CA1072448A - Protein containing cleaning composition - Google Patents

Abstract

ABSTRACT

This invention relates to compositions in liquid form which protect keratinous material, particularly skin, from the deleterious effects of detergents or other harsh materials such as solvents, and from adverse climatic conditions. The compositions of the invention accordingly help to maintain the keratinous material in good condition. The compositions in question comprise: (a) from about 0.1% to about 50% by weight of a surface active agent; (b) from about 1% to about 10% by weight of a soymeta protein, and optionally (c) up to about 15% by weight of a mono- or di- alcohol having from 2 to 8 carbon atoms, the balance of the composition being water.

Description

~C3 7Z~8 BACKGROUND OF l'HE INVENTION
The deleterious effects of compositions containing surfactants upon keratin are well known. These effects are caused, it is thought, by penetra-tion of the surfactant into the keratin surface leading to "leaching out" of oils and moisturi-zing components essential for good condition of the keratin.
This penetration by surfactant and "leaching out" of essential oils also effects the ability of the keratin, particularly in the case of skin, to retain water within the tissue and this again leads to poor condition of the keratinous material.
Many attempts have been made in the past to provide compositions for maintaining or improving the condition of skin and hair. The application of protein to skin and hair as cosmetic treatments probably antedates recorded history. Casein, in the form of milk, has been used as a time-honored beautifier and more recently has been recommended for use in ' , .

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toilet soaps. ~ritish Patent 1,160,485 describes -the addition of soypeptone to liquid detergents and lotions. Numerous other proteins and protein degradat;on products have also been recommended for use, either as protein soaps, or in combination with the usual soap components. For instance, British Patent 8,582 describes the addition of egg albumin treated with formalin, to toilet and shaving soaps. British Patent 159,083 makes a toilet soap containing 5 to 20% of -the solids obtained by evap-orating the waste whey derived from cheese factories. French Patent 342,691 suggests introducing wheat gliadin and glutenin into soap with the object of combining with free alkalis without introducing the disadvantages of superfatted soaps (tendency to become rancid).
Various other low-molecular weight polypeptides or mod-ified polypeptides derived from natural proteins are commercially available and recommended for use in cosmetic and shampoo formu-lations, for instance "Hydro Pro 220"1, "Hydro Pro 330"2 and "Maypon 4C"3 marketed by the Stepan Chemical Company; and "Wilson X250"4, "Wilson X1000"5 and "Wilson Aqua pro"6 marketed by the Wilson Chemical Company. However, it has been found that none of these compositions are especially effective in protecting keratin from the action of harsh detergents, and this is parti-cularly true when the proteins are incorporated in the detergent composition itself. The emolliency of these compositions can often be improved by addition of fatty or oily materials bu-t, when used, for instance, in liquid detergents, at an effective level, this usually leads to loss of foaming power or aesthetic changes which are generally considered undesirable by consumers.

1-6 inclusive. The terms bearing these superscript numerals are all trademarks.

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A Eurther difficulty encoun-tered when attempting to prepare liquid deteryent composi~ions comprising proteins isolated, particularly, from vegetable glycoprotein, is the problem of producing a homogeneous, preferably clear, formulation which is free from undesirable discoloration. Such formulations are, of course, preferred by consumers from an aesthetic view-point, and this poses a considerable limitation on the practical application of known protein technology to consumer-accep-table liquid detergent formulations.
The present invention therefore provides protein-containing compositions in liquid form which are particularly effective in protecting keratinous material, particularly skin, from the deleterious effects of detergents and other harsh mat-erials and from adverse climatlc conditions, which compositions are effective even when applied to keratin in foaming detergent solutions or dispersions, which result in no loss of foaming~
lathering or cleaning power for detergent solutions or disper-sions containing them, and which may be formulated as homogeneous, clear liquid compositions. Percentages and ratios are by weight and temperatures are Fahrenheit unless otherwise indicated.
SUMM~RY OF THE INVENTION
The present invention resides in a detergent or cosmetic composition in liquid form comprising: (a) from about 0.1% to about 50% by weight of the composition of a surface active agent;
(b) from about 1% to about 10% by weight of the composition of a soymetaprotein; (c) from about 0% to about 15% by weight of the composition of a water-soluble solvent selected from the group consisting of mono- and di-alcohols containing from two to about eight carbon atoms; and (d) the balance of the composition being water.
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DETAILED DESCRIPTION OF THE INVENTION
~ ccordingly the present inven-tion provides a liquid composition comprising a surface ac-tive agen~ and a derived -3a-1(37i~

soyprotein s~l~cted from the group consisting oE soymetaprotein or soyproteose. The derived soyprotein is preferably at least partly water-insoluble at its isoionic point pH (i.e. it comprises at least some metaprotein) preferably comprises substantially no heavy metal ions (e.g. Ca+~), acid derivatives of carbohydrates (such as phytate) or water-soluble or dispersible higher oligo- or polysaccharides such as stachyose and higher polysaccharides. In particular, the compositions should contain substantially no water-insoluble polysaccharides such as ~hemicelluloses.

