CN1259033A

CN1259033A - Hair spray compositions

Info

Publication number: CN1259033A
Application number: CN 98805780
Authority: CN
Inventors: 桑杰夫·米德哈; 小雷蒙德·E·博利希; 凯瑟琳·B·杰维登
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1997-04-25
Filing date: 1998-04-24
Publication date: 2000-07-05
Also published as: EP0977542A1; AU7160598A; WO1998048771A1; BR9812296A; CA2288040A1; JP2001507368A

Abstract

The present invention relates to hair styling compositions and in particular to hair spray compositions. These compositions comprise a silicone containing adhesive copolymer, and a solvent for said copolymer selected from the group consisting of water, ethanol, n-propanol, isopropanol, and mixtures thereof. The spray compositions, when dried, have a cohesive strength of greater than about 0.5 kgf/mm<2>, a total energy absorption per unit volume of greater than about 0.55 kgfmm/mm<3> and, preferably an impact strength of greater than about 7000 ergs. The hair spray embodiments of the present invention preferably provide improved removeability from hair as defined by a hair stiffness value of from 0 to about 3.5 (0 to 4 scale) and a hair flaking value of from 0 to about 3.5 (0 to 4 scale) as determined by the removeability methodology defined herein.

Description

Hairspray compositions

Technical field

The present invention relates to hair setting composition, comprise Hairspray compositions, particularly have the Hairspray compositions of improved removability from hair, this removability is defined by hair hardness number and the hair value of delaminating.These Hairspray compositions provide good hair style retention performance, and can not harden or be clamminess.These compositionss contain the adhesive copolymer of siloxanes and the solvent that this copolymer is used, and this solvent is selected from water, ethanol, normal propyl alcohol, isopropyl alcohol and composition thereof.The adhesion strength of this Hairspray compositions during dry state is greater than about 0.5kgf/mm ², per unit volume total absorption energy greater than about 0.55kgfmm/mm ³Said composition during dry state preferably also presents the impact strength greater than about 7000 ergs.

Background of invention

People generally wish to make hair to keep specific shape.Realize that this ideal modal method is from the aerosol container of mechanical holdable pump spray apparatus or pressurization compositions to be sprayed onto on the hair usually.This compositions provides temporary transient fixedly benefit, usually can water or hair washing send out and remove.The material of using in the Hairspray compositions is resin, natural gum and binder polymer normally.

Many people wish that the hair style that obtains height from Hairspray compositions keeps or reservation.There is shortcoming in most of present Hairspray compositions.Eruption product with good retention performance when drying often too firmly or too sticking.The compositions of hardening is brittle often and rupture under as bending, brushing, combing at common stress.The compositions of hardening often feels and looks unnatural.The compositions that is clamminess has overcome many aforesaid drawbacks of the compositions of hardening, because it is more flexible often and hair is finalized the design again to issue tacking compositions at stress.But the compositions that is clamminess stays thick, coating sense to hair, and makes hair have soft and unengaging outward appearance.Simultaneously, be clamminess compositions make hair rapidly by common polluter such as dust, foul, cotton fiber, sebum etc. make dirty.Therefore, need a kind ofly to provide good hair style to keep and do not harden or the Hairspray compositions of the shortcoming of the compositions that is clamminess.

The present invention provides the Hairspray compositions that has good hair style maintenance and can not harden or be clamminess astoundingly.Under common stress condition and above-mentioned other factors, keep finely by the hair style of using these compositionss to obtain.Importantly, this based composition provides the permission user that hair is finalized the design once more and has not needed repaste to apply the benefit of eruption product.Hairspray compositions of the present invention touches up hair and looks all very natural.Simultaneously, these products do not have and make rapidly dirty once more shortcoming of hair.

Because consumer is to the growing understanding of environment, so need reduce the Hairspray compositions of VOC (being VOC) amount.Usually the Hairspray compositions that has reduced the VOC amount contains 80% or still less VOC, and the Hairspray compositions of convention amount VOC contains the VOC greater than 80%.In certain embodiments, Hairspray compositions of the present invention can be mixed with the Hairspray compositions that has reduced the VOC amount.

Contain the binder copolymer of some siloxanes and the solvent that this copolymer is used by use, compositions of the present invention provides described benefit, and described solvent is selected from: water, ethanol, normal propyl alcohol, isopropyl alcohol and composition thereof.The adhesion strength of these Hairspray compositions during dry state is greater than about 0.5kgf/mm ², per unit volume total absorption energy greater than about 0.55kgfmm/mm ³, preferred impact strength is greater than about 7000 ergs.Without being limited by theory, these physical characteristics that it is believed that exsiccant Hairspray compositions have been explained viewed benefit.

Find also that now preferred Hairspray compositions of the present invention has improved removability from hair in the hair washing process, wherein removability defines with 0 hair hardness number and hair value of delaminating (flaking value) to about 3.5 (0-4 scales).These hair hardness numbers and the hair value of delaminating are the indirect measurements of Hairspray compositions removability.Defined method is determined each of these values according to the present invention.

Therefore, an object of the present invention is to provide hair setting composition, Hairspray compositions especially, it provides improved hair style to keep or lasting benefit, and can not make hair harden or be clamminess.

Another object of the present invention provides the Hairspray compositions that looks and touch up all nature.

Another object of the present invention provides the Hairspray compositions that satisfies conventional VOC amount and reduced the requirement of VOC amount.

Another object of the present invention provides shaping hair and makes the persistent method of hair.

By following detailed, these and other objects will be conspicuous.

Summary of the invention

The present invention relates to hair setting composition, Hairspray compositions especially, it comprises:

(a) contain the adhesive copolymer of siloxanes, its weight average molecular weight is 10,000-5,000,000;

(b) the used solvent of described copolymer, it is selected from water, ethanol, normal propyl alcohol, isopropyl alcohol and composition thereof,

Wherein the adhesion strength of this Hairspray compositions during dry state is greater than 0.5kgf/mm ², per unit volume total absorption energy greater than about 0.55kgfmm/mm ³This Hairspray compositions preferably also has improved removability from hair, and wherein this removability is defined by 0 hair hardness number and 0 hair value of delaminating to about 3.5 (0-4 scales) to about 3.5 (0-4 scales).

In other embodiments, the present invention relates to impact strength when dry state greater than the Hairspray compositions of about 7000 ergs.

In other embodiments, the present invention relates to shaping hair and/or make the persistent method of hair, it comprises that compositions with effective dose is coated on the step on the hair, said composition contains:

Wherein the adhesion strength of this Hairspray compositions during dry state is greater than 0.5kgf/mm ², per unit volume total absorption energy greater than about 0.55kgfmm/mm ³

Brief Description Of Drawings

Fig. 1 is for being used to measure physical property, as described herein the vertical view of the plane exsiccant Hairspray compositions membrane sample of total endergonic dumbbell shape of adhesion strength and per unit volume.

Fig. 2 is for showing the cross-sectional view of dumbbell shape desciccator diaphragm thickness shown in Figure 1.

Detailed Description Of The Invention

Necessary component of the present invention is as described below. Also comprise the description of the non-exclusionism of various optional and preferred ingredient used in embodiment of the present invention.

The present invention can comprise any required or optional component, and/or qualifications described here, or by above-mentioned these form or basically by above-mentioned these form the institute consist of.

Unless otherwise noted, all percentage and ratio are all take weight as benchmark. Unless otherwise noted, all percentage number averages are based on whole composition meters.

All molecular weight all are weight average molecular weight, and g/mol to provide as unit.

Unless otherwise noted, the content of all components all refers to the effective content of this component, and does not comprise solvent, accessory substance, or other impurity that may exist in the commercially available source of goods.

Unless otherwise noted, all measurements are all carried out under ambient room temperature, and it is about 73 °F.

All documents of institute of the present invention reference comprise the publication of patent, patent application and printing, and it is introduced the present invention as a reference in full.

Terminology used here " is applicable to people's hair ", refers to that described composition or its component are applicable to hair, scalp and the skin contact with the people, and can not bring unsuitable toxicity, incompatibility, unstability, allergic reaction etc.

Term kgf is that the acceleration of gravity that expression is subject to is 9.82m/s²The standard physical term of kilogram.

The binder copolymer of silicone-containing

Composition of the present invention contains about 0.1-30% of composition weight, preferably about 0.5-20%, the adhesive copolymer of the silicone-containing of 0.5-10% more preferably from about.

" adherence " refers to that this copolymer forms film or combination when its form with solution is applied to a surface such as hair fiber and drying. Such just as one of ordinary skill in the understanding, this film or combination have certain adhesion strength and cohesive strength.

" silicone-containing " means copolymer and contains one or more alkyl or aryl oxyalkylene segments, as in the specification further definition.

Copolymer of the present invention is selected from: silicone block copolymer that polysiloxane grafted copolymer, the copolymer of siloxane blocks, the copolymer that contains the siloxanes of sulphur connection, sulphur connect and composition thereof.

Term " polysiloxane grafted copolymer " is that the those of ordinary skill in polymer science field is familiar with, and the present invention uses this term to describe polymer siloxane part (i.e. " graft ") added or be grafted on another polymer moieties that is commonly referred to " main chain " and the copolymer of generation.The molecular weight of main chain is usually than grafted height.Therefore, polysiloxane grafted copolymer can be described as having the polymer of polymer siloxane side chain, its by with polymer siloxane side chain " grafting " to or join on the main polymer chain and form.Main polymer chain can be homopolymer or copolymer.Graft copolymer is derived by multiple monomeric unit.In addition, these copolymers can contain from the graft of the big monomer derived that contains non-silicone, as and big monomer that form partially polymerized by acrylate, methacrylate and other alkene.Can select these big monomers to have the Tg value of height (＞25 ℃) or low (＜25 ℃).Term Tg refers to glass transformation temperature, and it is that the those of ordinary skill in polymer science field is familiar with.

Term " block copolymer " is that the those of ordinary skill in polymer science field is familiar with, and this paper uses this term to describe to have the copolymer of tactic part or block (it further is made of less repetitive).Block copolymer of the present invention comprises siloxane blocks and non-silicone block.Block copolymer can be represented by following structure: the A-B structure, and it contains two block segments; The A-B-A structure, it contains three block segments; With-(A-B) _n-, wherein n is 2 or bigger integer, it contains a plurality of blocks.

Term in term " sulfur connect polysiloxane grafted copolymer " and " silicone block copolymer that sulfur is connected " " the sulfur connection " means and contains the sulfur connection (promptly-S-), disulfide bond (promptly-S-S-) and sulfydryl (copolymer polysiloxane grafted or block promptly-SH).

