AU678007B2 - High foaming nonionic surfactant based liquid detergent - Google Patents

Abstract

A high foaming, nonionic surfactant based, light duty liquid detergent with desirable cleansing properties and mildness to the human skin comprising: a water soluble nonionic surfactant; at least one water soluble or dispersible foaming, anionic surfactant; a zwitterionic betaine surfactant, and a dialkyl sulfosuccinate ester.

Description

1

AUSTRALIA

Patents Act 1990 COLGATE-PALMOLIVE COMPANY

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT s o Invention Title: "High foaming nonionic surfactant based liquid detergent" o The following statement is a full description of this invention including the best method of performing it known to us:- Background Of The Invention The present invention relates to novel light duty liquid detergent compositions with high foaming properties, containing a nonionic surfactant, at least one anionic surfactant, a Zwitterionic betaine surfactant and a dialkyl sulfosuccinate, all of which c are dissolved in an aqueous medium.

Nonionic surfactants are in general chemically inert and stable toward pH change and are therefore well suited for mixing and formulation with other materials.

The superior performance of nonionic surfactants on the removal of oily soil is well recognized. Nonionic surfactants are also known to be mild to human skin. However, tO as a class, nonionic surfactants are known to be low or moderate foamers.

Consequently, for detergents which require copious and stable foam, the application of nonionic surfactants is limited. There have been substantial interest and efforts to develop a high foaming detergent with nonionic surfactants as the major ingredient.

Little has been achieved.

1c The prior art is replete with light duty liquid detergent compositions containing nonionic surfactants in combination with anionic and/or betaine surfactants wherein Sthe nonionic detergent is not the major active surfactant, as shown in U.S. Patent No.

3,658,985 wherein an anionic based shampoo contains a minor amount of a fatty acid alkanolamide. U.S. Patent No. 3,769,398 discloses a betaine-based shampoo ?0 containing minor amounts of nonionic surfactants. This patent states that the low foaming properties of nonionic detergents renders its use in shampoo compositions non-preferred. U.S. Patent No. 4,329,335 also discloses a shampoo containing a betaine surfactant as the major ingredient and minor amounts of a nonionic surfactant and of a fatty acid mono- or di-ethanolamide. U.S. Patent No. 4,259,204 discloses a dS shampoo comprising 0.8-20% by weight of an anionic phosphoric acid ester and one additional surfactant which may be either anionic, amphoteric, or nonionic. U.S.

Patent No. 4,329,334 discloses an anionic-amphoteric based shampoo containing a

~L

major amount of anionic surfactant and lesser amounts of a betaine and nonionic surfactants.

U.S. Patent No. 3,935,129 discloses a liquid cleaning composition based on the alkali metal silicate content and containing five basic ingredients, namely, urea, S glycerin, triethanolamine, an anionic detergent and a nonionic detergent. The silicate content determines the amount of anionic and/or nonionic detergent in the liquid cleaning composition. However, the foaming property of these detergent compositions is not discussed therein.

U.S. Patent No. 4,129,515 discloses a heavy duty liquid detergent for tV laundering fabrics comprising a mixture of substantially equal amounts of anionic and nonionic surfactants, alkanolamines and magnesium salts, and, optionally, zwitterionic surfactants as suds modifiers.

U.S. Patent No. 4,224,195 discloses an aqueous detergent composition for laundering socks or stockings comprising a specific group of nonionic detergents, 5 namely, an ethylene oxide of a secondary alcohol, a specific group of anionic detergents, namely, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, and an amphoteric surfactant which may be a betaine, wherein either the anionic or nonionic surfactant may be the major ingredient.

The prior art also discloses detergent compositions containing all nonionic *r0 surfactants as shown in U.S. Patent Nos. 4,154,706 and 4,329,336 wherein the shampoo compositions contain a plurality of particular nonionic surfactants in order to effect desirable foaming and detersive properties despite the fact that nonionic surfactants are usually deficient in such properties.

U.S. Patent No. 4,013,787 discloses a piperazine based polymer in $c conditioning and shampoo compositions which may contain all nonionic surfactant or all anionic surfactant.

