CN1972663A

CN1972663A - Aqueous preparations comprising a water-soluable or water-dispersible copolymer which contains at least one monomer having a nitrogen atom

Info

Publication number: CN1972663A
Application number: CN200580020647.XA
Authority: CN
Inventors: M·皮耶罗邦; S·恩古延金; P·赫斯塞尔
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-06-21
Filing date: 2005-06-15
Publication date: 2007-05-30
Anticipated expiration: 2025-06-15
Also published as: DE102004029773A1; CN1972663B

Abstract

Aqueous preparation comprises: at least a water solution or water dispersible copolymer with cationogen groups comprising: at least one monomer with at least one protonizable nitrogen atom; and at least one additional copolymerizable monomer; and at least one cosmetically acceptable carrier, where the pH of is 4-6.

Description

Comprise and contain at least a the have monomeric water solublity of nitrogen-atoms or the aqueous compositions of water-dispersible copolymer

The present invention relates to comprise at least a the have water solublity of YANG hyperactivity suppressing ionic group or the aqueous compositions of water-dispersible copolymer and at least a cosmetics acceptable carrier, described copolymer comprises copolymerized form at least aly has monomer that at least one can protonated nitrogen-atoms and other monomer of at least a copolymerization with it, and wherein the pH of aqueous compositions is 4-6.

The method that the invention further relates to the purposes of these aqueous compositions and prepare them.

Cosmetics and pharmaceutically acceptable water-soluble polymer are widely used in cosmetics and the medicine.For example in soap, frost and lotion, they are used as reagent preparation such as thickening agent, foam stabiliser or water absorbing agent, the dermal administration that perhaps is used to alleviate the stimulation of other composition or is used to improve active component usually.

Their tasks in cosmetic hair are the performances that influences hair.In medicine, they for example are used for the solid Types of Medicine as coating material or binding agent.

For cosmetic hair, film forming polymer for example is used to improve dried unclogging and readjusting property, wet unclogging and readjusting property, feel, gloss and outward appearance and is used for giving the hair antistatic property as conditioner.Knownly water-soluble polymer with Cationic functional groups can be used for hair conditioner, they have stronger affinity and prevent hair carry static for the hair surface that has negative charge owing to reasons in structure.The structure of various hair treatment polymer and model of action are described in Cosmetic ﹠amp; Toiletries 103 (1988), in 23.Commercially available standard cation conditioner polymer for example is a cationic hydroxyethyl cellulose, based on cationic polymer such as the copolymer of N-vinyl pyrrolidone and quaternised N-vinyl imidazole or the copolymer of acrylamide and diallyldimethylammonium chloride of N-vinyl pyrrolidone.

For fixing hair style, the polymer that for example uses vinyl lactam homopolymer and copolymer and contain the carboxylate group.To the requirement of hair styling resin for example be typing by force under high atmospheric humidity, elasticity, the performance washed off from hair, the compatibility preparaton, the film forming alap viscosity of institute's shape and with the comfortable feel of the hair of its processing.

The frequent inconvenient product that provides with complicated performance characteristic.Therefore, need cosmetic formulations to have following performance: can form essentially smooth, non-sticky thin film, this thin film is given hair and good confirmable sensory property such as the comfort feel of skin, has good conditioning effect and typing effect simultaneously.

EP-A-670 333 has described crosslinked water soluble polymer dispersions, if it can comprise at least a water-soluble monomer, at least a cross-linking agent and the suitable hydrophobic and/or monomeric monomer mixture of amphiphilic obtains by polymerization in the presence of polymeric dispersant.Except that a large amount of other monomers, operable water-soluble monomer also is N-vinyl pyrrolidone and monomer such as N-vinyl imidazole with cation/cationizable groups.

EP-A-929 285 has instructed the vinyl formamide unit that will comprise copolymerized form and the unitary water solubility copolymer of the vinyl imidazole component as cosmetic composition.

If WO 00/27893 has described the aqueous polymer dispersion based on N-vinyl formamide and suitable comonomer, wherein except that a large amount of other monomers, N-vinyl pyrrolidone, N-vinyl imidazole and N-vinyl imidazole derivant have also been mentioned.Be aggregated under at least a polymeric dispersions existence and carry out.

WO 03/92640 relates to the cosmetic composition that comprises at least a water solubility copolymer, this copolymer can be by making acrylamide and/or Methacrylamide and other water miscible a of copolymerization with it, if β-alefinically unsaturated compounds is suitable free-radical polymerized and obtain in the presence of water miscible polymer graft substrate.

Under the situation of the known preparation that is applied to cosmetics and medicine, still need Continual Improvement by prior art.Especially have outside the good filming performance for comprising, can also regulate the preparation of polymer of the rheological property (this is meant that they for example can be mixed with mousse, foam or gel) of product.

The objective of the invention is to find a kind of being particularly useful for to have the mousse of improvement shaping performance and the cosmetic formulations of foam applications, described mousse and foamy extra significantly part are to produce the elasticity hair style, simultaneously even have a strong typing under high atmospheric humidity, its feature further is the good performance of washing off, alap viscosity and with the comfortable feel of the hair of its processing.

This purpose at least aly has the water solublity of YANG hyperactivity suppressing ionic group or the aqueous compositions of water-dispersible copolymer and at least a cosmetics acceptable carrier is realized by comprising, described copolymer comprises copolymerized form at least aly has monomer that at least one can protonated nitrogen-atoms and other monomer of at least a copolymerization with it, and wherein the pH of aqueous compositions is 4-6.

Therefore the present invention provides the aqueous compositions that comprises following composition:

A) at least a water solublity or water-dispersible copolymer A with YANG hyperactivity suppressing ionic group), it comprises copolymerized form:

A) at least a have monomer that at least one can protonated nitrogen-atoms and

B) other monomer of at least a copolymerization with it, and

B) at least a cosmetics acceptable carrier,

Wherein the pH of aqueous compositions is 4-6.

For the purpose of the present invention, can protonated nitrogen-atoms be preferably to change into those nitrogen-atoms of cationic charge electriferous state by protonated by acid.

Regulate DH

PH for by Sorensen to the hydrogen ion concentration c (H that represents with mol/L in the aqueous solution ⁺) negative log ₁₀The term of introducing.

At the pH of 22 ℃ of following water (neutral pH scope) is 7.0.PH depends on temperature and descends with the temperature rising.Use pH electrode (glass electrode) to measure pH or use indicator dye (pH reagent paper, litmus paper, pH rod) colorimetric determination pH by the known potential measurement of those skilled in the art.The example of indicator is at Ullmann ' s Encyclopedia of Industrial Chemistry, and the 6th edition, the 17th volume provides in the 645-655 page or leaf.For using electrode measurement pH, can use all commercially available pH meters.

The pH of preparation of the present invention measures down at 20-25 ℃ by the known said method of those skilled in the art.

According to the present invention, the pH of aqueous compositions is 4-6.Preferably regulate this pH by adding Bronsted acid.Preferred Bronsted acid is water miscible organic and mineral acid.

Possible organic acid can be the aliphatic series and the aromatic carboxylic acid of monobasic and polybasic optional replacement, the aliphatic series of the aliphatic series of monobasic and polybasic optional replacement and aromatic sulfonic acid and monobasic and polybasic optional replacement and aromatics carboxylic phosphonic acids.

Preferred organic acid is a hydroxy carboxylic acid, and promptly wherein one or more H atoms are by the displaced carboxylic acid derivates of hydroxyl.

The example of the hydroxy carboxylic acid that can mention is hydroxyacetic acid, lactic acid, tartaric acid and citric acid.

Therefore preferred by adding the pH of hydroxy acid adjusting preparation, wherein preferred especially lactic acid.

The preferred mineral acid that can mention is phosphoric acid, phosphorous acid, sulphuric acid, sulfurous acid and hydrochloric acid.

In preferred embodiments, the pH of aqueous compositions is at least 4.5, and is preferred 5, preferred especially 5.2, especially 5.4, and at the most 6, and preferred 5.8, especially 5.6.Yet according to the present invention, preferred pH can be 5.1,5.3,5.5,5.7 or 5.9.

According to the present invention,, regulate the pH of preparation when promptly polymerization is finished preferably at preparation component A.

The content of the unreacted monomer in preparation less than 5, preferably less than 2, especially preferably less than 0.1, very particularly preferably less than 0.05 o'clock, thinks that the preparation of component A is finished based on the gross mass of component A.

According to the present invention, can regulate the pH of preparation in any time after the preparation of component A is finished.

According to the present invention, except that after the preparation of component A is finished, regulating the pH of aqueous compositions, also can be before preparation component A or in the process, with the pH regulator of monomer solution to 6-7.

Therefore, according to the present invention, also maybe advantageously before polymerization or in the process, with the pH regulator of raw material monomer to 6-7, and when polymerization is finished with the pH regulator of aqueous compositions to 4-6.

Therefore the present invention further provides a kind of method for preparing preparation of the present invention, wherein at component A) preparation finish after with pH regulator to 4-6.

In particularly preferred embodiments, the pH that has been its administration form re-adjustment preparation when being the form of gel, foam, spray, ointment, frost, emulsion, suspension, lotion, Emulsion or paste formulation at preparation.

According to the present invention, therefore preferably the acceptable gel of cosmetics, foam, spray, ointment, frost, emulsion, suspension, lotion, Emulsion or paste formulation are regulated pH.

For the purpose of the present invention, term " alkyl " comprises straight chain and branched-alkyl.According to the present invention, suitable short-chain alkyl for example is straight chain or branching C ₁-C ₇Alkyl, preferred C ₁-C ₆Alkyl, preferred especially C ₁-C ₄Alkyl.These groups especially comprise methyl, ethyl, propyl group, isopropyl, normal-butyl, the 2-butyl, sec-butyl, the tert-butyl group, n-pentyl, the 2-amyl group, the 2-methyl butyl, the 3-methyl butyl, 1, the 2-dimethyl propyl, 1, the 1-dimethyl propyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, the n-hexyl, the 2-hexyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 3-dimethylbutyl, 1, the 1-dimethylbutyl, 2, the 2-dimethylbutyl, 3, the 3-dimethylbutyl, 1,1,2-trimethyl propyl group, 1,2,2-trimethyl propyl group, the 1-ethyl-butyl, the 2-ethyl-butyl, 1-ethyl-2-methyl-propyl, n-heptyl, the 2-heptyl, the 3-heptyl, the 2-ethyl pentyl group, 1-propyl group butyl, octyl group etc.

Suitable long-chain C ₈-C ₃₀Alkyl and C ₈-C ₃₀Alkenyl is straight chain and branched-alkyl and alkenyl.These groups preferably are mainly linear alkyl, its also come across natural or synthetic fatty acid and aliphatic alcohol and oxo alcohol in, if that suitable its also can be is single-, two or how unsaturated.These groups just for example comprise oneself (alkene) base, positive heptan (alkene) base, positive hot (alkene) base, positive ninth of the ten Heavenly Stems (alkene) base, positive last of the ten Heavenly stems (alkene) base, n-undecane base (thiazolinyl), dodecyl (thiazolinyl), n-tridecane base (thiazolinyl), n-tetradecane base (thiazolinyl), Pentadecane base (thiazolinyl), n-hexadecyl (thiazolinyl), n-heptadecane base (thiazolinyl), n-octadecane base (thiazolinyl), AI3-36122 base (thiazolinyl) etc.

Cycloalkyl is preferably C ₅-C ₈Cycloalkyl such as cyclopenta, cyclohexyl, suberyl or ring octyl group.

Aryl comprises the aryl that does not replace and replace, preferred phenyl, tolyl, xylyl, 2,4,6 trimethylphenyls, naphthyl, fluorenyl, anthryl, phenanthryl, naphthacenyl (naphthacenyl), especially phenyl, tolyl, xylyl or 2,4,6 trimethylphenyls.

Hereinafter, being derived from the chemical compound of acrylic acid and methacrylic acid can be in some cases be called for short and be derived from acrylic acid chemical compound by introducing byte " (methyl) ".

Preparation of the present invention can advantageously be mixed with foam under common condition.

For the purpose of the present invention, the implication of water-soluble monomer and polymer is interpreted as that under 20 ℃ the dissolubility in water is monomer and the polymer of 1g/L at least.

The implication of water dispersible monomer and polymer is interpreted as in applied shear force, for example by stirring under the applied shear force disintegrate be the monomer and the polymer of particle dispersion.

Hydrophilic monomer is preferably the water solublity or the monomer of water dispersible at least.

Be the preparation copolymer A), use has the monomer that at least one can protonated nitrogen-atoms, especially N-vinyl imidazole and/or its derivant, and α, β-olefinic unsaturated monocarboxylic acid and α, β-olefinic unsaturated dicarboxylic acid and amide with diamidogen of at least one primary amino radical or secondary amino group.In a preferred embodiment of the invention, therefore copolymer A) comprise at least a monomer that has at least one can protonated nitrogen-atoms, described monomer is selected from N-vinyl imidazole and/or its derivant of on-quaternised form, and α, β-olefinic unsaturated monocarboxylic acid and α, β-olefinic unsaturated dicarboxylic acid and amide with diamidogen of at least one primary amino radical or secondary amino group.

With regard to " quaternized ", its implication for example is interpreted as by alkylation rather than the cation electriferous state by the protonated nitrogen-atoms that produces.

Also can use other the charged N-vinyl imidazole (derivant) that is different from uncharged N-vinyl imidazole (derivant) to prepare copolymer A).In addition, can use other YANG hyperactivity suppressing ion that is different from N-vinyl imidazole (derivant) and/or cationic monomer (promptly not, other monomer of partially or completely protonated and/or quaternized form).

Preferred copolymer A) do not comprise the monomer of latent anion of having of copolymerized form and/or anionic group.

Monomer a)

Based on being used for polymeric total monomer weight, be used for the copolymer A of preparation of the present invention) preferably comprise the 0.5-40 weight % of copolymerized form, preferred especially 1-30 weight %, very particularly preferably at least a monomer of 3-20 weight %, especially 3-15 weight % is a).In specific embodiment, monomer content a) is 25 weight % at the most.

The copolymer A that is used for preparation of the present invention) at least a monomer that has at least one can protonated nitrogen-atoms that comprises copolymerized form.

Preferably having the monomer that at least one can protonated nitrogen-atoms is the N-vinyl imidazole chemical compound of general formula (I).Therefore special preferred copolymer A) comprise copolymerized form at least a general formula (I) N-vinyl imidazole chemical compound as monomer a):

R wherein ⁷-R ⁹Be hydrogen, C independently of each other ₁-C ₄Alkyl or phenyl.Formula (I) examples for compounds is as shown in table 1 below:

Table 1

R ⁷	R ⁸	R ⁹
R ⁷	R ⁸	R ⁹
H	H	H
H	H	H	Me	H	H
H	Me	H	Me	H	H

H	H	Me
H	H	Me	Me	Me	H
H	Me	Me	Me	Me	H
H	Me	Me	Me	H	Me
Ph	H	H	Me	H	Me
Ph	H	H	H	Ph	H
H	H	Ph	H	Ph	H
H	H	Ph	Ph	Me	H
Ph	H	Me	Ph	Me	H
Ph	H	Me	Me	Ph	H
H	Ph	Me	Me	Ph	H
H	Ph	Me	H	Me	Ph
Me	H	Ph	H	Me	Ph

The Me=methyl

The Ph=phenyl

Monomer very particularly preferably is 1-vinyl imidazole (a N-vinyl imidazole) a).

In addition, spendable monomer that can be protonated is acrylic-amino Arrcostab and amino alkyl methacrylate and the aminoalkyl acrylamide and the aminoalkyl Methacrylamide of general formula (II) a):

Wherein

R ¹⁴And R ¹⁵Be selected from hydrogen, C independently of each other ₁-C ₈Straight or branched alkyl, methoxyl group, ethyoxyl, 2-hydroxyl-oxethyl, 2-methoxy ethoxy and 2-ethoxyethyl group.Preferred hydrogen, methyl or ethyl,

R ¹⁷Be hydrogen or methyl,

R ¹⁸Be alkylidene or hydroxy alkylidene with 1-24 carbon atom, optional by alkyl, preferred C ₂H ₄, C ₃H ₆, C ₄H ₈, CH ₂-CH (OH)-CH ₂Replace,

G is 0 or 1,

Z is nitrogen when g=1, is oxygen when g=0,

R ²⁵And R ²⁶Be selected from hydrogen, C in each case independently of each other ₁-C ₄₀Straight or branched alkyl, formoxyl, C ₁-C ₁₀Straight or branched acyl group, N, N-dimethyl aminoethyl, 2-hydroxyethyl, 2-methoxy ethyl, 2-ethoxyethyl group, hydroxypropyl, methoxy-propyl, ethoxycarbonyl propyl or benzyl.Preferred hydrogen, methyl, ethyl, n-pro-pyl and benzyl.

Amide can not replace, N-alkyl list replaces or N-alkyl amino list replaces or N, and the N-dialkyl group replaces or N, and N-dialkyl amido two replaces, and wherein alkyl or alkyl amino are derived from C ₁-C ₄₀Linear, C ₃-C ₄₀Side chain or C ₃-C ₄₀The carbocyclic ring unit.

Preferably the comonomer that formula (II) can be protonated is (methyl) acrylic acid N a), N-dimethylamino methyl ester, (methyl) acrylic acid N, N-diethylamino methyl ester, (methyl) acrylic acid N, N-dimethylamino ethyl ester, (methyl) acrylic acid N, N-diethylamino ethyl ester, (methyl) acrylic acid N, N-dimethylamino butyl ester, (methyl) acrylic acid N, N-diethylamino butyl ester, (methyl) acrylic acid N, the own ester of N-dimethylamino, (methyl) acrylic acid N, N-dimethylamino monooctyl ester, (methyl) acrylic acid N, N-dimethylamino dodecyl ester.

Also preferred N-[2-(dimethylamino) ethyl] acrylamide, N-[2-(dimethylamino) ethyl] Methacrylamide, N-[3-(dimethylamino) propyl group] acrylamide, N-[3-(dimethylamino) propyl group] Methacrylamide, N-[4-(dimethylamino) butyl] acrylamide, N-[4-(dimethylamino) butyl] Methacrylamide, N-[2-(diethylamino) ethyl] acrylamide, N-[4-(dimethylamino) cyclohexyl] acrylamide, N-[4-(dimethylamino) cyclohexyl] Methacrylamide, N-[8-(dimethylamino) octyl group] Methacrylamide, N-[12-(dimethylamino) dodecyl] Methacrylamide, N-[3-(diethylamino) propyl group] Methacrylamide and N-[3-(diethylamino) propyl group] acrylamide.

Methacrylic acid N very particularly preferably, N-dimethyl aminoethyl ester, N-[3-(dimethylamino) propyl group] Methacrylamide, methacrylic acid N-methylamino ethyl ester, N-[3-(methylamino) propyl group] Methacrylamide, methacrylic acid amino-ethyl ester and N-[3-aminopropyl] Methacrylamide.

Especially preferred N-[3-(dimethylamino) propyl group] Methacrylamide.

In addition, a) diallylamine of also optional self-drifting (III) of monomer that can be protonated:

R wherein ²⁷Be hydrogen or C ₁-C ₂₄Alkyl.Preferred especially N, N-diallylamine and N, N-diallyl-N-methyl amine, especially N, N-diallyl-N-methyl amine.

In addition, monomer a) can be selected from following chemical compound: 1, and the dibasic vinyl amine of the N-of 3-divinyl imidazolidin-2-one or general formula (IV):

(R ²⁸) ₂N-(CH ₂) _n-CR ¹⁵＝CHR ¹⁴ (IV)

Wherein

N be 0,1 or 2 and

R ²⁸Be selected from hydrogen, C ₁-C ₄₀Straight or branched alkyl, formoxyl, C ₁-C ₁₀Straight or branched acyl group, N, N-dimethyl aminoethyl, 2-hydroxyethyl, 2-methoxy ethyl, 2-ethoxyethyl group, hydroxypropyl, methoxy-propyl, ethoxycarbonyl propyl or benzyl, preferable methyl, ethyl, n-pro-pyl and benzyl.If n=0, then R ²⁸Should not be hydrogen simultaneously.

