[0001] This invention relates to an improved light duty liquid cleaner in the form of a
microemulsion designed in particular for cleaning hard surfaces and which is effective
in removing grease soil and/or kitchen soil and in leaving unrinsed surfaces with
a shiny appearance.
Background Of The Invention
[0002] In recent years liquid detergents have become widely accepted for cleaning hard surfaces,
e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or
tile floors, washable wall paper, etc.. Such 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 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.
[0003] In view of the environmentalist's efforts to reduce phosphate levels in ground water,
improved all-purpose liquids containing reduced concentrations of inorganic 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.
[0004] However, these prior art 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 rinsing of the cleaned
surfaces which is a time-consuming chore for the user.
[0005] In order to overcome the foregoing disadvantage of the prior art, 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 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.
[0006] Another approach to formulating hard surface liquid detergent compositions 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 product stability. By definition, an o/w
microemulsion is a spontaneously forming colloidal dispersion of "oil" phase particles
having a particle size in the range of about 25 to about 800 Å 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.
[0007] Patent disclosures relating to use of grease-removal solvents in o/w microemulsions
include, for example, European Patent Applications EP 0137615 and EP 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.
[0008] It also is known from British Patent Application GB 2144763A 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 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.
[0009] However, since the amount of water immiscible and sparingly soluble components which
can be present in an o/w microemulsion, with low total active ingredients 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 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.
[0010] 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) lying 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
15°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 C13-C24 fatty acid; a calcium sequestrant from about .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., 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.
[0011] Furthermore, the present inventors have observed that in formulations containing
grease-removal assisting magnesium compounds, the addition of minor amounts of builder
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.
Summary of the Invention
[0012] The present invention provides an improved, clear light duty liquid cleaning composition
having improved interfacial tension which improves cleaning hard surface in the form
of a microemulsion which is suitable for cleaning hard surfaces such as dishes, plastic,
vitreous and metal surfaces having a shiny finish. The light duty liquid microemulsion
compositions of the instant invention can be generally described as comprising by
weight:
(a) 15% to 36%, preferably 18% to 34%, of a magnesium metal salt of a sulfonate surfactant;
(b) 1% to 20%, more preferably 2% to 18% of an alkali metal salt or ammonium salt
of a C8-C18 alkyl polyethenoxy sulfate surfactant, wherein the ratio of sulfonate surfactant
to the sulfate surfactant is preferably 8:1 to 1:8, more preferably 7:1 to 1:2;
(c) 0% to 10%; more preferably 1% to 5% of an alkyl polyglucoside surfactant;
(d) 0.4% to 10.0%, more preferably 2.0% to 7.0% of a perfume, an essential oil or
a water insoluble hydrocarbon;
(e) 1% to 25%, more preferably 2 to 8% of a cosurfactant;
(f) 0 to 5%, more preferably 0.1 to 3% of at least one hydrotrope;
(g) 0 to 4%; more preferably 0.1 to 2% of magnesium sulfate;
(h) 0 to 5%, more preferably 0.5 to 3% of an alkyl monoalkanol amide or an alkyl dialkanol
amide and mixtures thereof; and
(i) water. Such a composition has a Brookfield viscosity at 25°C at 3 rpms using a
#18 spindle spindle of 20 to 500 cPa.S (cps), more preferably 100 to 450 cPa.s (cps),
a pH of 5 to 7, and a light transmission of at least 95%, more preferably at least
98%.
Detailed Description of the Invention
[0013] The present invention relates to a stable microemulsion composition comprising by
weight: 0% to 10% of an alkyl polyglucoside surfactant, 15% to 36% of a magnesium
salt of a sulfonate anionic surfactant, 1% to 20% of a metal or ammonium salt of C
8-C
18 alkyl ether polyethenoxysulfate surfactant, 1% to 25% of a cosurfactant, 0.4% to
10% of a water insoluble hydrocarbon, essential oil or a perfume, 0 to 5% of at least
one hydrotrope, 0 to 4% of magnesium sulfate, 0 to 5% of an alkyl monoalkanolamide
or an alkyl dialkanol amide and mixtures thereof and water. Such a composition has
a light transmission of at least 95%, more preferably at least 98%.
[0014] According to the present invention, the role of the hydrocarbon is provided by a
water insoluble 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 oils and
aromatic compounds which are generally not water-soluble. Therefore, by incorporating
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.
[0015] 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).
[0016] Second, the need for use of solubilizers, which do not contribute to cleaning performance,
is eliminated.
