Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07K—PEPTIDES
  • C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
  • C07K1/12—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by hydrolysis, i.e. solvolysis in general
  • C07K1/126—Aminolysis
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
  • A61K8/65—Collagen; Gelatin; Keratin; Derivatives or degradation products thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/02—Preparations for cleaning the hair

Definitions

• ABSTRACT A hair cosmetic preparation containing the acylation products of protein aminolyzates which have been prepared by reacting natural proteins with diand/or poly-amines containing 2 to 10 carbon atoms and containing additional N-hydroxyalkyl groupings.
• It is a further object of the present invention to provide a hair cosmetic preparation comprising a composition containing from about 0.1 to by weight of the acylation product of protein-aminolyzates having at least one additional N-hydroxyalkyl substituent, said protein-aminolyzate being the reaction product of a natural protein with an amine selected from the group consisting of diamine with 2 to 10 carbon atoms, polyamine with 2 to 10 carbon atoms and the mixtures thereof.
• It is another object of the present invention to provide a process for treating human hair comprising applying to said hair an effective amount of a composition containing from about 0.1 to 10% by weight of the acylation product of protein-aminolyzates having at least one additional N-hydroxyalkyl substituent, said protein-aminolyzate being the reaction product of a natural protein with an amine selected from the group consisting of diamine with 2 to 10 carbon atoms, polyamine with 2 to 10 carbon atoms and the mixtures thereof, in an aqueous preparation.
• the present invention is directed to a hair cosmetic preparation comprising a composition containing from about 0.1 to 10% by weight of the acylation product of proteinaminolyzates having at least one additional N- hydroxyalkyl substituent, said protein-aminolyzate being the reaction product of a natural protein with an amine selected from the group consisting of diamine with 2 to 10 carbon atoms, polyamine with 2 to 10 carbon atoms and the mixtures thereof.
• the present invention is further directed to a process for treating human hair comprising applying to said hair an effective amount of a composition containing from about 0.1 to 10% by weight of the acylation prodnet of protein-aminolyzates having at least one additional N-hydroxyalkyl substituent, said proteinaminolyzate being the reaction product of a natural protein with an amine selected from the group consisting of diamine with 2 to 10 carbon atoms, polyamine with 2 to 10 carbon atoms and the mixtures thereof, in an aqueous preparation.
• the protein aminolyzates starting materials are known from the literature, and their preparation may be carried out, for example, according to the procedure described in the German Pat. No. 1,959,651. These protein aminolyzates preferably have molecular weights from 300 to 1000.
• the protein may be derived from any vegetable or animal proteins, for example glue, gelatin, albumin, collagen, keratin, casein, feather protein, hair protein, cottonseed protein or soya protein.
• glue for the aminolysis of such proteins, diamines and/or polyamines with 2 to 10 carbon atoms are used. These amines are preferably those aliphatic amines having the formula:
• n 2 to 10 and m l to 5 with the proviso that the total number of carbon atoms does not exeed 10.
• these preferred aliphatic amines are ethylenediamine, 1,4-diaminobutane, diethylenetriamine, 1,6-diaminohexane, triethylenetetramine, or tetraethylenepentamine.
• the aminolysis of the proteins with the abovementioned diamines and/or polyamines may be effected in known way by heating the proteins with at least an equal amount by weight of diamine and/or polyamine under reduced pressure at temperatures between and 200C until an aliquot part of the reaction mixture is soluble in dilute acid.
• An especially preferred embodiment for carrying out the aminolysis comprises adding an amount by weight of water, equal to or greater than the amount by Weight of protein, to an amount by weight of diamine or polyamine which is equal to the weight of protein, heating the amine water mixture to C to C in a protective gas and then introducing the protein therein. The temperature was then, also in presence of protective gas, raised to C. As soon as the reaction product was soluble in acid, water and excess amine which might be present were removed under reduced pressure.
• the molecular weights of the aminolyzates from proteins and the above-described diamines and/or polyamines generally lie in the range of 300 to 1000.
• Preferred starting substances for the process according to the invention are proteinaminolyzates with a molecular weight lying in the range from 350 to 700.