Monomer b)

Based on being used for polymeric total monomer weight, be used for the copolymer A of preparation of the present invention) preferably comprise the 20-99.5 weight % of copolymerized form, at least a other monomer b of the copolymerization with it of preferred especially 20-70 weight %, especially 30-70 weight %).In specific embodiment, monomer b) content is at least 50 weight %.

Monomer b1)

Preferred copolymer A) additionally comprises at least a N-vinyl lactam b1 of copolymerized form).Suitable monomers b1) be unsubstituted N-vinyl lactam and N-vinyl lactam derivant, it for example can have one or more C ₁-C ₆Alkyl substituent such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.These monomers for example comprise N-vinyl pyrrolidone, N-vinyl piperidones, N-caprolactam, N-vinyl-5-N-methyl-2-2-pyrrolidone N-, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidones, N-vinyl-6-ethyl-2-piperidones, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam etc. and composition thereof.

Preferred N-vinyl pyrrolidone, N-caprolactam or its mixture of using.

In specific embodiment, preparation of the present invention only comprise by above-mentioned monomer a) and b1) the copolymer formed of monomeric unit as component A).

Thereby preferred these copolymer A) comprise the 0.5-40 weight % of copolymerized form, at least a monomer of preferred especially 1-30 weight %, especially 3-20 weight % a).Correspondingly, these copolymer A) preferably comprise the 60-99.5 weight % of copolymerized form, at least a monomer b of preferred especially 70-99 weight %, especially 80-97 weight %).

In preferred embodiments, preparation of the present invention comprise except that above-mentioned monomer a) with b1) also contain at least a different with it other monomer b2 of copolymerized form) copolymer as component A).

Monomer b2)

Copolymer A) can additionally comprise at least a be different from component a) and b1) and the non-ionic water-soluble monomer b2 of copolymerization with it).

Preferred monomers b2) content is 0-50 weight % based on being used for polymeric total monomer weight, preferred especially 5-50 weight %, especially 10-40 weight %.

Preferred ingredient b2) be selected from:

B2.1) saturated C ₁-C ₈Monocarboxylic N-vinylamide,

B2.2) α, the primary amide of β-olefinic unsaturated monocarboxylic acid and N-alkyl and N, the N-dialkyl derivatives, it also has 8 other carbon atoms at the most except that the carbonylic carbon atom of acylamino-,

B2.3) α, β-olefinic unsaturated monocarboxylic acid and α, the ester of β-olefinic unsaturated dicarboxylic acid and glycol,

B2.4) α, β-olefinic unsaturated monocarboxylic acid and α, β-olefinic unsaturated dicarboxylic acid and amide with amino alcohol of primary amino radical or secondary amino group,

B2.5) acrylic acid polyester ether,

And composition thereof.

Be suitable as monomer b2.1) open chain N-vinylamide chemical compound for example be N-vinyl formamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl propionic acid amide., N-vinyl-N-methyl propanamide and N-vinyl butyramide.

Suitable monomers b2.2) for example is acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-(normal-butyl) (methyl) acrylamide, N-(tert-butyl group) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, piperidyl (methyl) acrylamide and morpholinyl (methyl) acrylamide, wherein preferred (methyl) acrylamide, special preferable methyl acrylamide.

Suitable monomers b2.3) for example is acrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, ethylacrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate, acrylic acid 3-hydroxypropyl acrylate, methacrylic acid 3-hydroxypropyl acrylate, acrylic acid 3-hydroxy butyl ester, methacrylic acid 3-hydroxy butyl ester, acrylic acid 4-hydroxy butyl ester, methacrylic acid 4-hydroxy butyl ester, the own ester of acrylic acid 6-hydroxyl, the own ester of methacrylic acid 6-hydroxyl, acrylic acid 3-hydroxyl-2-Octyl Nitrite and methacrylic acid 3-hydroxyl-2-Octyl Nitrite.

Suitable monomers b2.4) for example is 2-ethoxy acrylamide, the 2-hydroxyethyl methacrylamide, 2-ethoxy ethyl acrylamide, 2-hydroxypropyl acrylamide, 2-hydroxypropyl methyl acrylamide, 3-hydroxypropyl acrylamide, 3-hydroxypropyl methyl acrylamide, 3-hydroxyl butyl acrylamide, 3-hydroxyl butyl methyl acrylamide, 4-hydroxyl butyl acrylamide, 4-hydroxyl butyl methyl acrylamide, 6-hydroxyl hexyl acrylamide, 6-hydroxyl hexyl methyl acrylamide, 3-hydroxyl-2-ethylhexyl acrylamide and 3-hydroxyl-2-ethylhexyl Methacrylamide.

Suitable monomers b2.5) be acrylic acid polyester ether, for the purpose of the present invention, its implication is generally understood as α, β-olefinic unsaturated monocarboxylic acid and α, the ester of β-olefinic unsaturated dicarboxylic acid and Aethoxy Sklerol.Suitable Aethoxy Sklerol is linearity or the branched substances with the terminal hydroxy group that comprises ehter bond.Usually, their molecular weight is 150-20000.Suitable Aethoxy Sklerol is poly alkylene glycol such as Polyethylene Glycol, polypropylene glycol, PolyTHF and oxyalkylene copolymers.The oxyalkylene that is applicable to the preparation oxyalkylene copolymers for example is ethylene oxide, propylene oxide, chloropropylene oxide, 1,2-butylene oxide and 1,3-butylene oxide.Oxyalkylene copolymers can comprise the oxyalkylene units of random form or block form copolymerization.Preferred ethylene oxide/propylene oxide copolymer.

As components b 2.5), the acrylic acid polyester ether of preferred formula V:

Wherein

The order of oxyalkylene units is arbitrarily,

K and l are the integer of 0-1000 independently of each other, and wherein k and l sum are at least 5,

R ⁴Be hydrogen, C ₁-C ₃₀Alkyl or C ₅-C ₈Cycloalkyl,

R ⁵Be hydrogen or C ₁-C ₈Alkyl,

Y ²Be O or NR ⁶, R wherein ⁶Be hydrogen, C ₁-C ₃₀Alkyl or C ₅-C ₈Cycloalkyl.K is preferably the integer of 1-500, especially the integer of 3-250.Preferred I is the integer of 0-100.

Preferred R ⁵Be hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl or n-hexyl, especially hydrogen, methyl or ethyl.

Preferred R ⁴In formula IV hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, n-pentyl, n-hexyl, octyl group, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl.

Preferred Y ²In formula IV O or NH.

Suitable acrylic acid polyester ether b2.5) for example is above-mentioned α, β-olefinic unsaturated monocarboxylic acid and/or α, the polycondensation product of β-olefinic unsaturated dicarboxylic acid and acid chloride, amide and anhydride and Aethoxy Sklerol.Suitable Aethoxy Sklerol can be by making ethylene oxide, 1,2-propylene oxide and/or chloropropylene oxide and starting molecule such as water or short chain alcohol R ⁴-OH reacts and preparation easily.Oxyalkylene can use separately or be used alternatingly or use as mixture.Acrylic acid polyester ether c) can be used alone or as a mixture, to prepare polymer used according to the invention.

Suitable acrylic acid polyester ether b2.5) has urethane (methyl) acrylate of oxyalkylene group in addition.This compounds is described in DE 198 38 851 (component e2)) in, it is incorporated herein by reference fully herein.

Above-mentioned monomer b2) can use separately or use with mixture arbitrarily.

In a preferred embodiment of the invention, preparation comprise contain copolymerized form 5-15 weight % monomer a), 30-70 weight % monomer b1) and 20-35 weight % monomer b2) trimer as component A, condition is that monomer amount sum a)-b2) is 100 weight %.

Monomer b3)

Copolymer A) can additionally comprise being different from a) of copolymerized form, b1) and at least a water-soluble monomer b3 b2)), it is selected from the α of possess hydrophilic property cation group, the unsaturated water soluble compound of β-olefinic.

Preferred monomers b3) content is 0-30 weight % based on being used for polymeric total monomer weight, preferred especially 0-20 weight %, especially 0-10 weight %.

Components b 3) cation group is preferably nitrogen-containing group, as quaternary ammonium group.

These charged cation groups can produce by quaternized amine nitrogen atom, for example use for a) described alkylating agent of said components.The example of alkylating agent is C ₁-C ₄Alkyl halide or sulfuric ester such as ethyl chloride, bromoethane, chloromethanes, Celfume, dimethyl sulfate and dithyl sulfate.Quaternizedly can before or after polymerization, carry out usually.

Suitable monomers b3) chemical compound for can a) obtaining by quaternized component.The charged monomer b3 of this class) example is quaternised N-vinyl imidazole, especially 3-methyl isophthalic acid-vinyl imidazole  chloride and Methylsulfate salt.

Suitable compound b3) also has α, β-olefinic unsaturated monocarboxylic acid and/or α, the quaternized products of the ester of β-olefinic unsaturated dicarboxylic acid and amino alcohol.Preferred amino alcohol is C on the amine nitrogen atom ₁-C ₈Alkylating C ₁-C ₁₂Amino alcohol.Be suitable as these esters acid constituents for example be acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid .beta.-methylacrylic acid, maleic anhydride, butyl maleate and composition thereof.Preferred acrylic acid, methacrylic acid and composition thereof of using is as acid constituents.

Preferred monomers b3) is the quaternized products of following compounds: (methyl) acrylic acid N, N-dimethylamino methyl ester, (methyl) acrylic acid N, N-dimethylaminoethyl, (methyl) acrylic acid N, N-lignocaine ethyl ester, (methyl) acrylic acid N, N-dimethylamino propyl ester, (methyl) acrylic acid N, N-lignocaine propyl ester and (methyl) acrylic acid N, N-dimethylamino cyclohexyl.

Suitable monomers b3) also has above-mentioned α, β-olefinic unsaturated monocarboxylic acid and α, the quaternized products of amide of β-olefinic unsaturated dicarboxylic acid and diamidogen with at least one primary amino radical or secondary amino group.The diamidogen that preferably has uncle amino and primary amino radical or secondary amino group.

Suitable monomers b3) also have the quaternized products of following compounds: N-[2-(dimethylamino) ethyl] acrylamide, N-[2-(dimethylamino) ethyl] Methacrylamide, N-[3-(dimethylamino) propyl group] acrylamide, N-[3-(dimethylamino) propyl group] Methacrylamide, N-[4-(dimethylamino) butyl] acrylamide, N-[4-(dimethylamino) butyl] Methacrylamide, N-[2-(lignocaine) ethyl] acrylamide, N-[4-(dimethylamino) cyclohexyl] acrylamide and N-[4-(dimethylamino) cyclohexyl] Methacrylamide.

Suitable monomers b3) also has N, N-diallylamine and N, the quaternized products of N-diallyl-N-alkylamine.Alkyl is preferably C herein ₁-C ₂₄Alkyl.Preferred N, N-diallyl-N, N-Dimethyl Ammonium chemical compound, for example chloride and bromide.These chemical compounds especially comprise N, N-diallyl-N, N-alkyl dimethyl ammonium chloride (DADMAC).

Suitable monomers b3) also has the azacyclo-of various vinyls and pi-allyl replacement such as the quaternized products of 2-vinylpyridine, 4-vinylpridine, 2-allyl pyridine and 4-allyl pyridine.

In each case, above-mentioned monomer b3) can use separately or use with mixture arbitrarily.

In a preferred embodiment of the invention, preparation comprise contain copolymerized form 5-15 weight % monomer a), 30-70 weight % monomer b1), 20-35 weight % monomer b2) and 0-10 weight % monomer b3) polymer as component A, condition is that monomer amount sum a)-b3) is 100 weight %.

Monomer c)

What copolymer A) can additionally comprise copolymerized form is different from monomer at least a monomer c a)-b3)).Additional monomers c) is preferably selected from α, β-olefinic unsaturated monocarboxylic acid and α, β-olefinic unsaturated dicarboxylic acid and C ₁-C ₃₀The ester of alkanol, N-alkylamide and N, the N-dialkyl amide also has the α of at least 9 carbon atoms, β-olefinic unsaturated monocarboxylic acid, vinyl alcohol and allyl alcohol and C except that the carbonylic carbon atom of acylamino- ₁-C ₃₀Monocarboxylic ester, vinyl ethers, vinyl aromatic compounds, vinyl halide, ethenylidene dihalide, C ₁-C ₈Monoolefine has non-aromatic hydrocarbon of at least two conjugated double bonds and composition thereof.

Preferred monomers c) content is 0-15 weight % based on being used for polymeric total monomer weight, preferred especially 0.1-10 weight %.

Suitable additional monomers c) is (methyl) acrylic acid methyl ester., the ethylacrylic acid methyl ester, (methyl) ethyl acrylate, the ethyl propylene acetoacetic ester, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, the ethyl propylene tert-butyl acrylate, (methyl) acrylic acid n-octyl, (methyl) acrylic acid 1,1,3,3-tetramethyl butyl ester, (methyl) EHA, (methyl) acrylic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) acrylic acid n-undecane base ester, (methyl) tridecyl acrylate, (methyl) acrylic acid myristin, (methyl) acrylic acid pentadecyl ester, (methyl) acrylic acid Petiolus Trachycarpi ester, (methyl) acrylic acid heptadecyl ester, (methyl) acrylic acid nonadecyl ester, (methyl) acrylic acid arrachinyl ester, (methyl) acrylic acid behenyl alcohol ester, (methyl) acrylic acid tetracosa carbon thiazolinyl (lognocerenyl) ester, (methyl) acrylic acid 26 carbon backs (cerotinyl) ester, (methyl) acrylic acid 30 carbon backs (melissinyl) ester, (methyl) acrylic acid hexadecene base (palmitoleinyl) ester, (methyl) acrylic acid grease, inferior oil base (linolyl) ester of (methyl) acrylic acid, (methyl) acrylic acid Caulis et Folium Lini base (linolenyl) ester, (methyl) stearyl acrylate base ester, (methyl) lauryl acrylate and composition thereof.Preferred monomer c) be α, β-olefinic unsaturated monocarboxylic acid and dicarboxylic acids and C ₁-C ₄The ester of alkanol.

Suitable additional monomers c) also has N-(n-octyl) (methyl) acrylamide, N-(1,1,3, the 3-tetramethyl butyl) (methyl) acrylamide, N-ethylhexyl (methyl) acrylamide, N-(n-nonyl) (methyl) acrylamide, N-(positive decyl) (methyl) acrylamide, N-(n-undecane base) (methyl) acrylamide, N-tridecyl (methyl) acrylamide, N-myristyl (methyl) acrylamide, N-pentadecyl (methyl) acrylamide, N-palmityl (methyl) acrylamide, N-heptadecyl (methyl) acrylamide, N-nonadecyl (methyl) acrylamide, N-arrachinyl (methyl) acrylamide, N-mountain Yu base (methyl) acrylamide, N-tetracosa carbon thiazolinyl (lignocerenyl) (methyl) acrylamide, N-26 carbon backs (cerotinyl) (methyl) acrylamide, N-30 carbon backs (melissinyl) (methyl) acrylamide, N-hexadecene base (palmitoleinyl) (methyl) acrylamide, N-oil base (methyl) acrylamide, inferior oil base (linolyl) (methyl) acrylamide of N-, N-Caulis et Folium Lini base (linolenyl) (methyl) acrylamide, N-stearyl (methyl) acrylamide and N-lauryl (methyl) acrylamide.

Suitable additional monomers c) also has vinyl acetate, propionate, vinyl butyrate and composition thereof.

Suitable additional monomers c) also has ethylene, propylene, isobutene., butadiene, styrene, α-Jia Jibenyixi, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, fluorothene, vinylidene fluoride and composition thereof.

Above-mentioned additional monomers c) can use separately or use with the form of any mixture.

Cross-linking agent d)

If necessary, copolymer A) can comprise at least a cross-linking agent of copolymerized form, promptly have the chemical compound of the unsaturated unconjugated double bond of two or more olefinics.

The consumption of preferred cross-linking agent is 0.01-3 weight % based on being used for polymeric total monomer weight, preferred especially 0.1-2 weight %.

Suitable crosslinking agent d) for example is acrylate, methacrylate, allyl ether or the vinyl ethers of dihydroxylic alcohols at least.The OH base of parent alcohol can be wholly or in part by etherificate or esterification; Yet cross-linking agent comprises at least two ethylenically unsaturated groups.

The example of parent alcohol is that dihydroxylic alcohols is as 1,2-ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butanediol, 1, the 3-butanediol, 2, the 3-butanediol, 1, the 4-butanediol, but-2-ene-1, the 4-glycol, 1, the 2-pentanediol, 1, the 5-pentanediol, 1, the 2-hexanediol, 1, the 6-hexanediol, 1, the 10-decanediol, 1, the 2-dodecanediol, 1, the 12-dodecanediol, neopentyl glycol, the 3-methyl isophthalic acid, the 5-pentanediol, 2,5-dimethyl-1, the 3-hexanediol, 2,4,4-trimethyl-1, the 3-pentanediol, 1, the 2-cyclohexanediol, 1, the 4-cyclohexanediol, 1,4-two (methylol) cyclohexane extraction, the neopentyl glycol single hydroxy new pentane acid ester, 2,2-two (4-hydroxyphenyl) propane, 2,2-two [4-(2-hydroxypropyl) phenyl] propane, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), dipropylene glycol, tripropylene glycol, four propylene glycol, 3-sulfo-pentane-1, the 5-glycol and separately molecular weight be the Polyethylene Glycol of 200-10000, polypropylene glycol and PolyTHF.Except that the homopolymer of oxidation ethylene or propylene oxide, can also use the block copolymer of ethylene oxide or propylene oxide or comprise the ethylene oxide that mixes and the copolymer of propylene oxide group.Example with parent alcohol of two above OH bases is a trimethylolpropane, glycerol, and tetramethylolmethane, 1,2,5-penta triol, 1,2, the 6-hexanetriol, the triethoxy cyanuric acid, anhydro sorbitol, sugar is as sucrose, glucose and mannose.Certainly, also can use respectively with the polyhydric alcohol of ethylene oxide or corresponding ethoxylate of the reacted conduct of propylene oxide and propoxylate form.Also can at first make polyhydric alcohol be converted into corresponding glycidyl ether with the chloropropylene oxide reaction.

Other suitable crosslinking agent d) is vinyl esters or unsaturated monohydric alcohol and the unsaturated C of olefinic ₃-C ₆The ester of carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.The example of this class alcohol is 1-propenol-3,1-butylene-3-alcohol, 5-hexen-1-ol, 1-octene-3-alcohol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecene-1-alcohol, cinnamyl alcohol, citronellol, crotonyl alcohol. or suitable-9-vaccenic acid-1-alcohol.Yet, also can make unsaturated monohydric alcohol esterification with polybasic carboxylic acid such as malonic acid, tartaric acid, trimellitic acid, phthalic acid, p-phthalic acid, citric acid or succinic acid.

Other suitable crosslinking agent d) be the ester of unsaturated carboxylic acid and above-mentioned polyhydric alcohol, as the ester of oleic acid .beta.-methylacrylic acid, cinnamic acid or 10-9-undecylenic acid.

Suitable crosslinking agent d) for having straight chain or branching, linearity or ring-type, aliphatic series or the aromatic hydrocarbon of at least two two keys, under the situation of aliphatic hydrocarbon, described pair of key must be non-conjugated, as divinylbenzene, divinyl toluene, 1,7-octadiene, 1,9-decadinene, 4-vinyl-1-cyclohexene, trivinyl cyclohexane extraction or molecular weight are the polybutadiene of 200-20000.

Other suitable crosslinking agent d) is bifunctional amine's at least acrylamide, Methacrylamide and N-allyl amine.This class amine for example is 1,2-diaminourea methane, 1,1,3-diaminopropanes, 1,4-diaminobutane, 1,1,12-dodecane diamidogen, piperazine, diethylenetriamines or isophorone diamine.The amide of allyl amine and unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or above-mentioned dicarboxylic acids at least also is suitable.