U.S. Patent No. 4,450,091 discloses high viscosity shampoo compositions containing a blend of an amphoteric betaine surfactant, a

I---I

polyoxybutylenepolyoxyethylene nonionic detergent, an anionic surfactant, a fatty acid alkanolamide and a polyoxyalkylene glycol fatty ester.

U.S. Patent No. 4,595,526 describes a composition comprising a nonionic surfactant, a betaine surfactant, an anionic surfactant and a C 1 2-

C

14 fatty acid monoethanolamide foam stabilizer.

However, none of the above-cited patents discloses a high foaming, nonionic based, liquid detergent composition containing a nonionic surfactant, at least one anionic surfactant, a dialkyl sulfosuccinate and a foaming zwitterionic surfactant selected from betaine type surfactants, wherein the composition does not contain any fO amine oxide, calcium carbonate, alkali metal carbonate, polymeric or clay thickeners, abrasive, clays, silicas, alkanol amides, (for example cocodiethanol amide), alkyl glycine surfactant, cyclic imidinium surfactant, or more than 3.0 wt. of a fatty acid or i: a metal salt of the fatty acid compounds.

S Summary Of The invention IS.. It has now been found that a high foaming liquid detergent can be formulated with a nonionic surfactant which has desirable cleaning properties, mildness to the human skin.

Another object of this invention is to provide novel, liquid aqueous detergent compositions containing a nonionic surfactant, at least one anionic surfactant, a dialkyl sulfosuccinate and a zwitterionic betaine surfactant, wherein the composition does not contain amine oxide, a fatty acid alkanolamide foam stabilizer, an alkali metal or alkaline earth metal carbonate, polymeric or clay thickeners, clays, abrasives, alkyl glycine surfactants, cyclic imidinium surfactants, silicas or more than 3 wt. of a fatty acid or a metal salt of a fatty acid.

<S Still another object of this invention is to provide a novel, liquid detergent with desirable high foaming and cleaning properties which is mild to the human skin.

Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.

To achieve the foregoing and other objects and in accordance with the purpose of the present invention, as embodied and broadly described herein the novel, high foaming, light duty liquid detergent of this invention comprises four essential surfactants: a water soluble, ethoxylated, nonionic surfactant, at least one foaming anionic surfactant selected from the group consisting of water soluble organic sulfates, an ethoxylated alkyl ether sulfate and organic sulfonates; a foaming water soluble, fO zwitterionic surfactant selected from the class of betaines and a dialkyl sulfosuccinate, wherein the ingredients are dissolved in an aqueous vehicle and the composition does not contain any amine oxide, alkanolamide ingredients, clays, silicas, builder salts or abrasives.

More specifically, the present invention relates to a high foaming, nonionic based, liquid detergent comprising: a nonionic surfactant selected from the group consisting of water soluble primary aliphatic alcohol ethoxylates secondary aliphatic alcohol ethoxylates, alkyl phenol ethoxylates and alcohol ethylene oxide propylene oxide condensates; and supplementary amounts of at least one an anionic surfactants selected from the group consisting of water soluble salts of C8-C18 alkyl sulfates, C8- C16 benzene sulfonates, C10-C20 paraffin sulfonates, alpha C10-C24 olefin sulfonates, a C8-C18 ethoxylated alkyl ether sulfate, and C8-C18 acyl taurates and a water soluble zwitterionic betaine surfactant, wherein the surfactants are dissolved in an aqueous vehicle.

The total amount of surfactants may constitute 10% 55%, preferably 20% 40%, most preferably 25% 35%, by weight of the liquid composition.

Detailed Description Of The Invention The high foaming nonionic based light duty liquid detergent compositions of the instant invention comprise approximately by weight: 10 to 30 wt. of a water soluble nonionic surfactant; 1 to 10 wt. of at least one water soluble or dispersible anionic 9- -g I surfactant; 0.5 to 8 wt. of a dialkyl sulfosuccinate ester surfactant; 0.5 to 8.0 wt. of a betaine surfactant; and 44 to 87 wt. of water, wherein the compositions do not contain any amine oxides, fatty acid alkanol amides, (for example cocodiethanolamide), alkali metal or alkaline earth metal carbonate, polymeric or clay thickeners, abrasives, clays, silicas, alkyl glycine surfactants, cyclic imidinium surfactants, or more than 3 wt. of a fatty acid or a metal salt of the fatty acid.

