CA2040963A1 - Hair setting composition - Google Patents
Hair setting compositionInfo
- Publication number
- CA2040963A1 CA2040963A1 CA002040963A CA2040963A CA2040963A1 CA 2040963 A1 CA2040963 A1 CA 2040963A1 CA 002040963 A CA002040963 A CA 002040963A CA 2040963 A CA2040963 A CA 2040963A CA 2040963 A1 CA2040963 A1 CA 2040963A1
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- Canada
- Prior art keywords
- weight
- monomer
- parts
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- vinylcaprolactam
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
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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
- A61K8/817—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
-
- 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
- C08F26/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
O.Z. 0050/41581 Abstract of the Disclosure: The hair setting compositions contain as film former a polymer based on N-vinylcapro-lactam formed from group I
- from 35 to 100 % by weight of N-vinylcaprolactam (monomer A) - from 0 to 65 % by weight of N-vinylimidazole (mono-mer B) or a mixture of from 5 to 50 parts by weight of monomer B and from 10 to 60 parts by weight of N-vinylpyrrolidone (monomer C) or a mixture of from 5 to 15 parts by weight of monomer B and from 10 to 35 parts by weight of an alkyl acrylate or methacry-late having from 1 to 4 carbon atoms in the alkyl moiety (monomer D) - from 0 to 4 % by weight of further monomer E capable of free radical copolymerization or group II
- from 35 to 100 % by weight of monomer A
- from 0 to 65 % by weight of a mixture of from 20 to 60 parts by weight of monomer D and from 5 to 15 parts by weight of acrylic or methacrylic acid (monomer F) or of a mixture of from 15 to 50 parts by weight of monomer D and from 5 to 15 parts by weight of an alkyl acrylate or methacrylate having from 1 to 4 carbon atoms in the alkyl moiety which additionally carries unsubstituted or C1-C4-alkyl-substituted amino (monomer G) - from 0 to 4 % by weight of further monomer E capable of free radical copolymerization, any carboxyl groups of the polymer having been partly or wholly neutralized with an amine, as well as customary ingredients for this purpose.
- from 35 to 100 % by weight of N-vinylcaprolactam (monomer A) - from 0 to 65 % by weight of N-vinylimidazole (mono-mer B) or a mixture of from 5 to 50 parts by weight of monomer B and from 10 to 60 parts by weight of N-vinylpyrrolidone (monomer C) or a mixture of from 5 to 15 parts by weight of monomer B and from 10 to 35 parts by weight of an alkyl acrylate or methacry-late having from 1 to 4 carbon atoms in the alkyl moiety (monomer D) - from 0 to 4 % by weight of further monomer E capable of free radical copolymerization or group II
- from 35 to 100 % by weight of monomer A
- from 0 to 65 % by weight of a mixture of from 20 to 60 parts by weight of monomer D and from 5 to 15 parts by weight of acrylic or methacrylic acid (monomer F) or of a mixture of from 15 to 50 parts by weight of monomer D and from 5 to 15 parts by weight of an alkyl acrylate or methacrylate having from 1 to 4 carbon atoms in the alkyl moiety which additionally carries unsubstituted or C1-C4-alkyl-substituted amino (monomer G) - from 0 to 4 % by weight of further monomer E capable of free radical copolymerization, any carboxyl groups of the polymer having been partly or wholly neutralized with an amine, as well as customary ingredients for this purpose.
Description
--- 2 ~ 6 ~
O.Z. 0050/41581 Hair settina composition The present invention relates to hair setting compositions which, besides the ingredients customary for this purpose, contain as film former polymars based on N-vinylcaprolactam formed from group I
- from 35 to 100 % by weight of N-vinylcaprolactam (monomer A) - from 0 to 65 % by weight of N-vinylimidazole (mono-mer B) or a mixture of from 5 to 50 parts by weight of monomer B and from 10 to 60 parts by weight of N-vinylpyrrolidone (monomer C) or a mixture of from 5 to 15 parts by weight of monomer B and from 10 to 35 parts by weight of an alkyl acrylate or methacr~-late having from 1 to 4 carbon atoms in the alkyl moiety (monomer D) - from 0 to 4 % by weight of further monomer E capable of free radical copolymerization or group II
20 - from 35 to lO0 % by weight of monomer A
- from 0 to 65 % by weight of a mixture of from 20 to 60 parts by weight of monomer D and from 5 to 15 parts by weight of acrylic or methacrylic acid (monomer F) or of a mi~ture of from 15 to 50 partq by weight of monomer D and from 5 to 15 parts by weight of an alkyl acrylate or methacrylate having from 1 to 4 carbon atoms i~ the alkyl moiety which additionally carries unsubstituted or Cl-C4-alkyl-substituted amino (monomer G) 30 ~ from 0 to 4 ~ by weight of further monomer E capable of free radical copolymerization, any carboxyl groups of the polymer having been partly or wholly neutralized with an amine.
Some of the polymers are novel substances.
Therefore the present invention also relates to these novel substances.
DE-A-32 27 334 ~1) relates to copolymers of from -- 2~a~63 - 2 - O.Z. 0050/41581 20 to 75 parts by weight of a C2-C20-alkyl ester of acrylic or methacrylic acid, from 5 to 50 parts by weight of a nitrogen-containing neutral water-soluble monomer, for example N-vinylcaprolactam or N-vinylpyrrolidone, from 1 to 25 parts by weight of a monomer which contains cationic groups, for example N-vinylimidazole, and from 1 to 25 parts by weight of a copolymerizable, olefinic-ally unsaturated C3-C5-carboxylic acid, for example acrylic acid or methacrylic acid. The copolymers are used as film formers in hair treatment compositions.
EP-B-074 191 (2) relates to a conditioning composition containing a terpolymer of a relatively large proportion of N-vinylcaprolactam, a relatively small proportion of N-vinylpyrrolidone and an ammonium deriva-tive monomer, for example a dialkylaminoalkyl acrylate.
US-A-3 145 147 (3) relates to a film-forming composition comprising a copolymer of from 80 to 95 % by weight of N-vinylcaprolactam and from 5 to 20 % by weight of a polymerizable monomer, namely a vinyl ester of from 3 to 6 carbon atoms, an alkyl acrylate of 4 or 5 carbon atoms or an acrylamide, acrylonitrile or alkyl vinyl ether each of 3 to 4 carbon atoms.
DE-C-12 61 822 (4) describes copolymers of N-vinylcaprolactam with, for example, N-vinylimidazole or with N-vinylimidazole and N-vinylpyrrolidone. The copoly-mers are used as agent4 for reducing pigment migration in the dyeing of fiber material wit]h pigment dye liquors.
DE-A-21 12 549 (5) relates to water-soluble te~rapolymers of an N-vinyllactam, for example N-vinyl-pyrrolidone or N-vinylcaprolactam, an alkyl acrylate, an alkyl methacrylate or an olefinically unsaturated carbox-ylic acid. The N-vinyllactam is preferably used in an amount of from 10 to 30 % by weight, based on the tetra-polymer. The tetrapolymers are used as film formers for surface coatings, textile sizes, adhesives, hair sprays and binders for sand grains and for manufacturing rocket sleeves.
"` 20~6~
- 3 - O.Z. 0050/41581 Hair products are increasingly sprays containing hydrocarbons instead of halogenated hydrocarbons as propellants. The prior art copolymers used as film formers in such sprays still need to be improved in some instances in respect of their compatibility ~ith the apolar hydrocarbons of the sprays; that is, the copolymers are still not sufficiently soluble in the hydrocarbons. Moreover, the hair setting effect of these copolymers usually still leaves something to be desired.
Also, the moisture uptake of hair treated with these copolymers is still frequently too high.
It is an object of the present invention to provide film formers for hair care which should be highly compatible with apolar propellants based on hydrocarbons and shoulcl also possess a good hair setting effect and a low moisture uptake.
We have found that this object is achieve~ by the hair settin~ compositions defined at the beginning.
Group I comprise~ N-vi.nylimidazole-containing polymers, group II the N-vinylim:idazole-free polymers.
For the purposes of the present invention N-vinylcaprolactam (monomer A) is ~-vinyl-~-caprolactam.
Suitable monomers D are in particular the methyl, ethyl, n-propyl, isopropyl, n-but:yl, i~obutyl, sec-butyl and tert-butyl ester~ o~ acrylic acid and of methacrylic acid. O~ these, preference is gi~en to the bu~yl esters, especially to the tert-butyl esters.
To achieve ~light modification of the properties of the pol~mer, further monomers E capable of free radical copolymerization may be present in an amount of up to 4 ~ by weight, in particular up to 3 ~ by weight.
Suitable monomers E are for example vinyl acetate, vinyl propionate and hydroxypropyl acetate.
Monomer F is acrylic acid or preferably methacry-lic acid.
Monomer G can be in particular the methyl, ethyl,n-propyl or n-butyl esters of acrylic or methacrylic acid 20~963 - 4 - O.Z. 0050~41581 which have an unsubstituted or preferably mono- or disubstituted amino group in paxticular at the end of the alkyl group. Particular preference is givento 2-(dialkyl-amino)ethyl methacrylates such as 2-(dimethylamino)ethyl and 2-(diethylamino)ethyl methacrylates.