Triallylamine and triallyl monoalkyl ammonium salt such as triallyl ammonio methacrylate or Methylsulfate triallyl ammonium methyl also are suitable as cross-linking agent d).

The N-vinyl compound of urea derivative, dual functional at least amide, cyanurate or urethane, for example the N-vinyl compound of urea, ethylidene-urea, propylidene urea or tartaric acid amide also is suitable, N for example, N '-divinyl ethylidene-urea or N, N '-divinyl propylidene urea.

Other suitable crosslinking agent d) is divinyl two  alkane, tetraallyl silane or tetrem thiazolinyl silane.

Certainly, also can use above-claimed cpd d) mixture.The preferred water-soluble cross-linker d that uses).

The especially preferred cross-linking agent d that uses) for example is methylene-bisacrylamide, triallylamine, triallyl alkylammonium salt, divinyl imidazoles, pentaerythritol triallyl ether, N, the methacrylate and the acrylate of the product of N '-divinyl ethylidene-urea, polyhydric alcohol and acrylic or methacrylic acid, the methacrylate of polyoxyalkylene and acrylate or the polyhydric alcohol that reacted with ethylene oxide and/or propylene oxide and/or chloropropylene oxide.

Cross-linking agent d very particularly preferably) be pentaerythritol triallyl ether, methylene-bisacrylamide, N, N '-divinyl ethylidene-urea, triallylamine, the acrylate of triallyl monoalkyl ammonium salt and ethylene glycol, butanediol, trimethylolpropane or glycerol, perhaps with the acrylate of ethylene glycol, butanediol, trimethylolpropane or the glycerol of the reaction of ethylene oxide and/or chloropropylene oxide.

Preferred copolymer A wherein) comprise the preparation of the following component of copolymerized form:

A) N-vinyl imidazole and/or its derivant and

B1) at least a N-vinyl lactam

B2) if the suitable at least a non-ionic water-soluble monomer that is selected from following chemical compound:

B2.1) saturated C ₁-C ₈Monocarboxylic N-vinylamide,

B3) if the suitable at least a monomer that is selected from the quaternized products of N-vinyl imidazole and dimethylamino-propyl Methacrylamide,

Wherein the pH of aqueous compositions is 4-6.

A) the N-vinyl imidazole of 0.5-40 weight % and/or its derivant,

B1) at least a N-vinyl lactam of 20-99.5 weight %,

B2) 0-50 weight % at least a be different from component a) and b1) and the non-ionic water-soluble monomer of copolymerization with it and

B3) at least a α that is selected from the possess hydrophilic property cation group of 0-30 weight %, the monomer of the unsaturated water soluble compound of β-olefinic, condition is that component is a) to b3) the amount sum be 100 weight %,

Wherein the pH of aqueous compositions is 4-6.

A) the N-vinyl imidazole of 1-30 weight % and/or its derivant,

B1) at least a N-vinyl lactam of 20-70 weight %,

B2) 5-50 weight % at least a be different from component a) and b1) and the non-ionic water-soluble monomer of copolymerization with it and

B3) at least a α that is selected from the possess hydrophilic property cation group of 0-20 weight %, the monomer of the unsaturated water soluble compound of β-olefinic, condition is that component is a) to b3) the amount sum be 100 weight %,

Wherein the pH of aqueous compositions is 4-6.

Further preferred copolymer A wherein) comprise the preparation of the following component of copolymerized form:

A) the N-vinyl imidazole of 3-20 weight % and/or its derivant,

B1) at least a N-vinyl lactam of 30-70 weight %,

B2) 10-40 weight % at least a be different from component a) and b1) and the non-ionic water-soluble monomer of copolymerization with it and

B3) at least a α that is selected from the possess hydrophilic property cation group of 0-10 weight %, the monomer of the unsaturated water soluble compound of β-olefinic, condition is that component is a) to b3) the amount sum be 100 weight %,

Wherein the pH of aqueous compositions is 4-6.

In preferred embodiments, copolymer A) only by be derived from above-mentioned monomer a), b1) and if suitable b2) and/or b3) repetitive form.

In particularly preferred preparation, copolymer A) comprise the following component of copolymerized form:

A) 3-15 weight %N-vinyl imidazole

B) 30-70 weight %N-vinyl pyrrolidone

C) 20-35 weight % Methacrylamide

D) the quaternised N-vinyl imidazole of 0-10 weight %,

Condition is that component is a) to b3) the amount sum be 100 weight %,

Copolymer A) can be according to the known conventional method of those skilled in the art, as preparing by solution, precipitation, suspension or emulsion polymerisation.Preferably prepare by solution or precipitation polymerization.

Being used for polymeric preferred solvent is aqueous solvent, the mixture of water and water and following water miscibility solvent for example: alcohol is as methanol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, hexanol and Hexalin, dihydroxylic alcohols such as ethylene glycol, propylene glycol and butanediol, the methyl ether of dihydroxylic alcohols or ethylether, diethylene glycol, the Polyethylene Glycol of 2,2'-ethylenedioxybis(ethanol)., number-average molecular weight about at the most 3000, glycerol and two  alkane.Particularly preferably in the water or in water/alcohol mixture, for example polymerization in water/alcohol mixture.

If make water, then preferably use demineralized water as solvent composition.

Precipitation polymerization for example carries out in as the ester of solvent such as ethyl acetate or butyl acetate.Can be by conventional method as from reaction solution, isolating the resulting polymers solids precipitation by being lower than an atmospheric pressure filtration.The molecular weight of resulting polymers is usually above polymerisation in solution in precipitation polymerization.

Polymerization temperature is preferably about 30 ℃ to 120 ℃, preferred 40-100 ℃ especially.Usually polymerization under atmospheric pressure is depressed polymerization but also can or add in decompression.Suitable pressure is the 1-5 crust.

Be the preparation polymer A), can make monomer polymerization by the initiator that forms free radical.

The initiator that can be used for radical polymerization is per-compound and/or the azo-compound that is generally used for this, the peroxydisulfate of alkali metal or ammonium for example, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, cross the neopentanoic acid tert-butyl ester, cross the 2 ethyl hexanoic acid tert-butyl ester, tert butyl permaleic acid, cumyl hydroperoxide, cross the diamino acid diisopropyl ester, peroxidating two (adjacent toluyl), didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, t-butyl peroxy-isobutylate, t-butyl peroxy-acetate, peroxidating two tertiary pentyls, t-butyl hydroperoxide, azodiisobutyronitrile, 2,2 '-azo two (2-amidine propane) hydrochlorate is (from Wako PureChemicals Industries, Ltd. V50), or 2,2 '-azo two (2-methylbutyronitrile).Initiator mixture or redox initiation system such as ascorbic acid/ferrous sulfate (II)/sodium persulfate, t-butyl hydroperoxide/sodium sulfite, t-butyl hydroperoxide/sodium hydroxymethanesulfinate, H ₂O ₂/ Cu ^IAlso be suitable.

For regulating molecular weight, polymerization can be carried out in the presence of at least a regulator.Spendable regulator is the known compounds that routinize of those skilled in the art, for example sulfur-containing compound such as mercaptoethanol, 2-ethylhexyl mercaptoacetate, TGA or dodecyl mercaptans and three bromochloromethanes or other chemical compound of the molecular weight of resulting polymers being had regulating action.Preferred regulator is a cysteine.

For obtaining the very pure polymer of low residual monomer content, after polymerization (main polymerization), can carry out post polymerization.Post polymerization can with the identical or different initiator system of main polymerization in the presence of carry out.Post polymerization preferably carries out under identical with main polymerization at least temperature, but preferably carries out under than the high temperature of main polymerization.If necessary, after the polymerization or between first and second polymerization procedures, reactant mixture is carried out stripping or carries out steam distillation with steam.

According to the present invention, can be before or after carrying out stripping with steam or carrying out steam distillation with the pH regulator of aqueous compositions to 4-6.

If organic solvent is used to prepare polymer, then this solvent can be removed as under reduced pressure distilling by the known conventional method of those skilled in the art.

Polymerization is carried out under the pH of preferred especially 6.5-7.5 preferably at 6-9.Regulate pH by adding suitable acid or adding suitable alkali.

The gained liquid polymer composition can be converted into powder type by various drying meanss such as spray drying, fluidization and spray-drying, drum drying or lyophilization.The preferred spray drying of using.Can be advantageously with the dry polymer powder that so obtains respectively by dissolving in water or redispersion and be converted into aqueous solution or aqueous dispersion once more.The advantage that copolymer powder has be storage property better and easier transportation and be not subject to microbiological attack usually.

Another theme of the present invention be after polymerization is finished and dry and/or be converted into powder type before with the pH regulator of liquid polymer composition to 4-6.

Cosmetics acceptable carrier B)

Preparation of the present invention has cosmetics and/or drug acceptable carrier B), it is selected from:

I) water,

Ii) water miscibility organic solvent, preferred C ₂-C ₄Alkanol, especially ethanol,

Iii) oily, fatty, wax,

Iv) C ₆-C ₃₀The ester of monocarboxylic acid and monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, this ester be with iii) different,

V) saturated non-cyclic hydrocarbon and cyclic hydrocarbon,

Vi) fatty acid,

Vii) aliphatic alcohol,

Viii) propellant gas

And composition thereof.

Formulation example of the present invention is selected from following oil or fatty ingredient B as having): low nonpolar hydrocarbon such as mineral oil; Preferably contain the linear saturated hydrocarbons that surpasses 8 carbon atoms such as the tetradecane, hexadecane, octadecane etc.; Cyclic hydrocarbon such as decahydronaphthalene; Branched hydrocarbon; Animal oil and vegetable oil; Wax; Wax ester; Vaseline; Ester, the ester of preferred fatty acid, for example C ₁-C ₂₄Monohydric alcohol and C ₁-C ₂₂Monocarboxylic ester such as isostearic acid isopropyl ester, myristic acid n-propyl, isopropyl myristate, Palmic acid n-propyl, isopropyl palmitate, Palmic acid cerul ester, Palmic acid octacosyl ester, Palmic acid melissyl ester, Palmic acid dotriacontyl ester, Palmic acid tetratriacontane base ester, stearic acid cerul ester, stearic acid octacosyl ester, stearic acid melissyl ester, stearic acid dotriacontyl ester, stearic acid tetratriacontane base ester; Salicylate, for example C ₁-C ₁₀Salicylate such as ethylhexyl salicylate; Benzoate such as benzoic acid C ₁₀-C ₁₅Arrcostab, benzyl benzoate; Other cosmetics ester such as fatty acid triglyceride, propylene glycol list lauryl, polyethyleneglycol lauryl, lactic acid C ₁₀-C ₁₅Arrcostab etc. and composition thereof.

Suitable silicone oil B) for example is linear polydimethylsiloxane-, poly-(methyl phenyl siloxane), cyclic polysiloxanes and composition thereof.The number-average molecular weight of polydimethylsiloxane and poly-(methyl phenyl siloxane) is preferably about 1000 to 150 000g/mol.Preferred cyclic polysiloxanes has 4-8 unit ring.Suitable cyclic polysiloxanes is for example commercially available with cyclomethicone.

Preferred oil or fatty ingredient B) be selected from paraffin and liquid paraffin; Vaseline; Natural fat and oil are as Oleum Ricini, Oleum Glycines, Oleum Arachidis hypogaeae semen, olive oil, sunflower oil, Oleum sesami, American Avocado Tree oil, cupu oil, almond oil, peach kernel oil, Oleum Ricini, cod liver oil, leaf fat, spermaceti, sperm oil, whale oil, Semen Tritici aestivi germ oil, macadimia nut oil, Radix Oenotherae erythrosepalae oil, Jojoba oil; Aliphatic alcohol such as lauryl alcohol, myristyl alcohol, spermol, stearyl alcohol, oleyl alcohol; Fatty acid such as myristic acid, stearic acid, Palmic acid, oleic acid, linoleic acid, linolenic acid and various different with it saturated, unsaturated and substituted fatty acid; The mixture of wax such as Cera Flava, Brazil wax, candelilla wax (candililla wax), spermaceti and above-mentioned oil ﹠ fat component.

Suitable cosmetics and drug compatibility oil or fatty ingredient B) be described in Karl-HeinzSchrader, Grundlagen und Rezepturen der Kosmetika[cosmetic base and preparaton], second edition, Verlag H ü thig, Heidelberg, the 319-355 page or leaf is introduced into this paper as a reference.

Suitable hydrophilic carrier B) monohydric alcohol, dihydroxylic alcohols or the polyhydric alcohol that is selected from water and preferably contains 1-8 carbon atom, for example ethanol, normal propyl alcohol, isopropyl alcohol, propylene glycol, glycerol, Sorbitol etc.

Cosmetic formulations of the present invention can be skin cosmetic composition, composition of hair cosmetics, dermatosis, health or pharmaceutical composition.Because their filming performance, above-mentioned preparation is specially adapted to hair and cosmetics for skin.

Preparation of the present invention preferably is the form of gel, foam, spray, mousse, ointment, frost, emulsion, suspension, lotion, Emulsion or paste.If necessary, also can use liposome or microsphere.

Cosmetics of the present invention or pharmaceutically active preparation can comprise cosmetics and/or dermatosis active component and auxiliary agent in addition.

Cosmetic formulations of the present invention preferably comprises at least a copolymer A as defined above), at least a carrier B as defined above) and at least a component different with it and that be selected from following material: cosmetic active ingredient, emulsifying agent, surfactant, antiseptic, aromatic oil, thickening agent, the hair polymer, hair and skin conditioning agent, graft polymers, water solublity or water dispersible contain polysiloxane polymer, light stability agent, bleach, gel former, nursing agent, coloring agent, toner, suntan, dyestuff, pigment, denseness agent (consistency agents), wetting agent, fatting agent (refatting agent), collagen, protein hydrolysate, lipoid, antioxidant, defoamer, antistatic additive, isostearyl glyceryl pentaerythrityl ether and softening agent.

Conventional thickening agent in this class preparaton is crosslinked polyacrylic acid and derivant thereof, polysaccharide and derivant thereof such as xanthan gum, agar, alginate or tylose, cellulose derivative such as carboxymethyl cellulose or hydroxyl carboxymethyl cellulose, aliphatic alcohol, monoglyceride and fatty acid, polyvinyl alcohol and polyvinylpyrrolidone.The non-anionic thickener of preferred use.

Preferred preparation of the present invention comprises at least a non-anionic thickener in addition.

Suitable cosmetics and/or dermatosis active component for example are painted active component, skin and hair coloring agent, toner, suntan, bleach, the keratin hardening material, the antimicrobial acivity composition, the optical filtering active component, anthelmintic activity composition (repellent active ingredients), material with hyperemization, material with keratin-dissolving and hyperkeratosis (keratoplastic) effect, the anti-dandruff active component, antiinflammatory, composition with keratinization effect, active component with antioxidation or free radical scavenging effect, make skin wet or make it keep moistening material, the stuffing active component, anti-erythema (antierythematous) or antiallergic activity composition and composition thereof.

Make artificial skin tanned and be applicable to tanning and need not nature or manually be exposed to ultraviolet active component for example for dihydroxy acetone, alloxan (alloxane) and Endocarpium Juglandis extract.Suitable keratin hardening material is generally the active component that also is used for anti-perspirant, for example aluminium potassium sulfate, aluminium chlorhydroxide, aluctyl. etc.The antimicrobial acivity composition is used for the elimination of micro-organisms or is used to suppress their growths, therefore simultaneously as antiseptic and the formation of minimizing body odor and the deodorization material of intensity.These for example comprise the known conventional preservatives of those skilled in the art such as p-Hydroxybenzoate, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid etc.This class deodorization material for example is alkanolamide, triethyl citrate, hibitane (chlorhexidine) of ricinoleic acid zinc, pure as jade pure (triclosan), 9-undecylenic acid etc.Suitable optical filtering active component is the ultraviolet material that is absorbed in UV-B and/or UV-A scope.Suitable UV filtering agent for example is 2,4,6-triaryl-1,3, the 5-triazine, wherein aryl can respectively carry the substituent group that at least one is preferably selected from following group: hydroxyl, alkoxyl, especially methoxyl group, alkoxy carbonyl, especially methoxycarbonyl and ethoxy carbonyl and composition thereof.Suitable in addition is p-aminobenzoate, cinnamate, benzophenone, camphor derivatives and cover ultraviolet pigment such as titanium dioxide, Talcum and zinc oxide.Suitable anthelmintic activity composition be for can make some animal, and especially insecticide is away from human or drive away their chemical compound.These chemical compounds for example comprise 2-ethyl-1,3-hexanediol, N, toluamide etc. between the N-diethyl.Suitable material with hyperemization and chafe blood flow for example for quintessence oil such as oleum pini pumilionis, lavandula angustifolia, Herba Rosmarini Officinalis, Juniperus oxycedrus, horse foxtail millet extract, white birch leaf extract, hayseed extract, ethyl acetate, Camphora, menthol, Oleum menthae, Herba Rosmarini Officinalis extract, Folium eucalypti globueli (Eucalyptus globulus Labill.) wet goods.Suitable keratolytic and hyperkeratosis material for example are salicylic acid, calcium mercaptoacetate, TGA and salt, sulfur etc.Suitable anti-dandruff active component for example is sulfur, sulfur Polyethylene Glycol Arlacel-80 (sulfur polyethylene glycol sorbitanmonooleate), sulfur Semen Ricini alcohol polyethoxylate (sulfur ricinol polyethoxylate), 1-oxygen 2-mercaptopyridine zinc, 1-oxygen 2-mercaptopyridine aluminum etc.Offset skin irritant suitable antiinflammatory and for example be allantoin, bisabolol, α-bisabolol (Dragosantol), chamomile extract, pantothenylol etc.

Cosmetic formulations of the present invention can comprise at least a other cosmetics or the medicine acceptable polymer as cosmetics and/or active constituents of medicine (and if suitable for auxiliary agent).These comprise very general cation, both sexes and neutral polymer.

Aqueous compositions of the present invention also can comprise and be different from copolymer A) water-soluble polymer.

Suitable polymers for example is called the cationic polymer of polyquaternary ammonium salt (Polyquaternium) for INCI, as vinyl pyrrolidone/N-vinyl imidazole  salt copolymer (Luviqua  FC, Luviquat  HM, Luviquat  MS, Luviquat  Care, Luviquat  UltraCare), with the quaternised N-vinyl pyrrolidone/copolymer of dimethylaminoethyl methacrylate of dithyl sulfate (Luviquat  PQ 11), N-caprolactam/N-vinyl pyrrolidone/N-vinyl imidazole  salt copolymer (Luviquat  Hold); Cationic cellulose derivative (polyquaternary ammonium salt-4 and polyquaternary ammonium salt-10), acrylamide base co-polymer (polyquaternary ammonium salt-7) and chitosan.Suitable cation (quaternized) polymer also has Merquat  (based on the polymer of dimethyl diallyl ammonium chloride), Gafquat  (by making the quaternary ammonium polymer that forms of polyvinylpyrrolidone and quaternary ammonium compound reaction), polymer JR (hydroxyethyl-cellulose with cation group) and based on the cationic polymer of plant, for example the guar gum polymer is as the Jaguar  board from Rhodia.

Other suitable polymers also be neutral polymer such as polyvinylpyrrolidone, N-vinyl pyrrolidone and vinyl acetate and/or propionate and/or (methyl) stearyl acrylate base ester copolymer, polysiloxanes, Vinylcaprolactam homopolymer and with other copolymer, polyaziridine and salt thereof, polyvinylamine and salt thereof, cellulose derivative, polyaspartic acid salts and the derivant of N-vinyl pyrrolidone.These polymer for example comprise Luviflex  Swing (polyvinyl acetate of partial hydrolysis and the copolymer of Polyethylene Glycol are from BASF) or Kollicoat  IR.

Suitable polymers is described in those of WO 03/092640 in addition, especially as embodiment 1-50 (table 1, the 40th page and each page subsequently) and embodiment 51-65 (table 2, the 43rd page) described (methyl) acrylamide copolymer, be introduced into as a reference fully herein.

