CN1700903A

CN1700903A - Composition containing block polymer and gelling agent

Info

Publication number: CN1700903A
Application number: CN 03825354
Authority: CN
Inventors: X·布林; V·费拉里
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2002-09-26
Filing date: 2003-09-26
Publication date: 2005-11-23
Anticipated expiration: 2023-09-26
Also published as: CN1700900A; CN1708279A; ES2362275T3; CN1703194A; CN1700904A; ES2353495T3; CN100594879C; CN100360113C; CN1700902A; ES2355374T3; ES2354975T3; CN100360110C; ES2355972T3; ES2354152T3; ES2356311T3; CN1700901A; ES2361010T3

Abstract

The invention relates to a cosmetic composition comprising at least one non-elastomer, filmogenic, linear, sequenced, ethylenic polymer and in a cosmetically acceptable liquid medium and a gelling agent of said organic liquid medium. The invention also relates to the combination of said sequenced polymer and a gelling agent in order to improve the texture and application of said composition on keratin fibres.

Description

The compositions that comprises block polymer and gellant

The present invention relates to be used for the skin (comprising scalp) of the person and face, people's lip or the cosmetic of epidermis derivant (as hair, eyebrow, eyelashes or fingernail) or the cosmetic composition of nursing, described cosmetic composition comprises specific block polymer.

Described compositions can be that powder, foundation cream, kermes, eye shadow, covering loose or that compress apply some make up, rouge, lip pomade, lip fat, the lip pomade that adds lustre to, liner, eyeliner, mascara, eyeliner, nial polish or be used for that health is made up or the product of dye.

Known compositions shows on its color especially through postadhesion power is poor after a while.The adhesive force of this difference is characterised in that change color (variable color, fade), normally because the antiperspirant results of interaction (as foundation cream, kermes or eye shadow) of discharging with sebum and/or skin, or since with saliva results of interaction (as lip pomade).This variation forces user frequently to be refined the make-up, thereby has wasted the time.

Be used for lip and skin to be known as " non-transfer " cosmetic composition be the compositions that has the following advantages: the deposit of formation to small part is not deposited on its carrier that contacts (for example glass, medicated clothing, medicated cigarette, fabric).

Known non-metastatic composition is usually based on silicones and volatile silicone oils; though improved adhesive force; but weak point is after volatile silicone oil evaporation; on skin and lip, stay thin film; this thin film makes us uncomfortable (dry and tight sensation) after after a while, so some Ms is reluctant to use this class lip pomade.

Known non-metastatic composition comprises ethereal oil and is dissolvable in water film forming polymer in the oil so that the transfer of restrict colors.But the shortcoming of introducing these polymer in the solution of volatile solvent is to cause sometimes preparation viscosity low (specifically being because used viscosity low-down oil, particularly ethereal oil).The problem that this low rheological characteristic produces is to use thorny and have no attraction, and because the drying that the existence of volatile matter causes can make deposit inhomogeneous.

To good adhesive force and good texture texture are arranged, be easy to use and obtain uniform sedimental non-transfusion cosmetics and continue that demand is arranged.

Product, particularly said composition that compositions of the present invention can be in particular the health, lip or the cosmetic of epidermis derivant that are used for the people have non-treatment and/or nursing characteristic.Compositions of the present invention can be specially lip pomade or the lip pomade that adds lustre to, kermes, eye shadow, the product of tatooing, mascara, eyeliner, nial polish, the pitch-dark product of artificial skin, hair dyeing or hair products.

The compositions table that the inventor is unexpected to be found to comprise acceptable organic liquid medium on the cosmetics, at least a specific block polymer and be used for the gellant of described medium reveals good expansion and lubrication property, and can obtain uniform dressing effect.In addition, described compositions glossy, do not shift and have good adhesive force.

More particularly, at first the invention provides a kind of cosmetic composition, described compositions is included in linear olefinic block polymer of at least a stiff film forming in the acceptable organic liquid medium and the film former that is used for described organic liquid medium on the cosmetics.

The present invention also provides a kind of cosmetic composition, and described compositions is at least a film former that does not contain the linear olefinic block polymer of film forming of styrene units and be used for described organic liquid medium in the acceptable organic liquid medium on comprising cosmetics.

The invention still further relates to a kind of method of making up for skin and/or lip and/or epidermis derivant, described method comprises aforesaid compositions is applied to skin and/or lip and/or epidermis derivant.

Compositions of the present invention can be applied to skin (face, scalp or health), mucosa (as the inboard of lip, palpebra inferior) and epidermis derivant (as fingernail, eyebrow, hair, eyelashes and even chaeta).

Preferred compositions of the present invention is not an eluting type compositions.

The invention still further relates to compositions as defined above and be used to improve the inhomogeneity cosmetic use of the cosmetic of skin and/or lip and/or epidermis derivant.

The invention provides the purposes of gellant in comprising the compositions of aforesaid block polymer at last, its objective is in order to obtain having good texture, to be easy to use and to obtain having gloss, can not shift and/or have good adhesive force and/or uniform sedimental compositions.

Block polymer

Compositions of the present invention comprises at least a block polymer.Term " block polymer " is meant and comprises at least two kinds of different blocks, preferably comprises the polymer of at least three kinds of different blocks.

According to an embodiment, the block polymer of compositions of the present invention is an ethylenic polymer.Term " ethylenic polymer " is meant by polymerization and contains the polymer that the monomer of ethylenic unsaturated bond obtains.

According to an embodiment, the block polymer of compositions of the present invention is a line polymer.On the contrary, the polymer of non-linear structure is as being branching, asterism (starburst) or the isostructural polymer of grafting.

According to an embodiment, the block polymer of compositions of the present invention is a film forming polymer.Term " film forming polymer " is meant itself or can forms the polymer of the successive film that is attached to carrier (particularly keratin material) in the presence of secondary film formers.

According to an embodiment, the block polymer of compositions of the present invention is a non-elastic polymer.

Term " non-elastic polymer " is meant such base polymer, when it is stretched (as stretching 30% with respect to initial length) by stress, if stop stress, can not get back to the length that equals its initial length substantially.

More particularly, term " non-elastic polymer " is meant that percentage elongation is at 30% o'clock, instantaneous answer R _i＜50%, postpone to reply R _2h＜70% polymer.Preferred R _i＜30%, R _2h＜50%.

More particularly, the inelastic behaviour of polymer is determined in accordance with the following methods:

The polymer solution impouring being scribbled in the mould of Teflon and prepare thin polymer film, is that 23 ± 5 ℃, relative humidity are under 50 ± 10% the environment dry 7 days in temperature subsequently.

Obtain the thick thin film of about 100 μ m thus, this thin film is cut into the rectangle sample of (as using stamping machine) wide 15mm, long 80mm.

Under the temperature and humidity identical, use the equipment of Zwick that this sample is applied tensile stress with dry run.

With the speed tensile sample of 50mm/min, and the distance between the chuck is 50mm, and this distance is corresponding to the initial length (l of sample ₀).

Measure instantaneous answer R in the following method _i:

-with sample stretching 30% (ε _Max), promptly extended length is initial length (l ₀) about 0.3 times,

-discharge coaction by applying the recovery rate (being 50mm/min) that equals rate of extension, after coaction is zero, measure the elongation (ε of the remnants of sample _i).

Instantaneous answer percent (R _i) obtain by following formula:

R _i＝((ε _max-ε _i)/ε _max)×100

To postpone to reply in order measuring, to get back to zero back 2 hours, measure the elongation (ε of the remnants of sample at coaction _2h).

