Note: Descriptions are shown in the official language in which they were submitted.
CA 02205404 1997-0~-14
W O 96/15217 PCTrUS95/14583
MICROEMULSION ALL PURPOSE LIQUID CLEANING COMPOSITIONS
Field of the Invention
This invention relates to an improved all-purpose liquid cleaner in the form of a
5 liquid crystal or 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~k~round 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 synthetic 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
15 water-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
llquid, 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
CA 0220~404 1997-0~-14
WO 96/15217 PCT/US95/14583
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 surfaced or all-purpose liquid detergent
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
dispersion of "oil" phase particles having a particle size in the range of 25 A to 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 2144763A to Herbots et al,
published March 13,1985, that magnesium salts enhance grease-removal performanceof 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
CA 02205404 1997-05-14
WO 96/1',217 PCT/US95/14583
preferably at least 5% 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 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 1% to 20% of a synthetic anionic, nonionic, amphoteric or
zwitterionic surfactant or mixture thereof;
(b) from 0.5% to 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 0.5% 10% of a polar solvent having a solubility in water at 1 5C in
the range of from 0.2% to 10%. Other ingredients present in the formulations disclosed
in this patent include from 0.05% to 2% by weight of an alkali metal, ammonium or
alkanolammonium soap of a C1 3-C24 fatty acid; a calcium sequestrant from 0.5% to
13% by weight; non-aqueous solvent, e.g., alcohols and glycol ethers, up to 10% by
weight; and hydrotropes, e.g., urea, ethanolamines, salts of lower alkylaryl sulfonates,
CA 0220~404 1997-0~-14
WO 96/15217 PCT/US95/14583
up to 10% by weight. All of the formulations shown in the Examplas of this patent
include relatively large amounts of detergent builder salts which are detrimental to
surface shine.
Furthermore, the present inventors have observed that in formulations containing5 grease-removal assisting magnesium compounds, the addition of minor amounts ofbuilder salts, such as alkali metal polyphosphates, alkali metal carbonates,
nitrilotriacetic acid salts, and so on, tends to make it more difficult to form stable
microemulsion systems.
U.S. Patent 5,082,584 discloses a microemulsion composition having an anionic
10 surfactant, a cosurfactant, nonionic surfactant, perfume and water; however, these
compositions do not possess the low ecotoxicity profile and the improved interfacial
tension properties as exhibited by the compositions of the instant invention.
British Patent No 1,453,385 discloses polyesterified nonionic surfactants similar
to the polyesterified nonionic surfactants of the instant invention. However, these
nonionic surfactants of British Patent 1,453,385 do not disclose the formula (Il) portion
of the instant composition. Additionally, the formulated compositions of British Patent
1,453,385 fail to disclose the critical limitations of the instant invention.
A number of patents teach esterified ethoxylated glycerol compounds for various
applications. These patents are Great Britian 1,453,385; Japan 59-1600 and Japan 58-
206693 and European Patent Application 0586,323A1. These publications fail to
appreciate that a mixture of esterified ethoxylated glycerol and nonesterified
ethoxylated glycerol, when used in a hard surface cleaning composition, functions as a
grease release agent.
Summary of the Invention
The present invention provides an improved, clear, liquid cleaning composition
having improved interfacial tension which improves cleaning hard surface in the form of
a liquid crystal or a microemulsion which is suitable for cleaning hard surfaces such as
plastic, vitreous and metal surfaces having a shiny finish. More particularly, the
improved cleaning compositions exhibit good grease soil removal properties due to the
CA 0220~7404 1997-0~7-14
improved interfacial tensions, when used in undiluted (neat) form and leave the cleaned
surfaces shiny without the need of or requiring only minimal additional rinsing or wiping.
The latter characteristic is evidenced by little or no visible residues on the unrinsed
cleaned surfaces and, accordingly, overcomes one of the disadvantages of prior art
products. The instant compositions exhibit a grease release effect in that the instant
compositions impede or decrease the anchoring of greasy soil on surfaces that have
been cleaned with the instant compositions as compared to surfaces cleaned with a
liquid crystal composition or a commercial microemulsion composition which meansthat the grease soiled surface is easier to clean upon subsequent cleanings.
Surprisingly, these desirable results are accomplished even in the absence of
polyphosphate or other inorganic or organic detergent builder salts and also in the
complete absence or substantially complete absence of grease-removal solvent.
The instant compositions are more friendly for the environment due to the low
ecotoxicity of the ethoxylated glycerol type compounds used in the instant
1 5 compositions.
The compositions of the instant invention have an ecotoxocity value as
measured by the LC 50 test as deferred by The Organization for Economic Cooperation
and Development (OECD)(of which the United States is a member) in OECD Test No.
202 of at least 0.18 ml/L measured on Daphniae microorganisms.
In one aspect, the invention generally provides a stable, clear all-purpose, hard
surface cleaning composition especially effective in the removal of oily and greasy oil,
which is in the form of a substantially dilute oil-in-water microemulsion having an
aqueous phase and an oil phase. The dilute o/w microemulsion comprises on a weight
basis:
from 0.1% to 20% of an anionic surfactant;
from 0.1% to 50% of a water-mixable cosurfactant having either limited ability or
substantially no ability to dissolve oily or greasy soil;
0.1% to 20% of a compound which is a mixture of a partially esterified
ethoxylated polyhydric alcohol, a fully esterified ethoxylated polyhydric alcohol and a
AM~NDED SI~EET
CA 0220~404 1997-0~-14
nonesterified ethoxylated polyhydric alcohol, said mixture being (herein after referred to
as an ethoxylated glycerol type compound);
0 to 15% of magnesium sulfate heptahydrate;
0.1 to 10.0% of a perfume or water insoluble hydrocarbon; and
10 to 85% of water, said proportions being based upon the total weight of the
composition.
In another aspect, the invention generally provides a stable, clear all-purpose,hard surface cleaning composition especially effective in the removal of oily and greasy
oil, which is in the form of a substantially dilute oil-in-water microemulsion having an
aqueous phase and an oil phase. The aqueous phase of the dilute o/w microemulsion
comprises on a weight basis:
from 0.1% to 20% of an anionic surfactant;
from 0.1% to 50% of a water-mixable cosurfactant having either limited ability or
substantially no ability to dissolve oily or greasy soil;
0.4% to 1.0% of a trialkyl ester of citric acid;
0.1% to 10% of a mixture of a partially esterified ethoxylated polyhydric alcohol,
a fully esterified ethoxylated polyhydric alcohol and a nonesterified polyhydric alcohol,
(said mixture being herein after referred to as an ethoxylated glycerol type compound);
0 to 15% of magnesium sulfate heptahydrate;
2(~ 0.4 to 10.0% of a perfume or water insoluble hydrocarbon; and
10 to 85% of water, said proportions being based upon the total weight of the
composition.
In another aspect, the invention generally provides a stable, clear all-purpose,hard surface cleaning composition especially effective in the removal of particle soil,
which is in the form of a substantially dilute oil-in-water microemulsion having an
aqueous phase and an oil phase. The dilute o/w microemulsion comprises on a weight
basis:
from 0.1% to 20% of an anionic surfactant;
AM~ND~ SHE~T
CA 0220~404 1997-0~-14
from 0.1% to 50% of a water-mixable cosurfactant having either limited ability or
substantially no ability to dissolve oily or greasy soil;
0.1% to 20% of an ethoxylated polyhydric alcohol;
0 to 15% of magnesium sulfate heptahydrate;
0.1 to 10.0% of a perfume or water insoluble hydrocarbon; and
l O to 85% of water, said proportions being based upon the total weight of the
composition. This composition can also contain 0 to 10 wt. % of a monoester of an
ethoxylated polyhydric alcohol depicted by the formula:
R'
CH2 O (cH2cH O )x B
R'
[ CH O (CH2CH O )y Blw
R'
CH2 O (CH2CH O )z B)
15 wherein w equals one to four. Two of the B's are hydrogen and one B is selected from
the group consisting of a group represented by:
o
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon
20 atoms, more preferably 11 to 15 carbon atoms and alkenyl groups having 6 to 22
carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most
preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals
about 2 to about 100. This composition can also contain 0 to 2 wt. %, of a diester of an
ethoxylated polyhydric alcohol depicted by the formula
A~NGE~ Sn~ET
CA 0220~404 1997-0~-14
R'
CH2 O (cH2cH O )x B
[CH O (CH2CH O )yB]w
R'
CH2 O (CH2CH O )z B
wherein w equals one to four. One of the B's is hydrogen and two B's are selected from
the group consisting of a group represented by:
o
10C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon
atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow
alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0
and 60, provided that (x+y+z) equals 2 to 100. This composition can also contain 0 to
15 1.0 wt. %, of a triester of an ethoxylated polyhydric alcohol depicted by the formula
R'
CH2 O (CH2CH O )x B
R'
[ CH O (CH2CH O )y B]w
20 R'
CH2 O (CH2CH O )z B
wherein w equals one to four. The three B's are selected from the group consisting of a
group represented by:
O
25; C R
wherein R is selected from the group consisti-ng of alkyl group having 6 to 22 carbon
atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow
alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0
and 60, provided that (x+y+z) equals about 2 to about 100.
