CN1071331A

CN1071331A - The hair spray compositions that contains the ion styling polymer

Info

Publication number: CN1071331A
Application number: CN 92110865
Authority: CN
Inventors: M·M·佩夫利; N·J·霍尔茨舒; P·M·托格森
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1991-08-19
Filing date: 1992-08-19
Publication date: 1993-04-28
Also published as: NZ243996A; PT100791A; CZ35294A3; HUT67488A; SK19294A3; AU2502892A; HU9400475D0; MX9204802A; WO1993003704A1; MA22628A1; CA2115154A1; JPH06509807A; EP0600008A1; FI940771A0; BR9206388A; FI940771A

Abstract

The liquid shaping composition of eruption usefulness comprises:

(a) mean molecule quantity is at least about 300000 ion and sends out polymer surely;

(b) be selected from water, C ₁-C ₆Liquid phase carrier in monohydric alcohol and their mixture;

(c) can reduce the ionic strength adjustor system of the effective dose of composition viscosity, described system is made up of on-surface-active cation and anionic mixture substantially, and wherein said cation and anion to small part is dissolvable in water in the liquid phase carrier.

Another aspect of the present invention is to obtain having the poor hair spray compositions of the volatile organic solvent that improves hair texture, and it comprises the hair fixing copolymer, the ionic strength adjustor system that reduces the effective dose of composition viscosity that contain silicone, contains water and one or more C ₁-C ₆The liquid phase carrier of mixture of monohydric alcohol.

Description

The hair spray compositions that contains the ion styling polymer

The invention relates to and contain macromolecule styling polymer hair spray compositions.More particularly, the invention relates to contain the macromolecule styling polymer and improved sprayability hair spray compositions.

Keeping certain hair style is general hope, and the common for it practice is that typing or " haircuting " compositions are applied to hair, generally is on the hair that wets or do.But the typing effect of these compositionss is of short duration, and water and/or shampoo can disappear.Generally, the material that is used for the generation typing effect of compositions is to use with the form of mousse, gel, shampoo or spray.

Use hair setting composition can expect to keep well or fixing hair style in the mode of spray.Generally, utilize resin, provide as AMPHOMER(National Starch) and GANTREZ SP 225(GAF provide) can keep hair style.Be generally as the mean molecule quantity that is used to discuss these resins of selling the hair spray goods about 40,000-150,000.When this resinoid is encased in pump formula or the aerosol hair spray device, said resin can suitably keep hair style, can provide good sprayability again simultaneously." sprayability " is meant atomization quality and distribution form.Hair spray its good sprayability mark sheet branch cloth cover of spraying now of filling a prescription is big, can not form the center as wet as the drizzle, and drop is enough little, can form the mist of exquisiteness.

Therefore, await providing having and improve fixing and keep the hair spray compositions of hair style performance.It is to utilize the molding resin of higher molecular weight that a kind of shaping performance that makes the liquid hair spray compositions is able to improved technology.In addition, in order to keep specific hair style, can reduce resin demand.When these macromolecule styling polymers are used for commerce, generally be the form that they is mixed with gel, washing liquid or other non-composite spray.Regrettably, the macromolecule resin sprayability in the liquid hair spray prescription is bad.Particularly, the characteristics of the atomization quality of this class prescription are that the spraying distribution diameter reduces, and the center is wet and phenomenon that drip increases, and mist is opposite with forming, and can produce big drop or liquid stream and spray.Above-mentioned these characteristics may cause the spraying concentration at part hair place excessive, make the hair at those places too stiff, and other place spray very little, and the result can not keep and fixing hair style in good condition.

Therefore, the purpose of this invention is to provide the liquid hair spray compositions that contains the macromolecule molding resin, said resin can keep hair style better, and good atomization characteristics is provided.

The polymer of some band silicone macromole part of recent findings can make hair produce good typing effect, can also improve hair quality simultaneously; In other words, compare with the resin that does not generally contain silicone, these contain the macromolecular polymer of silicone can give hair with sensation of softness and make hair obtain conditioning.The prescription that contains silicone macromole styling polymer and contain these polymer is disclosed, and for example, people's such as Hayama EPO applies for 90307528.1(EP-0408311A ₂, 1991,1,11 is open), people's such as Suzuki US 5,061,481(1991,10,29 bulletins), people's such as Bolich US 5,106,609(1992,4,21 bulletins), people's such as Bolich US 5,100,658(1992,3,31 bulletins), people's such as Ansher-Jackson US 5,100,657(1992,3,31 bulletins), people's such as Bolich US 5,104,646(1992,4,14 bulletins), people's such as Bolich application number 07/758,319(1991,8,27 applications), people's such as Torgerson application number 07/758,320(1991,8,27 applications), above content is hereby incorporated by reference document.

These contain the macromolecular polymer of sending out surely of silicone can produce ideal hair conditioning effect, and can make whole hair fixings intact.Compare with most of commodity, the polymer that is used for hair spray preferably has quite high molecular weight (although also can adopt the eruption resin of more common molecular weight, as mean molecule quantity is about 50,000-150,000), yet, they be difficult to be formulated into have good sprayability hair spray compositions.

Therefore, another object of the present invention provides and contains the liquid hair spray compositions that the band high molecular weight silicone is sent out polymer surely, and wherein said polymer can improve spray characteristics.

The present invention also requires to prepare volatile organic solvent such as ethanol, hair spray compositions that the propanol equal size is low.A kind of implementation method is under the condition that reduces volatile organic solvent, increases the water content in the compositions.It's a pity, can produce adverse influence to the performance of hair spray like this, the texture of drying time, atomization quality and hair when especially influence is used contains the compositions of the low volatile organic solvent content of silicone molding resin for employing, and this is distinct issues very.The atomization quality that will obtain with the compositions of high-moisture and texture are difficulties particularly.

A further object of the invention is to obtain to contain to have the improvement hair spray compositions that contains the macromolecular resin of haircuting of silicone that reduces volatile organic solvent.

The all purposes that it will be apparent to those skilled in the art can both obtain from the present invention, and it is documented in the following description description.Except as otherwise noted, all herein percent and ratio are all by weight.

The invention provides improve sprayability the hair spray compositions of pbz polymer styling polymer, said polymer can produce the effect that perfect typing/maintenance is finalized the design after eruption.

According to the present invention, can improve the sprayability of high molecular polymer by using the ionic strength adjustor system of forming by on-surface-active anion and cation mixt substantially.A necessary aspect of the present invention is that to send out polymer surely also should be ionic.

More particularly, the present invention relates to the liquid shaping composition that is used to erupt, it comprises:

(a) mean molecule quantity is at least about 300,000 ion and sends out polymer surely;

(b) be selected from water, C ₁-C ₆, C preferably ₂-C ₄Monohydric alcohol and a kind of liquid phase carrier in their mixture;

(c) a kind of ionic strength adjustor system that can reduce the effective dose of composition viscosity, described system is made up of on-surface-active cation and anionic mixture substantially, and wherein said cation and anion to small part dissolves in the above-mentioned liquid phase carrier;

Said compositions pH is about 10 or less than 10.

One aspect of the present invention is that it can be the typing of any general category in the prior art or the polymer of haircuting that macromolecule is sent out polymer surely, promptly not with silicone polymer partly.

Another aspect of the present invention is that high molecular polymer is to contain the macromolecular polymer of sending out surely of silicone.With the polymer phase ratio that does not contain silicone, it can make hair fixing and keep typing, can also improve the pliability of hair simultaneously.A further aspect of the present invention, promptly provide and have the low hair spray compositions of volatile organic solvent content that improves hair texture, said composition comprises the hair fixing copolymer that contains silicone, a kind of ionic strength adjustor system (as mentioned above) that reduces the effective dose of composition viscosity, contains water and one or more C ₁-C ₆, best C ₂-C ₄The liquid phase carrier of the mixture of monohydric alcohol, wherein said compositions contain about 10%(weight at least) water.

What put down in writing below is necessary component and various selectivity component.

Styling polymer

Compositions of the present invention contains the macromolecule styling polymer of effective dose, can make hair keep certain hair style after the use.Here used " styling polymer " is meant can give any natural or synthetic polymer of hair with good typing effect.This base polymer is that prior art is known.General its use amount is about 0.1%(weight of compositions at least), be generally about 0.1%-15%, preferably about 0.5%-8%.

The used styling polymer of the present invention also is ionic simultaneously." the ion styling polymer " that the said monomer that comprises with styling polymer or with this styling polymer of this paper is relevant or " ionic " speech meaning are meant that styling polymer is anionic, cationic, amphoteric, zwitterionic, or other is present in the polymer of sending out surely in the compositions liquid phase carrier with free form.

The present invention can use and dissolve in the ion styling polymer that maybe can be scattered in any kind in the liquid phase carrier, and various this type of styling polymers are that prior art is known.

Ion styling polymer of the present invention can be homopolymer, copolymer, terpolymer etc., and " polymer " used herein speech comprises the polymer of all these types.

As the content of necessity, polymer of the present invention must contain the monomer of tool ion characteristic, and for ease of describing polymer, the monomeric unit in the polymer can be meant the monomer that can access polymer.Ion monomer can be modified derived from the polymerisable ion initial monomers or the self energy of deriving, and aggregates into the polymerizable non-ionic monomer with ion characteristic then.Monomer example of the present invention also comprises corresponding to monomeric salt, bronsted lowry acids and bases bronsted lowry.