Postpone to reply percent (R _2h) obtain by following formula:

R _2h＝((ε _max-ε _2h)/ε _max)×100

Only as instructing the instantaneous answer R of the polymer of one embodiment of the invention _iBe 10%, postpone to reply R _2hBe 30%.

According to another embodiment, the block polymer of compositions of the present invention does not comprise any styrene units." polymer that does not contain styrene units " is meant and comprises less than 10%, preferably less than 5%, preferably less than 2%, be more preferably less than the i of 1% weight) formula-CH (C ₆H ₅)-CH ₂-styrene units or the polymer of the styrene units (as methyl styrene, chlorostyrene or 1-chloro-4-methyl-benzene) that ii) replaces.

According to an embodiment, the block polymer of compositions of the present invention derives from aliphatic olefinic type monomers.Term " aliphatic monomers " is meant the monomer that does not contain aryl.

According to an embodiment, described block polymer is for deriving from the monomeric ethylenic polymer of aliphatic olefinic, and described olefinic type monomers comprises carbon-to-carbon double bond and at least one ester group-COO-or acylamino--CON-.Described ester group can be connected in two unsaturated carbons one by carbon atom or oxygen atom.Described acylamino-can be connected in two unsaturated carbons one by carbon atom or nitrogen-atoms.

According to an embodiment, described block polymer comprises at least a first block and at least a second block.

Term " at least a block " is meant one or more blocks.

In the context of this article, think term " first " and the order of the described absolutely not block of " second " block (or segment) in polymer architecture.

According to an embodiment, described block polymer comprises at least one first block and at least one second block with different glass transition temperature (Tg).

In this embodiment, first and second blocks can link together by the mid-block of glass transition temperature between the glass transition temperature of first and second block.

According to an embodiment, described block polymer comprises at least a first block and at least a second block that links together by mid-block, and described mid-block comprises the compositing monomer of at least a first block and the compositing monomer of at least a second block.

Preferred described mid-block is mainly derived from the compositing monomer of first block and second block.

Term " mainly " is that how is at least 85%, preferably at least 90%, more preferably 95%, even more preferably 100%.

The mid-block that preferably comprises the compositing monomer of the compositing monomer of at least a first block and at least a second block is an atactic polymer.

According to an embodiment, described block polymer is included in inconsistent at least a first block and at least a second block in the organic liquid medium of compositions of the present invention.

Term " mutual exclusive block " is meant under room temperature (25 ℃) and normal pressure (105Pa), the mixture unmixing in liquid that forms by the first block corresponding polymer and the second block corresponding polymer, this liquid is for accounting for most liquid in the organic liquid medium of described compositions, wherein the content of this mixture of polymers is more than or equal to 5% of described mixture (polymer and main organic liquid) gross weight, and condition is:

I) relative weight of described polymer in described mixture than scope be 10/90 to 90/10 and

Ii) equal average (weight average or number average) molecular weight ± 15% of described block polymer corresponding to average (weight average or number average) molecular weight of the various polymer of first and second blocks.

When described organic liquid medium comprises organic mixtures of liquids, under the identical situation of the mass ratio of two or more liquid, non-miscible at least a therein liquid medium of described polymeric blends.

When described organic liquid medium only comprised a kind of organic liquid, this liquid had obviously accounted for major part on weight.

Term " organic liquid medium " is meant the medium that comprises at least a organic liquid, and is promptly at least a at room temperature (25 ℃) and normal pressure (10 ⁵Pa) be the organic compound of liquid down.According to an embodiment, the main liquid of described liquid medium is volatility or nonvolatile oil (lipoid material).Preferred described organic liquid is acceptable on the cosmetics (acceptable toleration, toxicity and sensation) organic liquid.Described organic liquid medium is acceptablely on the cosmetics to be meant that it is compatible with keratin substances, is used for the oil or the organic solvent of cosmetic composition as routine.

According to an embodiment, most of liquid of described organic liquid medium is the polymer solvent of block polymer as described below or a kind of polymer solvent wherein.

Term " polymer solvent " is meant solvent or mixed solvent.Described polymer solvent can be selected from ethyl acetate, butyl acetate, alcohol (as isopropyl alcohol and ethanol), aliphatic alkanes (as Fancol ID) and composition thereof especially.Mixture or Fancol ID that preferred described polymer solvent is butyl acetate and isopropyl alcohol.

Usually, when being easy to prepare, described block polymer can be incorporated in the described compositions, reach high solid content, usually greater than 10% of described composition total weight, greater than 20%, more preferably greater than 30% with more preferably greater than 45%.

Preferably in the main chain of described block polymer, do not comprise silicon atom.Term " main chain " is meant the main skeleton of this polymer, and is relative with the side chain that hangs.

Preferred polymer of the present invention in room temperature (25 ℃), do not change pH, activity substance content is at least is not water miscible under 1% weight, the water insoluble or water of promptly described polymer and contain the mixture of the straight or branched low-grade monobasic alcohol (as ethanol, isopropyl alcohol or normal propyl alcohol) of 2 to 5 carbon atoms.

According to an embodiment, the polydispersity index I of described block polymer is greater than 2.

The polydispersity index I that is used for the block polymer of compositions of the present invention is preferably greater than 2 (are 2 to 9 as scope), be preferably greater than or equal 2.5 (are 2.5 to 8 as scope), and more preferably more than or equal to 2.8, particularly scope is 2.8 to 6.

The polydispersity index I of described polymer equals the ratio of weight average molecular weight Mw and number-average molecular weight Mn.

Weight average molecular weight (Mw) and number-average molecular weight (Mn) are by gel infiltration liquid chromatography for measuring (solvent is THF, sets up calibration trace, RI-detector with linear polystyrene standards matter).

The weight average molecular weight of preferred described block polymer (Mw) is less than or equal to 300 000, is 35 000 to 200 000 as weight average molecular weight, and more preferably 45 000 to 150 000.

The number-average molecular weight of preferred described block polymer (Mn) is less than or equal to 70 000, is 10 000 to 60 000 as number-average molecular weight, and more preferably 12 000 to 50 000.

Each block of described block polymer derives from one type monomer or derives from two or more dissimilar monomers.

This is meant that each block can be made up of homopolymer or copolymer, and this copolymer of forming described block itself can be random or alternate copolymer.

The glass transition temperature of first and second blocks theory T g value that the theory T g value of compositing monomer of each block is determined of can serving as reasons, can be referring to handbook (as " polymer handbook (thePolymer Handbook)) ", the third edition, 1989, John Wiley), determine according to the following relation that is known as the Fox law:

Be the mass fraction of the monomer i in the block of being considered, Tg _iGlass transition temperature for the homopolymer of monomer i.

Except as otherwise noted, the Tg value of first and second blocks of indication is theory T g value otherwise in the description of the present invention.

Usually the difference between the glass transition temperature of first and second block is preferably greater than 20 ℃, more preferably greater than 30 ℃ greater than 10 ℃.

Particularly described block polymer comprises at least a first block and at least a second block, and first block can be selected from:

A) Tg is greater than or equal to 40 ℃ block,

B) Tg is less than or equal to 20 ℃ block,

C) Tg is the block between 20 and 40 ℃,

And second block can be selected from be different from first block a), b) or the c) block of class.

Statement in the present invention, " ... with ... between " scope of numerical value do not comprise two end points, " ... extremely ... .. " and the scope of " scope is ... extremely ... " numerical value comprise two end points.

A) Tg is greater than or equal to 40 ℃ block

Tg such as scope that Tg is greater than or equal to 40 ℃ block are 40 to 150 ℃, preferably are greater than or equal to 50 ℃, be 50 ℃ to 120 ℃ as the Tg scope, and more preferably be greater than or equal to 60 ℃, and be 60 ℃ to 120 ℃ as scope.