Suitable polymers also has non-ionic water-soluble or aqueous dispersion polymers or oligomer, for example Vinylcaprolactam homopolymer such as Luviskol  Plus (BASF), perhaps polyvinylpyrrolidone and copolymer thereof are especially with the copolymer such as the Luviskol  VA 37 (BASF) of vinyl esters such as vinyl acetate; For example based on the polyamide of itaconic acid and aliphatic diamine for example described in DE-A-43 33 238.

Suitable polymers also has amphiphilic polymers or amphoteric ion polymer, octyl acrylamide/methyl methacrylate/t-butylaminoethyl methacrylate/methacrylic acid 2-hydroxypropyl acrylate the copolymer that for example can Amphomer  (National Starch) obtains, and for example be disclosed in amphoteric ion polymer among German patent application DE 39 29 973, DE 21 50 557, DE 28 17 369 and the DE 37 08 451.Preferred amphoteric ion polymer is acrylamido oxypropyl trimethyl ammonium chloride/acrylic or methacrylic acid copolymer and alkali metal salt and ammonium salt.Other suitable amphoteric ion polymer is with the commercially available methacryl ethyl betanin/methacrylate copolymer of Amersette  (AMERCHOL)) and hydroxyethyl methylacrylate, methyl methacrylate, methacrylic acid N, N-dimethylaminoethyl and acrylic acid copolymer (Jordapon ).

Suitable polymers also has nonionic to contain water solublity or aqueous dispersion polymers such as polyether silicone such as the Tegopren  (Goldschmidt) or the Belsil  (Wacker) of siloxanes.

Biopolymer also is suitable, the polymer that is promptly obtained by the natural reproducible raw material and be made of natural monomer structure unit, for example cellulose derivative, chitin, chitosan, DNA, hyaluronic acid and RNA derivant.

Other preparation of the present invention comprises at least a other water-soluble polymer, especially has the chitosan (poly-(D-glycosamine)) of variation molecular weight and/or the derivant of chitosan.

Anionic polymer

Other polymer that is fit to preparation of the present invention is the copolymer that contains hydroxy-acid group.But these copolymers are for having the polyelectrolyte of relatively large anion dissociation group on main chain and/or side chain.They can with copolymer A) form compound polyelectrolyte (symplexes).

In preferred embodiments, the compound polyelectrolyte that is used for the present composition has excessive latent anion/anionic group.

Except that comprising at least a above-mentioned copolymer A), compound polyelectrolyte also comprises at least a polymer that contains acidic-group.

It is 50: 1 to 1: 20 that compound polyelectrolyte preferably comprises weight ratio, 5 copolymer A) and contain the polymer of acidic-group preferred especially 20: 1-1:.

Suitable carboxy-containing acid group's polymer can be for example by making α, β-ethylenically unsaturated monomer radical polymerization and obtaining.Use per molecule to comprise the α of at least one free redical polymerization, the monomer m1 of β-ethylenical unsaturated double bonds and at least one latent anion and/or anionic group herein).

In addition, suitable carboxy-containing acid group's polymer is carboxy-containing acid group's polyurethane.

Monomer is preferably selected from monoethylenically unsaturated carboxylic acid, sulfonic acid, phosphonic acids and composition thereof.

Monomer m1) comprise and contain 3-25 that the monoene of preferred 3-6 carbon atom belongs to unsaturated monobasic and dicarboxylic acids, they also can be with the form use of its salt or anhydride.These monomeric examples are acrylic acid, methacrylic acid, ethylacrylic acid, α-Lv Bingxisuan .beta.-methylacrylic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconate, equisetic acid and fumaric acid.Monomer comprises also and contains 4-10 that the monoene of preferred 4-6 carbon atom belongs to the monoesters of unsaturated dicarboxylic acid such as maleic acid, for example maleic acid one methyl ester.Monomer comprises that also monoene belongs to unsaturated sulfonic acid and phosphonic acids, for example vinyl sulfonic acid, allyl sulphonic acid, acrylic acid sulfo group ethyl ester, methacrylic acid sulfo group ethyl ester, acrylic acid sulfo group propyl ester, methacrylic acid sulfo group propyl ester, 2-hydroxyl-3-acryloxy propyl sulfonic acid, 2-hydroxy-3-methyl acryloxy propyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinyl phosphonate and pi-allyl phosphonic acids.Monomer also comprises the salt of above-mentioned acid, especially sodium salt, potassium salt and ammonium salt and with the salt of above-mentioned amine.Monomer can directly use or use as mutual mixture.Described weight fraction number average is based on sour form.

Monomer m1) is preferably selected from acrylic acid, methacrylic acid, ethylacrylic acid, α-Lv Bingxisuan .beta.-methylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconate, equisetic acid and composition thereof, preferred especially acrylic acid, methacrylic acid and composition thereof.

Above-mentioned monomer ml) can use independently of one another or use with the form of any mixture.

The comonomer that is suitable for preparing carboxy-containing acid group's polymer in principle is above-mentioned as copolymer A) the compound a of component) to d), prerequisite is the molar fraction of the molar fraction of the latent anion of the copolymerized form that comprises of carboxy-containing acid group's polymer and anionic group greater than YANG hyperactivity suppressing ion and cation group.

In preferred embodiments, carboxy-containing acid group's polymer comprise at least a copolymerized form and be selected from above-mentioned cross-linking agent d) monomer.With reference to suitable and preferred cross-linking agents d).

Carboxy-containing acid group's polymer further preferably comprises at least a monomer m2 of copolymerized form), it is selected from the chemical compound of general formula (VI):

Wherein

R ¹Be hydrogen or C ₁-C ₈Alkyl,

Y ¹Be O, NH or NR ³And

R ²And R ³Be C independently of each other ₁-C ₃₀Alkyl or C ₅-C ₈Cycloalkyl, wherein alkyl can be inserted into many 4 the non-conterminous O of being selected from, S and NH hetero atom or contain heteroatom group.

Preferred R ¹In VI hydrogen or C ₁-C ₄Alkyl, especially hydrogen, methyl or ethyl.

Preferred R ²In VI C ₁-C ₈Alkyl, preferable methyl, ethyl, normal-butyl, isobutyl group, the tert-butyl group or formula-CH ₂-CH ₂-NH-C (CH ₃) ₃Group.

If R ³Be alkyl, then it is preferably C ₁-C ₄Alkyl is as methyl, ethyl, n-pro-pyl, normal-butyl, isobutyl group or the tert-butyl group.

Suitable monomers m2) is (methyl) acrylic acid methyl ester., the ethylacrylic acid methyl ester, (methyl) ethyl acrylate, the ethyl propylene acetoacetic ester, (methyl) tert-butyl acrylate, the ethyl propylene tert-butyl acrylate, (methyl) acrylic acid n-octyl, (methyl) acrylic acid 1,1,3,3-tetramethyl butyl ester, (methyl) EHA, (methyl) acrylic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) acrylic acid n-undecane base ester, (methyl) tridecyl acrylate, (methyl) acrylic acid myristin, (methyl) acrylic acid pentadecyl ester, (methyl) acrylic acid Petiolus Trachycarpi ester, (methyl) acrylic acid heptadecyl ester, (methyl) acrylic acid nonadecyl ester, (methyl) acrylic acid arrachinyl ester, (methyl) acrylic acid behenyl alcohol ester, (methyl) acrylic acid tetracosa carbon thiazolinyl (lignocerenyl) ester, (methyl) acrylic acid 26 carbon backs (cerotinyl) ester, (methyl) acrylic acid 30 carbon backs (melissinyl) ester, (methyl) acrylic acid hexadecene base (paimitoleinyl) ester, (methyl) acrylic acid grease, inferior oil base (linolyl) ester of (methyl) acrylic acid, (methyl) acrylic acid Caulis et Folium Lini base (linolenyl) ester, (methyl) stearyl acrylate base ester, (methyl) lauryl acrylate and composition thereof.

Suitable monomers m2) also has acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-(normal-butyl) (methyl) acrylamide, N-(tert-butyl group) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, piperidyl (methyl) acrylamide, morpholinyl (methyl) acryloyl, N-(n-octyl) (methyl) acrylamide, N-(1,1,3, the 3-tetramethyl butyl) (methyl) acrylamide, N-ethylhexyl (methyl) acrylamide, N-(n-nonyl) (methyl) acrylamide, N-(positive decyl) (methyl) acrylamide, N-(n-undecane base) (methyl) acrylamide, N-tridecyl (methyl) acrylamide, N-myristyl (methyl) acrylamide, N-pentadecyl (methyl) acrylamide, N-palmityl (methyl) acrylamide, N-heptadecyl (methyl) acrylamide, N-nonadecyl (methyl) acrylamide, N-arrachinyl (methyl) acrylamide, N-mountain Yu base (methyl) acrylamide, N-tetracosa carbon thiazolinyl (lignocerenyl) (methyl) acrylamide, N-26 carbon backs (cerotinyl) (methyl) acrylamide, N-30 carbon backs (melissinyl) (methyl) acrylamide, N-hexadecene base (palmitoleinyl) (methyl) acrylamide, N-oil base (methyl) acrylamide, inferior oil base (linolyl) (methyl) acrylamide of N-, N-Caulis et Folium Lini base (linolenyl) (methyl) acrylamide, N-stearyl (methyl) acrylamide and N-lauryl (methyl) acrylamide.

In addition, carboxy-containing acid group's polymer preferably comprises at least a monomer m3 of copolymerized form), it is selected from the chemical compound of general formula VII:

Wherein

The order of oxyalkylene units is arbitrarily,

K and l are the integer of 0-1000 independently of each other, and k and l sum are at least 5,

R ⁴Be hydrogen, C ₁-C ₃₀Alkyl or C ₅-C ₈Cycloalkyl,

R ⁵Be hydrogen or C ₁-C ₈Alkyl,

Y ²Be O or NR ⁶, R wherein ⁶Be hydrogen, C ₁-C ₃₀Alkyl or C ₅-C ₈Cycloalkyl.

Preferred k is the integer of the integer of 1-500, especially 3-250 in formula VII.Preferred l is the integer of 0-100.

Preferred R ⁴In formula VII hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, n-pentyl, n-hexyl, octyl group, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl.

Preferred Y ²In formula VII O or NH.

Suitable acrylic acid polyester ether VII) for example is above-mentioned α, the polycondensation product of β-olefinic unsaturated monocarboxylic acid and/or dicarboxylic acids and acid chloride, amide and anhydride and Aethoxy Sklerol.Suitable Aethoxy Sklerol can be by making ethylene oxide, 1,2-propylene oxide and/or chloropropylene oxide and starting molecule such as water or short chain alcohol R ⁴-OH reacts and preparation easily.Oxyalkylene can use separately or be used alternatingly or use as mixture.Acrylic acid polyester ether VII) can use separately or be used to prepare polymer used according to the invention as mixture.Suitable acrylic acid polyester ether II) has urethane (methyl) acrylate of oxyalkylene group in addition.This compounds is described in (component e2) among the DE 198 38 851, it is incorporated herein by reference fully herein.

Preferably the anionic polymer as carboxy-containing acid group's polymer for example is homopolymer and the copolymer and the salt thereof of acrylic acid and methacrylic acid.These polymer also comprise the acrylic acid cross linked polymer that can INCI name Carbomer obtains.The acrylic acid cross-linked homopolymer of this class for example is the commercially available Carbopol  from Noveon.Also the cross-linked polyacrylate polymer of preferred hydrophobically modified is as the Carbopol  Ultrez 21 from Noveon.

Be suitable for being mixed with gel such as hair fixing glue and be used to prepare foam with advantageous manner based on the homopolymer of acrylic acid and methacrylic acid and the compound polyelectrolyte of copolymer.

Other example of suitable anionic polymer is the copolymer and the salt thereof of acrylic acid and acrylamide; The sodium salt of polyhydroxycarboxyliacid acid, water solublity or water-dispersible polyester, polyurethane and polyureas.Specially suitable polymer is the copolymer of (methyl) acrylic acid and acrylic acid polyester ether, and wherein polyether chain is by C ₈-C ₃₀Alkyl-blocked.These polymer for example comprise acrylate/polyoxyethylene (25) behenyl alcohol ether metacrylic acid ester copolymer, and it can be obtained with Aculyn  by Rohm und Haas.In addition, specially suitable polymer is a tert-butyl acrylate, ethyl acrylate, the copolymer of methacrylic acid is (as Luvimer  100P, Luvimer  Pro55), the copolymer of ethyl acrylate and methacrylic acid (as Luvimer  MAE), N tert butyl acrylamide, ethyl acrylate and acrylic acid copolymer (Ultrahold  8, Ultrahold  Strong), vinyl acetate, if the copolymer of .beta.-methylacrylic acid and suitable other vinyl esters (as Luviset  board), if it is suitable and pure, anion polysiloxane such as carboxy-functionalized anion polysiloxane, tert-butyl acrylate, the copolymer-maleic anhydride of metering system acid reaction (as Luviskol  VBM), the C of acrylic acid and methacrylic acid and hydrophobic monomer such as methyl (acrylic acid) ₄C ₃₀Arrcostab, C ₄-C ₃₀Alkyl vinyl ester, C ₄-C ₃₀Alkyl vinyl ether and hyaluronic copolymer.In addition, the example of anionic polymer is for example with Resyn  (National Starch) and the commercially available vinyl acetate/.beta.-methylacrylic acid copolymer of Gafset  (GAF), and the vinyl pyrrolidone/vinyl acrylate copolymer that for example can trade name Luviflex  (BASF) obtains.Other suitable polymers is vinyl pyrrolidone/acrylate terpolymer that can Luviflex  VBM-36 (BASF) obtains and the polyester that contains the polyamide of sodium sulfonate or contain sodium sulfonate.

The anionic polymer that this class is suitable for example also comprises Balance  CR (National Starch; Acrylate copolymer), Balance  0/55 (National Starch; Acrylate copolymer), Balance  47 (National Starch; Octyl acrylamide/acrylate/methacrylic acid fourth amino ethyl ester copolymer), Aquaflex  FX 64 (ISP; Isobutene ./ethyl maleimide/ethoxy maleimide copolymer), Aquaflex  SF-40 (ISP/National Starch; VP/ caprolactam/DMAPA acrylate copolymer), Allianz  LT-120 (ISP/Rohm ﹠amp; Haas; Acrylate/C1-2 succinate/hydroxy acrylate copolymer), Aquarez  HS (Eastman; Polyester-1), Diaformer  Z-400 (Clariant; Methacryl ethyl betanin/methacrylate copolymer), Diaformer  Z-711 (Clariant; Methacryl ethyl n-oxide/methacrylate copolymer), Diaformer  Z-712 (Clariant; Methacryl ethyl n-oxide/methacrylate copolymer), Omnirez  2000 (ISP; The mono ethyl ester of poly-(ethylene methacrylic ether/maleic acid) in ethanol), Amphomer  HC (National Starch; Acrylate/octyl acrylamide copolymer), Amphomer  28-4910 (National Starch; Octyl acrylamide/acrylate/methacrylic acid fourth amino ethyl ester copolymer), Advantage  HC 37 (ISP; The terpolymer of caprolactam/vinyl pyrrolidone/dimethylaminoethyl methacrylate), Advantage  LC55 and LC80 or LC A and LC E, Advantage  Plus (ISP; VA/ maleic acid butyl ester/isobornyl acrylate copolymer), Aculyne  258 (Rohm ﹠amp; Haas; Acrylate/hydroxy ester acrylate copolymer), Luviset  P.U.R. (BASF, polyurethane-1), Luvmex  Silk (BASF), Eastman  AQ 48 (Eastman), Styleze  CC-10 (ISP; The VP/DMAPA acrylate copolymer), Styleze  2000 (ISP; VP/ acrylate/lauryl methacrylate copolymer), DynamX  (National Starch; Polyurethane-14 AMP-acrylate copolymer), Resyn XP  (National Starch; Acrylate/octyl acrylamide copolymer), Fixomer  A-30 (Ondeo Nalco; Polymethylacrylic acid (with) the acrylamido methyl propane sulfonic acid), Fixate  G-100 (Noveon; AMP-acrylate/allyl methacrylate copolymer).

Suitable carboxy-containing acid group's polymer is described in US 3,405 in addition, vinyl pyrrolidone/(methyl) acrylic acid C in 084 ₁-C ₁₀Arrcostab, cycloalkyl ester and aryl ester and acrylic acid terpolymer.Suitable carboxy-containing acid group's polymer also has at the vinyl pyrrolidone described in EP-A-0 257 444 and the EP-A-0 480280, (methyl) tert-butyl acrylate and (methyl) acrylic acid terpolymer.Suitable carboxy-containing acid group's polymer is described in the copolymer of at least a (methyl) among the DE-A-42 23 066 and that comprise copolymerized form acrylate, (methyl) acrylic acid and N-vinyl pyrrolidone and/or N-caprolactam in addition.The disclosed content of these documents is incorporated herein by reference.

Above-mentioned carboxy-containing acid group's polymer is by known method, as preparing by solution, precipitation, suspension or emulsion polymerisation, as above to copolymer A) described.

Suitable carboxy-containing acid group's polymer also has carboxy-containing acid group's polyurethane.

EP-A-636361 discloses the suitable block copolymer with polysiloxane block and polyurethane/polyurea block, and it has hydroxy-acid group and/or sulfonic acid group.The suitable polyurethane that contains polysiloxanes also is described among WO 97/25021 and the EP-A-751 162.

Suitable polyurethane also is described among the DE-A-42 25 045, and it is incorporated herein by reference fully.

The acidic-group of carboxy-containing acid group's polymer partially or completely can be neutralized.Then, at least some acidic-groups are and take off proton form, and counter ion counterionsl gegenions are preferably selected from alkali metal ion such as Na ⁺, K ⁺, ammonium ion and organic derivative thereof.

Preparation of the present invention also can be used for drug world.The preparation matrix optimization of pharmaceutical preparation of the present invention comprises the medicine acceptable assistant.The medicine acceptable assistant is the known auxiliary agent that can be used for medicine, food technology and association area, and especially listed those and its performance are not got rid of other auxiliary agent that the physiology uses in relevant pharmacopeia (as DAB Ph.Eur.BP NF).

Proper auxiliary agent can be lubricant, wetting agent, emulsifying agent and suspending agent, antiseptic, antioxidant, the irritation material, chelating agen, emulsion stabilizer, film former, gel former, stink covers material, resin, hydrocolloid, solvent, solubilizer, nertralizer, penetration enhancer, pigment, quaternary ammonium compound, fatting agent, superfatting agent, ointment base, the frost base, oil base, polyorganosiloxane ramification, stabilizing agent, antibacterial, propellant, desiccant, opacifier, thickening agent, wax, softening agent, white oil.Relevant preparation is based on those skilled in the art's knowledge, for example be described in Fielder, H.P.Lexikon der Hilfsstoffe f ü r Pharmazie, Kosmetik und angrenzende Gebiete, [the auxiliary agent dictionary of medicine, cosmetics and association area] the 4th edition, Aulendorf:ECV-Editio-Kantor-Verlag is in 1996.

Be preparation dermatological formulation of the present invention, active component can be mixed with suitable auxiliary agents or with its dilution (excipient).Excipient can be solid, semisolid or fluent material, and it can be used as active component vehicle, carrier or medium.If necessary, sneak into other auxiliary agent in the known mode of those skilled in the art.In addition, preparation is suitable as auxiliary agent and is used for medicine, preferably is used for solid dosage forms with coating material or binding agent.They also can be used for frost and be used as sheet coating material and sheet binding agent.

According to preferred embodiment, preparation of the present invention is a skin cleansing compositions.

Preferred skin clean preparation is a liquid to the soap of gluey denseness such as transparent soap, senior fancy soap, deodorant soap, paste of soap (cream soaps), baby's soap, skin protection soap, abrasive soap, synthetic detergent, paste soap (pasty soaps), soft soap, cleaning paste, liquid lotion, shower and bath in a tub preparation such as cleaning mixture, shower agent and bath gels, the foam bath agent, oil bath agent and scouring preparation, and shaving foam, lotion and frost.

