DE2544778A1 - LIQUID DETERGENT, CLEANING AGENTS, COSMETIC AGENTS AND PROCESS FOR THEIR MANUFACTURING - Google Patents

Description

The Procter & Gamble Company
Cincinnati, Ohio, V.St.A.

Liquid washing, cleaning or cosmetic products
Means and process for its production

The invention relates to liquid agents that protect the keratinous material, in particular skin, from the harmful Effects of detergents or other harsh materials, such as solvents, and from unfavorable protect climatic conditions. The agents according to the invention therefore serve to treat the keratin-containing To keep material, especially the skin and also the hair, in good condition.

The deleterious effects of surfactant-containing compositions on keratin are known. It is believed that these effects are caused by the surfactant penetration into the keratin surface and this for the
"Leaching" of oils and moisture-retaining ingredients leads to a good condition of the

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Keratins are essential. This penetration of surface active Agent and "leaching" of the essential oils also affects the ability of the keratin, in particular in the case of the skin, to retain water in the tissue, and this in turn leads to poor State of the keratinous material.

Many attempts have been made to maintain or improve the condition of the skin and hair. Casein in the form of milk was used as a beautifying agent from an early age and has recently been recommended for use in toilet soaps. GB-PS 1 16O 485 describes the addition of soy peptone to liquid cleaning agents and lotions. Numerous other proteins and protein breakdown products have also been recommended for use either as protein soaps or in combination with conventional soap ingredients. For example, GB-PS 8 582 describes the addition of egg albumin, which has been treated with formalin, to toilet and shaving soaps. GB-PS 159 083 describes the production of a toilet soap with a solids content of 5 to 20% obtained by evaporating the waste whey from cheese factories. FR-PS 3 ^ 2 691 proposes to incorporate wheat gliadin and glutenin in soaps in order to bind free alkali without having to accept the disadvantages of over-fat soaps (tendency to become rancid).

Many other polypeptides or modified low molecular weight polypeptides derived from natural Proteins are derived, are commercially available and are for use in cosmetic preparations as well Shampoo recommended. Examples of such

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Preparations are Hydro Pro 220, Hydro Pro 330, and Maypon ¹ JC sold by Stepan Chemical Company; and Wilson X25Q, Wilson X100 and Wilson Aqua Pro sold by Wilson Chemical Company. However, none of these compositions have been found to be particularly effective in protecting keratin from exposure to harsh detergents, and this is especially true when the proteins are incorporated into the detergent mixture itself. The softening effect of these compositions can often be improved by the addition of greasy or oily substances, but if they are used, for example, in liquid detergents in an effective amount, this usually leads to a loss of foaming power or to aesthetic changes, which are generally considered by the consumer be viewed undesirably.

Another difficulty associated with attempting to make liquid detergent mixtures which contain proteins that have been isolated in particular from vegetable glycoprotein, consists in a to produce a homogeneous and preferably clear formulation that does not contain any undesirable discoloration. Such preparations are of course preferred by consumers from the aesthetic point of view, and this turns the practical application of known protein techniques to consumer-accepted ones liquid detergents and cosmetic preparations are considerably restricted.

The present invention therefore provides proteinaceous Preparations in liquid form, which are particularly effective for protecting keratinous material, in particular Skin, from the harmful effects of detergents and other sharp materials and from unfavorable climatic

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-Iltian conditions are taking these preparations even are effective when applied to keratin in lathering detergent solutions or dispersions and they are not a waste of the detergent solutions or dispersions containing them the foaming power, the soaping effect or the cleaning effect and lead to homogeneous, clear liquid preparations can be formulated.

The present invention therefore relates to a liquid washing, cleaning or cosmetic agent which contains a surface-active agent and a derived soy protein from the group of soy metaproteins or soy proteoses. The derived soy protein is preferably at least partially insoluble in water at its pH value at the isoionic point (i.e. it contains at least some metaprotein), preferably contains practically no heavy metal ions (e.g. Ca ^; ), acid derivatives of carbohydrates (such as phytates) or water-soluble or dispersible higher oligo- or polysaccharides such as stachyose and higher polysaccharides. In particular, the agents according to the invention should contain practically no water-insoluble polysaccharides such as hemicelluloses.

The invention further relates to a method for producing the liquid washing, cleaning or cosmetic agents, in which an isolated soy protein preparation is mixed with acid or alkali in a weight ratio of protein preparation to anhydrous acid or anhydrous alkali of 4: 1 to 25: 1 and the mixture is heated at 40 to 110 ⁰ C, until the mixture is at least 20 and preferably at least 30 wt -.% soy

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metaprotein along with water soluble derived Contains soy protein, and the soy metaprotein and / or water soluble derived soy protein at a pH in the range of 5 * 5 to 8.5 with the remaining ingredients the detergent, cleaning agent or cosmetic agent mixes.

The term "soy protein" as understood here means a protein extracted from soybeans; The expression "derived soy protein ^11" is understood to mean a protein whose primary chemical structure has been degraded by splitting peptide bonds or sulfur-sulfur bonds; the expression "soy metaprotein" means a derived soy protein which is insoluble in pure water at the ionic point of the derived protein and by the term "soy proteose" is meant a derived protein which is soluble in pure water but which is insoluble in water which is semi-saturated with ammonium sulphate.

