WO1993006816A1 - Fixateurs polymeres des cheveux - Google Patents

Fixateurs polymeres des cheveux Download PDF

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Publication number
WO1993006816A1
WO1993006816A1 PCT/US1992/007012 US9207012W WO9306816A1 WO 1993006816 A1 WO1993006816 A1 WO 1993006816A1 US 9207012 W US9207012 W US 9207012W WO 9306816 A1 WO9306816 A1 WO 9306816A1
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WO
WIPO (PCT)
Prior art keywords
vinyl
weight
water
solution
polymer
Prior art date
Application number
PCT/US1992/007012
Other languages
English (en)
Inventor
Stephen L. Kopolow
Mohammed Tazi
Edward W. Walls, Jr.
Yoon Tae Kwak
Jeffrey M. Cohen
Original Assignee
Isp Investments Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/773,795 external-priority patent/US5182098A/en
Priority claimed from US07/796,998 external-priority patent/US5221531A/en
Priority claimed from US07/820,173 external-priority patent/US5185143A/en
Application filed by Isp Investments Inc. filed Critical Isp Investments Inc.
Publication of WO1993006816A1 publication Critical patent/WO1993006816A1/fr

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Classifications

    • 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)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/046—Aerosols; Foams
    • 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

Definitions

  • the present invention relates to hair fixatives: (1) a terpolymer hair fixative comprising vinyl
  • caprolactam vinyl pyrrolidone and methacryloamidopropyl trimethylammonium chloride
  • vinyl caprolactam vinyl pyrrolidone, dimethylaminoethyl methacrylate and acrylic acid
  • vinyl caprolactam vinyl pyrrolidone and vinyl acetate
  • the terpolymer hair fixatives of the present invention suitably comprise about 5-70%, preferably 10 to 30%, by weight of vinyl caprolactam, about 25-90%, preferably 35 to 70%, by weight of vinyl pyrrolidone and about 5-20%, preferably 10 to 15%, by weight of methylacryloamidopropyl
  • terpolymers are conveniently prepared in aqueous solution by subjecting the above monomers, either in admixture or while being added sequentially into a reactor, to a temperature of about 40° to 120°C.,
  • catalysts include organic and inorganic peroxides, e.g. hydrogen peroxide, Lupersol 11, or an azo compound, e.g. azobisisobutyronitrile,
  • Another embodiment provides a polymer hair fixative comprising 5-80% vinyl caprolactam (VCL), 25-90% vinyl pyrrolidone (VP), 2-15% dimethylaminoethyl
  • DMAEMA methacrylate
  • AA acrylic acid
  • the polymer hair fixatives (2) comprises about 5-80%, preferably 10 to 70%, by weight of vinyl caprolactam, about 25-90%, preferably 35 to 80%, by weight of vinyl pyrrolidone, about 2-15%, preferably 3 to 10%, by weight of dimethylaminoethyl methacrylate and
  • the polymerization may be a run in 100% water solvent, or in mixtures of water and alcohol, e.g.
  • polystyrene resin to provide polymer have specific viscosities of about 0.2-5, preferably about 0.5-2, and most preferably about 1.0.
  • specific viscosity of the polymer obtained is about 1.5 to 3.5, whereas in water-alcohol mixtures, the specific viscosities produced were about 0.3-1.5, generally about 0.4-1.2.
  • reaction product in water-alcohol mixtures, can be stripped of alcohol to provide an all water
  • the polymerization is run at a solids contents (of monomers) of about 10-40%, preferably 15-30%, and most preferably about 20%.
  • the residual VP content of the product is less than 0.1%, preferably less than 0.05% and most preferably 0%.
  • the terpolymer hair fixatives can suitably comprise about 5-70% by weight of vinyl caprolactam, about 20-80% by weight of vinyl pyrrolidone and about 5-50% by weight of vinyl acetate.
  • Terpolymers comprising 5-30%, preferably 10-20%, VCL; 50-85%, preferably 70-80% VP; and 5-20%, preferably 10-15% VA, usually are prepared in aqueous or
  • aqueuous-alcoholic solution whereas terpolymers comprising 10-70%, preferably 30-60%, VCL; 20-80%, preferably 20-50%, VP; and 5-50%, preferably 10-30%, VA usually are prepared in alcoholic solution.
  • the relative viscosity of the terpolymers produced in 100% water generally is in the range of about 2.5 to 4.8.
  • the terpolymers can be prepared in a mixture of water and an alcohol, i.e. isopropanol.
  • the preferred all-water product can be obtained by stripping the alcohol and replacing it with water.
  • the relative viscosity of the terpolymer decreases as the ratio of alcohol-to-water increases.
  • the terpolymers also can be made in an
  • the terpolymer product is a random or alternating structure comprising essentially maleic
