CN1129396A - Hair cosmetic compositions - Google Patents
Hair cosmetic compositions Download PDFInfo
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- CN1129396A CN1129396A CN94193095A CN94193095A CN1129396A CN 1129396 A CN1129396 A CN 1129396A CN 94193095 A CN94193095 A CN 94193095A CN 94193095 A CN94193095 A CN 94193095A CN 1129396 A CN1129396 A CN 1129396A
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- hair
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- 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
- A61K8/91—Graft copolymers
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- 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
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- 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
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
Abstract
A liquid hair cosmetic composition comprising: a) from about 0.1% by weight to about 10% by weight (acid basis) of a silicone-containing polycarboxylic acid hair styling copolymer having a vinyl polymeric backbone, and having grafted to the backbone a silicone-containing macromer having a weight average molecular weight of from about 1,000 to about 50,000; b) from about 0.01% by weight to about 10% by weight of a non-silicone-containing hair styling resin; and c) the balance comprising a carrier suitable for application to hair. The liquid hair cosmetic products demonstrate excellent hair styling and feel attributes .
Description
Technical field
The present invention relates to hair cosmetic compositions.More particularly, the present invention relates to the liquid hair make-up composition of the non-silicone that contains polysiloxane grafted hair fixing copolymer and contain hair styling resin.
It is widely that hair is kept the needs of special shape.The commonsense method of finishing this purpose is with hair fixing, or uses " typing " compositions on hair (generally at moistening or exsiccant hair).These compositionss provide temporary transient typing effect, and it can be removed by water and/or shampoo.Be used for providing the material of the compositions of typing effect normally to use with the form of mousse, hair jelly, shampoo or hair spray.
When hair setting composition is used as hair spray, generally can obtain high hold hair style.Hair style to maintain representational be by resin (AMPHOMER (RTM) that provides as National Starch, and the GANTREZ SP 225 (RTM) that provides of GAF) is provided.As the eruption product that is used in commercial distribution, the weight average molecular weight of these resins is generally about 40,000 to about 150,000.When these resins joined pump or aerosol eruption product, they can provide excellent typing characteristic.But such resin is being weak aspect the texture of hair, and particularly they make hair that gluing sensation be arranged.
The known neutral polymer that certain contains the siloxane macromer component can provide the effect of finalizing the design preferably, and improved hair texture also is provided simultaneously.In other words, with respect to the resiniferous non-silicone of routine, such polymer that contains siloxane macromer can produce soft hand feeling and hair conditioning, and hair does not have the common adhesion sense relevant with the non-silicone hair fixing copolymer.Contain the hair fixing copolymer of siloxane macromer and contain their prescription open, for example, the US-A-5100657 (Ansher-Jackson etc.) of the EP-A-0408311 (Hayama etc.) of promulgation on January 11st, 1991, the US-A-5061481 (Suzuki etc.) of promulgation on October 29th, 1991, the US-A-5106609 (Bolich etc.) of promulgation on April 21st, 1992, the US-A-5100658 (Bolich etc.) of promulgation on March 31st, 1992, promulgation on March 31st, 1992 and promulgation on April 14th, 1992 US-A-5104646 (Bolich etc.).Also known in hair setting composition, need to use to greatest extent the hair fixing copolymer that contains siloxane macromer to the neutral form of small part.Specifically, silicone grafted copolymer can be with inorganic or organic neutralizer or the neutralization of its mixture.
So need have excellent typing function, hair nursing effect, nothing adhesion sense, remove while product and its viscosity stabilization and the completely stable hair setting composition of preservation under long-term and abominable temperature easily.
Have now found that, in the liquid hair dressing composition that contains the conventional hair molding resin, add the such copolymer that contains siloxanes of low content and can give the excellent sense of sending out, obtain the good styling relevant simultaneously with conventional resins.In other words, adding the copolymer that contains siloxanes with low relatively amount reduces or has eliminated the shortcoming of conventional resins hair feel adhesion and do not disturbed its whole typing characteristic.
According to one aspect of the present invention, it provides the liquid hair dressing composition, and it contains:
A) about 0.1% to about 10% (weight is calculated with acid) have the vinyl polymerization skeleton and contain weight average molecular weight be about 1,000 to 50,000 be grafted to the macromonomer that contains siloxanes on the skeleton contain siloxanes polycarboxylic acids hair fixing copolymer;
B) the non-silicone hair styling resin of about 0.01% to 10% (weight); And
C) surplus comprises the carrier that is suitable for hair.
Be used for the mixture that compositions herein comprises siloxanes hair fixing copolymer and non-silicone hair styling resin.The total amount of hair fixing reagent (siloxanes and non-silicone) is preferred to be existed with 0.11% to about 20% content approximately, and more preferably from about 0.5% to about 15%, and preferred about 1% to about 10% (weight) especially.In the further preferred embodiment of the present invention, the weight ratio of silicone copolymers and non-siloxane resin is about 1000: 1 to about 1: 1000, preferred about 100: 1 to about 1: 100, and more preferably from about 10: 1 to about 1: 10 and preferred about 5: 1 to about 1: 5 especially.
The basic optional components that reaches of the present invention is described below.Unless stated otherwise, all content and ratio are the weight in compositions.
Contain silicone copolymers
Compositions of the present invention contains has an appointment 0.1% to about 10.0%, preferred about 0.5% to about 8.0% and especially preferred about 1% to about 6% special qualification contain silicone copolymers.These polymer are to the invention provides unique hair care effect and hair fixing characteristic just, and improve the tactile characteristics of non-siloxane resin component.The weight average molecular weight of polymer is preferably about 10,000 to about 1,000,000, and preferred about 30,000 to about 300,000, and more preferably from about 90,000 to about 300,000, and preferably its Tg value is at least-20 ℃ of pacts.Be used for the vitrification point that herein abbreviation " Tg " is meant the non-silicone skeleton, abbreviation " Tm " is meant the crystal melting point (if there is such transformation in given polymer) of non-silicone skeleton.
