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
  • A61K8/8141—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
• • 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
  • C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
• • 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
  • C08F22/00—Homopolymers and 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; Salts, anhydrides, esters, amides, imides or nitriles thereof
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S424/00—Drug, bio-affecting and body treating compositions
  • Y10S424/01—Aerosol hair preparation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S424/00—Drug, bio-affecting and body treating compositions
  • Y10S424/02—Resin hair settings

Definitions

• Film forming substances used as hair fixatives or setting agents should be soluble both in water and in alcohols since preparations for hair setting are used as solutions in water-alcohol mixtures. Water solubility of the film former is desired even when a purely alcoholic preparation such as, for example, a sprayable preparation is used, in order that it can be readily removed from the hair, e.g., by shampooing.
• Substances which are to be used as film formers for sprayable hair fixatives must fulfill a number of requirements, i.e., they must be good film formers and adhere well to the hair; they must have good solubility in the lower molecular weight solvents which are usually used in such preparations, e.g., ethanol and isopropanol; they must be miscible and compatible with the various propellants used in hair sprays, e.g., polyhalogenated lower hydrocarbons; they must give a glossy and clear film which is sufficiently flexible to hold the hair in place permanently despite the usual movements of the head or in wind, on the other hand, the film must be sufficiently brittle so the hair can be readily combed and brushed without collapsing and loss of the hair set through complete removal of the film coating; they must give a film which is soluble in cold water but which does not become sticky in moist atmospheres and, finally, they must be physiologically inoffensive.
• a polymer which is to be used as a hair fixative in the form of an aerosol preparation must thus, on the one hand, be water soluble or at least capable of swelling therein and therefore be removable by the usual shampoos, while, on the other hand, it must, at least in combination with organic solvents, be soluble in the liquid propellant medium.
• the solution of the polymer when sprayed on the hair should dry out to a glossy and clear film which is flexible and the film should adhere well to the hair in order to achieve a long-lasting action of the hair fixative.
• the polymers hitherto used as film formers in hair dressing agents have numerous disadvantages. Many have the desired solubility properties but, as a consequence of high hygroscopicity, give the hair a sticky feel at high humidities. Other polymers have good hygroscopicity, but exhibit unsatisfactory solvent properties particularly being difficulty soluble in the alcohol-propellant mixtures generally used for hair sprays. Some polymers, however, have good hygroscopicity and are sufficiently soluble in the alcoholpropellant mixtures, but are not sufficiently water-soluble and therefore are difficult to wash out of the hair. Other polymers do not adhere to the hair well with the result that the hair to which it is applied sticks together and the individual hairs are not set-so that when the hair is combed, it loses its set and collapses.
• component (a) essentially vinyl esters with up to seven carbon atoms, it is to be understood that part of said component (a) can have a higher molecular structure. It has been found that said component (a) may contain up to 25 percent of vinyl esters derived from acids with up to 18 carbon atoms.
• esters defined by component (b) are those of a,B-unsaturated monoand dicarboxylic acids, e.g., acrylic acid monoethyleneglycol ester, methacrylic acid monoethyleneglycol ester, crotonic acid monoethyleneglycol ester, crotonic acid monopropyleneglycol ester, maleic acid ght of an a,B-unacid ble for use as component (c) are acrylic ,acid,
• methacrylic acid a-chloroacrylic acid, maleic acid, fumaric acid, crotonic acid and the like.
• Particularl suitable is'crotonic acid B-methacrylic acid.
• copolymers of vinyl acetate and/or vinyl propionate, fl-methacrylic acid B-hydroxyethyl ester and B-methacrylic acid are especially preferred.
• the amounts by weight of the components of the copolymerizates are governed by the desired properties of the end products.
• component'(a) e.g., a vinyl esteror of a vinyl ester mixture whose composition is determined by the desired consistency of the end product
• component (b) e.g., a monoester of a substituted or unsubstituted aliphatic, olefinically unsaturated mon'oor .dicarboxylicacid and about Oto l0 parts'by weightof component (c), e.g.,an nip-unsaturated carboxylicacid, are used per 100 parts by weight of component mixture.