[0017] As used herein and in the appended claims the term "perfume" is used in its ordinary
sense to refer to and include any water insoluble 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 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%, usually from 10% to 70% by weight, the essential oils themselves being volatile
odoriferous compounds and also serving to dissolve the other components of the perfume.
[0018] In the present invention the precise composition of the perfume is of no particular
consequence to cleaning performance so long as it meets the criteria of water immiscibility
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.
[0019] The hydrocarbon such as a perfume is present in the dilute o/w microemulsion in an
amount of from 0.4% to 10% by weight, preferably from 1.0% to 8.0% by weight, especially
preferably from 2% to 7% by weight. If the amount of hydrocarbon (perfume) is less
than 0.4% by weight it becomes difficult to form the o/w microemulsion. If the hydrocarbon
(perfume) is added in amounts more than 10% by weight, the cost is increased wihout
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 taken up in the oil
phase of the microemulsion will decrease proportionately.
[0020] 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 include less than 20%, usually
less than 30%, of such terpene solvents.
[0021] 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 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.
[0022] In place of the perfume one can employ an essential oil such as d-limonene or alpha-terpineol,
a water insoluble paraffin or isoparaffin having 6 to 18 carbon at a concentration
of 0.4 to 10.0 wt. percent, more preferably 2.0 to 7.0 wt. %.
[0023] Suitable water-soluble non-soap, anionic detergents include those surface-active
or detergent compounds which contain an organic hydrophobic group containing generally
8 to 26 carbon atoms and preferably 10 to 18 carbon atoms in their molecular structure
and at least one sulfonate group so as to form a water-soluble detergent. Usually,
the hydrophobic group will include or comprise a C
8-C
22 alkyl, alkylaryl or acyl group. Such detergents are employed in the form of magnesium
salts.
[0024] Examples of suitable sulfonated anionic detergents 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 or branched chain,
C
8-C
15 alkyl toluene sulfonates and C
8-C
15 alkyl phenol sulfonates.
[0025] A preferred sulfonate is linear alkyl benzene sulfonate 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 correspondingly low. Particularly preferred materials are set forth
in U.S. Patent 3,320,174.
[0026] Other examples of suitable anionic sulfonate detergents are the paraffin sulfonates
containing 10 to 20, preferably 13 to 17, carbon atoms. 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 Nos. 2,503,280; 2,507,088; 3,260,744; 3,372,188: and German Patent 735,096.
[0027] The proportion of the nonsoap-anionic sulfonate detergent will be in the range of
15% to 36%, preferably from 18% to 34%, by weight of the dilute o/w microemulsion
composition.
[0028] Examples of satisfactory anionic sulfate detergents are the C
8-C
18 alkyl ether polyethenoxy sulfate salts having the formula R(OC
2H
4)
n OSO
3M wherein n is 1 to 12, preferably 1 to 5, and M is a solubilizing cation selected
from the group consisting of alkali metal cations such as sodium or potassium, alkaline
earth metal cations such as magnesium, ammonium, and mono-, di- and triethanol ammonium
ions, wherein sodium, potassium and ammonium are preferred. The alkyl ether polyethenoxy
sulfates are obtained by sulfating the condensation product of ethylene oxide with
a C
8-C
18 alkanol and neutralizing the 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 ether polyethenoxy sulfates contain 10 to 16 carbon
atoms in the alkyl group.
[0029] The C
8-C
12 alkylphenyl ether polyethenoxy sulfates containing from 2 to 6 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.
[0030] Of the foregoing non-soap anionic detergents, the preferred detergents are the magnesium
C
9-C
15 linear alkylbenzene sulfonates and the magnesium C
13-C
17 paraffin or alkane sulfonates. Particularly, preferred compounds are magnesium C
10-C
13 alkylbenzene sulfonate and magnesium C
13-C
17 alkane sulfonate.
[0031] Generally, the proportion of the nonsoap-anionic alkyl ether polyethenoxy sulfate
detergent will be in range 1% to 20%, preferably 2% to 18% by weight of the dilute
o/w microemulsion composition, wherein the ratio of paraffin sulfonate to the alkyl
ether polyethenoxy sulfate is preferably 8:1 to 1:8, more preferably 7:1 to 1:2.
[0032] The cosurfactant may play an essential role in the formation of the 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 to form
either a micellar solution (low concentration) or form an oil-in-water emulsion. 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 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 bending); (3) droplet dispersion 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 and 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.