4;-~N~ ET
CA 0220C7404 1997 0C7 14
The dispersed oil phase of the o/w microemulsion is composed essentially of the
water-immiscible or hardly water-soluble perfume.
Quite surprisingly although the perfume is not, per se, a solvent for greasy or oily
soil, -- even though some perfumes may, in fact, contain as much as 80% of terpenes
which are known as good grease solvents -- the inventive compositions in dilute form
have the capacity to solubilize up to 10 times or more of the weight of the perfume of
oily and greasy soil, which is removed or loosened from the hard surface by virtue of
the action of the anionic and nonionic surfactants, said soil being taken up into the oil
phase of the o/w microemulsion.
In another aspect, the invention generally provides highly concentration
microemulsion compositions in the form of either an oil-in-water (o/w) microemulsion or
a water-in-oil (w/o) microemulsion which when diluted with additional water before use
can form dilute o/w microemulsion compositions. The concentrated microemulsion
compositions comprise, by weight, 0.1% to 20% of an anionic surfactant, 0.1% to 20%
15 of an ethoxylated glycerol type compound, 0% to 2.5% of a fatty acid, 0.1% to 10% of
perfume or water insoluble hydrocarbon having 6 to 18 carbon atoms, 0.1% to 50% of a
cosurfactant, and 20% to 97% of water.
In another aspect of the invention, liquid crystal compositions are provided which
comprise by weight 0.1% to 20% of an anionic surfactant, 0.1% to 20% of an
20 ethoxylated glycerol type compound, 0 to 2.5% of a fatty acid, 0.1% to 10% of a
perfume, more preferably 1% to 10%, 1% to 50% of cosurfactant selected from the
group consisting of propylene glycol monobutylether, dipropylene glycol monobutylether
and tripropyleneglycol monobutyl ether and mixtures thereof and the balance being
water.
In another aspect, the invention provides highly concentration microemulsion
compositions in the form of either an oil-in-water (o/w) microemulsion or a water-in-oil
(w/o) microemulsion which when diluted with additional water before use can form dilute
o/w microemulsion compositions. The concentrated microemulsion compositions
comprise, by weight, 0.1% to 20% of an anionic surfactant, 0.1% to 20% of an
CA 0220~404 1997-0~-14
ethoxylated glycerol type compound, 0% to 2.5% of a fatty acid, 0.1% to 10% of
perfume or water insoluble hydrocarbon having 6 to 18 carbon atoms, 0.1% to 50% of a
cosurfactant, and 20% to 97% of water.
In another aspect, the invention generally provides highly concentration
5 microemulsion compositions in the form of either an oil-in-water (o/w) microemulsion or
a water-in-oil (w/o) microemulsion which when diluted with additional water before use
can form dilute o/w microemulsion compositions. The concentrated microemulsion
compositions comprise, by weight, 0.1% to 20% of an anionic surfactant, 0.1% to 20%
of an ethoxylated polyhydric alcohol, 0.1% to 10% of perfume or water insoluble
hydrocarbon having 6 to 18 carbon atoms, 0.1% to 50% of a cosurfactant, and 20% to
97% of water.
In another aspect of the invention, liquid crystal compositions are provided which
comprise by weight 0.1% to 20% of an anionic surfactant, 0.1% to 20% of an
ethoxylated polyhydric alcohol, 0.1% to 10% of a perfume, 1% to 50% of cosurfactant
15 and the balance being water.
Detailed Description of the Invention
The present invention relates to a stable liquid crystal or microemulsion
composition comprising by weight: 0.1% to 20% of an anionic suRactant, 0.1% to 50%
of a cosurfactant, 0.1% to 20% of an ethoxylated glycerol type compound, 0.1% to 10%
20 of a water insoluble hydrocarbon or a perfume and the balance being water, said
composition having an ecotoxocity value as measured by the LC50 test of at least 0.18
ml/L measured on Daphniae microorganisms.
The present invention relates to a stable liquid crystal or microemulsion
composition comprising by weight: 0.1% to 20% of an anionic surfactant, 0.1% to 50%
25 of a cosurfactant, 0.4 to 1.0 wt. % of a trialkyl ester of citric aicd such as tri-n butyl
citrate, 0.1% to 20% of an ethoxylated glycerol type compound, 0.1% to 10% of a water
insoluble hydrocarbon or a perfume and the balance being water, said compositionhaving an ecotoxocity value as measured by the LC50 test of at least 0.18 ml/L
measured on Daphniae microorganisms.
CA 0220~404 1997-0~-14
11
The present invention relates to a stable liquid crystal or microemulsion
composition comprising by weight: 0.1% to 20% of an anionic surfactant, 0.1% to 50%
of a cosurfactant, 0.1% to 20% of an ethoxylated polyhydric alcohol, 0.1% to 10% of a
water insoluble hydrocarbon or a perfume and the balance being water. This
composition can also contain 0 to 10 wt. % of a monoester of an ethoxylated polyhydric
alcohol depicted by the formula
R'
CH2 O (CH2CH O )x B
R'
[CH O (CH2CH Q )y B]w
R'
CH2 O (CH2CH O )z B
wherein w equals one to four. Two of the B's are hydrogen and one B is selected from
the group consisting of a group represented by:
O
C R
wherein R is selected from the group consisting of alkyl group having about 6 to 22
carbon atoms, and alkenyl groups having about 6 to 22 carbon atoms, wherein a
hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have
20 a value between 0 and 60, provided that (x+y+z) equals about 2 to about 100. This
composition can also contain 0 to 2 wt. % of a diester of an ethoxylated polyhydric
alcohol depicted by the formula
R'
CH2 O (CH2CH O )x B
R'
[CH O (CH2CH O )y B]w
R'
CH2 O (CH2CH O )z B
CA 0220~404 1997-0~-14
wherein w equals one to four. One of the B's is hydrogen and two B's are selected from
the group consisting of a group represented by:
o
C R
S wherein R is selected from the group consisting of alkyl group having about 6 to 22
carbon atoms, and alkenyl groups having about 6 to 22 carbon atoms, wherein a
hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have
a value between 0 and 60, provided that (x+y+z) equals about 2 to about 100. This
composition can also contain 0 to about 1.0 wt. % of a triester of an ethoxylated
10 polyhydric alcohol depicted by the formula
R'
CH2 O (CH2CH O )x B
R'
[ CH O (CH2CH O )y B]w
R'
CH2 O (CH2CH O )z B
wherein w equals one to four. The three B's are selected from the group consisting of a
group represented by:
o
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon
atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow
alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0
and 60, provided that (x+y+z) equals 2 to 100.
According to the present invention, the role of the hydrocarbon is provided by anon-water-soluble perfume Typically, in aqueous based compositions the presence of
a solubilizers, such as alkali metal lower alkyl aryl sulfonate hydrotrope,
triethanolamine, urea, etc., is required for perfume dissolution, especially at perfume
levels of 1% and higher, since perfumes are generally a mixture of fragrant essential
p~N~D ~
CA 0220~404 1997-0~-14
oils and aromatic compounds which are generally not water-soluble. Therefore, byincorporating the perfume into the aqueous cleaning composition as the oil
(hydrocarbon) phase of the ultimate o/w microemulsion composition, several different
important advantages are achieved.