The nonionic surfactant which constitutes the major ingredient in the liquid detergent composition is present in amounts of 10 to 30%, preferably 12 to 25% by weight of the composition and provides superior performance in the removal of oily to' soil and mildness to human skin.

The water soluble nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxidepropylene oxide condensates on primary alkanols, such a Plurafacs (BASF) and (5 condensates of ethylene oxide with sorbitan fatty acid esters such as the Tweens (ICI).

The nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to foFm a water soluble nonionic detergent. Further, the length of the polyethenoxy hydrophobic and hydrophilic elements.

The nonionic detergent class includes the condensation products of a higher alcohol an alkanol containing 8 to 18 carbon atoms in a straight or branched dcS chain configuration) condensed with 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with 16 moles of ethylene oxide tridecanol condensed with 6 to moles of EO, myristyl alcohol condensed with 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms in length and wherein the condensate contains either 6 moles of EO per mole of total alcohol or 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.

A preferred group of the foregoing nonionic surfactants are the Neodol G ethoxylates (Shell which are higher aliphatic, primary alcohol containing 9-15 carbon atoms, such as C9'-C 11 alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23- C12-15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12), C14alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like.

1'O Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of 8 to 15 and give good O/W emulsification, whereas ethoxamers with HLB values below 8 contain less than 5 ethyleneoxide groups and tend to be poor emulsifiers and poor S detergents.

Additional satisfactory water soluble alcohol ethylene oxide condensates are S the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are C11-C15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.

Other suitable nonionic detergents include the polyethylene oxide condensates of one moleof alkyl phenol containing from 8 to 18 carbon atoms in a straight- or S branched chain alkyl group with 5 to 30 moles of ethylene oxide. Specific examples Sof alkyl phenol ethoxylates include nonyl condensed with 9.5 moles of EO per mole of nonyl phenol, dinonyl phenol condensed with 12 moles of EO per mole of dinonyl dS phenol, dinonyl phenol condensed with 15 moles of EO per mole of phenol and diisoctylphenol condensed with 15 moles of EO per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.

6/1 Other suitable nonionic detergents also include condensates of Cu-Ci, alkyphenol with 5 to 30 moles of ethylene oxide and propylene oxide having a weight ratio of total alkylene oxide content of 60% to 85% by weight.

e ee e« e e

LI

Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri- C1 0

-C

2 0 alkanoic acid esters having a HLB of 8 to 15 also may be employed as the nonionic detergent ingredient in the described shampoo. These surfactants are well known and are available from Imperial Chemical Industries under the Tween trade S name. Suitable surfactants include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, po!yoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.

The anionic surfactant, used in the liquid detergent composition, constitutes 1% to 10%, preferably 2% to by weight thereof and provides good foaming properties.

So However, preferably reduced amounts are utilized in order to enhance the mildne,5s of the skin property desired in the inventive compositions.

The at least one anionic surfactant which may be used in the liquid detergent of the invention are water soluble such as triethanolamine salt and include the sodium, potassium, ammonium and ethanolammonium salts of: CS-C18 alkyl sulfates such as lauryl sulfate, myristyl sulfate and the like; linear C8-C16 alkyl benzene sulfonates; C10-C20 paraffin sulfonates; alpha olefin sulfonates containing 10-24 carbon atoms; S and C8-C18 ethoxylated alkyl ether sulfates. Preferred anionic surfactants are the S water soluble C12-C16 alkyl sulfates, the C10-C15 alkylbenzene sulfonates, the C12- S C17 paraffin sulfonates, C8-C18 ethoxylated alkyl ether sulfates and the alpha C12- ~t 0 C18 olefin sulfonates.