According to another preferred embodiment, preparation of the present invention is skin nursing and skin protection apply some make up preparation, manicure compositions and color make-up preparation.

The suitable skin cosmetic formulations for example is cleansing milk, facial film, deodorizer and other astringent.The compositions that is used for color make-up for example comprises covering rod, stage color make-up, mascara, eye shadow, lip pomade, eye cosmetic (kohl) pen, eyeliner, kermes, end powder and eyebrow pencil.

Skin care compositions and methods of the present invention especially is W/O or O/W protective skin cream, day cream, late frost, eye cream, facial cream, crease-proof cream, skin lotion frost, bleaching frost, vitamin cream, skin lotion, conditioning liquid and moisturizing emulsions.

Skin cosmetic composition and dermatosis compositions table based on above-mentioned preparation reveal favourable effect.Described preparation can especially help to moisturize the skin and nurse one's health and improve dermal sensation.Described preparation also can be used as thickening agent and is used for preparaton.By in some preparaton, adding polymer of the present invention, can significantly improve skin-friendliness.

Cosmetics for skin preparation of the present invention and dermatological formulation preferably comprise at least a copolymer A), its amount is about 0.001 to 30 weight % based on the gross weight of compositions, preferred 0.01-20 weight %, very particularly preferably 0.1-12 weight %.

Compare with conventional auxiliary agent such as polyvinylpyrrolidone, based on copolymer A) light stability agent especially have and increase the performance that UV absorbs the composition time of staying.

Depend on application, the present composition can be used with the form that is suitable for skin nursing, for example frost, foam, gel, rod, mousse, Emulsion, spray (hands is by pump type spray or contain the spraying of propellant) or lotion.

Except that comprising copolymer A) and suitable carriers, the cosmetics for skin preparation also can comprise in the cosmetics for skin commonly used and aforesaid other active component and auxiliary agent.These preferably include emulsifying agent, antiseptic, aromatic oil, cosmetic active ingredient such as phytantriol (phytantriol), vitamin A, vitamin E, vitamin C, retinol, bisabolol, pantothenylol, light stability agent, bleach, coloring agent, toner, suntan, collagen, protein hydrolysate, stabilizing agent, the pH regulator agent, dyestuff, salt, thickening agent, gel former, denseness agent, polysiloxanes, wetting agent, fatting agent and other conventional additives.

The oil ﹠ fat component of preferred skin cosmetic composition and dermatosis compositions is above-mentioned mineral oil and artificial oil such as paraffin, silicone oil and the aliphatic hydrocarbon that has above 8 carbon atoms, animal and plant oil is as sunflower oil, Oleum Cocois, American Avocado Tree oil, olive oil, lanoline, perhaps wax, fatty acid, fatty acid ester such as glycerol three C ₆-C ₃₀Fatty acid ester, wax ester such as Jojoba oil, aliphatic alcohol, vaseline, hydrogenated lanolin and acetylated lanolin and composition thereof.

Set up particular characteristic if desired, then also preparation of the present invention can be mixed with conventional polymer.

For setting up particular characteristic, for example improve the bonding of sense of touch, spreading property, water resistance and/or active component and auxiliary agent such as pigment, cosmetics for skin preparation and dermatological formulation can comprise the conditioning material based on polysiloxane compound in addition.Suitable polysiloxane compound for example is poly-alkylsiloxane, poly-aryl siloxanes, poly-aryl alkyl siloxanes, polyether silicone or organic siliconresin.

Preparation cosmetics or dermatological formulation can be undertaken by the known conventional method of those skilled in the art.

Preferred cosmetics and dermatosis compositions are emulsion form, especially are Water-In-Oil (W/O) or oil-in-water (O/W) emulsion form.Yet, also can select the preparaton of other type such as aqueous dispersion, gel, oil, oleogel, multiple emulsion as being W/O/W or O/W/O emulsion form, anhydrous ointment or ointment base etc.

Prepare emulsion by known method.Except that at least a copolymer A), in the presence of water, emulsion also comprises conventional component such as aliphatic alcohol usually, fatty acid ester, especially fatty acid triglyceride, fatty acid, lanoline and derivant thereof, natural oil, artificial oil or wax and emulsifying agent.The preparation example that depends on the selection of additive of emulsion type and suitable emulsion is as being described in Schrader, Grundlagenund Rezepturen der Kosmetika[cosmetic base and preparaton], Hiithig BuchVerlag, Heidelberg, the 2nd edition, 1989, in the third part, be introduced into this paper as a reference.

The suitable emulsion that for example is used for protective skin cream etc. generally includes water, by suitable emulsifier system with this water oil phase or fat mutually in emulsifying.Can use formulation preparation water of the present invention.

Preferably the fatty ingredient that can exist in mutually at the fat of emulsion is: hydrocarbon ils such as liquid paraffin, purcellin oil, perhydro-squalene and the solution of microwax in these oil; Animal or plant oil is as Semen pruni armeniacae oil, American Avocado Tree oil, Calophyllum (calophylum) oil, lanoline and derivant thereof, Oleum Ricini, Oleum sesami, olive oil, Jojoba oil, karit é oil, breast sour jujube Channa argus (hoplostethus) oil; Begin distillation under atmospheric pressure and about 250 ℃, the distillation end point temperature is 410 ℃ mineral oil such as a vaseline oil; The ester of satisfied fatty acid or unsaturated fatty acid, for example myristic acid Arrcostab such as isopropyl myristate, butyl myristate or cetyl myristate, stearic acid cetyl ester, ethyl palmitate, isopropyl palmitate, tricaprylin, tricaprin and ricinoleic acid cetyl.

Fat also can comprise mutually and dissolves in other oily silicone oil, for example polydimethylsiloxane, poly-(methyl phenyl siloxane) and siloxanes/glycol copolymer, fatty acid and aliphatic alcohol.

Except that copolymer A), wax such as Brazil wax, candelilla wax, Cera Flava, microwax, ceresine and calcium oleate, magnesium oleate, aluminum oleate, calcium myristate, magnesium myristate, aluminium myristate, calcium linoleate, magnesium linoleate, linoleic acid aluminum, calcium stearate, magnesium stearate and aluminium stearate can also be used.

In addition, emulsion of the present invention can exist with the O/W emulsion.This emulsion comprises oil phase usually, makes the stable emulsifying agent and the water of oil phase of aqueous phase, and water exists with the thickening form usually.Suitable emulsifying agent is preferably the glyceride of O/W emulsifying agent such as polyglycerin ester, Isosorbide Dinitrate, partial esterification.

According to another preferred embodiment, preparation of the present invention is shower gels, hair-washing composition or bath in a tub preparation.

This class preparaton of the present invention comprises at least a copolymer A) and anion surfactant commonly used as the basic surface activating agent, and as the both sexes and/or the non-ionic surface active agent of cosurfactant.Active component that other is suitable and/or auxiliary agent are selected from lipoid, aromatic oil, dyestuff, organic acid, antiseptic and antioxidant and thickening agent/gel former usually, skin conditioning agent and wetting agent.

Based on the gross weight of preparaton, these preparatons preferably comprise 2-50 weight %, preferred 5-40 weight %, the surfactant of preferred especially 8-30 weight %.

All anion, neutrality, both sexes or cationic surfactants that are generally used in the clean body compositions may be used to detergent compositions, shower preparation and bath in a tub preparation.

Suitable anion surfactant for example is alkyl sulfate, alkyl ether sulfate, alkylsulfonate, alkylaryl sulfonates, alkyl succinate, alkyl sulfo succinate, N-alkanoyl sarcosinate (N-alkoylsarcosinate), acyl taurine salt, acyl isethinate, alkylphosphonic, alkyl ether phosphate, alkyl ether carboxy acid salt, alpha-alkene sulfonate, especially alkali metal salt and alkali salt such as sodium salt, potassium salt, magnesium salt and calcium salt and ammonium salt and triethanolamine salt.Alkyl ether sulfate, alkyl ether phosphate and alkyl ether carboxy acid salt can have 1-10 ethylene oxide or propylene oxide unit in molecule, preferred 1-3 ethylene oxide unit.

These for example comprise sodium lauryl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, Zetesol AP, sodium lauryl sarcosinate, oil base sodium succinate, lauryl 2-Sulfosuccinic acid ammonium, dodecylbenzene sodium sulfonate, DBSA triethanolamine.

Suitable amphoteric surfactant for example is an alkyl betaine, the alkyl amido CAB, the alkyl sulfobetaines, p dialkylaminobenzoic acid salt, the alkyl carboxyl Glycinates, N-(alkyl amido ethyl)-N-(ethoxy) Glycinates (alkyl amphoacetate), N-(alkyl amido ethyl)-N-(ethoxy) aminopropionate (alkyl amphopropionate), N-(alkyl amido ethyl)-amino diacetin of N-(ethoxy) or N-(alkyl amido ethyl)-amino dipropionate of N-(ethoxy).

For example, can use cocoyl dimethyl sulfopropyl betaine, lauryl betaine, cocoamidopropyl or N-(cocoamidoethyl)-N-(ethoxy) alanine sodium.

Suitable non-ionic surface active agent for example is aliphatic alcohol or has the product of alkyl phenol and the ethylene oxide and/or the propylene oxide of 6-20 carbon atom on the alkyl chain that can be linearity or branching.The amount of oxyalkylene is about 6 to 60 moles of every mol of alcohol.In addition, the fatty acid ester of alkyl amine oxide, monoalkyl alkanolamide, dialkyl group alkanolamide, Polyethylene Glycol, ethoxylated fat amide, alkyl poly glucoside or anhydro sorbitol ether-ether also are suitable.

Detergent compositions, shower preparation and bath in a tub preparation also can comprise conventional cationic surfactant, for example quaternary ammonium compound such as cetyl trimethyl ammonium chloride.

In addition, shower gels/hair washing preparaton can comprise thickening agent, for example sodium chloride, PEG-55, polypropylene glycol oleate, PEG-120 methyl glucoside dioleate etc., and antiseptic, other active component and auxiliary agent and water.

According to another preferred embodiment, preparation of the present invention is a hair-treatment composition.

Hair-treatment composition of the present invention preferably comprises at least a copolymer A), its amount is about 0.1-30 weight % based on the gross weight of compositions, preferred 0.5-20 weight %.

Hair-treatment composition of the present invention preferably is typing foam, hair mousse, hair gel, shampoo, hair spray, hair foam, impaired making a start use fluid, and the form that is used for the nertralizer of long-acting setting lotion, hair dye and the processing of bleach Huo treatment oil.Depend on application, the cosmetic hair preparation can use with the form of (aerosol type) spray, (aerosol) foam, gel, gel spray, frost, lotion or wax.The hands that hair spray comprises the aerosol type spray simultaneously and do not contain propellant is by pump type spray.The hands that the hair foam comprises aerosol foam simultaneously and do not contain propellant is by pumped foam.Hair spray and hair foam preferably mainly or only comprise water solublity or water dispersible component.If being used for the foamy chemical compound of hair spray of the present invention and hair is water dispersible, then they can be generally 1-350nm with particle diameter, and the form of the moisture differential prose style free from parallelism of preferred 1-250nm is used.Here the solid content of these preparations is generally about 0.5 to 20 weight %.Usually, these differential prose style free from parallelisms do not need emulsifying agent or surfactant to make them stable.

In preferred embodiments, cosmetic hair preparaton of the present invention comprises:

A) at least a copolymer A of 0.05-20 weight %),

B) water of 20-99.95 weight % and/or alcohol,

C) at least a propellant gas of 0-50 weight %,

D) at least a emulsifying agent of 0-5 weight %,

E) at least a thickening agent of 0-3 weight % and

F) other composition of 25 weight % at the most.

Wherein the pH of preparaton is 4-6.

The implication of alcohol is interpreted as alcohol such as ethanol, isopropyl alcohol and the normal propyl alcohol that all are usually used in cosmetics.

The implication of other composition is interpreted as the additive that is usually used in cosmetics, and for example propellant, defoamer, surface active cpd are surfactant, emulsifying agent, foaming agent and solubilizer.The surface active cpd that uses can be anion, cation, both sexes or neutrality.In addition, conventional component for example can also be antiseptic, aromatic oil, opacifier, active component, UV filtering agent, care substance such as pantothenylol, collagen, vitamin, protein hydrolysate, alpha-hydroxy carboxylic acid compounds and beta-hydroxycarboxylic acids, stabilizing agent, pH regulator agent, dyestuff, viscosity modifier, gel former, salt, wetting agent, fatting agent, compounding ingredient and other conventional additives.

These also comprise known all typings and conditioning polymer in cosmetics, if set up very special performances, then itself and combination of polymers of the present invention can be used.

Suitable conventional cosmetic hair polymer is above-mentioned cation, anion, neutrality, nonionic and amphiphilic polymers for example, is introduced into as a reference herein.

For setting up property, described preparation can comprise the conditioning material based on polysiloxane compound in addition.Suitable polysiloxane compound for example is poly-alkylsiloxane, poly-aryl siloxanes, poly-aryl alkyl siloxanes, polyether silicone, silicones or dimethicone copolyol (CTFA) and amino-functional polysiloxane compound such as amino-terminated polydimethylsiloxane (CTFA).

Polymer of the present invention is particularly suitable as setting agent and is used for the hair style preparation, especially hair spray (aerosol type spray and the hands that do not contain propellant gas are by pump type spray) and hair foam (aerosol foam and the hands that do not contain propellant gas are by pumped foam).

In preferred embodiments, spray agent comprises:

A) at least a copolymer A of 0.1-3 weight %),

B) at least a other polymer of 0.1-3 weight %,

C) water of 20-99.9 weight % and/or alcohol,

D) at least a propellant of 0-70 weight %,

E) other component of 0-20 weight %,

Wherein the pH of preparation is 4-6.

Propellant is the propellant that is generally used for hair spray or aerosol foam.The mixture of preferably propane/butane, pentane, dimethyl ether, 1,1-Difluoroethane (HFC-152a), carbon dioxide, nitrogen or compressed air.

Preferred hair aerosol foam comprises with preparaton according to the present invention:

A) at least a copolymer A of 0.1-10 weight %),

B) water of 55-99.8 weight % and/or alcohol,

C) propellant of 5-20 weight %,

D) emulsifying agent of 0.1-5 weight %,

E) other component of 0-10 weight %,

Wherein the pH of preparation is 4-6.

Operable emulsifying agent is for being generally used for foamy all emulsifying agents of hair.Suitable emulsifying agent can be nonionic, cation or anion or amphoteric emulsifier.

The example of nonionic emulsifier (INCI name) is laureth class such as lauryl polyoxyethylene (4) ether; Ceteth such as cetyl glycol ether, Polyethylene Glycol cetyl ether; 16/polyoxyethylene octadecanol class is as 16/octodecyl alcohol polyoxyethylene (25) ether, polyethylene glycol fatty acid glyceride, hydroxylated lecithin, the lactoyl ester of fatty acid, alkyl poly glucoside.

The example of cationic emulsifier is cetyl dimethyl-2-ethoxy Ammonium biphosphate, cetyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, Methylsulfate cocos nucifera oil trimethyl ammonium, Quaternium-1 to Quaternium-x (INCI).

Anion emulsifier for example can be selected from alkyl sulfate, alkyl ether sulfate, alkylsulfonate, alkylaryl sulfonates, alkyl succinate, alkyl sulfo succinate, N-alkanoyl sarcosinate, acyl taurine salt, acyl isethinate, alkylphosphonic, alkyl ether phosphate, alkyl ether carboxy acid salt, alpha-alkene sulfonate, especially alkali metal salt and alkali salt such as sodium salt, potassium salt, magnesium salt or calcium salt and ammonium salt and triethanolamine salt.Alkyl ether sulfate, alkyl ether phosphate and alkyl ether carboxy acid salt can have 1-10 ethylene oxide or propylene oxide unit in molecule, preferred 1-3 ethylene oxide unit.

The preparation that is applicable to hair styling gel having according to the present invention can for example have following composition:

A) at least a copolymer A of 0.1-10 weight %),

B) water of 80-99.85 weight % and/or alcohol,

C) 0-3 weight %, the gel former of preferred 0.05-2 weight %,

D) other composition of 0-20 weight %,

Wherein the pH of preparation is 4-6.

Can advantageously use special rheological property or other performance characteristic of gel former to set up gel.Operable gel former is all gel formers that are usually used in cosmetics.

These for example comprise cellulose derivative such as hydroxypropyl cellulose, hydroxyethyl-cellulose, cation-modified cellulose, polysaccharide such as xanthan gum, tricaprylin/decanoin, sodium acrylate copolymer, polyquaternium-32 (with) paraffin oil (Paraffinum Liquidum) (INCI), sodium acrylate copolymer (with) paraffin oil (with) PPG-1 tridecyl polyoxyethylene (6) ether, acrylamido oxypropyl trimethyl ammonium chloride/acrylamide copolymer, stearyl polyoxyethylene (10) ether allyl ether acrylate copolymer, polyquaternary ammonium salt-37 (with) paraffin oil (with) PPG-1 tridecyl polyoxyethylene (6) ether, polyquaternary ammonium salt-37 (with) the propylene glycol dicaprate dicaprylate (with) PPG-1 tridecyl polyoxyethylene (6) ether, polyquaternary ammonium salt-7, polyquaternary ammonium salt-44.

Preparation of the present invention can be used as conditioner and is used for cosmetic formulations.

Preparation of the present invention can preferably be used for the preparaton of having one's hair wash as setting agent and/or conditioner.Preferred hair washing preparaton comprises:

A) at least a copolymer A of 0.05-10 weight %),

B) water of 25-94.95 weight %,

C) surfactant of 5-50 weight %,

D) other conditioner of 0-5 weight %,

E) other components of cosmetics of 0-10 weight %,

Wherein the pH of preparation is 4-6.

In the hair washing preparaton, can use all aniones, neutrality, both sexes or the cationic surfactant that are usually used in shampoo.

Suitable anion surfactant for example is alkyl sulfate, alkyl ether sulfate, alkylsulfonate, alkylaryl sulfonates, alkyl succinate, alkyl sulfo succinate, N-alkanoyl sarcosinate, acyl taurine salt, acyl isethinate, alkylphosphonic, alkyl ether phosphate, alkyl ether carboxy acid salt, alpha-alkene sulfonate, especially alkali metal salt and alkali salt such as sodium salt, potassium salt, magnesium salt and calcium salt and ammonium salt and triethanolamine salt.Alkyl ether sulfate, alkyl ether phosphate and alkyl ether carboxy acid salt can have 1-10 ethylene oxide or propylene oxide unit in molecule, preferred 1-3 ethylene oxide unit.

For example, suitable is sodium lauryl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, Zetesol AP, sodium N-lauroyl sarcosinate, oil base sodium succinate, lauryl 2-Sulfosuccinic acid ammonium, dodecylbenzene sodium sulfonate, DBSA triethanolamine.

Suitable amphoteric surfactant for example is alkyl betaine, alkyl amido CAB, alkyl sulfobetaines, p dialkylaminobenzoic acid salt, alkyl carboxyl Glycinates, N-(alkyl amido ethyl)-N-(ethoxy) Glycinates, N-(alkyl amido ethyl)-N-(ethoxy) aminopropionate, N-(alkyl amido ethyl)-N-(ethoxy) diacetin or N-(alkyl amido ethyl)-amino dipropionate of N-(ethoxy).

Suitable non-ionic surface active agent for example is aliphatic alcohol or has the product of alkyl phenol and the ethylene oxide and/or the propylene oxide of 6-20 carbon atom on the alkyl chain that can be linearity or branching.The amount of oxyalkylene is about 6 to 60 moles of every mol of alcohol.Suitable in addition is the fatty acid ester of alkyl amine oxide, monoalkyl alkanolamide, dialkyl group alkanolamide, Polyethylene Glycol, alkyl poly glucoside or anhydro sorbitol ether-ether.

In addition, the hair washing preparaton can comprise conventional cationic surfactant, for example quaternary ammonium compound such as cetyl trimethyl ammonium chloride.