First, the cosmetic properties of the ultimate cleaning composition are improved:
the compositions are both clear (as a consequence of the formation of a microemulsion)
and highly fragranced (as a consequence of the perfume level).
Second, the need for use of solubilizers, which do not contribute to cleaning
performance, is eliminated.
Third, an improved grease release effect and an improved grease removal
capacity in neat (undiluted) usage of the dilute aspect or after dilution of the concentrate
can be obtained without detergent builders or buffers or conventional grease removal
solvents at neutral or acidic pH and at low levels of active ingredients while improved
cleaning performance can also be achieved in diluted usage.
As used herein and in the appended claims the term "perfume" is used in its
ordinary sense to refer to and include any non-water soluble fragrant substance or
mixture of substances including natural (i.e., obtained by extraction of flower, herb,
blossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and
synthetically produced substance) odoriferous substances. Typically, perfumes are
20 complex mixtures of blends of various organic compounds such as alcohols, aldehydes,
ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes) such
as from 0% to 80%, by weight, the essential oils themselves being volatile odoriferous
compounds and also serving to dissolve the other components of the perfume.
In the present invention the precise composition of the perfume is of no particular
25 consequence to cleaning performance so long as it meets the criteria of waterimmiscibility and having a pleasing odor. Naturally, of course, especially for cleaning
compositions intended for use in the home, the perfume, as well as all other
ingredients, should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.. The
~MENDE~ SI~Er~T
CA 0220~404 1997-0~-14
14
instant compositions show a marked improvement in ecotoxocity as compared to
existing commercial products.
The hydrocarbon such as a perfume is present in the dilute o/w microemulsion in
an amount of from 0.1% to l O% by weight. If the amount of hydrocarbon (perfume) is
5 less than 0.4% by weight it becomes more difficult to form the o/w microemulsion In
the case of the liquid crystal one need at least 0.5 weight % of perfume. If thehydrocarbon (perfume) is added in amounts more than 10% by weight, the cost is
increased without any additional cleaning benefit and, in fact, with some diminishing of
cleaning performance insofar as the total amount of greasy or oily soil which can be
10 taken up in the oil phase of the microemulsion will decrease proportionately.Furthermore, although superior grease removal performance will be achieved for
perfume compositions not containing any terpene solvents, it is apparently difficult for
perfumers to formulate sufficiently inexpensive perfume compositions for products of
this type (i.e., very cost sensitive consumer-type products) which includes less than
15 20%, usually less than 30%, of such terpene solvents.
Thus, merely as a practical matter, based on economic consideration, the dilute
o/w microemulsion detergent cleaning compositions of the present invention may often
include as much as 0.2% to 7% by weight, based on the total composition, of terpene
solvents introduced thereunto via the perfume component. However, even when the
20 amount of terpene solvent in the cleaning formulation is less than 1.5% by weight, such
as up to 0.6% by weight or 0.4% by weight or less, satisfactory grease removal and oil
removal capacity is provided by the inventive diluted o/w microemulsions.
Thus, for a typical formulation of a diluted o/w microemulsion according to thisinvention a 20 milliliter sample of o/w microemulsion containing 1% by weight of25 perfume will be able to solubilize, for example, up to 2 to 3 ml of greasy and/or oily soil,
while retaining its form as a microemulsion, regardless of whether the perfume contains
0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8% by weight of terpene solvent.
In other words, it is an essential feature of the compositions of this invention that grease
A~4EI~DED SHE~,
CA 0220~404 1997-0~-14
removal is a function of the result of the microemulsion, per se, and not of the presence
or absence in the microemulsion of a "greasy soil removal" type of solvent.
In place of the perfume one can employ a water insoluble paraffin or isoparaffinhaving 6 to 18 carbon at a concentration of 0.4 to 8.0 wt. percent.
The water-soluble organic detergent materials which are used in forming the
ultimate o/w microemulsion compositions of this invention may be selected from the
group consisting of water-soluble, non-soap, anionic surfactants mixed with a fatty acid
and the solubilizing agent which is a partially esterified ethoxylated polyhydric alcohol
such as a partially esterified ethoxylated glycerol.
Although conventional nonionic surfactants can be used in the instant
compositions, the employment of such conventional nonionic in the instant composition
will decrease the environmental profile of the composition as well as having an adverse
effect on the grease release and grease + particulate soil removal properties of the
composition.
Regarding the anionic surfactant present in the o/w microemulsions any of the
conventionally used water-soluble anionic surfactants or mixtures of said anionic
detergents and anionic detergents can be used in this invention. As used herein the
term "anionic surfactant" is intended to refer to the class of anionic and mixed anionic-
nonionic surfactants providing detersive action.
Suitable water-soluble non-soap, anionic suRactants include those surface-activeor detergent compounds which contain an organic hydrophobic group containing
generally 8 to 26 carbon atoms in their molecular structure and at least one water-
solubilizing group selected from the group of sulfonate, sulfate and carboxylate so as to
form a water-soluble surfactant. Usually, the hydrophobic group will include or
comprise a Cg-C22 alkyl, alkyl or acyl group. Such surfactants are employed in the
form of water-soluble salts and the salt-forming cation usually is selected from the
group consisting of sodium, potassium, ammonium, magnesium and mono-, di- or tri-
C2-C3 alkanolammonium, with the sodium, magnesium and ammonium cations again
being preferred.
~EN~E~
CA 0220~404 1997-0~-14
r ~
Examples of suitable sulfonated anionic surfactants are the well known higher
alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates
containing from 10 to 16 carbon atoms in the higher alkyl group in a straight orbranched chain, Cg-c1s alkyl toluene sulfonates and C8-c1s alkyl phenol sulfonates.
A preferred sulfonate is iinear alkyl benzene suifonate having a high content of 3-
(or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or
lower) phenyl isomers, that is, wherein the benzene ring is preferably attached in large
part 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
10 correspondingly low. Particularly preferred materials are set forth in U.S. Patent
3,320,174.
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
15 prepared in a known manner by the reaction of sulfur trioxide (SO3) with long-chain
olefins containing 8 to 25, and having the formula RCH=CHR1 where R is a higher alkyl
group of 6 to 23 carbons and R1 is an alkyl group of 1 to 17 carbons or hydrogen to
form a mixture of sultones and alkene sulfonic acids which is then treated to convert the
sultones to sulfonates. Olefin sulfonates contain from 14 to 16 carl~on atoms in the R
20 alkyl group and are obtained by sulfonating an a-olefin.
Other examples of suitable anionic sulfonate surfactants are the paraffin
sulfonates containing 10 to 20. Primary paraffin sulfonates are made by reacting long-
chain alpha olefins and bisulfites and paraffin sulfonates having the sulfonate group
distributed along the paraffin chain are shown in U.S. Patents Nos2,503,280;
25 2,507,088; 3,260,744; 3,372,188; and Gerrnan Patent 735,096.
Examples of satisfactory anionic sulfate surfactants are the Cg C1 g alkyl sulfate
salts and the Cg-C1 g alkyl sulfate salts and the Cg-C1 g alkyl ether polyethenoxy sulfate
salts having the formula R(OC2H4)n OSO3M wherein n is 1 to 12, and M is a
solubilizing cation selected from the group consisting of sodium, potassium, ammonium,
NDED S~
CA 0220~404 1997-0~-14
17 .~
magnesium and mono-, di- and triethanol ammonium ions. The alkyl sulfates may beobtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or
tallow or mixtures thereof and neutralizing the resultant product. On the other hand, the
alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of
5 ethylene oxide with a C8-cl8 alkanol and neutralizing the resultant product. 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. On the
other hand, the alkyl ether polyethenoxy sulfates are obtained by sulfating the
condensation product of ethylene oxide with a Cg-C1g alkanol and neutralizing the
10 resultant product. The alkyl ether polyethenoxy sulfates differ from one another in the
number of moles of ethylene oxide reacted with one mole of alkanol. Preferred alkyl
sulfates and preferred alkyl ether polyethenoxy sulfates contain 10 to 16 carbon atoms
in the alkyl group.