The molecular weight and the molecular weight distribution that are used for the polymer of compositions among the present invention are determined by exciusion chromatography (SEC).In fact, contain their peculiar property of polymer generation that the molecular weight kind distributes.The separation of molecule is to finish by exciusion chromatography, uses glue polystyrene-divinylbenzene (MW scope=100-107) post and differential refractive index detector and differential viscosity meter.Monodisperse polystyrene reference material by known molecular amount (MW) and molecular weight distribution (MWD) is made the universal calibration curve.The MW of given polymer and MWD determine according to its concentration and viscosity with respect to calibration curve.
Preferred polymer contains ethene polymers skeleton (preferred Tg is higher than-20 ℃ approximately) and the molecular weight that is grafted on the skeleton is about 1,000 to about 50,000 (preferred about 5000 to about 40000, most preferably from about 10,000 to about 20,000) the macromonomer that contains siloxanes.When polymer was made final hair care composition, when drying, polymer phase entered discontinuous phase that contains siloxane macromer and the continuous phase that contains skeleton respectively.Can believe that this phase separation property can provide the especially orientation of polymer to hair, thereby produce required hair care and hair fixing effect.
Broad sense, the copolymer that is used for the application contain monomer (B) and the optional lipophile monomer (A) that siloxanyl monomers (after this being called C) and hydrophilic contain carboxylate.
Example of available copolymer and preparation method thereof is described in detail among the US-A-4728571 (Clemens etc.) of the US-A-4693935 (Mazurek) of JIUYUE in 1987 promulgation on the 15th, promulgation on March 1st, 1988.These copolymers contain monomer A, B and the C that is defined as above.In a preferred embodiment, A comprises the polymerisable vinyl monomer of at least one free radical, but B contains one at least with the reinforcing monomer of A copolymerization and be selected from the monomer that contains carboxylate and Tg or Tm and be higher than-20 ℃ macromonomer.In the monomer total amount of copolymer, the content of B can preferably be no more than 80%, more preferably no more than 30% up to about 98%.In the polymer monomers total amount, the content of monomer C is about 0.1% to about 50.0%.
The monomeric representative example of A (hydrophobicity) is C
1-C
18Alcohol is (as methanol, ethanol, methyl cellosolve, the 1-propanol, the 2-propanol, the 1-butanols, 2-methyl isophthalic acid-propanol, the 1-amylalcohol, the 2-amylalcohol, the 3-amylalcohol, 2-methyl-1-butene alcohol, 1-methyl isophthalic acid-butanols, 3-methyl isophthalic acid-butanols, 1-methyl-1-pentene alcohol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, the tert-butyl alcohol (2-methyl isophthalic acid-propanol), Hexalin, new decanol, 2-ethyl-1-butanols, the 3-enanthol, benzyl alcohol, sec-n-octyl alcohol, 6-methyl isophthalic acid-enanthol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, the 1-dodecanol, the 1-hexadecanol, 1-octadecanol etc., have about 1-18 carbon atom average atom number and be the alcohol of about 4-12 carbon atom) the acrylic or methacrylic acid esters, styrene, the polystyrene macromolecular monomer, vinyl acetate, vinyl chloride, vinylidene chloride, propionate, α-Jia Jibenyixi, t-butyl styrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene, and composition thereof.Preferred A monomer comprise methacrylic acid n-butyl, methacrylic acid isobutyl, methacrylic acid 2-ethyl hexyl ester, methyl methacrylate, acrylic acid tertiary butyl ester, methacrylic acid tertiary butyl ester, and composition thereof.
Contain carboxy moiety can in and the representative example of monomers B (hydrophilic) comprise half ester .beta.-methylacrylic acid and the clothing saccharic acid of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic anhydride.Preferred B monomer comprises acrylic acid, methacrylic acid and composition thereof.
The C monomer preferably has general formula (I):
X(Y)
nSi(R)
3－mZ
m (I)
Wherein X be can with the vinyl of A and B monomer copolymerizable; Y is a divalent linker; R is hydrogen, C
1-C
4Alkyl, aryl, alkyl amino, three (C
1-C
4Alkyl) siloxy or C
1-C
4Alkoxyl; Z is the monovalent siloxane polymeric part; N is 0 or 1; And m is 1 to 3 integer.The number-average molecular weight of C is at least 500, and preferred 1,000 to 50,000.Preferred C monomer is to be selected from the one or more monomers with general formula (II to VII).
In these structures, m is 1,2 or 3 (preferred m=1); P is 0 or 1; R ＂ is alkyl or hydrogen; Q is 2 to 6 integer; X is
R
1Be hydrogen or-COOH (preferred R
1Be hydrogen); R
2Be hydrogen, methyl or-CH
2COOH (preferred R
2Be methyl); Z is
R
4Be alkyl, alkoxyl, alkyl amino, aryl or hydroxyl (preferred R
4Be alkyl); And r is 5 to 700 integer, and is preferred 50 to 500, more preferably 150 to 300.In above-mentioned all general formulas, general formula I I is preferred, particularly when p=0 and q=3.
Polymer generally contains 0% to about 98% (preferred about 5% to about 92% as used herein, more preferably from about 50% to about 90%) monomer A, about 1% to the monomers B of about 98% (preferred about 7.5% to about 80%) and the about 0.1% monomer C to about 50% (preferred about 0.5% to about 40%, most preferably from about 2% to about 25%).The monomeric mixture of A and B preferably account for polymer about 50.0% to about 99.9% (more preferably from about 60% to about 99.5%, most preferably from about 75% to 98%).
Containing silicone copolymers as used herein is preferably selected from:
Acrylic acid/methacrylic acid n-butyl/polydimethylsiloxane (PDMS) macromonomer-20000 molecular weight (mw) (10/70/20 w/w/w);
Acrylic acid/methacrylic acid isobutyl/PDMS macromonomer-20000 molecular weight (mw) (20/60/20w/w/w);
Acrylic acid/PDMS macromonomer-20000mw (80/20w/w);
Acrylic acid tertiary butyl ester/acrylic acid (AA)/PDMS macromonomer-10000mw (60/20/20);
Acrylic acid/methacrylic acid isobutyl/PDMS macromonomer-20000 molecular weight (mw) (10/70/20w/w/w);
Acrylic acid/methyl methacrylate/PDMS macromonomer-20000 molecular weight (mw) (40/40/20);
Acrylic acid/methacrylic acid isopropyl esters/PDMS macromonomer-20000 molecular weight (mw) (25/65/15);
Acrylic acid/methacrylic acid methoxy ethyl ester/PDMS macromonomer-20000 molecular weight (mw) (60/25/15);
Acrylic acid/PDMS macromonomer-20000mw (80/20);
And composition thereof.