The example of anionic monomer comprises:

(ⅰ) unsaturated carboxylic acid is as acrylic acid, methacrylic acid, maleic acid, maleic acid half ester, itaconic acid, fumaric acid and butenoic acid;

(ⅱ) unsaturated multi-anhydride half ester, as reaction such as the acrylate of succinic anhydrides, phthalic anhydride etc. and hydroxyl and/or methacrylate such as 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate and Hydroxypropyl acrylate and half ester;

(ⅲ) contain sulfonic monomer, as styrene sulfonic acid, acrylic acid sulphur ethyl ester and methacrylic acid sulphur ethyl ester etc.;

(ⅳ) monomer of phosphorous acidic group, as the acid phosphorus acyloxy ethyl ester of acrylic acid and methacrylic acid, 3-chloro-2-acid phosphorus acyloxy ethyl ester of acrylic acid and methacrylic acid or the like.

The example of cationic monomer comprises:

(ⅰ) monomer that is obtained by the quaternized epihalohydrin product of the trialkylamine that 1-5 carbon atom arranged on acrylic or methacrylic acid [below be collectively referred to as (methyl) acrylic acid] and the alkyl is as (methyl) acryloxy oxypropyl trimethyl ammonium chloride and (methyl) acryloxy propyl group triethyl group ammonium bromide;

(ⅱ) by (methyl) acrylic acid or (methyl) acrylamide with contain C ₁-C ₄(methyl) acrylic acid amine derivative that the dialkyl group alkanolamine of alkyl obtains or the amine derivative of (methyl) acrylamide, as (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid dimethylamino propyl ester, or dimethylaminopropyl (methyl) acrylic acid amides;

(ⅲ) above-mentioned (ⅱ) organizes the derivant of product by following manner: (1) and a kind of sour example hydrochloric acid or lactic acid neutralization reaction, (2) with haloalkyl such as chloromethane, chloric ethane, bromomethane or iodic ether modification, (3) with halogenated aliphatic acid ester such as ethyl chloride, or one methyl chloropropionate modification and (4) with sulphuric acid dialkyl such as dimethyl sulfate or dithyl sulfate modification.

In addition, the cation unsaturated monomer comprises the amine derivative of allyl compound, as diallyldimethylammonium chloride etc.

These cation unsaturated monomers can be with cationic form polymerization, in addition also can be with their precursor forms polymerization, and modification becomes the cation thing then, for example utilizes quaternizing agent (as ethyl chloride, dimethyl sulfate etc.) modification.

The example of ampholytic monomer comprises zwitterionic derivative, they be amine derivative by aforementioned (methyl) acrylic acid amine derivative or (methyl) acrylamide as (methyl) acrylic acid dimethylamino ethyl ester, reaction such as the amino methyl propylate of dimethylaminopropyl (methyl) acrylamide and halogenated aliphatic acid salt such as chloroacetic acid potassium, monobromo sodium propionate, chloroacetic acid and the triethanolamine salt of chloroacetic acid and; Also comprise as discussed above with (methyl) acrylic acid of propane sultone modification or the amine derivative of (methyl) acrylamide.

As above-mentioned cationic monomer, these ampholytic monomers can amphoteric form polymerization; Another kind method is the precursor forms polymerization with them, is converted into bisexual state then.

Preferred ion monomer comprises acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, maleic acid, maleic anhydride half-ester, butenoic acid, itaconic acid, diallyldimethylammonium chloride, polar vinyl heterocycle such as vinyl imidazole, vinylpyridine, styrene sulfonate (ester) and its mixture.Particularly preferred ion monomer comprises acrylic acid, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate and their mixture.

The above-mentioned listed acid and the salt of amine monomers also can use, for example, and the salt of sodium, potassium or other alkali or alkaline-earth metal.

Polymer of the present invention should contain about 1%(weight at least) ion monomer, preferably at least about 2%, more preferably at least about 5%.

The present invention sends out polymer surely also can contain non-ionic monomer, comprises high polar monomer and low polar monomer.

The present invention sends out the non-ionic monomer that polymer generally contains about ion monomer of 1% to 100% and 0% to about 99% surely, preferred about 2% to about 75% ion monomer and about 25% to about 98% non-ionic monomer, more preferably about 5% to about 50% ion monomer and about 50% to about 95% non-ionic monomer.

Representative low polarity non-ionic monomer is C ₁-C ₂₄The acrylate or the methacrylate of alcohol, said alcohol is methanol for example, ethanol, the 1-propanol, the 2-propanol, the 1-butanols, 2-methyl isophthalic acid-propanol, the 1-amylalcohol, the 2-amylalcohol, the 3-amylalcohol, 2-methyl-1-butene alcohol, 1-methyl isophthalic acid-butanols, 3-methyl isophthalic acid-butanols, 1-methyl-1-pentene alcohol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, the tert-butyl alcohol, Hexalin, 2-ethyl-1-butanols, the 3-enanthol, benzyl alcohol, sec-n-octyl alcohol, 6-methyl isophthalic acid-enanthol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, the 1-dodecanol, the 1-hexadecanol, 1-octadecanol etc., these carbon atoms are the preferably about 4-18 of average carbon atom number, the more preferably from about alcohol of 4-12 in about 1-24 alcohol; Styrene; Chlorostyrene; Vinyl esters such as vinyl acetate; Vinyl chloride; Vinylidene chloride; Acrylonitrile; α-Jia Jibenyixi; Tert-butyl-styrene; Butadiene; Cyclohexadiene; Ethylene; Propylene; Vinyltoluene; (methyl) alkoxyalkyl acrylate is as (methyl) acrylic acid methoxyl group ethyl ester, (methyl) acrylic acid butoxy ethyl ester; And their mixture.Other non-ionic monomer comprises the derivant of acrylate and methacrylate, the allyl ester of acrylic acid and methacrylic acid for example, the cyclohexyl of acrylic acid and methacrylic acid, the oleyl alcohol ester of acrylic acid and methacrylic acid, acrylic acid and benzyl methacrylate, the tetrahydrochysene bran ester of acrylic acid and methacrylic acid, glycol diacrylate and dimethylacrylate, 1,3-butanediol diacrylate and dimethylacrylate, N-[2-(2-methyl-4-oxopentyl), (methyl) isobornyl acrylate etc.

Preferred non-ionic monomer comprises n-BMA, isobutyl methacrylate, methacrylic acid 2-Octyl Nitrite, methyl methacrylate, tert-butyl acrylate, metering system tert-butyl acrylate and their mixture.

Representative polarity non-ionic monomer comprises that acrylamide, N,N-DMAA, Methacrylamide, N tert butyl acrylamide, methacrylonitrile, acrylamide, acrylic acid alcohol ester are (as C ₂-C ₆The example of acrylic acid alcohol ester is 2-(Acryloyloxy)ethanol and Hydroxypropyl acrylate), acrylic acid methyl ester., Hydroxypropyl methacrylate, vinyl pyrrolidone, vinyl ethers, as methyl vinyl ether, acyl group lactone, vinylpyridine, allyl alcohol, vinyl alcohol and caprolactam.

The example of anion eruption polymer is copolymer, the vinylacetate of vinyl acetate and butenoic acid, the terpolymer of butenoic acid and α-monocarboxylic vinyl esters of side chain radical of saturated aliphatic such as vinyl neodecanoate; The copolymer of methyl vinyl ether and maleic anhydride (about 1: 1 of mol ratio), 50% of this copolymer are contained 1～4 carbon atom such as ethanol or the esterification of butanols radical of saturated aliphatic alcohol; Contain with acrylic or methacrylic acid as the acrylic copolymer of anionic group and terpolymer as containing the copolymer of methacrylic acid, butyl acrylate, ethyl methacrylate, or the like.Another example that can be used for the acrylate copolymer of the present composition is the polymer of tert-butyl group acrylamide, acrylic acid and ethyl acrylate.

The example that can be used for amphiphilic polymers of the present invention is octyl acrylamide/acrylates (ester)/metering system acid butyl amino ethyl ester copolymer, the polymer of suitable molecular weight of the present invention is the polymer of uncle N--octyl acrylamide, methyl methacrylate, Hydroxypropyl methacrylate, acrylic acid and methacrylic acid tert-butyl amino ethyl ester, it has been recorded in US.4, in 192,861.

The example of cation eruption polymer is following monomeric copolymer; The acrylate monomer of band amido functional group such as acrylic acid low alkylaminoalkyl, or methacrylate monomer such as dimethylaminoethyl methacrylate and the compatible monomer such as the copolymer of N-vinyl pyrrolidone or alkyl methacrylate such as methyl methacrylate and ethyl methacrylate and alkyl acrylate such as acrylic acid methyl ester. and butyl acrylate.The cationic polymer that contains the N-vinyl pyrrolidone is bought from GAF company.

Also available other organic ion is sent out polymer surely, comprise the copolymer, kayexalate, PVP/ ethyl methacrylate/metering system acid ter-polymer, vinylacetate/butenoic acid/vinyl neodecanoic acid ester copolymer, octyl acrylamide/acrylates (ester) copolymer of copolymer, PVA and the maleic anhydride of carboxymethyl cellulose, PVA and butenoic acid, the single ethyl ester and octyl acrylamide/acrylates (the ester)/metering system acid butyl amino ethyl ester copolymer of poly-(methyl ethyl ether-maleic acid), also can utilize mixture of polymers.