The Cg-C12 alkylphenyl ether polyethenoxy sulfates containing from 2 to 6
15 moles of ethylene oxide in the molecule also are suitable for use in the inventive
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.
Obviously, these anionic surfactants will be present either in acid form or salt20 form depending upon the pH of the final composition, with salt forming cation being the
same as for the other anionic detergents.
Of the foregoing non-soap anionic surfactants, the preferred surfactants are theCg-C1s linear alkylbenzene sulfonates and the C13-C17 paraffin or alkane sulfonates.
Particularly, preferred compounds are sodium C10-c13 alkylbenzene sulfonate and
25 sodium C13-C17 alkane sulfonate.
Generally, the proportion of the nonsoap-anionic surfactant will be in the range of
0.1% to 20.0%, by weight of the dilute o/w microemulsion composition.
The instant composition contains a composition (herein after referred to as
ethoxylated glycerol type compound) which is a mixture of a fully esterified ethoxylated
AMENDED S~EEr
CA 0220~404 1997-0~-14
18 `' ;~
polyhydric alcohol, a partially esterified ethoxylated polyhydric alcohol and a
nonesterified ethoxylated polyhydric alcohol, wherein the preferred polyhydric alcohol is
glycerol, and the compound is:
R'
5CH2 O (CH2CH O )x B
R'
1CH O (CH2CH O )yB]w Formula
R' (I)
CH2 O (CH2CH O )z B
10and
R'
CH2 O (CH2CH O )X H
R'
[CH O (CH2CH O )Y H]W Formula
15 R' (Il)
CH2 O (CH2CH O )z H
wherein w equals one to four. B is selected from the group consisting of hydrogen or a
group represented by:
o
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon
atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow
alkyl chain or a coco alkyl chain is most preferred, wherein at least one of the B groups
is represented by said
O
C R,
and R' is selected from the group consisting of hydrogen and methyl groups; x, y and z
have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in
Formula (I) the ratio of monoester / diester / triester is 45 to 90 / 5 to 40 / 1 to 20,
AMENO~ E~T
CA 0220~404 1997-0~-14
19 ~ . , .
wherein the ratio of Formula (I) to Formula (Il) is a value between 3 to 0.02, wherein it is
most preferred that there is more of Formula (Il) than Formula (I) in the mixture that
forms the compound.
The ethoxylated glycerol type compound used in the instant composition is
5 manufactured by the Kao Corporation and sold under the trade name LEVENOL suchas Levenol F-200 which has an average EO of 6 and a molar ratio of coco fatty acid to
glycerol of 0.55 or LEVENOL V501/2 which has an average EO of.17 and a molar ratio
of tallow fatty acid to glycerol of 1Ø It is preferred that the molar ratio of the fatty acid
to glycerol is less than 1.7, more preferably less than 1.5 and most preferably less than
1Ø The ethoxylated glycerol type compound has a molecular weight of 400 to 1600,
and a pH (50 grams / liter of water) of 5-7. The LEVENOL compounds are substantially
non irritant to human skin and have a primary biodegradabillity higher than 90% as
measured by the Wickbold method Bias-7d.
Two examples of the LEVENOL compounds are LEVENOL V-501/2 which has
15 17 ethoxylated groups and is derived from tallow fatty acid with a fatty acid to glycerol
ratio of 1.0 and a molecular weight of 1465 and LEVENOL F-200 has 6 ethoxylated
groups and is derived from coco fatty acid with a fatty acid to glycerol ratio of 0.55.
Both LEVENOL F-200 and Levenol V-501/2 are composed of a mixture of Formula (I)
and Formula (Il). The LEVENOL compounds has ecoxicity values of algae growth
2u inhibition > 100 mg/iiter; acute toxiciiy for Daphniae > i û0 mg/iiter and acute fish toxicity
> 100 mg/liter. The LEVENOL compounds have a ready biodegradability higher than
60% which is the minimum required value according to OECD 301 B measurement to be
acceptably biodegradable.
Polyesterified nonionic compounds also useful in the instant compositions are
25 CROV`OL PK-40 and CROVOL PK-70 manufactured by Croda GMBH of the
Netherlands. CROVOL PK-40 is a polyoxyethylene (12) Palm Kernel Glyceride which
has 12 EO groups. CROVOL PK-70 which is prefered is a polyoxyethyiene (45) Palm
Kernel Glyceride have 45 EO groups.
~N~
CA 0220~404 1997-0~-14
20 " ;'`;
In the dilute o/w microemulsion compositions or liquid crystal compositions the
ethoxylated glycerol type compounds or the polyesterified nonionic compounds will be
present in admixture with the anionic detergent. The proportion of the ethoxylated
glycerol type compound or the polyesterified nonionic solubilizing agent based upon the
weight of the liquid crystal composition or the final dilute o/w microemulsion composition
will be 0.1% to 20%, by weight.
Furthermore, in the more preferred compositions the weight ratio of nonsoap
anionic detergent to the ethoxylated glycerol type compound will be in the range of 3:1
to 1:3 with especially good results being obtained at a weight ratio of 2:1.
The ethoxylated polyhydric alcohol such as an ethoxylated glycerol of the instant
invention is depicted by the following formula
R'
CH2 O (CH2CH O )x H
R'
[CH O (CH2CH O )y Hlw
R'
CH2 O (CH2CH O )z H
wherein w equals one to four, x, y and z have a value between 0 and 60, provided that
(x+y+z) equals 2 to 100.
In the dilute o/w microemulsion compositions or liquid crystal compositions the
ethoxylated alcohol will be present in admixture with the anionic surfactant. The
proportion of the ethoxylated glycerol type based upon the weight of the liquid crystal
composition or the final dilute o/w microemulsion composition will be 0.1% to 20% by
weight.
Furthermore, in the more preferred compositions the weight ratio of nonsoap
anionic surfactant to the ethoxylated polyhydric alcohol will be in the range of 3:1 to 1:3
with especially good results being obtained at a weight ratio of 2:1.
The instant composition can also contain 0 to 10 wt. %, of a monoester of an
ethoxylated polyhydric alcohol depicted by the formula
~ 3 ~tiEE~
CA 0220~404 1997-0~-14
21 ` `
R'
CH2 O (CH2CH O )X B
R'
1CH O (CH2CH 0 )Y B]W
R'
CH2 O (CH2CH O )Z B
wherein w equals one to four. Two of the BS are hydrogen and one B jS selected from
the group consisting of a group represented by:
o
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon
atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tailow
alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0
and 60, provided that (x+y+z) equals 2 to 100
The instant composition can also contain 0 to 2 wt %, of a diester of an
ethoxylated polyhydric alcohol depicted by the formula
R'
CH2 O (CH2CH O )X B
R'
[ CH O (CH2CH O )Y B]W
R'
CH2 O (CH2CH O )Z B
wherein w equals one to foun One of the BS jS hydrogen and two BS are selected from
the group consisting of a group represented by:
O
C R
wherein R jS selected from the group consisting of alkyl group having 6 to 22 carbon
atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow
~3,~ ?~ r, !
. CA 0220~404 1997-0~-14
22 `` ~
alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0
and 60, provided that (x+y+z) equals about 2 to 100.
The instant composition can also contain 0 to 1.0 wt. %, of a triester of an
ethoxylated polyhydric alcohol depicted by the formula
R'
CH2 O (CH2CH O )x B
R'
[CH O (CH2CH O )y B]w
R'
CH2 O (CH2CH O )z B
wherein w equals one to four. The three Bs are selected from the group consisting of a
group represented by:
o
C R
15 wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon
atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow
alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0
and 60, provided that (x+y+z) equals 2 to 100.
The instant compositions contain 0 to 1.0 wt. % of a tri-alkyl citrate such as tri-n-
20 butyl citrate, tri-n-propyl citrate, tri-isopropyl citrate, tri-isobutyl citrate, tri-n-pentyl citrate,
tri-isopentyl citrate and tri-n-hexyl, wherein tri-n-butyl citrate is preferred. The tri-n-butyl
citrate functions in the formula as a foam control agent in that the foam is more readily
collapsed such that the article can be rinsed more effectively.