  • a typical terpolymer composition comprises the monomers, respectively, in a molar ratio of about 0.35-1:1:0,05-0.25, preferably 0.6-0.8:1:0.08-0.12, and, most preferably, 0.75:1:0.1, which are prepared by a solution polymerization process.
  • the process comprises adding the monomers, individually or premixed, preferably in the above
  • acetone solvent for both the monomers and the terpolymer, wherein they are polymerized in the presence of a free radical initiator under conditions of agitation at a temperature of between about 40° and about 90°C., preferably between about 50° and about 70oC.
  • the initiator can be added to the monomer mixture before or after the monomers have been charged into the solution medium.
  • the reaction is carried out under an inert atmosphere which can be maintained by purging with nitrogen to eliminate air and oxygen.
  • the polymerization reaction is carried under constant agitation over a period of from about 4 to 24 hours, although usually about 4 to 12 hours is sufficient to complete the reaction and form the terpolymer product.
  • the terpolymer product which is in the form of the free maleic acid product, can be esterified
  • the terpolymer is esterified with a C 4 -C 5 alkanol, such as butanol or
  • the terpolymer can be
  • the solution in the kettle then was purged with nitrogen for 30 minutes with the dip tube was positioned at the bottom of the reactor. The nitrogen flow was continued and the dip tube was raised above the solution.
  • the solution then was heated to 65°C. and a feed of VP/MAPTAC* monomers was pumped into the kettle at a rate such that the feed was completed in 2 hours. The start of addition of the feed was considered to be time zero.
  • a first initiator charge of Lupersol 11 was added at time 10 minutes, a second shot of the same amount at 60 minutes, and the remaining third at the completion of the monomer feed. The total addition took approximately 120 minutes whereafter 0.8 g. of initiator had been added. The reaction mixture then was held at 65°C. for an
  • reaction mixture was maintained at 90°C. for 8 hours, cooled and discharged.
  • MAPTAC is available from The Virginia Carolina Chemicals Company as methacrylamidopropyl trimethylammonium chloride
  • containing three weight levels of MAPTAC were prepared, namely, 5%, 10%, and 15% by weight.
  • the VCL/VP ratio in the terpolymer was varied, the VCL content increasing from 5 to 20% by weight.
  • the pH of the aqueous solution ranged from 3.95 to 4.81, the relative viscosity was 2.01 to 2.51, and the % VP residual was essentially zero.
  • the pH for the series with 10% MAPTAC was 4.2 to 5.2, the relative viscosity was 3.56-4.31, and the % VP residual also was essentially zero.
  • the pH range was 4.3 to 5.7; the relative viscosity was 3.24 to 5.98; residual VP again was absent from the
  • VCL/VP/MAPTAC suitably comprises about 2 to 10%, preferably 3 to 6%, by weight of the terpolymer, about 10 to 60%, preferably 15 to 50%, by weight of water, about 20 to 40%, preferably 30 to 35%, by weight of dimethylether, and 0 to 15%, preferably 0 to 10%, by weight of ethanol.
  • Such compositions are one-phase systems, can be made directly from the terpolymer solutions prepared by the aqueous solution process, meet VOC standards, and exhibit excellent performance characteristics in use as a hair spray.
  • the formulation was tested in the conventional manner for hold (curl retention at 90% RH and 80°F.) showed 85% average % curl retention after 90 minutes of treatment.
  • Terpolymer solution (Exs. 2, 3 or 4) 10 g.
  • compositions showed a 70% curl retention after 90 minutes.
  • the solution in the kettle then was purged with nitrogen for 30 minutes with the dip tube was positioned at the bottom of the reactor. The nitrogen flow was continued and the dip tube was raised above the solution.
  • the solution then was heated to 65°C. and a feed of VP/DMAEMA monomers and sodium acrylate were pumped into the kettle at a rate such that the feeds were completed in 2 hours. The start of addition of the feed was considered to be time zero.
  • a first initiator charge of Lupersol 11 was added at time 10 minutes, a second shot of the same amount at 60 minutes, and the remaining third at the completion of the monomer feed. The total addition took approximately 120 minutes whereafter 0.8 g. of initiator had been added.
  • the reaction mixture then was held at 65°C. for an additional 3 hours, heated to 90°C. and 1 g. of t-butyl peroctoate (Triganox 21) was added as an additional initiator.
  • the reaction mixture was
  • VCL/VP/DMAEMA/AA polymers produced according to this general method are summarized in Table III below.