Can be with conventional conditioner and copolymer A) combination is used for having one's hair wash preparaton to obtain special-effect.These conditioners for example comprise above-mentioned cationic polymer, especially vinyl pyrrolidone/N-vinyl imidazole  salt copolymer (Luviquat  FC, Luviquat  HM, Luviquat  MS, Luviquat  Care, Luviquat  UltraCare) according to INCI polyquaternary ammonium salt by name, use the quaternised N-vinyl pyrrolidone/copolymer of dimethylaminoethyl methacrylate of dithyl sulfate (Luviquat  PQ 11), N-caprolactam/N-vinyl pyrrolidone/N-vinyl imidazole  salt copolymer (Luviquat  Hold); Cationic cellulose derivative (polyquaternary ammonium salt-4 and polyquaternary ammonium salt-10), acrylamide copolymer (polyquaternary ammonium salt-7).The conditioning material that can also use protein hydrolysate and for example gather alkylsiloxane, poly-aryl siloxanes, poly-aryl alkyl siloxanes, polyether silicone or silicones based on polysiloxane compound.Other suitable polysiloxane compound is dimethicone copolyol (CTFA) and amino-functional polysiloxane compound such as amino-terminated polydimethylsiloxane (CTFA).In addition, can use cationic guar gum derivant such as guar hydroxypropyl trimonium chloride (INCI).

Be described in more detail the present invention by following non-limiting example.

Embodiment

Monomer provides with weight %.

1. prepare copolymer (radical polymerization in solution)

Embodiment S1:N-vinyl pyrrolidone (VP)/N-vinyl imidazole (VI)/Methacrylamide

(MAM) copolymer of (55/10/35)

Initial charge: monomer mixture comprises:

121.5g demineralized water

17.5g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

0.75g N-vinyl imidazole

4.12g N-vinyl pyrrolidone

0.03g Wako ^V 50[2,2 '-azo two (2-amidine propane) dihydrochloride]

Charging 1: monomer mixture comprises:

78.5g N-vinyl pyrrolidone

14.2g N-vinyl imidazole

332g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

Charging 2: initiator solution comprises:

0.6g Wako ^ V 50

20.97g demineralized water

Charging 3: initiator solution comprises:

0.45g Wako ^ V 50

10.5g demineralized water

In having the 1L pilot scale agitator (pilot stirrer) of metering device, reflux condenser, internal thermometer and 3 feed arrangements that separate, initial charge is heated to 70 ℃ in blanket of nitrogen with under stirring.In case temperature reaches 70 ℃, be metered into charging 1 through 3 hours and be metered into charging 2 through 4 hours.Made the mixture post polymerization then 2 hours.

Under 70 ℃, be metered into charging 3 through 10 minutes and made the mixture post polymerization again 4 hours.Then with mixture steam distillation 30 minutes and be cooled to 40 ℃.

Embodiment S2:N-vinyl pyrrolidone (VP)/N-vinyl imidazole (VI)/Methacrylamide (MAM)/copolymer of N-vinyl imidazole Methylsulfate salt (QVI) (60/5/30/5)

Initial charge: monomer mixture comprises:

The 164g demineralized water

14.4g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

0.36g N-vinyl imidazole

4.32g N-vinyl pyrrolidone

0.8g N-vinyl imidazole Methylsulfate saline solution (concentration is the aqueous solution of 45 weight %)

0.04g Wako ^V 50[2,2 '-azo two (2-amidine propane) dihydrochloride]

Charging 1: monomer mixture comprises:

86.0g N-vinyl pyrrolidone

7.1g N-vinyl imidazole

285.0g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

16.0g N-vinyl imidazole Methylsulfate saline solution (concentration is the aqueous solution of 45 weight %)

Charging 2: initiator solution comprises:

0.85g Wako ^ V 50

20.97g demineralized water

Charging 3: initiator solution comprises:

0.45g Wako ^ V 50

10.49g demineralized water

In having the 1L pilot scale agitator of metering device, reflux condenser, internal thermometer and 3 feed arrangements that separate, initial charge is heated to 65 ℃ in blanket of nitrogen with under stirring.In case temperature reaches 65 ℃, be metered into charging 1 through 3 hours and be metered into charging 2 through 4 hours.Made the mixture post polymerization then 2 hours.

Under 65 ℃, be metered into charging 3 and also made the mixture post polymerization again 4 hours through 10 minutes.Then with mixture steam distillation 30 minutes and be cooled to 40 ℃.

Embodiment S3:N-vinyl pyrrolidone (VP)/N-vinyl imidazole (VI)/Methacrylamide (MAM)/copolymer of N-vinyl imidazole Methylsulfate salt (QVI) (55/5/35/5)

Initial charge: monomer mixture comprises:

121.5g demineralized water

0.37g N-vinyl imidazole

4.1g N-vinyl pyrrolidone

0.82g N-vinyl imidazole Methylsulfate saline solution (concentration is the aqueous solution of 45 weight %)

0.04g Wako ^V 50 [2,2 '-azo two (2-amidine propane) dihydrochloride]

Charging 1: monomer mixture comprises:

78g N-vinyl pyrrolidone

7.1g N-vinyl imidazole

332.5g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

15.9g N-vinyl imidazole Methylsulfate saline solution (concentration is the aqueous solution of 45 weight %)

Charging 2: initiator solution comprises:

0.70g Wako ^ V 50

20.97g demineralized water

Charging 3: initiator solution comprises:

0.45g Wako ^ V 50

10.49g demineralized water

In having the 1L pilot scale agitator of metering device, reflux condenser, internal thermometer and 3 feed arrangements that separate, initial charge is heated to 70 ℃ in blanket of nitrogen with under stirring.By adding the pH regulator to 5.5 of lactic acid with charging 1.In case temperature reaches 70 ℃, be metered into charging 1 through 3 hours and be metered into charging 2 through 4 hours.Made the mixture post polymerization then 2 hours.

Under 70 ℃, be metered into charging 3 and also made the mixture post polymerization again 4 hours through 10 minutes.Then with mixture steam distillation 30 minutes and be cooled to 40 ℃.

Embodiment S4:N-vinyl pyrrolidone (VP)/N-vinyl imidazole (VI)/Methacrylamide (MAM)/copolymer of N-vinyl imidazole Methylsulfate salt (QVI) (55/5/35/5)

Initial charge: monomer mixture comprises:

121.5g demineralized water

0.37g N-vinyl imidazole

4.04g N-vinyl pyrrolidone

0.04g Wako ^V 50 [2,2 '-azo two (2-amidine propane) dihydrochloride]

Charging 1: monomer mixture comprises:

78g N-vinyl pyrrolidone

7.1g N-vinyl imidazole

Charging 2: initiator solution comprises:

0.70g Wako ^ V 50

20.97g demineralized water

Charging 3: initiator solution comprises:

0.45g Wako ^ V 50

10.49g demineralized water

In having the 1L pilot scale agitator of metering device, reflux condenser, internal thermometer and 3 feed arrangements that separate, initial charge is heated to 70 ℃ in blanket of nitrogen with under stirring.In case temperature reaches 70 ℃, be metered into charging 1 through 3 hours and be metered into charging 2 through 4 hours.Made the mixture post polymerization then 2 hours.

Embodiment S5:N-vinyl pyrrolidone (VP)/N-vinyl imidazole (VI)/Methacrylamide (MAM) copolymer of (55/10/35)

Initial charge: monomer mixture comprises:

121.5g demineralized water

0.75g N-vinyl imidazole

4.10g N-vinyl pyrrolidone

0.03g Wako ^V 50 [2,2 '-azo two (2-amidine propane) dihydrochloride]

Charging 1: monomer mixture comprises:

78.0g N-vinyl pyrrolidone

14.0g N-vinyl imidazole

Charging 2: initiator solution comprises:

0.55g Wako ^ V 50

20.97g demineralized water

Charging 3: initiator solution comprises:

0.45g Wako ^ V 50

10.49g demineralized water

Embodiment S6:N-vinyl pyrrolidone (VP)/N-vinyl imidazole (VI)/Methacrylamide (MAM) copolymer of (55/10/35)

Initial charge: monomer mixture comprises:

The 121g demineralized water

17.65g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

0.7g N-vinyl imidazole

3.77g N-vinyl pyrrolidone

0.03g Wako ^V 50[2,2 '-azo two (2-amidine propane) dihydrochloride]

0.3g lactic acid

Charging 1: monomer mixture comprises:

79.0g N-vinyl pyrrolidone

14.0g N-vinyl imidazole

Charging 2: monomer mixture comprises:

332.0g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

4.8g lactic acid

Charging 3: initiator solution comprises:

0.6g Wako ^ V 50

20.97g demineralized water

Charging 4: initiator solution comprises

0.45g Wako ^ V 50

10.5g demineralized water

In having the 1L pilot scale agitator of metering device, reflux condenser, internal thermometer and 4 feed arrangements that separate, initial charge is heated to 70 ℃ in blanket of nitrogen with under stirring.In case temperature reaches 70 ℃, be metered into charging 1 through 3 hours and be metered into charging 2 and 3 through 4 hours.Made the mixture post polymerization then 2 hours.Under 70 ℃, be metered into charging 3 and also made the mixture post polymerization again 4 hours through 10 minutes.Then with mixture steam distillation 30 minutes and be cooled to 40 ℃.

Embodiment S7:N-vinyl pyrrolidone (VP)/N-vinyl imidazole (VI)/Methacrylamide (MAM)/copolymer of N-vinyl imidazole Methylsulfate salt (QVI) (55/5/35/5)

Initial charge: monomer mixture comprises:

121.5g demineralized water

0.37g N-vinyl imidazole

4.10g N-vinyl pyrrolidone

0.83g N-vinyl imidazole Methylsulfate saline solution (concentration is the aqueous solution of 45 weight %)

0.04g Wako ^V 50 [2,2-azo two (2-amidine propane) dihydrochloride]

Charging 2: monomer mixture comprises:

79.0g N-vinyl pyrrolidone

16.0 N-vinyl imidazole Methylsulfate saline solution (concentration is the aqueous solution of 45 weight %)

7.1g N-vinyl imidazole

Charging 1: monomer mixture comprises:

Charging 3: initiator solution comprises:

0.70g Wako ^ V 50

20.97g demineralized water

Charging 4: initiator solution comprises

0.45g Wako ^ V 50

10.49g demineralized water

In having the 1L pilot scale agitator of metering device, reflux condenser, internal thermometer and 4 feed arrangements that separate, initial charge is heated to 65 ℃ in blanket of nitrogen with under stirring.By adding the pH regulator to 6.0 of lactic acid with charging 2.In case temperature reaches 65 ℃, be metered into charging 1 and 3 and be metered into charging 2 through 3 hours through 4 hours.Made the mixture post polymerization then 2 hours.Under 65 ℃, be metered into charging 4 and also made the mixture post polymerization again 4 hours through 10 minutes.Then with mixture steam distillation 30 minutes and be cooled to 40 ℃, by adding lactic acid with pH regulator to 5.5.

Embodiment S8:N-vinyl pyrrolidone (VP)/N-vinyl imidazole (VI)/Methacrylamide (MAM)/copolymer of N-vinyl imidazole Methylsulfate salt (QVI) (55/8/29/8)

Initial charge: monomer mixture comprises:

166.0g demineralized water

15.7g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

0.65g N-vinyl imidazole

4.45g N-vinyl pyrrolidone

1.45g N-vinyl imidazole Methylsulfate saline solution (concentration is the aqueous solution of 45 weight %)

0.04g Wako ^V 50 [2,2 '-azo two (2-amidine propane) dihydrochloride]

Charging 1: monomer mixture comprises:

274.0g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

78g N-vinyl pyrrolidone

25.2g N-vinyl imidazole Methylsulfate saline solution (concentration is the aqueous solution of 45 weight %)

11.3g N-vinyl imidazole

Charging 2: initiator solution comprises:

0.70g Wako ^ V 50

20.97g demineralized water

Charging 3: initiator solution comprises

0.45g Wako ^ V 50

10.49g demineralized water

In having the 1L pilot scale agitator of metering device, reflux condenser, internal thermometer and 3 feed arrangements that separate, initial charge is heated to 70 ℃ in blanket of nitrogen with under stirring.By adding the pH regulator to 6.0 of lactic acid with charging 1.In case temperature reaches 70 ℃, be metered into charging 1 through 3 hours and be metered into charging 2 through 4 hours.Made the mixture post polymerization then 2 hours.Under 70 ℃, be metered into charging 3 and also made the mixture post polymerization again 4 hours through 10 minutes.Then with mixture steam distillation 30 minutes and be cooled to 40 ℃, by adding lactic acid with pH regulator to 5.5.

Embodiment S9:N-vinyl pyrrolidone (VP)/N-vinyl imidazole (VI)/Methacrylamide (MAM)/copolymer of N-vinyl imidazole methochloride (QVI) (55/10/29/6)

Initial charge: monomer mixture comprises:

166.0g demineralized water

0.80g N-vinyl imidazole

4.45g N-vinyl pyrrolidone

1.10g N-vinyl imidazole methochloride solution (concentration is the aqueous solution of 45 weight %)

0.04g Wako ^V 50 [2,2 '-azo two (2-amidine propane) dihydrochloride]

Charging 1: monomer mixture comprises:

78.0g N-vinyl pyrrolidone

19.0g N-vinyl imidazole methochloride solution (concentration is the aqueous solution of 45 weight %)

14.2g N-vinyl imidazole

Charging 2: initiator solution comprises:

0.70g Wako ^ V 50

20.97g demineralized water

Charging 3: initiator solution comprises:

0.45g Wako ^ V 50

10.49g demineralized water

In having the 1L pilot scale agitator of metering device, reflux condenser, internal thermometer and 3 feed arrangements that separate, initial charge is heated to 70 ℃ in blanket of nitrogen with under stirring.By adding the pH regulator to 6.0 of lactic acid with charging 1.In case temperature reaches 70 ℃, be metered into charging 1 through 3 hours and be metered into charging 2 through 4 hours.Made the mixture post polymerization then 2 hours.Under 70 ℃, be metered into charging 3 and also made the mixture post polymerization again 4 hours through 10 minutes.Then with mixture steam distillation 30 minutes and be cooled to 40 ℃.

Embodiment S10:N-vinyl pyrrolidone (VP)/N-vinyl imidazole (VI)/Methacrylamide (MAM)/copolymer of N-vinyl imidazole Methylsulfate salt (QVI) (55/10/29/6)

Initial charge: monomer mixture comprises:

324.0g demineralized water

31.8g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

1.6g N-vinyl imidazole

9.0g N-vinyl pyrrolidone

2.2g N-vinyl imidazole Methylsulfate saline solution (concentration is the aqueous solution of 45 weight %)

0.08g Wako ^V 50[2,2 '-azo two (2-amidine propane) dihydrochloride]

Charging 1: monomer mixture comprises:

548.0g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

156g N-vinyl pyrrolidone

37.8g N-vinyl imidazole Methylsulfate saline solution (concentration is the aqueous solution of 45 weight %)

28.5g N-vinyl imidazole

Charging 2: initiator solution comprises:

1.4g Wako ^ V 50

41.9g demineralized water

Charging 3: following solution:

1.28g concentration is 70% t-butyl hydroperoxide

The 20g demineralized water

Charging 4: following solution:

0.76g sodium sulfite

The 11g demineralized water

In having the 2L pilot scale agitator of metering device, reflux condenser, internal thermometer and 3 feed arrangements that separate, initial charge is heated to 70 ℃ in blanket of nitrogen with under stirring.By adding the pH regulator to 6.5 of phosphoric acid with charging 1.In case temperature reaches 70 ℃, be metered into charging 1 through 3 hours and be metered into charging 2 through 4 hours.Made the mixture post polymerization then 2 hours.Temperature is risen to 75 ℃.Under 75 ℃, charging 3 is metered in batches.After 10 minutes, add charging 4 and made the mixture post polymerization 3 hours through 5 minutes branch two parts.Then with mixture steam distillation 30 minutes and be cooled to 40 ℃.

Embodiment S11:N-vinyl pyrrolidone (VP)/dimethylamino-propyl Methacrylamide (DMAPMAM)/copolymer of Methacrylamide (MAM)

Initial charge: monomer mixture comprises:

121.5g demineralized water

0.75g dimethylamino-propyl Methacrylamide

4.12g N-vinyl pyrrolidone

0.03g Wako ^V 50 [2,2 '-azo two (2-amidine propane) dihydrochloride]

Charging 1: monomer mixture comprises:

82.5g N-vinyl pyrrolidone

15g dimethylamino-propyl Methacrylamide

350g methacryl amine aqueous solution (concentration is the aqueous solution of 15 weight %)

Charging 2: initiator solution comprises:

0.6g Wako ^ V 50

20.97g water

Charging 3: initiator solution comprises:

0.45g Wako ^ V 50

10.5g water

Application Example

To be prepared into foam preparaton (embodiment SF1-SF16) by following composition according to the synthetic copolymer of synthetic embodiment S1-S11.

SF1-SF16: foam preparaton:

2.00g Luviquat ^ Mono LS

0.20g aromatic oil

2.00g AI ^*Polymer

0.10g Euxyl ^ K 100

An amount of Phenonip ^

Add to the 100g demineralized water

10.00g propane/butane 3.5 crust

Preparation: component is weighed adding also at room temperature by stirring slow homogenize.In the suitable containers of then preparation being packed into and add propellant gas.

^*AI: the active component polymer representative polymer quality of representing with g in the whole preparaton of 100g.

SF2, SF4, SF7, SF9, SF14: use the lactic acid will be based on the pH regulator of the foam preparaton of the polymer that describes in detail in the table 2 to pH shown in the table 2.

SF11 and SF12 are the foam preparaton of adjusted aqueous compositions pH after polymerization is finished but before being mixed with foams wherein.

SF16, SF18: use the phosphoric acid will be based on the pH regulator of the foam preparaton of the polymer that describes in detail in the table 2 to pH shown in the table 2.

SF1, SF3, SF5, SF6, SF8, SF10, SF13 and SF15 be not for wherein regulating the foam preparaton (Comparative Examples) of the pH of aqueous compositions as yet after polymerization is finished.

Measure the K value

According to Fikentscher, Cellulosechemie [cellulose chemistry], the 13rd volume, 58-64 page or leaf (1932) is being measured the K value under 25 ℃ and the K value is the tolerance of mole in water/ethanol or alcoholic solution.In 100ml solution, the water/ethanol of polymer or alcoholic solution comprise the 1g polymer.If polymer is the aqueous dispersion form, depend on the polymer content of dispersion, the dispersion of corresponding amount is transferred to 100ml with ethanol, so that concentration is for containing the 1g polymer in 100ml solution.The K value is measured in the M Ic type Micro-Ubbelohde capillary tube from Schott.

By water composed correction and calculating K value in alcohol

Only relate to such capillary tube under the measurement temperature at 25 ℃ in the following factor that is used for the composed correction formula.

The calculating of K value:

The K value:

K＝k*1000；z＝ηrel

k = \frac{(1.5 \log z - 1) c &PlusMinus; \sqrt{[{(1.5 \log z - 1)}^{2} c^{2} + 4 (75 c + 1.5 c^{2}) (\log z)]}}{2 (75 c + 1.5 c^{2})}

Relative viscosity:

η _rel＝(t _SLN-HC _SLN)/(t _SOL-HC _SOL)

The calculating of composed correction:

The mixture of water in ethanol shows solvent mixture viscosity with respect to the disproportionate variation of water content.

Because the essence of sample (aqueous polymer dispersion), water is introduced by the initial weight of sample in the ethanol sample solution.This water yield relies on composed correction to be included in the operating time of solvent, thereby proofreaies and correct relative viscosity suitably according to the water that adds.