The cosurfactant may play an essential role in the formation of the the liquid
25 crystal composition or dilute o/w microemulsion and the concentrated microèmulsion
compositions. Three major classes of compounds have been found to provide highly
suitable cosurfactants for the microemulsion over temperature ranges extending from
5 C to 43 C for instance; (1 ) water-soluble C3-C4 alkanols, polypropylene glycol of the
formula HO(CH3CHCH2O)nH wherein n is a number from 2 to 18 and monoalkyl ethers
p~,4F~ SH~
CA 0220~404 1997-0~-14
23 .:.
and esters of ethylene glycol and propylene glycol having the structural formulas
R(X)nOH and R1 (x)noH wherein R is C1-c6 alkyl, R1 is C2-C4 acyl group, X is
(OCH2CH2) or (ocH2(cH3)cH) and n is a number from 1 to 4; (2) aliphatic mono- and
di-carboxylic acids containing 2 to 10 carbon atoms, preferably 3 to 6 carbons in the
molecule; and (3) triethyl phosphate. Additionally, mixtures of two or more of the four
classes of cosurfactant compounds may be employed where specific pH's are desired.
When the mono- and di-carboxylic acid (Class 2) cosurfactants are employed in
the instant microemulsion compositions at a concentration of 2 to 10 wt. %, the
microemulsion compositions can be used as a cleaners for bathtubs and other hardsurfaced items, which are acid resistant thereby removing lime scale, soap scum and
greasy soil from the surfaces of such items damaging such surfaces. If these surfaces
are of zirconium white enamel, they can be damaged by these compositions.
An aminoalkylene phophonic acid at a concentration of 0.01 to 0.2 wt. % can be
optionally used in conjunction with the mono- and di-carboxylic acids, wherein the
aminoalkylene phophonic acid helps prevent damage to zirconium white enamel
surfaces. Additionally, 0.05 to 1% of phosphoric acid can be used in the composition.
Methanol and ethanol are explicitly excluded from the instant composition
because of their low flash point.
Representative members of the polypropylene glycol include dipropylene glycol
and polypropylene glycol having a molecular weight of 200 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, propylene glycol tertiary butyl ether, ethylene glycol monoacetate and
dipropylene glycol propionate. When these glycol type cosurfactants are at a
concentartion of at least 1.0 weight %, in combination with a perfume at a concentration
of at least 0.5 weight %, one can form a liquid crystal composition
Representative members of the aliphatic carboxylic acids include C3-C6 alkyl
and alkenyl monobasic acids and dibasic acids such as glutaric acid and mixtures of
N~ED Sl i~
CA 0220~404 1997-0~-14
24 ~ ~ .
glutaric acid with adipic acid and succinic acid, as well as mixtures of the foregoing
acids as well as acrylic acid or propionic acid.
While all of the aforementioned glycol ether compounds and acid compounds
provide the described stability, the most preferred cosurfactant compounds of each
type, on the basis of cost and cosmetic appearance (particularly odor), are diethylene
glycol monobutyl ether and a mixture of adipic, glutaric and succinic acids? respectively.
The ratio of acids in the foregoing mixture is not particularly critical and can be modified
to provide the desired odor. Generally, to maximize water solubility of the acid mixture
glutaric acid, the most water-soluble of these three saturated aliphatic dibasic acids, will
10 be used as the major component.
Generally, weight ratios of adipic acid: glutaric acid:succinic acid is 1-3:1-8:1-5,
can be used with equally good results.
Still other classes of cosurfactant compounds providing stable microemulsion
compositions at low and elevated temperatures are the mono-, di- and triethyl esters of
15 phosphoric acid such as triethyl phosphate.
The amount of cosurfactant required to stabilize the liquid crystal compositionsor the microemulsion compositions will, of course, depend on such factors as thesurface tension characteristics of the cosurfactant, the type and amounts of the primary
surfactants and perfumes, and the type and amounts of any other additional ingredients
20 which may be present in the composition and which have an influence on the
thermodynamic factors enumerated above. The amounts of cosurfactant in the rangeof from 0.5% to 15%, by weight provide stable dilute o/w microemulsions for the above-
described levels of primary surfactants and perfume and any other additional
ingredients as described below.
As will be appreciated by the practitioner, the pH of the final microemulsion will
be dependent upon the identity of the cosurfactant compound, with the choice of the
cosurfactant being effected by cost and cosmetic properties, particularly odor. For
example, microemulsion compositions which have a pH in the range of 1 to 10 may
employ either the class 1 or the class 4 cosurfactant as the sole cosurfactant, but the
~ ?~ S~
CA 0220~404 1997-0~-14
pH range is reduced to 1 to 8.5 when the polyvalent metal salt is present. On the other
hand, the class 2 cosurfactant can only be used as the sole cosurfactant where the
product pH is below 3.2. However, where the acidic cosurfactants are employed inadmixture with a glycol ether cosurfactant, compositions can be formulated at a
5 substantially neutral pH (e.g., pH 7+1.5).
The ability to formulate neutral and acidic products without builders which havegrease 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.
In addition to their excellent capacity for cleaning greasy and oily soils, the low
10 pH o/w microemulsion formulations also exhibit excellent cleaning performance and
removal of soap scum and lime scale in neat (undiluted) as well as in diluted usage.
The final essential ingredient in the inventive microemulsion compositions having
improved interfacial tension properties is water. The proportion of water in themicroemulsion compositions generally is in the range of 20% to 97%, by weight of the
15 usual diluted o/w microemulsion composition.
As believed to have been made clear from the foregoing description, the dilute
o/w microemulsion liquid all-purpose cleaning compositions of this invention areespecially effective when used as is, that is, without further dilution in water, since the
properties of the composition as an o/w microemulsion are best manifested in the neat
20 (undiluted) form. However, at the same time it should be understood that depending on
the levels of surfactants, cosurfactants, perfume and other ingredients, some degree of
dilution without disrupting the microemulsion, per se, is possible. For example, at the
preferred low levels of active surfactant compounds (i.e., primary anionic and nonionic
surfactants) dilutions up to 50% will generally be well tolerated without causing phase
25 separation, that is, the microemulsion state will be maintained.
However, even when diluted to a great extent, such as a 2- to 1 0-fold or more
dilution, for example, the resulting compositions are still effective in cleaning greasy,
oily and other types of soil. Furthermore, the presence of magnesium ions or other
N~3~SH~FT
CA 0220~404 1997-0~-14
26 ` ;; ~
polyvalent ions, e.g., aluminum, as will be described in greater detail below further
serves to boost cleaning performance of the primary detergents in dilute usage.
On the other hand, it is also within the scope of this invention to formulate highly
concentrated microemulsions which will be diluted with additional water before use.
The present invention also relates to a stable concentrated microemulsion or
acidic microemulsion composition comprising by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated glycerol type compound;
(c) 2 to 30% of a cosurfactant; ~
(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 18% of at least one dicarboxylic acid;
(f) 0 to 1% of phosphoric acid;
(g) 0 to 0.2% of an aminoalkylene phosphonic acid;
(h) 0 to 15% of magnesium sulfate heptahydrate;
(i) 0 to 1.0% of a tri-alkyl citrate; and
(h) balance being water, wherein the composition has an ecotoxocity as
measured by the LC 50 test of at least 0.18 ml/L measured on Daphniae
microorganisms.
The present invention also relates to a stable liquid crystal microemulsion or
20 acidic microemulsion composition comprising by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated glycerol type compound;
(c) 0 to 2.5% of a fatty acid;
(d) 2 to 30% of a cosurfactant;
(e) 0.5 to 10% of a water insoluble hydrocarbon or perfume;
(f) 0 to 15% of magnesium sulfate heptahydrate;
(9) 0 to 1.0% of a tri-alkyl citrate; and
~ENDED S~E
CA 0220~404 1997-0~-14
27 ;, ;
(h) balance being water, wherein the composition has an ecotoxocity as
measured by the LC 50 test of at least 0.18 ml/L measured on Daphniae
mlcroorganlsms.
The present invention also relates to a stable concentrated microemulsion or
5 acidic microemulsion composition comprising approximately by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated polyhydric alcohol such as an ethoxylated
glycerol;
(c) 2 to 30% of a cosurfactant;
(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 18% of at least one dicarboxylic acid;
(f) 0 to 1% of phosphoric acid;
(g) 0 to 0.2% of an aminoalkylene phosphonic acid;
(h) 0 to 15% of magnesium sulfate heptahydrate; and
(i) the balance being water.
