CA1051312A - Toilet bar - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
This invention provides cosmetic or detergent compositions in solid form containing a surface active agent selected from the group consisting of water soluble soaps, non-soap anionic detergents, nonionic detergents, ampholytic detergents, zwitter-ionic detergents, and mixtures thereof, and from 0.1% to 10%
by weight of defatted soyprotein, derived proteins and/or mixtures thereof having an isoionic point (pI) in the range of pH4 to pH7 and a molecular weight greater than 5000 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 containing derived proteins have an in-use pH of from 9 to (pI+5.5).

Description

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BACKGROUND OF THE I~VENTION
The deleterious effects of compositions containing surfactants upon keratin are well known. These effects are caused, it is thought, by penetration of the surfactant (detergent) into the keratin surface leading to "leaching out" of oils and moisturizins components essential for good conditlon of the keratin. This penetration by the surfactant and "leaching out" of essential oils also affects 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 zs a time-honored beautifier and more recently has been recommended i for use in toilet soaps. Numerous other proteins and protein `A

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degradation products have also been recommended for use, , either as protein soaps, or in combination with the usual soap components. For instance, British Patent 8582 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 evaporating the waste when 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 which have a tendency to become rancid.
Various other low-molecular weight polypeptides or modified polypeptides derived from natural proteins are ; commercially available and recommended for use in cosmetic lS and shampoo formulations, for instance nHydro Pro 220nl, Hydro Pro 300n2 and "Maypon 4cn3 marketed by the Stepan Chemical Company; and "Wilson X250n4, Wilson XlOOOn5 and Wilson Aqua Pron6 marketed by the Wilson Chemical Company. However, it has been found that none of these compositions are especially ~-20 effective in protecting keratin from the action of harsh detergents, and this is particularly-true when the proteins are incorporated in the detergent composition itself and the detergent composition is diluted in a large excess of ` water. The emolliency of detergent compositions can often be improved by addition of oily materials but, when used, for instance, in toilet soaps, at an effective level, this usually leads to loss of foaming power or aesthetic changes such as a greasy feeling which are generally considered l.Trademark

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undesirable by consumers The twin objectives of providing increased conditioning effectiveness from a bar soap and at the same time maintaining its traditional performance characteristics, such as suds level and stability, bar wear S rate, wet cracking and smearing performance, are in-general mutuaily contradictory, in that increased conditioning effectiveness is generally only accomplished at the expense of other bar characteristics.
- It is an object of the present invention that ; 10 the conditioning effectiveness of the soap bar is optimized without compromising those physical characteristics which ~re all-important for producing a highly consumer-acceptable ; soap bar.
The present invention therefore provides protein-containing compositions in solid form which are particularly effective in protecting keratinous material, particularly skin, from the deleterious effects of detergents and Gther harsh materials and from adverse climatic conditions, the compositions being effective even when applied to skin in relatively dilute foaming detergent solutions or dispersions, ; this effectiveness being achieved without loss of foaming or cleaning power and without compromising the conventional physical characteristics of the composition.
Percentages and ratios are by weight and temperatures ; 25 are centigrade unless indicated otherwise. Where the term ~soap bar" is used, it is understood that synthetic detergents , and mixtures of soap and synthetic detergents are included therein.

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. SUMMARY OF THE INVENTION
The present invention, broadly,resides in a solid ~:. cosmetic or detergent composition comprising a surface active agent selected from the group consisting of water-soluble soaps, . non-soap anionic detergents, nonionic detergents, ampholytic ;'. detergents, zwitterionic detergents and mixtures thereof; and from 0.1~ to about 10% by weight of a material selected from the . group consisting of defatted soyprotein, derived soyprotein and . mixtures thereof having a molecular weight greater than 5000 :
and an isoionic point in the range from pH4 to pH7.
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In a more particular aspect this invention resides in a . soap composition in solid form comprising:
.~ (i) from about 5 to about 90% by weight of soap having :~ a C12 content of from about 5 to about 45% by weight and a C18 . content from about 15 to about 70% by weight of the soap; and !.~' (ii) from about 0.1% to about 10% by weight of a derived protein having an isoionic point tpI) in the range from pH4 to pH7, ~; and containing an average of at least five free carboxylate groups ~`: per molecule, said protein having a molecular weight greater than .. ` 20 5000; said soap composition having an in-use pH greater than 9 and . less than (pI + 5.5).
,:'` DETAILED DESCRIPTION OF THE INVENTION
As used in the specification, the term defatted soy-~: protein means a form of soyprotein containing at least 70% by weight -: of protein as measured on a dry weight basis. The term "derived ~!'' protein" means protein in which the protein chemical structure has . . .
~`. been degraaed by rupture of peptide and/or sulfur-sulfur bonds, ; and includes primary and secondary protein derivatives formed by :~
;-; hydrolytic cleavage of a protein,.ammoniolytic or aminolytic :
degradation products and reductive degradation products.
The proteinaceous materials suitable for use in the . ~., .

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?51312 . compositions of the invention may be derived from many sources, for instance by thermal degradation, hydrolysis, reduction, ` aminolysis, ammoniolysis of globular or structural proteins from animal, vegetable or even biochemical sources, proteins ; such as collagen, keratin, casein, whey, wheat, soybean . :.
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or cottonseed protein. Particularly preferred protein sources,however, are collagen and soybeans.
Soybeans comprise about 20% oil and about 40%
` protei~, the bulk of their protein being contained in storage sites called aleurone grains-protein bodies of 2 - 20 microns diameter, each surrounded by a membrane thought to consist of phospholipids. Soybeans are usually processed into a variety of forms in which the ordered ~truGt~re of the int~ct seed is destroyed. The s~mplest processing consists of steaming the beans and removing the ~i hulls, which are more than 85~ carbohydrate. Sub~ecting ., .
~ the soybeans to excessive heat treatment denatures the , protein, however, and this tends to render the subsequent protein extracts water insoluble. Undenatured soyproteins, which are preferred for use in the present invention, may therefore be prepared by avoidance of excessive heat treatment in the initial processing steps. Grinding ~ the dehulled material yields full-fat flours, the cr~dest form of `; soy proteinaceous material. Defatted flours, having a protein '` 20 content of 50% or more, are obtained upon extraction of the soybean oil with hexane, while protein concentrates having ,~ .
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 isolates from which the bulk of the oil and carbohydrates has been separated, leaving less than 10% non-protein material (ash and minor constituents). Such isolates are generally prepared by extracting undenatured flakes or flour with dilute alkali at pH 8 - 9, the clarified extract possibly then being ` 30 acidified to pH 4.5 to precipitate soyprotein globulins.