According to another aspect of the invention, a process of ma~ing a liquid detergent composition comprises the steps of contacting soyprotein isolate with acid or alkali in a wei~ht ratio of protein isolate to anhydrous acid or al~ali of between ~i to 1 and 25 to 1, while heating the mixture to a temperature in the range from 40 to 100C for a time suffic'ent to give a mixture comprising at least 20% and preferably at least 30% by weight of soymetaprotein together with water soluble soy derived protein and admixing the soymetaprotein and/or water-soluble derived protein with the remaining detergent composition components at a pH in the range from 5.5 to 8.5.
For the purposes of this specification, soyprotein means protein which has been extracted from soybeans; derived soyprotein means protein in which the primary chemical structure has been degraded by rupture of peptide bonds or sulfur-sulfur linkages; soymetaprotein is derived soyprotein which is insoluble in pure water at the isoionic point of the dexived protein, and soyproteose is derived protein which is soluble in pure water ~7Z~

but which is insoluble in water wh:ich is hal~-saturated with ammonium sulfate.
Soybeans comprise about 20% oil and about ~0~O protein, the bulk of their protein being contained in storage sit~s called aleurone grains, protein bodies of 2 to 20 microns diameter, each surrounded by a membrane thought to consis-t of phospholipids.
Soybeans are usually processed into a variety of forms in which the ordered structure of the intact seed is destroyed. The simplest processing consists of steaming the beans and removing the hulls, which are more than 85% carbohydrate. Subjectlng the soybeans to excessive heat treatment dena~ures the protein, however, and this tends to render the subsequellt protein extracts water insoluble. Undenatured soyproteins, which are preferred in the present invention, may therefore be prepared by avoidance of exc~ssive heat treatment in the initial processing steps. Grinding the dehulled material yields full-fat flours, the crudest form of soy proteinaceous material. Defatted flours, having a protein content of 50~ or more, are obtained upon extraction of the soybean oil with hexane, while protein concentrates havin~ protein levels of 70~ or more are obtained by extraction with solvents such as aqueous alcohols or dilute acids. The purest protein forms are the protein iso]ates from which the bulk of the oil and carbohydrates has been separated, leaving less than 10o non-protein material (ash and minor constituents). Such isolates are generally prepared by extl-actincJ
undenatured flakes or flour with dilute alkali at pH 8 to 9, the clarified extract possibly then being acidi~ied to pH 4.5 to precipitate soyprotein globulins. The derived protein suitab1e 1L072~

for use in the liquid surface-active compositions of the invention has preferably been subjected to all of the above defatting and purification procedures, so that it will generally contain at least 70%, preferably at least 90~ and more preferab~y at least S 95~ o~ actual protein material. It is especially pre~erred that the derived protein contain substantially no carbohydrate as this has been found to deleteriously affect the clarity and color of the resulting liquid composition.
The derive2 soyproteins suitable for use in the lic~uid compositions of the invention are yenerally the products of partial degradation of soybean extract, for instance, by thermal degradation, hydrolysis, reduction, ammoniolysis or aminolysi.s. ~ydrolytic degradation has long been used in the food industry to increase the water-solubility of soyprotein to enhance taste and flavor. There exist numerous processes for the hydrolysis of protein, and these may be divided into three classes according to the hydrolyzing agent used, namely acid, alkaline and enzymatic hydrolysis. The derived protein may also be obtained by thermal degradation, for instance, by the action of superheated steam. ~moniolytic degradation may be accomplished by the action of relatively concentrated ammonia solutions (in which case ammoniolysis is accompanied by a deg.ree of hydrolysis) or by the action of ammonia gas, while aminolytic degradation is brought about by treatment with mono- or polyamino compounds.
The preferred derived soyproteins for use in the present invention axe at least partly wate.r-insoluble at the isoioni.c point pH of the protein, and may be substantially water-insoluble 7~44~

at this pH. Th~ proteins should of course be substantially water-soluble at a pH value removed from the isoionic point pH, for instance, at the pH of the composition when dissolved or dispersed in water in the normal manner of use.
Protein degradation is preferably carried out with aqueous alkali, for instance, solutions of caustic soda, caustic potash, slaked lime, dilute ammonia. The process consists of treating a slurry or solution of, for instance, protein isolate with aqueous alka]i at a temperature of, preferably 50 to 95C for a period of, generally, between l and 4 hours, the amount of alkali being used ordinarily lying between 5Q~ and 15~ by weight of the weight of soyprotein. The amount of alkali used, the temperature and length of time of the treatment will be determined by the degree of hydrolysis desired. As stated above the h~drolysis should pxeferably be tern~inated ~efore the protein is hydrolyzed to the point that it would be soluble at its isoionic point pH. Following hydrolysis or, if desired, simultaneously ~herewith, the protein containing liquor may be trea-ted with an oxidizing agent, prefer-ably an agent which provides a ready source of peroxide ions in solution, for instance, hydrogen peroxide, alkali metal or alkaline earth metal peroxides, or addition complexes of hydrogen peroxide such as sodium perborate, urea or guanidine peroxide or even organic peroxides. The purpose of the oxidlzing agent is to react with organic and inorganic sulfhydryl species which invariably are formed upon alkaline hydrolysis, turning the aqueous solution into a dark, evil-smelling liquid.
After the oxidation stage, the protein may be isolatc-d, for ~ 8 ins-tance, by treeze drying, ace-tone precipitation or isoionic point precipi-ta-tion, or -the pro-tein solutlon may be immediately used to prepare the compositions of -the invention as described below.
Enzymatically hydrolyzed soyproteins may also be incor~
porated in the compostions of the invention. The enzyme generally used is a protease enzyme but certain materials containing both protease and amylase enzymes may also be used.
Thes enzyme materials are obtained from a variety of animal, plant, bacterial and fungal sources. Special mention may be made of the following enzymes: papain (E.C. 3.4.22.2), bromelin (E.C. 3.4.22.3; E.C. 3.4.22.5), ficin (E.C. 3.4.22.3), chymopapain (E.C. 3.4.22.6), try~in (E.C. 3.4.21.4), chymo-~_____ trypsin (E.C.3.4.21.1), pancreatin (E.C. 3.1.4~5; E.C.

3.1.4.22; E.C. 3.4.21.11), pepsin (E.C. 3.4.23.1), erepsin, fungal enzymes of ~L~r~ll ~ (E.C. 3.4.24.4; E.C.