The present invention also relates to a stable liquid crystal microemulsion or
acidic microemulsion composition comprising approximately by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated polyhydric alcohol such as an ethoxylated
20 glycerol;
(c) 2 to 30% of a cosurfactant;
(d) 0.5 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 15% of magnesium sulfate heptahydrate; and
(f) the balance being water.
Such concentrated microemuisions can be diiuted by mixing with up to 20 times
or more, their weight of water to form o/w microemulsions similar to the dilutedmicroemulsion compositions described above. While the degree of dilution is suitably
chosen to yield an o/w microemulsion composition after dilution, it should be recognized
p~~ 3 S~~
CA 0220~404 1997-0~-14
28 ` '~ '
that during the course of dilution both microemulsion and non-microemulsions may be
successively encountered.
In addition to the above-described essential ingredients required for the
formation of the liquid crystal composition or the microemulsion composition, the
5 compositions of this invention may often and preferably do contain one or moreadditional ingredients which serve to improve overall product performance.
One such ingredient is an inorganic or organic salt of oxide of a multivalent metal
cation, particularly Mg++. The metal salt or oxide provides several benefits including
improved cleaning performance in dilute usage, particularly in soft water areas, and
10 minimized amounts of perfume required to obtain the microemulsion state. Magnesium
sulfate, either anhydrous or hydrated (e.g., heptahydrate), is especially preferred as the
magnesium salt. Good results also have been obtained with magnesium oxide,
magnesium chloride, magnesium acetate, magnesium propionate and magnesium
hydroxide. These magnesium salts can be used with formulations at neutral or acidic
15 pH since magnesium hydroxide will not precipitate at these pH levels.
Although magnesium is the preferred multivalent metal from which the salts
(inclusive of the oxide and hydroxide) are formed, other polyvalent metal ions also can
be used provided that their salts are nontoxic and are soluble in the aqueous phase of
the system at the desired pH level. Thus, depending on such factors as the pH of the
20 system, the nature of the primary surfactants and cosurfactant, and so on, as well as
the availability and cost factors, other suitable polyvalent metal ions include aluminum,
copper, nickel, iron, calcium, etc. It should be noted, for example, that with the
preferred paraffin sulfonate anionic detergent calcium salts will precipitate and should
not be used. It has also been found that the aluminum salts work best at pH below 5 or
25 when a low level, for example 1 weight percent, of citric acid is added to the
composition which is designed to have a neutral pH. Alternatively, the aluminum salt
can be directly added as the citrate in such case. As the salt, the same general classes
of anions as mentioned for the magnesium salts can be used, such as halide (e.g.,
bromide, chloride), sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc.
p~~ S~
CA 0220~404 1997-0~-14
29
In the dilute compositions the metal compound is added to the composition in an
amount sufficient to provide at least a stoichiometric equivalence between the anionic
surfactant and the multivalent metal cation. For example, for each gram-ion of Mg++
there will be 2 gram moles of paraffin sulfonate, alkylbenzene sulfonate, etc., while for
S each gram-ion of A13+ there will be 3 gram moles of anionic surfactant. Thus, the
proportion of the multivalent salt generally will be selected so that one equivalent of
compound will neutralize from 0.1 to 1.5 equivalents, of the acid form of the anionic
surfactant.
At higher concentrations of anionic surfactant, the amount of multivalent salt will
10 be in range of 0.5 to 1 equivalents per equivalent of anionic surfactant.
The liquid crystal composition or the o/w microemulsion compositions comprises
from 0% to 2.5%, by weight of the composition of a C8-C22 fatty acid or fatty acid soap
as a foam suppressant. The addition of fatty acid or fatty acid soap provides animprovement in the rinseability of the composition whether applied in neat or diluted
15 form. Generally, however, it is necessary to increase the level of cosurfactant to
maintain product stability when the fatty acid or soap is present. If more than 2.5wt %
of the fatty acid is used in the instant compositions, the composition will become
unstable at low temperatures as well as having an objectionable smell.
As example of the fatty acids which can be used as such or in the form of soap,
20 mention can be made of distilled coconut oil fatty acids, "mixed vegetable" type fatty
acids (e.g. high percent of saturated, mono-and/or polyunsaturated C18 chains); oleic
acid, stearic acid, palmitic acid, eiocosanoic acid, and the like, generally those fatty
acids having from 8 to 22 carbon atoms being acceptable.
The all-purpose liquid cleaning composition of this invention may, if desired, also
25 contain other components either to provide additional effect or to make the product
more attractive to the consumer. The following are mentioned by way of example:
Colors or dyes in amounts up to 0.5% by weight; bactericides in amounts up to 1% by
weight; preservatives or antioxidizing agents, such as formalin, 5-bromo-5-nitro-dioxan-
1,3; 5-chloro-2-methyl-4-isothaliazolin-3-one, 2,6-di-tert.butyl-p-cresol, etc., in amounts
~ C~ S~E~
CA 0220~404 1997-0~-14
up to 2% by weight; and pH adjusting agents, such as sulfuric acid or sodium
hydroxide, as needed. Furthermore, if opaque compositions are desired, up to 4% by
weight of an opacifier may be added.
The instant compositions of the instant invention explicitly exclude zwitterionic
5 surfactant such as betaines because these zwetterionic surfactants are extremely high
foaming which, if used in the instant composition, would cause the instant compositions
to have to high a foam profile and that too much foam would leave residue on thesurface being cleaned.
In final form, the all-purpose liquids are clear oil-in-water microemulsions or liquid
10 crystal compositions and exhibit stability at reduced and increased temperatures. More
specifically, such compositions remain clear and stable in the range of 5 C to 50 C.
Such compositions exhibit a pH in the acid or neutral range depending on intended end
use. The liquid microemulsion compositions are readily pourable and exhibit a viscosity
in the range of 6 to 60 milliPascal . second (mPas.) as measured at 25 C. with a15 Brookfield RVT Viscometer using a #1 spindle rotating at 20 RPM.
The compositions are directly ready for use or can be diluted as desired and in
either case no or only minimal rinsing is required and substantially no residue or streaks
are left behind. Furthermore, because the compositions are free of detergent builders
such as alkali metal polyphosphates they are environmentally acceptable and provide a
20 better "shine" on cleaned hard surfaces.
When intended for use in the neat form, the liquid compositions can be packaged
under pressure in an aerosol container or in a pump-type sprayer for the so-called
spray-and-wipe type of application.
Because the compositions as prepared are aqueous liquid formulations and
25 sincè- no particular mixing is required to form the o/w microemulsion, the compositions
are easily prepared simply by combining all the ingredients in a suitable vessel or
container. The order of mixing the ingredients is not particularly important andgenerally the various ingredients can be added sequentially or all at once or in the form
of aqueous solutions of each or all of the primary detergents and cosurfactants can be
CA 0220~404 1997-0~-14
31 , . .
separately prepared and combined with each other and with the perfume. The
magnesium salt, or other multivalent metal compound, when present, can be added as
an aqueous solution thereof or can be added directly. It is not necessary to useelevated temperatures in the formation step and room temperature is sufficient.
The instant microemulsion formulas explicitly exclude alkali metal silicates andalkali meta 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.
It is contemplated within the scope of the instant invention that the ethoxylated
glycerol type compound can be employed in hard surface cleaning compositions such
as wood cleaners, window cleaners and light duty liquid cleaners, wherein
improvements in a grease release effect in desirable.
The following examples illustrate liquid cleaning compositions of the described
15 invention. Unless otherwise specified, all percentages are by weight. The exemplified
compositions are illustrative only and do not limit the scope of the invention. Unless
otherwise specified, the proportions in the examples and elsewhere in the specification
are by weight.
CA 0220.,404 1997 - 0., - 14
WO 96/15217 PCT/US95/14583
32
such as alkali metal polyphosphates they are environmentally acceptable and provide a
better "shine" on cleaned hard surfaces.
When intended for use in the neat form, the liquid compositions can be packaged
under pressure in an aerosol container or in a pump-type sprayer for the so-called
spray-and-wipe type of application.