Carboxyl groups present in the polymers are neutralized in whole or in part, advantageously up to from 5 to 100 %, preferably from 30 to 90 ~, with an amine. The amine used is preferably - a mono-, di- or trialkanolamine having from 2 to 5 carbon atoms in the alkanol moiety, which may be in etherified form, for example mono-, di- or tri-ethanolamine, mono-, di- or tri-n-propanolamine, mono-, di- or triisopropanolamine, 2-amino-2-methyl-propanol or di~2-methoxyethyl)amine, - an alkanediolamine of from 2 to 5 carbon atoms, for example 2-amino-2-methyl-1,3-propanediol or2-amino-2-ethyl-1,3-propanediol, or - a primary, secondary or tertLary alkylamine of from 5 to 10 carbon atoms in total, for example N,N-diethylpropylamine.
Partic~llarly good results are obtained on neut-ralizing with 2-amino-2-methylpropanol, triisopropanol-amine and 2-amino-~-ethyl-1,3-propanediol.
Preferred polymers have the following composi-tions:
- from 96 to 100 % by weight of N-vinylcaprolactam (monomer A) and from 0 to 4 % by weight of mono- . .-mer E;
- from 35 to 100, preferably from 50 to 90, % by weight of monomer A, from 0 to 65, preferably from lO to 50, % by weight of N-vinylimidazole (mono-mer B) and from 0 to 4 % by weight of monomer E;
- from 35 to 100, preferably from 35 to 65, % by weight of monomer A, from 0 to 65, preferably from 35 to 65, % by weight of a mixture of from 5 to 50 parts by weight of monomer B and from 10 to ' ` ' 2 0 ~
- 5 - ~.Z. 0050/41581 60 parts by weight of N-vinylpyrrolidone (monomer C) and also from 0 to 4 % by weight of monomer E;
- from 35 to 100, preferably from 50 to 85, % by weight of monomer A, from 0 to 65, preferably from 15 to 50, % by weight of a mixture of from 5 to 15 parts by weight of monomer B and from 10 to 35 parts by weigh~ of monomer D and also from 0 to 4 ~ by weight of monomer E;
- from 35 to 100, preferably 35 to 75, % by weight of monomer A, from 0 to 65, preferably from 25 to 65, ~
by weight of a mixture of from 20 to 60 parts by weight of monomer D and from 5 to 15 parts by weight of monomer F, and also from 0 to 4 % by weight of monomer E;
lS - from 35 to 100, preferably from 45 to 80, ~ by weight of monomer A, from 0 to 65, preferably from 20 to 55, % by weight of a mixture of from 15 to 50 parts by weight of monomer D and from S to 15 parts by weight of monomer G, and also from 0 to 4 % by weight o~ monomer E.
Here the monomer combinations A + B + C and in particular A + B + D, A + D + F and also A + D + G, each with or without small amounts oE E, represent particu-larly preferred embodiments.
The polymers are prepareld by free radical poly-merization or copolymerization of monomers A to G. ~he customary polymerization techniques are employed, for examplel the methods of suspension, emulsion or solution polymerization.
A particularly advantageous choice is solution polymerization in an organic solvent, in general an alcohol. The polymerization is customarily carried out at from 60 to 130C, at atmospheric pressure or under autogenous pressure.
The initiators used for the free radical polymer-ization reaction are the customary peroxo or azo compounds, for example dibenzoyl peroxide, tert-butyl ` -`= 2~0~
O.Z. 0050/41581 Hair settina composition The present invention relates to hair setting compositions which, besides the ingredients customary for this purpose, contain as film former polymars based on N-vinylcaprolactam formed from group I
- from 35 to 100 % by weight of N-vinylcaprolactam (monomer A) - from 0 to 65 % by weight of N-vinylimidazole (mono-mer B) or a mixture of from 5 to 50 parts by weight of monomer B and from 10 to 60 parts by weight of N-vinylpyrrolidone (monomer C) or a mixture of from 5 to 15 parts by weight of monomer B and from 10 to 35 parts by weight of an alkyl acrylate or methacr~-late having from 1 to 4 carbon atoms in the alkyl moiety (monomer D) - from 0 to 4 % by weight of further monomer E capable of free radical copolymerization or group II
20 - from 35 to lO0 % by weight of monomer A
- from 0 to 65 % by weight of a mixture of from 20 to 60 parts by weight of monomer D and from 5 to 15 parts by weight of acrylic or methacrylic acid (monomer F) or of a mi~ture of from 15 to 50 partq by weight of monomer D and from 5 to 15 parts by weight of an alkyl acrylate or methacrylate having from 1 to 4 carbon atoms i~ the alkyl moiety which additionally carries unsubstituted or Cl-C4-alkyl-substituted amino (monomer G) 30 ~ from 0 to 4 ~ by weight of further monomer E capable of free radical copolymerization, any carboxyl groups of the polymer having been partly or wholly neutralized with an amine.
Some of the polymers are novel substances.
Therefore the present invention also relates to these novel substances.
DE-A-32 27 334 ~1) relates to copolymers of from -- 2~a~63 - 2 - O.Z. 0050/41581 20 to 75 parts by weight of a C2-C20-alkyl ester of acrylic or methacrylic acid, from 5 to 50 parts by weight of a nitrogen-containing neutral water-soluble monomer, for example N-vinylcaprolactam or N-vinylpyrrolidone, from 1 to 25 parts by weight of a monomer which contains cationic groups, for example N-vinylimidazole, and from 1 to 25 parts by weight of a copolymerizable, olefinic-ally unsaturated C3-C5-carboxylic acid, for example acrylic acid or methacrylic acid. The copolymers are used as film formers in hair treatment compositions.
EP-B-074 191 (2) relates to a conditioning composition containing a terpolymer of a relatively large proportion of N-vinylcaprolactam, a relatively small proportion of N-vinylpyrrolidone and an ammonium deriva-tive monomer, for example a dialkylaminoalkyl acrylate.
US-A-3 145 147 (3) relates to a film-forming composition comprising a copolymer of from 80 to 95 % by weight of N-vinylcaprolactam and from 5 to 20 % by weight of a polymerizable monomer, namely a vinyl ester of from 3 to 6 carbon atoms, an alkyl acrylate of 4 or 5 carbon atoms or an acrylamide, acrylonitrile or alkyl vinyl ether each of 3 to 4 carbon atoms.
DE-C-12 61 822 (4) describes copolymers of N-vinylcaprolactam with, for example, N-vinylimidazole or with N-vinylimidazole and N-vinylpyrrolidone. The copoly-mers are used as agent4 for reducing pigment migration in the dyeing of fiber material wit]h pigment dye liquors.
DE-A-21 12 549 (5) relates to water-soluble te~rapolymers of an N-vinyllactam, for example N-vinyl-pyrrolidone or N-vinylcaprolactam, an alkyl acrylate, an alkyl methacrylate or an olefinically unsaturated carbox-ylic acid. The N-vinyllactam is preferably used in an amount of from 10 to 30 % by weight, based on the tetra-polymer. The tetrapolymers are used as film formers for surface coatings, textile sizes, adhesives, hair sprays and binders for sand grains and for manufacturing rocket sleeves.
"` 20~6~
- 3 - O.Z. 0050/41581 Hair products are increasingly sprays containing hydrocarbons instead of halogenated hydrocarbons as propellants. The prior art copolymers used as film formers in such sprays still need to be improved in some instances in respect of their compatibility ~ith the apolar hydrocarbons of the sprays; that is, the copolymers are still not sufficiently soluble in the hydrocarbons. Moreover, the hair setting effect of these copolymers usually still leaves something to be desired.
Also, the moisture uptake of hair treated with these copolymers is still frequently too high.
It is an object of the present invention to provide film formers for hair care which should be highly compatible with apolar propellants based on hydrocarbons and shoulcl also possess a good hair setting effect and a low moisture uptake.
We have found that this object is achieve~ by the hair settin~ compositions defined at the beginning.
Group I comprise~ N-vi.nylimidazole-containing polymers, group II the N-vinylim:idazole-free polymers.
For the purposes of the present invention N-vinylcaprolactam (monomer A) is ~-vinyl-~-caprolactam.
Suitable monomers D are in particular the methyl, ethyl, n-propyl, isopropyl, n-but:yl, i~obutyl, sec-butyl and tert-butyl ester~ o~ acrylic acid and of methacrylic acid. O~ these, preference is gi~en to the bu~yl esters, especially to the tert-butyl esters.
To achieve ~light modification of the properties of the pol~mer, further monomers E capable of free radical copolymerization may be present in an amount of up to 4 ~ by weight, in particular up to 3 ~ by weight.
Suitable monomers E are for example vinyl acetate, vinyl propionate and hydroxypropyl acetate.
Monomer F is acrylic acid or preferably methacry-lic acid.
Monomer G can be in particular the methyl, ethyl,n-propyl or n-butyl esters of acrylic or methacrylic acid 20~963 - 4 - O.Z. 0050~41581 which have an unsubstituted or preferably mono- or disubstituted amino group in paxticular at the end of the alkyl group. Particular preference is givento 2-(dialkyl-amino)ethyl methacrylates such as 2-(dimethylamino)ethyl and 2-(diethylamino)ethyl methacrylates.