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; The proteinaceous material suitable for use in the solid . . .
' 8urface-active compositions of the invention has preferably been subjected to all the above defatting and purification procedures, so that it wiil generally contain at least 70%, . . .:
, 5 preferably at least 90% and more preferably at least 95% of soyprotein.
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i~- Hydrolytic degradation of proteins has long been .~, . .
u~ed in the food industry, for instance, to increase the ;, water-solubility of soyprotein to enhance taste and flavor.
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`' 10 There exist numerous processes for the hydrolysis of protein, ,~.1,. . .
c l ~nd these may be divided into three classes according to the hydrolysing 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. Ammoniolytic degradation may be accomplished by the action of relatively concentrated ammonia solutions (in which case ammoniolysis is accompanied by a degree of hydroly-~, sis) or by the action of ammonia gas, while aminolytic degradation is brought about by treatment with mono- or , 20 polyamino compounds.
, ~ydrolytic degradation is preferably carried out with aqueous alkali, for instance, solutions of caustic soda, caustic ~ Çj ~` potash, slaked lime, dilute ammonia. The process consists of treating a slurry or solution of, for instance, soyprotein isolate with aqueous alkali at a temperature of, preferably ~: S0 - 95C. for a period of, generally, between 1/2 and 4 hours, ... .
i the amount of alkali being used ordinarily lying between 5% and 15% by weight of the weight of the sopprotein. The .. . .
amount of alkali used, the temperature and length of time . ~, ;

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of the treatment will be determined by the degree of hydroly-8i8 desired. If desired, the hydrolysis may be terminated before the protein is hydrolyzed to the point that it would be soluble at its isoionic point pH. Following hydrolysis 5 or, if desired, simultaneously therewith, the protein con-~- - t~ining liquor may be treated with an oxidizing agent, ~ preferably 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 10 complexes of hydrogen peroxide such as sodium perborate, urea or guanidine peroxide or even organic peroxides, for instance, peracetic acid. The purpose of the oxidizing agent ' i8 to react with organic and inorganic sulphydryl species which invariably are formed upon alkaline hydrolysis, turning ; the agueous solution into a dark, evil-smelling liquid. In ? this way, the cysteine content of the protein is substantially ;
eliminated. After the oxidation stage, the protein may be isolated, for instance,by freeze drying, acetone precipitation r,~, or isoionic point precipitation, or the protein solution . .~ .
20 may be immediately used to prepare the compositions of the invention as described below.
Enzymatically hydrolyzed proteins may also be ; incorporated in the compositions of the invention. The enzyme generally used is a protease enzyme but certain ., .; , .
25 materials containing both protease and amylase enzymes may ; also be used. These enzyme materials are obtained from a variety of animal, plant, bacterial and fungal sources.
Special mention may be made of papain, bromelin, ficin, ,. , :i:

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chymopapain, trypsin, chymotrypsin, pancreatin, pepsin, , erepsin, the fungal enzymes of Aspergillus oryzae and . ~. . . .
AspergillUs niger and the bacterial enzymes of the Bacillus ,, genus, for example B, mycoides, B. amyloliquifaciens, B. cereus, B. maceranS, B. megaterium, B. sphaericus, B. circulans, and especially B. subtilis. 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 40C. pepsin treatment may suffice.
r~ 5 Acid hydrolysis may be carried out with aqueous hydrochloric or sulfuric acid, typically the aqueous liquid ,~ being heated under reflux with 10 to 50% aqueous acid for a period of 5 to 20 hours. Alternatively, the mixture may ~'~`i, ' . .
;~ be heated at superatmospheric pressure with more dilute acid, ~20 e.g. 5% by weight, for a short period of time.
Ammoniolysis, possible acc~mpanied by hydrolysis, may be accomplished by heating a protein source, for example, soyprotein isolate with 10% by wt. (or greater) ammonia solution at a temperature of 50 - 100 for a period of `25 10 to 30 hours. Excess ammonia is simply removed by evapora-tion and the ammoniolyzed protein may then be isolated, for instance by acetone precipitation, or used immediately , in the compositions of the invention. -Protein aminolysates are prepared by heating protein with a mono-, di or polyamine or derivatives thereof, ~: "