Because the compositions as prepared are aqueous liquid formulations and
since no particular mixing is required to form the o/w microemulsion, the compositions
are easily prepared simply by combining all the ingredients in a suitable vessel or
container. The order of mixing the ingredients is not particularly important and10 generally the various ingredients can be added sequentially or all at once or in the form
of aqueous solutions of each or all of the primary detergents and cosurfactants can be
separately prepared and combined with each other and with the perfume. The
magnesium salt, or other multivalent metal compound, when present, can be added as
an aqueous solution thereof or can be added directly. It is not necessary to use15 elevated temperatures in the formation step and room temperature is sufficient.
The instant microemulsion formulas explicitly exclude alkali metal silicates andalkali meta 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
20 residue on the surface being cleaned.
It is contemplated within the scope of the instant invention that the ethoxylated
glycerol type compound can be employed in hard surface cleaning compositions such
as wood cleaners. window cleaners and light duty liquid cleaners, wherein
improvements in a grease release effect in desirable.
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 the invention. Unless
otherwise specified, the proportions in the examples and elsewhere in the specification
are by weight.
- - - -
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Exam~le 1
The following compositions in wt. % were prepared:
A B C D EF Mr. Proper St Marc
Lemon
Sodium C1~ -C17 4.7 4.3 4 4.314.1 7.05 2.9
Paraffin sul onate
EO/PO nor onic - - - - - - - 3.2
Levenol F-200 2.3 2.2 2 2.2 6.3 345
C13-C15 EO 14 - - - - - - 3.3
nonionic
DEGMBE 4 4 . 4 12 6 4.4 3
Fatty acid C 7 0.5 ~.~ C 72.25 1.125 0.65 0.3
M~SO4 7 H20 . 2 . . 6.3 3.15
Per'ume(a) ~ . 0.75 0.~ . 2.4 1.2 presentpresent
Soc ium Citrate - - - - - - 3.2
Wa-er Bal Bal Bal Bal Bal Bal Bal Bal
pH 7 7 7 7 7 7 9.5 7
Degreasing test
Neat (b) 30 35 35 35 30 30 70 >100
Dilute (b) 45 60 60 60 45 45 ~90 90
Residue Equal Equal Equal Equal Equal Equal WorseEqualto ref.
to ref. to ref. to ref. to ref. to ref. to ref.
Foam in hard Water Equal Equal Equal Equal Equal Equal Equal to Equal to ref.
to ref. to ref. to ref. to ref. to ref. to ref. ref.
LC50-Ecotoxicityon 0.18 - - - - - 0.1 mVI0.033 mVI
Daphniae (c) mVI
G H
Linear alkyl benzene sulfonic 4.7 4.5 5
r-cjd
~laOH to reach pH 7 ~. 0.57 0.64
evenol F-200 . 2.5 2
DEGMBE . 6 .2
Fattyacid C.7 ~.75 0 75
M~SO4 7 H20 .1 .~6
Perfume(a) ~.8 ~. .
Water Bal Ba Ba
pH 7 7 7
(a) contains 25% by weight of terpenes.
(b) the lower the number of strokes, the better the degreasing performance.
(c) the higher the results, the lower the ecotoxicity.
Furthermore, "dissolution power" of the o/w microemulsion of this example is
10 compared to the "dissolution power" of an identical composition except that an equal
amount (5 weight percent) of sodium cumene sulfonate hydrotrope is used in place of
the diethylene glycol monobutyl ether cosurfactant in a test wherein equal
concentrations of heptane are added to both compositions. The o/w microemulsion of
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34
this invention solubilizes 12 grams of the water immiscible substance as compared to
1.4 grams in the hydrotrope containing liquid composition.
In a further comparative test using blue colored cooking oil--a fatty triglyceride
soil --, the composition of Example 1 is clear after the addition of 0.2 grams of cooking
5 oil whereas the cooking oil floats on the top of the composition containing the sulfonate
hydrotrope.
When the concentration of perfume is reduced to 0.4% in the composition of
Example 1, a stable o/w microemulsion composition is obtained. Similarly, a stable o/w
microemulsion is obtained when the concentration of perfume is increased to 2% by
10 weight and the concentration of cosurfactant is increased to 6% by weight in Example
1.
The present invention also relates to an aqueous solution of a grease release
system which comprises:
(a) 0.1 to 20.0 wt. % of a mixture of:
R'
CH2 O (CH2CH O )x B
R'
[ CH O (CH2CH O )y B]w
R' (I)
CH2 O (CH2CH O )z B
and
R'
CH2 O (CH2CH O )x H
R'
[ CH O (CH2CH O )y H]w
R' (I 1)
CH2 O (CH2CH O )z H
wherein w equals one to four. B is selected from the group consisting of hydrogen or a
group represented by:
:
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o
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon
atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B
5 groups is represented by said
o
C R,
R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have
a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I)
the ratio of monoester / diester / triester is 40 to 90 / 5 to 35 / 1 to 20, wherein the ratio
of Formula (I) to Formula (Il) is a value between 3 to 0.02, more preferably 3 to 0.1, and
most preferably 1.5 to 0.2, wherein it is most preferred that there is more of Formu!a (!!)
than Formula (I) in the mixture; and
(b) the balance being water.
The aqueous solution of the grease release agent can be coated onto a hard
surface. The treated hard surface will prevent the adhering of grease to the hard
surface thereby providing easier cleaning of the hard surface with a conventional hard
surface cleaning composition.
Exam~le 2
The example illustrates a typical formulation of a ~'concentrated" o/w
microemulsion based on the present invention:
% by wei~ht
Coco fatty acid 4
Sodium C13-C17 Paraffin Sulfonate 20.75
Levenol F-200 12
Diethylene glycol monobutyl ether 20
Perfume (a) 12.5
Water Bal to 100
pH: 7.0 + 0.2
This concentrated formulation can be easily diluted, for example, five times with
tap water, to yield a diluted o/w microemulsion composition. Thus, by using
microemulsion technology it becomes possible to provide a product having high levels
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36
of active detergent ingredients and perfume, which has high consumer appeal in terms
of clarity, odor and stability, and which is easily diluted at the usual usage concentration
for similar all-purpose hard surface liquid cleaning compositions, while retaining its
cosmetically attractive attributes.
Naturally, these formulations can be used, where desired, without further dilution
and can also be used at full or diluted strength to clean soiled fabrics by hand or in an
automatic laundry washing machine.
Example 3
This example illustrates a diluted o/w microemulsion composition according to
10 the invention having an acidic pH and which also provides improved cleaning
performance on soap scum and lime scale removal as well as for cleaning greasy soil.
% by wei~ht
Sodium C13-C17 paraffin sulfonate 4.7
Levenol F-200 2.3
Mg SO4 7H20 2.2
Mixture of succinic acid/glutaric acid/adipic acid (1:1:1 ) 5
Perfume (d) 1.0
Water, minors (dye) balance to 100
Phosphonic acid 0.2
Amino tris - (methylene-phosphonic acid) 0.03
pH=3 iO.2
(d) contains 40% by weight of terpene
Example 4
Formula A of Example I was tested for the removal of a combination of grease
and particulate soil as well as for a grease release effect and compared to commercial
AjaxtmNME
1. Grease + particulate soil removal;
Test Method
A) Soil composition:
70 9 of mineral oil
35 9 of particulate soil (vacuum cleaner dust + 1% of
carbon black)
35 9 C2CI4
-
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B) Soil Dreparation:
- Weigh cleaned/dried glass tiles
- Soil the tiles with the grease + particulate soil
- Bake the tiles 1 hour at 80C
- Weigh the soiled tiles which aged 2 hours at RT.
C) Soil removal:
The soiled tiles are soaked for 15 minutes at RT in
the test products, then they are delicately rinsed
with tap water.
After drying 45 minutes at 50C, the tiles are
weighed again.
Results
Grease + particulate soil
% of removal
me -n of 6 tiles
Commercial Ajaxtm NME I 60
Formula A of Example I ¦ 95
Formula A exhibits improved grease + particulate soil removal over the
Commercial Ajaxtm NME
Il. Grease release effect
Test Method
A) Soil composition:
20% hardened tallow
80% beef tallow
fat blue dye
B) Soil preparation:
The fat mixture is heated and sprayed with an
automatic spraying device on cleaned and dried
ceramic tiles.