Carboxyl groups present in the polymers are neutralized in whole or in part, advantageously up to from 5 to 100 %, preferably from 30 to 90 ~, with an amine. The amine used is preferably - a mono-, di- or trialkanolamine having from 2 to 5 carbon atoms in the alkanol moiety, which may be in etherified form, for example mono-, di- or tri-ethanolamine, mono-, di- or tri-n-propanolamine, mono-, di- or triisopropanolamine, 2-amino-2-methyl-propanol or di~2-methoxyethyl)amine, - an alkanediolamine of from 2 to 5 carbon atoms, for example 2-amino-2-methyl-1,3-propanediol or2-amino-2-ethyl-1,3-propanediol, or - a primary, secondary or tertLary alkylamine of from 5 to 10 carbon atoms in total, for example N,N-diethylpropylamine.
Partic~llarly good results are obtained on neut-ralizing with 2-amino-2-methylpropanol, triisopropanol-amine and 2-amino-~-ethyl-1,3-propanediol.
Preferred polymers have the following composi-tions:
- from 96 to 100 % by weight of N-vinylcaprolactam (monomer A) and from 0 to 4 % by weight of mono- . .-mer E;
- from 35 to 100, preferably from 50 to 90, % by weight of monomer A, from 0 to 65, preferably from lO to 50, % by weight of N-vinylimidazole (mono-mer B) and from 0 to 4 % by weight of monomer E;
- from 35 to 100, preferably from 35 to 65, % by weight of monomer A, from 0 to 65, preferably from 35 to 65, % by weight of a mixture of from 5 to 50 parts by weight of monomer B and from 10 to ' ` ' 2 0 ~
- 5 - ~.Z. 0050/41581 60 parts by weight of N-vinylpyrrolidone (monomer C) and also from 0 to 4 % by weight of monomer E;
- from 35 to 100, preferably from 50 to 85, % by weight of monomer A, from 0 to 65, preferably from 15 to 50, % by weight of a mixture of from 5 to 15 parts by weight of monomer B and from 10 to 35 parts by weigh~ of monomer D and also from 0 to 4 ~ by weight of monomer E;
- from 35 to 100, preferably 35 to 75, % by weight of monomer A, from 0 to 65, preferably from 25 to 65, ~
by weight of a mixture of from 20 to 60 parts by weight of monomer D and from 5 to 15 parts by weight of monomer F, and also from 0 to 4 % by weight of monomer E;
lS - from 35 to 100, preferably from 45 to 80, ~ by weight of monomer A, from 0 to 65, preferably from 20 to 55, % by weight of a mixture of from 15 to 50 parts by weight of monomer D and from S to 15 parts by weight of monomer G, and also from 0 to 4 % by weight o~ monomer E.
Here the monomer combinations A + B + C and in particular A + B + D, A + D + F and also A + D + G, each with or without small amounts oE E, represent particu-larly preferred embodiments.
The polymers are prepareld by free radical poly-merization or copolymerization of monomers A to G. ~he customary polymerization techniques are employed, for examplel the methods of suspension, emulsion or solution polymerization.
A particularly advantageous choice is solution polymerization in an organic solvent, in general an alcohol. The polymerization is customarily carried out at from 60 to 130C, at atmospheric pressure or under autogenous pressure.
The initiators used for the free radical polymer-ization reaction are the customary peroxo or azo compounds, for example dibenzoyl peroxide, tert-butyl ` -`= 2~0~
- 6 - O.Z. 0050/41581 perpivalate, tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide, tert-butyl hydxoperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexaneorazobisisobutyronitrile, advantageously in amounts of from 0.1 to 2 % by weight, S based on the weight of the monomers.
The amounts of monomer and solvent are advantage-ously chosen in such a way as to produce 30-80 ~ strength by weight solutions of the copolymers. Any organic solvent in the solution can be removed in a conventional manner, for example by distillation, and be replaced by water if a waterborne hair setting composition is desired.
The polymers should have K values of from 10 to 60, preferably from 20 to 55. The desired K value can be set in a conventional manner through choice of the polymerization conditions, for example the polymerization time and the initiator concentration. The K values are measured by the method of Fikentscher, Cellulosechemie 13 (1932), 58-64, at 25C in 1 % strength by weight in ethanol, and represent a measure of the molecular weight.
S-lch polymers customarily have glass transition temperatures of from 80 to 180, prefexably ~rom 90 to 150C.
Some of the polymers are novel substances. ~or this rea50n the pre~ent invention also provides copoly-mers obtainable by free radical polymerization of - from 35 to 95 % by weight of N-vinylcaprolactam ~monomer A) - from 5 to 65 ~ by weight of a mixture ~f from 5 to 15 parts by weight of N-vinylimidazole (monomer ~) and ~rom 10 to 35 parts by weight of monomer D
- from 0 to 4 ~ by weiyht of further monomer E capable of free radical copolymerization.
These polymers usually have K values of from 10 to 60, in particular from 20 to 55.
The present invention further provides copolymers obtainable by free radical polymerization of ' ~
. - , `: .
2 0 ~
The amounts of monomer and solvent are advantage-ously chosen in such a way as to produce 30-80 ~ strength by weight solutions of the copolymers. Any organic solvent in the solution can be removed in a conventional manner, for example by distillation, and be replaced by water if a waterborne hair setting composition is desired.
The polymers should have K values of from 10 to 60, preferably from 20 to 55. The desired K value can be set in a conventional manner through choice of the polymerization conditions, for example the polymerization time and the initiator concentration. The K values are measured by the method of Fikentscher, Cellulosechemie 13 (1932), 58-64, at 25C in 1 % strength by weight in ethanol, and represent a measure of the molecular weight.
S-lch polymers customarily have glass transition temperatures of from 80 to 180, prefexably ~rom 90 to 150C.
Some of the polymers are novel substances. ~or this rea50n the pre~ent invention also provides copoly-mers obtainable by free radical polymerization of - from 35 to 95 % by weight of N-vinylcaprolactam ~monomer A) - from 5 to 65 ~ by weight of a mixture ~f from 5 to 15 parts by weight of N-vinylimidazole (monomer ~) and ~rom 10 to 35 parts by weight of monomer D
- from 0 to 4 ~ by weiyht of further monomer E capable of free radical copolymerization.
These polymers usually have K values of from 10 to 60, in particular from 20 to 55.
The present invention further provides copolymers obtainable by free radical polymerization of ' ~
. - , `: .
2 0 ~
- 7 - O.Z. 0050/41581 - from 35 to 95 % by weight of N-vinylcaprolactam (monomer A) - from 5 to 65 % by weight of a mixture of from 15 to 50 parts by weight of monomer D and from 5 to 15 parts by weight of monomer ~
- from 0 to 4 ~ by weight of further monomer E capable of free radical copolymerization.
These polymers usually have K values of from 10 to 60, in particular from 70 to 55.
The hair setting compositions according to the present invention are employed for example in the form of lotions, mousses, gels and in particular sprays.
An advantageous formulation of a hair setting lotion contains:
15 - from 1 to 20 % by weight of the unneutralized or partially or completely neutralized polymer, - from 0 to 99 % by weight of a customary solvent such a~ in particular acetone, ethanol, n-propanol, isopropanol or 1-methoxy-2-~propanol or a mixture thereof, and - from 0 to 99 % by weight of water.
A preferred hair setting lotion is predominantly aqueous and contains from 2 to 15 % by weight of polymer, from 60 to 98 % by weight of water and optionally, as remainder to 100 % by weight, onl3 of the abovementioned solvents or mi~tures thereof.
An advantageous and convenient composition for hair mousse~ has the following recipe:
- from 1 to 15 % by weight, preferably from 2 to 10 ~
by weight, of the unneutralized or partially or completely neutralized polymer, - from S to 90 % by weight, preferably from 60 to 85 %
by weight, of water, - from 0 to 20 % by weight of a customary solvent such as in particular acetone, ethanol, n-propanol, isopropanol or l-~ethoxy-~-propanol or a mixture thereof, and - 2 0 ~
- from 0 to 4 ~ by weight of further monomer E capable of free radical copolymerization.
These polymers usually have K values of from 10 to 60, in particular from 70 to 55.
The hair setting compositions according to the present invention are employed for example in the form of lotions, mousses, gels and in particular sprays.
An advantageous formulation of a hair setting lotion contains:
15 - from 1 to 20 % by weight of the unneutralized or partially or completely neutralized polymer, - from 0 to 99 % by weight of a customary solvent such a~ in particular acetone, ethanol, n-propanol, isopropanol or 1-methoxy-2-~propanol or a mixture thereof, and - from 0 to 99 % by weight of water.
A preferred hair setting lotion is predominantly aqueous and contains from 2 to 15 % by weight of polymer, from 60 to 98 % by weight of water and optionally, as remainder to 100 % by weight, onl3 of the abovementioned solvents or mi~tures thereof.
An advantageous and convenient composition for hair mousse~ has the following recipe:
- from 1 to 15 % by weight, preferably from 2 to 10 ~
by weight, of the unneutralized or partially or completely neutralized polymer, - from S to 90 % by weight, preferably from 60 to 85 %
by weight, of water, - from 0 to 20 % by weight of a customary solvent such as in particular acetone, ethanol, n-propanol, isopropanol or l-~ethoxy-~-propanol or a mixture thereof, and - 2 0 ~
- 8 - O.Z. 0050/41581 - from 10 to 50 ~ by weight of a customary propellant such as propane, n-butane, isobutane, 2,2-dimethyl-propane, isopentane or dLmethyl ether or a mixture thereof.