Soybeans contain about 20 % oil and about 40 % protein, with the main amount of this protein being contained in storage places, which are called aleurone grains and represent protein bodies with a diameter of 2 to 20 μια , each surrounded by a membrane, which is assumed becomes that it consists of phospholipids. Soybeans are usually made into a variety of. Processed products in which the orderly structure of the intact seeds is destroyed. The simplest processing consists of steaming the beans and removing the hulls, which are more than 85 % carbohydrates. However, if the soybeans are subjected to excessive heat treatment, the protein will be denatured and this will result in the other

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subsequently obtained protein extracts are water-insoluble. Undenatured soy proteins, which are preferred for use in the present invention, can therefore be made by avoiding excessive heat treatment in the initial processing stages. By grinding the material freed from the hulls, full-fat flours are obtained, the coarsest form of soy protein-containing material. Defatted flours that have a protein content of 50 % or more are obtained by extracting the soybean oil with hexane, while protein concentrates that have a protein content of 70 % or more are obtained by extraction with solvents such as aqueous alcohols or dilute acids . The purest protein supplements are the isolated protein supplements (protein isolates), from which most of the oil and carbohydrates have been separated, leaving less than 10 % non-protein material (ash and other minor components). Such isolated protein preparations are generally made by extracting undenatured flakes or undenatured flour with dilute alkali at a pH of 8 to 9, after which the clarified extract is optionally acidified to a pH of 4.5 to the Precipitate soy protein globulins. The derived soy protein preparation suitable for use in the surfactant-containing liquid compositions of the present invention has preferably been subjected to all of the foregoing degreasing and cleaning processes so that it is generally at least 70 %, preferably at least 90 %, and more preferably Contains at least 95 % actual protein material. In a particularly preferred embodiment, the derived soy protein preparation contains practically no

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Carbohydrate, as this has been shown to reduce the clarity and color of the liquid compositions according to the invention in adversely affected.

The derived soy protein supplements that are for use in liquid laundry detergent, cleaning or cosmetic Agents of the invention are suitable are generally partially degraded products of soybean extracts, E.g. products that are partially degraded by thermal degradation, hydrolysis, reduction, ammonolysis or Aminolysis were obtained. Hydrolytic degradation has been used in the food industry for a long time, to increase the water solubility of the soy protein and thus improve its taste and aroma. There are numerous methods of hydrolyzing protein, and these may vary depending on the hydrolyzing agent used can be divided into three classes, namely acid, alkaline and enzymatic processes Hydrolysis. The derived protein preparation can also be caused by thermal degradation, e.g. by the action of superheated steam. Ammonolytic degradation can be caused by the action of relatively concentrated Ammonia solutions (in which case ammonolysis is accompanied to some extent by hydrolysis) or be brought about by the action of ammonia gas, while an aminolytic degradation by treatment with Mono- or polyamino compounds is achieved.

The preferred soy derived proteins for use in the compositions of the invention are at pH of the isoionic point of the protein is at least partially insoluble in water and can be practically at this pH value be insoluble in water. The proteins should of course be at a pH that is different from the pH of the isoionic

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Point away, e.g. at the pH value at which the agent is dissolved in water during normal use or dispersed, be practically water soluble.

The protein degradation is preferably carried out with aqueous alkali, e.g. solutions of sodium hydroxide, potassium hydroxide or slaked lime or with diluted ammonia, The method consists in making a slurry or solution of, for example, an isolated protein preparation for a period of generally 1 to 4 hours. a temperature of preferably 50 to 95 ° C with treated with aqueous alkali, the amount of alkali used usually between 5 and 15 wt .- #, based on the soy protein. The amount of alkali used, the temperature and the duration of the treatment are determined by the desired degree of hydrolysis. As stated above, the hydrolysis should preferably terminated before the protein is hydrolyzed to such an extent that it is at its isoionic pH Point is soluble. After the hydrolysis or, if appropriate, at the same time during the hydrolysis the protein-containing liquid can be treated with an oxidizing agent, preferably with an agent that in Solution is an easily accessible source of peroxide ions, such as 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 adding the oxidizing agent is that this Oxidizing agents with organic and inorganic sulphhydryl compounds should react, which are constantly formed in the alkaline hydrolysis and the aqueous Turn the solution into a dark, foul-smelling liquid. After the oxidation stage, the protein can be iso-

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be lated, e.g. by freeze-drying, precipitation with Acetone or precipitation at the isoionic point, or the protein solution can be used directly for the preparation of the invention Means can be used as described below.

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Enzymatically hydrolyzed soy proteins can also be incorporated into the agents according to the invention. A protease is generally used as the enzyme for this hydrolysis, but it is also possible to use certain preparations which contain both proteases and amylases as enzymes. These enzyme preparations are obtained from various animal, vegetable, bacterial and fungal sources. For example, the following special enzyme preparations may be mentioned: papain, bromelin, ficin, chymopapain, trypsin, chymotrypsin, pancreatin, pepsin, erepsin, the fungal enzymes from Aspergillus oryzae and Aspergillus niger and the bacterial enzymes from Bazillus genus, for example B. Mycoides, B. Amyloliquaciens B. Cereus, B. Macerans, B. Megaterium, B. Sphaericus, B. Circulans and especially B. Subtilis. The enzymatic hydrolysis is typically at temperatures above 25 ° C and generally at temperatures above ¹ IO ⁰ C, for example at 50 ° -7O ° C, at a pH that favors the greatest possible effectiveness of the enzyme, and for a Duration, which is generally in the range of 5 to 20 hours, carried out. The conditions used also depend on the nature of the protein treatment prior to enzymatic hydrolysis; for example, when the protein was previously subjected to a mild acid or alkaline hydrolysis, as a mild pepsin treatment at 25- ¹ JO can satisfy ⁰ C.

The acid hydrolysis can be carried out with aqueous hydrochloric acid or sulfuric acid, the aqueous Liquid, for example, under reflux with 10-40 g aqueous acid for a period of 5 to 20 hours is heated. However, the mixture can also be used at overpressure with more dilute acid, for example 5 wt. SS, for one be heated for a short time.