The above-mentioned copolymer that contains siloxanes can by contain siloxanes or contain silicone monomers and non-silicone or the monomeric Raolical polymerizable of non-silicone synthetic.The General Principle of free radical polymerization reaction method is known.For example, see Odian, " polymerization principle (Pri-nciples of Polymerization) ", second edition, John Wiley﹠amp; Sons, 1981, the 179-318 page or leaf.
In compositions of the present invention, need unreactedly contain siloxanyl monomers and be the copolymer of 10,000,000 centistoke and lower siloxanes-macromole graft polymers purification of silicone containing by removing 25 ℃ of following viscosity.For example, this can finish by hexane extraction.Behind the dry resin, the hexane extraction of reactant can be finished by the Tg that adds excessive hexane and be heated near non-silicone part in the polymer in reactant from reaction dissolvent.Mixture remains on this temperature and stirred 30 minutes, is cooled to room temperature again.Remove hexane by vacuum draw.Preferably carry out twice hexane extraction circulation again according to method same as described above.After the 3rd circulation.Remove the hexane that residues in the product by distillation and vacuum drying.
Contain silicone monomers and polymer and by carrier pipe it is shifted from residual polymer with the dissolving of postcritical carbon dioxide is low-molecular-weight, carrier pipe remains under the identical temperature and pressure with extraction container.In extraction container, collect the material that is extracted.After the extraction,, from extraction container, reclaim the polymer that is extracted with system decompression and dry.
The hair styling resin of non-silicone
Except that containing siloxanes hair fixing copolymer, compositions of the present invention contains the non-silicone hair styling resin as second basis.The hair styling resin of this non-silicone preferably becomes colloid to be scattered in or is dissolved in the carrier of cosmetic hair with containing siloxanes hair fixing copolymer.It is important keep these two kinds of hair fixing reagent to be scattered in and to be dissolved in being considered to unique hair fixing effect and excellent hair feel characteristic is provided in the hair sprays solvent.This is the present composition purpose that will reach just.
The non-silicone hair styling resin composition of liquid hair dressing composition of the present invention comprises anion, both sexes, nonionic or cationic polymerization material or its mixture.The hair styling resin that is used for liquid hair dressing composition of the present invention is preferably anion or amphoteric.
The non-silicone hair styling resin preferably accounts for composition weight about 0.5% to about 10%, and more preferably from about 1% to about 5%.Being suitable for hair styling resin as used herein comprises and dissolves in or become colloid to be scattered in any resin in the cosmetic hair carrier.Carrier is a kind of alcohol solvent in a preferred embodiment, it can choose wantonly contain be not higher than about 15% (preferably be not higher than about 10%, more preferably no higher than about 7%) water as cosolvent.Dissolubility and dispersibility are measured under temperature and pressure (25 ℃ and 101.3kPa (1atm)) environment.
The resin that is preferred for the present composition comprises anion, nonionic and amphoteric resin and composition thereof.Preferred resin is selected from as used herein: acrylate/acrylamide copolymer, the polyvinyl methyl ethermaleic anhydride copolymer, vinyl acetate/.beta.-methylacrylic acid copolymer, octyl acrylamide/acrylate/metering system acid butyl amino-ethyl ester copolymer, polyvinylpyrrolidone (PVP), the copolymer of polyvinylpyrrolidone and methyl methacrylate, the copolymer of polyvinylpyrrolidone and vinyl acetate (VA), polyvinyl alcohol, the copolymer of polyvinyl alcohol and .beta.-methylacrylic acid, the copolymer of polyvinyl alcohol and maleic anhydride, hydroxypropyl cellulose, hydroxypropyl guar gum, kayexalate, polyvinylpyrrolidone/methacrylic acid ethyl ester/metering system acid ter-polymer, vinyl acetate/.beta.-methylacrylic acid/vinyl neodecanoate copolymer, octyl acrylamide/acrylate copolymer, poly-(methyl vinyl ether-maleic acid) single ethyl ester, starch ocentyl succinic aluminum (aluminium starch octenyl-succinate) and composition thereof.The particularly preferred resin that is used for the present composition comprises acrylate/acrylamide copolymer of selling with trade name Ultra Hold 8 (RTM) (from BASF Corp.), polyvinyl methyl ethermaleic anhydride copolymer with trade name Gantrez (RTM) (from GAF Corp.) sale, vinyl acetate/.beta.-methylacrylic acid copolymer with trade name Luviset CA-66 (RTM) (from BASFCorp.) sale, octyl acrylamide/acrylate/metering system acid butyl amino-ethyl ester copolymer with trade name Amphomer (RTM) (from National Starch) sale, caprolactam/vinyl pyrrolidone/dimethylaminoethyl acrylate methyl base amino-ethyl ester terpolymer with trade name Hold EP 1 (RTM) (from GAF) sale, polyvinylpyrrolidone, polyvinylpyrrolidone with trade name Luviskol (RTM) sale, polyvinylpyrrolidone and vinyl acetate copolymer (for example LuviskolVA64 (PVA/VA 60/40)), and composition thereof.Most preferred resin is Ultra Hold8 (RTM) and Amphomer (RTM) and composition thereof in the present composition.The weight average molecular weight of required hair fixing copolymer resin generally about 2,000 to about 2,000,000 scope.
In addition, can use cation and non-ionic resin, see for details hereinafter.Being suitable for as used herein, polycation hair care fluoropolymer resin is described below.For ease of describing its polymer, the monomer unit that exists in polymer can refer to can be from deutero-monomer wherein.Cationic monomer can be derived from polymerizable cation initial monomers or polymerizable non-ionic monomer (changing into cationic characteristic after its polymerization).
These unsaturated cationic monomers can the cationic form polymerization, or they can its precursor forms polymerization, and then changes over cation, for example, and by quaternizing agent (as monochloro ethyl acetate, dimethyl sulfate etc.).The preferred cation monomer comprises dimethylaminoethyl acrylate methyl base amino-ethyl ester, quaternized dimethylaminoethyl acrylate methyl base amino-ethyl ester, chlorination diallyl dimethyl ammonium, vinyl imidazole quaternary ammonium salt monomer and composition thereof.