These compositions have added to them, based on the total weight, from about 0.1 to about 1 % by weight of conventional foam formation and foam stabilization : assistants.
of course, the abovementioned hair setting lotions and mousses may contain further customary additives, such as scents, preservatives, etc., in the customary amounts.
As regards hair sprays, particular preference is given to those which contain the following constituents:
- from 0.1 to 20, preferably from 0.5 to 12, in particular from 2 to 10, % by weight of the un-neutralized or part~ally or completely neutralized polymer, - from 10 to 95, preferably from 20 to 60, in parti-cular from 25 to 50, ~ by weight of a customary solvent such as, in particular, ethanol and iso-propanol but also acetone, n-propanol, n-butanol, 2-methoxy-l-propanol, n-pentane, n-hexane, cyclo-hexane, n-heptane or dichloromethane or a mixture ~hereof, - from 5 to 90, pre~erably from 30 to 80, in parti cular from 45 to 70, ~ by weight of a customary propellant such as propane, n-butane, isobutane, 2,2-dimethylbutane, isopentane, dimethyl ether, 3~ fluorotrichloromethane, dichlorodifluoromethane or dichlorotetrafluoroethane or mixtures thereof. Of the propellants mentioned, in particular the hydro-carbons are used, especially pxopane and n-butane in a mixture in a weight ratio of for example from 40 : 60 or 25 : 75 or n-butane alone. If desired, one or more of the chlorofluorocarbons are included in the propellant mixture, but only in small 2 ~ 3 - 9 - O.Z. 0050/41581 amounts, say up to 20 ~ by weight, based on the propellant mixture.
Additionally these sprays may contain small amounts of perfume oils, for example from 0.1 to 5.0 % by weight.
The customary constituents and compositions of o~her hair setting products are ~nown to those skilled in the art and consequently need not be e~plained here at length.
The polymers of the hair setting compositions according to the present invention are highly compatible with the apolar propellants employed in sprays, in par~icular with hydrocarbons such as propane or n-butane or a mixture thereof. In general, they produce compat-ibility values within the range from 50 to 85, in parti-cular from 70 to 85, % by weight coupled with a remark-ably good hair setting effect, as evidenced by the high curl retention values, which in their case is normally within the range from 70 to 95 ~, in particular from 85 ~0 to 95 %. The moisture uptake of the treated hair is low, within the range from 3 to 18, in particular from 3 to 10, % by weight, as a result of which the hair is kept in place for longer and is less stick~.
Furthermore, the hair setting compositions according to the pre~ent invention are in fact notable for not causing the hair to stick together to any prac-tical extent; it remains readily comba~le. The treated hair has a natural appearance. The stiffening effeot achieved on the hair with compositions according to the 0 present invention is ger.erally good.
EXAMPLES
The known polymers used in the hair setting compositions according to tha present invention were prepared by the usual methods of solution polymerization.
In what follows, the preparation of the polymer of Example 10 will be described and should be taken as representative of all the other methods of preparation.
2 ~ 3 - 10 - O.Z. 0050/41581 Preparation of a polymer of 60 % by weight of N-vinyl-caprolactam, 10 % by weight of N-vinylimidazole and 30 %
by weight of tert-butyl acrylate.
A solution of 30 g of N-vinylcaprolactam, 5 g of N-vinylimidazole, 15 g of tert-butyl acrylate and 0.53 g of tert-butyl perpivalate (75 % strength by weight) in 275 g of ethanol was heated to 75C. Once the polymeriz-ation has started, as evidenced by an increase in the viscosity, a mixture of 270 g of N-vinylcaprolactam, 45 g of N-vinylimidazole, 135 g of tert-butyl acrylate and 100 g of ethanol and a solution of 2.4 g of tert-butyl perpivalate (75 ~ strength by weight) and 60 g of ethanol were added simultaneously in the course of 3 hours while the temperature was maintained at 77-80C with slow boiling. Thereafter a solution of 2.4 g of tert-butyl perpivalate (75 % strength by weight) in 60 g of ethanol was added dropwise at the same temperature in the course of a further 3 hours.
Then 3.0 g of 2,5-dLmethyl-2,5-di~tert-butyl-peroxy)hexane were added all at once. The reaction vessel was sealed pressure-tight, heatedlto 130C and maintained at that temperature for 3 hours.
Properties of the polymers Tables 1 to 6 below show the composition, K
value, hydrocarbon compatibility, hair setting effect and moisture uptake of the polymers used in the compositions according to the present invention.
The K value was measured at 25C on a 1.0 strength by weight solution in ethanol.
The hydrocarbon compatibility, determined with a 25 : 75 w/w mixture of propane and n-butane, indicates the maximum weight percentage of this propellant gas mixture-which may be present in a spray formulation which,:besides ethanol as solvent, contains 3 % by weight of the copolymer, whose carboxyl groups, if it has any, ar~: 7~ % neutralized with 2-amino-2-methylpropanol, without causing cloudiness at 0C.
- 2 0 ~
These compositions have added to them, based on the total weight, from about 0.1 to about 1 % by weight of conventional foam formation and foam stabilization : assistants.
of course, the abovementioned hair setting lotions and mousses may contain further customary additives, such as scents, preservatives, etc., in the customary amounts.
As regards hair sprays, particular preference is given to those which contain the following constituents:
- from 0.1 to 20, preferably from 0.5 to 12, in particular from 2 to 10, % by weight of the un-neutralized or part~ally or completely neutralized polymer, - from 10 to 95, preferably from 20 to 60, in parti-cular from 25 to 50, ~ by weight of a customary solvent such as, in particular, ethanol and iso-propanol but also acetone, n-propanol, n-butanol, 2-methoxy-l-propanol, n-pentane, n-hexane, cyclo-hexane, n-heptane or dichloromethane or a mixture ~hereof, - from 5 to 90, pre~erably from 30 to 80, in parti cular from 45 to 70, ~ by weight of a customary propellant such as propane, n-butane, isobutane, 2,2-dimethylbutane, isopentane, dimethyl ether, 3~ fluorotrichloromethane, dichlorodifluoromethane or dichlorotetrafluoroethane or mixtures thereof. Of the propellants mentioned, in particular the hydro-carbons are used, especially pxopane and n-butane in a mixture in a weight ratio of for example from 40 : 60 or 25 : 75 or n-butane alone. If desired, one or more of the chlorofluorocarbons are included in the propellant mixture, but only in small 2 ~ 3 - 9 - O.Z. 0050/41581 amounts, say up to 20 ~ by weight, based on the propellant mixture.
Additionally these sprays may contain small amounts of perfume oils, for example from 0.1 to 5.0 % by weight.
The customary constituents and compositions of o~her hair setting products are ~nown to those skilled in the art and consequently need not be e~plained here at length.
The polymers of the hair setting compositions according to the present invention are highly compatible with the apolar propellants employed in sprays, in par~icular with hydrocarbons such as propane or n-butane or a mixture thereof. In general, they produce compat-ibility values within the range from 50 to 85, in parti-cular from 70 to 85, % by weight coupled with a remark-ably good hair setting effect, as evidenced by the high curl retention values, which in their case is normally within the range from 70 to 95 ~, in particular from 85 ~0 to 95 %. The moisture uptake of the treated hair is low, within the range from 3 to 18, in particular from 3 to 10, % by weight, as a result of which the hair is kept in place for longer and is less stick~.
Furthermore, the hair setting compositions according to the pre~ent invention are in fact notable for not causing the hair to stick together to any prac-tical extent; it remains readily comba~le. The treated hair has a natural appearance. The stiffening effeot achieved on the hair with compositions according to the 0 present invention is ger.erally good.
EXAMPLES
The known polymers used in the hair setting compositions according to tha present invention were prepared by the usual methods of solution polymerization.
In what follows, the preparation of the polymer of Example 10 will be described and should be taken as representative of all the other methods of preparation.
2 ~ 3 - 10 - O.Z. 0050/41581 Preparation of a polymer of 60 % by weight of N-vinyl-caprolactam, 10 % by weight of N-vinylimidazole and 30 %
by weight of tert-butyl acrylate.
A solution of 30 g of N-vinylcaprolactam, 5 g of N-vinylimidazole, 15 g of tert-butyl acrylate and 0.53 g of tert-butyl perpivalate (75 % strength by weight) in 275 g of ethanol was heated to 75C. Once the polymeriz-ation has started, as evidenced by an increase in the viscosity, a mixture of 270 g of N-vinylcaprolactam, 45 g of N-vinylimidazole, 135 g of tert-butyl acrylate and 100 g of ethanol and a solution of 2.4 g of tert-butyl perpivalate (75 ~ strength by weight) and 60 g of ethanol were added simultaneously in the course of 3 hours while the temperature was maintained at 77-80C with slow boiling. Thereafter a solution of 2.4 g of tert-butyl perpivalate (75 % strength by weight) in 60 g of ethanol was added dropwise at the same temperature in the course of a further 3 hours.