What contain silicone sends out polymer surely

It is the polymer that contains silicone that preferred ion is sent out polymer surely.Containing silicone macromolecular ionomer is documented in as people's such as Hayama european patent application 90307528.1(EP-0408311A _z, be disclosed in 1991,1,11), people's such as Suzuki United States Patent (USP) 5,061,481(1991,10,29 bulletins), people's such as Bolish United States Patent (USP) 5,106,609(1992,4,21 bulletins), people's such as Bolish United States Patent (USP) 5,100,658(1992,3,31 bulletins), people's such as Ansher-Jackson United States Patent (USP) 5,100,657(1992,3,31 bulletins), people's such as Bolish United States Patent (USP) 5,104,646(1992,4,14 bulletins), people's such as Bolish Application No. 07/758,319(1991,8,27 applications) and people's such as Torgerson Application No. 07/758,320(1991,8,27 applications) in, above document is hereby incorporated by reference.

The example of suitable polymers and their method of preparation also at length are recorded in the United States Patent (USP) 4,693 of Mazurek, 935(1987,9,15 bulletins), people's such as Clemens United States Patent (USP) 4,728,571(1988,3,1 bulletins), two pieces of documents are hereby incorporated by reference more than.

Preferably contain the macromolecular ionomer of silicone and comprise an organic polymer skeleton, preferred Tg is higher than the vinyl backbone of-20 ℃ (more preferably being higher than about 20 ℃) approximately, and the mean molecule quantity that is grafted to the polysiloxane macromonomer on this skeleton is preferably at least about 500, and better about 1,000 to about 100,000, preferably about 2,000 to about 50,000, most preferably be about 5,000 to about 20,000.Except above-mentioned graft copolymerization beyond the region of objective existence, the polymer that contains silicone also comprises block copolymer, and it preferably contains up to about 50%(weight) one or more siloxane blocks and one or more non-silicone block (as acrylates (ester) or vinyl) of (best about 10% to about 40%).

Be preferred for of the present invention contain the macromolecular polymer of silicone be those when being mixed with the hair care composition finished product and being dried, polymer phase is divided into discontinuous phase that comprises silicone part and the continuous phase that comprises organic moiety.

Contain the macromolecular ion of silicone and send out polymer surely and generally comprise above-mentioned non-ionic monomer that contains silicone and ion monomer, also can comprise the above-mentioned non-ionic monomer that does not contain silicone.Siliceous one monomers also can be ionized and have electric charge, partly or wholly influences the charge density of whole polymer therefrom.

The silicone that contains of the present invention is sent out polymer surely and is generally comprised about siliceous one monomers of 0.01%～about 50%, and preferred about 0.5% to about 40%, and most preferably from about 2% to about 25%.

The monomer general formula that contains silicone is:

Wherein X be can with the vinyl of other monomer copolymerization of polymer: Y is a divalent linker; R is that hydrogen, low alkyl group are (as C ₁-C ₄), aryl, alkaryl, alkylamino or alkoxyl; Z is a monovalence siloxane polymerization part, and its mean molecule quantity is at least about 500, and is the side group of organic polymer skeleton; N is 0 or 1; M is an integer of 1～3.Certainly, Z is nonreactive substantially under polymerizing condition.The monomer mean molecule quantity that contains silicone is at least about 500, and preferred about 1,000 to about 100,000, and more preferably from about 2,000 to about 50,000, most preferably from about 5,000 to about 20,000.Its preferred general formula:

Wherein m be 1,2 or the preferred m=1 of 3(); P is 0 or 1; Q is 2～6 integer; X is

R ²Be hydrogen or-the preferred R of COOH( ²Be hydrogen), R ³Be hydrogen, methyl or-CH ₂The preferred R of COOH( ³Be methyl); Z is

R ³, R ⁴, R ⁵, R ⁶Be respectively alkyl, alkoxyl, alkyl amino, aryl, alkaryl, hydrogen or hydroxyl (preferred alkyl, most preferable); R is at least an integer of about 10, preferred about 5 to about 1500(more preferably r be about 75 arrive about 700, most preferably from about 100 to about 250).When p=0 and q=3, be particularly preferred monomer.

The siliceous one monomers of ionomer of the present invention can carry out polymerization with the form of siliceous one monomers.On the other hand, it can carry out polymerization with the precursor forms that does not contain silicone, adds the silicone group then.For example, contain carboxylate monomer such as acrylic acid can carry out after the polymerization again with an end be that the silicone compounds that contains of epoxide group reacts.The result generally be the siliceous one monomers in the polymer have be equivalent to above-mentioned X(Y) nSi(R) _3-mZ _mStructure, and comprised in the present invention.

Be used for the silicone polymer that preferably contains of the present invention and generally comprise 0% to about 98% non-ionic monomer (preferred about 5% to about 98%, more preferably from about 50% to about 90%), about ion monomer of 1% to 98% (preferred about 15% to about 80%), with about 0.1% to about 50% siliceous one monomers (preferred about 0.5% to about 40%, most preferably from about 2% to about 25%).In the polymer the bonded monomer that does not contain silicone preferably about 50% to about 99%(more preferably from about 60% arrive about 99%, most preferably from about 75% to about 95%).

Be used for the example that contains silicone polymer of the present invention and comprise following material:

(ⅰ) acrylic acid/n-BMA/polydimethylsiloxane (PDMS) macromole-molecular weight is 20,000

(ⅱ) dimethylaminoethyl methacrylate/isobutyl methacrylate/methacrylic acid 2-Octyl Nitrite/PDMS macromole-molecular weight is 20,000

(ⅲ) tert-butyl acrylate/acrylic acid/PDMS macromole-molecular weight is 10,000

(ⅳ) tert-butyl acrylate/acrylic acid/PDMS macromole-molecular weight is 10,000

Have the ion that contains silicone comprising of carboxylate or other acidic functionality and do not contain silicone send out surely polymer in the present composition preferably so that the neutral form of small part use, to promote dissolubility and the dispersibility of polymer in carrier.In addition, use such in and form help to remove hair spray compositions with shampoo.Generally, the acid monomer of the neutral polymer of institute is about 10% to 100%, more preferably about 20% to about 90%, and more preferably from about 40% to about 85%.

Organic or the metal base of any common usefulness all can be used for the neutralization of acidic polymer.In hair spray compositions of the present invention, the nertralizer that is suitable for is the hydroxide of alkali metal and alkaline-earth metal.Those skilled in the art recognize that the various cationes with polymer in supplying also belong to above-mentioned ionic strength adjustor system.

The nertralizer that is preferred for hair spray compositions of the present invention is potassium hydroxide and sodium hydroxide.

The nertralizer example that it is suitable that other is used for hair spray compositions of the present invention comprises aminated compounds, especially amino alcohol, as 2-amino-2-methyl-1, ammediol (AMPD), 2-amido-2-ethyl-1, ammediol (AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanols (AB), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monoisopropanolamine (MIPA), diisopropanolamine (DIPA) (DIPA), triisopropanolamine (TIPA) and dimethyl steramine(DMS).To neutralizing useful especially is the mixture of amine and metal base.

There is the most handy sour example hydrochloric acid of polymer of basic functionality such as amino group to neutralize at least in part.

Liquid phase carrier

Hair spray compositions of the present invention also comprises liquid phase carrier.It can comprise any liquid phase carrier that is usually used in the resin hair spray prescription.Liquid phase carrier in the hair spray compositions of the present invention account for whole compositions about 80% to about 99%, preferred about 85% to about 99%, more preferably from about 90% to about 98%.

The organic solvent that is applicable to present composition liquid phase carrier is C ₁-C ₆Alkanol, carbitol, acetone and their mixture.Be preferred for the C of the present composition ₁-C ₆Alkanol is C ₂-C ₄Monohydric alcohol such as ethanol, isopropyl alcohol and their mixture.Water also is the preferred solvent that is used for hair spray compositions liquid phase carrier of the present invention.

The liquid phase carrier of the present composition preferably is selected from by C ₁-C ₆A kind of in alkanol, water, carbitol, acetone and their mixture form one group is to select Free water and C better ₂-C ₄In the group that monohydric alcohol such as ethanol and isopropyl alcohol and their mixture constitute.

Generally, liquid phase carrier can be anhydrous, can all be water also, and most preferred liquid phase carrier is the mixture of water and organic solvent.

Utilize water and ORGANIC SOLVENT MIXTURES, during as water-ethanol or water-isopropyl alcohol-ethanol, the content of water generally accounts for about 0.5% to about 99%, preferred about 5% to about 50% of whole composition weights in the compositions, and organic solvent generally accounts for the 0.5%-99% of whole composition weights, preferably about 50%-95%.

By an aspect of of the present present invention, the mean molecule quantity of the resin of haircuting is very high, and promptly mean molecule quantity is greater than about 300,000, especially greater than about 500,000.Found to utilize these high molecular weight resins and ionic strength adjustor system mixing energy to obtain unexpected eruption characteristic effect.The present invention especially effectively provides the resin of the certain feature of tool for hair spray compositions, particularly select those quite high-molecular weight silicone macromole resins of haircuting that contains for use, and like this, said compositions promptly has good atomization quality.