Copolymer of the present invention or its salt are that solubilized maybe can be scattered in the solvent, this solvent is selected from: water, ethanol, normal propyl alcohol, isopropyl alcohol and composition thereof, its concentration under about 73 is at least about 0.1 mg/ml, preferably at least about 0.5 mg/ml with more preferably at least about 1 mg/ml.

The weight average molecular weight of copolymer of the present invention is at least about 10,000, and its unit is a gram/mole.Molecular weight does not have the upper limit, but except those molecular weight owing to restriction practicality of the present invention such as the reason of reality such as viscosity, processability, aesthetic characteristic spreadability, the preparation compatibilitys.Weight average molecular weight is usually approximately less than 5,000, and 000, more generally approximately less than 2,500,000, typically usually approximately less than 1,500,000.Weight average molecular weight preferably is about 10,000-5,000,000, be more preferably 20,000-1,000,000, further preferably be about 30,000-500,000, be most preferably 50,000-300,000.

The various adhesive copolymers that contain siloxanes can be used among the present invention, as long as satisfy the physical parameter of exsiccant Hairspray compositions film and the dissolubility or the dispersibility of copolymer requires and the molecular weight requirement.

Polysiloxane grafted copolymer

Polysiloxane grafted copolymer of the present invention is formed by vinyl monomer unit and the random copolymerization that contains the big monomeric unit of polysiloxane, this big monomeric unit contain a polymer moieties and one can with the vinyl segment of vinyl monomer unit copolymerization.After polyreaction was finished, the siloxane polymer of big monomeric unit partly formed the polysiloxanes side chain of copolymer.The vinyl monomer unit of big monomeric unit and vinyl segment form main chain.Vinyl monomer can be selected from various structures with the big monomeric unit that contains polysiloxanes, as long as copolymer has desired properties described in the invention.

Just as one of ordinary skill in the known, especially clearer from embodiment, copolymer can have one or more polysiloxanes side chains that are grafted on the main chain.In addition, except that described copolymer, compositions of the present invention can comprise a spot of corresponding copolymer that does not contain the polysiloxanes side chain that is grafted on the main chain.As well known in the art, synthetic graft copolymerization process can produce the mixture of polymer molecule, and this mixture does not contain, contains the one or more polysiloxanes side chain that is covalently bound on the main polymer chain and becomes its side chain.The number-average molecular weight of the amount of the side chain from polymer samples and number-average molecular weight, polymer samples can calculate the average number of the polysiloxanes side chain in each main polymer chain.

Grafted copolymer should satisfy following three conditions:

(1) copolymer is separated when drying, forms discontinuous phase that comprises the polymers grafted pendant moiety and the continuous phase that comprises non-pendant moiety;

(2) the polymer side chain part links to each other with main chain part covalency; With

(3) number-average molecular weight of polymer side chain part is about 1000～50000.

Without being limited by theory, it is believed that the performance that is separated makes copolymer have special orientation, this will bring required sense of touch, film forming or bond properties, and the combination property of exsiccant ability promptly and up hill and dale.The phase separation property of the present composition can followingly be measured.

With copolymer curtain coating from solvent is solid film.Then this film is cut and under transmission electron microscope, detect.Shown the existence of micron-scale phase separation by observation to alloy in the continuous phase.These alloys should have the suitable dimension that is complementary with side chain dimensions (typically, being hundreds of nm or littler), and the proper density that is complementary with the side chain amount.For polymer with this structure, this behavior be recorded in the document (for example referring to, the thesis for the doctorate of S.D.Smith, University of Virginia, 1987, and its list of references of quoting, this paper all be incorporated by herein with reference to).

Polyreaction by vinyl monomer and polysiloxane macromonomer prepares copolymer of the present invention.Copolymer can be incompatible synthetic by monomer and big monomeric radical polymerization.The General Principle of radical polymerization is that people are known.For example referring to, Odian, " polymerization principle ", the 3rd edition, John Wiley﹠amp; Sons, 1991, pp.198-334.Required vinyl monomer and polysiloxane macromonomer are all placed a reactor, together with the mutual solvent of q.s so that reaction when finishing its viscosity reasonable.Remove undesirable terminator, particularly oxygen on demand.This realizes as argon or nitrogen wash by finding time or using noble gas.If use thermal initiator, then introduce initiator and reaction is risen to initiation required temperature takes place.Or, also can use oxidoreduction or radiation initiator system.Make polyreaction proceed to the high conversion that will reach as required, the time is several hours to several days usually.By evaporation or adding non-solvent the copolymer precipitation being removed desolvates.Copolymer can be further purified as required.

As substituting of batchwise polymerization, can prepare copolymer by semicontinuous or continuous polymerization.In semi-continuous process, to carry out twice in the polymerization process or repeatedly monomer or monomer addition greatly.When copolymer by several polymerizations in the different monomer of reaction rate when making, this is favourable.In the monomer ratio that the different feed points that react add, can regulate by those of ordinary skill in the art, make final polymer product have more uniform structure.In other words, for the monomer that adds the each type in the reaction, final polymer product will have the content of monomer distribution of homogeneous more.

The example of related copolymers and their preparation are described in detail in the U.S.P.4693935 of the Mazurek that 1987.9.15 authorizes, and the U.S.P.4728571 of the Clemens that 1988.3.1 authorizes etc. draws it here and is reference.Other silicone grafted polymers also is described in EPO application 90307528.1 by Hayama etc., apply for that as EPO 0408311 A2 is open at 1991.1.11,1991.10.29 the U.S.P.5061481 of the Suzuki that authorizes etc., 1992.4.21 the U.S.P.5106609 of the Bolich that authorizes etc., 1992.3.31 the U.S.P.5100658 of the Bolich that authorizes etc., 1992.3.31 the U.S.P.5100657 of the Ansher-Jackson that authorizes etc., 1992.4.14 the U.S.P.5104646 of the Bolich that authorizes etc., 1991.8.27 the U.S. serial number 07/758319 of the Bolich of application etc., with the U.S. serial number 07/758320 of the Torgerson of 1991.8.27 application etc., the full content of all these all draws here and is reference.

Polymerization by vinyl monomer and polysiloxane macromonomer prepares copolymer.Copolymer compositions is characterised in that and adds each monomeric amount in the polymer reactor, perhaps is each used monomeric amount in continuous or the semi-continuous process on the other hand.

By suitable selection with make up concrete vinyl monomer unit and the polysiloxane macromonomer unit, and by selecting each unitary concrete relative scale in those of ordinary skills' limit of power, in the various physical properties of copolymer and the hair care purposes usually the compatibility of other used component can optimize.

Vinyl monomer unit

Silicone copolymers of the present invention contains the 50-98% that has an appointment, preferably about 60-95%, the vinyl monomer unit of 70-90% weight more preferably from about.

But vinyl monomer unit is selected from the monomer of copolymerization, preferably ethylenically unsaturated monomer.Can use the combination of vinyl monomer unit or two or more vinyl monomer units of single type.Select vinyl monomer to satisfy the needs of copolymer.Used " but the copolymerization " of the present invention means is using one or more conventional synthesis techniques, in the polyreaction as ion, emulsion, dispersion, Ziegle-Natta, free radical, group transfer or step growth polymerization, vinyl monomer can with polysiloxane macromonomer reaction or with its polymerization.But preferably use the monomer and the big monomer of conventional free radical elicitation technique copolymerization among the present invention.Terminology used here " olefinic is unsaturated " is meant, contains at least one polymerisable carbon-to-carbon double bond, and it can be one, two, three or quaternary material.

Monomeric unit can be the mixture from hydrophilic monomer (normally polar monomer) or this class hydrophilic monomer and hydrophobic monomer (normally low polar monomer), as long as satisfy the dissolubility property of whole copolymer.Used " hydrophilic monomer " of the present invention means and forms the monomer of water-soluble homopolymer basically; And " hydrophobic monomer " means and forms the monomer of water-insoluble homopolymer basically.

The monomer of the unrestricted type that the present invention is used is selected from: unsaturated alcohols, the unsaturated monocarboxylic acid class, the unsaturated dicarboxylic acid class, the unsaturated acid anhydride class, the alkoxide of unsaturated monocarboxylic acid, the alkoxide of unsaturated dicarboxylic acid, the alkoxide of unsaturated acid anhydride, the oxyalkylated esters of unsaturated monocarboxylic acid, the oxyalkylated esters of unsaturated dicarboxylic acid, the oxyalkylated esters of unsaturated acid anhydride, the aminoalkyl esters of unsaturated monocarboxylic acid, the aminoalkyl esters of unsaturated dicarboxylic acid, the aminoalkyl esters of unsaturated acid anhydride, the amide-type of unsaturated monocarboxylic acid, the amide-type of unsaturated dicarboxylic acid, the amide-type of unsaturated acid anhydride, the salt of unsaturated monocarboxylic acid, the salt of unsaturated dicarboxylic acid, the salt of unsaturated acid anhydride, unsaturated hydro carbons, unsaturated heterocycle class and composition thereof.

The monomeric representative example of this class comprises acrylic acid, methacrylic acid, N, the N-DMAA, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, Methacrylamide, N tert butyl acrylamide, maleic acid, maleic anhydride and half ester thereof, butenoic acid, itaconic acid, acrylamide, the acrylate alcohols, hydroxyethyl methylacrylate, diallyldimethylammonium chloride, vinyl pyrrolidone, vinyl ethers (as methyl vinyl ether), maleimide, vinylpyridine, vinyl imidazole, other polar vinyl heterocyclic, styrene sulfonate, allyl alcohol, vinyl alcohol (as the hydrolyzate of vinylacetate after polymerization), caprolactam, the C of methacrylic acid ₁～C ₁₈The esters of alcohol, these alcohol for example are methanol, ethanol, methyl cellosolve, the 1-propanol, 2-propanol, 1-butanols, 2-methyl isophthalic acid-propanol, 1-amylalcohol, 2-amylalcohol, the 3-amylalcohol, 2-methyl-1-butene alcohol, 1-methyl isophthalic acid-butanols, 3-methyl isophthalic acid-butanols, 1-methyl-1-pentene alcohol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, the tert-butyl alcohol (2-methyl-2-propanol), Hexalin, new decanol, 2-ethyl-1-butanols, 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, 1-dodecanol, 1-hexadecanol, 1-octadecanol etc., these alcohol have 1～18 carbon atom, and preferred carbon number is 1～12; Acrylic acid dicyclopentenyl esters, acrylic acid 4-biphenyl esters; The acrylic acid pentachlorophenyl ester; Acrylic acid 3,5-dimethyladamantane ester; Methacrylic acid 3,5-dimethyladamantane ester; Methacrylic acid 4-methoxycarbonyl phenyl ester; Methacrylic acid trimethyl silyl ester; Styrene; The phenylethylene that alkyl replaces comprises α-Jia Jibenyixi and t-butyl styrene; Vinyl ester comprises vinylacetate, new n-nonanoic acid vinyl acetate, new vinyl acetate acid and propionate; Vinyl chloride; Vinylidene chloride; Vinyltoluene; Alkyl vinyl ether comprises IVE and sec-butyl vinyl ethers; Butadiene; Cyclohexadiene; Bicycloheptadiene; 2,3-dicarboxyl methyl isophthalic acid, 6-hexadiene; Ethylene; Propylene; Indenes; Norborene; Nopinene; Australene; The acid that the front is listed and the salt of amine, and composition thereof.With other monomer copolymerization of graft copolymer before or after can carry out quaternised monomer quaternary ammoniated.