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- , usually in at least equal an amount by weigh~t under reduced or atmospheric pressure at temperatures between SOC and 200C. Preferred amines include C2 to C10 alkamines and alkanolamines, and C2 to C12 diamines and polyamines.
Other means of degrading proteins include thermal degradation, ~for instance by pressure steam heating a protein slurry rapidly and substantially instantaneously to a temperature above 220F. wi~h mechanical wor~ing, ; . ; 10 followed, possibly, by an enzymatic hydrolysis treatment;
and reductive cleavage of inter-molecular disulfide cross-links with, for instance, metal hydrides (such as sodium borohydride), sulphydryl compounds (such as 0.01 M
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~ mercaptoethanol), sulphites, thioglycollates etc.
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Derived proteins suitable for use in the presen.
; , invention may be partly water-insoluble at the isoionic point pH of the protein and therefore include the so-called metaproteins. The proteins are preferably, of course, substantially water-soluble at a pH value removed from the ; 20 isoionic point pH, for instance, at the pH of the composition when dissolved or dispersed in water in the normal manner of use. Other suitable derived proteins include proteoses and peptones, for instance soyproteose and soypeptone, and ~ gelatin (the hydrolysis product of collagen).
;; 25 Particularly preferred derived proteins are also ` characterized by specific values of molecular weight, isoionic point, and anionic molecular charge. The average `~ minimum molecular anionic charge, determined by the mlmber of carboxylate groups per molecule, should be at least ` 30 five. The isoionic point preferably lies in the range ' :
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1~5~312 ; from pH4 to 7, desirably from 4.5 to 6. Derived protein having an isoionic point greater than pH5 preferably have a weight average molecular weight greater than 5000 and desirably ,~ greater than lU,0U0. Derived protein having an isoionic point ~: 5 less than pH 5 preferably have a weight average molecular weight greater than 1500, desirably greater than 3000, and - especially greater than 5000.
By way of comparison, the preferred protein components of the compositions of the invention have the following characteristics. The collagen derived proteins are gelatins having isoionic point values in the range from pH4 to 7. Preferably, they are Type B gelatins having isoionic point values in the range from pH5 to 6, and weight ;~ average molecular weight values in the range from 15,000 to 200,000, preferably from 20,000 to 120,000 and most preferably from 25,000 to 80,000. Collagen-derived proteins ,~ with average molecular weights in the range 5000 to 10,000 ~ have been found to be only marginally effective in providing i- mildness and skin-conditioning effects. On the other hand, while gelatins with molecular weights in the range 120,000 ,................................................................... . to 200,000 are effective, it has been found that the use of ~ such gelatins leads to inferior soap bar performance s cnaracteristics, ln particular to lower bar heterogeneity and to inferior lathering characterlstics. Average molecular `l25 weights in the range from 25,000 to 80,000 are preferred ~ . .
~` because this produces an optimum balance of mildness characteristics and soap bar performance characteristics.
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Soyglobulins isolated auring isoelectric pre-cipitatiOn have an isoionic point of about pH 4.9 to 5Ø
~uch soyglobulins should be dissolved or dispersed .
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in an alkaline matrix before incorporation in the composi-tions of the invention. Base hydrolyzed soyproteins have a somewhat lower isoionic point pH, about p~ 4.5, while acid hydrolyzed proteins (about pH 5.5) and enzy~me hydrolyzed .,.;, . .
S proteins (about pH6) have higher values. Ammoniolyzed soyproteins have isoionic point values in the range of about pH 5.5 to-6.5, while aminolyzed proteins may have much ... .
higher isoionic point pH values, up to 8 or 9 or even higher. The highly preferred aerived soyproteins are the ~ ,;J ' .
~^ 10 al~ali hydrolysates which desirably have average molecular ; weights greater than 1500.
- Isoionic point pH values may be determined in :":
; ; the following manner: "Amberliten* acid resin (IR 120) and base resin (IR 400) are washed with several volumes of ; -, ~
`i'15 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 tempera-ture. The resin mixture (8.4 g) is added, the solution is ~ stirred for five minutes, the mixture is filtered and the ! `20 pH of the filtrate is the isoionic point pH of the protein.
The molecular weight values guoted for the various protein materials have been obtained by ultracentri-fuge measurements or by gel filtration on a column previously ` calibrated against the ultra-centrifuge.
~25 The optimum choice of protein for any particular ~` composition depends upon the pH of the composition in use, ,: .., i.e. the pH. This in-use pH may, depending upon the type of application, be the pH of the composition itself, or ,. . .: _ be the ~H of an aqueous solution or dispersion of the ~Trademark of Rohm and Raas Company for an ion exchange resin.

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10513~2 : composition at a concentration of use which may be as little as 0.01%., for example, in the case of a bathing composition, up to about 0.5% in the case of a laundry x detergent, or even as high as 10% in the case of soap bar ~: 5 detergent designed for personal washing use.
Preferably the in-use pH, i.e. the pH of appli-cation to keratin, should lie in the pH range from (pI + 2) to ~pI + S.5), and more preferably in the range from (pI + 3) to (pI + 5), wher-e pI is t~he soionic point pH of protein.
The in-use pH may vary widely, of course, depending upon the purpose and manner of use of the compositions. Composi-.~ . ..
tions designed as hand or face creams 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, r; ~` 15 generally, from S to 9. Detergent compositions such as ~- granular dishwashing and bathing compositions and heavy-duty granular 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 ~ 20 range from U.01% to 2% by weight. Builder-free detergent ; compositions, for instance, will have an in-use pH of about

7; built heavy-duty detergents generally have an in-use pH
in the alkaline range of from about 8 to about 11. Soap bar compositions are applied to skin as an aqueous solution or dispersion of the soap bar ingredients at a concentration, generally in the range from 5 to 15 wt %. The pH of the ,.
soap dispersion may vary, depending upon the type of soap bar employed, from a pH of S.~ to about lO.S. In the preferred embodiment of the invention, however, a soap bar ..

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~; based upon certain mixtures of alkali metal salts of C12 and C18 based fatty acids, the in-use pH lies generally in the range from pH9 to 10.5, preferably from pH 9.5 to 10Ø The free (unneu~ralized) fatty acid content is preferably less than 10% generally from about 0.5% to ~bout 8%.
The amount of protein present in the composition of the invention may also vary widely. While levels of up t~ 50% may ~e envisaged in, ~r-example, a cosmetic gel, ; 10 generally the protein will comprise from 0.1 to 10%, ~ preferably from 1 to 8% and especially from 2 to 6% of the - composition.
Surfactant materials which may be used in the compositions of the invention can be selected from water-~ 15 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.
` 20 A. Anionic Soap and Non-Soap Synthetic Detergents , ~ The preferred class of detergents for use in the ;~ present invention is the alkali soap class including the sodium, potassium, ammonium, alkylammonium and alkylammonium salts of higher fatty acids containing from 8 to 24 carbon atoms and preferably from 10 to 20 carbon atoms. Suitable fatty acids can be obtained from natural sources, such as 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 oxidation of , . .

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petroleum or by hydrogenation of carbon monoxide by the '. Fischer Tropsch process). Resin acids are suitable, such as, ro~ln and those resin acids in tall oil. Naphthenic acids ~. are also sultable. Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralizati.on of the free fatty acids which are prepared ~: in a separate manufacturing process. Particularly useful .Y are the sodium, potassium, and triethanol-ammonium salts of ~...... ~ .
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.` the mixtur.es o.f.~a.tty acids.. deri~ed from coconut oil and X.;` 10 tallow, e.g. sodium or potassium tallow and coconut soaps.
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.~. 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 radical containing from ~ to ~2 carbon atoms and a sulfonic acid or sulfuric acid ester radical.
~?,` (Included in the term alkyl is the alkyl portion of higher . acyl radicals.) Examples of this group of synthetic deter-~;!` gents which form a part of the preferred compositions of .~", ,~ .
~ the present invention are the alkali metal, e.g. sodium or , . .
.'~ 20 potassium, alkyl sulfates, especially those obtained by ,.1 ~. sulfating the higher alcohols (8 to 18 carbon atoms) produced -~ by reducing the glycerides of tallow or coconut oil; the alkali metal olefin sulfonates of from 8 to 24 carbon atoms ~ .
described, for example, in U. S. Patent 3,332,880; and the alkali metal alkyl glyceryl ether sulfonates, especially ~:.
those ethers of the higher alcohols derived from tallow ~` and coconut oil. Other anionic detergents include the ., .
alkali metal alkylbenzene sulfonates, in which the alkyl . group contains from 9 to 15 carbon atoms, including those . . ~
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:~ 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 monoglyceride sulfates and sulfonates; salts S of alkyl phenol ethylene oxide ether sulfates with 1 to 12 unlts of ethylene oxlde per molecule and in which the alkyl radicals contain from 8 to 18 carbon atoms; the reaction product of fatty acids esterified with isethionic and neutralized wi~h sodium hydr~xide where, for example the fatty acid is oleic or derived from coconut oil; sodium or potassium slats of fatty acid amide of a methyl tauride in - which the fatty acids, for example, are derived from coconut oil; sodium or potassium ~-acetoxy- or B-acetamido-alkane sulfonates where the alkane has from 8 to 22 carbon atoms;
~; 15 and others known in the art. A number are specifically set forth in United States Patents Nos. 2,286,921; 2,486,922;
and 2,3i6,278.