Then 3.0 g of 2,5-dLmethyl-2,5-di~tert-butyl-peroxy)hexane were added all at once. The reaction vessel was sealed pressure-tight, heatedlto 130C and maintained at that temperature for 3 hours.
Properties of the polymers Tables 1 to 6 below show the composition, K
value, hydrocarbon compatibility, hair setting effect and moisture uptake of the polymers used in the compositions according to the present invention.
The K value was measured at 25C on a 1.0 strength by weight solution in ethanol.
The hydrocarbon compatibility, determined with a 25 : 75 w/w mixture of propane and n-butane, indicates the maximum weight percentage of this propellant gas mixture-which may be present in a spray formulation which,:besides ethanol as solvent, contains 3 % by weight of the copolymer, whose carboxyl groups, if it has any, ar~: 7~ % neutralized with 2-amino-2-methylpropanol, without causing cloudiness at 0C.
- 2 0 ~
11 - O.Z. ~050/41581 The hair setting effect is measured in terms of curl xetention. Curl retention is measured in an in vitro test on curls formed from approximately 15 cm long strands of hair by a customary shalnpoo-and-set treatment and sprayed with the particular spray formulation from a distance of 10 cm for 4 seconds. After the suspended curls have been conditioned in 2 conditioning cabinet at 25C and 90 % relative humidity for 5 hours, the relative opening-out or uncurling of the curls is determined relative to their original shape. A high value denotes high shape retention; that is, a value of 100 % would denote that the original shape was completely retained.
The curl retention values for the pol~ners designated in Tables 1 to 6 were determined in each case with the following standard spray formulation:
6.3 % by weight of polymer which, if any carboxyl groups were present, has been 75 ~
neutralized with 2-amino-2-methyl-propanol, 33.7 % by weight of ethanol and 60.0 % by weight 25:75 propane/n-butane.
The moisture uptake of the polymer-treated hair from the surrounding air was measured after 7 days at 75 % relati~e humidity.
... ~ - . . .. ; ~ :
2~dO~
The curl retention values for the pol~ners designated in Tables 1 to 6 were determined in each case with the following standard spray formulation:
6.3 % by weight of polymer which, if any carboxyl groups were present, has been 75 ~
neutralized with 2-amino-2-methyl-propanol, 33.7 % by weight of ethanol and 60.0 % by weight 25:75 propane/n-butane.
The moisture uptake of the polymer-treated hair from the surrounding air was measured after 7 days at 75 % relati~e humidity.
... ~ - . . .. ; ~ :
2~dO~
- 12 - O.Z. 0050/41581 Polymers of monomers A and E
Ex- Composition K value Hydro- Curl Mois-ample carbon reten- ture s compat- tion up-ibility take with 25:75 propane/-n-butane ~% by ~% by ~% by weight] weight] [%] weight]
1100 of N-vinyl- 32.1 75 82 9.3 caprolactam 297 of N-vinyl- 20.4 74 83 9.4 caprolactam 3 of vinyl acetate 20 For comparison:
A80 of N-vinyl- 29.8 72 83 9.7 caprolactam 20 of vinyl acetate Example A was prepared according to reference ~3); the aqueous solution of A, unlike those of Examples 1 and 2, was not colorless and the hair treated with A was gray and scaly.
;
:
.~ . .
-- ` 2 ~ 3 - 13 - O.Z. 0050/~1581 TABLE 2 ~ -.
Polymers of monomers A and B
Ex- Composition K value Hydro- Curl Mois-ampla carbon reten- ture compat- tion up-ibility take with 25:75 propane/-n-butane [% by [% by [% by weight] weight] [~] weight]
.
340 of N-vinyl- 45.0 50 83 18.0 caprolactam 60 of N-vinyl-imidazole 450 of N-vinyl- 43.9 56 85 14.7 caprolactam 50 of N-vinyl-imidazole 560 of N-vinyl- 42.8 57 87 16.6 caprolactam 40 of N-vinyl-imidazole 670 of N-vinyl- 43.2 61 88 15.4 caprolactam 30 of N-vinyl-imidazole 780 of N-vinyl- 43.6 65 91 13.7 caprolactam 20 of N-vinyl-imidazole . _ . .
, , 2 ~
Ex- Composition K value Hydro- Curl Mois-ample carbon reten- ture s compat- tion up-ibility take with 25:75 propane/-n-butane ~% by ~% by ~% by weight] weight] [%] weight]
1100 of N-vinyl- 32.1 75 82 9.3 caprolactam 297 of N-vinyl- 20.4 74 83 9.4 caprolactam 3 of vinyl acetate 20 For comparison:
A80 of N-vinyl- 29.8 72 83 9.7 caprolactam 20 of vinyl acetate Example A was prepared according to reference ~3); the aqueous solution of A, unlike those of Examples 1 and 2, was not colorless and the hair treated with A was gray and scaly.
;
:
.~ . .
-- ` 2 ~ 3 - 13 - O.Z. 0050/~1581 TABLE 2 ~ -.
Polymers of monomers A and B
Ex- Composition K value Hydro- Curl Mois-ampla carbon reten- ture compat- tion up-ibility take with 25:75 propane/-n-butane [% by [% by [% by weight] weight] [~] weight]
.
340 of N-vinyl- 45.0 50 83 18.0 caprolactam 60 of N-vinyl-imidazole 450 of N-vinyl- 43.9 56 85 14.7 caprolactam 50 of N-vinyl-imidazole 560 of N-vinyl- 42.8 57 87 16.6 caprolactam 40 of N-vinyl-imidazole 670 of N-vinyl- 43.2 61 88 15.4 caprolactam 30 of N-vinyl-imidazole 780 of N-vinyl- 43.6 65 91 13.7 caprolactam 20 of N-vinyl-imidazole . _ . .
, , 2 ~
- 14 - O.Z. 0050/41581 Polymers of monomers A, B and C
Ex- Composition R value Hydro- Curl Mois-ample carbon reten- ture compat- tion up-ibility taXe with 25:75 propane/-n-butane [% by [% by [% by weigh~] weight] [~] weight]
835 of N-vinyl- 46.1 52 79 18.0 caprolactam 50 of N-vinyl-imidazole 15 of N-vinyl-pyrrolidone 960 of N-vinyl- 40.4 63 93 14.1 caprolactam 30 of N-vinyl-imidazole lO of N-vinyl-pyrrolidone . _ . . .
` -` 2 0 ~
- 15 - O.Z. 0050/41581 Polymers of monomers A, B and D
Ex- CompositionK value Hydro- Curl Mois-~mple carbon reten- ture compat- tion up-ibility take with 25:75 propane/-n-butane [~ by [% by [% by weight] weight] [%] weight]
60 of N-vinyl- 27.6 76 89 5.8 caprolactam 10 of N-vinyl-imidazole 30 of tert butyl acrylate 11 75 of N-vinyl- 29.3 75 87 6.4 caprolactam 5 of N-vinyl-imidazole 20 of tert-butyl acrylate 12 75 of N~vinyl- 27.8 60 86 8.0 caprolactam 5 of N-vinyl-imidazole 20 of methyl acrylate 13 75 of N-vinyl- 53.0 74 84 7.1 caprolactam 5 of N-vinyl~
imidazole 20 of ethyl acrylate ~ .. . . _ 2 Q ~
Ex- Composition R value Hydro- Curl Mois-ample carbon reten- ture compat- tion up-ibility taXe with 25:75 propane/-n-butane [% by [% by [% by weigh~] weight] [~] weight]
835 of N-vinyl- 46.1 52 79 18.0 caprolactam 50 of N-vinyl-imidazole 15 of N-vinyl-pyrrolidone 960 of N-vinyl- 40.4 63 93 14.1 caprolactam 30 of N-vinyl-imidazole lO of N-vinyl-pyrrolidone . _ . . .
` -` 2 0 ~
- 15 - O.Z. 0050/41581 Polymers of monomers A, B and D
Ex- CompositionK value Hydro- Curl Mois-~mple carbon reten- ture compat- tion up-ibility take with 25:75 propane/-n-butane [~ by [% by [% by weight] weight] [%] weight]
60 of N-vinyl- 27.6 76 89 5.8 caprolactam 10 of N-vinyl-imidazole 30 of tert butyl acrylate 11 75 of N-vinyl- 29.3 75 87 6.4 caprolactam 5 of N-vinyl-imidazole 20 of tert-butyl acrylate 12 75 of N~vinyl- 27.8 60 86 8.0 caprolactam 5 of N-vinyl-imidazole 20 of methyl acrylate 13 75 of N-vinyl- 53.0 74 84 7.1 caprolactam 5 of N-vinyl~
imidazole 20 of ethyl acrylate ~ .. . . _ 2 Q ~
- 16 - O.Z. 0050/41581 TABLE S :
Polymers of monomers A, D and F
Ex- Composition K value Hydro- Curl Mois-ample carbon reten- ture S compat- tion up-ibility take with 25:75 propane/-n-butane [~ by [~ by [% by weight] weight] [%] weight]
1440 of N-vinyl- 24.2 77 90 4.0 lS caprolactam 55 of tert-butyl acrylate 5 of methacrylic acid lS40 of N-vinyl- 27.6 71 90 5.7 caprolactam 50 o:E tert-butyl acrylate 10 o:E methacrylic acid 1640 of N-vinyl- 26.3 61 89 6.5 caprolactam 45 of tert-butyl acrylate 15 of methyacrylic acid 1750 of N-vinyl- 25.1 75 90 5.4 caprolactam 45 of tert-butyl acrylate 5 of methacrylic acid 1860 03E N-vinyl- 26.9 75 90 7.1 caprolactam 35 of tert-butyl acrylate 5 o~E methacrylic acid , . . .