The representational example of non-ionic monomer is C
1-C
24Alcohol is (as methanol, ethanol, the 1-propanol, the 2-propanol, the 1-butanols, 2-methyl isophthalic acid-propanol, the 1-amylalcohol, the 2-amylalcohol, the 3-amylalcohol, 2-methyl-1-butene alcohol, 1-methyl isophthalic acid-butanols, 3-methyl isophthalic acid-butanols, 1-methyl-1-pentene alcohol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, the tert-butyl alcohol, Hexalin, 2-ethyl-1-butanols, the 3-enanthol, benzyl alcohol, sec-n-octyl alcohol, 6-methyl isophthalic acid-enanthol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, the 1-lauryl alcohol, the 1-hexadecanol, 1-octadecanol etc., has about 1-24 carbon atom, preferred about 4-18 carbon atom alcohol) acrylic or methacrylic acid esters, styrene, chlorostyrene, vinyl esters such as vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, α-Jia Jibenyixi, t-butyl styrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene, (methyl) alkoxyalkyl acrylate (as (methyl) acrylic acid methoxy ethyl ester and (methyl) butoxyethyl acrylate), and composition thereof.Other non-ionic monomer comprises oleyl alcohol ester, acrylic acid and methacrylic acid benzyl ester, acrylic acid and tetrahydrofurfuryl methacrylate, diacrylate and two (methacrylic acid) glycol ester, diacrylate and two (methacrylic acid) 1,3 butylene glycol ester, N-[2-(2-methyl-4-oxopentyl), (methyl) isobornyl acrylate etc. of cyclohexyl ester, acrylic acid and methacrylic acid of allyl ester, acrylic acid and the methacrylic acid of the derivant of acrylate and methacrylate such as acrylic acid and methacrylic acid.
Preferred non-ionic monomer comprise methacrylic acid n-butyl, methacrylic acid isobutyl, methacrylic acid 2-ethyl hexyl ester, methyl methacrylate, acrylic acid tertiary butyl ester, methacrylic acid tertiary butyl ester, and composition thereof.
Representational polarity non-ionic monomer comprises that the acrylate of acrylamide, N,N-DMAA, Methacrylamide, N tert butyl acrylamide, methacrylonitrile, acrylamide, alcohol is (as C
2-C
6The acrylate of alcohol such as hydroxyethyl acrylate, acrylic acid hydroxypropyl ester), methacrylic acid hydroxyethyl ester, hydroxypropyl methacrylate, vinyl pyrrolidone, vinyl ethers such as methyl vinyl ether, acyl group lactone and vinylpyridine, propenyl, vinyl alcohol and caprolactam.
The preferred polycationic polymer resin of Shi Yonging comprises cationic guar gum herein, cationic polysaccharide, the homopolymer of chlorination dimethyldiallylammonium, the copolymer of chlorination dimethyldiallylammonium and acrylamide, the cation amino functional group's of derived from propylene acid and/or methacrylic acid (the particularly dimethyl aminoethyl ester of the alkylaminoalkyl of acrylic acid and methacrylic acid such as acrylic acid and methacrylic acid) homopolymer and copolymer, poly-(alkylidene) imines of poly-(alkylidene) imines and ethyoxyl, vinyl imidazole/vinyl pyrrolidone quaternized copolymer, and composition thereof.
Neutralized system
Hair fixing copolymer herein preferably uses so that the shampoo of liquid hair make-up composition can be removed down to the neutral form of small part.In the compositions of the present invention, can be by using in a kind of inorganic base (preferred potassium hydroxide) and hair fixing copolymer (as polysiloxane grafted tBA/AA copolymer).But also can use the organic base (preferred AMP (amino methyl propanol)) and the mixture of inorganic base and organic base to reach the required neutralization levels of hair cosmetic product of the present invention.About 30% of the acid monomer total amount of every kind of used polymer is used the alkali neutralization to about 95% (preferred about 55% to about 75%, most preferably from about 60% to 70%).
During any conventional use alkali (organic or inorganic) can be used for and at this special acidic polymer that uses.The hydroxide of alkali metal, alkaline-earth metal and amino alcohol are the suitable nertralizers that is used for this liquid hair make-up composition.
The example that can be included in the suitable organic neutralization reagent in the hair cosmetic compositions of the present invention comprises amine, particularly amino alcohol such as 2-amino-2-methyl-1, ammediol (AMPD), 2-amino-2-ethyl-1, ammediol (AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanols (AB), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monoisopropanolamine (MIPA), diisopropanolamine (DIPA) (DIPA), triisopropanolamine (TIPA), dimethyl steramine (DMS) and amino methyl propanol (AMP) and composition thereof.
Preferred potassium hydroxide of the neutralization reagent that uses in the hair cosmetic compositions of the present invention and sodium hydroxide.
The amount (g) of any given needed alkali of polymer of neutralizing (Z) can be from the acid number (A) of polymer, the amount (W) of polymer, the molecular weight (B) of alkali, the molecular weight (M) and the required neutral degree (N) of acidic moiety.
Z(g)＝W×A/100×1/M×B×N％
In the example below, calculated the amount that 2.6g acrylic copolymer (acid number is 20) is neutralized to 60% the required potassium hydroxide of neutralization levels.
Z(g)＝2.6×20/100×1/72×56×0.60
Z＝0.24g
Note, can be by determine acid number or original acid content (acid value that promptly contains the polymer of 20% acid monomer the is 20) acid number of deriving theoretically by the consideration copolymer with the specific quantitative test of alkalimetric titration polymer.
Liquid hair dressing composition of the present invention also comprises carrier.This can comprise any material that is usually used in the resin hair spray, comprises the optional member of solvent, propellant and other liquid hair cosmetics.The weight percentage of carrier is generally about 60% to about 99.8%, preferred about 68% to about 98% in the liquid hair make-up composition.More preferably carrier accounts for about 70% to about 98% of total composition weight.