Preferred monomer comprises acrylic acid, methacrylic acid, N,N-DMAA, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, vinyl pyrrolidone, the C of acrylic or methacrylic acid ₁～C ₁₈The esters of alcohol, styrene, α-Jia Jibenyixi, t-butyl styrene, vinylacetate, propionate, acrylic acid 2-methoxyl group ethyl ester, acrylic acid 2-ethoxy ethyl ester, n-BMA, isobutyl methacrylate, tert-butyl acrylate, metering system tert-butyl acrylate, methacrylic acid 2-Octyl Nitrite, methyl methacrylate, above listed any acid and the salt of amine, and composition thereof.

The polysiloxane macromonomer unit

Copolymer of the present invention contains about 2-50% of copolymer weight, preferably about 5-40%, the polysiloxane macromonomer unit of 10-30% weight more preferably from about.

The polysiloxane macromonomer unit can be with the vinyl monomer copolymerization, and described big monomeric unit preferably has vinyl segment.The present invention can use the big monomeric unit of single type or the combination of two or more big monomeric units.Select big monomeric unit to satisfy the needs of copolymer.Used " but the copolymerization " of the present invention means in the polyreaction of using one or more conventional synthesis techniques, polysiloxane macromonomer can with the vinyl monomer reaction or with its polymerization, as previously described.

But the used polysiloxane macromonomer of the present invention comprises the part of polymer moieties and copolymerization, and it is the unsaturated part of olefinic preferably.The monomer that preferred big monomer normally seals with the vinyl segment end.Used " the end envelope " of the present invention means vinyl segment on big monomeric end position or near it.

Use has the various standard synthetic methods that the polymer chemistry worker of ordinary skill is familiar with and synthesizes big monomer.And these big monomers can begin to synthesize from commercially available polymer.Big monomeric weight average molecular weight is 1000-50000 usually approximately.

Polysiloxane macromonomer is by following chemical formulation:

X(Y) _nSi(R) _3-m(Z) _m

Wherein: X be can with the vinyl of described vinyl monomer unit combined polymerization; Y is a divalent linker; Each R is independently selected from: hydrogen, hydroxyl, C ₁-C ₆Alkyl, C ₁-C ₆Alkoxyl, C ₂-C ₆Alkylamino, styryl, phenyl, C ₁-C ₆The phenyl that alkyl or alkoxyl replace; Z is that number-average molecular weight is at least 1000 monovalence siloxane polymerization part, essentially no reactivity under copolymerization conditions, and after polymerization, become the side chain of described polyvinyl main chain; N is 0 or 1; M is 1 to 3 integer.The weight average molecular weight of polysiloxane macromonomer is about 1000 to 50000, and is preferred about 5000 to 30000, more preferably from about 8000 to 25000.

Polysiloxane macromonomer is selected from following structural:

Or X-CH ₂-(CH ₂) _s-Si (R ¹) _3-m-Z _m

Or 0

。

X-C-0-(CH ₂) _q-(0) _p-Si(R ¹) _3-mZ _m

S is 0 to about 6 integer in these structures, and is preferred 0,1 or 2, more preferably 0 or 1; M is 1 to 3 integer, preferred 1; P is 0 or 1; Q is 2 to 6 integer; Each R ¹Be selected from: hydrogen, hydroxyl, C ₁～C ₆Alkyl, C ₁～C ₆Alkoxyl, C ₂～C ₆Alkylamino, phenyl, C ₁～C ₆The phenyl that alkyl or alkoxyl replace, preferred C ₁～C ₆Alkyl, or C ₁～C ₆The phenyl that alkyl or alkoxyl replace is more preferably C ₁～C ₆Alkyl, further methyl preferably; R ²Be selected from: C ₁～C ₆Alkyl or C ₁～C ₆The phenyl that alkyl replaces, preferable methyl; N is the integer of 0-4, preferred 0 or 1, be more preferably 0; X is

R ³For hydrogen or-COOH, preferably R ³Be hydrogen; R ⁴Be hydrogen, methyl or-CH ₂COOH, preferably R ⁴Be methyl; Z is

R ⁵, R ⁶And R ⁷Be independently selected from: hydrogen, hydroxyl, C ₁～C ₆Alkyl, C ₁～C ₆Alkoxyl, C ₂～C ₆Alkylamino, styryl, phenyl, C ₁～C ₆The phenyl that alkyl or alkoxyl replace, preferably R ⁵, R ⁶And R ⁷Be C ₁～C ₆Alkyl is more preferably methyl; R is about integer of 14 to 700, and preferred about 60 to 400, more preferably r is about 100 to 170.

Silicone block copolymer

The silicone block copolymer that contains polysiloxane repetition block unit also is suitable among the present invention.

The example that contains the block copolymer of siloxanes is described in following document: US5 was issued to people such as Geck on June 4th, 523,365,1996; US4 was issued to Crivello on August 25th, 689,289,1987; US4 was issued to Crivello on April 22nd, 584,356,1986; Macromolecular Design, Concept ﹠amp; Practice, M.K. Mishra edits, PolymerFrontiers International, Inc., Hopewell Jct., NY (1994), with Block Copolymers, A.Noshay and J.E.McGrath, Academic Press, NY (1977) introduces the present invention as a reference with these documents.

The block copolymer that contains siloxanes of the present invention can by general formula: A-B, A-B-A and-(A-B) _n-describe, wherein n is 2 or bigger integer.A-B represents the diblock structure, and A-B-A represents three block structures ,-(A-B) _n-represent many block structures.

The siloxane blocks part A is represented by the following polymers structure:

-(SiR ₂O) _m-

Wherein each R is independently selected from: hydrogen, hydroxyl, C ₁～C ₆Alkyl, C ₁～C ₆Alkoxyl, C ₂～C ₆Alkylamino, styryl, phenyl, C ₁～C ₆The phenyl that alkyl or alkoxyl replace, preferably wherein R is a methyl.In the formula in front, m is about 10 or bigger integer, is preferably about 40 or bigger integer, more preferably about 60 or bigger integer, most preferably be about 100 or bigger integer.

The non-silicone B block comprises and is selected from the vinyl monomer that silicone grafted copolymer described above is used.

Block copolymer can contain mixture and a spot of homopolymer of many blocks of diblock, three blocks and Geng Gao.

Contain the silicone block copolymer that the copolymer of the siloxanes that sulfur connects is connected with sulfur

Containing the silicone block copolymer that the copolymer of the siloxanes that sulfur connects is connected with sulfur also is applicable among the present invention.Just as described previously, term " sulfur connects " mean these copolymers that contain the siloxanes that sulfur connects and block copolymer contain sulfide linkage (promptly-S-), disulfide bond (promptly-S-S-) or the sulfur hydrogen bond (promptly-SH).

These contain the copolymer of the siloxanes that sulfur connects and block copolymer by following general formula:

Wherein

G ₅Expression monovalence part, it can be identical or different independently, it is selected from: alkyl, aryl, alkaryl, alkoxyl, alkylamino, fluoro-alkyl, hydrogen and-ZSA; A represents basic by the polymeric polyvinyl segment that can constitute by the monomer of radical polymerization, and Z is a divalent linker.Useful divalent linker Z includes, but is not limited to following groups: C ₁～C ₁₀Alkylidene, alkyl arylene, arlydene and alkoxyl arlydene.For the reason of commercial availability, preferred Z is selected from methylene and propylidene.

G ₆Expression monovalence part, it can be identical or different independently, it is selected from: alkyl, aryl, alkaryl, alkoxyl, alkylamino, fluoro-alkyl, hydrogen and-ZSA;

G ₂Contain A;

G ₄Contain A;

R ₁Expression monovalence part, it can be identical or different independently, it is selected from: alkyl, aryl, alkaryl, alkoxyl, alkylamino, fluoro-alkyl, hydrogen and hydroxyl.For the reason of commercial availability, preferred R ₁Expression monovalence part, it can be identical or different independently, it is selected from: C _1-4Alkyl and hydroxyl.Most preferred R ₁It is methyl.

R ₂Can be identical or different independently, the expression divalent linker.Suitable divalent linker includes, but is not limited to following groups: C ₁～C ₁₀Alkylidene, arlydene, alkyl arylene and alkoxyl arlydene.For the reason of easy synthetic compound, preferred R ₂Be selected from C ₁～C ₃Alkylidene and C ₇～C ₁₀Alkyl arylene.Most preferably, R ₂Be selected from-CH ₂-, trimethylene, and

R ₃Expression monovalence part, it can be identical or different independently, it is selected from: alkyl, aryl, alkaryl, alkoxyl, alkylamino, fluoro-alkyl, hydrogen and hydroxyl.For the reason of commercial availability, preferred R ₃Expression monovalence part, it can be identical or different independently, it is selected from: C _1-4Alkyl and hydroxyl.Most preferred R ₃It is methyl.

R ₄Can be identical or different independently, the expression divalent linker.Suitable divalent linker includes, but is not limited to following groups: C ₁～C ₁₀Alkylidene, arlydene, alkyl arylene and alkoxyl arlydene.For the reason of easy synthetic compound, preferred R ₄Be selected from C ₁～C ₃Alkylidene and C ₇～C ₁₀Alkyl arylene.Most preferably, R ₄Be selected from-CH ₂-, trimethylene, and

X is the integer of 0-3;

Y is 5 or bigger integer; Preferred y is the integer of about 14-700, and more preferably y is the integer of about 100-170;

Q is the integer of 0-3;

In the wherein following condition at least one set up:

Q is at least 1 integer;

X is at least 1 integer;

G ₅Contain at least one-the ZSA part;

G ₆Contain at least one-the ZSA part.

Just as noted earlier, A is by the formed vinyl polymerization segment of polymeric monomer by radical polymerization.The selection of A is normally based on the desired use of compositions, in order to realize the prerequisite performance of its desired use copolymer.Under the situation of block copolymer, if A contains a block, then will obtain having the polymer of AB and ABA structure, this depends on that mercapto functional group-SH is connected respectively to of silicone compounds of mercapto functional group or is connected on two end silicon atom.The weight ratio of the polyvinyl block of copolymer or segment and siloxanes segment can change.The weight ratio of polyvinyl segment and siloxanes segment is about 98: 2 to 50: 50 in the preferred copolymer, and purpose is that copolymer has each different inherent performance of polymer segment, keeps the dissolubility of whole polymer simultaneously.