2 ~ 3 - 17 - O.Z. 0050/41581 TABLE 5 (continued) Ex- Composition K value Hydro- Curl Mois-ample carbon reten- ture compat- tion up-ibility take with 25:75 propane/-n-butane [% by [~ by [% by weight] weight] [%] weight]
1970 of N-vinyl- 28.7 75 88 7.3 caprolactam 25 of tert-butyl acrylate 5 of methacrylic acid 2070 of N-vinyl- 29.4 74 82 9.3 caprolactam 25 of n-butyl acrylate S of methacrylic acid 2170 of N-vinyl- 29.3 66 70 10.0 caprolactam 20 of n-butyl acrylate 10 of methacrylic acid 2275 of N-vinyl- 33.3 75 ~4 6.3 caprolactam 20 of n-butyl methacrylate 5 of methacrylic acid 2370 of N-vinyl- 27.6 64 72 7.4 caprolactam A .
25 of ethyl acrylate 5 of methacrylic acid -` 2 ~ 3 ~ 18 - O.Z. 0050/41581 TABLE S (continued) Ex- Composition K value Hydro- Curl Mois-ample carbon reten- ture compat- tion up-ibility take with 25:75 propane/-n-butane [% ~Y [% ~Y
[% by weight] weight] [%] weight]
: For comparison:
B20 of N-vinyl- 17.0 65 22 7.4 pyrrolidone 9 of N-vinyl-imidazole 64 of tert-butyl acrylate 7 of acrylic acid Example B corresponds to Example 5 of reference (1).
Polymers of monomers A, D and G
Ex- Composition K value Hydro- Curl Mois-ample earbon reten- ture eompat- tion up-.ibility take with '25:75 -propane/-n-butane [~ by [% by ~% by weight] weight~ [%] wEight]
2445 of ~-vinyl- 24.3 80 95 3.3 caprolactam 45 of tert-butyl acrylate 10 of DMAEN~
2555 of N-vinyl- 24.4 80 96 3.8 caprolaetam 40 of tert-butyl acrylate 5 of DMAENA
; .
~ ' '' -- 20~6~
- l9 - O.Z. 0050/41581 TABL2 6 tcontinued) Ex- CompositionK value Hydro- Curl Mois-ample carbon reten- ture compat- tion up-ibility take with 25:75 propane/-n-butane [~ by [% by [% by weight] weight] [%] ~eight]
2660 of N-vinyl- 25.6 75 90 7.1 caprolactam 35 of tert-butyl acrylate 5 of DMAEMA
2765 of N-vinyl- 27.3 78 96 5.3 caprolactam 30 of tert-butyl ac.rylate 5 of DMAEMA
2875 of N-vinyl- 27.2 76 86 6.9 caprolactam 20 of tert-butyl ac.rylate 5 of DMAEMA
2965 of N-vinyl- 39.8 75 ~3 6.3 caprolactam 30 of n-butyl methacrylate S of DMAEMA
3075 of N-vinyl- 33.3 84 75 6.7 caprolactam 20 of n-butyl methacrylate .
S of DMAEMA
For comparison:
C47.5 of N-vinyl- 43.9 80 70 3.9 caprolactam 47.5 of N-vinyl-pyrrolidone 5 of DMAE~A
45 DNAEMA: 2-(dimethylamino)ethyl methacrylate :
2 ~ $ ~
- 20 O.Z. 0050/41581 Example C corresponds to the third example of Table III of reference (2~, where, however, the curl retention was found to be 89-90 ~ under significantly gen~ler conditions (45 minutes instead of 5 hours).
Formulation examples for hair setting compositions Hair setting lotion with alcohol 10.0 ~ by weight of N-vinylcaprolactam polymer of Example 1 5.0 % by weight of ethanol 85.0 % by weight of water The solution obtained was slightly opalescent.
Hair setting lotion without alcohol 5 10.3 % by weight of N-vinylcaprolactam/tert-butyl acrylate/methacrylic acid polymer of Example 19, 100 ~ neutralized with 2~amino-2-methylpropanol O.2 % by weight of customary preservative 89.5 % by weight of water The solution obtained was clear.
EXAMPLE 3.3 Hair mousse with setting ingredient 6.0 ~ by weight of N-vinylcaprolactam polymer of Example 9 0.1 % by weight of addition product of cetyl-stearyl alcohol with 25 mol of ethylene oxide O.3 % by weight of cetyldimethyl-2-hydroxyethylammonium dihydrogenphosphate 0.4 ~ by weight of customary perfume 0.2 % by weight of customary preservative 83.0 ~ by weight of water 10.0 ~ by weight of 25:75 propane/n-butane The result was an appealing, firm and somewhat creamy mousse.
-- .
.
2 ~ $ 3 - 21 - O.Z. 0050/41581 Hair mousse with conditioner and setting ingredient 4.0 % by weight of N-vinylcaprolactam polymer of Example 9 S.0 % by weight of vinylpyrrolidone/vinylimidazolium methohloride copolymer 0.5 % by weight of cetyldLmethyl-2-hydroxyethylammonium dihydrogenphosphate 0.4 % by weight of customary perfume 0.2 % by weight of customary preservative 79.9 % by weight of water 10.0 % by weight of 25:75 propanetn-butane The result obtained was a firm, dry mousse.
Hair gel 6.0 ~ by weight of N-vinylcaprolactam polymer of Example 9 `
0.6 % by weight of polyacrylic acid 11.0 ~ by weight of N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediamin~
20.0 ~ by weight of ethanol 62.4 % by weight of water The result obtained was an opalescent gel having a yood setting effect.
Hair spray formulation tstandard~
6.3 % by weight of N-vinylcaprolactam/tert-butyl acrylate/2-(dimethylamino)ethyl meth-acrylate polymer of Example 25 33.7 ~ by weight of ethanol 60.0 % by weight of 25:75 propane~n-butane The cloud point was below -35C. A predominant portion of the ethanol was replaceable by n-pentane or n-hexane without adverse effect on the hair setting action.
- 2 ~
.
- 22 - O.Z. OOS0/41581 Hair spray formulation 4.1 % by weight of N-vinylcaprolactam/tert-butyl acrylate/methacrylic acid polymer of S Example 19, 75 % neutralized with 2-amino-2 methylpropanol 35.9 % by w~ight of ethanol 60.0 % by weight of n-butane The clo~ld point was below -35C.
Hair spray formulation 8.5 % by weight o N-vinylcaprolactam/tert-butyl acrylate/methacrylic acid polymer of Example 16, 75 ~ neutralized with 2-amino-2-methylpropanol 51.5 % by weight of ethanol 40.0 ~ by weight of n-butane The cloud point was below -35C.
Hair spray formulation 12.0 ~ by weight o N-vinylcaprolactam/N-vinyl-imidazole/N-vinylpyrrolidone polymer of Example 9 38.0 % by weight of ethanol 50.0 % by weight of n-butane ~he cloud point was below -35C.
; ` ~
:' '
Polymers of monomers A, D and F
Ex- Composition K value Hydro- Curl Mois-ample carbon reten- ture S compat- tion up-ibility take with 25:75 propane/-n-butane [~ by [~ by [% by weight] weight] [%] weight]
1440 of N-vinyl- 24.2 77 90 4.0 lS caprolactam 55 of tert-butyl acrylate 5 of methacrylic acid lS40 of N-vinyl- 27.6 71 90 5.7 caprolactam 50 o:E tert-butyl acrylate 10 o:E methacrylic acid 1640 of N-vinyl- 26.3 61 89 6.5 caprolactam 45 of tert-butyl acrylate 15 of methyacrylic acid 1750 of N-vinyl- 25.1 75 90 5.4 caprolactam 45 of tert-butyl acrylate 5 of methacrylic acid 1860 03E N-vinyl- 26.9 75 90 7.1 caprolactam 35 of tert-butyl acrylate 5 o~E methacrylic acid , . . .
2 ~ 3 - 17 - O.Z. 0050/41581 TABLE 5 (continued) Ex- Composition K value Hydro- Curl Mois-ample carbon reten- ture compat- tion up-ibility take with 25:75 propane/-n-butane [% by [~ by [% by weight] weight] [%] weight]
1970 of N-vinyl- 28.7 75 88 7.3 caprolactam 25 of tert-butyl acrylate 5 of methacrylic acid 2070 of N-vinyl- 29.4 74 82 9.3 caprolactam 25 of n-butyl acrylate S of methacrylic acid 2170 of N-vinyl- 29.3 66 70 10.0 caprolactam 20 of n-butyl acrylate 10 of methacrylic acid 2275 of N-vinyl- 33.3 75 ~4 6.3 caprolactam 20 of n-butyl methacrylate 5 of methacrylic acid 2370 of N-vinyl- 27.6 64 72 7.4 caprolactam A .