  • VCL/VP/DMAEMA/AA suitably comprises about 2 to 10%
  • compositions are one-phase systems, can be made directly from the polymer solutions prepared by the aqueous solution process, meet VOC standards, and exhibit excellent
  • the formulation was tested in the conventional manner for hold (curl retention at 90% RH and 80°F.) showed 85% average % curl retention after 90 minutes of treatment.
  • a one-liter glass resin kettle, fitted with an anchor agitator, a temperature controller, a nitrogen inlet, a monomer feed tube, a reflux condenser, and a vacuum take-off was charged with VCL and solvent, i.e.
  • the solution in the kettle then was purged with nitrogen for 30 minutes with the dip tube was positioned at the bottom of the reactor. The nitrogen flow was continued and the dip tube was raised above the solution.
  • the solution then was heated to 65°C. and a feed of VP/VA monomers was pumped into the kettle at a rate such that the feed was completed in 2 hours. The start of addition of the feed was considered to be time zero.
  • a first initiator charge of Lupersol 11 was added at time 10 minutes, a second shot of the same amount at 60 minutes, and the remaining third at the completion of the monomer feed. The total addition took approximately 120 minutes whereafter 0.8 g. of initiator had been added.
  • reaction mixture then was held at 65°C. for 18 hours. The reaction mixture was then cooled and discharged.
  • VCL/VP/VA terpolymers produced by the processes are given in Table V below.
  • the one-phase water-based hair spray compositions of the invention containing the terpolymer hair fixative of VCL/VP/VA terpolymers suitably comprises about 2 to 10%, preferably 3 to 6%, by weight of the terpolymer, about 10 to 60%, preferably 15 to 50%, by weight of water, about 20 to 40%, preferably 30 to 35%, by weight of dimethylether, and 0 to 15%, preferably 0 to 10%, by weight of ethanol.
  • the formulation was tested in the conventional manner for hold (curl retention at 90% RH and 80oF.) showed 85% average % curl retention after 90 minutes of treatment.
  • compositions showed a 70% curl retention after 90 minutes.
  • the vinyl acetate reactant may be substituted by other vinyl ester monomers.
  • vinyl ester monomeric components are those
  • the isobornyl acrylate reactant may be substituted other acrylate or methacrylate esters, of which suitably acrylate and/or methacrylate esters of isoborneol,
  • exonorborneol and endo-norborneol are preferred, and the isobornyl ester is the most preferred.
  • the preferred bicycl compounds are those having a hydrocarbon bridge and are generally defined by the formula
  • each of R, R 1, R 2 and R 3 is hydrogen or methyl.
  • the terpolymeric resins thus prepared by solution polymerization are employed as the active ingredient in a non-aerosol pump hair spray formulation and employed in a cosmetic product fitted with a suitable nozzle pump valve.
  • the present resins are employed in concentrations between about 6 to 20% solids, preferably 8 to 15% solids.
  • Such cosmetic products can be used over an extended period of time to generate fine spray mists without experiencing any nozzle clogging.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention se rapporte aux fixateurs des cheveux: un fixateur terpolymère des cheveux se compose de (1) capro-lactame de vinyle, pyrrolidone de vinyle et chlorure méthacryloamidopropyle triméthylammonium; ou (2) de capro-lactame de vinyle, pyrrolidone de vinyle, méthacrylate diméthylaminoéthyle et acide acrylique; (3) de capro-lactame de vinyle, pyrrolidone de vinyle et acétate de vinyle; et (4) l'invention se rapporte également à un procédé de fabrication d'un mélange monomère d'anhydride maléique, d'acétate de vinyle et d'acrylate ou de méthacrylate isobornyle.
PCT/US1992/007012 1991-10-09 1992-08-24 Fixateurs polymeres des cheveux WO1993006816A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US07/773,795 US5182098A (en) 1991-10-09 1991-10-09 Terpolymer hair fixatives, aqueous solution process for making same and water-based hair spray formulations which meet VOC standards
US773,795 1991-10-09
US79699791A 1991-11-25 1991-11-25
US796,998 1991-11-25
US796,997 1991-11-25
US07/796,998 US5221531A (en) 1991-11-25 1991-11-25 Polymer hair fixatives, aqueous-based solution process for making same and water-based hair spray formulations therewith which meet VOC standards
US820,173 1992-01-13
US07/820,173 US5185143A (en) 1992-01-13 1992-01-13 Terpolymer hair fixative resins prepared by solution polymerization of maleic anhydride, vinyl acetate and isobornyl acrylate