Tg is greater than or equal to 40 ℃ block and can be homopolymer or copolymer.

Tg is greater than or equal to glass transition temperature that 40 ℃ block can all or part ofly derive from one or more homopolymer prepared therefrom and is greater than or equal to 40 ℃ monomer.

At this block is under the situation of homopolymer, and the glass transition temperature that this block derives from homopolymer prepared therefrom is greater than or equal to 40 ℃ monomer.This first block can be the homopolymer of only being made up of a kind of monomer (Tg of the corresponding homopolymer of this kind monomer is greater than or equal to 40 ℃).

At first block is under the situation of copolymer, and this block can be all or part of derived from one or more monomers, selects these monomeric character and concentration to make the Tg of the copolymer that obtains be greater than or equal to 40 ℃.Described copolymer can comprise as following monomer:

The Tg of-homopolymer prepared therefrom is greater than or equal to 40 ℃ monomer, is 40 ℃ to 150 ℃ as the Tg scope, preferably is greater than or equal to 50 ℃, be 50 ℃ to 120 ℃ as scope, and more preferably be greater than or equal to 60 ℃, as scope be 60 ℃ to 120 ℃ and

The Tg of-homopolymer prepared therefrom is lower than 40 ℃ monomer, the Tg that this monomer is selected from its homopolymer as described below is that the Tg of monomer between 20 ℃ and 40 ℃ and/or its homopolymer is less than or equal to 20 ℃ monomer, as the Tg scope is-100 ℃ to 20 ℃, preferably be lower than 15 ℃, particularly scope is-80 ℃ to 15 ℃, and more preferably being lower than 10 ℃, is-50 ℃ to 0 ℃ as scope.

The glass transition temperature of corresponding homopolymer is greater than or equal to 40 ℃ monomer and is preferably selected from following monomer (these monomers also are known as principal monomer):

-Shi CH ₂=C (CH ₃)-COOR ₁Methacrylate, R wherein ₁Representative comprises the unsubstituted straight or branched alkyl of 1 to 4 carbon atom, as methyl, ethyl, propyl group or isobutyl group, perhaps R ₁Represent C ₄-C ₁₂Cycloalkyl;

-Shi CH ₂=CH-COOR ₂Acrylate, R wherein ₂Represent C ₄-C ₁₂The cycloalkyl (as isobornyl acrylate) or the tert-butyl group;

(methyl) acrylamide of-following formula:

R wherein ₇And R ₈Can be identical or different, represent the C of hydrogen atom or straight or branched separately ₁-C ₁₂Alkyl, as normal-butyl, the tert-butyl group, isopropyl, isohesyl, iso-octyl or different nonyl, or R ₇Represent H and R ₈Represent 1,1-dimethyl-3-oxo butyl, and R ' represents H or methyl.The monomeric example that can mention has: N-butyl acrylamide, N tert butyl acrylamide, N-N-isopropylacrylamide, N,N-DMAA and N, N-dibutyl acrylamide;

-and composition thereof.

Particularly preferred principal monomer is methyl methacrylate, (methyl) Isobutyl 2-propenoate and (methyl) isobornyl acrylate and composition thereof.

B) Tg is less than or equal to 20 ℃ block

Tg such as scope that Tg is less than or equal to 20 ℃ block are-100 ℃ to 20 ℃, preferably are less than or equal to 15 ℃, and particularly scope is-80 ℃ to 15 ℃, and more preferably is less than or equal to 10 ℃, are-50 ℃ to 0 ℃ as scope.

Tg is less than or equal to 20 ℃ block and is can be homopolymer or copolymer.

Tg is less than or equal to glass transition temperature that 20 ℃ block can all or part ofly derive from one or more homopolymer prepared therefrom and is less than or equal to 20 ℃ monomer.

At this block is under the situation of homopolymer, and the glass transition temperature that this block derives from homopolymer prepared therefrom is less than or equal to this second block of monomer of 20 ℃ and is can be the homopolymer of only being made up of a kind of monomer (Tg of the corresponding homopolymer of this kind monomer is less than or equal to 20 ℃).

The block of being less than or equal to 20 ℃ at Tg is under the situation of copolymer, and this block can be all or part of derived from one or more monomers, selects these monomeric character and concentration to make the Tg of the copolymer that obtains be less than or equal to 20 ℃.

Described copolymer can comprise as following monomer:

The Tg of-one or more corresponding homopolymer is less than or equal to 20 ℃ monomer, is-100 ℃ to 20 ℃ as the Tg scope, preferably is lower than 15 ℃, and particularly scope is-80 ℃ to 15 ℃, and more preferably is lower than 10 ℃, as scope be-50 ℃ to 0 ℃ and

The Tg of-aforesaid one or more corresponding homopolymer is higher than 20 ℃ monomer, be greater than or equal to 40 ℃ monomer as the Tg of its homopolymer, Tg scope as its homopolymer is 40 ℃ to 150 ℃, preferably be greater than or equal to 50 ℃, as scope is 50 ℃ to 120 ℃, and more preferably being greater than or equal to 60 ℃, is that the Tg of 60 ℃ to 120 ℃ monomer and/or its homopolymer is the monomer between 20 ℃ and 40 ℃ as scope.

It is homopolymer that preferred Tg is less than or equal to 20 ℃ block.

The Tg of its homopolymer is less than or equal to 20 ℃ monomer and is preferably selected from following monomer or principal monomer:

-Shi CH ₂=CHCOOR ₃Acrylate, R ₃Represent unsubstituted straight or branched C ₁-C ₁₂Except the alkyl, the tert-butyl group, wherein can choose the hetero atom that inserts one or more O of being selected from, N and S wantonly;

-Shi CH ₂=C (CH ₃)-COOR ₄Methacrylate, R ₄Represent unsubstituted straight or branched C ₆-C ₁₂Alkyl wherein can be chosen the hetero atom that inserts one or more O of being selected from, N and S wantonly;

-Shi R ₅-CO-O-CH=CH ₂Vinyl esters, R wherein ₅Represent straight or branched C ₄-C ₁₂Alkyl;

-C ₄-C ₁₂Alkyl vinyl ether;

-N-(C ₄-C ₁₂) alkyl acrylamide, as the N-octyl acrylamide;

-and composition thereof.

Especially preferably the principal monomer of being less than or equal to 20 ℃ block as Tg is the alkyl acrylate that comprises 1 to 10 carbon atom (except that the tert-butyl group) on the alkyl chain, as acrylic acid methyl ester., Isobutyl 2-propenoate and 2-EHA and composition thereof.

C) Tg is the block between 20 ℃ and 40 ℃

Tg is that the block between 20 ℃ and 40 ℃ can be homopolymer or copolymer.

Tg is that the block between 20 ℃ and 40 ℃ can all or part of glass transition temperature derived from one or more homopolymer prepared therefrom be the monomer between 20 ℃ and 40 ℃.

Tg be the block between 20 ℃ and 40 ℃ can all or part of Tg be greater than or equal to derived from its corresponding homopolymer 40 ℃ monomer with and the Tg of corresponding homopolymer be less than or equal to 20 ℃ monomer.

At this block is under the situation of homopolymer, and this block is a monomer (or principal monomer) between 20 ℃ and 40 ℃ derived from the glass transition temperature of homopolymer prepared therefrom.This first block can be the homopolymer of only being made up of a kind of monomer (the Tg scope of the corresponding homopolymer of this kind monomer is 20 ℃ to 40 ℃).

The glass transition temperature of its homopolymer is that the monomer between 20 ℃ and 40 ℃ is preferably selected from n-BMA, acrylic acid ring ester in the last of the ten Heavenly stems, acrylic acid peopentyl ester and isodecyl acrylamide and composition thereof.