Another aspect of the present invention provides volatile organic solvent poor hair spray compositions, and it comprises a kind of macromolecular ion of silicone haircut resin, a kind of described ionic strength adjustor system and liquid phase carrier of containing.The poor hair spray compositions of volatile organic solvent of the present invention comprises and is not more than 80% volatile organic solvent (by purpose of the present invention, comprise volatile silicone liquid, dewater side by side).In other embodiment, hair spray compositions can contain and is not more than about 65%, 55%, 50% or the volatile organic solvent of other numerical value, and manufacturer can select voluntarily.In the hair spray product of low volatile organic solvent content, its compositions comprises 10%(weight at least) water; Contain at least about 11%, 12%, 13%, 14%, 15% or more water also be worthy of consideration especially.The mean molecule quantity that contains the macromolecular resin of haircuting of silicone can be any suitable numerical value that reaches effective typing, and generally at least about 50,000, more typical is to be at least about 70,000, preferably at least about 100,000.The volatile organic solvent that the present invention uses be meant have at least a carbon atom and in the time of 20 ℃ vapour pressure greater than those solvents of 0.1mmHg.

To this, more preferred of the present invention is, the mean molecule quantity of resin is about 70,000 to about 1,000,000, most preferably from about 100,000 to about 750,000.

Generally, the compositions of low volatile organic solvent content of the present invention comprises up to about 90%, preferably up to about 70%, more preferably up to about 60%, most preferably up to about 50% water; The volatile organic solvent that comprises is about 10% to about 80%, and preferred about 20% to about 80%, more preferably from about 40% to about 80%.Can consider especially that also the volatile organic solvent in the limit combination is to being not more than its highest limit, as be not more than about 75%, 65% or 55% or the like.

For compositions of the present invention, the mean molecule quantity of styling polymer can only be limited by practice, is usually less than approximately 10,000,000, preferably is lower than approximately 3,000,000, is preferably lower than about 1,000,000.

The ionic strength adjustor system

Compositions of the present invention says with respect to the same combination that lacks ionic strength adjustor, and it comprises as neccessary composition, is used to reduce the ionic strength adjustor system of the effective dose of sending out compositions viscosity surely.Generally, the ionic strength adjustor of the present composition is at least about 0.01%(weight).Those skilled in the art will appreciate that the increase along with the compositions ionic strength, sending out polymer surely will finally break away from solution, perhaps no longer be dissolved or dispersed in the liquid phase carrier.The upper limit of ionic strength adjustor system consumption will depend on concrete ionic strength adjustor, liquid phase carrier, send out polymer and be present in other component in the compositions and change surely.For example, in the liquid phase carrier compositions of moisture content less, the maximum of used ionic strength adjustor will be lower than its amount in containing the compositions of more water.Usually, compositions comprises about 4%(weight) or ionic strength adjustor still less; Be about 2% or still less more at large; Typically be about 1% or still less.Preferably, compositions comprises about 0.01% to about 0.5%, more preferably is about 0.01% to about 0.1% ionic strength adjustor system.

The ionic strength adjustor system contains monomer cation and anionic mixture.This ionic strength adjustor system intermediate ion is non-surface active, and promptly they can not reduce surface tension significantly.Concerning the object of the invention, on-surface-active means that the ion of 0.5% concentration of aqueous solution reduces surface tension and is no more than 5.0dynes/cm ²Generally, the ion characteristic of ionic strength adjustor system is that each electric charge has maximum four or carbon atoms still less, preferred two or carbon atom still less in any fat chain or straight chain or branched organic heterochain.

The ionic strength adjustor system comprises the monomer ion of Acid-Base product type.Therefore, alkalescence and acid ion OH ^-And H ⁺They do not constitute ionic strength adjustor system part, although can be present in the compositions.The ion of introducing in the compositions is present in the compositions with the free ion form, promptly exists with free form.The ion of unnecessary all addings all is present in the compositions as free ion, but they must be to small part solubilized or free in compositions.Ionic strength adjustor can be introduced and send out surely in the compositions, for example, and by the interpolation soluble-salt, or the mixture of interpolation bronsted lowry acids and bases bronsted lowry, or add their mixture.The important aspect of the present invention be the anion of ionic strength adjustor system and cation the two to be included in the compositions.

The cation that is suitable for for example comprises: alkali metal such as lithium, sodium and potassium, alkaline-earth metal such as magnesium, calcium and strontium.Bivalent cation preferably magnesium, monovalent metallic ion preferred lithium, sodium and potassium, particularly sodium and potassium.The suitable ionic species that joins the present composition for example comprises, adds with the form such as the hydroxide of alkali, as sodium hydroxide and potassium hydroxide, and adds the anionic salt of those monomers as described below with the salt that dissolves in liquid phase carrier.

Other cation that is suitable for comprises organic ion, and for example quaternary ammonium ion and cationic amine are as ammonium, list, two and ammonium ions such as triethanolamine, triethylamine, morpholine, amino methyl propanol (AMP), amino-ethyl propylene glycol.Ammonium and amine are preferably supplied with example hydrochloric acid salt with the form of salt.

Available monomer anion comprises halide ion, as chloride, fluoride, bromide and iodide, especially chloride, sulphuric acid, ethyl-sulfate, Methylsulfate, sulfamic acid cyclohexyl ester, thiosulfate, toluene fulfonate, xylenesulfonate, citrate, nitrate, bicarbonate, adipate, succinate, hexose hydrochlorate, benzoate, lactate, borate, isethionate, tartrate, and other can be present in the monomer anion of sending out surely in the compositions with free form.These aniones can join in the compositions of the present invention, for example, add so that small part dissolves in the form of the acid of liquid phase carrier or salt, as the acetate of sodium or potassium, citrate, nitrate, chloride, sulfate etc.Preferably, these salt all dissolve in the carrier.

The water equivalent pH value of the present composition is for being approximately equal to or less than 10, preferred about 3～and about 10, more preferably from about 5～about 10.For purposes of the invention, the water equivalent pH value is corresponding to the pH of the compositions that contains whole composition component, except dual reverse osmosis (DRO) water of the weight such as nonaqueous component quilt of carrier replaces.

The hair spray compositions of the preferred low volatile organic solvent content of the present invention contains 0.01% to about 2% the fluorine surfactant of having an appointment; About 0.1% to about 15% ion exchange resin, said resin comprise that mean molecule quantity is 300,000 and is higher or lower than 300,000 resin, comprises that also those have or do not have the resin of silicone macromole part; Also contain above-mentioned ionic strength adjustor system and liquid phase carrier, said liquid phase carrier comprises about 10% to about 45%(weight) water and about 50% arrive about 80%(with composition weight meter) organic solvent, this solvent is preferentially selected ethanol, isopropyl alcohol or their mixture for use.

The amount of general used ionic strength adjustor system provides in the above, and recognize, improve the hair spray performance or for reaching optimum performance for reaching, for in the specific hair spray compositions must with the concrete amount of ionic strength adjustor system can be dependent on many factors and change, these factors comprise particular type and its molecular weight and the amount in compositions of selecting resin for use, concrete ionic strength adjustor system, the content of its water, the optional ingredient that exists in the type of volatile organic solvent and amount and the system.Generally, along with the reduction of the molecular resin amount and/or the water yield, the ionic strength adjustor system that may need high level is to obtain improved effect.Compositions of the present invention generally contains the ionic strength adjustor system of effective dose at least so that under the shaping performance of certain level or improved atomization quality situation hair quality is improved.

The selectivity composition

Compositions of the present invention also contains other selective substances except above-mentioned ionic strength regulation system, thereby improves the sprayability of compositions.Especially wish the use that combines of the on-surface-active anion of ionic strength adjustor system and cation and ionic surface active agent.

The kinds of surface activating agent can be introduced compositions valuably, and these surfactants comprise anion, cation, amphoteric, zwitterionic surfactant, also comprises the surfactant of fluorizated surfactant (following) and nonfluorinated.

Anion surfactant for example comprises: alkyl and alkenyl sulfate; The ethoxylated sulfate of alkyl and alkenyl (preferred ethoxyquin meansigma methods is 1～10); The dialkyl of succinamic acid ester surfactant such as sulfosuccinamic acid Arrcostab and sulfosuccinamic acid; The sulfonate of neutral isethionic acid fatty acid ester and alkyl and alkenyl comprises as ethylenic sulfonate and β-alkoxyl alkyl sulfonate.The ethoxylated sulfate of the sulfate of alkyl and alkenyl and alkyl and alkenyl preferably is as C ₁₂-C ₁₈Sodium sulfate and ammonium salt and ethoxyquin degree 1 to about ethoxyquin sulfate of 6, preferred 1 to about 4 such as lauryl sulfate and laureth(3.0) sulfate.

Amphoteric surfactant comprises that those are described as the derivant that the fat base is the aliphatic secondary and tertiary amine of straight or branched widely, one of them aliphatic substituent group contains about 8 to about 18 carbon atoms, an aliphatic substituent group contains the anionic group that is dissolvable in water water, for example, carboxyl, sulfonate, sulfate, phosphate or phosphonate.The example that belongs to the chemical compound of this definition is the 3-sodium dodecyl aminopropionitrile; the N-alkyl taurine is as pressing United States Patent (USP) 2; 658; the 072 described preparation by the reaction of dodecyl amine and hydroxyethyl sulfonate, the higher alkyl-aspartic acid of N-is as pressing United States Patent (USP) 2,438; those products of 091 preparation; and sell and be documented in United States Patent (USP) 2,528 with trade mark " Miranol ", the product in 278.Other example comprises both sexes glycine alkyl ester, preferred C ₆-C ₂₂, C most preferably ₈-C ₁₂Ester; The both sexes alkyl propionates, preferred C ₆-C ₂₂, C most preferably ₈-C ₁₂Ester; And their mixture.