The silicone copolymers that sulfur connects has been made detailed description: USP 5,468,477 in following document, authorize people such as Kumar November 21 nineteen ninety-five, and PCT application number WO95/03776, transfers 3M, February 9 nineteen ninety-five is open, and above-mentioned document is introduced the present invention as a reference in full.

Neutral copolymer

Just as known in the art, usually so that the neutral form of small part uses the polymer with acidic functionality such as carboxyl to promote the solubility/dispersibility of polymer.In addition, help exsiccant Hairspray compositions to be removed from hair with form in the use by hair washing.When in and the time, preferably, about 10-100% of copolymer, more preferably from about 20-90%, further the acid monomer of preferred about 40-85% is neutralized.

Can use any conventional alkali that uses comprise the alkali of organic or inorganic (metal or other) come in and polymer.In compositions of the present invention, metal base is useful especially.Wherein cation is that the hydroxide of ammonium, alkali metal or alkaline-earth metal is the nertralizer that is applicable to Hairspray compositions of the present invention.The preferred nertralizer that Hairspray compositions of the present invention is used is potassium hydroxide and sodium hydroxide.The example that can be included in other the suitable nertralizer in the Hairspray compositions of the present invention comprises amine, especially amino alcohol such as 2-amino-2-methyl-1, ammediol (AMPD), 2-amino-2-ethyl-1, ammediol (AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanols (AB), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), an isopropanolamine (MIPA), diisopropanolamine (DIPA) (DIPA), triisopropanolamine (TIPA) and dimethyl stearylamine (DMS).Particularly preferred nertralizer is the mixture of amine and metal base.

Polymer with basic functionality such as amino preferably neutralizes with sour example hydrochloric acid to small part.

Can realize neutralization by technology well known in the art, before or after containing the monomer polymerization of graft copolymer.

As described above, the dissolubility of copolymer should be measured in neutralization (if carrying out) with after other component that copolymer/dicyandiamide solution can contain adds.

The preferred polymer of the present invention

The non-limiting instance of preferred polymer of the present invention comprises that those are selected from following material: poly-[(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-acrylic acid)-grafting-poly-(dimethyl siloxane)], poly-[(tert-butyl acrylate-copolymerization-acrylic acid 2-methoxyl group ethyl ester-copolymerization-acrylic acid)-grafting-poly-(dimethyl siloxane)], poly-(tert-butyl acrylate-copolymerization-acrylic acid)-grafting-[poly-(isobutene .); Poly-(dimethyl siloxane)], poly-(4-t-butyl styrene-copolymerization-methacrylic acid)-grafting-poly-(isobutene .); Poly-(dimethyl siloxane)], poly-[(4-t-butyl styrene-copolymerization-methacrylic acid)]-grafting-[poly-(methacrylic acid 2-Octyl Nitrite); Poly-(dimethyl siloxane)], poly-[(tert-butyl acrylate-copolymerization-own ester-copolymerization of acrylic acid 2-methoxyl group-methacrylic acid)]-grafting-[poly-(n propyl methacrylate-copolymerization-methacrylic acid); Poly-(dimethyl siloxane)], poly-[(tert-butyl acrylate-copolymerization-acrylic acid 2-methoxyl group ethyl ester-copolymerization-methacrylic acid)]-grafting-[poly-(n propyl methacrylate-copolymerization-acrylic acid); Poly-(dimethyl siloxane)], poly-[(tert-butyl acrylate-copolymerization-acrylic acid 2-methoxyl group ethyl ester-copolymerization-methacrylic acid)]-grafting-[poly-(styrene-copolymerization-methacrylic acid); Poly-(dimethyl siloxane)], [poly-(dimethyl siloxane)-block-poly-(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-acrylic acid-copolymerization-methacrylic acid)] _n, [poly-(dimethyl siloxane)]-block-poly-(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-acrylic acid-copolymerization-methacrylic acid)-block-poly-(dimethyl siloxane)], poly-(dimethyl siloxane)-block-poly-(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-acrylic acid-copolymerization-methacrylic acid) and composition thereof.

The non-limiting instance of the preferred polymer of the present invention comprises and is selected from following material: poly-[(tert-butyl acrylate-copolymerization-acrylic acid 2-methoxyl group ethyl ester-copolymerization-methacrylic acid)]-grafting-[poly-(n propyl methacrylate-copolymerization-methacrylic acid); Poly-(dimethyl siloxane)], poly-[(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-acrylic acid)-grafting-poly-(dimethyl siloxane)], [poly-(dimethyl siloxane)-block-poly-(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-acrylic acid-copolymerization-methacrylic acid)] _n, [poly-(dimethyl siloxane)]-block-poly-(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-acrylic acid-copolymerization-methacrylic acid)-block-poly-(dimethyl siloxane)].

The more concrete example of the copolymer of copolymer of the present invention comprises following, and wherein compositions provides (that is, the monomer of adding and big monomeric percetage by weight) with every kind of used in the polyreaction monomeric percetage by weight.

Poly-[(tert-butyl acrylate-copolymerization-acrylic acid 2-methoxyl group ethyl ester-copolymerization-acrylic acid)]-grafting-[poly-(n propyl methacrylate-copolymerization-methacrylic acid); Poly-(dimethyl siloxane)], its weight average molecular weight is about 150,000, contain 22% tert-butyl acrylate of having an appointment, 36% acrylic acid 2-methoxyl group ethyl ester, 18% acrylic acid, 6% weight average molecular weight and be 10000 poly-(dimethyl siloxane) big monomer, 18% weight average molecular weight and be poly-(n propyl methacrylate-copolymerization-methacrylic acid) big monomer of 6000.

[poly-(dimethyl siloxane)-block-poly-(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-acrylic acid-copolymerization-methacrylic acid)] _n, its weight average molecular weight is about 100,000, contains poly-(dimethyl siloxane) macromole azo initiator of 62% tert-butyl acrylate of having an appointment, 11% acrylic acid, 10% methacrylic acid, 17% molecular weight about 10000.

Poly-(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-methacrylic acid-copolymerization-acrylic acid)-grafting-poly-(dimethyl siloxane), its weight average molecular weight is about 150,000, contain poly-(dimethyl siloxane) big monomer of 43% tert-butyl acrylate of having an appointment, 27% n-butyl acrylate, 10% methacrylic acid, 10% acrylic acid, 10% molecular weight about 10000.

Poly-(tert-butyl acrylate-copolymerization-acrylic acid 2-methoxyl group ethyl ester-copolymerization-acrylic acid)-grafting-[poly-(isobutene .); Poly-(dimethyl siloxane)], its weight average molecular weight is about 200,000, contain poly-(dimethyl siloxane) big monomer of 40% tert-butyl acrylate, 20% n-butyl acrylate, 20% acrylic acid, 10% molecular weight about 10000 and poly-(isobutene .) big monomer of 10% molecular weight about 4000.

Solvent

Compositions of the present invention contains about 70-99.9% of composition weight, preferably about 75-98%, the solvent used of the copolymer of 85-98% more preferably from about.Solvent is selected from following material: water, ethanol, normal propyl alcohol, isopropyl alcohol and composition thereof.

When making water and alcohol mixture, for example, water-ethanol or water-isopropyl alcohol-ethanol, the water content scope in the compositions is generally about 0.5-99% of whole composition weight, preferably about 5-50%.In this class mixture, the common content range of alcoholic solvent is about 0.5-99% of whole composition weight, preferably about 50-95%.

Another aspect of the present invention provides the Hairspray compositions that contains the content that has reduced VOC such as solvent.Term used herein " VOC " or " VOC " contain to be less than 12 carbon atoms or vapour pressure those organic compound greater than about 0.1 millimetres of mercury.The Hairspray compositions that has reduced content of volatile organic compound that contains of the present invention contains and is not more than 80% VOC.

The performance of exsiccant Hairspray compositions

The Hairspray compositions of the present invention that is dry state has the concrete physical property by the total absorptivity definition of cohesive strength and per unit area.The Hairspray compositions of dry state also presents concrete impact strength performance.Hairspray compositions preferably also has with the hardness of hair and the defined improved removability of the value of peeling off.

Cohesive strength (kgf/mm ²)

Cohesion is a sample, as the intensity of the key that forms in the exsiccant Hairspray compositions.With kgf/mm ²The cohesive strength of (every square millimeter kilogram) expression is when the displacement under being stretched, and material is with the maximum unit of the stress that bears.Stress is the load the measured (original cross section (mm of kg * f) and sample ²) ratio.

Measure the cohesive strength of the dry Hairspray compositions of the present invention with following method.This method is based on the ASTM regulation: D 638-91, and the standard method of test of plastic tensile performance, 1992.1 publish, and it are drawn to be reference here.The method of testing of following cohesive strength is similar to the ASTM standard, changes to represent the tensile property of exsiccant Hairspray compositions thin film better but done several places.Measurement is carried out under about 73 and about 50% relative humidity.Especially, method of testing described here has been used the dumbbell shaped sheet about 0.4mm of a kind of thickness, improved, and (available from Instron Corp., Canton MA) applies power for the polymeric film sample as testing machine to use Instron Model Mini-55.

Be coated with PFA (perfluoro alkoxy) Teflon ^Flat aluminum die in dry a certain amount of Hairspray compositions (that is, contain the adhesive copolymer of siloxanes and be selected from the solvent of water, ethanol, normal propyl alcohol, isopropyl alcohol and composition thereof, and any other optional components) prepare a dry film sample.Dry polymer thin film under about 73 and about 50% relative humidity reaches " constant weight " up to thin film." constant weight " means during 24 hours the example weight fluctuation less than 1%.The zone that is not subjected to airflow influence should be remained on during desciccator diaphragm, the formation of drying heterogeneous and bubble will be caused because air flows.Co-polymer membrane is cut into dumbbell shaped to be tested.Sample should not have defective basically, as crack, breach, tear etc.Fig. 1 and 2 illustrates the plane dumbbell shaped film that the extension test of the total absorptivity that is used for cohesive strength and per unit volume described here is used.Fig. 1 is the vertical view of dumbbell-shaped specimen.Fig. 2 is the sectional view of dumbbell-shaped specimen.The width of the narrow part 1 of dumbbell is 3mm (1=3mm).The length of the narrow part 3 of the 3mm of dumbbell is about 13mm (3=13mm).The measuring length 2 of narrow part is for measuring the used initial film length of sample strain.Measuring length is equal to or less than the length of narrow part, preferably equals the length (being 2=3) of narrow part.The width 4 of dumbbell end is about 10mm (4=10mm).The spacing 5 of film end portion is about 28mm (5=28mm).The length overall 6 of film is about 64mm (6=64mm).The length of the wide end of film is about 18mm ((6-5)/2=18mm).The about 6.5mm of length (i.e. (5-3)/2=6.5mm) of the wide end of film and the transition portion between narrow part.The end and the middle body of narrow part are answered smooth curved, to prevent any stress point in sample.The radius 7 of transition portion curve should be about 0.5 to 5 inch, and should link to each other with narrow part with tangential direction.The thickness 8 of formed film is 0.4mm (8=0.4mm).With the further balance of dumb-bell shape sample to " constant weight "." constant weight " means during selected 4 days, the weight of before 4 days, measuring with respect to the dumb-bell shape sample, the increase and decrease of average weight should be not more than 0.2%, between twice successive measurement in during 4 days viewed weight change be not more than ± 0.2%.Reaching this dumb-bell shape sample of 7 days build-in tests of this constant weight.