C) Soil removal:
Product used neat: 2.5 9 on sponge
Product used dilute: 1.2% sol in tap water- 10 ml
of the solution on the sponge
The cleaning procedure is done with the gardner
device for both product concentrations.
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Results
A) On treated ceramic tiles (treated with the product before spraying the
soil)
Neat ¦ Dilute
Number of Strokes
First grease layer deposHionmean of 4mean of 6
tiles tiles
Commercial Current Ajaxtm NME27 19
19 5~
Second grease layer deposHion on the mean of 4 mean of 6
same tile tiles tiles
Commercial Ajaxtm NME 25 48
1 8*
B) On untreated ceramic tiles
In addition to the previous test, the 3 following procedures were used to
verify that Formula A remains on the surface a~ter rinsing or wiping. After the first
cleaning procedure and before the second spraying:
1) the tiles were allowed to dry in open air
2) the surface was wiped with paper towel
3) the surface was rinsed with wet sponge
1) dry in open air
Neat ¦ Dilute
Number of Strokes
First grease layer deposHionmean of 4mean of 6
tiles tiles
Commercial Ajaxtm NME 29 30
Formula A 27 32
Second grease layer cleposHion on themean of 4 mean of 6
same tile tiles tiles
Commercial Ajaxtm NME 33 21
FormulaA 30 6
2) wipe dry the surface
Neat ¦ Dilute
Number cf Strokes
First grease layer depositionmean of 4mean of 6
tiles tiles
Commercial Ajaxtm NME 29 30
FormulaA 27 32
Second grease layer deposition on themean of 4 mean of 6
same tile tiles tiles
Commercial Ajaxtm NME 35 46
FormulaA 30 48.5
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3) wet wiping the surface
Neat ¦ Dilute
Number Gf Strokes
First grease layer depos~ n mean of 4 mean of 6
tiles tiles
Commercial Ajaxtm NME 29 30
Formula A 27 32
Second grease layer del~os;li~n on the mean of 4 mean of 6
same tile . tiles tiles
Commercial Ajaxtm NME 34 58
Formula A 27 41
* highly significant difference
** after 5 strokes, 65% of the grease is already removed
These results clearly demonstrate the important grease release effect obtained
with Formula A especially when the product is used dilute.
Example ~
The following liquid crystal compositions were prepared by simple mixing procedure
B
Sodium C13-C17 Paraffin sulfonate~.~ 4.3 ~.3
Levenol F-200 ~ . 2.2 .. 2
Propylene glycol monbutyl eth;r
Dipropyl ne glycol monbutyl e ler - 3.5
ripropy ne ~Iycol monbutyl e-her
attyac ~ 0 5 ~ -
ulgS04 H20 1.6 .6 .6
P ~rfume (a) 1 . : .
~ater Bal Ba Ba
p~ 7 7 7
0 ExamDle 6
The following optically clear microemulsion compositions were made by forming first a
solution by mixing at 25C water, magnesium lauryl ether sulfate, Levenol V-510/2 and
1-Pentanol. To this solution with mixing at 25C was added the dodecane to form the
optically clear microemulsion. The formula are expressed in weight percent.
A B C D E F G H
Magnesium 7 2.04 3.04 4.99 3.01 6.38 5.01 4.02 2.99
Lauryl suHate
LevenolV-501/2 3.2 .1 7. . 7. 3.9 .~ 6. ~ 7.2
1-Pentanol .1 .0 4. ~.0 . 5.67 . . 1.13
Dodecane .2 ~C.717.' 6 1 .22 ~.: 7 15.2 2. ' . 2.9
water Ba Ba Bal Bal Bal Bal Ba Ba Bal
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Fxample 7
The following composition was prepared by simple mixing procedure:
Sodium C 1 3-C17 4.0
Paraffin Sulfonate
Levenol F-200 2.0
DEGMBE 4.5
Fatty Acid 0.5
MgSO4 7H2O 1.8
Perfume (a) 0.8
tri-n-butyl citrate 0.5
Water Balance
pH 7
Degreasing test
Neat (6)
Dilute (6)
Residue
Foam in hand
Water
(a) contains 25% by weight of terpenes
(b) the lower the number of strokes, the better the degreasing
performance.
The addition of the tri-n-butyl citrate improves the rinsability of the surface being
rinsed in that the collapse of the foam is improved as compared to a composition not
containing the tri-n-butyl citrate.
In summary, the described invention broadly relates to an improvement in
microemulsion compositions containing an anionic surfactant, an ethoxylated glycerol
type compound, a fatty acid, one of the specified cosurfactants, a hydrocarbon
ingredient and water which comprise the use of a water-insoluble, odoriferous perfume
as the essential hydrocarbon ingredient in a proportion sufficient to form either a dilute
o/w microemulsion composition or liquid crystal composition containing, by weight,
0.1% to 20.0% of an anionic detergent, 0.1% to 10% of an ethoxylated glycerol type
compound, 0% to 50% of cosurfactant, 0 to 1.0% of a tri-alkyl citrate, 0.4% to 10% of
perfume and the balance being water.
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Fxample 8
The following compositions in wt. % were prepared:
A B C D E F
Na C13-17 paraffin 4.7 4.7 4.7 4.7 4.7 4.7
sul~onate
DEGtv BE 4 4 4 4 4 4
Coco attyacidt.'5 C 7 C.75 C 7 ~.75 C 7
MgSO4 . . ~ .2 ~.
Perfume ~ .. .8
Compounc a) . j , 7 I , - ..
Compounc b) . ~~
~~ompounc c). ,~ . ~ .~
~,ompounc d) . 5 . 1. 78 . 2.3 --
~ eodol 91- -- -- -- -- -- 2.3
Water Bal. Bal.Bal. Bal. Bal. Bal.
PhasebehaviorOne One One One One One
phase phasephasephase phase phase
Particulate soil 71.079.8 84.0 86.0 88.7 51.0
(Kaolin removal
Compound (a) is
CH2 - 0 (cH2cH2o)2 R 1
CH - 0 (cH2cH2o)2 R2
CH2 - 0 (cH2cH2o)2 R3
wherein R1, R2 and R3 are coco alkyl chains
10 Compound (b) is
CH2 - 0 (CH2CH20)2 R4
CH - 0 (CH2CH20)2 Rs
CH2 - 0 (CH2CH20)2 H
wherein R4 and Rs are coco alkyl chains
15 Compound (c) is
CH2 - 0 (CH2CH20)2 R6
CH - 0 (CH2CH20)2 H
CH2 - 0 (CH2CH20)2 H
wherein R6 is a coco alkyl chains
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Compound (d) is
CH2 - O (CH2CH2O)2 H
CH - O (CH2CH2O)2 H
CH2 - O (CH2CHzO)2 H
In summary, the described invention broadly relates to an improvement in
microemulsion compositions for the removal of particulate soil containing an anionic
surfactant, an ethoxylated polyhydric alcohol a cosurfactantl a hydrocarbon ingredient
and water which comprise the use of a water-insoluble, odoriferous perfume as the
essential hydrocarbon ingredient in a proportion sufficient to form either a dilute o/w
microemulsion composition or liquid crystal composition containing, by weight, 0.1% to
20% of an anionic detergent, 0.1% to 20.0% of an ethoxylated polyhydric alcohol, 0% to
50% of cosurfactant, 0.4% to 10% of perfume and the balance being water
In summary, the described invention broadly relates to an improvement in
microemulsion compositions containing an anionic surfactant, an esterified
polyethoxyether nonionic surfactant, a fatty acid, one of the specified cosurfactants, a
hydrocarbon ingredient and water which comprise the use of a water-insoluble,
odoriferous perfume as the essential hydrocarbon ingredient in a proportion sufficient to
form either a dilute o/w microemulsion composition or liquid crystal compositioncontaining, by weight, 0.1% to 20% of an anionic detergent, 0.1% to 20.0% of a
solubilizing agent which is an ethoxylated glycerol type compound, 0% to 50% of
cosurfactant, 0.4% to 10% of perfume and the balance being water.