The zwitterionic surfactant that is applicable to the present composition can illustrate as follows, they are described as the aliphatic quaternary ammonium, Phosphonium that the fat base can be a straight or branched and the derivant of sulfonium compound widely, one of them aliphatic substituent group contains about 8-18 carbon atom, an aliphatic substituent group contains the anionic water-soluble group, for example, carboxyl, sulfonate, sulfate, phosphate or phosphonate.The general formula of these chemical compounds is:

R wherein ²Comprise and be respectively about 8 to about 18 carbon atoms, 0 alkyl, alkenyl and hydroxyalkyl to about 10 ethylene oxide moieties and 0-1 glyceryl part; Y is selected from nitrogen, p and s atom; R ³Be contain 1 to the alkyl of about 3 carbon atoms or-hydroxy alkyl; X is 1 when Y is sulfur or phosphorus, is 1 or 2 when Y is nitrogen; R ⁴Be 1 alkylidene or hydroxyl alkylidene to about 4 carbon atoms; Z is a group that is selected from the group that is made of carboxylate, sulfonate, sulfate, phosphonate and phosphate group.The kind of zwitterionic surfactant comprises alkyl amino sulfonate, alkyl betaine and alkyl acyl ammonia betanin.

The cationic surfactant that is used for the present composition comprises when being dissolved in Aquo-composition, positively charged amino or quaternary ammonium hydrophilic segment.The useful cationic surfactant of the present invention is disclosed in the following document and is hereby incorporated by reference document: M.C.Publishing Co., McCutcheon ' s, Detergents ﹠amp; Emulsifiers(North American edition 1979); People such as Schwartz, Surface Active Agents, Their Chemistry and Technology(New York:Interscience Publishers, 1949); The United States Patent (USP) 3,155 of Hilfer, 591(1964,11,3 bulletins); People's such as Laughlin United States Patent (USP) 3,929,678(1975,12,30 bulletins); People's such as Bailey United States Patent (USP) 3,959,461(1976,5,25 bulletins); Bolish, the United States Patent (USP) 4,387 of Jr., 090(1983,6,7 bulletins).

Being used for the cationic surfactant that the present invention contains quaternary ammonium is those materials with following general formula:

R wherein ₁Be the aliphatic group of 1～22 carbon atom, or the aromatic group of 12～22 carbon atoms, aryl or alkylaryl group; R ₂It is the aliphatic group that 12～22 carbon atoms are arranged; R ₃And R ₄It is respectively alkyl with 1～3 carbon atom; X is an anion, is selected from the root of halogen, acetate, phosphate, nitrate and alkyl sulfate.Except carbon and hydrogen atom, aliphatic group can also contain ehter bond and other group such as amino.Other useful quaternary ammonium salt is a di-quaternary ammonium salt.

Preferred quaternary ammonium salt comprises dialkyl dimethyl ammonium chloride, and wherein alkyl has 12～22 carbon atoms and derivation of self-long chain fatty acid such as the acid of hydrogenated animal fat.(tallow fatty acid provides R ₁And R ₂Be mainly the quaternary ammonium compound of 16～18 carbon atoms).

The primary, the salt of the second month in a season, uncle's fatty amine also is suitable as cationic surfactant, and preferred 12～22 carbon atoms of the alkyl of these amine also can be to replace or non-replacement.Secondary and tertiary amine is preferred, particularly preferably is tertiary amine.These useful amine comprise the amino propyl-dimethyl amine of stearoyl, diethylamino ethyl stearmide, dimethyl stearylamine, dimethyl Semen sojae atricolor amine, Semen sojae atricolor amine, tetradecylamine, tridecyl amine, ethyl stearmide, N-tallow propanediamine, ethoxylation (5mols E.O.) stearmide, dihydroxy ethyl stearmide and arachidic acid mountain Yu amine.The useful cationic amine surfactant of the present invention is disclosed in people's such as Nachtigal the United States Patent (USP) 4,275,055 (1981,6,23 bulletin), is hereby incorporated by reference document.

Suitable anionic surfactant salt comprises halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate.

Compositions of the present invention can also comprise non-ionic surface active agent, preferably average HLB(hydrophilic-lipophilic balance (HLB)) be less than or equal to about 7 non-ionic surface active agent.

The method of measuring HLB is that prior art is known, and any method wherein all can be used for the mensuration of HLB.The description and the assay method of HLB system is documented in (ICI Americas Inc. in " The HLB System:a time saving guide to emulsifier selection "; Wilmington, Delaware; 1976).

Ionic surfactant pack is drawn together polyethylene oxide condensation compound (the preferred C of alkylphenol ₆-C ₁₂Alkyl, ethoxylation degree are about 1 to about 6), the condensation substance of oxirane and expoxy propane and reacting ethylenediamine product, the condensation substance of aliphatic alcohol and oxirane, long-chain (promptly is generally C ₁₂-C ₂₂) tertiary amine oxide; Long-chain oxidation tertiary phosphine; Contain a chain alkyl or hydroxyalkyl and a short chain (preferred C ₁-C ₃) dialkyl sulphoxide of group; Silicone copolyol and have a C ₈-C ₂₂The C of the acid of aryl moiety ₁-C ₄Alkanolamide.

The fluorine surfactant (being fluorizated surfactant) that is used for the present composition can be straight or branched alkyl, alkenyl or alkaryl fluorohydrocarbon, and preferred 3～18 carbon atoms of its chain length are also completely or partially fluoridized.Hydrophilic segment can for example be sulfate, phosphate, phosphonate, sulfonate, amine, amine salt, quaternary ammonium, carboxylate and their any mixture.Also bridged bond can be arranged between hydrophilic segment and the hydrophobic part, for example the acylamino-alkenyl group.

The ion fluorine surfactant that is used for the present composition comprises the perfluorochemical of representing with following general formula:

Wherein Z is the water soluble group of organic or inorganic; X generally is 2～17 integer, particularly 7～11, and Y is 0～4 integer, and this chemical compound can be cation, anion, amphoteric or zwitterionic, and this depends on the character of the contained group of Z or several groups.The Z group can be maybe to comprise sulfate, sulfonate, carboxylate, amine salt, quaternary ammonium, phosphate, phosphonate and their mixture.Fluoridized chemical compound is that prior art is known, and these chemical compounds are documented in people's such as Cella United States Patent (USP) 4,176,176(1979,11,27 bulletins), people's such as Cella United States Patent (USP) 3,993,745(1976,11,23 bulletins), people's such as Cella United States Patent (USP) 3,993,744(1976,11,23 bulletins) in, they are hereby incorporated by reference document.

The cation fluorine surfactant that is preferred for the present composition comprises the fluorinated alkyl quaternary ammonium salt with various anionic counter-ions, and said anion comprises iodide, chloride, metilsulfate, phosphate and nitrate, preferred iodide; These fluorine surfactant general molecular formula R _fCH ₂CH ₂SCH ₂CH ₂N ⁺(CH ₃) ₃[CH ₃SO ₄] ^-, R wherein _f=F(CF ₂CF ₂) _3-8, as the ZONYL FSC(Wilmington that E.I.DuPont deNemours and Company provides, Delaware, USA; DuPont).Preferred fluorinated alkyl quaternary ammonium iodide is by Minnesota Mining ﹠amp; Manufacturing(st.Paul, Minnesota, USA; The FLUORAD FC-135 that 3M) provides.

The anionic fluorinated surfactant that is preferred for the present composition is single and the Fluoalkyl phosphate of enjoying a double blessing, and is for example provided and general molecular formula (R by DuPont _fCH ₂CH ₂O) (ONH P(O) ₄) ₂(R _fCH ₂CH ₂O) ₂P(O) (ONH ₄) ZONYL FSP, R wherein _f=F(CF ₂CF ₂) _3-8; Single and two Fluoalkyl phosphate, it cooperates with the quaternary ammonium (quats) (preferred aliphatic series quaternary ammonium metilsulfate) of nonfluorinated, salt with various cation counterbalancing ions such as ammonium, sodium, potassium, triethanolamine and diethanolamine, preferred ammonium salt, the ZONYL FSJ that provides as DuPont; It has the salt of various cation counterbalancing ions such as ammonium, sodium, potassium, triethanolamine and diethanolamine, particularly ammonium salt perfluoro alkyl sulfonic acid, as the also general molecular formula R that is provided by DuPont _fCH ₂CH ₂SO ₃The ZONYL TBS of X, wherein R _f=F(CF ₂CF ₂) _3-8And X=H or NH ₄O; The phosphate telomer, it has the salt of various cation counterbalancing ions such as ammonium, sodium, potassium, triethanolamine and diethanolamine, particularly diethanolamine salt, as the ZONYL RP that is provided by DuPont; Perfluoro alkyl sulfonic acid amine, the FLUORAD FC-99 that provides as 3M; The perfluoro alkyl sulfonic acid ammonium, FLUORAD FC-93, the FLUORAD FC-120 and the L-12402 that provide as 3M; Perfluoro alkyl sulfonic acid potassium, the FLUORAD-95 and the FLUORAD FC-98 that provide as 3M; Fluorinated alkyl carboxylic acid potassium, the FLUORAD FC-129 and the FLURAD FC-109 that provide as 3M; Ammonium perfluoroalkylcarbox,late, the Flurad FC-143 that provides as 3M

; And which general molecular formula R _fCH ₂CH ₂SCH ₂CH ₂CO ₂Li, wherein R _f=F(CF ₂CF ₂) _3-8Fluorine surfactant, the ZONYL FSA that provides of DuPont for example.