3.1.4.8.), Aspergillus niger, and the bacterial enzymes of the . . .
Bacillus genus, for example bacterial B.m~coides, B.amylo-liquifaciens (E.C. 3.4.21.15), B. cereus, B. macerans (E.C.
, ~ . . .

2.4.1.19), B megaterium, B. sphaericus, B. circulans, and especially that of B. subtilis (E.C. 3.4.21.14). Typically, enzymatic hydrolysis is carried out at temperatures above 25 and generally above 40C, for example at 50 to 70C, at a pH which will favor maximum activity of the enzyme employed, and for a period generally in the region of 5 to 20 hours. The conditions employed will also depend on the nature of protein treatment prior -to enzyme hydrolysis; for instance, if the protein has been subjected to a mild acid or alkaline hydrolysis stage, then a mild 25 to 40 pepsin trea-tment may suffice ~1~72~

Acid hydrolysis ~ay be carried out with aqueous hydrochloric or sulfuric acid, typically the aqueous liquid being heated under reflux with 10 to 40~ aqueous acid for a period of 5 to 2 0 ~, ~

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hours. Alternatively, the mixture may be hea-ted a-t super-atmospheric pressure with more dilute acid, e.g. 5% by weight, for a short period of time.
~ mmoniolysis, possibly accompanied by hydrolysis, may be accomplished by heating soyprotein, for example, protein isolate with 10% by weight (or greater) ammonia solution at a -tempera-ture of 50 - 100 for a period of 10 to 30 hours. Excess ammonia is simply removed by evaporation and the ammoniolysed protein may then be isolated, for instance by acetone precipitation, or used immediately in the compositions of the invention.
Soyprotein aminolysates are preared by heating soy-protein with a mon-, di or polyamine or derivatives thereof, usually in at least equal an amount by weight under reduced or atmospheric pressure at temperatures between 50C and 200C. Preferred amines include C2 to C10 alkamines and alkanolamines, and C2 to C12 diamines and polyamines.
Other means of degrading soyproteins include thermal degradation, for instance by pressure steam heating a protein slurry rapidly and substantially instantaneously -to a tempera-ture above 220 F with mechanical working, followed, possibly, by an enzymatic hydrolysis treatment; and reductive cleavage of intra-molecular disulphide cross-links with, for instance, metal hydrides (such as sodium borohydride), sulphydryl com-pounds (such as 0.01 M mercaptoethanol), sulphites, thioglycollates.
The derived soyproteins are generally present in an amount of from about 1 to about 10%, preferably from about 2 to about 6% by weight of the composition.

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Derived soyproteins suitable for use in the liquid com-positions of the invention are characterized by preferred values of molecular weight and isoionic points. The average molecular weight (measured using a standard ultra centrifuge -technique) is preferably at least about 1500, more especially at least 3000 and desirably at least 5000. The molecular weight of the derived proteins is also reflected in the viscosity characteristics of the proteins in aqueous solution. Preferably, the viscosity of a 10~ by weight solution in water at pH 9.5 and 48C is at least 0.8 centipoises, and desirably lies in the range from 1.5 to 20 centipoises.
The isoionic point pH values of the derived proteins -the pH at which equal concentrations of protein anions and cations exist in solution, generally spans the range from about 4.5 to about 9.
However, the optimum choice of protein for any parti-cular composition depends to a certain extent upon the pH of the composition in use, i.e. the pH of the carrier upon applica-tion to ceratin. This in-use pH may~ depending upon the type of applicationt be the pH of the composition itself, or be the pH
of an aqueous solution or dispersion of the composition at a concentration of use which may be as little as 0.01% and which may be as great as 10% or even higher. For instance, for a composition having an in-use pH in the region of neutrality, e.g. a dishwashing liquid or cosmetic lotion, the preferred derived proteins have an isoionic point less than (pH - 1), preferably less than (pH - 2). In the case of compositions with in-use pH values in the region of 8 to 10, e.g. a ~10- , built liquicl deter~ent, th~ isoionic point pll values may be relatively lower, f'or :instance less than (pH - 3).
'I'he in-use pll of the compositions of -the invention may vary widely of course, depending upon the purpose and manner of use of the composition. Compositions designed as hand and face lotions etc. are generally applied directly to the skin, and the in-use pH is the pH of -the composition itself. This may be any pH in the range, generally, from 5 to 9. Detergent compo-sitions such as liquid dishwashing and bathing compositions and heavy-duty liquid detergents are usually used in a large.
excess of water, and the in-use pH is the pH of an aqueous solution of the composition at a concentration generally in the range from 0.01% to 2% by weight. Builder-free de-tergent compo-sitions~ for instance, will have an in-use pH in the alkaline range up to a pH of about 11. Shampoo compositions on the other hand are generally applied in the presence of a small amount of water, and the in-use pH will again be close -to the pH of the composition, generally about 5 to 9. In practice, the in-use pH is frequently independent, or nearly so, of the concentration of the composition in those instances where the composition is diluted to use, and the in-use pH may therefore be determined at a standard concentration of 1%.
Once the in-use pH is known, the most approprlate derïved soyprotein for the particular application may be determined.
Whereas soyglobulins isolated during isoionic precipitation, have an isoionic point of about pH 4.9 - 5.0, base hydrolyzed soyproteins have a somewhat lower isoionic point, about pH 4.5, -- ~.1 --while acid hydrolyzed proteins (about pH 5.5) and enzyme hydro-lyzed proteins (about pH 6) have higher values. Ammoniolyzed soyproteins have isoionic point values in the range of about pH 5.5 to 6.5 while aminolyzed proteins have very much higher isoionic point pH values, up to 9, or even higher.
Isoionic point pH values may be determined in the following manner:
"Amberlite"* acid resin (IR 120) and base resin (IR 400) are washed with several volumes of water, filtered and mixed in the ratio 0.4:1. A 3 wt~ protein solution (20 mls) is prepared in 20~ aqueous urea with minimum warming and allowed to cool to constant temperature. The resin mixture (8.4 g) is added, the solution is stirred for five minutes, the mixture is filtered and the pH of the filtrate is the isoionic point pH of the pro-tein.
Surfactant materials which may be used in the composi-tions of the invention can be selected from water-soluble soap and synthetic anionic, nonionic, cationic, zwitterionic and amphoteric detergents described as follows. Preferably, the surfactants are foaming detergents or emulsifiers, in particular, anionic soap and synthetic detergents.
The compositions of the invention may, of course, comprise combinations of the soyprotein described herein and other proteins or modified proteins known to be beneficial to skin, for instance the modified proteins described in United States Patent No. 4,115,548 of R.A. Marsh, G.J. Mackie and Peter Hale, granted September 19, 1978.
A. Anionic Soap and Non-Soap Synthe-tic Detergents This class of detergents inclwdes ordinary alkali soaps *Trademark for a series of synthetic, high capacity cation and anion exchange resins. They are insoluble cross-linked polymers of various types.