Sample is tested on calibrated curve Instron Model Mini-55 cupping machine.Before sample is sent into testing machine, measure length 3, width 1 and the thickness 8 of the narrow part of dumbbell shape sample with gauged mircrometer gauge, be accurate to micron.Obtain calculating the needed dimension measurement value of stress on the per unit area by the Instron testing machine.The wide end of dumbbell shape sample is clamped on the Instron testing machine, and the crosshead rate of extension is 5 mm/min.What the Instron testing machine was measured is the whole power (as kgf) that are applied on the film.These power are distributed on the cross-sectional area of narrow part of film.The cohesive strength of copolymer is maximum unit power that Instron the measured cross-sectional area divided by the narrow part of film.

The cohesive strength of exsiccant Hairspray compositions of the present invention is greater than 0.5kgf/mm ², be preferably greater than 0.6kgf/mmm ², more preferably greater than 0.7kgf/mm ²

Total absorption energy of per unit volume is (as kgfmm/mm ³)

Total absorption energy of per unit volume, its unit is kgfmm/mm ³(every mm ³Kgfmm), be to arrive the required gross energy of the automatic breakaway poing (initial volume (mm of kgf * mm) and sample ³) ratio.Use standard technique to calculate by area under the load of working sample and displacement curve and arrive the required gross energy of breakaway poing.Total absorption energy of per unit volume is also referred to as polymer science and known " toughness " of testing of materials field those of ordinary skill.

Under about 73 and about 50% relative humidity, measure.

Total absorption energy of the per unit volume of exsiccant Hairspray compositions of the present invention is approximately greater than 0.55kgfmm/mm ³, preferably approximately greater than 0.75kgfmm/mm ³, more preferably from about greater than 1.10kgfmm/mm ³, further preferably approximately greater than 1.60kgfmm/mm ³, most preferably from about greater than 2.15kgfmm/mm ³

Impact strength

Impact strength is to destroy required average failure energy (quality * weight * highly) as produce sample in exsiccant Hairspray compositions.Sample is destructive to be characterised in that: normal naked eyes can be seen under normal laboratory optical condition by the fracture that weight produced or the crack that fall.

Use following method to measure the impact strength of exsiccant Hairspray compositions of the present invention.This method is stipulated based on ASTM: D5420-93, Standard Test Method for Impact Resistance of Flat.Rigid Plastic Specimen by Means of a Striker Impacted by a FallingWeight (Gardner Impact), nineteen ninety-five publishes, here it is drawn in full and be reference, change to represent the impact property of exsiccant thin film better but done several places.Measurement is carried out under about 73 and about 50% relative humidity.

Method of testing described here has specifically used thickness to be about the rectangular sample of 0.4mm, use GCA/ exact science penetrometer, it is retrofited fall 70 mm distance with probe with dull face, and being equipped with the used exact science helical controller of GCA penetrometer, surface area is 8 millimeters ²Cylindrical needle (the OK M﹠amp of dull face; T Corp.-part#WSU30) with the ruler of 1 millimeter increment measurement.

In measuring, cohesive strength use foregoing membrane drying process to prepare sample.Co-polymer membrane is cut into rectangle, as 10 millimeters * 20 millimeters.Sample thickness is 0.4 millimeter.The film thickness of various specimen should remain on 0.4 millimeter ± 15% in.

Use following measuring method.The probe of opening the helical operation discharges controller.Controller should begin the opening and closing that circulate as red light is indicated.Thereby thin film is not run on the sharp limit of guaranteeing probe face and shock surface co-altitude probe.Membranaceous sample is placed on the impact test instrument on the target area.Meter ruler is placed on the membranaceous sample gently.Light source is disposed across on the surface of sample, thus the surface co-planar of light source and thin film.Little crack in the thin film is with reflected light and detection easily.Probe is moved upwards up to required distance of fall.Suggestion apart from progression be: 1 millimeter, 3 millimeters, 5 millimeters, 10 millimeters, 15 millimeters, 20 millimeters, 25 millimeters, further with 5 millimeters increments to 70 millimeter.(70 millimeters is the upper limit of instrument).Open instrument switch, so that probe is fallen on the sample.The first step of impact energy test is sought the rupture scope of required probe height of film.The first step is with 1 millimeter beginning.Increase progressively lasting moving according to the distance of being advised up to observing the crack.When observing the crack, write down and move to new sample.Second step of determining impact energy in institute's research process is to place new sample, and the place begins to fall at observed breakaway poing.Place new film sample, probe is moved to next minimum set point.If the thin film fracture, the end of record repeats previous step.If thin film does not rupture, place new sample, move to next distance.Continue to place new sample and increase and fall apart from rupturing up to thin film.Continue this step, up to observing 5 breakaway poings.The amount of evaluation work energy, promptly use the fracture strength of following general formula:

W=m * g * h, wherein

The amount of W=work capacity, erg

The quality of m=probe (59.53 gram), (probe is dismountable, can replace with the probe of a different quality or collimeter area).

G=gravity constant (980.665 cels ²)

Ballistic average distance is removed in the operation of h=probe, centimetre.

The impact strength of exsiccant Hairspray compositions of the present invention is preferably greater than about 20000 ergs greater than about 7000 ergs, more preferably greater than about 50000 ergs.

The removability of Hairspray compositions

In the time of in being used in preferred eruption embodiment of the present invention, the adhesive copolymer here has improved removability.In this article, removability means in the hair washing process, and the cohesiveness copolymer is easier to be removed from hair or other coated surfaces.

In order to determine preferred Hairspray compositions of the present invention, hereinafter with after the removability method treatment of hair of describing, the hardness of assessment hair and the appearance situation of observable white plates are determined removability indirectly by basis.Have now found that, in the appearance of the removability of Hairspray compositions after the hair washing and white plates on the hardness/pliability of the hair of a series of hair washings circulations back gained and hair/do not occur relevant.Hairspray compositions of the present invention has high removability, as the hardness of reduction and the white plates of reduction.Therefore, term used herein " removability " refers to hair hardness number (0-4 scale) and white value of peeling off (0-4 scale) that basis is hereinafter measured the method for describing.

In order to determine preferred Hairspray compositions of the present invention, the removability of definite Hairspray compositions that defines with the combination of hair hardness number and the hair value of peeling off, wherein the scope of hair value of delaminating of providing of Hairspray compositions is about 0-3.5, preferred about 0-2.5,0-2.0 more preferably from about, the scope of hair hardness number is about 0-3.5, preferably about 0-2.5, more preferably from about 0-2.0.

Method: the removability of Hairspray compositions

Determine situation to occur and the removability of the indirect Hairspray compositions of assessing of the present invention according to following method with hair hardness and white plates.The repeatedly application of this method simulation Hairspray compositions and cycle applications are repeatedly removed this class Hairspray compositions from hair effectively so that determine indirectly to reach how easily.

Method described herein provides the method for blindly handling back assessment bundle of hair (hair switches) with Hairspray compositions of the present invention.To describe the method for handling each bundle of hair with Hairspray compositions in detail below, and the appraisal procedure of the removability of the bundle of hair of each processing.

Everyone is equal to bundle of hair or the hardness of a series of bundle of hair and the appearance situation of white plates of ground evaluation process two well-trained members of panel of expert.The member of panel of expert determines hair hardness number (0-4 scale) and value of peeling off (0-4 scale) of the bundle of hair of each processing independently then.The order randomization of the bundle of hair that will handle with different Hairspray compositions, and carry out successively.Two groups of bundle of hair that are equal to of preparation as described below are used for each member of panel of expert, so that everyone has the freshly prepd bundle of hair of assessment usefulness.Before the bundle of hair that assessment is blindly handled, each member of panel of expert also assess (blindly non-) with untreated bundle of hair as hair hardness and the zero reference sample that peels off.The bundle of hair of processing that each member of panel of expert also assesses a contrast as the bundle of hair of the processing of the reference sample (scale is 4) that peels off and another contrast as hair hardness reference sample (scale is 4).The defined hair hardness number of the present invention is that the hair hardness number that two members of panel of expert provide is on average determined.Similarly, the defined hair of the present invention value of peeling off is that hair value of peeling off that two members of panel of expert provide is on average determined.

According to the Hairspray compositions treatment of hair bundle of the following step with aerosol of the present invention and non-aerosol.Also prepared hair hardness reference sample and the reference sample of delaminating according to the following step, except each sample is handled with the corresponding Hairspray compositions of the table 2 that below will describe and 3.

1) bundle of hair (pure brown of 10 inches Europe, 20 grams) of cleaning is hung vertically in it and is pricked on the end, the whole bundle of hair of combing (black rubber comb, 5 inches * 1 inch, 1/2 serration) is to remove any entanglement.

2) if desired, use static gun to pile up with any static of eliminating on the bundle of hair.

3) for the non-aerosol product, from 4 inches distance fog-spray nozzle topknots, aspirating 10 times simultaneously is coated to product on the bundle of hair, and the mode of moving with the fluid high and low moves the spraying sample of atomizing to cover whole bundle of hair, perhaps for aerosol product, from 6 inches distances each bundle of hair of spraying, simultaneously the aerosol flow coat is applied to 3 seconds on the bundle of hair, and moves aerosol stream to cover whole bundle of hair in the mode of fluid high and low motion.

4) at the reverse side repeating step 3 of bundle of hair.

5) behind the reverse side of fog-spray nozzle topknot, the bundle of hair of handling is hung over it pricked on the end, make its under ambient temperature, pressure and humidity dry 1 hour.

6) use the rubber of black to comb (5 inches * 1 inch, 1/2 inch serration) by being held combing and the exsiccant bundle of hair of combing away from pricking of bundle of hair, but beginning is held combing with small stroke to not pricking, then gradually with bigger stroke combing, up to the whole length of not pricking of comb by the bundle of hair of processing.

7) repeating step 1 to 6.

