe@4C L,~ 0~ O~ 0~ O~ 0~ OK OK
ook ec 1 0 7~ ') 3~ .~ 50
ash o rt (~C) ~ 41 46
~liveoilemulsificationspeed(insec.)130 100 ~ 105 ~6 110
uds titration 4.4 4.1 5. 4.8 5.~ 5.8
A~)IENDED SHEET
CA 02207683 1997-06-13
18
J K L M N O P Q
C1416Paraffinsulfonate 14 14 17.3 17.3 17.3 17.3 17.3 20.6 20.6
sodium salt
C13 14 AEOS 2:1 EO 3 3 3.7 3.7 3.7 3.7 3.7 4.4 4.4
C12 14 Alkyl betaine - - -
Cocoamido propyl dimethyl 5 5 5 5 5 5 5 5 5
betaine
Nonionic Cg 1 1 7.5 - 8 EO 12 1 ' 8 8 8 8 8 4 4
Ethanol 3.~ 3. 3.6 3.6 3.9 3.6 3.3 3.6 3.9
Urea 2.' 2.~ 2.4 2.4 2.4 2.4 5 2.4 2.4
Terpineol 5 5 5 5 5 5 5 5 5
_imonene - - - - - - - - -
;oprooanol - - 2 4 2 - -- - 2
~EG~ BE
EG ~00
-~PM 6 6 6 6 6 6 ~ 6
ropylene glycol
linors
/Vater 48.3 4 4 44 4 .7 46 4 .7 4 4 .7
Appearance @ RT O C O C O C O ~ O C O IC O C O C O C
- Appearalce@4C (:!C OC O< O~ OC OC GC O~ O~
Brookfie d 1 .0 5 ~ 3 3
Flash Pont (~C) ~ 4
Olive oil emulsification speed (in130 J '. 120 - 15 120 110 10.
sec.)
Suds titration 4.4 4.3 5.6 5.4 6.1 5.9
R S T U V W X Y Z
C14-16 Paraffin sulfonate 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3 17.3
sodium salt
C13 14AEOS 2:1 EO 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7
C12 14 Alkyl betaine - - - - 5 5 - 4 4
Cocoamido propyl dimethyl 5 5 5 5 - - 5
betaine
Nonionic Cg-11 7.5 - 8 EO 8 8 8 8 8 8 9 9
Ethanol 3.3 3.3 3.3 3.3 3.3 3.3 3 3
Urea 5 5 - 2.4 5 7 5
Terpineol 5 5 5 5 5 5 5
. imonene
;opropanol
~EG~ BE - - - - 8 5.6
EG ~00
~PM 6 6 6 6 6 6 6 6 6
ropylene glycol
~inors 1 1 1 - 1 1 1 1 1
~Nater 4~ 4 45.7 4 .7 42.7 42.7 45.7 43.7 44.7
Appearance@ RT OC OC OC OC OK OK O~ OC OK
A.ppearalce@4C OC OC OC OC OK OK O~. O ' OK
rookfie d 1~ 0 : 3
lash Po nt (~C)
~)liveoil emulsification speed (in146 140 120 1 20 1 20
sec.)
Suds titration 16 5.2
A!~,EI''DED SHE-~T
i CA 02207683 1997-06-13
19
Fxample ?
The following compositions in wt. % were prepared by simple mixing
procedu re:
A B C D E F G H
C14 16 Paraffin sulfonate sodium salt 17.317.3 17.3 17.317.3 17.3 17.3 17.3
C13 14 AEOS 2:1 EO 3.7 3 7 3.7 3 7 3 7 3 7 3 7 3 7
C12 14 Akyl betaine
Cocoamico propyl dimethyl betaine 5
\onionic ~9-11 7.5 - 8 EO ~ ~ , 6
_ ~MEA
_thanol
Urea
T ~rpineol
Lmonene 5 - - - - - 4
A pha Pinene - - 4
Beta Pinene - - - 4
Isobornyl Acetate - - - - 4
henoxyethanol - - - - - - - 4
soprc~anol
-~EG~ BE
EG ~00 2
~PM 4 5 6 6 6 6 6 6
ropylene glycol
~inors
~Vater 4 4 4 4 49 4 4 4
Appearance @ RT o~ o~ oc o~ ok o~ o~ o~
Appeara~lce @ 4C o~ o~ o~ ha :y o~ o~
Brookfie d 8~ 70 1~0 ~ 7~ 50 ~ 70
lash Pont (~C) - - 4 .54 .5 , o - , , 90
Olive oil emulsification speed (in sec.) - - 6 2 5 64 5 84
udstitration - - 5.9 ~.4 5.~ 4.8 5.3
AMFNDFD S~ T
CA 02207683 1997-06-13
J K L M
C14 16 Paraffinsulfonatesodiumsalt17.317.317.3 17.3 17.3
C13 14 AEOS 2:1 EO 3.7 3.7 3.7 3.7 3.7
C12 14 Alkyl betaine
Cocoamido propyl dimethyl betaine 5 5 5 5
Nonionic Cg 11 7.5 -8 EO 6 6 6 6
LMMEA
Ethanol - - - -
Urea
Terpineol
Limonene
Benzyla cohol 4
Isonony acetate - 4
Terpino ene - - 4
Dicyclopentadienylacetate - - - 4
Benzylacetate - - - - 4
,opropanol
~EG~ BE
EG ~oo
~PM 6 6 6 6 6
ropylene glycol
~inors
~/ater 4 49 4 4, 4
Appearance @ RT o < ok o < o ~ o <
Appeara lce @ 4C o < h -y o ~ o < o <
Brookfie d 5 ~ _ 7~ - -
Flash Pont(~C) > 0 6
Olive oil emulsification speed (in sec.) 8 ~ 6 60 66
Suds titration
AMEND~9 SffE-tT