• the copolymerization reaction is carried out in the absence of oxygen in stirring vessels fitted with reflux condensers. In this process all components of the monomer mixture can either be added to the oxygen- I free solvent simultaneously with the initiators, or alternatively individual components of the monomer'mixture, mixed with'a portion of the initiators can be added during the reaction.
• the polymerization is generally initiated by heating the contents of the flask at reflux' cordance with the invention as component (b) can be made by conventional means, e.g., byrreaction of the appropriate carboxylic acids with ethylene oxide or simple alkyl derivatives thereof.
• copolymers produced by theiprocess-of thisin- I vention are suitable for use. infhair sprays used to retain hair set without encountering ,theproblems of -solubility, consistency and elasticity mentioned previously. These copolymers can also be prepared for usein combination with water miscible solvents and can'be 1 soluble in liquefied polyha logenated hydrocarbons which are gaseousat normal'temperature and pressure. P
• the hair fixative in accordance with the invention not only fulfills the conditions necessary for an aerosol preparation, especially, good adhesion to the hair, but also inhibits the formation of scale. on the comb and hair.
• the pressure of structural elements derived from carboxylic acids which are alkylated at the unsaturated C-atom causes an increase in the hardness of the end product.
• the expert is thus enabled to adjust the consistency and elasticity of the end product by suitable composition of the amounts of the components (a) and (b).
• the content of the components (a), (b) and (c) of the copolymers used can also be modified to achieve the desired water solubility of the film former.
• copolymers with increasing content of component (a) display increasing solubility in organic solvents and, decreasing solubility in water and vice versa.
• the water solubility depends primarily on the content of component (c) and only secondarily on the content of the component (b).
• the ethanol solubility of the copolymers depend primarily on the content of component (b).
• component (a) Per 100 parts by weight of the monomer mixture, there are generally used as component (a) 90 to 40 parts by weight (preferably 80 to 60 parts by weight) of a vinyl ester or of a vinyl ester mixture whose composition is determined by the desired elasticity and consistency of the end product, and as component (b) 10 to 60 parts by weight (preferably 20 to 40 parts by weight) of an ester of an aliphatic mfl'unsaturated dicarboxylic acid with a lower aikanediol, or of a mixture of an ester of an aliphatic oz,fl-unsaturated monocarboxylic acid with a lower alkanediol and as component (c) 0 to 10 parts by weight of an cap-unsaturated carboxylic acid whose proportion is governed by the amount of neutralizable carboxyl groups in the end product necessary for the achievement of the desired water solubility.
• component (c) 0 to 10 parts by weight of an cap-unsaturated carb
• the molecular weight influences the properties of the copolymers with a view to their technical usefulness. It has proved advantageous to use copolymers with low molecular weight, the limiting viscosity number of which ranges between about 0.08 and 0.30 dl/g copolymers of such kind can easily be prepared by using regulators such as buturaldehyde 0r mercaptans in the preparation of the copolymer.
• the copolymers generally in the form of powders are conveniently dissolved in 5 to 15 parts by weight of a water-soluble solvent advantageously ethyl or isopropyl alcohol, with the addition of another organic solvent such as methylene chloride, if required.
• a water-soluble solvent advantageously ethyl or isopropyl alcohol
• another organic solvent such as methylene chloride
• the resulting clear solution is neutralized by the addition of a base, preferably a higher-boiling alkanolamine.
• Additives which are usual in cosmetics, e.g., softeners, perfume essences, dyes, brightening agents and other hair dressing agents are then incorporated into the solution.
• the solutions conveniently contain not more than 9 to 12 percent of polymer, preferably about 10 percent.
• the commercially available polyhalogenated hydrocarbon propellants e.g., trichlorofluoromethane, dichlorodifluoromethane and sym. tetrafluoroethane are suitable.
• suitable propellants e.g., propane, butane, carbonic acid, vinyl chloride and the like can also be used. Mixtures of these propellants can be used to achieve desired propellant power.