The operating time of solvent mixture:

t _SOL＝t ₀+t _M

Operating time proofreaies and correct:

t _M＝-7.486100e-5*c _W ⁴+3.785884 E-3*c _W ³

-8.063441E-2*c _W ²+1.999207*c _W+2.959258E-2

Water content in the solvent:

c _W＝c/SC/100*(1-SC/100)

C measures the concentration [g/100ml] of solution

c _WThe concentration [g/100ml] of water in measuring solution

Solid content in the SC sample [g/100g]

HC _SOLThe Hagenbach of solvent proofreaies and correct [s]

HC _SLNThe Hagenbach that measures solution proofreaies and correct [s]

t _SOLThe operating time of solvent, composed correction [s]

t _SLNMeasure the operating time of solution, measure [s]

t ₀The operating time of solvent, measure [s]

t _MThe operating time of solvent mixture proofreaies and correct, and calculates [s]

The η of z in the Fikentscher formula _Rel(calculating of K value)

Retention rate curls

The topknot that will wet pushes between filter paper, and submergence is three times in polymer solution (preparaton that does not have propellant gas), strikes off solution with finger between each submergence, pushes between filter paper once more.Be wrapped in hair on the teflon rod then and use filter paper and elastic tape is fixed.Then with topknot in 70-80 ℃ heating cabinet dry 90 minutes.After being cooled to room temperature, when keeping shape, taking off curly hair and hang on the framework that specially for this reason prepares and and measure curly hair length (L according to incidental rule ₀).

For measuring the retention rate value of curling, should use 5 tufts curly hair.Curly hair is hung in the biotron of 20 ℃ and 75% or 90% relative humidity.After 5 hours, read length (Lt).

The following calculating retention rate that curls:

Retention rate curls

% = \frac{L - L_{t}}{L - L_{0}} \times 100

L=hair lengths (15.5 cm)

L ₀=dry curly hair length afterwards

L _tCurly hair length after=weather is handled

Curling retention rate is the meansigma methods of 5 independent measurements after 5 hours under 20 ℃ and 75% or 90% relative humidity.

Bending rigidity

With the dry topknot of weighing submergence three times in demineralized water, extract extruding and weighing between filter paper out.With topknot submergence three times in polymer solution to be tested (preparaton that does not have propellant gas), strike off solution then, extruding and weighing between filter paper equally with finger.Then with hands with the topknot molding, make them have as far as possible round cross section.Freely hanging topknot with clip in biotron (20 ℃ and 65% relative humidity) spends the night.

In 21 ℃ of biotrons with 65% relative atmospheric humidity, (Easytest 86 802 types Frank) are tested to use the tension/pressure test set.Topknot is symmetrically placed in (diameter 4mm is at a distance of 90mm) on two cylindrical rollers of specimen holder.Use then circular imprinter make topknot in the centre crooked from top to bottom 40mm (polymeric film breaks).Use measuring cell (50N or 10N) is measured required for this reason power and is represented with newton.Each polymer solution is measured the different topknot of 5 tufts.

Used result is the meansigma methods of 5 independent measurements.

His-and-hers watches 2 listed preparatons are measured K value, pH, curl retention rate and bending rigidity.

Table 2

The foam preparaton	Polymer from following embodiment	pH	VP [weight %]	MAM [weight %]	VI [weight %]	QVI [weight %]	The K value	Typing [cN]	Retention rate [%] curls
The foam preparaton	Polymer from following embodiment	pH	VP [weight %]	MAM [weight %]	VI [weight %]	QVI [weight %]	The K value	Typing [cN]	Retention rate [%] curls	SF1 ^*	S1	7.6	55	35	10	-	92	356	95
SF2	S1	5.4	55	35	10	-	92	465	97	SF1 ^*	S1	7.6	55	35	10	-	92	356	95
SF2	S1	5.4	55	35	10	-	92	465	97	SF3 ^*	S6	6.7	55	35	10		86.2	323	99

SF4	S6	5.5	55	35	10	-	86.2	378	99
SF4	S6	5.5	55	35	10	-	86.2	378	99	SF6 ^*	S2	7.4	60	30	5	5	92.8	388	92
SF7	S2	5.6	60	30	5	5	92.8	430	92	SF6 ^*	S2	7.4	60	30	5	5	92.8	388	92
SF7	S2	5.6	60	30	5	5	92.8	430	92	SF8 ^*	S4	7.4	55	35	5	5	97.5	349	95
SF9	S4	5.7	55	35	5	5	97.5	427	95	SF8 ^*	S4	7.4	55	35	5	5	97.5	349	95
SF9	S4	5.7	55	35	5	5	97.5	427	95	SF10 ^*	S3	6.1	55	35	5	5	86.8	256	94
SF11	S7	5.6	55	35	5	5	103.7	376	99	SF10 ^*	S3	6.1	55	35	5	5	86.8	256	94
SF11	S7	5.6	55	35	5	5	103.7	376	99	SF12	S8	5.8	55	29	8	8	102.9	411	96
SF13 ^*	S9	6.7	55	29	10	6	95.9	480	94	SF12	S8	5.8	55	29	8	8	102.9	411	96
SF13 ^*	S9	6.7	55	29	10	6	95.9	480	94	SF14	S9	5.5	55	29	10	6	95.9	550	97
SF15 ^*	S10	7.1	55	29	10	6	99.9	348	-	SF14	S9	5.5	55	29	10	6	95.9	550	97
SF15 ^*	S10	7.1	55	29	10	6	99.9	348	-	SF16	S10	5.5	55	29	10	6	99.9	406	-

The foam preparaton	Polymer from following embodiment	pH	VP [weight %]	MAM [weight %]	DMAPMAM [weight %]	The K value	Typing [cN]	Viscosity
The foam preparaton	Polymer from following embodiment	pH	VP [weight %]	MAM [weight %]	DMAPMAM [weight %]	The K value	Typing [cN]	Viscosity	SF17 ^*	S11	6.9	55	35	10	94.7	285	Little sticking
SF18	S11	5.6	55	35	10	94.7	320	Not sticking	SF17 ^*	S11	6.9	55	35	10	94.7	285	Little sticking

^*Contrast test

PF1-PF11) hands is pressed pump type spray

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	10.0
Chitosan (concentration is the aqueous solution of 2 weight %, with lactic acid pH is transferred to 6)	50.0		Sigma-Aldrich		10.0
	50.0		Sigma-Aldrich	Distilled water	44.0	Water

In addition, can add antiseptic, solubility ethoxylation polysiloxanes, aromatic oil and other cosmetics conventional ingredient in the preparation.

Preparation:, at room temperature slowly stir homogenize and pH is transferred to 5-6 with lactic acid or phosphoric acid with all components adding of weighing.

GF1-GF11) shaping glue 1

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	10.0
Glycerol	2.0				10.0
Glycerol	2.0			Natrosol ^250 HR (concentration is the aqueous solution of 2 weight %)	50.0	Hydroxyethyl-cellulose	Hercules
Lactic acid or phosphoric acid	Until pH is 5-6				50.0	Hydroxyethyl-cellulose	Hercules
Lactic acid or phosphoric acid	Until pH is 5-6			Distilled water	Add to 100	Water

GF12-GF22) shaping glue 2

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	5
Natrosol ^ 250 HR	2.0	Hydroxyethyl-cellulose	Hercules		5
Natrosol ^ 250 HR	2.0	Hydroxyethyl-cellulose	Hercules	D-panthenol USP	0.5	Pantothenylol	BASF
Karion F liquid	1.0	Sorbitol		D-panthenol USP	0.5	Pantothenylol	BASF
Karion F liquid	1.0	Sorbitol		Lactic acid or phosphoric acid	Until pH is 5-6
Distilled water	Add to 100.0	Water		Lactic acid or phosphoric acid	Until pH is 5-6

Preparation:, at room temperature slowly stir homogenize with all components adding of weighing.

HS1-HS11) contain the sailor by pump type spray

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	7.5
Luviskol ^VA64 (concentration is 30% water/alcoholic solution)	5.0	The VP/VA copolymer	BASF		7.5
	5.0	The VP/VA copolymer	BASF	Glycerol	3.0
Lactic acid or phosphoric acid	Until pH is 5-6			Glycerol	3.0
Lactic acid or phosphoric acid	Until pH is 5-6			Distilled water	Add to 100.0	Water

Prepare: all components is weighed to add also at room temperature slowly stir homogenize.

SF19-SF29) typing foam 1

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	7.5
Cremophor ^ A 25	0.2	16/octodecyl alcohol polyoxyethylene (25) ether	BASF		7.5
Cremophor ^ A 25	0.2	16/octodecyl alcohol polyoxyethylene (25) ether	BASF	Comperlan ^ KD	0.1	The cocoyl diethanolamine	Henkel
Dimethyl ether	10.0			Comperlan ^ KD	0.1	The cocoyl diethanolamine	Henkel
Dimethyl ether	10.0			Lactic acid or phosphoric acid	Until pH is 5-6
Distilled water	Add to 100.0	Water		Lactic acid or phosphoric acid	Until pH is 5-6

Prepare: component is weighed to add also at room temperature slowly stir homogenize.Then with preparation bottling and adding propellant.

SF30-SF40) typing foam 2

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	15.0
Cremophor ^ A 25	0.2	16/octodecyl alcohol polyoxyethylene (25) ether	BASF		15.0
Cremophor ^ A 25	0.2	16/octodecyl alcohol polyoxyethylene (25) ether	BASF	Comperlan ^ KD	0.1	The cocoyl diethanolamine	Henkel
Dimethyl ether	10.0			Comperlan ^ KD	0.1	The cocoyl diethanolamine	Henkel
Dimethyl ether	10.0			Lactic acid or phosphoric acid	Until pH is 5-6
Distilled water	Add to 100.0	Water		Lactic acid or phosphoric acid	Until pH is 5-6

Prepare: component is weighed to add also at room temperature slowly stir homogenize.Then with preparation bottling and adding propellant gas.

SF41-SF51) typing foam 3

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	15.0
Luviquat ^ Mono LS	2.00	Cocos nucifera oil trimethyl ammonium Methylsulfate salt	BASF		15.0
Luviquat ^ Mono LS	2.00	Cocos nucifera oil trimethyl ammonium Methylsulfate salt	BASF	D-panthenol USP	1.0	Pantothenylol	BASF
Propane/butane	(10.0 to 3.5 crust)	Propane/butane		D-panthenol USP	1.0	Pantothenylol	BASF
Propane/butane	(10.0 to 3.5 crust)	Propane/butane		Lactic acid or phosphoric acid	Until pH is 5-6
Distilled water	Add to 100.0	Water		Lactic acid or phosphoric acid	Until pH is 5-6

Prepare: component is weighed to add to open at room temperature slowly stir homogenize.Then with preparation bottling and adding propellant.

CS1-CS11) conditioning shampoo 1

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer
Phase A
Phase A				Texapon ^NSO concentration is 28%	50.0	Sodium laureth sulfate	Henkel
Comperlan ^ KD	1.0	The cocoyl diethanolamine	Henkel	Texapon ^NSO concentration is 28%	50.0	Sodium laureth sulfate	Henkel
Comperlan ^ KD	1.0	The cocoyl diethanolamine	Henkel	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	4.5
Lactic acid or phosphoric acid	Until pH is 5-6				4.5
Lactic acid or phosphoric acid	Until pH is 5-6			Distilled water	15.5	Water
Aromatic oil	In right amount			Distilled water	15.5	Water
Aromatic oil	In right amount
Phase B
Phase B				Distilled water	27.5	Water
Sodium chloride	1.5	Sodium chloride		Distilled water	27.5	Water
Sodium chloride	1.5	Sodium chloride		Antiseptic	In right amount

Phase A and B mutually weighed separately add and stirring and dissolving.With lactic acid (20 weight % are in water) pH regulator of phase A is supplied 100 weight % to 5-6 and water.Phase B is slowly stirred into phase A.

CS12-CS22) conditioning shampoo 2

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer

Phase A
Phase A				Tego Betain ^ L 7	15.00	Cocoamidopropyl	Degussa
Amphotensid ^ GB 2009	10.00	N-(the cocoamidoethyl)-amino oxalic acid disodium of N-(ethoxy)	Zschimmer & Schwarz	Tego Betain ^ L 7	15.00	Cocoamidopropyl	Degussa
Amphotensid ^ GB 2009	10.00		Zschimmer & Schwarz	Cremophor ^ PS 20	5.00	Anhydrous sorbitol polyoxyethylene (20) ether	BASF
Plantacare ^ 2000	5.00	The decyl glucosides	Cognis	Cremophor ^ PS 20	5.00	Anhydrous sorbitol polyoxyethylene (20) ether	BASF
Plantacare ^ 2000	5.00	The decyl glucosides	Cognis	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	0.5-5.0
Rhaball Gum CG-M 8M	0.15				0.5-5.0
Rhaball Gum CG-M 8M	0.15			Rewopal ^ LA 3	2.00	Lauryl polyoxyethylene (3) ether	Degussa
Lactic acid or phosphoric acid	Until pH is 5-6			Rewopal ^ LA 3	2.00	Lauryl polyoxyethylene (3) ether	Degussa
Lactic acid or phosphoric acid	Until pH is 5-6			Demineralized water	Add to 100	Demineralized water
Aromatic oil	In right amount			Demineralized water	Add to 100	Demineralized water
Aromatic oil	In right amount			Antiseptic	In right amount
				Antiseptic	In right amount
				Phase B
Stepan ^ PEG 6000 DS	3.00	Distearyl acid polyethylene glycol (150) ester	Stepan Co.	Phase B

CS23-CS33) conditioning shampoo 3

Texapon ^NSO, concentration is 28%	30.0	Sodium laureth sulfate	Henkel
Texapon ^NSO, concentration is 28%	30.0	Sodium laureth sulfate	Henkel	Dehyton ^ G	6.00	N-(cocoamidoethyl)-N-(ethoxy) Sodium Glycinate	Henkel
Dehyton ^ K	6.00	Cocoamidopropyl	Henkel	Dehyton ^ G	6.00	N-(cocoamidoethyl)-N-(ethoxy) Sodium Glycinate	Henkel
Dehyton ^ K	6.00	Cocoamidopropyl	Henkel	Euperlan ^ PK 771	3.00	Sodium laureth sulfate, glycol distearate, cocoyl monoethanolamine, lauryl polyoxyethylene (10) ether	Henkel
Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	0.5-5.0			Euperlan ^ PK 771	3.00		Henkel
	0.5-5.0			Luviquat ^ Care	7.70	Polyquaternary ammonium salt-44	BASF
Amino-terminated polydimethylsiloxane	2.00	Amino-terminated polydimethylsiloxane		Luviquat ^ Care	7.70	Polyquaternary ammonium salt-44	BASF
Amino-terminated polydimethylsiloxane	2.00	Amino-terminated polydimethylsiloxane		Sodium chloride	1.00	Sodium chloride
Lactic acid or phosphoric acid	Until pH is 5-6			Sodium chloride	1.00	Sodium chloride
Lactic acid or phosphoric acid	Until pH is 5-6			Demineralized water	Add to 100	Demineralized water

Preparation:, at room temperature slowly stir homogenize and with lactic acid or pH is transferred to 5-6 to phosphoric acid and water is supplied 100 weight % with the component adding of weighing.

CM1-CM11) conditioning mousse 1

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Luviquat ^ PQ 11	10.00	Polyquaternary ammonium salt-11	BASF

Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	0.5-5.0
	0.5-5.0			Luviquat ^ Mono CP	0.50	Hydroxyethyl hexadecyldimethyl benzyl ammonium ammonium phosphate	BASF
D-panthenol ^ USP	1.00	Pantothenylol	BASF	Luviquat ^ Mono CP	0.50		BASF
D-panthenol ^ USP	1.00	Pantothenylol	BASF	Lactic acid or phosphoric acid	Until pH is 5-6
Demineralized water	Add to 100	Demineralized water		Lactic acid or phosphoric acid	Until pH is 5-6
Demineralized water	Add to 100	Demineralized water		Propane/butane	6.00	Propane/butane

Preparation:, at room temperature slowly stir homogenize and with lactic acid or pH is transferred to 5-6 to phosphoric acid and water is supplied 100 weight % with the component adding of weighing.Then with preparation bottling and adding propellant gas.

CM12-CM22) conditioning mousse 2

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Polyquaternary ammonium salt-4	1.00
Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	4.0-10.00			Polyquaternary ammonium salt-4	1.00
	4.0-10.00			Luviquat ^ Mono CP	0.50	Hydroxyethyl hexadecyldimethyl benzyl ammonium ammonium phosphate	BASF
Lactic acid or phosphoric acid	Until pH is 5-6			Luviquat ^ Mono CP	0.50		BASF
Lactic acid or phosphoric acid	Until pH is 5-6			Demineralized water	Add to 100	Demineralized water
Propane/butane	6.00	Propane/butane		Demineralized water	Add to 100	Demineralized water

SM1-SM11) hair styling mousse 1

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Phase A
Luviquat ^Mono LS	2.00	Cocos nucifera oil trimethyl ammonium Methylsulfate salt	BASF	Phase A
Luviquat ^Mono LS	2.00	Cocos nucifera oil trimethyl ammonium Methylsulfate salt	BASF	Phase B
Luviflex ^Soft	6.70	Acrylate copolymer	BASF	Phase B
Luviflex ^Soft	6.70	Acrylate copolymer	BASF	AMP	0.60	The amino methyl propanol	Angus Chemical Company
Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	5.0-10.0			AMP	0.60	The amino methyl propanol	Angus Chemical Company
	5.0-10.0			Dimethicone copolyol	0.50	Dimethicone copolyol
Cremophor ^ A 25	0.20	16/octodecyl alcohol polyoxyethylene (25) ether	BASF	Dimethicone copolyol	0.50	Dimethicone copolyol
Cremophor ^ A 25	0.20	16/octodecyl alcohol polyoxyethylene (25) ether	BASF	D-panthenol ^ USP	0.20	Pantothenylol	BASF
Uvinul ^ P 25	0.10	PEG-25 PABA	BASF	D-panthenol ^ USP	0.20	Pantothenylol	BASF
Uvinul ^ P 25	0.10	PEG-25 PABA	BASF	Natrosol ^ 250 HR	0.20	Hydroxyethyl-cellulose	Aqualon GmbH
Lactic acid or phosphoric acid	Until pH is 5-6			Natrosol ^ 250 HR	0.20	Hydroxyethyl-cellulose	Aqualon GmbH
Lactic acid or phosphoric acid	Until pH is 5-6			Demineralized water	Add to 100	Demineralized water
Phase C				Demineralized water	Add to 100	Demineralized water
Phase C				Dymel HFC 152a	10.00	1, the 1-Difluoroethane	Dupont

Preparation: with the adding of weighing of phase A and the component of B mutually, at room temperature slowly stir homogenize, the pH with phase B transfers to 5-6 and phase B water is supplied 100 weight % with lactic acid or phosphoric acid.Then A and B are mixed, with preparation bottling and adding propellant gas (phase C).