The ammonolysis, optionally from a hydrolysis

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is accompanied, can be achieved by heating the soy protein, for example an isolated protein preparation with 10 wt .- / iiger (or more concentrated) ammonia solution at a temperature of 50-100 ⁰ C for a period of 10 to 30 hours, excess ammonia becomes easy removed by evaporation, and then the ammonolyzed protein can be isolated, for example by precipitating it with acetone, or it can be used directly for the preparation of the compositions according to the invention.

Soy protein aminolysates are made by heating the soy protein with a mono-, di- or polyamine or with Derivatives of these amines, which are usually used in at least an equal amount by weight, under reduced Pressure or at normal pressure to temperatures of 50-200 C manufactured. Preferred amines include the alkylamines and alkanolamines having 2-10 carbon atoms and the diamines and polyamines having 2-12 carbon atoms.

To the further reduction process for soy proteins is one of thermal decomposition, in which, for example, a protein slurry is heated rapidly and almost instantaneously under pressure with steam to a temperature above ⁰ C 1OM, being mechanically stirred. An enzymatic hydrolysis can then optionally be carried out. Another breakdown is the reductive cleavage of intramolecular disulphide crosslinks with, for example, metal hydrides (such as sodium borohydride), sulphydry compounds (such as 0.01 m mercaptoethanol), sulphites or thioglycolates.

The soy derived proteins are generally present in an amount of from about 1 to about 10%, preferably from about 2 to about 6% based on the weight of the composition _9, present in the inventive composition.

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Soy derived proteins suitable for use in the liquid compositions of the present invention preferably have certain molecular weights and isoionic points. The average Molecular weight (determined using the customary ultracentrifuge method) is preferably at least around 15OO, better at at least 3OOO and best at at least 5OOO. The molecular weight of the desired proteins is also reflected in the viscosity properties of the proteins in aqueous solution. the Viscosity of a 10% strength by weight solution in water at a pH value of 9.5 and a temperature of 58 C. preferably at least 0.8 cp and in particular should be in the range from 1.5 to 20 cp.

The pH values at the isoionic point of the derived proteins, i.e. the pH value at which the same in solution Concentrations of protein anions and cations present generally range from about 4.5 to about

The optimal selection of the protein for each particular liquid washing, cleaning or cosmetic agent depends, however, to a certain extent on the pH value of the agent in use, ie on the pH value of the carrier when applied to keratin. This pH value during use can, depending on the type of application, be the pH value of the agent itself or the pH value of an aqueous solution or dispersion of the agent at the use concentration, which in turn is between 0.01 and 10 % or even above this Area can lie. For example, in the case of an agent with an approximately neutral pH value in use, for example a liquid dishwashing detergent or a cosmetic lotion, the preferred derived proteins have an isoionic point below pH - 1, preferably below pH - 2. whose pH value in use is in the range from 8 to 10, for example a liquid detergent and cleaning agent containing builders, can have relatively low pH values at the isoionic point

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have, for example, pH values below half pH - 3.

The pH value of the agents according to the invention in use can of course be very different depending on the purpose and manner of application of the agent. Agents intended as hand and face lotions, etc., are generally applied directly to the skin so that the pH value in use corresponds to the pH value of the agent itself. This can be any pH in the general range of 5 to 9. Detergents and cleaning agents, such as liquid dishwashing detergents and bath additives as well as liquid "heavy duty detergents, are usually used in a large excess of water, so that the pH value in use is the pH value of an aqueous solution of the agent, which is generally a has% of the composition an unbuilt detergents have, for example, in use, a pH in the alkaline range up to a pH value of about 11. on the other hand, shampoos are generally in the presence of a small amount of water - concentration of 0.01 to 2 wt.. applied so that the pH in use is close to the pH of the agent, ie generally around 5 to 9. In practice, the pH in use is often independent or almost independent of the concentration of the agent, namely in those cases where the agent is diluted in use, the pH in use being a standard concentration of 1 % .

If the pH is known in use, the most suitable derived soy protein for the particular can be found Purpose to be determined. While soy globulins, which have been isolated by precipitation at the isoionic point, have an isoionic point of about pH 4.9 to 550, Soy proteins hydrolyzed by bases have a slightly lower isoionic point, for example around pH A, 5, while proteins hydrolyzed with acids (around pH 5.5) and proteins hydrolyzed with enzymes (around pH 6) are higher

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have isoionic points. Ammonolyzed soy proteins have isoionic points in the range from about pH 5 »5 to 6.5 »while aminoIysed proteins make a great deal have a higher isoionic point at pH values up to 9 or even higher.

PH values at the isoionic point can be determined in the following way:

An acidic ion exchange resin (Amberlit IR 120) and a basic ion exchange resin (Amberlit IR 40OJ are used washed with several times the volume of water, filtered and mixed in a ratio of 0.4: 1. Then a 3 wt Protein solution (20 ml) in 20% aqueous urine solution produced with minimal heating and cooled to a constant temperature. The resin mixture (8.4 g) is added, the solution is stirred for 5 minutes, the mixture is filtered and the pH of the filtrate is pH am isoionic point of protein.

Surfactants that can be used in the compositions of the present invention can are selected from water-soluble soaps and synthetic anionic, nonionic, cationic, zwitterionic and amphoteric detergents, which are explained in more detail below. Preferably they are Surface-active substances, foam-forming detergents or emulsifiers, in particular anionic soaps and synthetic detergents.

The agents of the present invention can, of course, include combinations of the soy proteins described above with other proteins or modified proteins known to be skin-friendly, for example the modified proteins which are described in BE-PS 817 791 contain.