The organic solvent that is suitable in the present composition carrier comprises C
1-C
6Alkanol, carbitol, acetone and composition thereof.Be preferred for the C of this compositions
1-C
6Alkanol is C
2-C
4MHA such as ethanol, isopropyl alcohol and composition thereof.
Liquid hair make-up composition of the present invention contains 0% to about 15% water (weight), and preferred 0% to about 10%, more preferably 0% to about 5% water (weight).
Plasticizer
Can be by nonvolatile plasticizer being joined the performance of improving liquid hair compositions of the present invention in the compositions arbitrarily.The amount that generally accounts for compositions according to plasticizer of the present invention is up to 25% (preferred 1% to 20%, more preferably 1% to 15%)." nonvolatile " plasticizer refers at normal pressure and 25 ℃ of plasticizers that do not have vapour pressure substantially as used herein.Right when hair cosmetic carrier volatilization, the plasticizer of the polymer-liquid-carrier solution substantial loss in weight that do not have is because may reduce polymer plasticization effect in use greatly like this.The general boiling point of plasticizer used herein is about 250 ℃ or higher.
In the art, plasticizer is known.General description is in Kirk-Othmer En-cyclopedia of Chemical Technology, second edition, the 15th volume, 720-789 page or leaf (John Wiley﹠amp; Sons, Inc.New York, 1968), title is " plasticizer " and " plasticizer technology) " book (J.Kern Sears and J.R.Darby) (John Wiley﹠amp; Sons, Inc.New York, 1982).Special in 983-1063 page or leaf Sears/Darby Table appendix A.9, a large amount of plasticizers is disclosed therein.
The plasticizer that is suitable in the present composition comprises ring and acyclic nonvolatile matter.The suitable classification of non-volatile plasticisers comprises adipate ester, phthalic acid ester, isophthalic acid ester, azelate, stearate, citrate, trimellitate, copolymeric siloxane alcohol, different C
14-C
22Alcohol, methyl alkyl siloxane, carbonic ester, sebacate, isobutyrate, oleate, phosphate ester, myristate, ricinoleate, pelargonate, valerate, Camphora, glycol, amine derivative, selected short chain alcohol and Oleum Ricini.
Particularly preferred plasticizer used herein comprises that glycol and citrate are the plasticizer of substrate such as propylene glycol, dipropylene glycol, citric acid acetyl three-just-butyl ester, citric acid three-just-butyl ester and citric acid acetyl three-2-ethyoxyl hexyl ester (the commodity Citroflex RTM by name that provides as Pfizer) and glycerol, amino methyl propanol (AMP), adipic acid diisobutyl ester (DIBA) and isopropyl alcohol.
Propellant
Compositions of the present invention can be made into the hair spray of aerosol or non-aerosol form.Aerosol hair spray agent if desired must comprise propellant in compositions.This reagent is responsible for other material discharged from container and form the hair spray characteristic.
Propellant gas can be the liquefiable gas that any routine is used for aerosol container.The density of preferred propellant and composition thereof less than 1 so that pure propellant be unlikely to overflow from container.The example that is suitable for doing the material of propellant is Arcton 11, dichlorodifluoromethane, dichlorotetra-fluoroethane, monochloro difluoromethane, trichorotrifluoroethane, dimethyl ether (as the Dimel 152A (RTM) that is provided by DuPont), propane, normal butane, iso-butane (being used alone or as a mixture) and propane butane (as CAP 80 (RTM)).Preferred Dimel 152A (RTM) and propane butane.
The amount of propellant gas is decided by the known regular element of aerosol art.For hair spray, the content of propellant generally account for total composition about 10% to about 40% (preferred about 20% to about 30%).If propellant (as dimethyl ether) uses air pressure inhibitor (as trichloroethane or dichloromethane), then the amount of inhibitor is included in the propellant component.
Hair cosmetic compositions of the present invention can use conventional form or hybrid technology preparation.Compositions of the present invention can prepare until dissolving by joining polymer in the ethanol and mixing in several hours.Add again plasticizer and in and composition and stir the solution of gained.And then add any remaining component such as water, ethanol and spice.
The manufacture method of hair cosmetic compositions of the present invention has more specifically been described in an embodiment.
Perhaps, can use the aerosol dispenser of pressurization, wherein not allow their contact by using special container (as the two Room jar types that provide by Americal National Can Corp with trade name SEPRO) that propellant is separated with the hair spray compositions.
The feature of the aerosol dispenser that other is suitable is will to charge in the allotter before use as the compressed air of propellant by pump or the equipment that is equal to.Such allotter be described in US-A-4077441 (on March 7th, 1978, Olofsson) and US-A-4850577 (on July 25th, 1989, TerStege).Present Procter﹠amp; Gamble Company sells the Compressed Gas aerosol container that is suitable for trade name VIDAL SASSOON AIRSPRAY (RTM) hair spray.
Also can use conventional non-aerosol pump jetting dispenser (being aerosol apparatus).
Other component
Liquid hair make-up composition of the present invention also can comprise a large amount of non-basic, component such as antiseptic, surfactant, block copolymer, thickening agent and viscosity modifier, electrolyte, aliphatic alcohol, pH regulator agent, perfumery oil, spice solubilizer, chelating agen, softening agents arbitrarily; Lubricant and penetrating agent such as different lanoline components; Protolysate and other protein derivatives; Ethylene adduct and polyoxyethylene cholesterol; Sun-prevention component and hair care property and non-hair care silicone liquid.Any component like this is known to those skilled in the art, for example, surfactant such as anion (as alkyl sodium sulfate), nonionic (amine oxide), both sexes (aliphatic secondary or tertiary amines derived thing), amphion (aliphatic quaternary ammonium, phosphorus or sulfur derivatives) and fluorinated surfactant (as Zonyl FSK) are (RTM); The diglycollic amide of thickening agent and viscosity modifier such as long-chain fatty acid; Pluronic (RTM) F 88 that the block polymer of ethylene oxide and propylene oxide such as BASF Wyandotte provide; Aliphatic alcohol such as spermol (cetearyl); Viscosity modifier such as sodium chloride, sodium sulfate and ethanol; Electrolyte such as earth metal and alkali salt; Quaternary ammonium ion and cationic amine and halogen ion; PH regulator agent such as citric acid, succinic acid, sodium hydroxide and triethanolamine; Perfumery oil such as Florasynth (RTM) spice; Perfumery oil solubilizer such as cithrol and chelating agen such as ethylenediaminetetraacetic acid.Each accounted for composition weight of these optional, materials about 0.05% to about 5% (preferred about 0.1% to about 3%).