At Tg is that block between 20 ℃ and 40 ℃ is under the situation of copolymer, and this block is all or part of derived from one or more monomers (or principal monomer), and selecting these monomeric character and concentration to make the Tg of the copolymer that obtains is between 20 ℃ and 40 ℃.

Preferred Tg is that the block between 20 ℃ and 40 ℃ is all or part of derived from following monomeric copolymer:

The Tg of-aforesaid corresponding homopolymer is greater than or equal to 40 ℃ principal monomer, is 40 ℃ to 150 ℃ as the Tg scope, preferably is greater than or equal to 50 ℃, as scope is 50 ℃ to 120 ℃, and more preferably be greater than or equal to 60 ℃, as be 60 ℃ to 120 ℃ of scopes, and/or

The Tg of-aforesaid corresponding homopolymer is less than or equal to 20 ℃ principal monomer, as the Tg scope is-100 ℃ to 20 ℃, preferably be less than or equal to 15 ℃, particularly scope is-80 ℃ to 15 ℃, and more preferably be less than or equal to 10 ℃, as scope is-50 ℃ to 0 ℃, and selecting the feasible Tg that forms the copolymer of first block of described monomer is between 20 ℃ and 40 ℃.

These principal monomers are as being selected from methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, butyl acrylate and 2-EHA and composition thereof.

The proportion that preferred Tg is less than or equal to 20 ℃ second block is 10% to 85% of a described polymer weight, more preferably 20% to 70%, more more preferably 20% to 50%.

Each self-contained at least a monomer that is selected from acrylic acid, acrylate, (methyl) acrylic acid and (methyl) acrylate and composition thereof of preferred first block and second block.

Preferred first and second blocks all derive from least a monomer that is selected from acrylic acid, acrylate, (methyl) acrylic acid and (methyl) acrylate and composition thereof separately.

But described block can comprise the compositing monomer of a small amount of at least a other blocks separately.

Therefore, first block can comprise the compositing monomer of at least a second block, and vice versa.

Except above-mentioned various monomers, first and/or second block also can comprise one or more other monomers that are known as " other monomers " that are different from above-mentioned principal monomer separately.

Select other monomers and various other monomeric property quality and quantities, make the block at their places have required glass transition temperature.

This other monomers are as being selected from following monomer:

A) hydrophilic monomer, as:

-comprise at least one carboxylic acid or sulfonic acid functional group's ethylenically unsaturated monomer, if any acrylic acid, methacrylic acid, butenoic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamido propane sulfonic acid, vinyl benzoic acid, vinylphosphonic acid and salt thereof;

-comprise the ethylenically unsaturated monomer of at least one tertiary amine functional group, if any 2-vinylpyridine, 4-vinylpridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylamino-propyl Methacrylamide and salt thereof;

-Shi CH ₂=C (CH ₃)-COOR ₆Methacrylate,

R wherein ₆Representative comprises the straight or branched alkyl of 1 to 4 carbon atom, as methyl, ethyl, propyl group or isobutyl group, the alkyl of described alkyl for being replaced by one or more substituent groups that are selected from hydroxyl (as being methacrylic acid 2-hydroxypropyl acrylate and methacrylic acid 2-hydroxyl ethyl ester) and halogen atom (Cl, Br, I or F) (as being trifluoroethyl methacrylate);

-Shi CH ₂=C (CH ₃)-COOR ₉Methacrylate,

R ₉Represent C ₆-C ₁₂The straight or branched alkyl, the one or more hetero atoms that are selected from O, N and S of wherein optional insertion, described alkyl is replaced by one or more substituent groups that are selected from hydroxyl and halogen (Cl, Br, I or F);

-Shi CH ₂=CHCOOR ₁₀Acrylate,

R ₁₀The straight or branched C that representative is replaced by one or more substituent groups that are selected from hydroxyl and halogen (Cl, Br, I or F) ₁-C ₁₂Alkyl (as being acrylic acid 2-hydroxypropyl acrylate and acrylic acid 2-hydroxyl ethyl ester), perhaps R ₁₀Represent the C of 5-30 oxygen ethylene repeating unit ₁-C ₁₂Alkyl-O-POE (polyoxyethylene), as methoxyl group-POE, or

R ₁₀Representative comprises the polyoxyethylene group of 5 to 30 oxygen ethylene unit,

B) comprise the ethylenically unsaturated monomer of one or more silicon atoms, as methacryloxypropyl trimethoxy silane and methacryloxypropyl three (trimethylsiloxy) silane;

-and composition thereof.

Particularly preferred other monomers are acrylic acid, methacrylic acid and trifluoroethyl methacrylate and composition thereof.

According to an embodiment, the monomer of each self-contained at least a being selected from (methyl) acrylate of first and second blocks of described block polymer and at least a other monomers (as (methyl) acrylic acid) of choosing wantonly and composition thereof.

According to another embodiment, first and second blocks of described block polymer separately all derived from the monomer of at least a being selected from (methyl) acrylate and optional at least a other monomers as ((methyl) acrylic acid) and composition thereof.

According to an embodiment preferred, described block polymer is a non-siloxane polymer, i.e. the polymer of silicon atoms not.

This or these other monomeric content is less than or equal to 30% weight of the first and/or second block gross weight usually, as is 1% to 30% weight, is preferably 5% to 20% weight, more preferably 7% to 15% weight.

Can obtain described block polymer by free radical solution polymerization according to following preparation method:

-partially polymerized solvent is introduced in the reactor that is fit to, and heat until the temperature (being generally between 60 ℃ and 120 ℃) that is fit to polyreaction,

-in case reach this temperature, in the presence of partially polymerized initiator, the compositing monomer of first block is introduced,

-through after being 90% time T corresponding to maximum conversion rate, introduce the compositing monomer and the remaining initiator of second block,

-this mixture is continued reaction a period of time T ' (scope is 3 to 6 hours), subsequently this mixture is cooled to room temperature,

-obtain being dissolved in the polymer in the polymer solvent.

First embodiment

According to first embodiment, the Tg described in described block polymer comprises as above a) is greater than or equal to 40 ℃ first block and as above b) described in Tg be less than or equal to 20 ℃ second block.

Preferred Tg is greater than or equal to 40 ℃ first block for be greater than or equal to the copolymer of 40 ℃ monomer (as above-mentioned monomer) derived from the glass transition temperature of homopolymer prepared therefrom.

It is the homopolymer that the glass transition temperature of homopolymer prepared therefrom is less than or equal to 20 ℃ monomer (as above-mentioned monomer) that preferred Tg is less than or equal to 20 ℃ second block.

The content range that preferred Tg is greater than or equal to 40 ℃ block is 20% to 90% of a described polymer weight, more preferably 30% to 80%, more more preferably 50% to 70%.

The content range that preferred Tg is less than or equal to 20 ℃ block is 5% to 75% of a described polymer weight, is preferably 15% to 50%, and more preferably 25% to 45%.

Therefore, according to first kind of scheme variant, polymer of the present invention can comprise:

-Tg is greater than or equal to 40 ℃, be 70 ℃ to 110 ℃ first block as the Tg scope, described first block is methyl methacrylate/acrylic copolymer,

-Tg is less than or equal to 20 ℃, be 0 ℃ to 20 ℃ second block as the Tg scope, described second block be the acrylic acid methyl ester. homopolymer and

-mid-block, described mid-block are methyl methacrylate/acrylic acid/methyl acrylate copolymer.