[0033] The highly suitable cosurfactants of the instant composition over temperature ranges
extending from 4°C to 43°C are water-soluble C
2-C
4 alkanols, polypropylene glycol of the formula HO(CH
3CHCH
2O)
nH wherein n is a number from 1 to 18 and monoalkyl ethers and esters of ethylene glycol
and propylene glycol having the structural formulas R(X)
nOH and R
1(X)
nOH wherein R is C
1-C
6 alkyl, R
1 is C
2-C
4 acyl group, X is (OCH
2CH
2) or (OCH
2CHCH
3) and n is a number from 1 to 4.
[0034] 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.
[0035] 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 glycerol, dipropylene glycol monomethyl ether
and propylene glycol. Less preferred cosurfactants are ethanol, propanol, isopropanol,
butanol, isobutanol and alkanols having 5 to 7 carbon atoms.
[0036] 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 perfumes, 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. Generally, amounts
of cosurfactant in the range of from 1% to 25%, preferably from 1% to 15%, especially
preferably from 2% to 8%, 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.
[0037] The essential ingredients discussed above can be solubilized in one prefered embodiment
of the invention in water and either an alkyl monoethanol amide such as C
12-C
14 alkyl monoethanol amide (LMMEA) at a concentration of 0 to 5 wt. %, or an alkyl diethanol
amides such as coco diethanol amide (CDEA) or lauryl diethanol amide (LDEA) at a concentration
of 0 to 5 wt. %, preferably 0.5 wt. % to 3 wt. % and mixtures thereof. The instant
formulas can contain both alkyl monoethanol amide and alkyl diethanol amide. The solubilizing
ingredient can also include 0 to 5 wt. %, preferably 0.1 wt. % to 3 wt. % of at least
one water soluble salt of a C
1-C
3 substituted benzene sulfonate hydrotrope such as sodium xylene sulfonate or sodium
cumene sulfonate or a mixture of said sulfonates. Inorganic alkali metal or alkaline
earth metal salts such as sodium sulfate, magnesium sulfate. sodium chloride and sodium
citrate can be added to the microemulsion at concentrations of 0.5 to 4.0 wt.%. Other
ingredients which have been added to the compositions at concentrations of 0.1 to
4.0 wt. percent are perfumes, preservatives, color stabilizers, sodium bisulfite,
ETDA, HETDA and proteins such as lexine protein.
[0038] In addition to the previously mentioned essential and optional constituents of the
light duty liquid microemulsion detergent, one may also employ normal and conventional
adjuvants, provided they do not adversely affect the properties of the detergent.
Thus, there may be used various coloring agents and perfumes; sequestering agents
such as ethylene diamine tetraacetates; magnesium sulfate heptahydrate; pearlescing
agents and opacifiers; pH modifiers; etc. The proportion of such adjuvant materials,
in total will normally not exceed 15% of weight of the detergent composition, and
the percentages of most of such individual components will be 0.1 to 5% by weight
and preferably less than 2% by weight. Sodium bisulfite can be used as a color stabilizer
at a concentration of 0.01 to 0.2 wt.%. Typical perservatives are dibromodicyano-butane,
citric acid, benzylic alcohol and poly (hexamethylene-biguamide) hydrochloride and
mixtures thereof.
[0039] The instant compositions can contain 0 to 10 wt. %, more preferably 1 wt. % to 6
wt. % of an alkyl polysaccharide surfactant. The alkyl polysaccharides surfactants,
which are used in conjunction with the aforementioned surfactant have a hydrophobic
group containing from 8 to 20 carbon atoms, preferably from 10 to 16 carbon atoms,
most preferably from 12 to 14 carbon atoms, and polysaccharide hydrophilic group containing
from 1.5 to 10, preferably from 1.5 to 4, most preferably from 1.6 to 2.7 saccharide
units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl; and/or galactosyl
units). Mixtures of saccharide moieties may be used in the alkyl polysaccharide surfactants.
The number x indicates the number of saccharide units in a particular alkyl polysaccharide
surfactant. For a particular alkyl polysaccharide molecule x can only assume integral
values. In any physical sample of alkyl polysaccharide surfactants there will be in
general molecules having different x values. The physical sample can be characterized
by the average value of x and this average value can assume non-integral values. In
this specification the values of x are to be understood to be average values. The
hydrophobic group (R) can be attached at the 2-, 3-, or 4- positions rather than at
the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside
or galactoside). However, attachment through the 1- position, i.e., glucosides, galactoside,
fructosides, etc., is preferred. In the preferred product the additional saccharide
units are predominately attached to the previous saccharide unit's 2-position. Attachment
through the 3-, 4-, and 6- positions can also occur. Optionally and less desirably
there can be a polyalkoxide chain joining the hydrophobic moiety (R) and the polysaccharide
chain. The preferred alkoxide moiety is ethoxide.