One of the anionic surfactants is a metal salt of an ethoxylated alkyl ether sulfate which is depicted by the formula: R-(OCHCH2)nOSO3M wherein n is 1 to 22 more preferably 1 to 3 and R is an alkyl group having 8 to 18 carbon atoms, more preferably 12 to 15 and natural cuts, for example, C12-14; C12a 15 and M is a metal cation most preferably sodium and n is 1 to 3. The solubilizing agent is present in the composition at a concentration of 0.5 to 8.0 wt. more preferably 1.0 to 7.0 wt. c The ethoxylated alkyl ether sulfate may be made by sulfating the condensation product of ethylene oxide and C8-10 alkanol, and neutralizing the resultant product.

The ethoxylated alkyl ether sulfates differ from one another in the number of carbon :toms in the alcohols and in the number of moles of ethylene oxide reacted with one g mole of such alcohol. Preferred ethoxylated alkyl ether polyethenoxy sulfates contain 12 to 15 carbon atoms in the alcohols and in the alkyl groups thereof, sodium myristyl (3 EO) sulfate.

The paraffin sulfonates may be monosulfonates or di-sulfonates and usually are mixtures thereof, obtained by sulfonating paraffins of 10 to 20 carbon atoms.

'o Preferred paraffin sulfonates are those of C12-18 carbon atoms chains, and more preferably they are of C14-17 chains. Paraffin sulfonates that have the sulfonate group(s) distributed along the paraffin chain are described in U.S. Patents, 2,503,280; 2,507,088; 3,260,744; and 3,372,188; and also in German Patent 735,096. Such compounds may be made to specifications and desirably the content of paraffin ,15 sulfonates outside the C14-17 range will be minor and will be minimized, as will be any contents of di- or poly-sulfonates.

Examples of suitable other sulfonated anionic detergents are the well known higher alkyl mononuclear aromatic sulfonates, such as the higher alkylbenzene sulfonates containing 9 to 18 or preferably 9 to 10 to 15 or 16 carbon atoms in the higher alkyl group in a straight or branched chain, or C8-15 alkyl toulene sulfonates.

A preferred.alkylbenzene sulfonate is a linear alkylbenzene sulfonate having a higher content of 3-phenyl (or higher) isomers and a correspondingly lower content (well below 50%) of 2-phenyl (or lower) isomers, such as those sulfonates wherein the benzene ring is attached mostly at the 3 or higher (for example, 4, 5, 6 or 7) position of eS the alkyl group and the content of the isomers in which te benzene ring is attached in the 2 or 1 position is correspondingly low. Preferred materials are set forth in U.S.

Patent 3,320,174, especially those in which the alkyls are of 10 to 13 carbon atoms.

The water-soluble zwitterionic surfactant, which is also an essential ingredient of present liquid detergent composition, constitutes 0.5 to preferaoly 1 to by I, I, __I I ~P~CI sPweight and provides good foaming properties and mildness to the present nonionic based liquid detergent. The zwitterionic surfactant is a water soluble betaine having the general formula:

R

2

I

R

1

N+-R

4

-COO-

R3 wherein R 1 is an alkyl group having 10 to 20 carbon atoms, preferably 12 to 16 c carbon atoms, or the amido radical: O H I 1 R -C N (CH2)a wherein R is an alkyl group having 9 to 19 carbon atoms and a is the integer 1 to 4; R 2 and R3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R4 is an S alkylene or hydroxyalkylene group having from 1 to 4 carbon atoms and, optionally, :one hydroxyl group. Typical alkyldimethyl betaines include decyl dimethyl betaine or ,0 2-(N-decyl-N, N-dimethyl-amMionia) acetate, coco dimethyl betaine or 2-(N-coco N, Ndirethylammonio) acetate, myristyl dimeth,! betaine, palmityl dimethyl betaine, lauryl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine, etc. The amidobetaines similarly include cocoamidoethylbetaine, cocoamidopropyl betaine and the like. A preferred betaine is coco (Cg-C18) amidopropyldimethyl betaine.

The dialkyl sulfosuccinate ester is present in the instant compoition at a concentration of 0.5 to 8.0 wt. more preferably 1.0 to 7.0 wt. and is depicted by the formula: 0 03S It C-C -OR1 C-C- OR2 0 wherein R1 and R2 can be the same or different aliphatic radicals each having from 6 to 18 carbon atoms, more preferably 7 to 14 carbon atoms and M is selected from the p consisting of an alkali metal cation, an alkaline earth metal cation, an 9 ammonium cation, and alkanolamine. Preferred are sodium or potassium, magnesium or ethanolamine.