According to second kind of scheme variant, polymer of the present invention can comprise:

-Tg is greater than or equal to 40 ℃, be 70 ℃ to 100 ℃ first block as scope, described first block is methyl methacrylate/acrylic acid/trifluoroethyl methacrylate copolymer,

-Tg is less than or equal to 20 ℃, be 0 ℃ to 20 ℃ second block as scope, described second block be the acrylic acid methyl ester. homopolymer and

-mid-block, described mid-block are methyl methacrylate/acrylic acid/acrylic acid methyl ester ./trifluoroethyl methacrylate random copolymer.

According to the third scheme variant, polymer of the present invention can comprise:

-Tg is greater than or equal to 40 ℃, be 85 ℃ to 115 ℃ first block as scope, described first block is isobornyl acrylate/isobutyl methacrylate copolymer,

-Tg is less than or equal to 20 ℃, is-85 ℃ to-55 ℃ second block as scope, described second block be the 2-EHA homopolymer and

-mid-block, described mid-block are isobornyl acrylate/isobutyl methacrylate/2-EHA random copolymer.

According to the 4th kind of scheme variant, polymer of the present invention can comprise:

-Tg is greater than or equal to 40 ℃, be 85 ℃ to 115 ℃ first block as scope, described first block is isobornyl acrylate/methylmethacrylate copolymer,

-mid-block, described mid-block are isobornyl acrylate/methyl methacrylate/2-EHA random copolymer.

According to the 5th kind of scheme variant, polymer of the present invention can comprise:

-Tg is greater than or equal to 40 ℃, be 95 ℃ to 125 ℃ first block as scope, described first block is isobornyl acrylate/isobornyl methacrylate copolymer,

-mid-block, described mid-block are isobornyl acrylate/isobornyl methacrylate/2-EHA random copolymer.

According to the 6th kind of scheme variant, polymer of the present invention can comprise:

-Tg is greater than or equal to 40 ℃, be 85 ℃ to 115 ℃ first block as scope, described first block is isobornyl methacrylate/isobutyl methacrylate copolymer,

-Tg is less than or equal to 20 ℃, is-35 ℃ to-5 ℃ second block as scope, described second block be the Isobutyl 2-propenoate homopolymer and

-mid-block, described mid-block are isobornyl methacrylate/isobutyl methacrylate/Isobutyl 2-propenoate random copolymer.

According to the 7th kind of scheme variant, polymer of the present invention can comprise:

-mid-block, described mid-block are isobornyl acrylate/isobornyl methacrylate/Isobutyl 2-propenoate random copolymer.

According to the 8th kind of scheme variant, polymer of the present invention can comprise:

-Tg is greater than or equal to 40 ℃, be 60 ℃ to 90 ℃ first block as scope, described first block is isobornyl acrylate/isobutyl methacrylate copolymer,

-mid-block, described mid-block are isobornyl acrylate/isobutyl methacrylate/Isobutyl 2-propenoate random copolymer.

The following examples are for example understood this first embodiment corresponding polymer in nonrestrictive mode.

Amount is with the gram expression.

Embodiment 1: in the reactor of the preparation of poly-(methyl methacrylate/acrylic acid/acrylic acid methyl ester .) polymer with 1 liter of 100g butyl acetate adding, in 1 hour temperature is increased to 90 ℃ from room temperature (25 ℃) subsequently.

Under 90 ℃, in 1 hour, add 180g methyl methacrylate, 30g acrylic acid, 40g butyl acetate, 70g isopropyl alcohol and 1.8g 2 subsequently, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, 5-dimethylhexane (Trigonox  141 derives from Akzo Nobel).

This mixture was kept 1 hour down at 90 ℃.

Subsequently still under 90 ℃, in 1 hour with 90g acrylic acid methyl ester., 70g butyl acetate, 20g isopropyl alcohol and 1.2g 2, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane adds in the said mixture.

This mixture was kept 3 hours down at 90 ℃, use 105g butyl acetate and 45g isopropanol subsequently, and with this mixture cooling.

Obtain the solution that comprises 40% polymer active material in butyl acetate/isopropanol mixture.

Poly-(methyl methacrylate/acrylic acid) first block, the Tg that obtain comprising Tg and be 100 ℃ are 10 ℃ polymethyl acrylate second block and the polymer of mid-block, and described mid-block is methyl methacrylate/acrylic acid/polymethyl acrylate atactic polymer.

The weight average molecular weight of this polymer is 52 000, and number-average molecular weight is 18 000, and promptly polydispersity sex index I is 2.89.

Embodiment 2: poly-(isobornyl acrylate/isobutyl methacrylate/2-EHA)

The preparation of polymer

In the reactor with 1 liter of 100g Fancol ID adding, in 1 hour, temperature is increased to 90 ℃ from room temperature (25 ℃) subsequently.

Under 90 ℃, in 1 hour, add 120g isobornyl acrylate, 90g isobutyl methacrylate, 110g Fancol ID and 1.8g 2 subsequently, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, 5-dimethylhexane (Trigonox  141 derives from Akzo Nobel).

This mixture was kept 1 hour 30 minutes down at 90 ℃.

Subsequently still under 90 ℃, in 30 minutes with 90g 2-EHA, 90g Fancol ID and 1.2g 2, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane adds in the said mixture.

This mixture was kept 3 hours down at 90 ℃, with postcooling.

Obtain the solution that comprises 50% polymer active material in Fancol ID.

Poly-(isobornyl acrylate/isobutyl methacrylate) first block, the Tg that obtain comprising Tg and be 80 ℃ are-70 ℃ polyacrylic acid 2-Octyl Nitrite second block and the polymer of mid-block, and described mid-block is isobornyl acrylate/isobutyl methacrylate/2-EHA atactic polymer.

The weight average molecular weight of this polymer is 77 000, and number-average molecular weight is 19 000, and promptly polydispersity sex index I is 4.05.

Embodiment 3: poly-(isobornyl acrylate/methyl methacrylate/2-EHA)

The preparation of copolymer

Under 90 ℃, in 1 hour, add 150g isobornyl acrylate, 60g methyl methacrylate, 110g Fancol ID and 1.8g 2 subsequently, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, 5-dimethylhexane (Trigonox  141 derives from Akzo Nobel).

This mixture was kept 1 hour 30 minutes down at 90 ℃.

This mixture was kept 3 hours whole subsequently cooling down at 90 ℃.

Obtain the solution that comprises 50% polymer active material in Fancol ID.

Poly-(isobornyl acrylate/methyl methacrylate) first block, the Tg that obtain comprising Tg and be 100 ℃ are-70 ℃ polyacrylic acid 2-Octyl Nitrite second block and the polymer of mid-block, and described mid-block is isobornyl acrylate/methyl methacrylate/2-EHA atactic polymer.

The weight average molecular weight of this polymer is 76 500, and number-average molecular weight is 22 000, and polydispersity index I is 3.48.

Embodiment 4: poly-(isobornyl acrylate/isobornyl methacrylate/acrylic acid 2-ethyl is own

Ester) preparation of polymer

Subsequently under 90 ℃, in 1 hour, add 105g isobornyl acrylate, 105g isobornyl methacrylate, 110g Fancol ID and 1.8g 2, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, 5-dimethylhexane (Trigonox  141 derives from Akzo Nobel).

This mixture was kept 1 hour 30 minutes down at 90 ℃.

This mixture was kept 3 hours down at 90 ℃, with postcooling.

Obtain the solution that comprises 50% polymer active material in Fancol ID.

Poly-(isobornyl acrylate/isobornyl methacrylate) first block, the Tg that obtain comprising Tg and be 110 ℃ are-70 ℃ polyacrylic acid 2-Octyl Nitrite second block and the polymer of mid-block, and described mid-block is isobornyl acrylate/isobornyl methacrylate/2-EHA atactic polymer.