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Other synthetic anionic detergents useful herein ... .
;~ are alkyl ether sulfates. These materials have the formula ,,., ~

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R O(c2H4o)xso3M

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~;~ wherein R2 is alkyl or alkenyl of about 8 to 24 carbon atoms, x is 1 to 30, and M is a salt-forming cation selected from alkali metal, ammonium and dimethyl-,trimethyl-triethyl-, dimethanol-, diethanol-, trimethanol- and triethanol-ammonium cations.

, r ` 1~51312 The alkyl ether sulfates are condensation products .s~'` .
~ of ethylene oxide and mon ~ dric alcohols ha~ing about 8 to 24 `, carbon atoms. Preferably, R2 has 14 to 18 carbon atoms. The alcohols can be ds~rived 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 from 1 to 12, especially 6, molar .
proportions of ethy'ene oxide and the resulting mixture of molecular species, havin~, for example an average of 6 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
~'' Specific examples of alkyl ether sulfates useful in the present invention are sodium coconut alkyl ethylene glycol ether sulfate; lithium tallow alkyl triethylene glycol ether sulfate; and sodium tallow alkyl hexaoxyethylene sulfate. Preferred herein for reasons of excellent cleaning ~; properties and ready availability are the alkali metal ~ . . .
coconut- and tallow-alkyl oxyethylene ether sulfates having '~ an average of 1 to 10 oxyethylene moieties per molecule. The ~20 alkyl ether sulfates are described in U. S. Patent 3,332,876.
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B. Nonionic Synthetic Detergents Nonionic synthetic detergents may be broadly de-fined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydro-~;2~ phobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hyarophilic 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 hydro-"`
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philic and hydrophobic elements.-For example, a well known class of nonionicsynthetic detergents is made available on the market under the trade mark of 'Pluronic'. These compounds are formed ~ 5 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 : 10 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 '1.~
;` product.
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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 ` 20 from 6 to 12 carbon atoms in either a straight-~` chain or branched-chain configuration, with ethylene 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.
` 2. Those derived from the condensation of ethylene oxide with the product resulting from the , .~ ~ , .'', ~
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~ reaction of propylene oxide and ethylene . .. .diamine. For example, compounds containing from 40% to 80% polyoxyethylene by weight and rhaving a molecular weight of from 5,000 to 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide. Said bases having a molecular weight of the order of 2,500 to 3,000 , . , are satisfactory.
3. The condensation product of aliphatic alcohols ~,~ having from 8 to 24 carbon toms, 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 alcohol fraction having from 10 to 14 carbon atoms.
4. Nonionic detergents include nonyl phenol condensed ~, 20 with either about 10 or about 30 moles of ~' ethylene oxide per mole of phenol and the condensation products of coconut alcohol with an average of either about 5.5 or about 15 moles of ethylene oxide per mole of alcohol and the condensation product of about 15 moles of ethylene oxide with one mole of tridecanol.

Other examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 15 moles ., . .

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. 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 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-is o-octylphenol ;s 10 condensed with 15 moles of ethylene oxide. j 5. A detergent having the formula , ", . . '.
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;''~' ' ' R3R4RSN '~ o , ~' ' .. :
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. (amine oxide detergent) wherein R is an !, alkyl group containing from 10 to 28 carbon .
115 atoms, from 0 to 2 hydroxy groups and from 0 to 5 ether linkages, there being at least one moiety . of R3 which is an alkyl group containing from .
; 10 to 18 carbon atoms and 0 ether linkages, and .
R4 and R5 are each selected from alkyl radicals :
.20 and hydroxyalkyl radicals containing from 1 to 3 ~::
. carbon atoms. Specific examples of amine oxide :
. detergents include: dimethyldodecylamine oxide, .
dimethyltetradecylamine oxide, ethylmethyltetra-;`; . decylamine oxide, cetyldimethylamine oxide, ~.25 dimethylstearylamine oxide, cetylethylpropylamine .
;. oxide, diethyldodecylamine oxide, diethyltetra- :
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: .

S~3~2 decylamine oxide, dipropyldodecylamine oxide, ... . .
~ bis-(2-hydroxyethyl) dodecylamine oxide, i bi~-(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 ~ .
'' R - S - R

.?
wherein R3 and R4 are as defined above. Specific examples of sulfoxide detergents include , ,~
dodecyl methyl sulfoxide tetradecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl 2-: .
~`~ hydroxyethyl sulfoxide and dodecylethyl sulfoxide.
7. The ammonia, monoethanol and diethanol amides .... .
of fatty acids having an acyl moiety of from ;~i 8 to 18 carbon atoms. These acyl moieties are ` normally derived from naturally occurring ;.r glycerides, e.g. coconut oil, palm oil, soybean I oil and tallow but can be derived synthetically, . ~

r ~ 2 0 :

.

11~513~Z
... . . .
. ....... .
- e.g. by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer ;~ Tropsch process.
,~ C. Am~holytic Synthetic Detergents Ampholytic synthetic detergents can be broadly ; described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which the , ,, "
aliphatic radical may be straight-chain or branched and f wherein one of the aliphatic substituents contain from 8 to ~ 10 18 carbon atoms and at least one contains an anionic water-~ .
solubilizing group, e.g. carboxy, sulpho or sulphato. Examples ~ of compounds falling within this definition are sodium ;~ 3-(dodecylamino)-propionate, sodium 3-(dodecylamino)propane-l-sulfonate, sodium 2-(dodecylamino)-ethylsulfate, sodium ; 15 2-(dimethylamino)-octadecanoate, disodium 3-(N-carboxymethyl dodecylamino)-propane-l-sulfonate, disodium octadecyl-iminodiazetate, sodium i-carboxymethyl-2-undecyl imidazole, ~ and sodium N,N-bis-(2-hydroxyethyl)-2-sulfato 3-dodecoxy-r propylamine.