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2B44778

A. Anionic Soaps and Non-Soap Synthetic Detergents This class of detergents includes common alkali soaps such as the sodium, potassium, ammonium, alkylammonium and alkylolammonium salts of higher fatty acids having 8 to 2 * 1 carbon atoms and preferably 10 to 20 carbon atoms. Suitable fatty acids can be obtained from natural sources, for example from vegetable or animal esters (for example palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, fat, lard and mixtures thereof). The fatty acids can also be produced synthetically (for example by oxidation of petroleum or by hydrogenation of carbon monoxide according to the Fischer Tropsch process). Resin acids, such as rosin, and resin acids from tall oil, are also suitable. Naphthenic acids are also suitable. Sodium and potassium soaps can be made by direct saponification of the fats and oils or by neutralizing the free fatty acids obtained in a separate manufacturing process. The sodium, potassium and triethanolammonium salts of the fatty acid mixtures obtained from coconut oil and tallow, for example sodium or potassium tallow and coconut soaps, are particularly useful.

This class of detergents also includes water-soluble salts, in particular the alkali metal salts of organic sulfuric acid reaction products that have an alkyl group of 8 to 22 carbon atoms in their molecule and contain a sulphonic acid or sulfuric acid ester group. (The term "alkyl group" also includes the Alkyl part of higher acyl radicals.) Examples of this group of synthetic detergents which are part of the Forming preferred agents of the present invention are the alkali metal alkyl sulphates (for example sodium or Potassium alkyl sulphates), especially those obtained by sulphating the higher alcohols with 8 to 18 carbon atoms were obtained, in turn, by reduction

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the glycerides made from tallow or coconut oil; the alkali metal oiefinsulphonate with 8 to 24 carbon atoms described, for example, in U.S. Patent 3,332,880; and the alkali metal aikylglyeeryläthersulphonate, especially those ethers of the higher alcohols derived from tallow and coconut oil. Other anionic detergents include the alkali metal alkylbenzenesulphonates having 9 to 15 carbon atoms in the alkyl group including the species described in U.S. Patents 2,220,099 and 2,477,383, wherein the alkyl group can be straight-chain or branched-chain; Sodium Coconut Oil Fatty Acid Monoglyceride Sulphate and sulphonates; Salts of alkylphenol ethylene oxide ether sulphates with 1 to 12 ethylene oxide units per Molecule whose alkyl groups have 8 to 18 carbon atoms contain; the reaction product of fatty acids that are esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acid consists of oleic acid or is derived from coconut oil; Sodium or potassium salts of fatty acid amides of a methyl tauride, in which the fatty acids are derived, for example, from coconut oil; Sodium or potassium ß-acetoxy- or -ß-acetamido-alkanesulfonate with 8 to 22 carbon atoms in the alk portion; as well as other known detergents of this type. One A number of these useful detergents are described in U.S. Patents 2,286,921, 2,486,922 and 2,396,278.

Other synthetic anionic detergents which are suitable for the compositions according to the invention are the alkyl ether sulfates. These compounds have the formula R ² O (C ₀ H ₁₁ O) SO, M, where R is an alkyl or alkenyl group with about 8 to 8 carbon atoms, χ is an integer from 1 to and M is a salt-forming cation from the group of Represents alkali metal, ammonium and dimethyl, trimethyl-triethyl, dimethanol, diethanol, trimethanol and triethanolammonium cations.

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The alkyl ether sulphates are condensation products of ethylene oxide and monohydric alcohols with about 8 to 2λ carbon atoms. Preferably R ^ contains 14 to 18 carbon atoms. The alcohols can be derived from fats, for example coconut oil or tallow, or can be produced synthetically. Lauryl alcohol and straight chain alcohols derived from tallow are preferred for the purposes of the invention. Such alcohols are reacted with 1 to 12, in particular 6, moles of ethylene oxide, and the resulting mixture of molecules containing, for example, an average of 6 moles of ethylene oxide per mole of alcohol, is sulphated and neutralized.

Specific examples of alkyl ether sulphates useful for the purposes of the present invention are Sodium coconut alkyl ethylene glycol ether sulphate; Lithium tallow alkyl-t riethylene glycol ether sulphate; and sodium tallow alkyl hexaoxyethylene sulphate. Particularly preferred for the purposes of the present invention because of their excellent properties The alkali metal coconut and tallow alkyl oxyethylene ether sulphates are easy to clean and easy to obtain with an average of 1 to 10 oxyethylene units per molecule. The alkyl ether sulphates are in U.S. Patent 3,332,876.

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OWGlNAL INSPECTED

B. Nonionic Synthetic Detergents

Nonionic synthetic detergents can be broadly defined as compounds produced by condensation
of alkylene oxide groups (hydrophilic nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic. The length of the
hydrophilic or polyoxyalkylene moiety condensed with any particular hydrophobic group can easily be adjusted to be a water-soluble compound
obtain the desired degree of equilibrium between
having hydrophilic and hydrophobic elements.

For example, a well-known one can be found on the
Market class of nonionic synthetic
Prepare detergents by using ethylene oxide
condensed a hydrophobic base, which was produced by the condensation of propylene oxide with propylene glycol. The hydrophobic part of the molecule, which of course is insoluble in water, has a molecular weight of 1,500 to 1,800. The addition of polyoxyethylene residues to this hydrophobic part increases the water solubility of the molecule as a whole and the liquid character of the product becomes
maintained to the point where the polyoxyethylene content is about 50 % of the total weight of the condensation product
amounts to.

Other suitable nonionic synthetic detergents
are the following:

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1. The polyethylene oxide condensates of alkylphenol, e.g. the condensation products of alkylphenols with a Alkyl group with 6 to 12 carbon atoms either in straight-chain or branched-chain configuration with ethylene oxide, the ethylene oxide being present in amounts of 5 to 25 moles of ethylene oxide per mole of alkylphenol. The alkyl substituent in such compounds, for example, may be derived from polymerized propylene, diisobutylene, octene or nonene.

2. Those resulting from the condensation of ethylene oxide with a product resulting from the reaction of propylene oxide and ethylenediamine is formed. For example, compounds with 40 to 80 wt. Polyoxyethylene and a molecular weight from 5,000 to 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base, which consists of the reactant product of ethylenediamine and excess propylene oxide. These bases molecular weights on the order of 2,500 to 3,000 are satisfactory.