Publications (1)

Publication Number Publication Date
WO1993006816A1 true WO1993006816A1 (fr) 1993-04-15

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AU (1) AU2495892A (fr)
WO (1) WO1993006816A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0638306A1 (fr) * 1993-07-09 1995-02-15 National Starch and Chemical Investment Holding Corporation Polymères fixateurs capillaires à bas poids moléculaire dans des compositions à faible teneur en composés organiques volatils
US6645478B2 (en) 2001-06-22 2003-11-11 L'oreal S.A. Reshapable hair styling composition comprising (meth)acrylic copolymers of four or more monomers
US6667378B2 (en) 2001-06-22 2003-12-23 L'oreal, S.A. Reshapable hair styling composition comprising heterogeneous (meth)acrylic copolymer particles
US6689346B1 (en) 2000-10-25 2004-02-10 L'oreal Reshapable hair styling composition comprising acrylic copolymers
EP2914239A4 (fr) * 2012-11-05 2016-06-01 Hercules Inc Composition comprenant un polymère de conditionnement et/ou de coiffage
WO2023123550A1 (fr) * 2021-12-30 2023-07-06 清华大学深圳国际研究生院 Procédé de préparation d'un terpolymère et son utilisation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4057533A (en) * 1972-07-03 1977-11-08 Gaf Corporation Process for preparation of quaternized cationic vinyllactam-acrylamide copolymers
US4521404A (en) * 1981-08-13 1985-06-04 Gaf Corporation Polymeric hair preparation
US4923694A (en) * 1988-08-25 1990-05-08 Gaf Chemicals Corporation Hydrolysis resistant vinyl lactam amino acrylamide polymers
US5073296A (en) * 1990-04-17 1991-12-17 Isp Investments Inc. Preparation of discrete microdroplets of an oil in water

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4057533A (en) * 1972-07-03 1977-11-08 Gaf Corporation Process for preparation of quaternized cationic vinyllactam-acrylamide copolymers
US4521404A (en) * 1981-08-13 1985-06-04 Gaf Corporation Polymeric hair preparation
US4923694A (en) * 1988-08-25 1990-05-08 Gaf Chemicals Corporation Hydrolysis resistant vinyl lactam amino acrylamide polymers
US5073296A (en) * 1990-04-17 1991-12-17 Isp Investments Inc. Preparation of discrete microdroplets of an oil in water

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0638306A1 (fr) * 1993-07-09 1995-02-15 National Starch and Chemical Investment Holding Corporation Polymères fixateurs capillaires à bas poids moléculaire dans des compositions à faible teneur en composés organiques volatils
US6689346B1 (en) 2000-10-25 2004-02-10 L'oreal Reshapable hair styling composition comprising acrylic copolymers
US6645478B2 (en) 2001-06-22 2003-11-11 L'oreal S.A. Reshapable hair styling composition comprising (meth)acrylic copolymers of four or more monomers
US6667378B2 (en) 2001-06-22 2003-12-23 L'oreal, S.A. Reshapable hair styling composition comprising heterogeneous (meth)acrylic copolymer particles
US7048916B2 (en) 2001-06-22 2006-05-23 L'oreal S.A. Reshapable hair styling composition comprising heterogeneous (meth)acrylic copolymer particles
US7122175B2 (en) 2001-06-22 2006-10-17 L'oreal S.A. Reshapable hair styling composition comprising (meth)acrylic copolymers of four or more monomers
EP2914239A4 (fr) * 2012-11-05 2016-06-01 Hercules Inc Composition comprenant un polymère de conditionnement et/ou de coiffage
WO2023123550A1 (fr) * 2021-12-30 2023-07-06 清华大学深圳国际研究生院 Procédé de préparation d'un terpolymère et son utilisation

Also Published As

Publication number Publication date
AU2495892A (en) 1993-05-03

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