Liquid hair make-up composition of the present invention is to use by conventional methods so that hair fixing effect of the present invention to be provided.Such method generally comprises the product that sprays effective dose in (or the two) before or after the typing on dry or moistening hair." effective dose " is meant that the length of considering hair and structure are enough to provide the amount of required hair volume and typing effect.
The present invention is by following non-limiting example explanation.
In an embodiment, all concentration are on 100% active matrix except as otherwise noted, and abbreviated form has to give a definition: silicone copolymers-60% acrylic acid tertiary butyl ester/20% acrylic acid/20% siloxanes PDMS.Weight average molecular weight (measuring with exciusion chromatography) is 150,000.The non-siliceous copolymer 2-Ultra of non-siliceous copolymer 1-Amphomer (RTM) Hold 8 (RTM) potassium hydroxide-potassium hydroxide solution contains 45% potassium hydroxide and 55% water and micro constitutent AMP-2-amino-2-methyl-1-propanol DRO water-two inverse osmosis aqueous solvent-ethanol
Example I-VI
Following liquid hair make-up composition is the hair spray composition forms that is applicable to the pump jetting dispenser, and it is representative of the present invention:
Polymer % 050 10 0 0DRO water 707007 surpluses of the polymer % 60 55 60 50 55 60AMP neutralization of the non-siliceous copolymer 2 of I II III IV V VI silicon-containing copolymer 0.5 6.0 4.5 5.0 2.0 3.0 non-siliceous copolymer 1 4.5 0.5-1.0-2.0--0.5-3.0-potassium hydroxide neutralization ... add to 100% with ethanol
Surplus contains ethanol and any optional component such as plasticizer, spice and surfactant.
The hair spray prescription is to prepare by polymer is directly added in the ethanol.Use magnetic stirrer or air agitator blending ingredients until polymer dissolution, generally need about 1 to 2 hour.Then nertralizer is added and be mixed in the mixture of front.Then, adaptable optional components and water are sneaked in the compositions.
Above-mentioned composition has the excellent transparency, and provides excellent hair texture to reach hair style retention performance preferably when being used for hair.
Example VII A-XII
Following liquid hair make-up composition is to be representative of the present invention with the hair spray concentrate composition form that is suitable for aerosol dispenser and it:
VII VIII IX X XI XII silicon-containing copolymer 8.0 4.0 4.0 4.5 1.0 2.0 non-siliceous copolymer 1 2.0-1.0--polymer % 055 10 0 5DRO water 0055 10 10 surpluses of the polymer % 60 55 55 60 60 50AMP neutralization of 2.0 non-siliceous copolymer 2-0.5-0.5 8.0-potassium hydroxide neutralizations ... add to 100%...... with ethanol
To VI, surplus contains ethanol and optional component such as plasticizer, spice and surfactant as example I.Compositions such as embodiment I-VI preparation.Concentrate is packed in the conventional aerosol injection jar, and charges into conventional liquefiable propellant (as CAP80 (propane/butane) (RTM)), and the weight rate of propellant and concentrate is 23: 77.
Above-mentioned composition has the excellent transparency to reach stability characteristic (quality) under long-term and severe temperatures, and provides excellent hair texture to reach hair style retention performance preferably when being used for hair.
Claims (17)
1, a kind of liquid hair make-up composition, it contains:
A) about 0.1% to about 10% (weight is calculated with acid) have a vinyl polymerization skeleton, and contain weight average molecular weight be about 1,000 to 50,000 be grafted on the skeleton contain siloxane macromer contain siloxanes polycarboxylic acids hair fixing copolymer;
B) the non-silicone hair styling resin of about 0.01% to 10% (weight); And
C) surplus comprises the carrier that is suitable for hair.
2,, wherein contain siloxane macromer and have general formula (I) according to the liquid hair make-up composition of claim 1:
X(Y)
nSi(R)
3－mZ
m (I)
Wherein X is a vinyl; Y is a divalent linker; R is hydrogen, alkyl, aryl, alkyl amino, trialkylsiloxy or alkoxyl; Z is that number-average molecular weight is at least 500 monovalent siloxane polymeric part; N is 0 or 1; And m is 1 to 3 integer.
3, according to the liquid hair make-up composition of claim 1 or 2, the weight average molecular weight that wherein contains silicone copolymers is 10,000 to 1,000,000, and this copolymer comprises the polar monomer (B) that contains the hydrophilic carboxylate; Optional lipophile, low polarity free redical polymerization vinyl monomer (A), itself and B copolymerization; And weight average molecular weight is 1,000 to 50,000, and is preferred 5,000 to 40,000, based on polydimethylsiloxane contain siloxane macromer (C), wherein macromonomer (C) is to be selected from have general formula one or more monomers of (II-VII).
Wherein, m is 1,2 or 3; P is 0 or 1; R ＂ is alkyl or hydrogen; Q is 2 to 6 integer; X is
R
1Be hydrogen or-COOH; R
2Be hydrogen, methyl or-CH
2COOH; Z is
R
4Be alkyl, alkoxyl, alkyl amino, aryl or hydroxyl; And r is 5 to 700 integer; Wherein contain silicone copolymers and contain 0% to 98% monomer A, 1% to 98% monomers B and 0.1% to 50% monomer C.
4, according to the liquid hair make-up composition in any one of the claim 1 to 3, wherein contain the monomer A that silicone copolymers contains 5% to 92% (weight), the monomers B of 7.5% to 80% (weight) and 0.1% to 50% monomer C.
5, according to the liquid hair make-up composition in any one of the claim 1 to 4, wherein monomer A is selected from C
1-C
18Acrylate, the C of alcohol
1-C
18The methacrylate, styrene, polystyrene macromolecular monomer, vinyl acetate, vinyl chloride, propionate, vinylidene chloride, α-Jia Jibenyixi, t-butyl styrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene of alcohol, and composition thereof.And preferable methyl n-butylacrylate, methacrylic acid isobutyl, methacrylic acid 2-ethyl hexyl ester, methyl methacrylate, acrylic acid tertiary butyl ester, methacrylic acid tertiary butyl ester, and composition thereof.