3. The condensation product of aliphatic alcohols with

8 to 24 carbon atoms, either straight-chain or branched-chain Configuration, with ethylene oxide, e.g. a coconut alcohol-ethylene oxide condensate with 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having 10 to 14 carbon atoms.

4. Nonylphenol is one of the non-ionic detergents either about 10 or about 30 moles of ethylene oxide per mole Phenol condenses and the condensation products of coconut alcohol averaging either about 5.5 or about 15 moles of ethylene oxide per mole of alcohol and the condensation

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sation product of about 15 moles of ethylene oxide with a Moles of tridecanol.

Other examples include dodecylphenol condensed with 12 moles of ethylene 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 each Moles of mercaptan; Bis (N-2-hydroxyethyl) rlauramide; Nonylphenol, condensed with 20 moles of ethylene oxide per mole of nonylphenol; Myristyl alcohol condensed with 10 moles of ethylene oxide each Moles 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 of the formula R-R R% -0 (amine oxide detergent), wherein R ^ is an alkyl group having 10 to 28 carbon atoms, with

0 to 2 hydroxyl groups and with 0 to 5 ether bonds, where at least part of R · ^ is an alkyl group with 10 to 18 carbon atoms and 0 ether bonds, and R and V? each have an alkyl radical or a hydroxyalkyl radical

1 to 3 carbon atoms mean. Specific examples of amine oxide detergents include:

Dimethyldodecylamine oxide, dimethyltetradecylamine oxide, Ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethyls tearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, Diethyl tetradecyl amine oxide, dipropyl dodecyl amine oxide , Bis (2-hydroxyäthy1) -dodecylamine oxide, Bis- (2-hydroxyethyl) -3-dodecoxy-l-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.

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6. A detergent of the formula R ^ -SR, where R- * and R are as defined above. Specific examples of sulfoxide detergents include dodecylmethyl sulfoxide, tetradecylmethyl sulfoxide, 3-hydroxytridecylmethyl sulfoxide, 3-methoxytridecylmethyl sulfoxide, 3-hydroxy-4-dodecoxybutylmethyl sulfoxide, octadecyl-2-hydroxyethyl sulfoxide and dodecyl-2-hydroxyethyl sulfoxide. ^%

7, The ammonia or the monoethanol and diethanol amides of fatty acids with an acyl radical of 8 to 18 carbon atoms. These acyl residues are usually derived from natural Occurring glycerides, e.g. coconut oil, palm oil, soybean oil and tallow oil, however, can also be synthetic can be obtained, e.g. by oxidation of petroleum or by hydrogenation of carbon monoxide according to the Fischer-Tropsch process.

C. Ampholytic synthetic detergents

Ampholytic synthetic detergents can broadly be described as derivatives of aliphatic amines or aliphatic Describe derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical is straight or can be branched and wherein one of the aliphatic Substituents containing 8 to 18 carbon atoms and at least one an anionic water-solubilizing group, for example Carboxy, sulfo or sulfate group contains. Examples for compounds that fall under this definition are sodium 3- (dodecylamino) propionate, sodium 3- (dodecylamino) propane-1-sulfonate, Sodium 2- (dodecylamino) ethyl sulfate, Sodium 2- (dimethylamine) octadecanoate, disodium 3- (N-

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carboxymethyldodecylamino) propane-1-sulfonate, disodium octadecyl-iminodiacetate, sodium-1-carboxymethyl-2-undecylimidazole and sodium-N _s N-bis- (2-hydroxyethyl) -2-sulfate-3-dodecoxypropylamine.

D. Zwitterionic Synthetic Detergents

Zwitterionic synthetic detergents can broadly be described as derivatives of aliphatic quaternary ammonium and describe phosphonium or tertiary sulfonium compounds in which the cationic atom is part of the heterocyclic Ringes and in which the aliphatic radical can be straight or branched chain and in which one of the aliphatic substituents 3 to 18 carbon atoms and at least one of the aliphatic substituents contains an anionic water-solubilizing group, such as Carboxy, sulfo or sulfate group. Examples of connections, which fall under this definition are 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypropane-isulphonate, 3 ~ (N, N-dimethyl-N-hexadecylammonio) -propane-1-sulfonate, 2- (N, N-dimethyl-N-dodecylammonio) acetate, 3- (N, N-dimethyl-N-dodecylammonio) propionate, 2- (N, N-dimethyl-N-octadecy lammonio) -läthylsulfat, 2- (S-methyl-S-tert.hexadecyl-sulfonio) ethane-1-sulfonat, 3- (S-methyl-S-dodecylsulfonio) propionate, 4- (S-methyl-S-tetradecylsulfonio) butyrate, 1- (2-Hydroxyethyl) -2-undecylimidazplium-1-acetate, 2- (trimethylammonio) octadecanoate and 3- (N, N-bis (2-hydroxyethyl) -N-octadecylammonio) -2-hydroxy-propane-1-sulfonate and 3- (N, N-dimethyl-N-1-methylalkylammonio) -2-hydroxypropane-isulphonate, the alkyl radical having an average of 13.5 to 14.5 carbon atoms. Some of these detergents are used in the U.S. Patents 2,129,264, 2,178,353, 2,77,786, 2,813,898, and 2,828,332.

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E. Cationic detergents

The cationic detergents include those of the formula R ⁶ -Ä (R ⁷ ), An ~, in which R ^{6 is} an alkyl chain with 8 to 20 carbon atoms, each R 'is an alkyl or alkanoyl radical with 1 to 4 carbon atoms or one Benzyl radical means, where normally not

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there is more than 1 benzyl radical and two R 'radicals can be linked by a carbon-carbon ether or imino bond to form a ring structure, or one R ⁷ radical is an alkyl chain with 8 to 20 carbon atoms and An is a halogen atom , Sulfate residue, nitrate residue or a pseudohalogen group. Specific examples are coconut alkyltrimethylamine chloride, dodecyldimethylbenzyl bromide, dodecylmethylmorpholinochloride and ditallow dimethylammonium chloride.