25 of ethyl acrylate 5 of methacrylic acid -` 2 ~ 3 ~ 18 - O.Z. 0050/41581 TABLE S (continued) Ex- Composition K value Hydro- Curl Mois-ample carbon reten- ture compat- tion up-ibility take with 25:75 propane/-n-butane [% ~Y [% ~Y
[% by weight] weight] [%] weight]
: For comparison:
B20 of N-vinyl- 17.0 65 22 7.4 pyrrolidone 9 of N-vinyl-imidazole 64 of tert-butyl acrylate 7 of acrylic acid Example B corresponds to Example 5 of reference (1).
Polymers of monomers A, D and G
Ex- Composition K value Hydro- Curl Mois-ample earbon reten- ture eompat- tion up-.ibility take with '25:75 -propane/-n-butane [~ by [% by ~% by weight] weight~ [%] wEight]
2445 of ~-vinyl- 24.3 80 95 3.3 caprolactam 45 of tert-butyl acrylate 10 of DMAEN~
2555 of N-vinyl- 24.4 80 96 3.8 caprolaetam 40 of tert-butyl acrylate 5 of DMAENA
; .
~ ' '' -- 20~6~
- l9 - O.Z. 0050/41581 TABL2 6 tcontinued) Ex- CompositionK value Hydro- Curl Mois-ample carbon reten- ture compat- tion up-ibility take with 25:75 propane/-n-butane [~ by [% by [% by weight] weight] [%] ~eight]
2660 of N-vinyl- 25.6 75 90 7.1 caprolactam 35 of tert-butyl acrylate 5 of DMAEMA
2765 of N-vinyl- 27.3 78 96 5.3 caprolactam 30 of tert-butyl ac.rylate 5 of DMAEMA
2875 of N-vinyl- 27.2 76 86 6.9 caprolactam 20 of tert-butyl ac.rylate 5 of DMAEMA
2965 of N-vinyl- 39.8 75 ~3 6.3 caprolactam 30 of n-butyl methacrylate S of DMAEMA
3075 of N-vinyl- 33.3 84 75 6.7 caprolactam 20 of n-butyl methacrylate .
S of DMAEMA
For comparison:
C47.5 of N-vinyl- 43.9 80 70 3.9 caprolactam 47.5 of N-vinyl-pyrrolidone 5 of DMAE~A
45 DNAEMA: 2-(dimethylamino)ethyl methacrylate :
2 ~ $ ~
- 20 O.Z. 0050/41581 Example C corresponds to the third example of Table III of reference (2~, where, however, the curl retention was found to be 89-90 ~ under significantly gen~ler conditions (45 minutes instead of 5 hours).
Formulation examples for hair setting compositions Hair setting lotion with alcohol 10.0 ~ by weight of N-vinylcaprolactam polymer of Example 1 5.0 % by weight of ethanol 85.0 % by weight of water The solution obtained was slightly opalescent.
Hair setting lotion without alcohol 5 10.3 % by weight of N-vinylcaprolactam/tert-butyl acrylate/methacrylic acid polymer of Example 19, 100 ~ neutralized with 2~amino-2-methylpropanol O.2 % by weight of customary preservative 89.5 % by weight of water The solution obtained was clear.
EXAMPLE 3.3 Hair mousse with setting ingredient 6.0 ~ by weight of N-vinylcaprolactam polymer of Example 9 0.1 % by weight of addition product of cetyl-stearyl alcohol with 25 mol of ethylene oxide O.3 % by weight of cetyldimethyl-2-hydroxyethylammonium dihydrogenphosphate 0.4 ~ by weight of customary perfume 0.2 % by weight of customary preservative 83.0 ~ by weight of water 10.0 ~ by weight of 25:75 propane/n-butane The result was an appealing, firm and somewhat creamy mousse.
-- .
.
2 ~ $ 3 - 21 - O.Z. 0050/41581 Hair mousse with conditioner and setting ingredient 4.0 % by weight of N-vinylcaprolactam polymer of Example 9 S.0 % by weight of vinylpyrrolidone/vinylimidazolium methohloride copolymer 0.5 % by weight of cetyldLmethyl-2-hydroxyethylammonium dihydrogenphosphate 0.4 % by weight of customary perfume 0.2 % by weight of customary preservative 79.9 % by weight of water 10.0 % by weight of 25:75 propanetn-butane The result obtained was a firm, dry mousse.
Hair gel 6.0 ~ by weight of N-vinylcaprolactam polymer of Example 9 `
0.6 % by weight of polyacrylic acid 11.0 ~ by weight of N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediamin~
20.0 ~ by weight of ethanol 62.4 % by weight of water The result obtained was an opalescent gel having a yood setting effect.
Hair spray formulation tstandard~
6.3 % by weight of N-vinylcaprolactam/tert-butyl acrylate/2-(dimethylamino)ethyl meth-acrylate polymer of Example 25 33.7 ~ by weight of ethanol 60.0 % by weight of 25:75 propane~n-butane The cloud point was below -35C. A predominant portion of the ethanol was replaceable by n-pentane or n-hexane without adverse effect on the hair setting action.
- 2 ~
.
- 22 - O.Z. OOS0/41581 Hair spray formulation 4.1 % by weight of N-vinylcaprolactam/tert-butyl acrylate/methacrylic acid polymer of S Example 19, 75 % neutralized with 2-amino-2 methylpropanol 35.9 % by w~ight of ethanol 60.0 % by weight of n-butane The clo~ld point was below -35C.
Hair spray formulation 8.5 % by weight o N-vinylcaprolactam/tert-butyl acrylate/methacrylic acid polymer of Example 16, 75 ~ neutralized with 2-amino-2-methylpropanol 51.5 % by weight of ethanol 40.0 ~ by weight of n-butane The cloud point was below -35C.
Hair spray formulation 12.0 ~ by weight o N-vinylcaprolactam/N-vinyl-imidazole/N-vinylpyrrolidone polymer of Example 9 38.0 % by weight of ethanol 50.0 % by weight of n-butane ~he cloud point was below -35C.
; ` ~
:' '
Claims (11)
1. A hair setting composition, containing as film former a polymer based on N-vinylcaprolactam formed from group I
- from 35 to 100 % by weight of N-vinylcaprolactam (monomer A) - from 0 to 65 % by weight of N-vinylimidazole (mono-mer B) or a mixture of from 5 to 50 parts by weight of monomer B and from 10 to 60 parts by weight of N-vinylpyrrolidone (monomer C) or a mixture of from 5 to 15 parts by weight of monomer B and from 10 to 35 parts by weight of an alkyl acrylate or methacry-late having from 1 to 4 carbon atoms in the alkyl moiety (monomer D) - from 0 to 4 % by weight of further monomer E capable of free radical copolymerization or group II
- from 35 to 100 % by weight of monomer A
- from 0 to 65 % by weight of a mixture of from 20 to 60 parts by weight of monomer D and from 5 to 15 parts by weight of acrylic or methacrylic acid (monomer F) or of a mixture of from 15 to 50 parts by weight of monomer D and from 5 to 15 parts by weight of an alkyl acrylate or methacrylate having from 1 to 4 carbon atoms in the alkyl moiety which additionally carries unsubstituted or C1-C4-alkyl-substituted amino (monomer G) - from 0 to 4 % by weight of further monomer E capable of free radical copolymerization, any carboxyl groups of the polymer having been partly or wholly neutralized with an amine, as well as customary ingredients for this purpose.
- from 35 to 100 % by weight of N-vinylcaprolactam (monomer A) - from 0 to 65 % by weight of N-vinylimidazole (mono-mer B) or a mixture of from 5 to 50 parts by weight of monomer B and from 10 to 60 parts by weight of N-vinylpyrrolidone (monomer C) or a mixture of from 5 to 15 parts by weight of monomer B and from 10 to 35 parts by weight of an alkyl acrylate or methacry-late having from 1 to 4 carbon atoms in the alkyl moiety (monomer D) - from 0 to 4 % by weight of further monomer E capable of free radical copolymerization or group II
- from 35 to 100 % by weight of monomer A
- from 0 to 65 % by weight of a mixture of from 20 to 60 parts by weight of monomer D and from 5 to 15 parts by weight of acrylic or methacrylic acid (monomer F) or of a mixture of from 15 to 50 parts by weight of monomer D and from 5 to 15 parts by weight of an alkyl acrylate or methacrylate having from 1 to 4 carbon atoms in the alkyl moiety which additionally carries unsubstituted or C1-C4-alkyl-substituted amino (monomer G) - from 0 to 4 % by weight of further monomer E capable of free radical copolymerization, any carboxyl groups of the polymer having been partly or wholly neutralized with an amine, as well as customary ingredients for this purpose.
2. A hair setting composition as claimed in claim 1, in which the polymer is formed from - 96 - 100 % by weight of N-vinylcaprolactam (monomer A) and - 0 - 4 % by weight of further monomer E capable of free radical copolymerization.
O.Z. 0050/41581
O.Z. 0050/41581
3. A hair setting composition as claimed in claim 1, in which the polymer is formed from - 35 100 % by weight of N-vinylcaprolactam (mono-mer A), - 0 - 65 % by weight of N-vinylimidazole (monomer B) - 0 - 4 % by weight of further monomer E capable of free radical copolymerization.