[0040] Typical hydrophobic groups include alkyl groups, either saturated or unsaturated,
branched or unbranched containing from 8 to 20, preferably from 10 to 18 carbon atoms.
Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group
can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to
30, preferably less than 10, alkoxide moieties.
[0041] Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl,
and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides,
fructosides, fructosyls, lactosyls, glucosyls and/or galactosyls and mixtures thereof.
[0042] The alkyl monosaccharides are relatively less soluble in water than the higher alkyl
polysaccharides. When used in admixture with alkyl polysaccharides, the alkyl monosaccharides
are solubilized to some extent. The use of alkyl monosaccharides in admixture with
alkyl polysaccharides is a preferred mode of carrying out the invention. Suitable
mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow
alkyl tetra-, penta-, and hexaglucosides.
[0043] The preferred alkyl polysaccharides are alkyl polyglucosides having the formula
RO(C
nH
2nO)
r(Z)
x
wherein Z is derived from glucose, R is a hydrophobic group selected from the group
consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which
said alkyl groups contain from 10 to 18, preferably from 12 to 14 carbon atoms; n
is 2 or 3 preferably 2, r is from 0 to 10, preferable 0; and x is from 1.5 to 8, preferably
from 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a long
chain alcohol (ROH) can be reacted with glucose, in the presence of an acid catalyst
to form the desired glucoside. Alternatively the alkyl polyglucosides can be prepared
by a two step procedure in which a short chain alcohol (C
1-6) is reacted with glucose or a polyglucoside (x=2 to 4) to yield a short chain alkyl
glucoside (x=1 to 4) which can in turn be reacted with a longer chain alcohol (ROH)
to displace the short chain alcohol and obtain the desired alkyl polyglucoside. If
this two step procedure is used, the short chain alkylglucosde content of the final
alkyl polyglucoside material should be less than 50%, preferably less than 10%, more
preferably less than 5%, most preferably 0% of the alkyl polyglucoside.
[0044] The amount of unreacted alcohol (the free fatty alcohol content) in the desired alkyl
polysaccharide surfactant is preferably less than 2%, more preferably less than 0.5%
by weight of the total of the alkyl polysaccharide. For some uses it is desirable
to have the alkyl monosaccharide content less than 10%.
[0045] The used herein, "alkyl polysaccharide surfactant" is intended to represent both
the preferred glucose and galactose derived surfactants and the less preferred alkyl
polysaccharide surfactants. Throughout this specification, "alkyl polyglucoside" is
used to include alkyl polyglycosides because the stereochemistry of the saccharide
moiety is changed during the preparation reaction.
[0046] An especially preferred APG glycoside surfactant is APG 625 glycoside manufactured
by the Henkel Corporation of Ambler, PA. APG25 is a nonionic alkyl polyglycoside characterized
by the formula:
C
nH
2n+1O(C
6H
10O
5)
xH
wherein n=10 (2%); n=12 (65%); n=14 (21-28%); n= 16 (4-8%) and n=18 (0.5%) and x (degree
of polymerization) = 1.6. APG 625 has: a pH of 6 to 10(10% of APG 625 in distilled
water); a specific gravity at 25°C of 1.1 g/ml; a density at 25°C of 1.09 kilograms/liter;
a calculated HLB of 12.1 and a Brookfield viscosity at 35°C, 21 spindle, 5-10 RPM
of 3,000 to 7,000 c Pa.s (cps).
[0047] The final essential ingredient in the inventive light duty liquid microemulsion compositions
having improved interfacial tension properties is water. The proportion of water in
the microemulsion compositions generally is in the range of 20% to 97%, preferably
70% to 97% by weight of the usual diluted o/w microemulsion composition.
[0048] As believed to have been made clear from the foregoing description, the light duty
liquid microemulsion compositions of this invention are especially effective when
used as is, that is. without further dilution in water, since the properties of the
composition as a microemulsion are best manifested in the neat (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 dilutions up to about 50% will generally be well tolerated
without causing phase separation, that is, the microemulsion state will be maintained.