The soap-like and soap-free anionic, nonionic and zwitterionic surfactants mentioned above Detergents can be used as the sole surfactant, or the various examples can are mixed together in the practice of the invention. Anionic and nonionic are particularly preferred surfactants. The amount of surfactants incorporated in the preparations depends on the intended one Intended use of the respective formulation. So it depends on the weight of the preparation as a whole, if it is directly is used on the skin, e.g. as a cosmetic lotion, or at the concentration at which it is used as a solution are soU, for example as dishwashing water or Bath water. In most cases, a content of 0.01 to 90 wt .- ^, based on the preparation, is suitable. Detergent

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Preparations for cleaning purposes in general contain 5 to 50 wt .- ^ of the surfactant, while cosmetic compositions is generally between 0.1 and 10 wt -.% Of the contained surfactant.

The liquid agents according to the invention generally contain a carrier based on water and / or a water-soluble solvent. Suitable solvents are Cp_g mono- and dialcohols, for example ethanol, butanol, methylpropanol-1 and -2, amylene or pentanol, butanediol, toluene, benzyl carbinol, ethylene glycol monobutyl ether, propylene glycol propyl ether and diethylene glycol dimethyl ether. They are generally present in amounts up to 15% by weight of the composition. Additional ingredients of liquid detergents include suds improvers such as higher alkyl amine oxides and alkylol amides of C 'QC ₁ ^, - carboxylic acids, thickeners, preservatives, opacifiers, perfumes, dyes, fluorescers, anti-graying agents, bactericides, hydrophobic oily materials and hydrotropes. Commonly used hydrotropes include common lower alkyl aryl sulfonates such as sodium and potassium toluene sulfonate, xylene sulfonate, benzenesulfonate, and cumene sulfonate. Urea and lower alkanol hydrotropes such as methanol, ethanol, propanol and butanol can also be used.

The hydrophobic oily materials suitable according to the invention include animal, vegetable and mineral oils and waxes such as beeswax, whale fat 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; Lanolin-

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Cholesterol derivatives and silicone oils. The invention Agents, in particular the cosmetic lotions, can also Contain ingredients that are intended to be moisturizing To increase the effect of the funds. Suitable ingredients include lower aliphatic alcohols with 2 to 6 carbon atoms and 2 to 3 hydroxyl groups, for example 1,4-butanediol, i, 2-propylene glycol and glycerin. Other suitable ingredients include urea or Urea derivatives such as guanidine, pyrrolidone or alantoin.

Base hydrolysis of soy protein

To 150 ml of vigorously stirred warm water was added 50 g of an edible soybean isolate (Promine P) to form a slurry. The mixture was heated to a slurry temperature of 90 to 95 ° C. and 5 g of sodium hydroxide pellets were added. After stirring for 4 hours, the liquid was cooled to 3O ⁰ C and treated with 2 ml of a 3O? 5igen hydrogen peroxide solution treated. The solution was stirred at room temperature for 20 minutes and then neutralized to pH 7. The protein obtained was isolated by adding 500 ml of acetone, the precipitated protein being washed with acetone / ether and finally dried ^{in a desiccator;} Yield 45g.

The hydrolyzed protein had a molecular weight of about 2,000 (weight average), the viscosity of a 10% solution at pH 9.5 and 48 ° C was 1.06 cP and the protein was at its isoionic point (pH = 4 , 5) insoluble up to 30%.

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A milder base hydrolysis of the same edible soybean isolate was also carried out, wherein the isolate was brought to pH 12 and heated to 70 ° C for 1 hour. In this case the hydrolyzate had a molecular weight of about 5,000, the protein was up to 85 % insoluble at its isoionic point, and the viscosity of an above solution at pH 9.5 and 48 ° C. was 1.56 centipoises .

Aminolysis of soy protein

125 ml of ethylene diamine were mixed with 20 g of the edible soybean isolate (Promine P) and then heated with stirring to 50 ⁰ C. After 4 days the mixture was cooled and 70 ml of water and then glacial acetic acid were added to a pH of 6 to 7. The liquid was then poured into 250 ml of acetone and the precipitate was washed with acetone and ether and finally vacuum-dried; Yield 15g.

Ammoniolysis of soy protein

26O ml of water were mixed with 25 g of des at 70 ° C. while stirring edible soybean isolate (Promine F). After the mixture was homogeneous, 52 ml of a 1: 5 ammonia / Water solution was added and the mixture was stirred in a closed vessel at 70 ° C. for about 20 hours, excess Ammonia was then removed by rotary evaporation and the

The resulting solution was added to 800 ml of acetone, a precipitate of the ammoniolysis product being formed.

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OMGlNAL INSPECTEO

This was washed with acetone and ether and finally vacuum dried; Yield 19g.

Acid hydrolysis of sqpprotein

250 ml of water were mixed with 20 g of the edible soybean isolate (Promine P) and then with 6.9 g of concentrated hydrochloric acid while stirring. The mixture was heated to 8O ⁰ C and stirred for 4 hours under a nitrogen atmosphere. After cooling, the pH of the solution was adjusted to 5 with sodium hydroxide and the precipitate was filtered off. After washing with a small amount of ice water

dried

the pesticide was dried with acetone and finally vacuum dried; Yield 15.5g; Molecular weight 3,200.