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'~107~h4~8 such as the sodium, po-tassium, amnlonium, al~ylammoni~n lnd alkylola~nonium salts of hic;her fatty acids containing from 1o 24 carbon atoms and preferably from lO to 20 carbon atoms.
Suitable~fatty acids can be obtained from natural sources, such 5 clS plant or animal esters (e.g. palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof). The fatty acids also can be synthetically prepared (e.g. by the oxida~ion of petrolewn or by hydrogenation of carbon monoxide by the Fischer Tropsch process).
Resin acids are suitable, such as rosin and those resin acids in tall oil. Naphthenic acids are also suitable. Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particu]arly useful are the sodium, potassium, and triethanolammoni1lm salts of the mixtures of fatty acids derived Erom coconut oil and tallow, e.g. sodium or potassium tallow and coconut soaps.
This class of detergents also includes water-soluble salts, particularly the alkali metal salts, of organic sulphuric reaction products having in their molecular structure an alkyl radieal containing from 8 to 22 carbon atoms and a sulphonlc acid or sulphuric acid ester radical. (Included in the term al]cyl is the alkyl portion of higher acyl radicals.) Examples of this group of synthetic detergents which form a part of the preferred compositions of the present invention are the alkali metal, e.g.
sodium or potassium, alkyl sulphates, especially those ob-tained by sulphating the hiyher alcohols (8 to 18 carbon atoms) produced by reducing the g1ycerides of tallow or coconut oil; the al].ali ~7~441~

metal ol~fill sulphona~:es of from 8 to 24 carbon atoms described, for example, in uS Pa~ent 3,332,~80; and ~he alkali metal alkyl glyceryl ether sulphonates, especially those ethers of the higher alcohols derived from tallow and coconut oil. Other anionic detergents include the alkali metal alkylben~ene sulphonates, in which the alkyl group contains from 9 to 15 carbon atoms, including ~hose of the types described in United States Patents Nos. 2,220,099 and 2,477,383 ~the alkyl radical can be a straight or branched aliphatic chain); sodium coconut oil fatty acid mono-glyceride sulphates and sulphonates; salts of alkyl phenolethylene oxide etller sulphates with 1 to 1.2 units of eth~rlene oxide per molecule and in wh.ich the alkyl radicals contain from 8 to 18 carbon atoms; the reaction product of fat-ty acids esteri-fied with isethionic and neutralized with sodium hydroxide where, for example, the fatty acid is oleic or derived from coconut oil;
sodi~-n or potassium salts of fatty acid amides of a methyl tauride in which the fatty acids, for example, are derived from coconut oil; sodium or potassium ~-acetoxy- or ~acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms;
and others kno~m in the art. A nu~er are specifical.ly set forth in United States Pa-tents Nos. 2,286,921; 2,486,922; and 2,396,278.
Other synthetic anionic detergents useful herein are alkyl ether sulphates. These materials have the formula R o(C2 4 )x 3 ~t72~

wherein ~ is alkyl or alkenyl of a~out ~ ~o 2~ carbon atoms, x is 1 to 30, and M is a sa]t-fGrMing cation selected ~rom alkali metal, preferably sodium or potassium, ammonium and dimethyl-, trimethyl-triethyl-, dimethanol-, diethanol-, trimethanol- and triethanol- ammonium cations.
The alkyl ether sulphates are condensation products o~
ethylene oxide and monohydric alcohols having about 8 to 2~
carbon atoms. Preferahly, R has 14 to 18 carbon atoms. The alcohols can be derived from fats, e.g. coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight-chain alcohols derived from tallow are preferred herein. Such alcohols are reacted with ~rom 1 to 12, especially 6, molar proportions of ethylene oxide and the rcsulting mixture of molecu]ar species, having, for example an average of 6 moles o~ ethylene oxide per mole of alcohol, is sulphated and neutralized.
Specific examples of alkyl ether sulphates useful in the present invention are sodium coconut alkyl ethylene glycol ether sulphate; lithium tallow alkyl triethylene glycol ether sulphate; and sodium tallow alkyl hexaoxyethylene sulphate.
Preferred herein ~or reasons of excellent cleaning properties and ready availability are the alkali metal coconut- and tallow--alkyl oxyethylene ether sulphates having an average o~ 1 to 10 oxy-ethylene moieties per molecule. The alkyl ether sulphates are described in US Patent 3,332,~76.
B Nonionic Synthetic Detergents .