The weight average molecular weight of this polymer is 103 900, and number-average molecular weight is 21 300, and promptly polydispersity sex index I is 4.89.

Second embodiment

According to second embodiment, described block polymer comprises as above c) described in glass transition temperature (Tg) be first block and as above b between 20 ℃ and 40 ℃) described in glass transition temperature be less than or equal to 20 ℃ second block or as above the glass transition temperature described in a) be greater than or equal to 40 ℃ second block.

Preferred Tg is that the content range of first block between 20 ℃ and 40 ℃ is 10% to 85% of a described polymer weight, more preferably 30% to 80%, even more preferably 50% to 70%.

When second block is Tg when being greater than or equal to 40 ℃ block, preferably its content range is 10% to 85% of a described polymer weight, more preferably 20% to 70%, even more preferably 30% to 70%.

When second block is Tg when being less than or equal to 20 ℃ block, preferably its content range is 10% to 85% of a described polymer weight, more preferably 20% to 70%, even more preferably 20% to 50%

Preferred Tg be between 20 ℃ and 40 ℃ first block for the Tg derived from corresponding homopolymer be greater than or equal to 40 ℃ monomer and accordingly the Tg of homopolymer be less than or equal to 20 ℃ monomeric copolymer.

Preferred Tg is less than or equal to 20 ℃ or Tg, and to be greater than or equal to 40 ℃ second block be homopolymer.

Therefore, according to first kind of scheme variant of this second embodiment, described block polymer can comprise:

-Tg is between 20 ℃ and 40 ℃, be 25 ℃ to 39 ℃ first block as Tg, described first block is the copolymer that comprises at least a methacrylate monomer, at least a methyl methacrylate monomer and at least a acrylic monomers,

-Tg is greater than or equal to 40 ℃, be 85 ℃ to 125 ℃ second block as scope, described second block be the homopolymer formed by methyl methacrylate monomer and

-mid-block, described mid-block comprise at least a acrylic acid methyl ester., methyl methacrylate monomer and

-mid-block, described mid-block comprise methyl methacrylate, at least a acrylic monomers and at least a methacrylate monomer.

According to second kind of scheme variant of this second embodiment, described block polymer can comprise:

-Tg is between 20 ℃ and 40 ℃, be 21 ℃ to 39 ℃ first block as Tg, described first block is the copolymer that comprises isobornyl acrylate/isobutyl methacrylate/2-EHA,

-Tg is less than or equal to 20 ℃, is-65 ℃ to-35 ℃ second block as scope, described second block be imperplex and

According to the third scheme variant of this second embodiment, described block polymer can comprise:

-Tg is between 20 ℃ and 40 ℃, be 21 ℃ to 39 ℃ first block as Tg, described first block is isobornyl acrylate/acrylic acid methyl ester ./acrylic copolymer,

-Tg is greater than or equal to 40 ℃, be 85 ℃ to 115 ℃ second block as scope, described second block be the isobornyl acrylate homopolymer and

-mid-block, described mid-block are isobornyl acrylate/acrylic acid methyl ester ./acrylic acid random copolymer.

Explanation as an example, but limited, can think following polymer corresponding to the polymer of this second embodiment:

Embodiment 5: the preparation of poly-(methyl methacrylate/acrylic acid methyl ester ./acrylic acid) polymer

In the reactor with 1 liter of 100g butyl acetate adding, in 1 hour, temperature is increased to 90 ℃ from room temperature (25 ℃) subsequently.

Subsequently under 90 ℃, in 1 hour, add 504g methyl methacrylate, 21g acrylic acid, 138.6g acrylic acid methyl ester., 40g butyl acetate, 70g isopropyl alcohol and 1.8g 2, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, 5-dimethylhexane (Trigonox  141 derives from AkzoNobel).

This mixture was kept 1 hour down at 90 ℃.

Subsequently still under 90 ℃, in 1 hour with 90g methyl methacrylate, 70g butyl acetate, 20g isopropyl alcohol and 1.2g 2, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane adds in the said mixture.

This mixture was kept 3 hours down at 90 ℃, subsequently with 105g butyl acetate and 45g isopropanol and cooling.

Obtaining comprising Tg is poly-(acrylic acid methyl ester ./methyl methacrylate/acrylic acid) first block of 35 ℃, the polymer that gathers (methyl methacrylate) second block and mid-block that Tg is 100 ℃, and described mid-block is methyl methacrylate/acrylic acid/polymethyl acrylate atactic polymer.

Embodiment 6: poly-(isobornyl acrylate/isobutyl methacrylate/2-EHA)

The preparation of polymer

Subsequently under 90 ℃, in 1 hour, add 54g isobornyl acrylate, 75.6g isobutyl methacrylate, 50.4g 2-EHA, 110g Fancol ID and 1.8g2, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, 5-dimethylhexane (Trigonox  141 derives from AkzoNobel).

This mixture was kept 1 hour 30 minutes down at 90 ℃.

Subsequently still under 90 ℃, in 1 hour with 120g 2-EHA, 90g Fancol ID and 1.2g 2, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane adds in the said mixture.

This mixture was kept 3 hours dilution, and whole cooling subsequently down at 90 ℃.

Obtain the solution that comprises 50% polymer active material in Fancol ID.

Poly-(isobornyl acrylate/isobutyl methacrylate/2-EHA) first block, the Tg that obtain comprising Tg and be 25 ℃ are-50 ℃ polyacrylic acid 2-Octyl Nitrite second block and the polymer of mid-block, and described mid-block is isobornyl acrylate/isobutyl methacrylate/2-EHA atactic polymer.

Compositions of the present invention comprises preferred 0.1% to 60% weight, preferred 0.5% to 50% weight, more preferably the polymer active material (solid polymer) of 1% to 40% weight.

Gellant

Compositions of the present invention also can comprise at least a reagent that is used for the organic liquid medium of the described compositions of gelling.When gellant is added organic liquid medium, can increase the viscosity of organic liquid medium and can obtain solid or flowable composition.

The gellant of the optional auto polymerization form of described gellant and the gellant of inorganic form.

In one embodiment, described gellant is insoluble to water or water.

Gellant of the present invention is preferably selected from by chemical crosslinking and realizes agglomerative reagent and realize agglomerative reagent by physical crosslinking.

Realize agglomerative gellant by chemical crosslinking

According to an embodiment, the crosslinked elasticity polysiloxane that preferably has three dimensional structure is as MQ silicones, poly-alkyl silsesquioxane (polyalkyl sesquioxanes) (particularly poly methyl silsesquioxane) and the resin by hydrosilylation cross-linking.These silicones can be with hydrophilic group, as polyethylene glycol oxide or ethylene oxide/propylene oxide copolymer.

The polysiloxane of the present invention that can be used for that can mention has patent application EP-A-0, the crosslinked elasticity polysiloxane of describing in 295,886, and the open of this patent application is attached to herein by reference.According to this application,, make at least following material carry out additive reaction and crosslinkedly obtain described crosslinked elasticity polysiloxane by in the presence of platinum class catalyst:

-(a) per molecule has at least two C ₂-C ₆The polysiloxane of low-grade alkenyl; With

-(b) per molecule has the polysiloxane of at least two hydrogen atoms that link to each other with silicon atom.Also can use the polysiloxane of describing in the United States Patent (USP) 5 266 321, the open of this patent is attached to herein by reference.According to this patent, described polysiloxane specifically is selected from:

-i) comprise R ₂SiO and RSiO _1.5Unit and optional R ₃SiO _0.5And/or SiO ₂Unitary polysiloxane, wherein radicals R ₁Independently be selected from hydrogen, alkyl (as methyl, ethyl or propyl group), aryl (as phenyl or tolyl), unsaturated aliphatic group (as vinyl) separately, unit R ₂SiO and unit R SiO _1.5The weight ratio scope be 1/1 to 30/1;

-ii) be insoluble to silicone oil but in silicone oil swollen polysiloxane, described polysiloxane obtains by poly-organohydrogensiloxanes (1) and additive reaction with polysiloxane (2) of unsaturated aliphatic group, the amount of hydrogen or unsaturated aliphatic group is respectively the 1-20% mole during for non-annularity when described polysiloxane in (1) and (2) like this, when described polysiloxane is respectively the 1-50% mole during for ring-type.Optional these polysiloxane can comprise 1-40 oxyalkylene group, as oxypropylene group and/or oxyethylene group.