Examples I to

A number of soy protein derivatives were made according to the above methods described and produced

individually incorporated into a liquid detergent of the following formulation:

Components parts by weight

Ammonium-linear-C.p "^. ^ -

alkyl benzene sulfonate 18.4

Sodium linear-C. ₉ ~ ^c i u ~

alcohol sulfate with ^x

3 ethylene oxide groups 18.4

Lauric acid monoethanolamide 4.5

Industrial denatured alcohol 13.0

Protein sodium salt 4.0

Water except for

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up to

In certain cases / 15 parts of urea were added to to facilitate familiarization. In all examples, the proteins obtained were incorporated as sodium salts.

The wetting behavior was measured using an in vitro test which was found to have a high level of agreement with a realistic in vivo test. The in vitro test (called calfskin occlusivity test) was based on the rate of water transpiration through a calfskin sample which was brought into contact with a 0.15 # strength aqueous solution of a detergent mixture (at 18 hardness). The occlusivity of the protein was expressed as a percentage Decrease in the rate of water transpiration of the proteinaceous surfactant solution compared to that for wJss ^ !. ^se i5ie results for the wet-up (at pH 7) were as follows:

Examples Protein Relative Occlusivity

I Edible soybean isolate degraded with ethylenediamine (Promine P)

II edible soybean isolate (Promine P) degraded with alkali hydroxide

III edible soybean isolate degraded with sodium borohydride (Promine P)

IV with ammonia / water (1: 5) degraded 9 edible soybean isolate (Promine F)

V Enzyme-degraded edible soybean isolate (Promine P) 5

VI Edible broken down with hydrochloric acid 3 Soybean Isolate (Promine P)

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Relative examples of protein occlusivity

Comparison connection

I no -6

II Wilson X 250 -3

III Wilson X 1000 -7

All of the above protein derivatives have a molecular weight between 2,000 to 6,000 (except for the borohydride reduced soy protein which is slightly higher in molecular weight) and in each case the protein is at least partially water insoluble at its isoionic pH point. It is seen therefrom that all the soy protein derivatives mediate the aqueous solutions of the surfactants advantages with respect to the _wet-s however, that these benefits are greatest for soy proteins, the älkalihydrolysiert are ammoniolysiert and aminolysis. It has also been found that these benefits are imparted without adversely affecting the cleaning and lathering power of the detergent.

Comparative data for two collagen-derived proteins, Wilson Protein X 250 and X 1000, are presented under Comparative Compounds II and III shown, and it can be determined that according to the in vitro calfskin test, protein hydrolysates, derived from collagen are essentially ineffective

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are in reducing the rate of water perspiration through the leather.

Examples VII to XII

Liquid detergent mixtures were prepared according to the formulations of Examples I to VI, but with a protein component as described below. The wetting behavior of these formulations was tested in customary multi-product hand immersion tests (HIT) measured. In this test, housewives dipped left and right hands for two weeks a week 5 days a day 3 χ 10 minutes in a row, i.e. half an hour, in different solutions. The differences between left and right hands were equalized, and it became a total of 32 hands, 16 right and 16 left hands, used. The hands were withdrawn and re-immersed every two minutes and the treatment solutions replenished every 10 minutes. The hands were assessed at the start of the test (Monday) before immersion and every Friday. They were divided into a skin rating scale, which ranged from 0 (good) to 10 (bad). The HIT values for protein / surfactant solutions were determined and rated on a scale in which a 0.15-5 aqueous solution of the detergent mixture of the examples I to VI, but without protein, the HIT value 0 and one 1 mg / ciP application of hand care lotion has a HIT value of 100 was assigned.

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25U778

Example of degraded protein HIT value

VII Edible soybean isolate (Promine F) degraded with borohydride 60

VIII HCl Hydrolyzate Soy Metaprotein 60

IX NaOH Hydrolyzate Soy Metaprotein 56

X NaOH hydrolyzate-35 # soy metaprotein + 42 653 »iges water-soluble soy hydrolyzate

XI enzyme hydrolyzed soy 36

XII Edible Soybean Isolate (Promine F) des. Hydrolyzed with NaOH Example 10 (9 parts),

1-Hydroxybuty! Gelatine (1 part) 35

The modified gelatin of Example XII had a molecular weight of about 180,000 and an isoionic point at pH 8.95. It is in BE-PS 817 described.

Examples XIII to XV

In Examples XIII through XV is the basic detergent formulation the same as in Examples I to VI. The degraded proteins of Examples XIII and XIV are hydrolysates of edible soybean isolate (Promine F) with NaOH in which the hydrolysis was carried out in the above manner. To After hydrolysis, the soy metaprotein fraction (Example XIII) was obtained by increasing the pH of the aqueous solution 4.5, the isoionic point of the degraded protein. and collected the precipitation. Sufficient ammonium sulfate was added to the filtrate to produce a half-saturated solution of the

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2 5 4 A 7 7 8

Salt and the resulting precipitate was collected. This is the soy proteose fraction of Example XIVj _1, the piltrate contained soy peptone, which was incorporated into Comparative Example VII.

In Example XV the degraded protein was soy metaprotein, obtained by borohydride reduction, and a number other protein hydrolyzates are listed in the "Comparative Compounds IV to VI indicated.

The moisturizing behavior of the various formulations was compared (see table below) by looking at the change in the rate of water loss from the epidermis of a normal human forearm when using a 0.15 # strength solution of each formulation at a water hardness of 12 ° and at an application temperature measured by HO C. The results were rated against comparison compound I as a negative control.

It can be seen from this that water-insoluble soy metaprotein is produced either by alkaline hydrolysis or reductive cleavage has been established to be extremely effective in slowing down the velocity of the water nerve pleasure is from the skin. Alkaline soy proteose is a little less effective, but it is still beneficial Reduction in water loss compared to Comparative Compound I. Soy peptone, on the other hand, is quite ineffective as a humectant, which is also the case with degraded wheat and corn proteins.