[0049] However, even when diluted to a great extent, such as a 2- to 10-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 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.
[0050] In addition to the above-described essential ingredients required for the formation
of the microemulsion composition, the compositions of this invention may possibly
contain one or more additional ingredients which serve to improve overall product
performance.
[0051] One such ingredient is an inorganic or organic salt or 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 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 pH since magnesium hydroxide will not
precipitate at these pH levels.
[0052] 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 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. can be employed. It should be noted, for example, that with the
preferred 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
when a low level, for example about 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.
[0053] The light duty liquid microemulsion composition of this invention may, if desired,
also 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-chloro-2-methyl-4-isothaliazolin-3-one,
2,6-di-tert.butyl-p-cresol, etc., in amounts up to 2% by weight; and pH adjusting
agents, such as sulfuric acid or sodium hydroxide, as needed.
[0054] 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 and 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 use elevated temperatures
in the formation step and room temperature is sufficient.
[0055] 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.
Example 1
[0056] The following compositions in wt. % were prepared by the previously described process:
| |
A |
B |
C* |
D |
E* |
| Mg (LAS)2 |
20 |
24 |
4 |
30 |
24 |
| NH4AEOS1.3EO |
12 |
8 |
30 |
4 |
8 |
| LMMEA |
2 |
2 |
0 |
0 |
2 |
| D-Limonene |
4 |
4 |
4 |
4 |
0 |
| Dipropylene glycol monomethyl ether |
4 |
4 |
4 |
4 |
0 |
| APG 625 |
0 |
0 |
0 |
0 |
2 |
| Sodium cumene sulfonate |
1. |
1 |
1 |
1 |
0 |
| Sodium xylene sulfonate |
1.2 |
1.2 |
0 |
0 |
1.2 |
| Water |
Bal. |
Bal. |
Bal. |
Bal. |
Bal. |
| pH |
7 |
7 |
7 |
7 |
7 |
| Light transmission % |
98 |
98 |
98 |
98 |
98 |
| Initial shake foam |
383 |
295 |
348 |
258 |
304 |
| Shake foam with sod |
183 |
11 |
17 |
78 |
168 |
| Miniplate |
36 |
40 |
33 |
42 |
45 |
| Lard removal |
37 |
50 |
0 |
44 |
76 |
| Shell foam ratio |
82 |
88 |
80 |
64 |
96 |
| Gardner Strokes |
|
|
|
|
|
| Neat |
8 |
9 |
10 |
8 |
>14 |
| |
F* |
G |
H |
I |
J |
| Mg (LAS)2 |
24 |
24 |
24 |
24 |
24 |
| NH4AEOS1.3EO |
8 |
8 |
8 |
8 |
8 |
| LMMEA |
2 |
2 |
2 |
2 |
2 |
| D-Limonene |
0 |
2 |
4 |
6 |
8 |
| Dipropylene glycol monomethyl ether |
0 |
2 |
4 |
6 |
8 |
| APG 625 |
0 |
0 |
0 |
0 |
0 |
| Sodium cumene sulfonate |
0 |
0 |
0 |
0 |
0 |
| Sodium xylene sulfonate |
1.2 |
1.2 |
1.2 |
1.2 |
1.2 |
| Water |
Bal. |
Bal. |
Bal. |
Bal. |
Bal. |
| pH |
7 |
7 |
7 |
7 |
7 |
| Light transmission % |
98 |
98 |
98 |
98 |
98 |
| Initial shake foam |
310 |
305 |
313 |
312 |
307 |
| Shake foam with soil |
192 |
174 |
195 |
162 |
171 |
| Miniplate |
46 |
46 |
44 |
45 |
43 |
| Lard removal |
65 |
69 |
60 |
68 |
-- |
| Shell foam ratio |
80 |
90 |
77 |
82 |
77 |
| Gardner Strokes |
|
|
|
|
|
| Neat |
>14 |
12 |
7 |
5 |
-- |
| |
K |
L |
M |
Dawn |
Palmolive |
| Mg (LAS)2 |
24 |
24 |
24 |
|
|
| NH4AEOS1.3EO |
8 |
8 |
8 |
|
|
| LMMEA |
2 |
2 |
2 |
|
|
| D-Limonene |
10 |
4 |
6 |
|
|
| Dipropylene glycol monomethyl ether |
10 |
4 |
6 |
|
|
| APG 625 |
0 |
1.5 |
1.5 |
|
|
| Sodium cumene sulfonate |
0 |
1 |
1 |
|
|
| Sodium xylene sulfonate |
1.2 |
1.2 |
1.2 |
|
|
| Water |
Bal. |
Bal. |
Bal. |
|
|
| pH |
7 |
7 |
7 |
6.5 |
7 |
| Light transmission % |
98 |
98 |
98 |
|
|
| Initial shake foam |
295 |
265 |
260 |
327 |
328 |
| Shake foam with soil |
187 |
120 |
107 |
218 |
140 |
| Miniplate |
46 |
45 |
46 |
49 |
35 |
| Lard removal |
-- |
49 |
51 |
40 |
46 |
| Shell foam ratio |
84 |
89 |
89 |
154 |
100 |
| Gardner Strokes |
|
|
|
|
|
| Neat |
-- |
9 |
6 |
14 |
>14 |
[0057] In summary, the described invention broadly relates to an improvement in a light
duty liquid microemulsion composition containing a mixture of a paraffin sulfonate
surfactant and an alkyl polyethenoxy ether sulfate surfactant, a biodegradable surfactant,
one of the specified cosurfactants, a hydrocarbon ingredient and water to form a light
duty liquid microemulsion composition.