All of the aforesaid ingredients in this light duty liquid detergent are water soluble or water dispersible and remain so during storage.

This particular combination of dialkyl sulfosuccinate ester surfactant, at least one anionic surfactant and a betaine surfactant provides a detergent system which coacts with the nonionic surfactant to produce a liquid detergent composition with desirable foaming, foam stability and detersive properties. Surprisingly, the resultant homogeneous liquid detergent exhibits the same or better foam performance, both as to initial foam volume and stability of foam in the presence of soils, and cleaning efficacy as an anionic based light duty liquid detergent (LDLD) as shown in the following examples.

The essential four ingredients discussed above are solubilized in an aqueous medium comprising water and optionally, solubilizing ingredients S 15 such as alcohols and dihydroxy alcohols such as water soluble salts of C 1

-C

3 "substituted benzene sulfonate hydrotropes, C-C, mono- and di-hydroxy alkanols, e.g. ethanol, isopropanol and propylene glycol, and mixtures thereof. Suitable water soluble hydrotropic salts include sodium, potassium, ammonium and mono-, di- and triethanolammonium salts. While the aqueous medium is primarily water, preferably said solubilizing agents are included in order to control the viscosity of the liquid composition and to control low temperature cloud clear properties. Usually, it is desirable to maintain clarity to a temperature in the range of 5 0 C to 100C. Therefore, the proportion of solubilizer generally will be from 0,5% to 15%, preferably 1% 25 to 15%, more preferably 0.5 to 8% by weight of the detergent composition with the proportion of ethanol, when present, being 5% of weight or less in order to provide a composition having a flash point above 46 0 C. Preferably the solubilizing ingredient will be propylene glycol. Another extremely effective solubilizing or cosolubilizing agent used at a concentration of 0.1 to 5 wt%, more preferably 0.5 to 4.0 wt% is isethionic acid or an alkali metal salt of isethionic acid having the formula -A 'JM"'X CH20HCH2SO3X wherein X is hydrogen or an alkali metal cation, preferably sodium.

The foregoing solubilizing ingredients also facilitate the manufacture of the inventive compositions because they tend to inhibit gel formation.

In addition to the previously mentioned essential and optional constituents of the light duty liquid 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; ultraviolet light absorbers such as the Uvinuls, which are products of GAF Corporation; sequestering agents such as ethylene diamine tetraacetates; magnesium sulfate heptahydrate; pearlescing tO 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 formate can be included in the formula as a perservative at a concentration of 0.1 to Sodium bisulfite can be used as a color stabilizer at a concentration of 0.01 to 0.2 Typical perservatives are dibromodicyano-butane, citric acid, benzylic alcohol and poly (hexamethylenebiguamide) hydr-chloride and mixtures thereof.

The instant compositions can contain 1 to 4 wt. more preferably 0.5 to 3.0 wt.

S of an alkyl polysaccharide surfactant. The alkyl polysaccharides surfactants, which .TD are used in'conjunction with the aforementioned surfactant have a hydrophobic group containing from 8 to abut 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 galactoside, glucoside, fructoside, glucosyl, fructosyl; and/or Sc 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 11 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 c are to be understood to be average values. The hydrophobic group can be attached at the 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, glucosides, galactoside, fructosides, etc., is preferred. In the preferred product the additional saccharide units are predominately Sattached to the previous saccharide unit's 2-position. Attachment through the 4-, and 6- positions can also occur. Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic moiety and the polysaccharide chain.

The preferred alkoxide moiety is ethoxide.

STypical hydrophobic groups include alkyl groups, either saturated or (c 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.

he 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.

Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, :o hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyls and mixtures thereof.

The alkyl monosaccharides are relatively less soluble in water than the higher alkyl polysaccharides. When used in admixture with alkyl polysaccharides, the alkyl 0c 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-, anc pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.