As the example that can be used for polysiloxane of the present invention, that can mention has with the following title sale or the product of preparation: the KSG6 of Shin-Etsu, the TrefilE-505C of Dow-Corning or Trefil E-506C, Gransil (the SR-CYC of Grant Industries, SRDMF10, SR-DC556) or those materials (KSG15 of Shin-Etsu that sells with pre-structuring gel (preconstituted gels) form, KSG17, KSG16, KSG18, KSG21, the Gransil SR 5CYC gel of General Electric, Gransil SR DMF 10 gel, Gransil SR DC556 gel, SF 1204 and JK 113).Also can use the mixture of these commodity.

Realize agglomerative gellant by physical crosslinking

Preferably realize gelling, be specially by molecular mixing (molecularagitation), hydrogen bond action or the crosslinked gellant of dipole effect by physical crosslinking, and the liposoluble polymer with liquid crystal group.

By molecular mixing realize agglomerative gellant be have high molecular, preferred molecular weight is higher than 500000 polymer, as silicone rubber.

Silicone rubber can have the structure of following formula:

Wherein:

R ₇, R ₈, R ₁₁And R ₁₂Identical or different, respectively doing for oneself is selected from the alkyl that contains 1 to 6 carbon atom,

R ₉And R ₁₀Identical or different, respectively doing for oneself is selected from alkyl and the aryl that contains 1 to 6 carbon atom,

X is selected from alkyl, hydroxyl and the vinyl that contains 1 to 6 carbon atom,

The selection of n and p makes the viscosity of described silicone rubber greater than 100 000mPa.s, as greater than 500 000mPa.s.

Usually, n and p can respectively do for oneself 0 to 5000, as 0 to 3000.

In can be used as the silicone rubber of gellant of the present invention, that can mention has those the wherein material of each group as giving a definition:

-substituent R ₇-R ₁₂With the X represent methylidene, p=0 and n=2700, as the SE30 of sale of General Electric company or production,

-substituent R ₇-R ₁₂With the X represent methylidene, p=0 and n=2300, as the AK 500 000 of sale of Wacker company or production,

-substituent R ₇-R ₁₂Represent methylidene, the substituent X representation hydroxy, p=0 and n=2700 are 13% the solution in D5, the Q2-1401 that sells or produce as Dow Corning company,

-substituent R ₇-R ₁₂Represent methylidene, the substituent X representation hydroxy, p=0 and n=2700 are 13% the solution in polydimethylsiloxane, the Q2-1403 that sells or produce as Dow Corning company,

-substituent R ₇, R ₈, R ₁₁, R ₁₂With X represent methylidene and substituent R ₉And R ₁₀Represent aryl, the molecular weight of described like this silicone rubber is about 600000, as Rh  ne-Poulenc (RhodiaChimie) company sell or produce 761.

The gellant of realizing the gelling organic liquid medium by hydrogen bond action is preferably selected from:

-amino silicones polymer has triazine radical or pyrimidine radicals with wherein amino bonded, and as described in the patent application EP 0 751170, this patent disclosure is attached to herein by reference,

-non-silicone polyamide, its end has ester or Disnalon (Ferrer). functional group, as the chemical compound of in following patent and patent application, describing: US 5 783 657, US 6 268 466, WO01/95871, WO00/40216, US 2002/0035237 and EP 1 068 856, these patent disclosures are attached to herein by reference

-polyurethane, as the chemical compound of in patent application DE 10022247 and FR 2 814 365, describing, these patent disclosures be attached to by reference herein and

-have vinyl and/or (methyl) acrylic polymer of the side group that can produce hydrogen bond action mutually, as the chemical compound of describing in patent application WO93/01797, this patent disclosure is attached to herein by reference.

Gellant also can be selected from following material:

-copolymer, as polystyrene-poly siloxanes or the polyethylene-polysiloxanes of describing in patent US 6 225 390, US 6 160 054, US 6 174 968 and US 6 225 390, the open of these patents is attached to herein by reference,

-comprise the copolymer of polysiloxane block and another kind of polyvinyl or poly-(methyl) acrylic compounds block or grafted chain, as those copolymers of describing in patent US 5,468 477 and US 5 725882, the open of these patents is attached to herein by reference,

-by comprising one or more ethylene linkages, the polymerization of the olefinic type monomers of preferred conjugated bonds (or diene) or polymer or the copolymer that copolymerization obtains,

Polymer or copolymer that-polymerization or copolymerization by olefinic type monomers obtains, concrete available have vinyl-based, acrylic compounds or a methacrylic copolymer.Described olefinic gellant can comprise the combination as styrene block (S), ring-alkylated styrenes block (AS), ethylene/butylene block (EB), ethylene/propene block (EP), butadiene block (B), isoprene block (I), acrylate block (A), methacrylate block (MA) or these blocks.

In one embodiment, use contains the copolymer of at least one styrene block as gellant.Can use triblock copolymer, polystyrene/polyisoprene or polystyrene/polybutadiene class are specifically arranged, as Luvitol HSB and polystyrene/ethylene-propylene copolymer class or the polystyrene/ethylene-butene copolymer class that BASF AG sells or produces, sell or the Kraton of production or the GelledPermethyl 99A of Penreco company as ShellChemical Co. company.Also can use styrene-methacrylate copolymer.

The olefinic gellant that can be used for compositions of the present invention that can mention for example has: KratonG1650 (SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS), KratonG1657X (SEBS), Kraton G1701X (SEP), Kraton G1702X (SEP), KratonG1726X (SEB), Kraton D-1101 (SBS), Kraton D-1102 (SBS), Kraton D-1107 (SIS), GeUed Permethyl 99A-750, Gelled Permethyl99A-753-58, Gelled Permethyl 99A-753-59, the Versagel5970 of Penreco company and Versagel 5960, and the OS 129880 of Lubrizol company, OS 129881 and OS 84383 (styrene-methacrylate copolymer).

Diblock or triblock copolymer as polystyrene-ethylene/propene copolymer or polystyrene-ethylene/butylene copolymers, also can comprise in the present invention as those copolymers of describing in patent application WO 98/38981 and US2002/0055562.

Realize that by the dipole effect agglomerative gellant is preferably selected from the chemical compound of describing in document WO 01/30886 and US 6228967, these openly are attached to herein by reference.Dipole effect as described in ionogen in the described chemical compound (as the amphion group) produces.

The also preferred gellant that uses as have the lipophilic polymer of liquid crystal group of the present invention, especially main chain is polysiloxanes, vinyl-based and/or (methyl) acrylic compounds and the lipophilic polymer with liquid crystal side group, be specially the chemical compound of describing in patent application FR 2 816 503, this patent disclosure is attached to herein by reference.

In another embodiment, described gellant can be inorganic form.