Nonionic synthetic detergents may be broadly defined as compounds produced by the condensation o~ alkylene oxide groups (hydrophilic in nature) ~ith an organic hydrophobic compound, . , 1~7Z4~8 which may be aliphatic or alkyl aromatic in na~ure. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
For example, a well known class of nonionic synthetic detergents is made available on the market under the Trade Mark of 'Pluronic'. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water-insolubility, has a molecular weight of from 1500 to 1800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product.
Other suitable nonionic synthetic detergents include the following:
1. The polyethylene oxide condensates of alkyl phenol, e.g.
the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight-chain or branched-chain configuration, with ethyl-ene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived, for example, from polymerized propylene, diisobutylene, octene or nonene.

' 107Z4~8 2. Those derived from the condcnsatlon of ethylene oxide with the product resultin~ from ~he reaction of propylene oxide and ethylene diamine. For example, compounds containing from 40~ to 80~ polyoxyethylene by ~^~eiyht and having a molecular wei~ht of from 5,000 to 11,000 resulting from the reacti,on of e-thylene oxide groùps with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide. 5aid bases having a molecular weight of the orcler of 2,500 -~o 3,000 are satisfactory.

3. The condensation product of aliphatic alcohols having from ~ to 24 caxbon atoms, in either straight~chain or branched-chain configuration with ethylene oxide, e.g. a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut a ! cohol fraction having from 10 to 14 carbon atoms.

4. Noni,onic detergents include nonyl phenol condensed wi*h either about 10 or about 30 moles of ethylene oxide per mole of phenol and the condensation products of coconut alcohol with an avera~e of either about 5.5 or about 15 moles of ethylene oxide per mole of alcohol and the condensation product of about 15 mo].es of ethylene oxi.de with one mole of tridecanol.
Other examples include dodecylphenol condensed with 12 moles of ethyle.ne oxide per mole of phenol; dinonylphenol condensed with 15 moles of ethylene oxide per mole of phenol; dodecyl mercaptan condensed with 10 moles of ethylene oxide per mole of mercaptan; bis~(N-2-hydroxyethyl) lauramide; nonyl phenol condensed with 20 moles of ethylene oxide per mole of nonyl Z~

phenol; myristyl alcohol condensed with 10 moles of ethylene oxide per mole of myristyl alcohol; lauramide condensed with 15 moles of ethylene oxide per mole of lauramide and di-iso-octylphenol condensed with 15 moles of ethylene oxide.

5. A detergent having the formula R3R R N - O (amine oxide detergent) wherein R is an al~yl group containin~ from 10 to 28 carbon atoms, preferably 12 to 18 carbon atoms, from 0 to 2 hydroxy ~roups and from 0 to 5 ether linkages, and R4 and R5 are each selected from alkyl radicals and hydroxyalkyl radicals containing from 1 to 3 carbon atoms. Specific examples of amine oxide detergents include: dimethyldodecy]amine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, di-ethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(2~hydroxyethyl) dodecylamine oxide, bis-(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, (2-hydroxypropyl) methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl-(2-hydroxydodecyl) amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologues of the above compounds.

6. A detergent having the formula R3-S-R~
i ~L~7~4~8 wherein ~3 and R~ are as clefined a~ove. Specific examples of sulphoxide detergents include dodecyl methyl sulphoxide, tetradecyl methyl sulphoxide, 3-hydroxytridecyl methyl sulphoxide, 3-methoxytridecyl methyl sulphoxide, 3-hydroxy-~-dodecoxybutyl methyl sulphoxide, octadecyl 2-hydroxyethyl sulphoxide and dodecylethyl sulphoxlde.

7. The am~onia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from 8 to 18 carbon atoms~
These acyl moieties are normally derived from naturally occurring glycerides, e.g. coconut oil, palm oil, soybean oil and tallow but can be derived synthetically, e.g. by the oxidation of petroleum, or by hydrogenacion of carbon monoxide by the Fischer Tropsch process.
C. Ampholytic Synthetic Detergents Ampholytic synthetic detergents can be broadly described a~ derivatives of aliphatic or aliphatic deri~atives of hetero~
cyclic secondary and tertiary amines, in which the aliphatic radical may be straight-chain or branched and wherein one of the aliphatic substituents contain from 8 to 18 carbon atoms and at least one contains an anionic water-sol~ilizing group, e.g.
carboxy, sulpho or sulphate. Examples of compounds falling within this definition are sodium 3-(dodecylamino)-propionate, sodium 3-(dodecylamino)-propane-1-sulphonate, sodium 2-(dodecylamino)-ethylsulphate, sodium 2-(dimethylamino)-octadecanoate, disodium 3-(N-carbocymethyl dodecylamino)~
propane-l-sulphonate, disodium octadecyl-iminodiazetate, sodium l-carboxymethyl-2-undecyl imidazole, and sodium N,N-bis-(2-hydroxyethyl)-2-sulphate 3-dodecoxypropylamine.