The preferred anionic surfactants fluorine surfactant is single and enjoy a double blessing Fluoalkyl phosphate, ammonium salt mixture; The list that cooperates with the aliphatic quaternary metilsulfate and two Fluoalkyl phosphate, ammonium salt mixture; Perfluoro alkyl sulfonic acid and ammonium salt; Blended phosphate telomer diethanolamine salt; Perfluoro alkyl sulfonic acid amine; The perfluoro alkyl sulfonic acid ammonium; Perfluoro alkyl sulfonic acid potassium; Fluorinated alkyl carboxylic acid potassium; Perfluoro alkyl sulfonic acid ammonium and ammonium perfluoroalkylcarbox,late.

The both sexes fluorine surfactant that is preferred for compositions of the present invention is the fluorinated alkyl amphoteric surfactant, and it can have been bought from 3M as FLUORAD FC-100.

The amphion fluorine surfactant that is preferred for the present composition is those general molecular formula R _fCH ₂CH(OCOCH ₃) CH ₂N ⁺(CH ₃) ₂CH ₂CO - ₂Fluorine surfactant, F wherein _f=F(CF ₂CF ₂) _3-8, the ZONYL FSK that provides of DuPont for example.

Preferred both sexes or the mixture of amphion fluorine surfactant and anionic fluorinated surfactant or the mixture of anion and cation fluorine surfactant of using.

In the compositions of low volatile organic solvent content, contain particularly that to use fluorine surfactant in the compositions of silicone macromolecule polyalcohol be ideal especially.

The amount preferred about 0.01% that is included in the surfactant in the compositions is to about 2%, and more preferably from about 0.01% to about 1.5%, and most preferably from about 0.01% to about 1%.

Plasticizer

In compositions, randomly add the performance that non-volatile plasticisers can be improved styling polymer.Plasticizer generally in compositions with plasticizer: styling polymer (weight ratio) about 1: 20 to about 1: 1 existed to about 1: 2 amount in preferred about 1: 15." non-volatile " of plasticizer of the present invention is meant that this plasticizer does not produce vapour pressure basically when atmospheric pressure and 25 ℃.For polymer one liquid phase carrier solution, when volatile vehicle evaporates, should can not cause the loss of plasticizer weight basically, because may in use reduce the plasticising of polymer so greatly.Generally, the boiling point of the used plasticizer of the present invention should be at about 250 ℃ or higher.

Plasticizer is known in the prior art, and is documented in (second edition, 15 volumes, pp720-789(John Wiley ﹠amp in kirk-Othmer Encyclopedia of chemical Technology one book all sidedly; Sons, Inc.New.York, 1968)), title is " plasticizer ", and (John Wiley ﹠amp among the textbook The Technology of Plasticizers of J.kem Sears and Joseph R.Darby; Sons, Inc.New York, 1982), the two is hereby incorporated by reference document.Especially referring to the Table A .9(983-1063 in the Sears/Darby appendix), it discloses a large amount of plasticizers.

Plasticizer comprises ring-type and acyclic nonvolatile matter.The non-volatile plasticisers of suitable kind comprises adipate ester, phthalic acid ester, isophthalic acid ester, azelate, stearate, citrate, 1,2,4-benzenetricarboxylic acid ester, silicone copolyol, different C ₁₄-C ₂₂Alcohol, methyl alkyl silicone, carbonic ester, sebacate, isobutgrates, oleate, phosphate ester, myristate, ricinoleate, pelargonate, valerate, Camphora and Oleum Ricini and silicone copolyol.

The example of adipate plasticizer comprises the derivant of adipic acid, as diisobutyl adipate, two (2-ethylhexyl) esters of adipic acid, diisodecyl adipate (DIDA), two (2-butoxyethyl group) ester and the di-n-hexyl adipates of adipic acid.

The example of phthalate plasticizers comprises the derivant of phthalic acid, as dibutyl phthalate, butyl octyl phthalate, dinoctyl phthalate, diisooctyl phthalate, two (2-ethylhexyl) esters of phthalic acid, n-octyl-n-decyl phthalate, the just own ester of phthalic acid two, iso-octyl isodecyl phthalate ester, diisooctyl phthalate, ditridecyl phthalate, phthalic acid fourth cyclohexyl, butyl benzyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, two (2-butoxyethyl group) esters of phthalic acid isodecyl benzyl ester and phthalic acid.

The M-phthalic acid ester plasticiser comprises two (2-ethylhexyl) esters of M-phthalic acid.The example of azelate plasticizer comprises the derivant of Azelaic Acid, as Azelaic Acid two (2-ethylhexyl) ester and two (2-ethylhexyl) esters of Azelaic Acid.

The example of stearate plasticizer comprises stearic derivant, as stearic acid n-butyl ester, acetate butyl stearate and butoxyethyl stearate.

The example of citrate plasticizer comprises the derivant of citric acid, as citric acid acetyl three-n-butyl ester, citric acid three-n-butyl ester, citric acid acetyl three-2-Octyl Nitrite.

1,2, the example of 4-benzenetricarboxylic acid ester plasticiser comprises 1,2,4-benzenetricarboxylic acid three (2-ethylhexyl) ester and 1,2,4-benzenetricarboxylic acid three isooctyl acrylate.

The example of other plasticizer comprises dibutyl carbonate, butyl oleate, the positive butyl ester of butanoic acid, isobutyl isobutyrate (IBIB), isopropyl isobutyrate, dibutyl carbonate, ethyl palmitate, iso-octyl palmitate, methyl ricinoleate, ricinoleic acid butyl ester, Plexol 201, three iso-butyl ester of phosphoric acid, isodecyl pelargonate, ethyl valerate, 2-Methylpentadecane alcohol, EICOSANOL, isopropyl myristate, the pure and mild C of having of isostearoyl ₂-C ₂₀Alkyl, 1 is to the unitary methyl alkyl silicone of about 500 siloxanyl monomers, silicone copolyol such as dimethyl polysiloxane copolyol.

Hair spray compositions

Hair spray compositions of the present invention can spray from aerosol atomizer or pump spray.These aerosol apparatus are that container is as well known to those skilled in the art, and can buy from many maker handss, comprise American National Can company and Continental Can company.

When hair spray compositions sprays from the aerosol container of pressurization, can use one or more known aerosol propellants to advance said composition.Generally, the propellant of Shi Yonging can be the used any common liquid gas of aerosol container.

Used suitable propellant is the volatile hydrocarbon propellant, and it comprises 3～4 carbon atom liquefaction lower hydrocarbon, as propane, butane and iso-butane.Other suitable propellant is a fluorohydrocarbon, is called 1 of Dymel 152A, 2-Difluoroethane (fluorohydrocarbon 152A) as what provided by DuPont.Other propellant example is dimethyl ether, nitrogen, carbon dioxide, nitrous oxide and air.

Preferably hydrocarbon, particularly iso-butane, it can use also can mix use with other hydrocarbon.

Aerosol propellants can mix with compositions of the present invention, and the mixing consumption of propellant is determined by the known common factor of aerosol art.Generally, the propellant consumption of liquefaction is about 10% about 60%, and preferred about 15% to about 50%(with whole composition weight meters).On the other hand, can utilize the aerosol atomizer of pressurization, wherein propellant and hair spray compositions split, as the bitubular jar of being sold with trade mark SEPRO by Americal National Can company.

Other suitable aerosol atomizer is the aerosol apparatus with following feature, can utilize pump or suitable with it device handle to pack in the aerosol apparatus as the compressed air of propellant before promptly using.These aerosol apparatus are documented in the United States Patent (USP) 4,077 of Olofsson, 441(1987,3,7) and the United States Patent (USP) 4,850 of Terstege, 577(1989,7,25) in, the two is hereby incorporated by reference document; People's such as Gosselin Application No. 07/839,648(1992,2,21 applications) document also incorporated by reference.Used proper compression air aerosol container is recently by The Procter ﹠amp; Gamble company is with trade mark VIDAL SASSOON AIRSPRAY

The eruption device is sold.

Also can use common non-aerosol pump spray, i.e. nebulizer.

Other component

Hair spray prescription of the present invention can randomly comprise known various other hair spray adjuvant of prior art.Generally, compositions can comprise about 0.05% to 5%(weight), preferred about 0.1% to 3%(weight) adjuvant.The hair spray adjuvant comprises: silicone; Softening agent; Lubricant; Penetrating agent such as various lanoline chemical compound; Protein hydrolysate and other protein derivatives; The ethylene adduct; The polyoxyethylene cholesterol; Dyestuff, hair dye and other coloring agent; Sunscreen and spice.

Using method

Use hair spray compositions of the present invention can make hair fixing/maintenance hair style intact by common method.General using method is to perform before or after the hair style or front and back usefulness all, and this product of effective dose is sprayed on the dried or wet hair." effective dose " is meant under the situation of the length of having considered hair and hair quality, can reaches the consumption of desired forming hair profile and hairdo really.

The following examples have been made detailed description to the present invention.These embodiment are as an illustration purpose only, is not limitation of the present invention, and many changes of the present invention only otherwise the spirit and scope that break away from invention all are feasible.