6, according to the liquid hair make-up composition in any one of the claim 1 to 5, wherein monomers B is selected from half ester .beta.-methylacrylic acid and furoate clothing of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic anhydride and composition thereof; And preferred acrylic acid and methacrylic acid and composition thereof.
7, according to the liquid hair make-up composition in any one of the claim 3 to 6, wherein contain siloxane macromer and have general formula (II), wherein p=0 and q=3, m is 1, R
4Be alkyl, R
1Be hydrogen and R
2It is methyl.
8, according to the liquid hair make-up composition in any one of the claim 1 to 7, wherein contain silicone copolymers and be selected from:
Acrylic acid/methacrylic acid n-butyl/polydimethylsiloxane (PDMS) macromonomer-20000 molecular weight (mw) (10/70/20);
Acrylic acid/methacrylic acid isobutyl/PDMS macromonomer-20000 molecular weight (mw) (20/60/20);
Acrylic acid/methacrylic acid isobutyl/PDMS macromonomer-20000 molecular weight (mw) (10/70/20);
Acrylic acid/methyl methacrylate/PDMS macromonomer-20000 molecular weight (mw) (40/40/20);
Acrylic acid/methacrylic acid isopropyl esters/PDMS macromonomer-20000 molecular weight (mw) (25/65/15);
Acrylic acid/methacrylic acid methoxy ethyl ester/PDMS macromonomer-20000 molecular weight (mw) (60/25/15);
Acrylic acid/PDMS macromonomer-20000mw (80/20);
And composition thereof.
9, according to the liquid hair make-up composition in any one of the claim 1 to 8, the molecular weight that wherein contains siloxanes hair fixing copolymer is 90,000 to 300,000.
10, according to the liquid hair make-up composition in any one of the claim 1 to 9, wherein the non-silicone hair styling resin can be anion, nonionic, both sexes or cationic polymerization material or its mixture, preferred anionic or amphiphilic polymers matter.
11, according to the liquid hair make-up composition in any one of the claim 1 to 10, wherein the molecular weight of non-silicone hair styling resin is about 40,000 to about 150,000, and it is soluble or dispersible in the hair cosmetic carrier system.
12, according to the liquid hair make-up composition in any one of the claim 1 to 11, wherein non-siloxane resin is copolymer that is selected from octyl acrylamide/acrylate/metering system acid butyl amino-ethyl ester copolymer, polyvinyl methyl ethermaleic anhydride copolymer, polyvinylpyrrolidone (PVP) and PVP/ vinyl acetate (VA) and composition thereof.
13, according to the liquid hair make-up composition in any one of the claim 1 to 12, the ratio that wherein contains siloxanes hair fixing copolymer and non-silicone hair styling resin is about 1000: 1 to about 1: 1000, preferred about 100: 1 to about 1: 100, more preferably from about 10: 1 to about 1: 10 and preferred about 5: 1 to about 1: 5 especially.
14, according to the liquid hair make-up composition in any one of the claim 1 to 13, the content that wherein contains siloxanes hair fixing copolymer is about 0.5% to about 8%, and preferred about 1% to about 6% (weight).
15, according to the liquid hair make-up composition in any one of the claim 1 to 14, wherein the content of non-silicone hair styling resin is about 0.05% to about 8%, and preferred about 0.1% to about 4% (weight).
16, according to the liquid hair make-up composition in any one of the claim 1 to 15, the total content that wherein contains siloxanes hair fixing copolymer and non-silicone hair styling resin is about 0.11% to about 20%, preferred about 0.5% to about 15%, and more preferably from about 1% to about 10% (weight).
17, a kind of hair cosmetic product that comprises the hair spray compositions and be used to contain and spray the spray distribution apparatus of this hair spray compositions, wherein the hair spray compositions contains:
A) about 0.1% to about 10% (weight is calculated with acid) have the vinyl polymerization skeleton and contain weight average molecular weight be about 1000 to 50,000 be grafted on the skeleton contain siloxane macromer contain siloxanes polycarboxylic acids hair fixing copolymer;
B) the non-silicone hair styling resin of about 0.01% to 10% (weight); And
C) contain the surplus that is suitable for the hair carrier.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB939312629A GB9312629D0 (en) | 1993-06-18 | 1993-06-18 | Hair cosmetic compositions |
| GB9312629.0 | 1993-06-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1129396A true CN1129396A (en) | 1996-08-21 |
Family
ID=10737400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94193095A Pending CN1129396A (en) | 1993-06-18 | 1994-05-11 | Hair cosmetic compositions |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0723433A1 (en) |
| JP (1) | JPH08511800A (en) |
| KR (1) | KR960703003A (en) |
| CN (1) | CN1129396A (en) |
| AU (1) | AU6910194A (en) |
| BR (1) | BR9406849A (en) |
| CA (1) | CA2165431A1 (en) |
| GB (1) | GB9312629D0 (en) |
| WO (1) | WO1995000108A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104822365A (en) * | 2012-11-29 | 2015-08-05 | 荷兰联合利华有限公司 | Hair care composition |
| CN112930216A (en) * | 2018-10-25 | 2021-06-08 | 莱雅公司 | Composition comprising at least one silicone acrylic copolymer and at least one cationic acrylic copolymer |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2291893B (en) * | 1994-07-29 | 1998-10-07 | Procter & Gamble | Hair styling compositions |