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D. Zwitterionic S~ tic Deterclents _ __ 2witterionic syn-thetic deteryents can be broadly described as derlvatives of aliphatic quaternary ammonium and phosphonium or tertiary sulphonium compounds, in which the cationic atom rnay be part of a heterocyclic ring, and in which the aliphatic radical may be straight-chain or branched and wherein one of theealiphatic substituents contains from 3 to 18 carbon atoms, and at leas-k one aliphatic substituent contains an anionic water-solubilizing group, e.g~ carboxy, sulpho or sulphate. Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecyl-ammonio)-2-hydroxypropane-1-sulphonate, 3--(N,N-dimethyl-N-hexadecylammonio)-propane-l-sulphonate, 2-(N,N-dimethyl-N dodecylammonio)acekate, 3-(N,N-dimethyl-N-dodecylammonio)propionate, 2-(N,N-dimethyl-N-octadecylammonio)-ethyl sulphate, 2-(S-methyl-S-tert.hexa-decyl-sulphonio)ethane-l-sulphonate, 3-(S-methyl-S-dodecyl-sulphonio)-propionate, 4-(S-methyl-S-tetradecylsulphonio) butyrate, l-(2-hydroxy-ethyl)2-undecyl imidazolium-l-acetate, 2-(trimethylammonio) octadecanoate, and 3-(N,N-bis-(2~
hydroxyethyl)-N-octadecylammonio)-2-hydroxy propane-1-sulphonate and 3-(N,N-dimethyl-N-l-methyl alkyl ammonio)-2-hydroxy propane-l-sulphonate, wherein alkyl averages 13.5 to 14.5 carbon atoms in length. Some of these detergents are described in US Patents Nos. 2,129,264; 2,178,353; 2,774,786;
2,813,8~8 and 2,828,332.
E. _tionic Detergen-ts Cationic detergents include those having the formula ~724~8 R -N(R )3~n wherein R6 is an alkyl chain containlng from 8 to 20 carbon atoms, each R7 is selected from alkyl and alkanol groups con~aining from 1 to 4 carbon atoms and benzyl groups, there being normally no more than one benzyl group, and two R7 groups can be joined by either a carbon-carbon e~her, or imino linkage to form a ring structure, or one R7 group is alkyl chain containing from 8 to 20 carbon aLoms, and An represents a halogen atom, sulphate group, nitrate group or a pseudohalogen group. Specific examples are coconut alkyl trimethyl amine chloride, dodecyl dimethyl benzyl bromide, dodecyl methyl morpholino chloride, and ditallow, dimethyl ammonium chloride.
The soap and non-soap anionic, nonionic and zwitterionic detergen-t surfactants mentioned above can be used as the sole surface-active agents, or the various examples may be mixed when used in the practice of the invention. Especially preferred are anionic and nonionic surface~active agents. The amount of surface-active agent incorporated in the preparations depends upon the intended use of the particular formulation. Thus it will relate to the weight of the preparation as a whole, when it is applied directly to skin, e.g. as a cosmetic lotion, or the concentration at which it will be used as a solution in, for example, dishwashing water or bath water. In most cases a content within the range of 0.1% to 90~ by weight o~ the preparation is suitable. More particularly, detergent com-positions for cleaning purposes will generally comprise between ~Q7~

5 and 50~ by w~ight of surface-active agent, while cosmetie compositions ~lill generally comprise between 0.1 and 10% by wei~ht of surface-active agent.
The liquid compositions of the invention generally comprise a earrier based upon water and/or a water-soluble solvent. Suitable solvents include C2 8 mono and di-alcohols, e.g. ethanol, butanol, methyl propanol-l and -2, am~lol or pentanol, butanediol, toluol, benzyl carbinol, ethyleneglycol monobutyl ether, propyleneglycol propyl ether and diethylene-~glyeol dimethyl ether. They are generally presen-t in amo~mts up to 15~ by weight o~ the eomp~sition. Additional eomponents of liquid detergent compositions include foam boosters, such as higher alkyl amine oxides and alkylolamides of C10-Cl4 carboxylic acids, thickeners, preservatives, opacifiers, perfumes, dyes, fluorescers, tarnish inhibitors, bactericides, hydrophobic oily materials and hydrotropes. Commonly employed hydrotropes include conventional lower alkylaryl sulphonates such as sodium and potassium toluene sulphonate, xylene sulphonate, benzene sulpho-nate and cumene sulphonate. Urea and lower alkanol hydrotropes such as methanol, ethanol, propanol and butanol may also be used.
Hydrophobic oily materials suitable for use in the present inven-tion include animal, vegetable and mineral oils and waxes, for example beeswax, spermaceti and carnauba wax;

fatty alcohols such as stearyl, myristyl and cetyl alcohols;
fatty esters and partial esters such as isopropyl myristate and glyceryl monostearate; fatty acids such as stearic acid; ]anolln and cholesterol derivatives; and silicone oils. The cornpositions of the invention, par~icularly the cosmetic lotions, may also ~7Z4~

comprise components designed to enhance the moisturizing e~fectiveness of the composltions. Suitable components include lower aliphatic alcohols having from ~ to 6 carbon a~oms and 2 to 3 hydroxy groups, for example 1,4 butanediol, 1,2-propylene glycol and glycerine. Other suitable components include urea or urea derivatives such as guanidine, pyrrolidone or allantoin.
sase Hydrolysis of Soy Protein "Promine F" (50 g), an edible grade soybean isolate ("Promine F" being a Trade Mark), was added to vigorously stirred warm water (150 mls) to form a slurry. The mixture was heated to a slurry temperature of 90-95C and sodium hydroxide pellets (5 g) were added. After stirring for 4 hours the liquid was cooled to 30C and treated with hydrogen peroxide solution (2 mls of 30%). The solution was stirred for 20 minutes at room temperature and then neutralized to pH 7. The derived protein was isolated by addition of acetone (500 mls), the precipitated protein being washed with acetone ether and finally desiccated to dryness (Yield 45 g).
The hydrolyzed protein was found to have a molecular 20 weight of about 2000; the viscosity of a 10% solution at pH
9.5 and 48C was 1.06 centipoises; and the protein was insoluble to an extent of 30% at its isoionic point pH (4.5). (Molecular weight is a weight average.) A milder base hydrolysis of "Promine F" was also under taken in which "Promine F" was heated at pH 12 and a-t a tempera-ture of 70C for a period of 1 hour. In this case, the hydro-lyzate had a molecular weight of about 5000, the protein was insoluble 1~7;~