Annotate: 1.60% tert-butyl acrylate/20% acrylic acid/20% silicone macromole (PDMS)-embodiment 1 mean molecule quantity is about 150,000; Embodiment II-VI mean molecule quantity about 1,700,000; Embodiment VII-XI V mean molecule quantity about 800,000; Embodiment X V-X VI mean molecule quantity about 120,000.

2. potassium hydroxide solution contains 45% potassium hydroxide, 55% water and micro-thing, is 10% potassium hydroxide aqueous solution but embodiment X V and X VI use.

3. dual anti-saturating infiltration.

4.ZONYL FSK contains 47% general molecular formula R _fCH ₂CH(OCOCH ₃) CH ₂N ⁺(CH ₃) ₂CH ₂CO - ₂(R _f=F(CF ₂CF ₂) _3-8) fluorine surfactant and 53% acetic acid and micro-thing, it is by E.I.DuPont de Nemours ﹠amp; Co., Inc.(Wilmington, Delaware USA) provides.

5.2-amino-2-methyl-1-propanol.

The preparation hair spray is: form the premix of polymer earlier in isopropyl alcohol, and then add ethanol.Embodiment I, X V and X VI are that polymer directly is added in the ethanol.Utilize magnetic moving or air agitator mixing each component is dissolved until polymer, be generally about 1 to 2 hour.If desired, add nertralizer (KOH or AMP, or the two) and mix again with premix.Fluorine surfactant, any salt and water (as the words of usefulness) are sneaked in the compositions subsequently.

Also adjuvant be can in compositions, add, spice or aromatic substance for example comprised.The hair spray compositions of this preparation is particularly suitable for adopting the form of pump spray.The characteristics of this compositions are to have good sprayability and constancy.

Embodiment X VII

The present invention is suitable for being prepared as follows of hair spray compositions of pump spray:

Component weight %

Ethanol, 200 degree 78.5

Isopropyl alcohol 10.4

Surely send out polymer ¹2.6

KOH（45%） 0.7

DRO water 7.0

FLUORAD FC-120 ²0.4

ZONYL FSK 0.5

1.60% tert-butyl acrylate/20% acrylic acid/20%PDMS macromole, mean molecule quantity about 1,700,000.

2.FLUORAD FC-120 is by Minnesota Mining and Manufacturing Co.(3M) (st.Paul, Minnesota USA) provide, and contain 25% perfluoro alkyl sulfonic acid ammonium, 37.5% ethanol, 37.5% water and micro-thing.

Preparation is as embodiment I-X VI.

Embodiment X VIII

Component weight %

Ethanol, 200 degree 89.1

Surely send out polymer ¹2.6

KOH（45%） 0.7

DRO water 7.0

FLUORAD FC-120 ²0.1

ZONYL FSK 0.5

Preparation is as embodiment I-X VI.

Embodiment X IX

Component weight %

Ethanol, 200 degree 78.8

Isopropyl alcohol 10.4

Surely send out polymer ¹2.6

KOH（45%） 0.8

KRO water 7.0

FLUORAD FC-120 ²0.4

ZONYL FSK 0.04

1.60% tert-butyl acrylate/20% acrylic acid/20%PDMS macromole, mean molecule quantity about 580,000.

Preparation is as embodiment I-X VI.

Embodiment XX-XX II

EXAMPLE Example embodiment

XX XXI XXII

Component (Wt %) (Wt %) (Wt %)

Ethanol, 200 degree 71.1 71.2 71.2

Isopropyl alcohol 9.5 9.5 9.5

Surely send out polymer ¹2.4 2.4 2.4

KOH?(45%) 0.6 0.6 0.6

DRO water 16.2 16.2 16.2

ZONYL TBS ²0.15 - 0.05

ZONYL?FSK 0.05 0.1 0.07

1,60% tert-butyl acrylate/20% acrylic acid/20%PDMS macromole, mean molecule quantity about 800,000.

2.ZONYL the TBS anion surfactant is provided by DuPont, contains 30-35% perfluoro alkyl sulfonic acid ammonium salt, 2.4% acetic acid and 65-70% water.

Embodiment I-X VI is pressed in preparation.

Embodiment XX III-XX V

EXAMPLE Example embodiment

XXIII XXIV XXV

Component (Wt %) (Wt %) (Wt %)

Ethanol, 200 degree 78.9 79.4 78.2

Isopropyl alcohol 10.4 10.4 11.2

Surely send out polymer ¹2.6 2.6 2.6

AMP 0.2 - -

KOH?(45%) 0.5 0.4 0.5

DRO water 7.0 7.0 7.0

FLUORAD?FC-120 0.1 0.1 0.2

ZONYL?FSK 0.05 0.05 0.09

ZONYL?TBS 0.07 - -

Aromatic substance 0.07 0.03-

The 1.60% acrylic acid tert-butyl group/20% acrylic acid/20% silicone macromole, mean molecule quantity is about 860,000(embodiment XX III), 1,500,000(embodiment XX IV) and 1,700,000(embodiment XX V).

Embodiment IX-X VI is pressed in preparation.

Embodiment XX VI

The present invention is suitable for being prepared as follows of hair spray concentrate composition of aerosol atomizer:

Component weight %

Ethanol, 200 degree 95.8

Surely send out polymer ¹3.0

KOH 0.6

AMP 0.4

ZONYL FSK ²0.25

1.60% tert-butyl acrylate/20% acrylic acid/20% silicone macromole, mean molecule quantity about 690,000.

2.ZONYL FSK is provided by DuPont, contains 40% list that cooperates with the aliphatic quaternary Methylsulfate and a two Fluoalkyl phosphate and ammonium salt, 15% isopropyl alcohol and 40-45% water.

Embodiment I-X VI is pressed in preparation.Concentrate packaging is in common aerosol spray jar and charge into common liquefied propellant, propellant: concentrate (weight ratio) is 30: 70.

Embodiment XX VII-XXX

Component XXVII XXVIII XXIX XXX

Ethanol, 200 degree 79.3 80.1 79.3 79.5

Isopropyl alcohol 10.4 10.4 10.4 10.4

Surely send out polymer ¹2.6---

Surely send out polymer ²-1.8--

Surely send out polymer ³--2.0-

Surely send out polymer ⁴---1.8

KOH (10% aqueous solution)--1.2 1.2

KCl (10% aqueous solution) 0.6 0.6--

DRO water 7.0 7.0 7.0 7.0

Potassium chloride 0.10 0.10 0.10 0.10

The amino own ester of the 1.15% methacrylic acid tert-butyl group/15% tert-butyl group acrylamide/70% ethyl methacrylate, mean molecule quantity about 1,200,000.

2.15% t-butylaminoethyl methacrylate/15% tert-butyl group acrylamide/60% ethyl methacrylate/10%PDMS macromole (mean molecule quantity about 10,000), mean molecule quantity about 1,200,000.

3.15% N,N-DMAA/70% isobutyl methacrylate/15% acrylic acid, mean molecule quantity about 1,200,000.

4.15% N,N-DMAA/60% isobutyl methacrylate/15% acrylic acid/10%PDMS macromole (mean molecule quantity about 10,000), mean molecule quantity about 1,200,000.

Embodiment I-X VI is pressed in preparation, except embodiment XX VII and XX VIII, adds the HCl as nertralizer.

When above-mentioned composition is used for hair, the sprayability that shows and provide send out effect surely.

In the above embodiments, to having adopted the compositions of grafting silicone macromole molding resin, viscosity is about 10,000 when removing 25 ℃, 000 centistoke or come the purification molding resin less than the silicon cave macromole graft polymers and the unreacted siliceous one monomers of this value may be ideal.For example can finish this process by hexane extraction.Behind the resin of drying from reaction dissolvent, can be by adding excessive hexane to product and being heated to the hexane extraction of finishing product near the Tg temperature of the non-silicone part of polymer.Keep mixture under this temperature, to stir about 30 minutes, be cooled to room temperature again.Remove hexane by vacsorb.Preferably by the twice above hexane extracting that circulate of above-mentioned same method.After the circulation, remove the residual hexane of staying in the product for the third time by distillation and vacuum drying.

Utilize about 1 hour of low-molecular-weight monomer that contains polysiloxanes of supercritical carbon dioxide dissolving and polymer, then by keeping carrier pipe with the same constant temperature and pressure of extraction vessel that itself and remaining polymer are separated and being transported away.Extract collects in the extraction vessel.After the extraction, system decompression is also dry, reclaims the polymer that obtains extracting from the extracting container.

Claims

1, a kind of liquid shaping composition that erupts usefulness is characterized in that described compositions comprises:

(a) mean molecule quantity is at least 300,000 ion and sends out polymer surely;

(c) the ionic strength adjustor system of the effective dose of reduction composition viscosity, described system is made up of monomer cation and the anionic mixture of monomer substantially, wherein said cation and anion are non-surface active, and are dissolvable in water in the described liquid phase carrier to small part;

The pH value of described compositions is equal to or less than 10.

2, liquid shaping composition as claimed in claim 1, it comprises 0.1%-15%(weight) the described polymer of sending out surely, 80%-99.5%(weight) described liquid phase carrier, 0.01%-4%(weight) described ionic strength adjustor system.

3, liquid shaping composition as claimed in claim 2, wherein said monomer cation is selected from monovalence metal, divalent metal, quaternary ammonium and cationic amine.

4, liquid shaping composition as claimed in claim 3, wherein said cation are sodium, potassium, magnesium or their mixture.