4. A hair setting composition as claimed in claim 1, in which the polymer is formed from - 35 - 100 % by weight of N-vinylcaprolactam (mono-mer A) - 0 - 65 % by weight of a mixture of 5 - 50 parts by weight of N-vinylimidazole (monomer B) and 10 - 60 parts by weight of N-vinylpyrrolidone (monomer C) - 0 - 4 % by weight of further monomer E capable of free radical copolymerization.
5. A hair setting composition as claimed in claim 1, in which the polymer is formed from - 35 - 100 % by weight of N-vinylcaprolactam (mono-mer A) - 0 - 65 % by weight of a mixture of 5 - 15 parts by weight of N-vinylimidazole (monomer B) and 10 - 35 parts by weight of monomer D
- 0 - 4 % by weight of further monomer E capable of free radical copolymerization.
- 0 - 4 % by weight of further monomer E capable of free radical copolymerization.
6. A hair setting composition as claimed in claim 1, in which the polymer is formed from - 35 - 100 % by weight of N-vinylcaprolactam (mono-mer A) - 0 - 65 % by weight of a mixture of 20 - 60 parts by weight of monomer D and 5 - 15 parts by weight of acrylic acid or methacrylic acid (monomer F) - 0 to 4 % by weight of further monomer E capable of free radical copolymerization.
7. A hair setting composition as claimed in claim 1, in which the polymer is formed from - 35 - 100 % by weight of N-vinylcaprolactam (mono-mer A) O.Z. 0050/41581 - 0 - 65 % by weight of a mixture of 15 - 50 parts by weight of monomer D and 5 - 15 parts by weight of monomer G
- 0 - 4 % by weight of further monomer E capable of free radical copolymerization.
- 0 - 4 % by weight of further monomer E capable of free radical copolymerization.
8. A copolymer as set forth in claim 5, obtainable by free radical polymerization of - from 35 to 95 % by weight of N-vinylcaprolactam (monomer A) - from 5 to 65 % by weight of a mixture of from 5 to 15 parts by weight of N-vinylimidazole (monomer B) and from 10 to 35 parts by weight of monomer D
- from 0 to 4 % by weight of further monomer E capable of free radical copolymerization.
- from 0 to 4 % by weight of further monomer E capable of free radical copolymerization.
9. A copolymer as set forth in claim 7, obtainable by free radical polymerization of - from 35 to 95 % by weight of N-vinylcaprolactam (monomer A) - from 5 to 65 % by weight of a mixture of from 15 to 50 parts by weight of monomer D and from 5 to 15 parts by weight of monomer G
- from 0 to 4 % by weight of further monomer E capable of free radical copolymerization.
- from 0 to 4 % by weight of further monomer E capable of free radical copolymerization.
10. A method for setting hair, which comprises using a copolymer as set forth in claim 1 as film former.
11. A hair setting composition in the form of a spray, containing from 0.1 to 20 % by weight of a polymer as set forth in claim 1, as well as customary solvents and propellants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4013872A DE4013872A1 (en) | 1990-04-30 | 1990-04-30 | HAIRFESTING AND HAIR CARE |
| DEP4013872.0 | 1990-04-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2040963A1 true CA2040963A1 (en) | 1991-10-31 |
Family
ID=6405450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002040963A Abandoned CA2040963A1 (en) | 1990-04-30 | 1991-04-22 | Hair setting composition |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0455081B1 (en) |
| JP (2) | JP3442407B2 (en) |
| CA (1) | CA2040963A1 (en) |
| DE (2) | DE4013872A1 (en) |
| ES (1) | ES2056516T3 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5635169A (en) * | 1994-10-29 | 1997-06-03 | Basf Aktiengesellschaft | Soluble copolymers for hair cosmetics |
| US5869032A (en) * | 1994-12-07 | 1999-02-09 | Basf Aktiengesellschaft | Quaternized copolymers suitable as active ingredients in cosmetic formulations, such as hair styling compositions |
| US6191188B1 (en) * | 1997-01-14 | 2001-02-20 | Basf Aktiengesellschaft | Aqueous compositions and their use |
| US8398963B2 (en) | 2000-02-23 | 2013-03-19 | Basf Se | Cosmetic agent |
| US20240124708A1 (en) * | 2022-09-30 | 2024-04-18 | L'oreal | Acidic bonding compositions and methods for restoring and color toning lightened hair |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2684874B1 (en) * | 1991-12-13 | 1994-07-01 | Oreal | AEROSOL SYSTEM FOR HAIR LACQUER. |
| FR2704771B1 (en) * | 1993-05-07 | 1995-07-13 | Oreal | Use of a terpolymer derived from vinyl lactam as a foaming agent in compositions forming an aerosol foam and composition for use. |
| DE4342281A1 (en) * | 1993-12-11 | 1995-06-14 | Basf Ag | Process for the preparation of powdery polymers based on N-vinylcaprolactam |
| FR2715064B1 (en) * | 1994-01-14 | 1996-02-09 | Oreal | Cosmetic aerosol compositions, aerosols containing them and uses. |
| FR2715841B1 (en) * | 1994-02-07 | 1996-03-29 | Oreal | Cosmetic hair composition containing a poly N-vinyl caprolactam and a copolymer of N-vinyl pyrrolidone and N-vinyl imidazolium and uses. |
| DE4438849A1 (en) * | 1994-11-02 | 1996-05-09 | Henkel Kgaa | Hair fixative |
| DE19510474A1 (en) * | 1995-03-27 | 1996-10-02 | Basf Ag | New hair fixatives |
| FR2759286B1 (en) * | 1997-02-10 | 2004-04-02 | Oreal | USE OF POLYMERS WITH CRITICAL TEMPERATURE OF THE LCST OR UCST TYPE IN AND FOR THE MANUFACTURE OF COSMETIC OR DERMATOLOGICAL FORMULATIONS COMPOSITIONS CONTAINING THEM |
| DE10150282A1 (en) * | 2001-10-12 | 2003-04-30 | Basf Ag | Hair cosmetic preparations |
| DE10245586A1 (en) * | 2002-09-27 | 2004-04-08 | Basf Ag | Use of polymers based on N-vinylcaprolactam |
| DE10357532A1 (en) * | 2003-12-08 | 2005-07-07 | Basf Ag | Use of polymers based on N-vinylcaprolactam for hair cosmetics |
| JP5235049B2 (en) * | 2006-07-25 | 2013-07-10 | 株式会社 資生堂 | Aerosol hair cosmetics |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3145147A (en) * | 1961-02-20 | 1964-08-18 | Gen Aniline & Film Corp | Film forming composition of copolymers of nu-vinyl-epsilon-caprolactam |
| JPS5849715A (en) * | 1981-08-13 | 1983-03-24 | ジ−・エ−・エフ・コ−ポレ−シヨン | Hair conditioner containing vinylcaprolactam / vinylpyrrolidone / alkyl acrylate |
| DE3209224A1 (en) * | 1982-03-13 | 1983-09-15 | Basf Ag | METHOD FOR THE PRODUCTION OF INSOLUBLE, LITTLE SWELLABLE POLYMERISATES OF BASIC VINYLHETEROCYCLES AND THE USE THEREOF |
-
1990
- 1990-04-30 DE DE4013872A patent/DE4013872A1/en not_active Withdrawn
-
1991
- 1991-04-20 DE DE59102050T patent/DE59102050D1/en not_active Expired - Fee Related
- 1991-04-20 EP EP91106394A patent/EP0455081B1/en not_active Expired - Lifetime
- 1991-04-20 ES ES91106394T patent/ES2056516T3/en not_active Expired - Lifetime
- 1991-04-22 CA CA002040963A patent/CA2040963A1/en not_active Abandoned
- 1991-04-30 JP JP09867891A patent/JP3442407B2/en not_active Expired - Fee Related
-
2000
- 2000-08-15 JP JP2000246452A patent/JP3469177B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5635169A (en) * | 1994-10-29 | 1997-06-03 | Basf Aktiengesellschaft | Soluble copolymers for hair cosmetics |
| US5869032A (en) * | 1994-12-07 | 1999-02-09 | Basf Aktiengesellschaft | Quaternized copolymers suitable as active ingredients in cosmetic formulations, such as hair styling compositions |
| US6191188B1 (en) * | 1997-01-14 | 2001-02-20 | Basf Aktiengesellschaft | Aqueous compositions and their use |
| US8398963B2 (en) | 2000-02-23 | 2013-03-19 | Basf Se | Cosmetic agent |
| US20240124708A1 (en) * | 2022-09-30 | 2024-04-18 | L'oreal | Acidic bonding compositions and methods for restoring and color toning lightened hair |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3442407B2 (en) | 2003-09-02 |
| DE4013872A1 (en) | 1991-10-31 |
| JP3469177B2 (en) | 2003-11-25 |
| JPH04225912A (en) | 1992-08-14 |
| DE59102050D1 (en) | 1994-08-04 |
| EP0455081B1 (en) | 1994-06-29 |
| JP2001097832A (en) | 2001-04-10 |
| ES2056516T3 (en) | 1994-10-01 |
| EP0455081A1 (en) | 1991-11-06 |
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| EEER | Examination request | ||
| FZDE | Dead |