8) bundle of hair of water (+15-20grain hardness, 38 ℃, 1 gallon per minute hydraulic pressure) wettability treatment.

Method shampoo of the present invention), and 9) along 1 milliliter of shampoo of front end length coating of the bundle of hair of moistening (table 1: along other 1 milliliter of shampoo of the reverse side length coating of the bundle of hair of moistening.

10) from the top to the bottom, pushed (both hands alternatively between thumb and finger) bundle of hair gently 15 seconds with per second 1 stroke.

11) water (+15-20grain hardness, 38 ℃, 1 gallon per minute hydraulic pressure) rinsing bundle of hair is 15 seconds.Between forefinger and middle finger, push hair gently, after 5 seconds, 10 seconds and last rinsing, finger is moved down in the bundle of hair.

12) bundle of hair of hang handling and make it in hot case dry two hours.

13) from hot case, remove exsiccant bundle of hair.

14) use the rubber of black to comb (5 inches * 1 inch, 1/2 inch serration) by being held combing and the exsiccant bundle of hair of combing away from pricking of bundle of hair, but beginning is held combing with small stroke to not pricking, then gradually with bigger stroke combing, up to the whole length of not pricking of comb by the bundle of hair of processing.

15) repeating step 1-14.

16) repeating step 1-13.

17) then by the bundle of hair of the member of a panel of expert evaluation process, by between the forefinger of the hands of its domination and middle finger, touching this bundle of hair, between its thumb and other finger, touch this bundle of hair and determine its hardness and bending resistance, determine a hair hardness number (0-4 scale) for then the bundle of hair of handling.This specified value is with respect to hair hardness reference value (4) and untreated reference value (0).

18) then the member of panel of expert according to the bundle of hair of step 14 combing described above assessment, the white plates of the bundle of hair of visually rank combing, coating and white mist then, and hair value of delaminating of definite bundle of hair (0-4 scale).Specified value is with respect to hair delaminate reference value (4) and untreated reference value (0).

Table 1: used shampoo in the method for the present invention

Component list	The percent of the compositions that adds	Chemical content, the percent of compositions
Component list	The percent of the compositions that adds	Chemical content, the percent of compositions	Sodium laureth sulfate	????40.0000	????10.0000
Water-USP purification	????30.3000	????30.3000	Sodium laureth sulfate	????40.0000	????10.0000
Water-USP purification	????30.3000	????30.3000	Sodium lauryl sulfate	????29.1000	????8.0025
The cocoyl diglycollic amide	??????.5000	?????.4000	Sodium lauryl sulfate	????29.1000	????8.0025
The cocoyl diglycollic amide	??????.5000	?????.4000	????Kathon?CG	??????.1000	?????.0015
Citric acid solution (50% active matter)	Regulate (notes: water yield capacity to 100%) from 0-1%		????Kathon?CG	??????.1000	?????.0015

Table 2: the height control sample of delaminating

Raw material

The percent of the compositions that adds

Chemical content, the percent of compositions

Octyl acrylamide/acrylate/fourth amino-ethyl methacrylate copolymer (national starch lot number: AF-6713)	????4.50	????4.50
	????4.50	????4.50	Water-USP purification	????15.50	????15.50
Ethanol (SDA40)	????80.00	????80.00	Water-USP purification	????15.50	????15.50

Table 3: high rigidity control sample

Raw material	The percent of the compositions that adds	Chemical content, the percent of compositions
Raw material	The percent of the compositions that adds	Chemical content, the percent of compositions	Octyl acrylamide/acrylate/fourth amino-ethyl methacrylate copolymer (national starch lot number: AF-6713)	????6.00	????6.00
The amino methyl propanol, 95%	????1.04	????0.99		????6.00	????6.00
The amino methyl propanol, 95%	????1.04	????0.99	Water-USP purification	????15.50	????15.50
Dibutyl adipate	????0.20	????0.20	Water-USP purification	????15.50	????15.50
Dibutyl adipate	????0.20	????0.20	Ethanol (SDA40)	????80.00	????80.00

Preparation and the described every kind of compositions of hybrid technology preparation table 1-3 according to routine.

Optional components

Compositions of the present invention also can contain the various various optional components that are fit to be applied on the human hair.

The compositions here can be chosen wantonly and contain the plasticizer that copolymer is used.Can use and be suitable for hair products or be fit to be locally applied to any plasticizer on hair or the skin.Various plasticizers are well known in the art.These comprise glycerol, diisobutyl adipate, butyl stearate, propylene glycol, citric acid three C ₂-C ₈Arrcostab comprises the analog of the triethyl citrate such as three propyl ester, tributyl, triamyl of triethyl citrate and citric acid.Triethyl citrate preferably.

Plasticizer dosage is 0.01-10%, preferably about 0.05-3%, the 0.05-1% more preferably from about of composition weight normally.Preferably, the weight ratio of graft copolymer and plasticizer is about 1: 1-40: 1, preferred about 2: 1-30: 1, more preferably from about 3: 1-25: 1.

Randomly, compositions of the present invention can contain the non-surface active ionic strength modifier system of viscosity that is used to reduce Hairspray compositions of effective dose.When using, ionic strength modifier content at least about 0.01% with composition weight in compositions of the present invention exists.The upper limit depends on the maximum of the ionic strength modifier that can exist in concrete compositions of the present invention, the resin of hair keeps dissolving or disperses thereby make fixedly.As well known in the art, when the ionic strength of compositions increased, resin will finally separate from solution, perhaps no longer kept dissolving or being dispersed in the hydrophilic liquid carrier.The upper limit of ionic strength modifier system content will change according to other composition that exists in concrete ionic strength modifier, liquid-carrier, resin and the compositions.Therefore, for example, compare with the compositions that contains more water, concerning the compositions with the liquid-carrier that contains less water, the maximum of operable ionic strength modifier is often lower.Usually, compositions will contain have an appointment 4% weight or lower, more preferably from about 2% or lower, most preferably from about 1% or lower ionic strength modifier.Preferably, compositions of the present invention will contain the 0.01-0.5% that has an appointment, the ionic strength modifier system of 0.01-0.1% more preferably from about.

The ionic strength modifier system contains monomer cation and anionic mixture.The ion of ionic strength modifier of the present invention is non-surface active, and promptly they can not obviously reduce surface tension.For the purposes of the present invention, on-surface-active means when 0.5% concentration of aqueous solution, and ion reduces capillary amount and is no more than 5.0 dynes per centimeter ²Usually, the ionic of ionic strength modifier system of the present invention be characterised in that in any aliphatic chain or the organic heterochain of straight or branched, and every electric charge is up to 4 or still less carbon atom, preferred two or carbon atom still less.

The ionic strength modifier system contains the monomer ion as Acid-Base product type.Therefore, alkalescence and acid ion OH ^-And H ⁺They do not constitute the part of ionic strength modifier system of the present invention, although may reside in the compositions.Ion of the present invention is joined in the compositions, thereby its form (promptly being dissociative form) with dissociated ion in compositions is existed.The ion that is not all addings all must be present in the compositions with the form of dissociated ion, but must be at least partially in the compositions being solubilized or dissociative.By for example adding soluble salt or add the mixture of bronsted lowry acids and bases bronsted lowry, or its combination adds ionic strength modifier in the hair setting composition.A necessary aspect of the present invention is that anion and the cation with the ionic strength modifier system all adds in the compositions.

The cation that is suitable for comprises for example alkali metal such as lithium, sodium and potassium and alkaline-earth metal such as magnesium, calcium and strontium.Preferred bivalent cation is a magnesium.Preferred monovalent metallic ion is lithium, sodium and potassium, preferably sodium and potassium.Add suitable method in the compositions of the present invention and comprise as with alkali such as hydroxide, the form of sodium hydroxide and potassium hydroxide add and as add to dissolve in the salt in the liquid-carrier such as the form of the anionic salt of monomer, such as will be described below.

Other suitable cation comprises organic ion such as quaternary ammonium ion and cationic amine, as ammonium, monoethanolamine, diethanolamine and triethanolamine, triethylamine, morpholine, amino methyl propanol (AMP), amino-ethyl propylene glycol etc.Ammonium and amine preferably provide with the form of salt example hydrochloric acid salt.

Operable monomer anion comprises that halide ion such as chloride ion, fluorion, bromide ion and iodide ion, particularly chloride ion, sulfate radical, ethyl ester sulfate radical, methyl ester sulfate radical, cyclohexyl sulfamic acid root, thiosulfate anion, tosylate, xylene monosulfonic acid root, citrate, nitrate anion, bicarbonate radical, adipic acid root, succinic, glucide acid group, benzoate anion, lactate, borate, isethionic acid root, tartrate anion and other can the disassociation form be present in the monomer anion in the hair setting composition.So that small part dissolves in the acid in the liquid-carrier or the form of salt, as the sodium of acetate, citrate, nitrate anion, chloride ion, sulfate radical etc. or the form of potassium salt anion is added in the compositions of the present invention.Preferably, this class salt is dissolved in the carrier fully.

The purposes of ionic strength modifier is to be particularly useful in the compositions that has reduced the volatile organic solvent amount.

Compositions of the present invention also can contain various hydrophobic volatile solvents such as Cyclomethicone (cyclomethicone) and volatile hydrocarbon such as Fancol ID and 2-Methylpentadecane.

Compositions of the present invention can contain various other optional components, comprising the component that is applicable to any kind in the Haircare composition well known in the art, and the fixing enriching substance (tonics) of hair fixing composition such as Hairspray compositions and hair especially.Usually, other adjuvant of this class accounts for about 0.05-5% weight, preferred about 0.1-3% weight altogether.The conventional optional adjuvant of this class is known to a person of ordinary skill in the art, include, but is not limited to: surfactant (it can be anion, cation, both sexes or amphion, and comprises fluorizated surfactant and silicone copolyol), propellant, hair conditioner (as siloxanes fluids, fatty acid ester, aliphatic alcohol, long chain hydrocarbon, cationic surfactant etc.); Emollient; Lubricant and penetrating agent such as various lanoline chemical compound; Proteolysis thing and other protein derivatives; Ethylene addition product and polyoxyethylene cholesterol; Dyestuff; Toner, bleach, Reducing agent and other coloring agent; The pH regulator agent; Sunscreen; Antiseptic, thickening agent (as polymer viscosifier such as xanthan gum); And spice.

The eruption product

The product that Hairspray compositions of the present invention can be used as spraying or atomizing distributes from container, and this container is pump spray dispenser or aerosol can.This class container is known to a person of ordinary skill in the art, can buy from many Producers, comprises American National Can Corp. and Continental CanCorp.