• EXAMPLE 1 A mixture of 87 parts of vinyl acetate, 10 partsof crotonic acid fl-hydroxyethyl ester, 3 parts of crotonic acid, 10 parts of butyraldehyde and 400 parts of water containing 1.4 parts of sodium bicarbonate is heated to 67 in a stirring flask under nitrogen. A mixture of 1.3 parts of dibenzoyl peroxide and 1.8 parts of potassium peroxydisulphate is then added and, during a time period of 4% hours, the bath temperature is increased to After brief introduction of steam, the resin is precipitated by addition of 5 parts 2-N hydrochloric acid, isolated, and dried in vacuum. The product obtained is a yellowish brittle resin, whose limiting viscosity number in acetone, 25, is 0.1 dl./g and its acid number is 21.5.
• EXAMPLE 3 A mixture of 65.5 parts of vinyl acetate, 29.5 parts of crotonic acid fl-hydroxyethyl ester, 5 parts of crotonic acid, 10 parts of butyraldehyde and 400 parts of water containing 2.4 parts of sodium bicarbonate is heated to 67 in a stirring flask under nitrogen. A mixture of 3.9 parts of potassium peroxydisulphate and 1.5 parts of dibenzoyl peroxide is then added and, within a time period of 7 hours, the bath temperature is increased to 95. After brief introduction of compressed air, the resin is precipitated in a separate flask by addition of 15 parts of 2-N hydrochloric acid, isolated, and dried in vacuum. The end product is a yellowish, brittle resin whose limiting viscosity number in acetone, 25 is 0.08 dl./g and its acid number is 29.3.
• EXAMPLE 4 A mixture of 72 parts of vinyl acetate, 5 parts of vinyl propionate, parts of crotonic acid B-hydroxyethel ester, 3 parts of crotonic acid, 10 parts of butyraldehyde and 400 parts of water containing 1.4 parts of sodium bicarbonate is heated to 67 in a stirring flask under nitrogen. A mixture of 2.9 parts of potassium peroxydisulphate and 1.3 parts of dibenzoyl peroxide is then added and, within a time period of 6 hours, the bath temperature is increased to 95. After brief introduction of steam, the resin is precipitated by addition of 15 parts of 2-N hydrochloric acid, isolated, and dried in vacuum. The end product is a yellowish, brittle resin whose limiting viscosity numberin acetone, is 0.09 dl./g and its acid number is 37.8.
• the resin is precipitated by addition of 15 parts of 2-N hydrochloric acid, isolated, and dried in vacuum; the product obtained is a colorless, viscous/hard resin whose limiting viscosity number in acetone, 25 is 0.28 dlJg and its acid number is 35.8.
• EXAMPLE 6 I parts of sodium bicarbonate is heated to 68 in a stirring flask under nitrogen. A mixture of 3 parts of potassium peroxydisulphate and 1.2 parts of dibenzoylperoxide is then added and, within a time period of 4.6 hours, the bath temperature is increased to 95. After brief introduction of steam, the resin is isolated by addition of 1.5 parts of 2-N hydrochloric acid and dried in vacuum. The product obtained is a yellowish, viscous/hard resin whose limiting viscosity number in acetone, 25 is 0.09 dl./g and its acid number is 52.8.
• EXAMPLE 7 A mixture of parts of vinyl acetate, 30 parts of acrylic acid B-hydroxyethyl ester, 670 parts of methyl ethyl ketone and 170 parts of water is heated at in a stirring flask under nitrogen in a heating bath, then a mixture of 1.8 parts of potassium peroxydisulphate is added and the mixture is polymerized for 20 hours. The polymer is precipitated from the resulting clear solution by addition of acetone, isolated, and dried in vacuum. The end product is a colorless, soft resin whose limiting viscosity number in water, 25 is 0.1 dl./g.
• EXAMPLE 8 A mixture of 87 parts of vinyl acetate, 13 parts of maleic acid mono-B-hydroxyethyl ester, 0.6 parts of dioctyl sodium sulphosuccinate and 200 parts of water containing 3.2 parts of sodium bicarbonate is heated to 68 in a stirring flask under nitrogen. A mixture of 1.3 parts of dibenzoyl peroxide and 1.4 parts of potassium peroxydisulphate is added and, within 1.3 hours, the temperature is raised to After brief introduction of steam, the resin is then precipitated by addition of 15 parts of 2-N hydrochloric acid, isolated and dried in vacuum. The product obtained is a v colorless, viscous/hard, odorless resin whose limiting viscosity number in acetone, 25? is 0.5 dl./g.