• the substances contained in the compositions according to the invention are preparable from the protein-aminolyzates by reacting them with epxoides containing 3 to 24 carbon atoms in the molar ratio 1:(0.5 to 1.5) at elevated temperature and acylating the reaction products.
• acylation products relates to corresponding derivatives of carboxylic acids with 10 to 24 carbon atoms.
• the N-hydroxyalkyl substituents present in the substances preferably contain 3 to 24 carbon atoms.
• the acyl substitutent having 10 to 24 carbon atoms may be added thereto by means of carboxylic acids or suitable carboxylic acid esters of corresponding chain length.
• the amount of the acylating agent should be in the range of about 0.5 to 1.5 mol per mol of protein-aminolyzate used.
• suitable epoxides which may be used are: glycide, penteneoxide-l ,2, octeneoxide-2,3, deceneoxide-l,2, dodeceneoxidel ,2, octadeceneoxidel ,2, docoseneoxidel ,2, tetracoseneoxide-l,2 alkylglycidyl ethers in which the alkyl has 7 to 21 carbon atoms.
• Suitable acylating agents include for example alkanoic acids of to 24 carbon atoms such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid, alkenoic acids of 10 to 24 carbon atoms such as oleic acid and erucic acid, hydroxy-alkanoic acids of 10 to 24 carbon atoms such as hydroxy-stearic acid, hydroxy-alkenoic acids of 10 to 24 carbon atoms such as ricinoleic acid, alkadienoic acids of 10 to 24 carbon atoms such as linoleic acid, alkatrienoic acids of 10 to 24 carbon atoms such as linolenic acid, and the mixtures thereof.
• alkanoic acids of to 24 carbon atoms such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lig
• the acylation may be effected at temperatures between 100C and 150C.
• a portion of the substances contained in the hair treatment compositions according to the invention can be prepared in an especially simple manner by reacting the abovementioned proteinaminolyzates with a glycidyl ester of a carboxylic acid which contains 10 to 24 carbon atoms in the acyl substituent and which correspond to the above mentioned carboxylic acids, at temperatures of 70 to 150C. According to this procedure the protein-aminolyzates are reacted with glycidyl esters of carboxylic acids of the general formula:
• R signifies an aliphatic hydrocarbon containing 9 to 23 carbon atoms.
• the aliphatic hydrocarbon R may be a straight or branched chain and be saturated or unsaturated.
• R is a straight chained member selected from the group consisting of alkyl of 9 to 23 carbon atoms, alkenyl of 9 to 23 carbon atoms, alkadienyl of 9 to 23 carbon atoms, hydroxy alkyl of 9 to 23 carbon atoms, hydroxyalkadienyl of 9 to 23 carbon atoms, and alkatrienyl of 9 to 23 carbon atoms, and the mixtures thereof.
• the relative proportions of the protein aminolyzate and the glycidyl ester of a carboxylic acid may vary within specified limits, depending on the type and molecular weight of the aminolyzate used. However, the range of 1 to 3 mol of glycidyl esters per mol of aminolyzate are preferable, since the products produced are more easily dispersible in water/alcohol mixtures.
• the temperatures to be used lie in the range of 70 to 150C.
• the reaction may be carried out without use of a solvent. Since, however, the reaction is strongly exothermic and local overheating influences the color quality of the products, the addition of a solvent in which the aminolyzates are soluble or at least dispersible is preferable. Suitable solvents are, for example, lower alcohols and/or water.
• the reaction may be carried out by adding the glycidylester portionwise to the aminolyzate heated to the desired reaction temperature, to which a solvent is optionally added, and thoroughly mixing the reaction material. After the termination of the glycidyl ester addition, heating and thorough mixing of the reaction mixture possibly after increasing the temperature is continued until epoxide oxygen is no longer detectable.
• the separation of the solvent which may be present, may be effected by distillation before or during the period subsequent to the reaction.
• the compositions according to the invention may contain 0.1 to 10% by weight, preferably 0.1 to 1.5% by weight of an aqueous or aqueousalcoholic dispersion of the described substances and in this form may be used, for example, as an after-rinsing preparation.
• the compositions may be adapted to for other uses, such as for example, hair shampoos, hair dressings, hair setting agents, and would therefore contain the customary components used in the usual proportions in these compositions.