, . .

., .
:,., ~ .
``"':'' ' ~ ~
.
5' '`

~ ...................................................................... ..
.: _ ,'~'', ' ~"

,:

;~
~ Q5~3~'~
: -.
: D. Zwitterionic Synthetic Detergents ;-.
Zwitterionic synthetic detergents can be broadly de~cribed as derivatives of aliphatic quaternary ammonium and phosphonium or tertiary sulfonium compounds, in which ~' S the cationic atom may be part of a heterocyclic ring, and in : .
which the aliphatic radical may be straight chain or ...... .
; branched and wherein one of the aliphatic substituents :' contains from 3 to 18 carbon atoms, and at least one aliphatic , . . .
substituent contains an anionic water-solubilizing group, e.g. carboxy, sulfo or sulfato. Examples of compounds falling , .;
within this definition are 3-(N,N-dimethyl-N-hexadecyl-ammonio)-2-hydroxypropane-1-sulfonate, 3-IN,N-dimethyl-N-hexadecylammonio)-propane-l-sulfonate, 2-(N,N-dimethyl-N-dodecylammonio)acetate, 3-~N,N-dimethyl-N-dodecylammonio)propionate, 2-(N,N-dimethyl-N-octadecylammonio)-ethyl sulfate, 2-(S-methyl-S-tert-hexadecyl-sulfonio)ethane-l-sulfonate, 3-~S-methyl-S-dodecyl-sulfonio)propionate, 4-~S-methyl-S-tetradecylsulfonio)butyrate, 1-(2-hydroxyethyl)2-undecyl imidazolium-l-acetate, 2-(tri-methylammonio)octadecanoate, and 3-(N,N-bis-(2-hydroxyethyl-N-octadecylammonio)-2-hydroxypropane-1-sulfonate and 3-(N,N-: ., dimethyl-N-l-methylalkyl ammonio)-2-hydroxy propane-l-sulfonate, wherein alkyl averages 13.5 to 14.5 carbon atoms in length.
,` Some of these detergents are described in U.S. Patents Nos.
2,129,264; 2,178,353; 2,774,786; 2,813,898 and 2,828,332.
~` 25 E. Cationic Detergents , Cationic detergents include those having the formula .

5~3~2 .

~ . . R - N(R )3An !, '. .
~ wherein R6 is an alkyl chain containing from 8 to 20 carbon :- .
.... . . .
,; atoms, each R7 is selected from alkyl and alkanol groups containing from 1 to 4 carbon atoms and benzyl groups, . 5 . there being normally no more than one benzyl groups, and two !~",' R7 groups can be joined-by either a carbon-carbon ether, or imino linkage to form a ring structure, and An represents - `
. a halogen atom, sulfate group, nitrate group or a pseudohalogen .
group. Specific examples are coconut alkyl trimethyl amine . ~.

10 chloride, dodecyl dimethyl benzyl bromide and dodecyl methyl .~ morpholino chloride.

The~above-mentiOned detergent components are particu-. j.~ .
,. larly envisaged for use, either singly or in combination, ; ~ .

:: in cosmetic and detergent compositions based upon derived ~.

soyprotein. However, it is an important feature of the ~;` present invention that certain specific combinations of :~

;~. soaps having specific fatty acid chain lengths, together with .

~ a derived protein having specific molecular weight and .`~!, . anionic group characteristics as described previously, ~`20 have unexpectedly enhanced mildness and conditioning ~:' characteristics compared with previously known soap compositions.
~;; Moreover, these conditioning characteristics obtained without :
detriment to other important characteristics of the soap compositions, for instance, the la~en~, wet-cracking, ~25 hardness, and smear characteristics of bar soap compositions.
i~ Accordingly, a preferrea embodiment of the invention comprises ,~, ~ , ,.
'.

~,-:, -............. '' ''" '' ' .' "

; iO5~31Z
::.`., j,i',f, ~ a maxture of soaps, one component of which has a C12 fatty :., ac~d content of from about 5 to 45%, preferably from about 8 to about 40%, more preferably from about 10 to about 30% by weight of the soap, and a second component of which S has a C18 fatty acid content of from 15 to 70% by weight of the soap. Providing the derived protein has the correct molecular weight and charge characteristics, it has been found that such combinations have significantly Lmpr~ved mildness characteristics compared, for example, with soap compositions having a higher C18 soap content, despite the fact that, as is well known, C18 soaps are conventionally marked by being very much milder than C12 soaps. As a result, all the advantages of incorporating C12 soaps in a soap bar -- superior lathering characteristics, for example --can be exploited, not just without detriment to the soap bar's mildness characteristics, but indeed with greatly ~` enhanced mildness and conditioning effectiveness.
~` The preferred C12 soaps are, of course, coconut oil soap and palm kernel oil soap. The preferred C18 soaps may be derived from many sources, including mutton and beef tallow, soybean oil, fish oils etc. Especially preferred is a mixture of tallow and coconut soaps in a ratio of 90:10 to 10:90, desirably from 84:16 to 20:80, and most preferably -; from 80:20 to 40:60.
` 25 It is another important feature of the present invention that, providing the derived protein has the right molecular weight and charge characteristics, the presence of free fatty acid also provides a synergistic enhancement of the mildness '`''' :
i .. . . . . . .
, S~lZ
of the soap compositions. Free fatty acid is a well-known lngredient of bar soaps, of course, its function being to react with excess alkali in the soap, therefore reducing the causticity of the composition. It is most unexpected, -however, that the presence of free fatty acid in the soap can produce such a synergistic increase in the mildness of the ~oap ccmpositions of the invention, an increase of quite extraordinary proportions in some cases. The syn~rgism is most marked for derived proteins having an isoionic point less than about 5, for instance for the derived soy, whey and wheat or corn proteins having molecular weights in the range of about 1500 to 10,000.
The preferred form of the soap compositions of the invention is that of a milled soap bar containing about 70 - 15 to 90~ real soap, although soap compositions in granular or .~:
~- flake form are also envlsaged. It is believed that milling ~` the soap composition is important for obtaining the ~ protein in a form uniformly dispersed through the soap bar `~ with the protein intimately associated with the soap crystallites.
The resulting soap bars have excellent hardness, smear and !i~ storage characteristics providing the moisture content is in .~.
~ the range from S to 15%, especially from 8 to 12% by weight ..~
` of the composition. The preferred process for making the soap bars is to amalgamate the derived protein as an aqueous ~; 25 solution or dispersion at about 40-50~ concentration, with .;~ the base soap composition after the conventional crutching ~; and drying stages (for instance, a Mazzoni drying stage) ~` but before the milling stage. The drying stage is taken to a ,...
s, .

