Classifications

• • 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
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • 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
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

Definitions

• Q is a radical having the following formula:
• R is selected from the group consisting of H and CH R is selected from the group consisting of H and COOH, q is a whole number between 1 and 5, inclusive, q is an integer from 0 to l inclusive, p is an integer from 0 to 1 inclusive, Q is a radical having the formula:
• R is selected from the group and lower alkyl, R, is selected from the group consisting of a lower alkyl and a radical having the formula consisting of hydrogen,
• m is a whole number lying between 2 and 4, inclusive.
• hair set in this manner retains the desired form only for a relatively short time, and that it is extremely-sensitive to humidity, since absorption of water by the hair results in destruction of the set.
• the essential object of these films is to protect the hair against humidity, but it is also necessary for them to improve, if possible, the sheen, flexibility and manageability of the hair. It is also essential that these films be easily removed from the hair by washing or brushing, without powdering, i.e. without having the film disintegrate into a. multitude of fine particles.
• compositions heretofore utilized for this purpose include vegetable resins, alginates, cellulosic derivatives, and
• the film is usually hygroscopic, so that the sheen of the hair deteriorates rapidly.
• An object of the present invention is to provide a new article of manufacture which consists of a polymer having SH groups, alkyl groups and amino alkyl groups in its molecule, characterized by the fact that it has the following formula:
• R and R which may or may not be identical, are selected from the group consisting of a hydrogen atom, a lower alkyl radical, a phenyl radical, and a lower alkoxy radical;
• R' may be a hydrogen atom, the OCOCH radical, the
• .n is awhole number
• Q is a radical having the following formula:
• R represents H or CH
• R represents H or COOH q is a whole number between 1 and 5, inclusive; q is equal to zero or 1,
• p is equal either to zero or 1
• Q is a radical having the following formula:
• R is a hydrogen atom or a lower alkyl
• R is a lower alkyl, a radical having the formula in which r and r are identical or difierent lower alkyls, or may form part of a heterocycle such as that of morpholine or piperidine; and
• m is a whole number equal to 2, 3 or 4.
• the proportions of the substituents Q and Q of Formula I may be varied within broad limits, for example from 1 to 99% and preferably from 20 to 80% of the thiols.
• a further object of the invention is to provide the new polymer having the above Formula I, in which R is a hydrogen atom, R" is the CH radical, and R is the -COOCH radical.
• the polymercapto condensation polymers hereinbefore defined have a value of n such that they are soluble in water, at least in an alkaline medium.
• Another object of the present invention is to provide a process for manufacturing the aforesaid polymers, which process consists, on the one hand, in condensing aminothiols or amino mercapto-amines having the following formula:
• R, R" and R' have the values hereinbefore indicated.
• compositions which may be substituted as Q in Formula II are B-mercaptoethylamine, cysteine, N- monomethyl mercaptoethylamine, and N,( 8-aminoethyl) thioglycolamide, but this list is not exhaustive.
• compositions which may be substituted as Q in Formula III are butylamine, N,N-diethyl-propylenediarnine and N-(B-amino-ethyl) morpholine, but this list is not exhaustive.
• the new polymers corresponding to Formula I may be easily prepared by reacting with polymers corresponding to Formula VI a mixture in the proportions previously specified of aminothiols or amido mercaptoamines according to Formula IV and amines according to Formula V. The reaction is carried out in an aqueous medium at room temperature. The desired product is then isolated by precipitation in an acid medium.
• plastic properties of the films formed by the polymers depend to a certain extent on the nature of the base which is used to neutralize the carboxylic function.
• compositions for setting the hair which form transparent, lustrous, colorless, flexible films.
• these polymers have an excellent affinity for the hair.
• the resinous polymers of this invention may be used as.setting compositions, either in the form of lotions containing a low percentage of polymers, or in the form of. gels having a high percentage of polymers. These compositions make it possible to make hair sets last considerably longer, while rendering the hair easy to manage, soft in appearance, lustrous and silky.
• the polymers of this invention may be used alone or mixed with other cosmetic agents, e.g., plasticizers such as glycol ethers, cationic surfactants such as quaternary ammoniums, swelling agents such as urea, perfumes, sequestrants, pigments, etc.