to an extent of 85~ at its isoionic point; and the viscosity of a 10% solution at pII 9.5 and 48C was 1.5~ centipoises.
Aminolysis of Soy Protein Promine F (20 g) was added to ethylenediamine (125 mls~
which was then heated to 50~C with stirring. After 4 days, the mixture was cooled and water (70 msl) was added, followed by glacial acetic acid until a pll of 6-7 was achieved. The liquid was then poured into 250 mls of acetone, and the precip-itate was eashed with acetone, ether and finally vacuum dried (Yield 15 g).
Ammoniolysis of Soy Protein ~Promine F (25 g) was added to water (260 mls) with stirring at 70C. When homogeneous, a 1:5 ammonia/water solution (S2 mls) was added, and the mixture was s-tirred at 70 for about 20 hours in an enclosed vessel. Excess a~nonia was then removed by rotary evaporation and the resulting solution was added to acetone (800 mls) to give a precipitate of the ammoniolysis productu This was washed with acetone, ether and finally vacuum dried (Yield 19 g).
Acid Hydrolysis of So~ Protein Promine F (20 g) was added to water (250 mls) with stirring and concentrated hydrochloric acid (6.9 g) was added.
The mixture was warmed to 80C and stirred for 4 hours under a nitroyen atmosphere. After cooling, the solution pH was adjusted to 5 with caustic soda and the precipitate filtered ~5 off. After washing with a little iced water, the solid was dried with acetone and finally vacuum dried. Yield 15.5 g.
Molecular weight 3200.

- 2~ -, ~7~413 EX~MPLE5 1 *O VI
A number of derived soyproteins were prepared by the methods described earlier and these proteins were sep~rately incorporated into a liquid detergent composition having a formulation as follows:
.
Components Parts by Wt.

Ammonium linear C12-C14 alkyl benzene sulfonate 18.4 Sodium linear ~12-C14 10 ~ alcohol sulfate including three ethylene oxide moieties 18.4 Lauric monoethanolamide4.5 Industrial methylated spirits 13.0 Protein-sod1um salt 4.0 Water to 100 Up to 15 parts of urea were added in certain instances to aid incorporation. In all the examples the derived protein was incorporated as the sodium salt.

Conditioning performance was measured by an in vitro test which has been found to have a high degree of correlation ~ith realistic in vivo testing. The in vitro test (called __ the calf-skin occlusivity test was based upon the rate o water transpiration through a sample of calf skin brought into contact with a 0.15% aqueous solution of a detergent composition (at 18 hardness). The occlusivity of the protein was measured as the percentage reduction in the rate of water transpiration for the proteinaceous surfactant solution compared with that for water. Conditioning performance results (at pI-I 7) were as follows:

. - 25 ~

1C~7;2~9L8 Relative Ex. Protein Occlusiv / D I Ethy1ene diamine deqraded 13 ~Promine F

II Caustic alkali degraded 10 "Promine F"

III Sodium borohydride degraded 10 "Promine F' IV ~mmonia water (1:5) degraded 9 'Promine F"
V Enzyme degraded Promine F 5 VI ~Iydrochlori.c acid degraded 3 "Promine F' ~ ~ ~ .
Standard 15I None -6 II 'Wilson X 250 -3 III Wllson X 1000 -7 All the above protein derivatives h~ve a molecular weight in the range 2000 to 6000 (except the borohydride reduced soyprotein which has a somewhat higher molecular weight), and in each case, the proteln is at least partly water-insoluble at its isoionic point pH. It can be seen that all the soyprotein derivatives are effective i.n providing conditioniny benefits from aqueous surfactant solution, but that these benefits are greatest for alkali hydrolyzed, ammoniolyzed and aminolyzed soyproteins. Furthermore, it has been found that these benefits are provided without detriment to the cleaning and foaming power of the detergent.

~ ~t~ 4~ ~

Comparativ~ data for two co]]agen-derived prsteins, ~ "
Wilson Proteins X 250 and X 1000, are shown under standards II and III and it may be seen th~t, accorAing to the in vitro calf-skin ~est, collagen-derived protein hydrolyzates are substantially lnefEective in reducing the rate of water trans-piration through skin.

EXAMPLES VII TO XII
Liquid deteryent compositions were prepared according to the formulation of Examples I to VI but with a protein component as defined below. Thb conditioning performance of these formulations was measured in conven-tional multi-product hand-immersion tests (IIIT). In this test, housewives irnmersed left and right hands in different solutions for three consecutive ten minute periods in halE an hour per day, five days per week for two weeks. Hands were balanced for left and right hand differences, and a total of 32 hands per product, 16 right and 16 left, were used. Hands were withdrawn and reimmersed every two minutes and treatment solutions were replenished every ten minutes. Hands were graded on the starting Monday (before immersion) and on each Friday of the test. They were graded on a 0 (good) - 10 (bad) skin scaling scale. HIT
grades for protein/surfactant solutions were determined and are quoted here, on a scale in which an 0.15% aqueous solution of the detergent composition of Examples I to VI, but containing no protein, was assigned HIT grades of 0, and a 1 mg/cm2 application of hand-care lotion was assigned HIT grades of 100.

- ~7 -~ 7;~48 Ex. Degraded Protein HIT Grade VII sorohydride reduced 60 "Promine F"