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Example degraded protein transepidermal

Water loss

XIII Soy ametaprotein
(NaOH hydrolyzate) no protein -24 * XIV Soy proteose
(NaOH hydrolyzate) Corn pepton (Vi-Zate 243-
Acid hydrolyzate) -12,536 XV Soy metaprotein
(reduced with borohydride) Mined wheat
(NaOH hydrolyzate) -20 * Comparison connection Soy peptone (Vi-Zate 115-
Acid hydrolyzate) I. Soy peptone
(NaOH hydrolyzate) + 7.5 * IV XVI to XXI + 1.0 * V * 3.0 % VI + 10.5 * VII > + 7 * Examples

The following examples serve to illustrate the invention liquid detergent mixtures. All percentages are percentages by weight.

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Examples

XVI XVII XVIII XIX

Dimethyldodecylamine oxide 8%

Coconut alcohol ethylene oxide (6) condensate

Diethanoi-C acid amide

₂ _

Coconut alcohol ethylene oxide O) -S Ulf at / Sodium saltζ

C ₁ , «, Q-paraffin sulfonate, sodium salt

C _12-lij - *: - 01ef insulf onate,
Ammonium salt 8 6 urea 11 13 Industrial fuel
spirit 2 4 Soy Metaprotein NaOH
hydrolyzate rest water Example XXII

2%
6th

13th

XX

2% 2

XXI

14th

13th

4 ■

A liquid dishwashing detergent that was mild to the skin had the following composition:

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- 55 -

Parts by weight

Coconut Alcohol Ethylene Oxide (12) -

sulfate, ammonium saltζ 18.75

Coconut alcohol sulfate, ammonium salt 5.8

Sodium alkyl glyceryl ether sulfonate (wherein the alkyl is derived from a middle cut coconut alcohol and has approximately the following composition:
2% C ₁₀ ; 662 C ₁₂ ; 21% C _ll} ; 9% C _{± 6} ) 4.0

Coconut alkyl dimethyl amine oxide

(where coconut is a medium cut) 5.0

Potassium chloride 2.5

Potassium toluene sulfate 0.5

Citric acid 0.1

Hydrochloric acid 0.8l

Ammonium xylene sulfate 5.0

Ethanol 8.75

Soy metaprotein ($ 20 + soy proteose)

NaOH hydrolyzate 4.0

Water on

Example XXIII

A cosmetic lotion had the following composition:

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Parts by weight Sodium lauryl sulfate 1.2 Glyceryl monostearate 3.0 mineral oil 1.0 Methyl p-hydroxybenzoate 0.2 Stearic acid 1.0 Glycerin 4.0 Soy Metaprotein NaOH Hydrolyzate 3.0 water to 100

609816/1 107

Claims (1)

Patent claims: (1) Liquid washing, cleaning or cosmetic products Agent characterized in that it contains a surfactant and a soy protein derived from the Group of soy metaproteins and soy proteoses and mixtures from it contains. 2. Means according to claim 1, characterized in that it as a derived soy protein by thermal, hydrolytic, ammonolytic, aminoIytic or reductiyen degradation of a soy protein contains partially degraded soy protein. 3. Composition according to claim 2, characterized in that it is a degradation product as a derived soy protein Contains soy protein obtained by hydrolysis catalyzed by a base. 4. Composition according to one of the preceding claims, characterized in that it contains a soy protein preparation as derived soy protein which contains less than 10 % of non-proteinaceous material. 5. Composition according to one of the preceding claims, characterized in that it contains a soy protein preparation as derived soy protein which contains less than 5 % of non-proteinaceous material. 6. Agent according to one of the preceding claims, characterized in that it is a derived soy protein Contains soy metaprotein obtained by precipitating out of water at a pH at or near the isoionic point 609816/1107 of the isoionic point was isolated. 7. Agent according to one of the preceding claims, characterized in that characterized in that it is a soy protein having an isoionic point below pH as the derived soy protein 6 contains. 8. Composition according to one of the preceding claims, characterized in that it is a derived soy protein Contains soy protein with an isoionic point below pH 5. 9. Composition according to one of the preceding claims, characterized in that it is a derived soy protein Contains soy protein with a weight average molecular weight greater than 1,500. 10. Composition according to one of the preceding claims, characterized in that it is a derived soy protein Contains soy protein with a weight average molecular weight greater than 3,000. 11. Composition according to one of the preceding claims, characterized in that it is a derived soy protein Contains soy protein with a weight average molecular weight greater than 5,000. 12. Composition according to one of the preceding claims, characterized in that the derived soy protein 1 to 10 wt -.% Makes the composition. 13. Agent according to one of the preceding claims, characterized in that it is used as a surface-active agent 609816/1107 ionic, zwitterionic or non-ionic synthetic Contains detergent or an anionic soap « lU. Agent according to claim 13, characterized in that it contains the detergent as a liquid washing and cleaning agent in an amount of 5 to 50 weight percent, based on the agent. 15 · Means according to one of claims 1 to 13, characterized characterized in that, as a cosmetic lotion, it additionally contains a water-insoluble, hydrophobic oily material. 16. A process for the preparation of the liquid washing, cleaning or cosmetic agent according to any one of the preceding claims, characterized in that an isolated soy protein preparation in a weight ratio of protein ^{preparation to anhydrous acid or anhydrous alkali of 1} IrI to 25: 1 with an acid or an alkali, the mixture is ^{heated to a temperature of 40 to HO 0} C until it is at least 20 wt. SS and preferably at least. 30 wt. of soy metaprotein together with water soluble soy derived protein, mixing the soy metaprotein and / or the water soluble derived protein with the surfactant and the remaining ingredients of the agent, and adjusting the pH of the agent to 5.5 to 8.5. For: The Procter & Gamble Company Cincinnati, Ohio, V.St.A. Dr.H.J.Wolff Attorney at Law 609816/1107