• plasticizers such as glycol ethers
• cationic surfactants such as quaternary ammoniums
• swelling agents such as urea, perfumes, sequestrants, pigments, etc.
• resinous polymers of this invention may be used as a mixture with each other, or they may be used in mixtures containing other known resins, previously used in cosmetic compositions.
• the polymers of this invention may be advantageously dissolved in aqueous alcoholic solutions of between 20 and 50 degrees and at concentrations preferably of the order of 2 to 3%, but which may rise to 10% or higher.
• Example 1 Condensation of B-mercapto ethylamine and N,N-diethylpropylene diamine on an ethylene/maleic anhydride copolymer
• the copolymer having the following repeating formula is prepared:
• the tertiary amine function is present in the form of the hydrochloride and that the product contains about 12.5% of sodium chloride, as determined by an analysis of the chloride ion content.
• the product is then purified by dissolving it in a mixture of dimethyl formamide and alcohol, the insoluble sodium chloride being eliminated by filtration.
• the desired product is precipitated from the filtrant by adding ether.
• Total --SH is used to indicate the sum of the free SH groups in the product and the SH groups which could be separated from the oxidized (-SS-) portion of the product by total reduction during the analysis.
• Example 2 Condensation of crysteine and the N,N-diethylpropylene diamine on an ethylene/maleic anhydride copolymer This is eifectuated under the same conditions as those described in Example 1, except that an equivalent quantity of crysteine is substituted for the B-mercapto ethylamine. This yields 47% by weight of a gum which, after purification by dissolving it in dimethyl formamide and precipitation with ether, appears in the form of a pulverulent mass which is soluble in water at a neutral or alkaline pH.
• Example 3 Condensation of N-(/3-aminoethyl)thioglycolamide and N,N-diethylpropylene diamine on an ethylene/maleic anhydride copolymer This process is carried out under the same conditions as those described in connection with Example 1, except that the fl-mercapto ethylamine is replaced by an equivalent quantity of N- (B-arninoethyl)thioglycolamide.
• the product thus obtained may be purified by dissolving it in dimethyl formamide and precipitating it with ether.
• N-(,Q-aminoethyl)thioglycolamide having the formula:
• 64 g. (1 mol.) of 96% ethylenediamine is placed in a recipient provided with an agitator, a reflux cooling column, a thermometer, a dropping funnel and a tube for supplying nitrogen.
• 126 g. (1 mol.) of a 95% solution of ethyl thioglycolate in 100 cc. of absolute alcohol is then introduced drop by drop, while constantly stirring and maintaining the temperature at about 4045 C.
• Example 4 Condensation of B-mercapto ethylamine and butylamine on an ethylene/maleic anhydride copolymer This condensation yields about 89% by weight when carried out as described in the foregoing examples, except that the N,N-diethyl-ethylene diamine is replaced by a corresponding quantity of butylamine.
• the isolated composition is not contaminated with sodium chloride, so that further purification is unnecessary.
• composition obtained has been analyzed as follows:
• Example 5 Condensation of fl-mercapto ethylamine and N-(fl-aminoethyl)morpholine on an ethylene/maleic anhydride copolymer The condensation is carried out with a yield of about 65% by proceeding as described in Example 1, except that the N,N-diethyl-ethylene diamine is replaced by an equivalent quantity of N-(fl-aminoethyDmorpholine.
• the product obtained is in the form of a powder which is soluble in water at a neutral or alkaline pH.
• the powder was analyzed with the following results:
• Example 6 Condensation of N-(p-aminoethyDthioglycolamide and butylamine on an ethylene/maleic anhydride copolymer The condensation is carried out with a yield of about by proceeding as described in Example 3, except that the N,N-diethyl-propylene diamine is replaced by an equivalent quantity of butylamine.
• Example 7 Condensation of fi-mercaptoethylamine and N,N-diethyl-propylenediamine on an ethylene/maleic anhydride copolymer
• the desired product is obtained with a yield of about 82% by weight by following the same procedure as in Example 1, except that the quantities of amino-thiol and diamine are altered so that each is equal to 0.5 mol. for a total of 1 mol. of ethylene/maleic anhydride copolymer.
• After drying the product obtained is a powder which is soluble in water at a neutral or alkaline pH. This powder has been analyzed with the following results:
• Example 8 --Condensation of B-mercapto ethylarnine and N,N-diethyl-propylenediamine on an ethylene/maleic anhydride copolymer
• the process is the same as that of Example 1, except that of a mol. of Si-mercapto ethylarnine hydrochloride is used for each mol. of N,N-diethylpropylene diamine.