• compositions may contain from 0 to about 50% by weight of surface-active components, usually being the anionic sulfate surface-active compounds such as higher fatty alcohol sulfates, higher fatty alcohol ether sulfates with 3 to 4 ethylene oxide units in the molecule, higher alkylphenol ethoxylated sulfates, monoglyceride sulfates, and also higher fatty acid-protein condensation products,- higher fatty acid sarcosides and higher fatty acid methyl taurides.
• amphoteric surface-active compounds such as for example, the imidazole derivatives known by the name miranoles.
• anionic surface-active compounds are present preferably in the form of their alkali metal, such as sodium, and triethanolamine salts and in certain cases such as, for example myristyl alcoholethoxylated sulfate, also in the form of the magnesium salts.
• Emulsifying agents which may be present in the compositions from 0 to about 10% by weight according to the invention are soaps of stearic, lauric and oleic acids in the form of their sodium, potassium or alkanolamine salts, as well as the above mentioned anionic sulfate surface-active compounds, and polyol-fatty acid esters, for example glycerine monostearate, propylene glycol monostearate, diethyleneglycol monostearate, some in admixture with anionic emulsifiers, fatty alcohol mixtures in combination with anionic emulsifiers; nonionic emulsifiers such as polyethylene oxide glycol esters, for example polyhydroxyethylene stearate, -laurate or -oleate, polyethylene oxide sorbitan esters, with higher fatty acids, simple sorbitan esters such as sorbitan monolaurate, -oleate, -sesqui-oleate, sterols, polyoxyethyleneglycol
• N-laurylaminopropionate N-lauryliminodipropionate, lauryl-diethyl-triaminoacetic acid, etc.
• the usual substances may also be added as thickeners, which are present from O to about 5% by weight, such as, for example, sodium alginates, fatty acid alkylolamides and some partial tylose slimes; also higher molecular weight polyoxyethylene-glycol-monoor -diesters of higher fatty acids, such as stearic acid and lauric acid.
• electrolytes such as sodium chloride or ammonium chloride are also used as thickeners in combination with alkyl polyoxyethylene sulfates.
• superfatting agents may also be added to the compositions according to the invention, in amounts of from to about by weight for example polyhydroxyethylated lanoline derivatives, lecithin derivatives or the aiready mentioned alkylolamides, to which a certain oiling action belongs.
• the latter may also serve as foam stabilizers in shampoos.
• compositions according to the invention may also contain lower aliphatic alcohols as solvents, such as lower alkylols of 1 to 6 carbon atoms for example ethanol or isopropanol.
• So-called builder components may be added from O to about by weight, such as paraffin, fats, lanolin and wool fat alcohols.
• Other usual components may be added from 0 to about 7% by weight, such as preservatives, especially formalin, sorbic acid and dehydroacetic acid, 6-acetoxy-2,4- dimethyl-dioxane, esters of p-hydroxybenzoic acid; biogenic substances such as plant extracts and vitamin complexes.
• Solution aid components may be added from O to about 10% by weight, such as lower alkylene glycols, for example 1,3-propanediol, 1,3- butyleneglycol, diethyleneglycol.
• Film forming components may be added from 0 to about 2% by weight such as polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, dimethylhydantoinformaldehyde resins, polymers of the 2-alkyl-2-oxazoline series.
• Acid adjusting agents, especially fruit acids, such as citric acid and/or lactic acid may be added from 0 to about 2 by weight.
• Relatively small contents of the protein-aminolyzate derivatives described above impart to hair cosmetic preparations of various compositions a good hair conditioning and structure-improving activity. Generally from about 0.1 to 10% by weight, preferably 0.1 to 1.5% by weight, based upon the total composition weight, is sufficient. For special preparations, which are to be used particularly for the treatment of substantially damaged hair, higher concentrations thereof could be used.