When Hairspray compositions distributes from the aerosol container of pressurization, can use the propellant of forming by one or more conventional known aerosol propellants to advance compositions.The suitable propellant that is fit to use can be any liquable gas that is generally used in the aerosol container.The propellant that is fit to use is the volatile hydrocarbon propellant, and it can comprise lower hydrocarbon such as propane, butane and the iso-butane of the liquefaction of 3-4 carbon atom.Other suitable propellant be fluorohydrocarbon as 1,2-Difluoroethane (hydrofluorocarbon152A) is supplied with Dymel 152A by DuPont.Other example of propellant is dimethyl ether, nitrogen, carbon dioxide, nitrous oxide and atmosphere.Preferably hydrocarbon, particularly iso-butane, use separately or with other hydrocarbon phase blending.

Aerosol propellants can mix mutually with Hairspray compositions of the present invention, and is by the known conventional controlling factors of aerosol art with the amount of blended propellant.Usually, for liquable propellant, the consumption of propellant is about 10-60% of whole composition weight, preferred about 15-50%.

On the other hand, can use the aerosol dispenser of pressurization, wherein propellant and Hairspray compositions be separated, as by the bi-component jar of American National Can Corp. with trade name SEPRO type sold.

Other suitable aerosol dispenser is characterised in that propellant is an air, and it is packed in the allotter by pump or suitable device before use.This class allotter is authorized the USP4 of Olofsson on March 7th, 1978,077, authorize 4 of Terstege in 41l and on July 25th, 1989, be described in 850,577, these two pieces of patents are incorporated herein by reference, and US serial number 07/839, on February 21st, 648,1992 was submitted to by people such as Gosselin, and it also is incorporated herein by reference.The air pressurized aerosol container that is fit to use is at present also by P﹠amp; G company is with its trade name VIDAL SASSOON AIRSPRAY ^Hairspray compositions is sold.

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

Other hair setting composition comprises enriching substance and washing liquid, and it distributes in the bottle of routine or pipe usually, and is applied directly on the hair, perhaps is assigned to earlier on hand, is coated on the hair then.

Preparation method

Can use conventional preparation and hybrid technique to prepare hair setting composition of the present invention.The cohesiveness copolymer and the solvent phase that will contain siloxanes mix so that uniform mixture to be provided.Add any other composition then, and mix to obtain final compositions.If in and polymer, then preferably before adding other component, nertralizer is added.For the eruption product, with the mechanical pump sprayer unit packaging compositions of routine, perhaps, under the situation of aerosol spray product, with the aerosol can packaging compositions of routine and suitable propellant system.

Using method

Compositions of the present invention can common mode be used, so that hair care effect of the present invention to be provided.This method is included in before or after the hair drying, the product of effective dose is coated on the hair of drying, wet slightly or moistening, and is processed into required hair style.Usually aerosol container by using suitable device such as mechanical pump aerosol apparatus, pressurization or the spraying of other suitable device or atomised product come application product.Then with composition dries or make its drying." effective dose " is meant provides lasting maintenance and the required enough amounts of typing effect to hair.Usually, about 0.5～30g product is coated on the hair, this depends on the length and the hair style of concrete formula for a product, types of dispensers, hair.

Following experiment and embodiment will further specify the embodiment in the scope of the invention.These embodiment only are that the present invention will be described, and are not restriction the present invention, because under the condition that does not break away from spirit and scope of the invention, the present invention can have many variations.

Embodiment

The following example further describes and illustrates the embodiment in the scope of the invention.These embodiment only are that the present invention will be described, and are not restriction the present invention, because under the condition that does not break away from spirit and scope of the invention, the present invention can have many variations.Each component is determined with chemical name or CTFA title.

Embodiment 1-4: monomer and copolymer is synthetic greatly

Embodiment 1

Poly-(n propyl methacrylate-copolymerization-methacrylic acid) of Ethenylbenzene cardinal extremity envelope is big monomeric synthetic

In being equipped with the round-bottomed flask of magnetic agitation, add oxolane (1 liter), trimethyl silyl methacrylate (100 grams, 0.632 mole) and n propyl methacrylate (100 grams, 0.780 mole) down at a little argon pressure (8psi).Solution is cooled to-80 ℃, causes the growth of chain by anionic polymerisation mechanism with the diphenyl hexyl lithium.After 0.5 hour, in solution, add vinyl benzene formyl chloride (8.33 milliliters, 0.05 mole) in continuous stirring, and continue to stir 0.5 hour.Then solution is warmed to ambient temperature, adds entry and stir 0.25 hour to remove to protect acidic group.By the final solution of precipitation in hexane, collecting precipitation thing and the dry big monomer that obtains weight average molecular weight about 6000 under vacuum.

Embodiment 2

Poly-(tert-butyl acrylate-copolymerization-acrylic acid 2-methoxyl group ethyl ester-copolymerization-acrylic acid)-grafting-[poly-(n propyl methacrylate-copolymerization-methacrylic acid); Poly-(dimethyl siloxane)] copolymer synthetic

In the round-bottomed flask that is equipped with reflux condenser, temperature controller, mechanical agitation mechanism a little argon pressure (8psi) add down acetone (0.5 liter), tert-butyl acrylate (22.3 gram), acrylic acid 2-methoxyl group ethyl ester (36 gram), acrylic acid (18 gram), poly-(dimethyl siloxane) big monomer (6 gram) (Chisso Corp. Tokyo, Japan) and (n propyl methacrylate-copolymerization-methacrylic acid) of Ethenylbenzene cardinal extremity envelope big monomer (18 gram) (from embodiment 1).Agitating solution all dissolves up to all components, is heated to 60 ℃ then.In system, add azodiisobutyronitrile (0.7 gram).After 10 hours, with the solution cooling, precipitation obtains silicone-modified graft copolymer in water.

Embodiment 3

[poly-(dimethyl siloxane)-block-poly-(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-acrylic acid-copolymerization-methacrylic acid)] _nSynthetic

62.4 parts of tert-butyl acrylates, 20.8 parts of acrylic acid, 200 parts of acetone (as solvent) and 15 parts of isopropyl alcohols (as chain-transferring agent) are put into round-bottomed flask.Individually, the big azo initiator of 16.8 parts of VPS-1001 (poly-(dimethyl siloxane) initiator) (from Wako Chemical USA, INC., Richmond, VA has bought) is dissolved in 200 parts of ethyl acetate, solution is joined in the addition funnel.With the argon cleaning reactor about 1 hour.After flushing, on airtight reaction system, keep constant malleation with argon.Reactant mixture is heated to 58 ℃.During 1 hour, the VPS-1001 drips of solution is added in the reaction flask.Keep heating and stirring 20 hours.By with reactor to atmosphere opening and cool to room temperature, with reaction terminating.

By 1 part of polymer solution is added in 15 parts of water, polymer is precipitated out from solution.Polymer with gained is placed in the vacuum drying oven with heat drying then.After drying, polymer is ground and use Soxhlet's extractor use hexane extraction 20 hours.Use heat in the stove with the polymer vacuum drying then.

Embodiment 4

Synthesizing of poly-(tert-butyl acrylate-copolymerization-n-butyl acrylate-copolymerization-methacrylic acid-copolymerization-acrylic acid)-grafting-poly-(dimethyl siloxane)

36 parts of tert-butyl acrylates, 27 parts of n-butyl acrylates, 10 parts of methacrylic acids and 12 parts of acrylic acid and 15 parts poly-(dimethyl siloxane) big monomer (from Chisso Corp. Tokyo, Japan has bought) are put into round-bottomed flask.The acetone that adds capacity as reaction dissolvent to produce the final monomer concentration of about 20% volume.With the argon cleaning reactor about 1 hour.After flushing, on airtight reaction system, keep constant malleation with argon.Reactant mixture is heated to 58 ℃.10% the azodiisobutyronitrile solution (with respect to monomeric weight is 0.5%) of preparation in acetone adds it in reactant mixture.Keep heating and stirring 20 hours.By with reactor to atmosphere opening and cool to room temperature, with reaction terminating.

By 1 part of polymer solution is added in 15 parts of water, polymer is precipitated out from solution.Polymer with gained is dissolved in the acetone more then.This step repeats 6 times, and final polymer is put into vacuum drying oven with heat drying.

Embodiment 5

The polyisobutylene of acryloyl cardinal extremity envelope is big monomeric synthetic

The Living Cationic Vinyl Polymerization reaction of the routine by isobutene. is (as G.Kaszas, Poly.Bull., 20,413 (1989) describe) to prepare 100 gram (0.024 mole) weight average molecular weight be the polyisobutylene polymer (PIB-OH) that the hydroxyl terminal of 4,172 gram/moles seals.The triethylamine that in solution, adds excessive (4.84 grams, 0.048 mole) of 2 times of moles.At 0 ℃ this drips of solution is added acryloyl chloride (4.35 grams, 0.048 mole) in the solution of anhydrous methylene chloride (100 gram).At room temperature stirred 12 hours, filtering mixt evaporates excessive triethylamine and dichloromethane to obtain the big monomer of polyisobutylene of acryloyl cardinal extremity envelope.

Embodiment 6

Poly-(tert-butyl acrylate-copolymerization-acrylic acid 2-methoxyl group ethyl ester-copolymerization-acrylic acid)-grafting-[poly-(isobutene .); Poly-(dimethyl siloxane)] synthetic

20 parts of acrylic acid, 40 parts of tert-butyl acrylates, 20 parts of n-butyl acrylates, 10 parts poly-(isobutene .) big monomer (4172MW) (from embodiment 5) and 10 parts are gathered (dimethyl siloxanes) put into flask.The oxolane that adds capacity as reaction dissolvent to produce about 20% final monomer concentration.Use noble gas, preferred nitrogen or argon cleaning reactor.Add initiator, (2,2 '-azodiisobutyronitrile) to obtaining the required amount that molecular weight was fit to.Usually this amount is a 0.5-1.0% weight with respect to monomeric amount.Be heated to 60 ℃, and under agitation kept this temperature 48 hours.By cool to room temperature with reaction terminating.Fall reaction dissolvent with polymer purification by drying in stove.In addition, can use acetone with substituted tetrahydrofuran, in this case, add entry polymer precipitation is gone out, the polymer of collecting precipitation is also dry.

Embodiment 7-14

The following example is represented non-aerosol Hairspray compositions of the present invention.