1. Flüssige Feinreinigungzusammensetzung in Form einer Mikroemulsion, die bezogen auf
das Gewicht umfaßt:
15 bis 36% eines Magnesiumsalzes eines Sulfonattensids, 1 bis 20% eines Metall-
oder Ammoniumsalzes eines C8- bis C18-Alkyletherpolyethenoxysulfattensids, 0 bis 10% eines Alkylpolyglukosids, 0,4 bis
10,0% eines wasserunlöslichen Kohlenwasserstoffs, essentiellen Öls oder Parfüms, 1
bis 25% eines Cotensids, 0 bis 5% mindestens eines Hydrotrops, 0 bis 4% Magnesiumsulfat,
0 bis 5% eines Alkylmonoalkanolamids oder eines Alkyldialkanolamids oder einer Mischung
derselben und Wasser.
2. Flüssige Feinreinigungszusammensetzung in Form einer Mikroemulsion nach Anspruch 1,
bei der das Sulfonat und das Alkyletherpolyethenoxysulfat in einem Verhältnis von
8:1 bis 1:8 vorhanden sind.
3. Reinigungszusammensetzung nach Anspruch 2, die ferner ein Salz eines mehrwertigen
Metallkations in einer Menge enthält, die ausreicht, um 0,5 bis 1,5 Äquivalente des
Kations pro Äquivalent des Sulfonattensids zu liefern.
4. Reinigungszusammensetzung nach Anspruch 3, bei der das mehrwertige Metallkation Magnesium
oder Aluminium ist.
5. Reinigungszusammensetzung nach Anspruch 3, bei der die Zusammensetzung 0,9 bis 1,4
Äquivalente des Kations pro Äquivalent des Sulfonattensids enthält.
6. Reinigungszusammensetzung nach Anspruch 4, bei der das mehrwertige Salz Magnesiumsulfat
ist.
7. Reinigungszusammensetzung nach Anspruch 2, die 2 bis 8 Gew.% des Cotensids und 2,0
bis 7,0 Gew.% des Kohlenwasserstoffs enthält.
8. Reinigungszusammensetzung nach Anspruch 2, bei der das Cotensid ein wasserlöslicher
Glykolether ist.
9. Reinigungszusammensetzung nach Anspruch 8, bei der der Glykolether ausgewählt ist
aus der Gruppe bestehend aus Ethylenglykolmonobutylether, Diethylenglykolmonobutylether,
Triethylenmonoglykolbutylether, Polypropylenglykol mit einem durchschnittlichen Molekulargewicht
von 200 bis 1000 und Propylenglykoltert.-butylether sowie Mono-, Di- und Tripropylenglykolmonobutylether
und Mischungen derselben.
10. Reinigungszusammensetzung nach Anspruch 9, bei der der Glykolether Dipropylenglykolmonomethylether
ist.
11. Reinigungszusammensetzung nach Anspruch 2, bei der das Sulfonattensid ein C9- bis C15- Alkylbenzolsulfonat oder ein C13- bis C17- Paraffinsulfonat ist.
12. Reinigungszusammensetzung nach Anspruch 1, bei der das Metall des Metallsalzes des
Alkyletherpolyethenoxysulfats ausgewählt ist aus Kalium und Natrium.