,:

J', '-'; .' ''' . .

. , . ~
' .

', ' 1~5~3~Z
base soap moisture content of about 4 to 5%, as opposed to ;~ the conventional 9% moisture, the remainder being made up on addition of the protein. Alternatively, the protein ~`~ may be added in undegraded form to the fatty acids at the crutcher stage, providing the conditions are chosen to - produce a final composition as defined earlier.
; The in~ention is also applicable to a variety of `~ other compositions which may come into contact with keratin in the normal course of use, for example granular dishwashing ~, ,~,. . . .
detergents, hand and face creams, granular bathing compositions, i, heavy-duty detergent compositions and hard-surface cleaning :; compositions. The physical form of the compositions, however, ,.. . .
i8 preferably limited to granular and continuous solids, gels and creams, i.e. compositions having a non-zero yield point.
The compositions of the invention may contain any of the other usual components conventionally present in detergent and cosmetic compositions. Thus, solid granular detergent ~ compositions may contain foam enhancers, foam depressents, ; bleaches, antiredeposition agents, enzymes, enzyme and bleach ~:` 20 activators, fluorescers, builders and so forth. Preferably :~"
. the builder is a material which will buffer the composition ~- so that the in-use pH is with the aforementioned units.
Examples of such builders are citrates and polyphosphates.
.. .
Soap bar compositions and cosmetic compositions may also contain additives such as skin creams and other hydrophobic oily materials. These 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 .`' lQ5~31'~

myristate and glyceryl monostearate; fatty acids such as stearic ac`id; lanolin and cholesterol derivatives; and silicone oils. The compositions of the invention, particularly the cosmetic creams, may also comprise components designed to enhance the moisturizing effectiveness of the compositions.
Suitable components include lower aliphatic alcohols having from 2 to 6 carbon atoms 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.

;~ Preparation of Base Hydrolyzed Proteins .: ~
Promine F (50 g), an edible grade soybean isolate ;.,~ , (Promine F being a trademark), 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 four hours, the liquid was cooled to 30C and treated with hydrogen I ~ .
peroxide solution (2 mls of 30%). The solution was stirred for 20 minutes at room temperature and then neutralized to pH 7 with inorganic or fatty acids. The derived protein ~;~ was isolated by addition of acetone (500 mls), the precipitated ~;~ protein being washed with acetone ether and finally dessicated to dryness (yield 45 g).
The hydrolyzed protein was found to have a weight average molecular weight of about 2000; and the prote-n was insoluble to an extent of 30% at its isoionic point pH (4.5).
~` A milder base hydrolysis of Promine F was also under-` taken in which Promine F was heated at pH 12 and at a temperature of 70C for a period of one hour. In this case, the hydrolysate :
' :

!~ , 27 -t,~
,:. . - :
.: :

r~

- 105~3~Z
. .
had a molecular weight of about 5000, the protein was insoluble to an extent of 85% at its isoionic point; and the viscosity of a 10% solution at pH 9.5 and 48C was 1.56 centipoises.
Essentially similar procedures are employed to produce S the base hydrolysates of other proteins suitable for use in the invention, especially whey, wheat and cottonseed protein.
Preparation of Aminolyzed Protein Promine F (20 g) was added to ethylenediamine (125 mls) which was then heated to 50C with stirring. After four days, the mixture was cooled and water (70 mls) was added, followed by glacial acetic acid until a pH of 6-7 was . . .
achieved. The liquid was then poured into 250 mls of acetone, .
; and the precipitate was washed with acetone, ether and f~nally vacuum dried (yield 15 g).
.~.
Preparation of Ammonolyzed Proteins ; Promine F (25 g) was added to water (260 mls~ with ` stirring at 70C. When homogeneous, a 1:5 ammonia/water ''5 solution (52 mls) was added, and the mixture was stirred at 70 for about 20 hours in an enclosed vessel. Excess ammonia was then removed by rotary evaporation and the resulting solution was added to acetone ~800 mls) to give a precipitate ~ of the ammoniolysis product. This was washed with acetone, ;- ether and finally vacuum dried ~yield 19 g).
Preparation of Acid Hydrolyzed Proteins 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 four hours under a nitrogen atmosphere. After cooling, the solution .

~()S1312 pH was adjusted to 5 with caustic soda and the precipitate filtered 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.
Any animal or vegetable protein may be used in place of the soyprotein in any of the above preparations, giving substantially similar results.
~, , .
Conditioning Tests Conditioning performance was measured in both o in vitro and in vivo tests, a high degree of correlation between the various test methods being found. The in v ro test measured the change in the rate of water-transpiration - through skin of a normal human forearm in contact with a 20% soap lather in water at 8 of hardness. Measurements were based on an electrolytic method. The in vivo test wa~ a consumer mildness study which may be summarized as ' follows:
Housewife subjects between the ages of 25 and 55 years old were given bars of a test product together with a standard size face cloth, both to be used at home for a ; week. The subjects were requested to wash their face at least twice a day massaging the face with the well soaped facecloth for at least 30 seconds each wash -- they were also requested to refrain from the use of greasy cosmetics.
Overall facial skin condition was assessed before and after usage by using a standard 0 (poor) to 10 (good) skin condition scale.
.

.

5~31Z
EXAMPLES I - III
An intimate aqueous mixture of sodium coconut soap ~22 parts), sodium tallow soap ~88 parts), free fatty acids (8.5 parts), titanium dioxide (0.65 parts), was prepared in a crutcher and vacuum dried to noodles of about 7% moisture. Simultaneously, a soyprotein hydrolysate of molecular weight 2000, prepared by hydrolysis of Promine F
with caustic alkali until the viscosity of a 10% solution at pH 9.5 and 48C was 1.06 centipoises, was then made up as a 50% solution in water and steam heated to a temperature of 50C for 30 minutes to give a homogeneous mixture. The protein solution, together with perfume and color, was then amalgamated with the soap noodles, and a bar was formed by milling at approximately 96F on a three roll mill for three passes, plodding and replodding at about 108F and cutting and stamping the bar in conventional equipment.
The final composition of the bar was as follows:

. :
Components Wt. %
Real soap (80% tallow/20%
coconut) 77.1 Free fatty acid 7.6 Moisture 9.2 Miscellaneous 2.1 Base hydrolyzed soybean isolate 4.0 The resulting bar was found to be beneficial to skin and to have undiminished lathering and hardness characteristics.