• the product is purified by dissolving it in dimethyl formamide and precipitating it with ether.
• the composition is obtained in the form of the hydrochloride, with a yield of about 50% by weight. It is soluble in water at a neutral or alkaline pH. The following analysis was made:
• Example 9 Condensation of B-rnercapto ethylarnine and butylamine on a styrene/maleic anhydride copolymer
• the copolymer having the following repeating formula is prepared:
• Example 10 Condensation of fi-mercapto-ethyl-amine and n-butyl-amine on a vinyl acetate/maleic anhydride copolymer A polymercapto condensation copolymer having the following repeating formula is prepared:
• the starting copolymer is a vinyl acetate/maleic anhydride copolymer obtained in a conventional manner by copolymerizing equimolecular quantities of vinyl acetate and maleic anhydride in toluene in the presence of benzoyl peroxide, which acts as a catalyst.
• This copolymer in a 1% solution in dimethyl formamide, has a specific viscosity of 0.17 at a temperature of 25 C.
• the anhydride function has been introduced in a proportion such that the molar ratio between the vinyl acetate and maleic anhydride in this polymer is 0.93/1.
• the copolymerization has been so carried out as to produce a copolymer which is water-soluble in a basic medium.
• the amine is then liberated from its hydrochloride by adding 3.3 cm. (0.033 mol.) of an aqueous 40% soda solution.
• the reaction is completed in three hours.
• the solution is then acidified with hydrochloric acid to precipitate the desired product, which yields 78% by weight, i.e. 19.5 grams of the copolymer according to the invention.
• the product is yielded in the form of a white powder which is water soluble at an alkaline pH, and which has the following analysis:
• Example 11 Condensation of fl-mercapto-ethyl-amine and N,N-diethyl-propylene-diamine on a methyl methacrylate/maleic anhydride copolymer
• a poly mercapto condensation polymer having the following repeating formula is prepared:
• the starting polymer is a methyl methacrylate/maleic anhydride copolymer obtained in a conventional manner by copolymerizing equimolecular quantities of methyl methacrylate and maleic anhydride in toluene in the presence of azo-bis-iso-butyronitrile, which acts as a catalyst.
• a 1% solution of this polymer in dimethyl-formamide has a specific viscosity of 0.088 at a temperature of 25 C.
• the molar ratio between the methyl methacrylate and the maleic anhydride in this polymer is determined by measurement of the anhydride function as equal to 1.52/1.
• Example lfl-mercaptoethyl amine and N,N-diethyl-propylene-diamine are condensed on the methyl methacrylate/maleic anhydride copolymer which has been obtained in the manner already described, using 0.5 mol. of aminothiol and 0.5 mol. of diamine per mol. of methyl methacrylate/maleic anhydride copolymer.
• Example 12 Condensation of N-(fi-amino-ethyDthioglycolamide and n-butylamine on an acrylonitrile/ maleic anhydride copolymer
• a polymercapto condensation polymer having the following repeating formula is prepared:
• An acrylonitrile/maleic anhydride copolymer is used as the starting copolymer. This is obtained by copolymerizing equimolecular quantities of acrylonitrile and maleic anhydride in toluene in the presence of benzoyl peroxide, which acts as a catalyst.
• the copolymer obtained when in a 1% solution in dimethyl formamide, has a specific viscosity of 0.055 at a temperature 25 C.
• the molar ratio between the acrylonitrile and the maleic anhydride is determined by measuring the amine function as equal to 1.19/ 1.
• the method is the same as that of Example 10, with the condensation of diamine and aminothiol on this copolymer, except that the B-mercapto-ethyl-amine is re placed by a molecularly equivalent quantity of N-(flaminoethyl)thioglycolamide, and the vinyl acetate is replaced by acrylonitrile.
• the product is in the form of a white powder which is water-soluble at an alkaline pH, and has been analyzed with the following results:
• a polymercapto condensation polymer having the following repeating formula is prepared:
• This copolymer as a 1% solution in dimethyl-formamide has a specific viscosity of 0.093 at a temperature of 25 C.
• the molar ratio between the methyl acrylate and maleic anhydride has been determined by measurement of the anhydride function to be equal to 0.9/ 1.
• Example 14 Process for producing a hair-setting lotion having following composition:
• the resin is first dissolved in 60 cc. of water in the presence of 2-amino-2-methyl-l-propanol until the pH reaches 8.2.
• the tetrasodium salt of ethylene diamine tetracetic acid is then added to serve as a sequestrant for metals, followed by the mixture of ethyl alcohol and perfume.
• the volume is then increased to 100 cc. by adding distilled water and, to a pH of 8.5, by adding 2-amino-2-methyl-1- propanol.
• the lotion which has just been described materially prolongs the life of the set while keeping the air in shape without maning it dull, even in very humid weather.