9 r I ~a The preferred alkyl polysaccharides are alkyl polyglucosides having the formula R20(CnH2nO)r(Z)x wherein Z is derived from glucose, R is a hydrophobic group selected from the group C, 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 can be reacted with glucose, in the presence of an acid catalyst to form the rO desired glucoside. Alternatively the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (R1OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (C1-6) is reacted with glucose or a polyglucoside (x=2 to 4) to yield a short

C

I

S chain alkyl glucoside (x=1 to 4) which can in turn be reacted with a longer chain alcohol (R2OH) to displace the short chain alcohol and obtain the desired alkyl S 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 most preferably 0% of the alkyl o, polyglucoside.

The amount of unreacted alcohol (the free fatty alcohol content) in the desired alkyl polysaccharide surfactant is preferably less than more preferably less than by weight of the total of the alkyl polysaccharide. For some uses it is desirable to have the alkyl monosaccharide content less than 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.

I- ~_I 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: CnH2n+ O(C6H1005)xH S wherein n=10 n=122 n=14 n=16 and n=18 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 250C of 1.1 g/ml; a density at 25°C of 9.1 Ibs/gallon; a calculated HLB of 12.1 and a Brookfield viscosity at 35°C, 21 spindle, RPM of 3,000 to 7,000 cps.

t' The instant compositions can contain a silk derivatives as part of the composition and generally constitute 0.01 to 3.0 by weight, preferably 0.1 to by weight, most preferably 0.2 to 2.5% by weight of the liquid detergent composition.

Included among the silk derivatives are silk fibers and hydrolyzate of silk fibers.

The silk fibers may be used in the form of powder in preparing the liquid detergent or S*:c as a powder of a product obtained by washing and treating the silk fibers with an acid.

Preferably, silk fibers are used as a product obtained by hydrolysis with an acid, alkali or enzyme, as disclosed in Yoshiaki Abe et al., U.S. Patent No. 4,839,168; Taichi Watanube et al., U.S. Patent No. 5,009,813; and Marvin E. Goldberg, U.S. Patent No.

5,069,898, each incorporated herein by reference.

Another silk derivative which may be employed in the composition of the present invention is protein obtained from degumming raw silk, as disclosed, for example, in Udo Hoppe et al., U.S. Patent No. 4,839,165, incorporated herein by reference. The principal protein obtained from the raw silk is sericin which has an empirical formula of C15H2503N5 and a molecular weight of 323.5.

Another example of a silk derivative for use in the liquid detergent composition of the present invention is a fine powder of silk fibroin in nonfibrous or particulate form, as disclosed in Kiyoshi Otoi et al., U.S. Patent No. 4,233,212, incorporated herein by reference.

I

The fine powder is produced by dissolving a degummed silk material in at least one solvent selected from, for example, an aqueous cupriethylene diamine solution, an aqueous ammoniacal solution of cupric hydroxide, an aqueous alkaline solution of cupric hydroxide and glycerol, an aqueous lithium bromide solution, an aqueous solution of the chloride, nitrate or thiocyanate of calcium, magnesium or zinc and an aqueous sodium thiocyanate solution. The resulting fibroin solution is then dialyzed.

The dialyzed aqueous silk fibroin solution, having P silk fibroin concentration of from 3 to 20% by weight, is subjected to at least one treatment for coagulating and precipitating the silk fibroin, such as, for example, by the addition of a coagulating salt, ro by aeration, by coagulation at the isoelectric point, by exposure to ultrasonic waves, by agitation at high shear rate and the like.

The resulting product is a silk fibroin gel which may be incorporated directly into the liquid detergent composition or the same may be dehydrated and dried into a powder and then dissolved in the liquid detergent composition.

The silk material which may be used to form the silk fibroin includes cocoons, raw silk, waste cocoons, raw silk waste, silk fabric waste and the like. The silk material is degummed or freed from sericin by a conventional procedure such as, for example, .:by washing in warm water containing a surfact-active agent or an enzyme, and then dried. The degummed material is dissolved in the solvent and preheated to a S. temperature of from 60 to 950C, preferably 70 to 85°C. Further details of the process of obtaining.the silk fibroin are discussed in U.S. Patent No. 4,233,212.

A preferred silk derivative is a mixture of two or more individual amino acids which naturally occur in silk. The principal silk amino acids are glycine, alanine, serine and tyrosine.