~(~5~3~Z
Examples II and III were prepared in a similar manner to the above, except that aminolyzed soybean isolate and ~mmonolyzed soybean isolate were incorporated in the soap bar in place of the base-hydrolyzed isolate.

S EXAMPLES IV - VI
.
Soap bàrs were prepared in similar manner to Example I b~t instead a gelatin of m~lecular weight 45,-~00 and isoionic point 5.5 was added to the bar at the amalgamator stage as a 50% solution. The compositions of the bars are given below, together with their ~ransepidermal water loss values. Also given are comparative values for the non-protein containing standards I and II. In the table, a positive transepidermal water loss value indicates reduction in water loss.

' 15 Examples Standards 1 Composition IV V VI I II
., . . _ Tallow soap 42.3 67.7 84.6 42.3 67.7 Coconut soap 42.3 16.9 0.042.316.9 Free fatty acid 0.0 0.00.0 0.0 0.0 Miscellaneous 2.2 2.2 2.22.2 2.2 Noisture 9.2 9.2 9.29.2 9.2 Gelatin 4.0 4.0 4.00.0 0.0 Transepidermal __ Water Loss Data +3.5 +2.0 +0.2 -21.0 -14.3 - -~1 15'~3~'~

: It may be seen that all the protein containing bars ~re significantly milder, in terms of depleting the skin of moisture, than their non-protein containing counterparts.
In addition, it may be seen that soap bars containing a S combination of tallow and coconut soaps are significantly ; milder than an all-tallow soap.

EXAMPLES VII - VIII
Soap bars were prepared having formulations as detailed in the table below:

.
. Examples Standards osition YII VIII II IV
Tallow soap 61.6 61.6 61.6 61.6 Coconut soap 15.4 15.4 15.4 15.4 Free fatty acid 7.6 7.6 7.6 7.6 Miscellaneous 2.2 2.2 2.2 2.2 ¦
Moisture 9.2 9.2 9.2 9.2 Gelatin: pI = 5.5:
MW = 45,000 4.0 _ _ _ Gelatin: pI = 5.5;
: 20 MW = 9000 _ 4.0 _ _ Gelatin: pI = 7.7;
: MW - 85,000 _ _ _ 4.0 Transepidermal Water Loss Data ~2.0 -5.8-9.0 -15.8 Legend pI = isoionic point pH. MW = Molecular weight 1~5~3~Z
It may be seen that low isoionic point gelatins of moderately high molecular weight are particularly effective in preventing moisture loss from skin. Low isoionic point proteins of low molecular weight, less than about 10,000, are only marginally effective in preventing water loss from ~kin. High isoionic pQint gelatin, even of high molecular weight, is on the other hand, completely ineffective in preventing moisture loss in a soap bar application.

EXAMPLES IX - XI
Soap bar formulations were prepared as detailed below and the bars were compared for mildness by transepi-d r~al w~eec los~ studies.

,, ,` .

t513~2 ..
., H l O r~ O N 1~10 ¦ O
" .1 o 1~ o ~ o _1 .
.~ . .
IIJ H¦ ~ O CO ~ N O O . .
~' ~3 ~ 1~ O O l ., .
~ U~
~1 ~ O O
, ' . ~ O l .
, . . _ ~ .
H ¦ 1~ a~ o ~1 ~ o o X I~ ~ o ~ ~ ~r ~
~ l ~ ' ' Q~'' ~ Xl ~ O ~D~i ~ N Cl~ ~ ~i ~ ' : ' ' Xl ~ O ~
~ ~ ~ _i ~o ~1 l ~' Ul ~
~
rl ~ H O 3 c ~ .. -- E~
O ~ O
~1 o I
~ U3 ~ ~ ,~
~ ~ ~ ~ ~ ~a U~ 3 ~ o O O ~ ~J ~ H h U~
Ql _l O ~ a Q.
~ ~ rl ~ ~ ~ U~
U ~IS 0 ~ 1 0 --I O h O
t~ E~ u) ~-1 . .
.

.

' ' '~ -- ~051~Z
It can be seen that the effect of free fatty acid is to produce a synergistic increase in the mildness of soap bars containing low isoionic point derived proteins. The in-use pH values of Example IX and Standard V are 9.5; the in-use p~ values of Example XI and Standard VII are 10Ø
This exemplifies the pH dependence for mildness benefit of the compositions of the invention.
' '' ' , ' .

; EXAMPLES XII - XVII
The following milled soap bar formulations were prepared and their mildness characteristics were compared in consumer mildness studies.
.: ' .
.~
.
, . ..

s =.= .~ . In U~ ~O ~ ~
Xl O O 1~ I I
.
o ~ . ..
1 H I I~ O ~ In o . ~q . l . H ¦ e~ ~ ~ ~ . I I
:,1 ~ ~D 1~ ~ ~ O
,. '' ____ . _ . ~ .

. . H I . . ~ ~ ~ O : ~
xl o o 1~ _1 .. ~
H H 11~ . ~0N '1 0 X I c~ 1` N
!~ ~1 ~ o. 1~ . ~ .
'~' W :~l ~ O ~
X I r~
H¦ ~D ~ '.0 ~ N O
X I ~ u~ I~ ~cn ~ o H ~ ~ U~
Xl I~ ~
_ ~__ ,' ~o ,.-~' ,~ ~ ~ ~q . ~, U"~ U~ H ~ ~
~0 o O ~ E~

3 ~ rl O

~,1 _ O~55 ~.~ C ~

In ~1 :

., . .. . - ~.

~ `
10513~Z
.
The consumer mildness gradings are given on a scale in which Standards ~III and IX are given the standard values O and -100, as indicated in the table. The in vivo consumer mildness studies are seen to verify the results of the trans-epidermal water loss studies, namely that mildness benefitsincrease synergistically with free fatty acid content and with higher coconut/tallow ratios.
Essentially similar results are obtained when the pro-teinaceous material is the alkali, acid or enzyme hydrolysis product, or thermal degradation product, or ammoniolysis, aminolysis, or a reductive cleavage product obtained from whey, casein, wheat, corn or cottonseed proteins.