• Example 16 A setting lotion having the following composition is prepared:
• Example 17 A setting lotion having the following composition is prepared in the same manner as described in connection with Example 16:
• Example 18 A setting lotion having the following composition is prepared in the same manner as described in connection with Example 14.
• Example 19 An aerosol bomb containing the following ingredients is used to provide an aerosol foam for setting the hair: Condensation product of ethylene/maleic anhydride copolymer with cysteine and N,N-diethyl-propylene diamine, obtained as in Example 2 g.. Ethyl alcohol, q.s.p degrees 25 2-amino-2-methyl-l-propanol, q.s.p. pH 8.5
• Emulsifying agent cetyl-stearyl alcohol condensed with mols. of ethylene oxide
• Propellant g 7 The aerosol bomb is made by first solubilizing the resin in 30 cc. of water in the presence of 2-amino-2- methyl-l-propanol. Cetyl-stearyl alcohol (which has first been dissolved in 20 cc. of water, while being slightly heated) is then added, after which the mixture of ethyl alcohol and perfume is added.
• the pH is then adjusted to 8.5 by adding the necessary quantity of 2-amino-2-methyl-l-propanol and the weight increased to 93 g. by adding distilled water.
• the bomb is completed by adding 7 g. of a conventional propellant such as the fluorinated hydrocarbon sold as Freon 12.
• a conventional propellant such as the fluorinated hydrocarbon sold as Freon 12.
• the product is applied in the form of a very transient foam, which facilitates its uniform distribution throughout the hair, which has previously been washed and dried.
• the hair is then set in the usual manner, with excellent results.
• Example 20 10 g 3 Ethyl alcohol, q.s.p degrees 25 2-amino-2-methyl-l-propanol, q.s.p. pH 8.5
• the process is begun by dissolving the resin in 60 cc. of Water in the presence of 2-amino-2-methyl-1-propanol to a final pH of 8.2.
• the tetrasodium salt of ethylene diamine tetracetic acid is added to serve as a sequestrant for metals, followed by the mixture of ethyl alcohol and perfume.
• the volume is increased to 100 cc. by adding distilled water and the pH adjusted to 8.5 by adding more 2-amino-2-methyl-1-propanol.
• the lotion which has just been described remarkably prolongs the life of the wave without causing the hair to become dull, even in very humid weather.
• Example 21 In accordance with the invention, a setting lotion having the following composition is prepared:
• Example 22 In accordance with the invention an aerosol foam for projection from a bomb to use in setting the hair is prepared from the following constituents:
• the aerosol bomb is made by first dissolving the resin in 30 cc. of water in the presence of 2-amino-2-methyl-1- propanol. Cetyl stearyl alcohol which has been dissolved in 20 cc. of water, while heating it slightly, is then added, after which the mixture of ethyl alcohol and perfume is added.
• the pH is then brought to 8.5 by adding the necessary quantity of 2-amino-2-methyl-l-propanol and the volume increased to 93 g. by adding distilled water.
• the aerosol bomb is pressurized by adding 7 g. of a conventional propellant such as the fluorinated hydro carbon sold under the trade name Freon 12.
• a conventional propellant such as the fluorinated hydro carbon sold under the trade name Freon 12.
• the product is applied as a very transient foam, thus facilitating its distribution through the previously washed and dried hair.
• the hair is then set in a conventional manner, with excellent results.
• R and R" are both selected from the group consisting of hydrogen, lower alkyl, phenyl, and lower alkoxy, R is selected from the group consisting of OCOCH COOCH and -CEN, Q is a radical having the following formula:
• R is selected from the group consisting of H and CH R is selected from the group consisting of H and COOH,
• q is a whole number between 1 and 5, inclusive
• q is an integer from to 1 inclusive
• p is an integer from 0 to 1 inclusive
• R is selected from the group consisting of hydrogen
• R is selected from the group consisting of a lower alkyl and a radical having the formula in which 1 is selected from the group consisting of lower alkyl amines and a heterocyclic ring,
• m is a whole number lying between 2 and 4, inclusive.
• a polymer as claimed in claim 1 which is watersoluble at an alkaline pH.

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Cited By (3)

Citations (2)

• 1965
  • 1965-01-18 FR FR2339A patent/FR87224E/fr not_active Expired
  • 1965-06-11 BE BE665342D patent/BE665342A/xx unknown
  • 1965-06-14 DE DE19651595064 patent/DE1595064A1/de active Pending
  • 1965-06-14 US US463953A patent/US3472820A/en not_active Expired - Lifetime
  • 1965-06-18 CH CH1030967A patent/CH450632A/fr unknown
  • 1965-06-18 CH CH853565A patent/CH455151A/fr unknown
  • 1965-06-21 GB GB26190/65A patent/GB1095838A/en not_active Expired
  • 1965-06-21 NL NL6507942A patent/NL6507942A/xx unknown

Patent Citations (2)

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