A silk amino acid mixture resulting irom the hydrolysis of silk of low molecular weight and having a specific gravity of at least 1 is produced by Croda, Inc. and sold under the trade name "CROSILK LIQUID" which typically has a solids content in the range of 27 to 31% by weight. Further details of the silk amino acid mixture can be found in Wendy W. Kim et al., U.S. Patent No. 4,906,460, incorporated herein by L- L I I ICI_ reference. A typical amino acid composition of "CROSILK LIQUID" is shown in the following Table AMINO ACID PERCENT BY

WEIGHT

Alanine 28.4 Glycine 34.7 Valine Leucine 1.2 Proline 1.2 Tyrosine 0.6 Phenylalanine 0.9 Serine 15.4 Threonine 1.9 Arginine Aspartic Acid 4.7 Glutamic Acid 4.1 Isoleucine 0.8 Lysine 1.4 Histidine 0.8 Cystine 0.1 Methionine 0.2 TOTAL 99.9 0 *0 0 00. 00 *c *00* 0 0.

The instant compositions can contain a viscosity modifying solvent at a concentration of 0.1 to 5.0 weight percent, more preferably 0.5 to 4.0 weight percent.

The viscosity modifying agent is an alcohol of the formula R2-CH-R3

I

OR1 wherein R1 CH3, CH2CH3 R2 CH3, CH2CH3 R3 CH20H, CH2CH20H; which is preferably 3-methyl-3-methoxy-butanol.

The 3-methyl-3-methoxy butanol is commercially available from Sattva Chemical Company of Stamford, Connecticut and Kuraray Co., Ltd., Osaka, Japan.

p_ L~BLIISl~rmP I The instant composition can contain 0.1 to 4.0% of a protein selected from the group consisting of hydrolyzed animal collagen protein obtained by an enzymatic hydrolysis, vegetal protein and hydrolyzed wheat protein and mixtures thereof.

The present nonionic based light duty liquid detergents such as dishwashing S liquids are readily made by simple mixing methods from readily available components which, on storage, do not adversely affect the entire composition. However, it is preferred that the nonionic surfactant be mixed with the solubilizing ingredients, e.g., ethanol and, if present, prior to the addition of the water to prevent possible gelation.

The nonionic based surfactant system is prepared by sequentially adding with t agitation the anionic surfactant and the betaine to the non-ionic surfactant which has been previously mixed with a solubilizing agent such as ethyl alcohol and/or sodium xylene sulfonate to assist in solubilizing said surfactants, and then adding with agitation the formula amount of water to form an aqueous solution of the nonionic based surfactant system. The use of mila oieating (up to 100OC.) assists in the t solubilization of the surfactants. The viscosities are adjustable by changing the total percentage of active ingredients. No polymeric or clay thickening agent is added. In all such cases the product made vmoJ be pourable from a relatively narrow mouth bottle cm. diameter) or opening, and the viscosity of the detergent formulation wo not be so low as to be like water. The viscosity of the detergent desirably will be at least 100 centipoises (cps) at room temperature, but may be up to 1,000 centipoises as measured with a Brookfield Viscometer using a number 2 spindle rotating at 30 rpm.

Its viscosity may approximate those of commercially acceptable detergents now on the market. The detergent viscosity and the detergent itself remain stable on storage for lengthy periods of time, without color changes or settling out of any insoluble cS materials. The pH of this formation is substantially neutral to skin, 4.5 to 8 and preferably 5 to 5.5. The compositions of the instant invention are optically clear that is they exhibit a light transmission of at least 95%, more preferably at least 98%.

These products have unexpectedly desirable properties. For example, the foam quality and detersive property is equal to or better than standard light duty liquid

\I

detergents while using a nonionic surfactant as the primary surfactant and minimal amounts of anionic surfactant, thereby achieving a mild, non-irritating liquid detergent.

The following examples are merely illustrative of the invention and are not to be construed as limiting thereof.