5, liquid shaping composition as claimed in claim 3, wherein said monomer anion is selected from chloride, sulfate, acetate, citrate and nitrate.

6, liquid shaping composition as claimed in claim 5, wherein said anion are sulfate, acetate, chloride or their mixture.

7, liquid shaping composition as claimed in claim 1, the mean molecule quantity that wherein said ion is sent out polymer surely is at least 500,000.

8, liquid shaping composition as claimed in claim 1, wherein said ion are decided the bill body and are comprised the ion monomer of 2%-75% and the non-ionic monomer of 25%-98%.

9, liquid hair spray compositions as claimed in claim 8, wherein said ion monomer are acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, maleic acid, maleic anhydride half-ester, butenoic acid, itaconic acid, diallyldimethylammonium chloride, vinylpyridine, vinyl imidazole, styrene sulfonate (ester) or their mixture.

10, liquid hair spray compositions as claimed in claim 9, wherein said non-ionic monomer is selected from C ₁-C ₂₄Acrylate, the C of alcohol ₁-C ₂₄Methacrylate, styrene, polystyrene macromolecular, vinylacetate, vinyl chloride, vinyl propionic ester, vinylidene chloride, α-Jia Jibenyixi, t-butyl styrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene and their mixture of alcohol.

11, a kind of liquid shaping composition that erupts usefulness is characterized in that said composition comprises:

(a) mean molecule quantity is at least 300,000 ion and sends out polymer surely; This ion is sent out polymer surely and is comprised the monomer that contains silicone, and wherein when dry compositions, this sends out the continuous phase that polymer is separated into the discontinuous phase that comprises this polymer silicone part and comprises non-silicone part surely;

(b) be selected from water, C ₂-C ₄The liquid phase carrier of monohydric alcohol and their mixture;

(c) the ionic strength adjustor system of the effective dose of reduction composition viscosity, this system is made up of monomer cation and the anionic mixture of monomer substantially, wherein said cation and anion are non-surface active, and are dissolvable in water in this liquid phase carrier to small part;

The pH value of said composition is equal to or less than 10.

12, as the liquid shaping composition of claim 11, wherein said polymer comprise at least 0.5% contain the macromolecular monomer of silicone.

13, as the liquid shaping composition of claim 12, it comprises ion monomer and the 5%-95% non-ionic monomer of 5%-95%.

14, as the liquid shaping composition of claim 11, wherein said monomer cation is selected from monovalence metal, divalent metal, quaternary ammonium and cationic amine.

15, as the liquid styling polymer of claim 12, wherein said cation is sodium, potassium, magnesium or their mixture.

16, as the liquid styling polymer of claim 12, wherein said monomer anion is selected from chloride, sulfate, acetate, citrate and nitrate.

17, as the liquid shaping composition of claim 16, wherein said anion is sulfate, acetate, chloride or their mixture.

18, as the liquid shaping composition of claim 11, the mean molecule quantity that wherein said ion is sent out compositions surely is at least 500,000.

19, a kind of liquid shaping composition that erupts usefulness is characterized in that said composition comprises:

(a) mean molecule quantity is at least 300,000 ion and sends out polymer surely; Described ion monomer comprise have a following general formula contain the silicone macromonomer:

Wherein X is a vinyl group; Y is a divalent linker; R is hydrogen, low alkyl group, aryl or alkoxyl; Z is the monovalence siloxane polymerization part of mean molecule quantity at least 500; N is 0 or 1; M is an integer of 1～3;

(b) be selected from water, C ₂-C ₄Liquid phase carrier in monohydric alcohol and their mixture;

(c) the ionic strength adjustor system of the effective dose of reduction composition viscosity, this system is made of monomer cation and the anionic mixture of monomer substantially, wherein said cation and anion are non-surface active, and are dissolvable in water in the described liquid phase carrier to small part; The pH value of said composition is equal to or less than 10.

20, as the liquid hair spray compositions of claim 19, the wherein said silicone macromonomer that contains is:

Wherein m is 1,2 or 3; P is 0 or 1; Q is an integer of 2～6; X is

, R ¹Be-H or-COOH, R ²Be-H ,-CH ₃, or CH ₂COOH, R ⁴Be alkyl, alkoxyl, alkylamino, aryl or hydroxyl; Z is

R wherein is the integer of 5-700.

21, as the liquid hair spray compositions of claim 11, wherein said ion monomer is acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, maleic acid, maleic anhydride half-ester, butenoic acid, itaconic acid, diallyldimethylammonium chloride, vinylpyridine, vinyl imidazole, styrene sulfonate (ester) or their mixture.

22, as the liquid hair spray compositions of claim 21, wherein said polymer comprises the ion monomer of 15%-80%, the non-ionic monomer of 50%-90% and the described siliceous one monomers of 2%-25%, and wherein non-ionic monomer is selected from C ₁-C ₂₄Acrylate, the C of alcohol ₁-C ₂₄Methacrylate, styrene, polystyrene macromolecular body, vinylacetate vinyl chloride, vinyl propionic ester, vinylidene chloride, α-Jia Jibenyixi, t-butyl styrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene and their mixture of alcohol.

23, as the liquid hair spray compositions of claim 20, wherein said ion monomer is acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, maleic acid, maleic anhydride half-ester, butenoic acid, itaconic acid, diallyldimethylammonium chloride, vinylpyridine, vinyl imidazole, styrene sulfonate (ester) or their mixture.

24, as the liquid hair spray compositions of claim 22, wherein said polymer comprises the ion monomer of 15%-80%, the described siliceous one monomers of the non-ionic monomer of 50-90% and 2%-25%, and wherein non-ionic monomer is selected from C ₁-C ₂₄Acrylate, the C of alcohol ₁-C ₂₄Methacrylate, styrene, polystyrene macromolecular body, vinylacetate, vinyl chloride, vinyl propionic ester, vinylidene chloride, α-Jia Jibenyixi, t-butyl styrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene and their mixture of alcohol.

25, a kind of liquid hair spray product comprises hair spray compositions and can hold and spray the sprayer device of said composition, and said compositions is packaged in the said spray apparatus device, it is characterized in that said hair spray compositions comprises:

(a) contain the macromolecular ion of silicone and send out polymer surely;

(b) be selected from water, C ₁-C ₆The liquid phase carrier of monohydric alcohol and their mixture;

(c) the ionic strength adjustor system of the effective dose of reduction composition viscosity, this system is made of monomer cation and the anionic mixture of monomer substantially, wherein said cation and anion are non-surface active, and are dissolvable in water in the described liquid phase carrier to small part; The pH value of said composition is equal to or less than 10, and contains 10%-90%(weight) water and 10%-80%(weight) described monohydric alcohol.

26, as the liquid hair spray product of claim 25, it comprises 0.1%-15%(weight) send out polymer, 80%-99.5%(weight surely) be selected from C ₂-C ₄The liquid phase carrier of monobasic alcohol and water and 0.01%-4%(weight) the ionic strength adjustor system.

27, as the liquid hair spray product of claim 26, monomer cation wherein is selected from monovalence metal, divalent metal, quaternary ammonium and cationic amine.

28, as the liquid hair spray product of claim 27, cation wherein is sodium, potassium, magnesium or their mixture.

29, as the Hairstyling composition of the liquid hair spray product of claim 27, monomer anion wherein is selected from chloride, sulfate, acetate, citrate and nitrate.

30, as the liquid hair spray product of claim 29, anion wherein is sulfate, acetate, chloride or their mixture.

31, as the liquid shaping composition of claim 12, it comprises the ion monomer of 5%-95% and the non-ionic monomer of 5%-95%, wherein said polymer contain at least about 0.5% contain the silicone macromonomer.

32, as the hair spray product of claim 31, its intermediate ion is sent out polymer monomer surely and is comprised and contain the macromolecular monomer of silicone that this monomer general formula is:

Wherein X is a vinyl group; Y is a divalent linker; R is hydrogen, hydroxyl, low alkyl group, aryl, alkylamino, alkaryl or alkoxyl; Z is the monovalence siloxane polymerization part of mean molecule quantity at least 500; N is 0 or 1; M is an integer of 1～3.

33, as the liquid hair spray product of claim 32, wherein said ion monomer is acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, maleic acid, maleic anhydride half-ester, butenoic acid, itaconic acid, diallyldimethylammonium chloride, vinylpyridine, vinyl imidazole, styrene sulfonate (ester), the salt of above-mentioned amine or acid, or their mixture.

34, as the liquid hair spray product of claim 33, wherein said polymer comprises the ion monomer of 15%-80%, the non-ionic monomer of 50%-90% and the siliceous one monomers of 2%-25%, and wherein said non-ionic monomer is selected from C ₁-C ₂₄Acrylate, the C of alcohol ₁-C ₂₄Methacrylate, styrene, polystyrene macromolecular body, vinylacetate, vinyl chloride, vinyl propionic ester, vinylidene chloride, α-Jia Jibenyixi, t-butyl styrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene and their mixture of alcohol.

35, a kind of method that can reach the effect of well haircuting comprises the compositions of spraying the claim 1 of effective dose to hair.

36, a kind of method that can reach the effect of well haircuting comprises the compositions of spraying the claim 11 of effective dose to hair.

37, a kind of method that can reach the effect of well haircuting comprises the compositions of spraying the claim 19 of effective dose to hair.

38, a kind of method that can reach the effect of well haircuting comprises the claim 25 product combination thing that sprays effective dose to hair.