• Hair Dressing 2 to 15 parts by weight of builder components (for example paraffin oil, fatty acid ester, wool fat) 1 to 10 parts by weight of emulsifier,
• builder components for example paraffin oil, fatty acid ester, wool fat
• solution aids especially lower polyalcohols
• thickeners 0 to 7 by weight of thickeners and other components (for example perfume, preservative, biogenic substances),
• Hair After-Rinsing Composition 0.5 to 5 parts by weight of protein derivative
• builder components for example paraffin oil, fatty acid esters, wool fat
• acid additives especially fruit acids or lactic acid
• Hair Setting Composition 0.5 to 2 parts by weight of film forming compound, 0 to 1 parts by weight of emulsifier, 0.5 to 1 parts by weight of protein derivative, 0.1 to 0.2 parts by weight of acid additives, especially fruit acids or lactic acid, 0 to 1 part by weight of other components (for example perfume, biogenic substances), 20 to 50 parts by weight of ethanol or isopropanol, Remainder to 100 parts by weight of water.
• Protein Derivative A A mixture of 1 kg of diethylenetriamine and 2 kg of water was heated in a round-bottomed flask to 90C. 1 kg of casein was added with stirring during a period of half an hour, and then the reaction temperature was raised to l 10C. The heating was continued until an aliquot part of the reaction mixture was soluble in dilute acid. Water and excess amine were distilled off in vacuo. The protein-aminolyzate product was obtained in the form of a paste after the cooling thereof, and it had an average molecular weight of 550. This proteinaminolyzate was then reacted with about an equimolar amount of hexadeceneoxide-l,2 at a temperature of about C. Then methyl stearate was added in about an equimolar amount and was reacted therewith at 130C under reduced pressure.
• Protein Derivative B Utilizing a procedure analogous to that described for obtaining Protein Derivative A, the reaction product of a protein-aminolyzate from gelatin and diethylenetriamine (mol. wt. 510) with hexadeceneoxide-l,2
• Protein Derivative C Utilizing a procedure analogous to that described for obtaining Protein Derivative A, the reaction product of a protein-aminolyzate from albumin and diethylenetriamine (mol.wt. 520) with hexadeceneoxidel ,2 and methyl stearate in about equimolar proportion, was produced.
• Protein Derivative D Utilizing a procedure analogous to that described for obtaining Protein Derivative A, the reaction product of a protein-aminolyzate from casein and tetraethylenepentamine (mol.wt. 590) with hexadeceneoxide-l ,2 and methyl stearate in about equimolar proportion, was produced.
• Protein Derivative E Protein Derivative F A procedure analogous to that described for obtaining Protein Derivative A was utilized except that the reaction product of a .protein-aminolyzate from gelatin and diethylenetriamine (mol.wt. 385) was reacted at 80 to 90C with glycidyl laurate in the molar ratio 1 :2.
• Protein Derivative G Utilizing a procedure analogous to that described for obtaining Protein Derivative F, the reaction product of a protein-aminolyzate from gelatin and diethylenetriamine (mol.wt. 385) with glycidyl oleate in the molar ratio 1:2, was produced.
• Protein Derivative H Utilizing a procedure analogous to that described for obtaining Protein Derivative F, the reaction product of a protein-aminolyzate from gelatin and diethylenetriamine (mol.wt. 385) with glycidyl stearate in the molar ratio 1:2, was produced.
• the hair was washed in each case, brushed and parted in the middle. Then the hair dressing compositions were applied to one half of the head and a blank experiment material (hair dressing composition with omission of the protein derivative but otherwise the same composition) was applied to the other half of the head. After a treatment time of 15 minutes the hair was rinsed with warm water, brushed and the wet combability and the body of the hair were judged.
• the hair was wound on rollers, dried and, after removal of the rollers, the curls were tested for firmness and elasticity.
• the body of the hair and the wet combability of the hair were improved by the addition of the Protein Derivatives A to H; the hair dried on rollers was firm as compared with the blank experiment and the curls had an improved springiness.
• Example 2 The technical application test was effected as described in Example 1; the treatment time was 5 minutes in each case. Ten experienced persons judged the body of the hair, the wet combability, the firmness and behavior of the hair dried on rollers. The hair showed noticeable improvements compared with blank experiments and comparative preparations which contained protein hydrolyzates (Trade names WSP X 250 and WSP X 1000), with otherwise the same composition, instead of the protein derivatives of the present inventron.