VIII HCl hydrolyzate - 60 soymetaprotein IX NaOH hydrolyzate - 56 soymetaprotein X NaOH hydrolyzate - 35~ 42 soymetaprotein + 65~
water-soluble soyhydrolyzate XI Enzyme hydrolyzed soy 36 XII NaOH hydrolyzed "Promine F" 35 of Example X (9 parts), l-hydroxybutyl gelatin (1 part) The modified gelatin of Example XII has a molecular weight of about 180,000 and an isoionic point of pH 8.95. It is described fully in United States ~atent No. ~,115,5~8 of R.A. Marsh et al., granted September 19, 1978.
EXAMPLES XIII TO XV
In Examples XIII to XV, the basic detergent formulation is the same as in Examples I to VI. The degraded proteins of Examples XIII and XIV are hydrolyzates of "Promine F" with NaO~
in which the hydrolysis has been performed in the manner des-cribed earlier. After hydrolysis the soymetaprotein fraction (Example XIII) was obtained by adjusting the ~H of the aqueous solution to 4.5, the isoionic point of the degraded protein, and collecting the precipitate. To the filtrate was added sufficient ammonium sulfate to prepare a half-saturated solution ~7Z~8 of- the salt, and the resulting precipitate was collected.
This is the soyproteose frac~;on of Example XIV. The filtrate contained soypeptone and this was incorporated in Standard VII.
In Example XV, the deyraded protein was soymetaprotein obtained by borohydride reduction, and a number of other protein hydrolyzates are given in Standards IV to VI.
The conditioning effectiveness of the various formulations was compared (see following Table) by measuring the change in the rate of water loss from ~he epidermis of a normal human forearm upon application of a 0.15% solution of each formulation at a water hardness of 12H and at a temperature at application of 40C. The results are quoted against Standard I as a negative control.

It may be seen that water-insoluble soymetaprotein, prepared by either alkaline hydrolysis or reductive cleavage, is extremely effective in reducing the rate of water-loss from the skin. Alkaline soyproteose is rather ]ess effective, but still produces a valuable reduction in water-loss in comparison with Standard I. Soypeptone on the other hand may be seen to be rather ineffective as a conditioning agent and this is also the case with deyxaded whey and corn proteins.

~L~72D~8 Ex. Degraded Protein Transepidermal Water Loss Data XIII Soymetaprotein -24 (NaOH hydrolyzate) XIV Soyproteose -12.5%
(NaOH hydrolyzate) XV Soymetaprotein -20%
(borohydride reduced) Standards I No protein +7.5%
IV Corn peptone - "ViZate 243"* +1.0%
(acid hydrolyzate) V Degraded whey +3.0%
(NaOH hydrolyzate) VI Soypeptone - "ViZate 115"** +10.5%
(acid hydrolyzate) VII Soypeptone >+7%
(NaOH hydrolyzate) EXAMPLES XVI TO XXI
The following examples serve to illustrate, but not to limit, liquid detergent compositions according to the present invention. All percentages indicated are by weight.

*Trademark **Trademark 1~7~8 oP
H ¦~ t` I O I
xl o~o I ~ ~ ~ o ~ I oo ~ In XI

~H ~ I ~r I o ~ ~

~ H dP ~,) X H t~
m H oP
H ~ I` I O O I ~D t~ ~ I
X ~ ~
~H ¦oP
~C I I ~ I I I ~ ~ ~ I

~d ~ ~ O a~
~) N
X ~ X ~, ~ h ~1 X ~ O ~rl O

O

r~
,~ ~ N S
o u~~-1 0 r~ V ~ ~ ~ ~
O r r h ~ r O

U r-l r~l U~ O S l O ~~) O ~-1 1 1 ~) n~ ~ ~ a) o ~D O U ~ Ir-l a) rd ~ -IJ
~r~ C)`~ ~r~ O U~ r~ r~ O td U~ -- 3 ~ -- o r-l r~

~L~37Z~

EXAMPLE XXII
A dishwashing liquid which is mild to skin has the following compositions:

~ Parts hy Wt.
Coconut alcohol-ethylene oxide (12) sulfate ammonium salt 18.75 Coconut alcohol sulfate, ammonium salt 5.8 Sodium alkyl glyceryl ether sulfonate ~whére the alkyl is derived from "middle-cut"
coconu~ alcohols and has the following approximate composi-tion: 2~ C10; 66~ C12; 23~
C14; 9~ C16J
Coconut alkyl dimethyl amine vxide (wherein the coconut is middle-cut~ 5.0 Potassium chloride 2.5 Potassium toluene sulfate 0.5 .
Citric acid 0.1 Hydrogen chloride 0.~1 An~onium xylene sulfate 5.0 Ethanol 8.75 Soymetaprotein (20%) + soyproteose (80%) - NaOH hydrolyzate 4.0 Water to 100 . .

31 ~7~8 "
EXA~PLE XXIII
A cosmetic lotion has the followiny composition:

Component Parts by Wt.
Sodium lauryl sulfate 1.2 Glyceryl monostearate 3.0 Mineral oil 1.0 Methyl p~hydroxy benzoate 0.2 Stearic acid 1.0 ~ Glycerine 4.0 Soymetaprotein NaOH hydrolyzate 3.0 Water to 100

Claims (9)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A detergent or cosmetic composition in liquid form comprising:
(a) from about 0.1% to about 50% by weight of the composition of a surface active agent;
(b) from about 1% to about 10% by weight of the composition of a soymetaprotein;
(c) from about 0% to about 15% by weight of the composition of a water-soluble solvent selected from the group consisting of mono- and di-alcohols containing from two to about eight carbon atoms; and (d) the balance of the composition being water.

2. A composition according to claim 1 wherein the soymetaprotein is a thermal, hydrolytic, ammoniolytic, aminolytic or reductive degradation product of soyprotein.

3. A composition according to claim 2 wherein the soymetaprotein is a base-catalyzed hydrolytic degradation product of soyprotein.

4. A composition according to claim 3 wherein the soymetaprotein comprises less than 10% of non-proteinaceous material.

5. A composition according to claim 4 wherein the soymetaprotein comprises less than 5% of non-proteinaceous material.

6. A composition according to claim 5 wherein the soymetaprotein has an isoionic point of less than pH 6.

7. A composition according to claim 6 wherein the soymetaprotein has an isoionic point of less than pH 5.

8. A composition according to claim 7 wherein the surface-active agent is an anionic, zwitterionic or nonionic synthetic detergent or an anionic soap.

9. A liquid detergent composition according to claim 8 wherein the detergent comprises from 5 to 50% by weight of the composition.