SM12-SM22) hair styling mousse 2

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Phase A
Luviquat ^ Mono LS	2.00	Cocos nucifera oil trimethyl ammonium Methylsulfate salt	BASF	Phase A
Luviquat ^ Mono LS	2.00	Cocos nucifera oil trimethyl ammonium Methylsulfate salt	BASF	Phase B
Luviquat ^ Care	7.70	Polyquaternary ammonium salt-44	BASF	Phase B
Luviquat ^ Care	7.70	Polyquaternary ammonium salt-44	BASF	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	5.0-10.0
Lactic acid or phosphoric acid	Until pH is 5-6				5.0-10.0
Lactic acid or phosphoric acid	Until pH is 5-6			Demineralized water	Add to 100	Demineralized water
Phase C				Demineralized water	Add to 100	Demineralized water
Phase C				Propane/butane	10.00

SM23-SM33) hair styling mousse 3

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Phase A
Luviquat ^ Mono LS	2.00	Cocos nucifera oil trimethyl ammonium Methylsulfate salt	BASF	Phase A
Luviquat ^ Mono LS	2.00	Cocos nucifera oil trimethyl ammonium Methylsulfate salt	BASF	Phase B
Styleze ^ 2000	2.00	VP/ acrylate/lauryl methacrylate copolymer	ISP	Phase B
Styleze ^ 2000	2.00	VP/ acrylate/lauryl methacrylate copolymer	ISP	AMP	0.53

Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	0.5-5
	0.5-5			Cremophor ^ A 25	0.20	16/octodecyl alcohol polyoxyethylene (25) ether	BASF
D-panthenol USP ^	0.50	Pantothenylol	BASF	Cremophor ^ A 25	0.20	16/octodecyl alcohol polyoxyethylene (25) ether	BASF
D-panthenol USP ^	0.50	Pantothenylol	BASF	vinul ^ MS 40	0.05	5-benzoyl-4-hydroxyl-2-methoxy benzenesulfonic acid	BASF
Dow Corning 949 ^Cation emulsion	0.20	Amino-terminated polydimethylsiloxane/hexadecyltrimethylammonium chloride/tridecyl polyoxyethylene (12) ether	Dow Corning	vinul ^ MS 40	0.05	5-benzoyl-4-hydroxyl-2-methoxy benzenesulfonic acid	BASF
Dow Corning 949 ^Cation emulsion	0.20		Dow Corning	96% ethanol	15.00	Ethanol
Lactic acid or phosphoric acid	Until pH is 5-6			96% ethanol	15.00	Ethanol
Lactic acid or phosphoric acid	Until pH is 5-6			Demineralized water	Add to 100	Demineralized water
Phase C				Demineralized water	Add to 100	Demineralized water
Phase C				Natrosol ^ 250 HR	0.20	Hydroxyethyl-cellulose	Aqualon GmbH
Phase D				Natrosol ^ 250 HR	0.20	Hydroxyethyl-cellulose	Aqualon GmbH
Phase D				Propane/butane	6.00	Propane/butane

Preparation: with the adding of weighing of phase A and the component of B mutually, at room temperature slowly stir homogenize, the pH with phase B transfers to 5-6 and phase B water is supplied 100 weight % with lactic acid or phosphoric acid.Then A and B are mixed, add phase C, with preparation bottling and adding propellant gas (phase D).

SM34-SM44) hair styling mousse 4

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Phase A
Hexadecyltrimethylammonium chloride	2.00	Hexadecyltrimethylammonium chloride		Phase A

Phase B
Phase B				Luviquat ^ Hold	7.00	Polyquaternary ammonium salt-46	BASF
Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	0.5-5			Luviquat ^ Hold	7.00	Polyquaternary ammonium salt-46	BASF
	0.5-5			Cremophor ^ A 25	0.20	16/octodecyl alcohol polyoxyethylene (25) ether	BASF
D-panthenol USP ^	0.50	Pantothenylol	BASF	Cremophor ^ A 25	0.20	16/octodecyl alcohol polyoxyethylene (25) ether	BASF
D-panthenol USP ^	0.50	Pantothenylol	BASF	Uvinul ^ MS 40	0.05	5-benzoyl-4-hydroxyl-2-methoxy benzenesulfonic acid	BASF
Dow Corning 949 ^Cation	0.20		Dow Corning	Uvinul ^ MS 40	0.05	5-benzoyl-4-hydroxyl-2-methoxy benzenesulfonic acid	BASF
Dow Corning 949 ^Cation	0.20		Dow Corning	96% ethanol	15.00	Ethanol
Lactic acid or phosphoric acid	Until pH is 5-6			96% ethanol	15.00	Ethanol
Lactic acid or phosphoric acid	Until pH is 5-6			Demineralized water	Add to 100	Demineralized water
Phase C				Demineralized water	Add to 100	Demineralized water
Phase C				Natrosol ^ 250 HR	0.20	Hydroxyethyl-cellulose	Aqualon GmbH
Phase D				Natrosol ^ 250 HR	0.20	Hydroxyethyl-cellulose	Aqualon GmbH
Phase D				Propane/butane	6.00	Propane/butane

SM45-SM55) hair styling mousse 5

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Phase A
Cremophor ^ RH 40	In right amount	Polyoxyethylene (40) castor oil hydrogenated	BASF	Phase A

Demineralized water	Add to 100	Demineralized water
Demineralized water	Add to 100	Demineralized water		Phase B
Flexan ^ 130	7.00	Kayexalate	National Starch	Phase B
Flexan ^ 130	7.00	Kayexalate	National Starch	Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	5.0-10.0
Cetyl trimethyl ammonium bromide	0.50	Cetyl trimethyl ammonium bromide			5.0-10.0
Cetyl trimethyl ammonium bromide	0.50	Cetyl trimethyl ammonium bromide		Lactic acid or phosphoric acid	Until pH is 5-6
Phase C				Lactic acid or phosphoric acid	Until pH is 5-6
Phase C				Propane/butane	6.00	Propane/butane

Preparation: phase A and B mutually weighed separately to add and stirring and dissolving and mixing.With lactic acid or phosphoric acid the pH of phase B is transferred to 5-6, if suitable other material such as antiseptic or the aromatic oil of in phase A or phase B, adding.Bottling also adds propellant gas (phase C).

SM56-SM66) hair styling mousse 6

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Phase A
Cremophor ^ RH 40	In right amount	Polyoxyethylene (40) castor oil hydrogenated	BASF	Phase A
Cremophor ^ RH 40	In right amount	Polyoxyethylene (40) castor oil hydrogenated	BASF	Demineralized water	Add to 100	Demineralized water
Phase B				Demineralized water	Add to 100	Demineralized water
Phase B				The ultraviolet care polymers	0.5	Polyquaternary ammonium salt-10	Amerchol
Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	5.0-10.0			The ultraviolet care polymers	0.5	Polyquaternary ammonium salt-10	Amerchol
	5.0-10.0			Cetyl trimethyl ammonium bromide	0.50
Lactic acid or phosphoric acid	Until pH is 5-6			Cetyl trimethyl ammonium bromide	0.50

Phase C
Phase C				Propane/butane	6.00	Propane/butane

SM67-SM77) hair styling mousse 7

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Phase A
Cremophor ^ RH 40	In right amount	Polyoxyethylene (40) castor oil hydrogenated	BASF	Phase A
Cremophor ^ RH 40	In right amount	Polyoxyethylene (40) castor oil hydrogenated	BASF	Demineralized water	Add to 100	Demineralized water
Phase B				Demineralized water	Add to 100	Demineralized water
Phase B				Luviquat ^ HM 552	10.00	Polyquaternary ammonium salt-16	BASF
Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	0.5-5.0			Luviquat ^ HM 552	10.00	Polyquaternary ammonium salt-16	BASF
	0.5-5.0			Luviquat ^ Mono CP	0.50	Hydroxyethyl hexadecyldimethyl benzyl ammonium ammonium phosphate	BASF
Lactic acid or phosphoric acid	Until pH is 5-6			Luviquat ^ Mono CP	0.50		BASF
Lactic acid or phosphoric acid	Until pH is 5-6			Phase C
Propane/butane	6.00	Propane/butane		Phase C

SM78-SM88) hair styling mousse 8

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Phase A

Luviquat ^ Mono LS	2.00	Cocos nucifera oil trimethyl ammonium Methylsulfate salt	BASF
Luviquat ^ Mono LS	2.00	Cocos nucifera oil trimethyl ammonium Methylsulfate salt	BASF
Phase B
Phase B				Hydagen HCMF	2.00	Chitosan	Cognis
Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	0.5-5.0			Hydagen HCMF	2.00	Chitosan	Cognis
	0.5-5.0			Dimethicone copolyol	0.50	Dimethicone copolyol
Cremophor ^ A 25	0.20	16/octadecanol polrvinyl chloride (25) ether	BASF	Dimethicone copolyol	0.50	Dimethicone copolyol
Cremophor ^ A 25	0.20	16/octadecanol polrvinyl chloride (25) ether	BASF	D-panthenol USP ^	0.20	Pantothenylol	BASF
Uvinul ^ P 25	0.10	G-25 PABA	BASF	D-panthenol USP ^	0.20	Pantothenylol	BASF
Uvinul ^ P 25	0.10	G-25 PABA	BASF	Lactic acid or phosphoric acid	Until pH is 5-6
Demineralized water	Add to 100	Demineralized water		Lactic acid or phosphoric acid	Until pH is 5-6
Demineralized water	Add to 100	Demineralized water		Phase C
HFC 152 A	10.00			Phase C

SM89-SM99) hair styling mousse 9

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Luviskol ^VA 64 W	10.00	The PVP/VA copolymer	BASF
Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	2.0-5.0			Luviskol ^VA 64 W	10.00	The PVP/VA copolymer	BASF
	2.0-5.0			Luviquat ^ Mono CP	0.20	Hydroxyethyl hexadecyldimethyl benzyl ammonium ammonium phosphate	BASF

Dimethicone copolyol	0.50	Dimethicone copolyol
Dimethicone copolyol	0.50	Dimethicone copolyol	Cremophor ^ A 25	0.20	16/octodecyl alcohol polyoxyethylene (25) ether	BASF
Ethanol	10.00	Ethanol	Cremophor ^ A 25	0.20	16/octodecyl alcohol polyoxyethylene (25) ether	BASF
Ethanol	10.00	Ethanol	Lactic acid or phosphoric acid	Until pH is 5-6
Demineralized water	Add to 100	Demineralized water	Lactic acid or phosphoric acid	Until pH is 5-6
Demineralized water	Add to 100	Demineralized water	Propane/butane	10.00	Propane/butane

Prepare: component is weighed to add and stirring and dissolving and mixing.With lactic acid or phosphoric acid pH is transferred to 5-6, if other material of suitable adding such as antiseptic or aromatic oil.Bottling also adds propellant gas.

Purposes in cosmetics for skin

C1-C11) standard O/W frost

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Oil phase
Cremophor ^ A6	3.5	16/octodecyl alcohol polyoxyethylene (6) ether (with) stearyl alcohol	BASF	Oil phase
Cremophor ^ A6	3.5		BASF	Cremophor ^ A25	3.5	16/octodecyl alcohol polyoxyethylene (25) ether	BASF
Glyceryl monostearate s.e.	2.5	Tristerin		Cremophor ^ A25	3.5	16/octodecyl alcohol polyoxyethylene (25) ether	BASF
Glyceryl monostearate s.e.	2.5	Tristerin		Paraffin oil	7.5	Paraffin oil
Spermol	2.5	Spermol		Paraffin oil	7.5	Paraffin oil
Spermol	2.5	Spermol		Luvitol ^ EHO	3.2	Sad 16/octadecane ester	BASF
Vitamin e acetate	1.0	Tocopherol acetas		Luvitol ^ EHO	3.2	Sad 16/octadecane ester	BASF
Vitamin e acetate	1.0	Tocopherol acetas		Nip-Nip	0.1	4-methyl hydroxybenzoate and propyl ester (7: 3)

Water
Water			Demineralized water	Add to 50	Demineralized water
Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	2.0-8.0		Demineralized water	Add to 50	Demineralized water
	2.0-8.0		1, the nursing of 2-propylene glycol	1.5	Propylene glycol
Germall II	0.1	Imidazolidinyl-urea	1, the nursing of 2-propylene glycol	1.5	Propylene glycol
Germall II	0.1	Imidazolidinyl-urea	Lactic acid or phosphoric acid	Until pH is 5-6

Preparation: oil phase and water weighed separately to add and stir homogenize under about 80 ℃ temperature, with lactic acid or phosphoric acid the pH of water is transferred to 5-6.Water slowly is stirred into oil phase.Under agitation slowly cool to room temperature.

T1-T11 day is used lotion

Composition	Weight %	The CTFA name	The manufacturer
Composition	Weight %	The CTFA name	The manufacturer	Oil phase
Cremophor ^ A6	1.5	16/octodecyl alcohol polyoxyethylene (6) ether (with) stearyl alcohol	BASF	Oil phase
Cremophor ^ A6	1.5		BASF	Cremophor ^ A25	1.5	16/octodecyl alcohol polyoxyethylene (25) ether	BASF
Glyceryl monostearate s.e.	5.0	Tristerin		Cremophor ^ A25	1.5	16/octodecyl alcohol polyoxyethylene (25) ether	BASF
Glyceryl monostearate s.e.	5.0	Tristerin		Uvinul ^ MS 40	0.5	5-benzoyl-4-hydroxyl-2-methoxy benzenesulfonic acid	BASF
Paraffin oil	3.5	Paraffin oil		Uvinul ^ MS 40	0.5	5-benzoyl-4-hydroxyl-2-methoxy benzenesulfonic acid	BASF
Paraffin oil	3.5	Paraffin oil		Spermol	0.5	Spermol
Luvitol ^ EHO	10.0	Sad 16/octadecane ester	BASF	Spermol	0.5	Spermol
Luvitol ^ EHO	10.0	Sad 16/octadecane ester	BASF	D-panthenol 50 P ^	3.0	Pantothenylol and propylene glycol
Vitamin e acetate	1.0	Tocopherol acetas		D-panthenol 50 P ^	3.0	Pantothenylol and propylene glycol
Vitamin e acetate	1.0	Tocopherol acetas		Tegiloxan ^ 100	0.3	Polydimethylsiloxane

Nip-Nip	0.1	4-methyl hydroxybenzoate and propyl ester (7: 3)
Nip-Nip	0.1	4-methyl hydroxybenzoate and propyl ester (7: 3)	Water
Concentration is the aqueous solution from one of polymer of S1-S11 of 20 weight %	2.5-5.0		Water
	2.5-5.0		1, the 2-propylene glycol	1.5	Propylene glycol
Germall II		Imidazolidinyl-urea	1, the 2-propylene glycol	1.5	Propylene glycol
Germall II		Imidazolidinyl-urea	Lactic acid or phosphoric acid	Until pH is 5-6
Demineralized water	Add to 50	Demineralized water	Lactic acid or phosphoric acid	Until pH is 5-6

Preparation: oil phase and water weighed separately to add and stir homogenize under about 80 ℃ temperature, and the pH with water transfers to 5-6 and slowly is stirred into oil phase with lactic acid or phosphoric acid.Under agitation slowly cool to room temperature.

Claims

1. aqueous compositions, it comprises:

A) at least a water solublity or water-dispersible copolymer A with YANG hyperactivity suppressing ionic group), it comprises the following component of copolymerized form:

A) at least a have monomer that at least one can protonated nitrogen-atoms and

B) other monomer of at least a copolymerization with it, and

B) at least a cosmetics acceptable carrier,

The pH of wherein said aqueous compositions is 4-6.

2. according to the aqueous compositions of claim 1, wherein said copolymer A) comprise the following component of copolymerized form:

A) at least a monomer that has at least one can protonated nitrogen-atoms, it is selected from:

N-vinyl imidazole, its derivant and α, β-olefinic unsaturated monocarboxylic acid and α, β-olefinic unsaturated dicarboxylic acid and amide with diamidogen of primary amino radical or secondary amino group, and

B) other monomer of at least a copolymerization with it.

3. according to the aqueous compositions of claim 1 or 2, wherein said copolymer A) comprise the following component of copolymerized form:

A) N-vinyl imidazole and/or its derivant, and

B) other monomer of at least a copolymerization with it.

4. according to the preparation of claim 3, wherein said copolymer A) comprise the following component of copolymerized form:

A) N-vinyl imidazole and/or its derivant, and

B1) at least a N-vinyl lactam.

5. according to each preparation among the claim 1-4, wherein said copolymer A) additionally comprise copolymerized form at least a be different from component a) and b1) and the non-ionic water-soluble monomer of copolymerization with it

B2), it is selected from:

B2.1) saturated C ₁-C ₈Monocarboxylic N-vinylamide,

B2.5) acrylic acid polyester ether

And composition thereof.

6. according to each preparation among the claim 1-5, wherein said copolymer A) additionally comprise at least a monomer b3 of copolymerized form), it is selected from the α of possess hydrophilic property cation group, the unsaturated water soluble compound of β-olefinic.

7. according to the preparation of claim 6, wherein said monomer b3) be selected from monomer quaternized products a).

8. according to each preparation among the claim 1-7, wherein said copolymer A) comprise the following component of copolymerized form:

A) the N-vinyl imidazole of 0.5-40 weight % and/or its derivant,

B1) at least a N-vinyl lactam of 20-99.5 weight %,

B2) at least a monomer b2 of 0-50 weight %), it is selected from:

B2.1) saturated C ₁-C ₈Monocarboxylic N-vinylamide,

B2.5) acrylic acid polyester ether and composition thereof, and

B3) at least a α that is selected from the possess hydrophilic property cation group of 0-30 weight %, the monomer of the unsaturated water soluble compound of β-olefinic,

Condition is that component is a) to b3) the amount sum be 100 weight %.

9. preparation according to Claim 8, wherein said copolymer A) comprise the following component of copolymerized form:

A) monomer of 1-30 weight % a),

B1) the monomer b1 of 20-70 weight %),

B2) the monomer b2 of 5-50 weight %) and

B3) the monomer b3 of 0-30 weight %),

Condition is that component is a) to b3) the amount sum be 100 weight %.

10. according to the preparation of claim 9, wherein said copolymer A) comprise the following component of copolymerized form:

A) monomer of 3-20 weight % a),

B1) the monomer b1 of 30-70 weight %),

B2) the monomer b2 of 10-40 weight %) and

B3) the monomer b3 of 0-10 weight %),

Condition is that component is a) to b3) the amount sum be 100 weight %.

11. each preparation according to Claim 8-10, wherein said copolymer A) comprise the following component of copolymerized form:

A) N-vinyl imidazole,

B1) N-vinyl pyrrolidone,

B2) optional at least a monomer b2),

B3) optional at least a monomer b3), it is selected from the quaternized products of N-vinyl imidazole and dimethylamino-propyl Methacrylamide.

12. according to each preparation among the claim 1-11, wherein said copolymer A) comprise the following component of copolymerized form:

A) 3-15 weight %N-vinyl imidazole

B1) 30-70 weight %N-vinyl pyrrolidone

B2) 20-35 weight % Methacrylamide

B3) the quaternised N-vinyl imidazole of 0-10 weight %,

Condition is that component is a) to b3) the amount sum be 100 weight %.

13. according to each preparation among the claim 1-12, wherein said B component) be selected from:

I water,

Ii water miscibility organic solvent, preferred C ₂-C ₄Alkanol, especially ethanol,

Iii oil, fat, wax,

IvC ₆-C ₃₀The ester of monocarboxylic acid and monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, this ester be with iii) different,

Saturated non-cyclic hydrocarbon of v and cyclic hydrocarbon,

The vi fatty acid,

The vii aliphatic alcohol,

The viii propellant gas

And composition thereof.

14. according to each preparation among the claim 1-13, it comprises at least a component A that is different from) and B) and be selected from the additive of following material: cosmetic active ingredient, emulsifying agent, surfactant, antiseptic, aromatic oil, thickening agent, the hair polymer, hair and skin conditioning agent, graft polymers, water solublity or water dispersible contain polysiloxane polymer, light stability agent, bleach, gel former, nursing agent, coloring agent, toner, suntan, dyestuff, pigment, the denseness agent, wetting agent, fatting agent, collagen, protein hydrolysate, lipoid, antioxidant, defoamer, antistatic additive, isostearyl glyceryl pentaerythrityl ether and softening agent.

15., comprise at least a other water-soluble polymer according to each preparation among the claim 1-14.

16. according to the preparation of claim 15, wherein said water-soluble polymer is chitosan and/or chitosan derivative.

17. according to each preparation among the claim 1-16, it is the form of gel, foam, spray, mousse, ointment, frost, emulsion, suspension, lotion, Emulsion or paste.

18. according to each preparation among the claim 1-17, it additionally comprises at least a non-ionic thickening agent.

19. according to each preparation among the claim 1-18, wherein pH is 5-6.

20., wherein regulate pH by adding hydroxy carboxylic acid according to each preparation among the claim 1-19.

21. according to each preparation among the claim 1-19, wherein by adding inorganic acid for adjusting pH.

22. a method for preparing according to each aqueous compositions among the claim 1-21 is wherein at component A) preparation regulate pH after finishing.

23. according among the claim 1-21 each preparation skin cleansing compositions, skin nursing and skin protection with compositions, manicure compositions, color make-up with the purposes in preparation and the hair-treatment composition.

24., in hair-treatment composition, be used as setting agent and/or conditioner according to the purposes of claim 23.

25. according to the purposes of claim 23 or 24, wherein said compositions is hair gel, shampoo, typing foam, refreshingly floods, hair spray or the foamy form of hair.