• protein hydrolyzates Trade names WSP X 250 and WSP X 1000
• Comparative experiments were carried out with preparations according to Comparative Example 3a, which contained, instead of the Protein Derivatives A to H the same amount of commercial protein hydrolyzates (Trade names WSP X 250 and WSP X 1000).
• the treated hair showed the same quality as one washed with the above described blank sample.
• EXAMPLE 4 Utilizing a hair setting agent of the following composition:
• a hair cosmetic preparation consisting essentially of a composition consisting essentially of (a) from about 0.1% to 10% by weight of an acylation product consisting essentially of (l) a natural protein having been reacted with an amine selected from the group consisting of diamine with 2 to 10 carbon atoms, polyamine with 2 to 10 carbon atoms and the mixtures thereof by heating said protein with at least an equal amount by weight of said amine at temperatures between C and 200C to produce a proteinaminolyzate, (2) said protein-aminolyzate having been reacted with an epoxide compound having 3 to 24 carbon atoms in the molar ratio of 1:(0.5 to 1.5) at elevated temperature to produce a protein-aminolyzate having at least one additional N-hydroxyalkyl substituent having from 3 to 24 carbon atoms, and (3) said protein-aminolyzate having said at least one substituent having been acylated with the acyl of a carboxylic acid having 10 to 24 carbon atoms with the amount of
• the hair cosmetic preparation of claim 1 in which the molecular weight of the protein-aminolyzate is in the range of 300 to 1000.
• composition comprises the said acylation products dispersed in a media selected. from the group consisting of aqueous dispersion and aqueous-alcoholic disper sion.
• the protein-aminolyzate is the reaction product of an aliphatic amine of the formula n is an integer from 2 to 10 m is an integer from 1 to 5 with the proviso that the total number of carbon atoms does not exceed 10, with a natural protein selected from the group consisting of glue, gelatin, albumin, collagen, keratin, casein, protein derived from feathers, hair protein, cottonseed protein and soya protein.
• the aliphatic amine is selected from the group consisting of ethylenediamine, 1,4-diaminobutane, diethylenetriamine, 1,6-diaminohexane, triethylenetetramine, and tetraethylenepentamine.
• a hair cosmetic preparation consisting essentially of a composition consisting essentially of (a) from about 0.1% to 10% by weight of an acylation product consisting essentially of (l) a natural protein having been reacted with an amine selected from the group consisting of diamine with 2 to 10 carbon atoms, polyamine with 2 to 10 carbon atoms and the mixtures thereof by heating said protein with at least an equal amount by weight of said amine at temperatures between 80C and 200C to produce a proteinaminolyzate, and (2) said protein-aminolyzate having been reacted with a glycidyl ester of a carboxylic acid having 10 to 24 carbon atoms, in the range of l to 3 mols of said glycidyl ester per mol of said proteinaminolyzate at temperatures in the range of 70 to 150C to produce the acylation product of said proteinaminolyzate having at least one additional N- hydroxyalkyl substituent, (b) from to about 50% by weight of a surface
• a process for treating human hair comprising applying to said hair an effective amount of the hair cos metic preparation of claim 1.
• a process for treating human hair comprising applying to said hair an effective amount of the hair cosmetic preparation of claim 7.

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Citations (1)

• 1971
  • 1971-10-18 DE DE2151740A patent/DE2151740C3/de not_active Expired
• 1972
  • 1972-09-25 SE SE7212356A patent/SE395607B/xx unknown
  • 1972-09-25 NL NLAANVRAGE7212957,A patent/NL176430C/xx not_active IP Right Cessation
  • 1972-10-02 US US294188A patent/US3904748A/en not_active Expired - Lifetime
  • 1972-10-13 IT IT30429/72A patent/IT1001507B/it active
  • 1972-10-17 AT AT889572A patent/AT324572B/de not_active IP Right Cessation
  • 1972-10-17 CH CH1514872A patent/CH567415A5/xx not_active IP Right Cessation
  • 1972-10-17 GB GB4775372A patent/GB1388760A/en not_active Expired
  • 1972-10-18 FR FR7236849A patent/FR2156781B1/fr not_active Expired

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