EXAMPLE XVIII
~ granular soap composition which is mild to skin has the following composition:

Components Parts by Wt.
Tallow soap 38.5 Palm kernel soap 38.5 Free coconut fatty acid 7.6 Miscellaneous 2.2 Moisture content 9.2 Degraded whey protein: 4.0 pI 5.0 MW 4,000 105~31Z
- EXAMPLE XIX
A granular soap composition which is mild to skin has the following composition:
.
-. Components Parts by Wt.
Tallow soap 42.7 ,, Coconut soap 10.7 Sodium silicate 7.1 Coconut monoethanolamide 2.3 Sodium tripolyphosphate 5.0 Moisture . 10.5 Sodium perborate 14.8 Miscellaneous 3.0 Alkali degraded soyprotein 4.0 pl 4.5 . MW 5000 EXAMPLE XX
A moisturizing hand cream in gel form has the following composition:

. ,,~

- ~
.
: . :

.
Components Parts by Wt.
Gelatin: pI 5.5;
MW 120,000 4.0 Stearic acid 12.0 Mineral oil 2.0 Cetyl alcohol 0.6 Glycerol 6.0 '' Triethanolamine 1.5 Borax . 0.9 Glyceryl monostearate 2.0 Methyl p-hydroxybenzoate 0.25 Acid degraded soyprotein:
pI 5.5 MW 5,500 . 4.0 Water to 100 , .
, EXAMPLE XXI
A cleaning and conditioning hand cream having mild abrasive propert1es h~s the following composition:

..

, .

. ~

10513~Z
.: .
Components Parts by wt.
Mineral oil 3 . Glycerol . 4 Stearic acid 12 S Tr~ethanolamine 1.5 ; Glyceryl monostearate . 2.0 Methyl p-hydroxybenzoate 0.25 Gelatin: pI 5.2 MW 80,000 15.0 ; 10 50% dispersion of Promine F
., . in caustic soda 7.0 ~-ter tO 100 ' - : -

Claims (30)

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

1. A solid cosmetic or detergent composition comprising a surface active agent selected from the group consisting of water-soluble soaps, non-soap anionic detergents, nonionic detergents, ampholytic detergents, zwitterionic detergents and mixtures thereof; and from 0.1% to 10% by weight of a material selected from the group consisting of defatted soyprotein, derived soyprotein and mixtures thereof having a molecular weight greater than 5000 and an isoionic point in the range from pH4 to pH7.

2. A composition according to claim 1 in which the derived protein is selected from the group consisting of hydrolytic, ammoniolytic, aminolytic and reductive degradation products of said defatted soyprotein.

3. A composition according to claim 2 in which the derived protein is a base-catalyzed hydrolytic degradation product of said defatted soy protein.

4. A composition according to claim 1 in which said derived protein has an isoionic point less than pH 6.

5. A composition according to claim 4 in which said derived protein has an isoionic point less than pH 5.

6. A composition according to claim 1 in which said derived protein contains an average of at least five free carboxylate groups per molecule.

7. A composition according to claim 1 in which the defatted soyprotein comprises at least 90% by weight of protein on a dry weight basis.

8. A composition according to claim 7 in which the defatted soyprotein comprises at least 95% by weight of protein on a dry weight basis.

9. A composition according to claim 1 wherein the surface active agent is selected from the group consisting of an anionic soap, a non-soap anionic synthetic detergent and nonionic synthetic detergent.

10. A composition according to claim 9 wherein the surface active agent is a soap.

11. A composition according to claim 9 wherein the surface active agent is a non-soap anionic synthetic detergent.

12. A composition according to claim 1 additionally comprising a water-insoluble hydrophobic oily material.

13. A soap composition in solid form comprising:
(a) from about 5 to about 90% by weight of soap having a C12 content of from about 5 to about 45% by weight of a C18 content from about 15 to about 70% by weight of the soap; and (b) from about 0.1% to about 10% by weight of a derived protein having an isoionic point (pI) in the range from pH 4 to pH 7, and containing an average of at least five free carboxylate groups per molecule;
said protein having a molecular weight greater than 5000;
the soap composition having an in-use pH greater than 9 and less than (pI + 5.5).

14. A composition according to claim 13 in which the derived protein is selected from the group consisting of partially degraded animal and vegetable protein.

15. A composition according to claim 14 in which the derived protein is selected from the group consisting of partially degraded collagen, keratin, casein, whey, wheat, soybean or cottonseed protein and mixtures thereof.

16. A composition according to claim 13 in which the derived protein is a base-hydrolyzed protein.

17. A composition according to claim 13 in which the derived protein is essentially free of cysteine units.

18. A composition according to claim 13 in which the derived protein has an isoelectric point greater than 5.

19. A composition according to claim 18 in which the derived protein has a weight averaged molecular weight greater than 10,000.

20. A composition according to claim 19 in which the derived protein is a Type B gelatin having a weight averaged molecular weight in the range from 15,000 to 200,000.

21. A composition according to claim 20 in which the gelatin has a weight average molecular weight in the range from 20,000 to 120,000.

22. A composition according to claim 21 in which the gelatin has a weight averaged molecular weight in the range from 25,000 to 80,000.

23. A composition according to claim 13 in which the derived protein is selected from the group consisting of partially degraded whey, wheat, and soybean cottonseed protein.

24. A composition according to claim 1 or claim 13 having an in-use pH greater than 9.5 and less than (pI + 5).

25. A composition according to claim 13 in which the soap comprises a mixture of tallow and coconut soaps in a weight ratio in the range from 90:10 to 10:90.

26. A composition according to claim 13 in which the soap has a C12 content of from about 8 to about 40% by weight of the soap.

27. A composition according to claim 26 in which the composition has a C12 content of from about 10 to about 30% by weight of the soap.

28. A composition according to claim 13 having a moisture content of from about 5 to about 15% by weight of the composition.

29. A composition according to claim 28 having a moisture content of from about 8 to about 12% by weight of the composition.

30. A milled soap bar composition comprising:
(a) from about 70 to about 90% by weight of soap having a C12 content of from about 5 to about 45% by weight and a C18 content of from about 15 to about 70% by weight of the soap; and (b) from about 0.1% to about 10% by weight of degraded collagen having an isoionic point (pI) in the range from pH/4 to 7, and a molecular weight of at least 10,000;
wherein the composition has an in-use pH of at least 9 and less than (pI + 5.5).