• EXAMPLE 9 One Part of the product of Example 1 is dissolved in 9 parts of absolute ethanol and neutralized by addition of 0.04 parts of diethanolamine. 0.01 parts of a silicone oil and 0.05 parts of perfume oil are thereupon added, and the mixture is filled into aerosol pressure vessels.
• EXAMPLE 12 One part of the product of Example 4 is dissolved in 9 parts of absolute ethanol and neutralized by addition of 0.04 parts of diethanolamine. 0.01 parts of a silicone oil and 0.05 parts of perfume oil are thereupon added. The mixture is then tilled into aerosol pressure vessels to which 18 parts of fluorotrichloromethane and 12 parts of difluorodichloromethane are then added under pressure. A sprayable hair fixative is thus obtained which binds the hair well and is capable of being combed without the formation of scale on comb and hair. The resin can be completely removed from the hair by simple shampooing, and is resistant to moist atmospheres.
• EXAMPLE 13 0.8 parts of the product of Example is dissolved in 9 parts of absolute ethanol and neutralized by addition of 0.1 1 parts of diethanolamine. 0.01 parts of a silicone oil and 0.05 parts of perfume oil are thereupon added. The mixture is then filled into aerosol pressure vessels to which 18 parts of fluorotrichloromethane and 12 parts of clifluorodiehloromethane are then added under pressure. l-lair sprayed with the hair fixative obtained is solidly bound, exhibits a fine gloss and low susceptibility to electrostatic charge. It can be rapidly and completely removed from the hair by a simple shampoo, and is resistant to moist atmospheres.
• EXAMPLE 16 A mixture of 52 parts of vinyl acetate, 20 parts of vinyl propionate, 8 parts of crotonic acid, 20 parts of crotonic acid B-hydroxyethyl ester and 20-parts of methyl ethyl ketone is heated at 75 in a stirring flask under pure nitrogen, then a mixture of 1 part of dibenzoyl peroxide and 1.7 parts of dilauroyl peroxide is added and the mixture is polymerized for 16-20 hours at 80-85.
• the clear solution obtained is mixed with 95 parts of acetone and the polymer precipitated in 350-420 parts of a petroleum ether diisopropyl ether mixture (123,3 volumes), isolated and dried in vacuo.
• the end product is a colorless and odorless brittle resin whose limiting viscosity number in acetone, 25 is 0.1 dl/g and its acid number is 58.6.
• EXAMPLE 17 One part of the resin obtained in Example 16 is dissolved in 9 parts of absolute ethanol and neutralized by addition of 0.11 part of diethanolamine. 0.01 part of a silicone oiland 0.05 part of perfume oil are then added,
• the resin is completely removable therefrom.
• a colorless brittle resin is obtained, whose limiting viscosity number in acetone, 25 is 0.1 dl/g and its acid number is 56.6.
• R is selected from the group consisting of hydrogen and carboxyl; R and R each are selected from the group consisting of hydrogen, halogen and lower alkyl containing up to four carbon atoms; about 1 to about 4 parts by weight of a propellant.

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• Chemical Kinetics & Catalysis (AREA)
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Cited By (13)

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Citations (4)

• 1966
  • 1966-07-29 CH CH1101466A patent/CH478569A/de not_active IP Right Cessation
• 1967
  • 1967-07-12 FR FR1553721D patent/FR1553721A/fr not_active Expired
  • 1967-07-21 GB GB33728/67A patent/GB1160477A/en not_active Expired
  • 1967-07-25 GR GR670136785A patent/GR36785B/el unknown
  • 1967-07-27 BE BE701894D patent/BE701894A/xx unknown
  • 1967-07-28 ES ES343514A patent/ES343514A1/es not_active Expired
  • 1967-07-28 NL NL6710488A patent/NL6710488A/xx unknown
• 1970
  • 1970-02-27 US US00015258A patent/US3723616A/en not_active Expired - Lifetime

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