EXAMPLE 1 A B C D *s C9-1 1 Alcohol EO 8:1 nonionic 19 19 19.0 19 SODIUM LAURYL SULFATE 4.0 C14-C17 paraffin sulfonate 5 7 2.0 012-14 Alcohol EO 2:1 Na Sulfate 2.0 Dioctyl sulfosuccinate ester 3.0 3.0 4.0 EDTA 0.1 0.1 0.1 0.1 Cocoamidopropyl 5 5 5 Betaine Urea 2.0 2.0 2.0 Formalin .1 .1 .1 .1 Sodium Bisulfite 0.05 0.05 0.05 0.05 Perfume 0.2 0.2 0.2 0.2 Water Balan Balan Balan Balan ce ce ce ce Miniplate test 34 33 38 43 Foam Vol. start ml 60 55 65 end ml 155 140 155 185 Hand Dishwashing Foam and 8 7 9 Point__ Viscosity, RT #2 spindle, 30 rpms 300 350 280 400 cps 0 0 0 0* 00 I -rewsa

Claims (9)

1. A high foaming, nonionic surfactant-based, light duty, liquid detergent comprising approximately, by weight, 10% to 30% of a water soluble nonionic surfactent selected from the group consisting of primary and secondary C 8 -C 1 alkanol condensates with 5 to 30 moles of ethylene oxide, condensates of C,-Cl, alkylphenol with to 30 moles of ethylene oxide and propylene oxide having a weight ratio of total alkylene oxide content of 60% to 85% by weight and condensates of 2 to moles of ethylene oxide with sorbitan mono and tri- C 10 -C20 alkanoic acid esters having an HLB of 8 to 1% to 10% of at least one water-soluble or water dispersible anionic surfactant selected from the group consisting of C 8 -Cl, alkyl sulfates, alkylbenzene sulfonates, Co-Co2 paraffin sulfonates, C-o-C,2 alpha olefine sulfonates and CB-CIa ethoxylated alkyl ether sulfates; 15 0.5% to 8% of a water-soluble t .taine; S: 0.5 to 8% of a dialkyl sulfosuccinate ester; and balance being water as an aqueous medium in which said nonionic surfactant, said anionic detergent, said dialkyl sulfosuccinate ester and said betaine are solubilized in said water, wherein said liquid detergent 20 composition does not contain amine oxide, fatty acid alkanol amide, alkali metal carbonate, alkaline earth metal carbonate, polymeric or clay thickeners, abrasives, clays, silicas, alkyl glycine surfactant, cyclic imidinium surfactant, or more than 3 wt% of a fatty acid or a metal salt of the fatty acid. 25

2. A liquid detergent composition according to claim 1 which includes, in addition, 1 to 15% by weight of a solubilizing agent selected from the group consisting of Cz-C 3 mono- and di-hydroxy alkanols, water soluble salts of C 1 -C 3 substituted benzene sulfonate hydrotropes and mixtures thereof.

3. A liquid detergent composition according to claim 2 wherein ethanol is present in the amount of 5% by weight or less.

4. A liquid detergent composition according to claim 2 wherein said nonionic surfactant is said condensate of a primary alkanol with 5-30 moles of ethylene oxide.

A liquid detergent composition according to claim 4, wherein said anionic detergent is selected from the group consisting of C. 1 alkyl II sulfates, C:,o-Ci5 alkylbenzene sulfonates, C1:r-C, paraffin sulfonates and C 12 C.j alpha olefine sulfonates.

6. A liquid detergent composition according to claim 1, wherein said anionic detergent is a C.I-Cj alkyl sulfate.

7. A liquid detergent composition, according to claim 1 further including a preservative.

8. A liquid detergent composition according to claim 1 further including a color stabilizer.

9. A liquid detergent composition according to claim 1 further including 0.5 to 8.0 wt%/ of a cosolubilizing agent. Dated this 14th day of March 1997. COLGATE-PALMOLIVE COMPANY Patent Attorneys for the Applicant: F.B. RICE CO. e* a *o:i I ABSTRACT OF DISCLOSURE A high foaming, nonionic surfactant based, light duty liquid detergent with desirable cleansing properties and mildness to the human skin comprising: a water soluble nonionic surfactant; at least one water soluble or dispersible foaming, anionic surfactant; a zwitterionic betaine surfactant, and a dialkyl suifosuccinate ester. g: a SS* *eo o -s~