| JPH11503760A (en) * | 1995-04-21 | 1999-03-30 | ザ、プロクター、エンド、ギャンブル、カンパニー | Topical personal care compositions containing alkenyl or styrene end-capped silicone graft copolymers |
| FR2739283B1 (en) * | 1995-09-29 | 1997-11-07 | Oreal | TOPICAL COMPOSITION CONTAINING A SILICONE GRAFT POLYMER AND AN AMPHIPHILIC FATTY CHAIN POLYMER |
| FR2739289B1 (en) * | 1995-09-29 | 1997-11-07 | Oreal | COSMETIC COMPOSITION COMPRISING AT LEAST ONE GRAFTED SILICONE POLYMER AND AT LEAST ONE ASSOCIATION OF AN ANIONIC POLYMER AND A CATIONIC POLYMER |
| FR2739286B1 (en) * | 1995-09-29 | 1997-10-31 | Oreal | HAIR COMPOSITION COMPRISING A SILICONE POLYMER GRAFT WITH ANIONIC, AMPHOTERIC OR NON-IONIC MONOMERS AND AN AMPHOTERIC POLYMER |
| FR2739288B1 (en) * | 1995-09-29 | 1997-11-07 | Oreal | TOPICAL COMPOSITION COMPRISING THE ASSOCIATION OF A NON-SILICONE SKELETON POLYMER WITH SILICON GRAFTS AND A POLYSILOXANE SKELETON POLYMER WITH NON-SILICON GRAFTS |
| FR2739282B1 (en) * | 1995-09-29 | 1997-10-31 | Oreal | TOPICAL COMPOSITION CONTAINING A POLYSILOXANE SKELETON POLYMER WITH NON-SILICON GRAFTS AND AN AMPHIPHILIC FATTY CHAIN POLYMER |
| FR2739285B1 (en) * | 1995-09-29 | 1997-11-07 | Oreal | COMPOSITION FOR THE TREATMENT OF KERATINIC MATERIALS COMPRISING AT LEAST ONE GRAFTED SILICONE POLYMER AND AT LEAST ONE THICKENING POLYMER OR COPOLYMER OF (METH) ACRYLAMIDE OR A (METH) ACRYLAMIDE DERIVATIVE AND USES THEREOF |
| FR2740033B1 (en) | 1995-10-18 | 1998-01-23 | Oreal | COSMETIC COMPOSITION FOR THE TREATMENT OF KERATINIC MATERIALS COMPRISING AT LEAST ONE GRAFTED POLYMER AND AT LEAST ONE AQUEOUS DISPERSION OF INSOLUBLE PARTICLES OF NON-IONIC OR CATIONIC POLYMER |
| FR2740032B1 (en) | 1995-10-18 | 1997-11-21 | Oreal | WATER-BASED LACQUER FOR THE TREATMENT OF KERATINIC MATERIALS, PACKAGED IN AN AEROSOL DEVICE, INCLUDING AT LEAST ONE SILICONE POLYMER GRAFT AND APPLICATIONS |
| JP3088468B2 (en) * | 1995-10-27 | 2000-09-18 | ザ、プロクター、エンド、ギャンブル、カンパニー | Hairdressing compositions containing non-silicone and silicone graft polymers and low levels of volatile hydrocarbon solvents |
| FR2745173B1 (en) * | 1996-02-22 | 1998-04-30 | Oreal | COSMETIC COMPOSITION FOR FIXING AND GLOSS IN AEROSOL AND METHODS |
| FR2755608B1 (en) * | 1996-11-12 | 1999-01-08 | Oreal | COSMETIC COMPOSITION COMPRISING AN ANIONIC OR NON-IONIC POLYMER AND A CARBOXYLIC SILICONE |
| JP3679569B2 (en) * | 1997-09-24 | 2005-08-03 | 花王株式会社 | Aqueous hair tonic composition for hair and scalp treatment |
| US6177063B1 (en) | 1998-04-28 | 2001-01-23 | The Procter & Gamble Company | Anhydrous aerosol hairspray compositions containing silcone grafted copolymers |
| ES2264268T3 (en) | 1998-08-26 | 2006-12-16 | Basf Aktiengesellschaft | AGENT FOR THE TREATMENT OF THE BASE HAIR OF (POLYMERIZABLE URETHANE ACRYLATES THROUGH RADICALS, CONTAINING SILOXANE GROUPS AND THEIR POLYMERIZATION PRODUCTS. |
| FR3109730B1 (en) * | 2020-04-30 | 2023-10-06 | Oreal | Aerosol device containing a composition comprising at least one silicone acrylic copolymer and at least one propellant |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4728571A (en) * | 1985-07-19 | 1988-03-01 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer release coating sheets and adhesive tapes |
| US4693935A (en) * | 1986-05-19 | 1987-09-15 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer pressure sensitive adhesive composition and sheet materials coated therewith |
| US5106609A (en) * | 1990-05-01 | 1992-04-21 | The Procter & Gamble Company | Vehicle systems for use in cosmetic compositions |
| US5120531A (en) * | 1990-04-06 | 1992-06-09 | The Procter & Gamble Company | Hair styling conditioners |
-
1993
- 1993-06-18 GB GB939312629A patent/GB9312629D0/en active Pending
-
1994
- 1994-05-11 BR BR9406849A patent/BR9406849A/en not_active Application Discontinuation
- 1994-05-11 AU AU69101/94A patent/AU6910194A/en not_active Abandoned
- 1994-05-11 KR KR1019950705775A patent/KR960703003A/en not_active Application Discontinuation
- 1994-05-11 CN CN94193095A patent/CN1129396A/en active Pending
- 1994-05-11 WO PCT/US1994/005253 patent/WO1995000108A1/en not_active Application Discontinuation
- 1994-05-11 EP EP95904335A patent/EP0723433A1/en not_active Withdrawn
- 1994-05-11 CA CA002165431A patent/CA2165431A1/en not_active Abandoned
- 1994-05-11 JP JP7502799A patent/JPH08511800A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104822365A (en) * | 2012-11-29 | 2015-08-05 | 荷兰联合利华有限公司 | Hair care composition |
| CN104822365B (en) * | 2012-11-29 | 2017-07-21 | 荷兰联合利华有限公司 | Hair care composition |
| CN112930216A (en) * | 2018-10-25 | 2021-06-08 | 莱雅公司 | Composition comprising at least one silicone acrylic copolymer and at least one cationic acrylic copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6910194A (en) | 1995-01-17 |
| BR9406849A (en) | 1996-04-16 |
| EP0723433A1 (en) | 1996-07-31 |
| WO1995000108A1 (en) | 1995-01-05 |
| KR960703003A (en) | 1996-06-19 |
| GB9312629D0 (en) | 1993-08-04 |
| CA2165431A1 (en) | 1994-12-19 |
| JPH08511800A (en) | 1996-12-10 |
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