	Embodiment number
	Embodiment number								Component (weight %)	7	8	9	10	11	12	13	14
Copolymer 6	4.00	5.00	6.00	4.00	---	---	---	---	Component (weight %)	7	8	9	10	11	12	13	14
Copolymer 6	4.00	5.00	6.00	4.00	---	---	---	---	Copolymer 2	---	---	---	---	3.00	3.50	2.50	4.00
Fancol ID ¹	1.00	---	---	---	---	1.0	2.0	---	Copolymer 2	---	---	---	---	3.00	3.50	2.50	4.00
Fancol ID ¹	1.00	---	---	---	---	1.0	2.0	---	Dibutyl adipate	0.40	---	0.90	0.55	---	---	---	0.40
Sodium hydroxide ²	0.96	1.20	1.44	---	---	1.20	---	1.35	Dibutyl adipate	0.40	---	0.90	0.55	---	---	---	0.40
Sodium hydroxide ²	0.96	1.20	1.44	---	---	1.20	---	1.35	Potassium hydroxide ³	--	---	---	1.21	1.00	---	0.70	---
Spice	0.10	0.10	0.10	0.10	0.10	0?15	0.10	0.15	Potassium hydroxide ³	--	---	---	1.21	1.00	---	0.70	---

Water	QS100	QS100	QS100	QS100	QS100	QS100	QS100	QS100
Water	QS100	QS100	QS100	QS100	QS100	QS100	QS100	QS100	Sodium benzoate	--	--	--	--	0.10	0.10	--	0.10
Ethanol ⁴	76.54	71.95	81.56	71.25	79.40	69.26	78.00	55.00	Sodium benzoate	--	--	--	--	0.10	0.10	--	0.10

1.PERMETHYL 99A, available from Presperse, Inc., South Plainfield, NJ, USA.2. sodium hydroxide is 30% active matter.3. potassium hydroxide is 45% active matter.(4.SDA40 100% ethanol).

Embodiment 15-20 the following example is represented aerosol hair spray compositions of the present invention.

	Embodiment number
	Embodiment number						Component (weight %)	15	16	17	18	19	20
Copolymer 3	5.00	4.00	3.50	---	---	---	Component (weight %)	15	16	17	18	19	20
Copolymer 3	5.00	4.00	3.50	---	---	---	Copolymer 4	---	---	---	4.00	3.00	4.00
Fancol ID ¹	0.50	---	---	--	---	0.50	Copolymer 4	---	---	---	4.00	3.00	4.00
Fancol ID ¹	0.50	---	---	--	---	0.50	Triethyl citrate ²	--	--	0.21	--	--	--
Dibutyl adipate	0.70	0.45	--	0.40	0.25	0.35	Triethyl citrate ²	--	--	0.21	--	--	--
Dibutyl adipate	0.70	0.45	--	0.40	0.25	0.35	Propylene glycol	--	--	0.30	--	--	---
Sodium hydroxide ³	1.00	--	--	--	1.0	---	Propylene glycol	--	--	0.30	--	--	---
Sodium hydroxide ³	1.00	--	--	--	1.0	---	Potassium hydroxide ⁴	--	0.94	1.20	1.04	---	1.20
Spice	0.10	0.10	0.10	0.10	0.10	0.10	Potassium hydroxide ⁴	--	0.94	1.20	1.04	---	1.20
Spice	0.10	0.10	0.10	0.10	0.10	0.10	Water	QS100	QS100	QS100	QS100	QS100	QS100
Sodium benzoate	0.10	0.10	--	0.10	0.20	--	Water	QS100	QS100	QS100	QS100	QS100	QS100
Sodium benzoate	0.10	0.10	--	0.10	0.20	--	Ethanol ⁵	56.69	57.42	72.0	50.0	30.00	54.5
Propellant-iso-butane	--	--	7.02	15.00	10.00	--	Ethanol ⁵	56.69	57.42	72.0	50.0	30.00	54.5
Propellant-iso-butane	--	--	7.02	15.00	10.00	--	Propellant-normal butane	10.00	---	--	--	--	--
Propellant-dimethyl ether ⁶	10.00	---	--	15.00	15.00	--	Propellant-normal butane	10.00	---	--	--	--	--
Propellant-dimethyl ether ⁶	10.00	---	--	15.00	15.00	--	Propellant-fluorohydrocarbon 152a ⁷	--	25.0	15.98	--	--	32.32

1.PERMETHYL 99A, available from Presperse, Inc., South Plainfield, NJ, USA.

2.CITROFLEX-2, available from Morflex, Inc., Greensboro, NC, USA.

3. sodium hydroxide is 30% active matter.

4. potassium hydroxide is 45% active matter.

(5.SDA40 100% ethanol).

6.DYMEL-A, available from Dupont.

7.DYMEL-152a, available from Dupont.

Prepare compositions as previously described, at first polymer mixes with ethanol, with in sodium hydroxide or the potassium hydroxide and polymer, under agitation adds (answering use) Fancol ID, plasticizer, spice and water then successively.If the use sodium benzoate, after adding entry with its adding.Most preferably, the pre-composition of preparation water and sodium benzoate, then after adding most of water with its adding.After all the other components of prepared compositions add, aerosol composition is added in the conventional aerosol container with propellant.

Hairspray compositions of the present invention described in the embodiment 5-18 has the high removability from the hair, and when assessing its removability with method of the present invention, it provides less than 2.0 hair hardness number with less than hair value of delaminating of 2.0.

Although illustrated and described specific embodiments of the invention, those of ordinary skill in the art should be understood that under the premise without departing from the spirit and scope of the present invention can carry out various variations and change.Therefore, appending claims comprises all these changes within the scope of the invention.

Claims

1. Hairspray compositions, it comprises:

2. the Hairspray compositions of claim 1, wherein described copolymer component solubilized maybe can be scattered in the described solvent in the time of 73 °F, and its concentration is at least 0.1 mg/ml.

3. claim 1 or 2 Hairspray compositions, wherein the adhesion strength of the described Hairspray compositions during dry state is greater than 0.7kgf/mm ², always absorb energy greater than about 1.10kgfmm/mm ³, impact strength is greater than 50,000 ergs.

4. claim 1 or 2 or 3 Hairspray compositions, wherein said copolymer is polysiloxane grafted copolymer, it contains main polymer chain and the polysiloxanes side chain that is grafted on this main chain, and wherein said copolymer is formed with containing the big monomeric unit random copolymerization of polysiloxanes by the vinyl monomer unit of following relative weight percent:

The vinyl monomer unit of the 50-98% of a. described copolymer weight, and

The big monomeric unit that contains polysiloxanes of the 2-50% of b. described copolymer weight, the weight average molecular weight that wherein contains the big monomeric unit of polysiloxanes is 1,000-5,000, it has following chemical formula:

X(Y) _nSi(R) _3-m(Z) _m

Wherein: X be can with the vinyl of described vinyl monomer unit combined polymerization;

Y is a divalent linker;

R is hydrogen, hydroxyl, C ₁-C ₆Alkyl, C ₁-C ₆Alkoxyl, C ₂-C ₆Alkylamino, phenyl, C ₁-C ₆The phenyl that alkyl or alkoxyl replace;

Z is that number-average molecular weight is at least 1000 monovalence siloxane polymerization part, essentially no reactivity under copolymerization conditions, and after polymerization, become the side chain of described polyvinyl main chain;

N is 0 or 1;

M is 1 to 3 integer.

5. the Hairspray compositions of claim 4, wherein said vinyl monomer unit is selected from: acrylic acid, methacrylic acid, N, the N-DMAA, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, vinyl pyrrolidone, the acrylic or methacrylic acid esters of C1-C18 alcohol, styrene, α-Jia Jibenyixi, t-butyl styrene, vinyl acetate, propionate, vinyl chloride, 1, the 1-dichloroethylene, vinyltoluene, butadiene, cyclohexadiene, ethylene, propylene, n-BMA, isobutyl methacrylate, tert-butyl acrylate, the metering system tert-butyl acrylate, methacrylic acid 2-Octyl Nitrite, methyl methacrylate, above listed any acid and the salt of amine, and combination.

6. claim 4 or 5 Hairspray compositions, the wherein said big monomeric unit that contains polysiloxanes is selected from:

X-CH ₂-(CH ₂) _s-Si(R ¹) _3-m-Z _m

With 0

。

X-C-0-(CH ₂) _q-(0) _p-Si(R ¹) _3-mZ _m

Wherein s is 0,1,2,3,4,5 or 6; M is 1,2 or 3; P is 0; Q is 2,3,4,5 or 6; R ¹Be selected from: hydrogen, hydroxyl, C ₁～C ₆Alkyl, C ₁～C ₆Alkoxyl, C ₂～C ₆Alkylamino, phenyl, C ₁～C ₆The phenyl that alkyl or alkoxyl replace; R ²Be selected from: C ₁～C ₆Alkyl or C ₁～C ₆The phenyl that alkyl replaces; N is 0,1,2,3 or 4; X is R wherein ³For hydrogen or-COOH; R ⁴Be hydrogen, methyl or-CH ₂COOH; Z is

R ⁵, R ⁶And R ⁷Be independently selected from: hydrogen, hydroxyl, C ₁～C ₆Alkyl, C ₁～C ₆Alkoxyl, C ₂～C ₆Alkylamino, phenyl, C ₁～C ₆The phenyl that alkyl or alkoxyl replace; R is about integer of 14 to 700.

7. claim 1,2 or 3 Hairspray compositions, wherein said copolymer is the copolymer of siloxane blocks, it is equivalent to be selected from: A-B, A-B-A and-(A-B) _n-structure, wherein said copolymer is by the A vinyl monomer unit of following relative weight percent and the random copolymerization of B siloxane unit and form:

The A siloxane unit of the 2-50% of a. described copolymer weight, and

The B vinyl monomer unit of the 50-98% of b. described copolymer weight,

Wherein n is 2 or bigger integer.

8. the Hairspray compositions of claim 7, wherein said vinyl monomer unit is selected from: acrylic acid, methacrylic acid, N,N-DMAA, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, vinyl pyrrolidone, C ₁-C ₁₈Acrylic or methacrylic acid esters, styrene, α-Jia Jibenyixi, t-butyl styrene, vinyl acetate, propionate, the vinyl chloride, 1 of alcohol, 1-dichloroethylene, vinyltoluene, butadiene, cyclohexadiene, ethylene, propylene, n-BMA, isobutyl methacrylate, tert-butyl acrylate, metering system tert-butyl acrylate, methacrylic acid 2-Octyl Nitrite, methyl methacrylate, top listed any acid and the salt of amine, and combination; Wherein the siloxane blocks part A is represented by the following polymers structure:

-(SiR ₂O) _m-

Wherein each R is independently selected from: hydrogen, hydroxyl, C ₁～C ₆Alkyl, C ₁～C ₆Alkoxyl, C ₂～C ₆Alkylamino, styryl, phenyl, C ₁～C ₆The phenyl that alkyl or alkoxyl replace; M is about 14 or bigger integer.

9. each Hairspray compositions among the claim 1-8, wherein Hairspray compositions provides 0 to about 2.0 hair hardness number and hair value of delaminating of 0 to 2.0.

10. method for styling hair comprises each compositions among the claim 1-9 of effective dose is coated on step on the hair.