Described gellant can be modified clay.The available modified clay that can mention has: use C ₁₀-C ₂₂The Strese Hofmann's hectorite. of fatty acid chlorination ammonium modification, as Strese Hofmann's hectorite. (being also referred to as the quatermium-18 bentonite) with the chloro distearyl dimethyl ammonium modification, as the Bentone 34 that Rheox company sells or produces, Claytone XL, Claytone 34 and Claytone 40 that Southern Clay company sells or produces; Be called quaternium-18 bentonite and zephiran alta-mud modification clay, as Claytone HT, Claytone GR and the Claytone PS of sale of Southern Clay company or production; With the clay (being called the steralkonium bentonite) of stearyl dimethylbenzoyl ammonium chloride modification, sell or the Claytone APA of production and the Baragel24 of Claytone AF and sale of Rheox company or production as Southern Clay company.

Other that can mention can be used for inorganic gel agent of the present invention silicon dioxide, as pyrogenic silica.The particle diameter of pyrogenic silica can be nanoscale or micron order, 5nm to 200nm according to appointment.

Pyrogenic silica can be by volatile silicon compound pyrohydrolysis in oxyhydrogen flame, obtains dispersive silicon dioxide in small, broken bits and makes.Adopt this method can obtain having the hydrophilic silicon dioxide of a large amount of silanol groups on its surface.Silanol groups can so just be obtained hydrophobic silica by for example hydrophobic group displacement.Hydrophobic group can be:

-trimethylsiloxy, this group specifically obtain by handle pyrogenic silica in the presence of hexamethyldisilane base amine.According to CTFA (the 6th edition, nineteen ninety-five), will be called " silicon dioxide silylanizing thing (silica silylate) " through the silicon dioxide of so handling.The Aerosil R812 that their example has Degussa company to sell or produce ^CAB-O-SIL TS-530 with sale of Cabot company or production ^

-dimethyl silane oxygen base or poly dimethyl first siloxy group, this group specifically obtain by handle pyrogenic silica in the presence of polydimethylsiloxane or dimethyldichlorosilane.According to CTFA (the 6th edition, nineteen ninety-five), will be called " silicon dioxide dimetylsilyl thing (silica dimethylsilylate) " through the silicon dioxide of so handling.The Aerosil R972 that their example has Degussa company to sell or produce ^With Aerosil R974 ^, and Cabot company sells or the CAB-O-SIL TS-610 of production ^With CAB-O-SIL TS-720 ^

-derived from the group of the reaction of pyrogenic silica and silane alkoxy groups thing or siloxanes.The Aerosil R805 that the example of these treated silicon dioxide has Degussa company to sell or produce ^

According to the present invention, can use hydrophobic silica (as pyrogenic silica) as gellant.

The concentration range of these gellant can be 0.05% to 35% of described composition total weight, and for example 0.5 to 20% or 1 to 10%.

Compositions of the present invention can comprise hydrophilic media, described hydrophilic media comprises the mixture of water or water and hydrophilic organic solvent, and hydrophilic organic solvent is as being alcohol (the straight or branched low-grade monobasic alcohol (as ethanol, isopropyl alcohol or normal propyl alcohol) and the polyhydric alcohol (as glycerol, diglycerol, propylene glycol, sorbitol, pentanediol and Polyethylene Glycol) that particularly comprise 2 to 5 carbon atoms) or C ₂Ether and C ₂-C ₄Aldehyde.

The content range of the mixture of water or water and hydrophilic organic solvent in compositions of the present invention can be 0.1% to 99% of described composition total weight, is preferably 10% to 80%.

Compositions of the present invention comprises acceptable organic liquid medium on the cosmetics (acceptable toleration, toxicity and sensation).

According to a particularly preferred embodiment, the organic liquid medium of described compositions comprises at least a organic solvent, and this organic solvent is the polymer solvent of aforesaid block polymer or a kind of polymer solvent wherein.Preferred described organic solvent is for accounting for the liquid of major part (by weight) in the organic liquid medium of described cosmetic composition.

According to an embodiment, described organic liquid medium comprises at room temperature (being generally 25 ℃) and is the lipoid material of liquid.This liquid aliphatic class material can derive from animal, plant, mineral or synthetic.

Can be used for of can mentioning, of the present inventionly at room temperature have for the lipoid material of liquid (so-called " oil "): zoogenous alkyl oil, as perhydro-squalene; Plant source alkyl oil, as contain liquid triglyceride (as triheptin or tricaprylin), Oleum Helianthi, Semen Maydis oil, soybean oil, Oleum Vitis viniferae, Oleum sesami, almond oil, macadimia nut oil, Oleum Ricini, American Avocado Tree oil, three sad/decanoins, Jojoba oil, the Adeps Bovis seu Bubali resin of the fatty acid of 4 to 10 carbon atoms; Mineral sources or synthetic straight or branched hydrocarbon are as liquid paraffin and derivant, vaseline, poly decene and Parleam (as parleam); The ester of synthetic ester and ether, particularly fatty acid and ether are as purcellin oil, myristic acid isopropyl, Palmic acid 2-Octyl Nitrite, stearic acid 2-octyl group dodecane ester, erucic acid 2-octyl group dodecane ester, the different stearyl ester of isostearic acid; The ester of hydroxylation is as the different stearyl ester of lactic acid, octyl hydroxystearate, hydroxy stearic acid octyl group dodecane ester, malic acid two different stearyl esters, citric acid three different cetyl and the enanthic acid of aliphatic alcohol, sad or decanoin; Polyol ester is as two sad propylene glycol esters, two enanthic acid DOPCP and two different n-nonanoic acid diethylene glycol ester and pentaerythritol esters; The aliphatic alcohol that comprises 12 to 26 carbon atoms is as octyldodecanol, 2-butyl capryl alcohol, 2-hexyldecanol, 2-undecyl pentadecanol and oleyl alcohol; Part alkyl and/or part polysiloxane group fluorocarbon oil; Silicone oil, as volatilization or nonvolatile, straight chain or cyclic polymethyl siloxane (PDMS), as ring first siloxanes (methicone), the optional diformazan siloxanes (as phenyl front three siloxanes, phenyl trimethylsiloxy diphenyl siloxane, diphenyl methyl dimethyl trisiloxanes, diphenyl diformazan siloxanes, phenyl diformazan siloxanes and PSI) that comprises phenyl; And composition thereof.

These oily amount scopes can be 0.01% to 90% of described composition total weight, and more preferably 0.1% to 85%.

The organic liquid medium of compositions of the present invention also can comprise acceptable organic solvent on one or more cosmetics (acceptable toleration, toxicity and sensation).

Usually the amount scope of these solvents can be 0.1% to 90% of described composition total weight, and is preferred 10% to 90%, and more preferably 30% to 90%.

Except above-mentioned hydrophilic organic solvent, the solvent that can be used for compositions of the present invention that can mention has and at room temperature is the following material of liquid: ketone, as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, isophorone, Ketohexamethylene and acetone; Propylene glycol is as propylene glycol monomethyl ether, propylene glycol methyl ether acetate and dipropylene glycol mono-n-butyl ether; Short-chain ester (comprising 3 to 8 carbon atoms altogether) is as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate and isoamyl acetate; Ether is as ether, methyl ether or dichlorodiethyl ether; Alkane is as decane, heptane, dodecane, Fancol ID and cyclohexane extraction; The aromatics cyclic compound is as toluene and dimethylbenzene; Aldehyde is as benzaldehyde and acetaldehyde; And composition thereof.

Except above-mentioned block polymerization beyond the region of objective existence, described compositions also can comprise other polymer (as film forming polymer).According to the present invention, term " film forming polymer " is meant self or in the presence of auxiliary film former, can forms the polymer that is attached to the continuous films on the carrier (particularly keratin material).

The film forming polymer that can be used for compositions of the present invention that can mention has the synthetic polymer free radical type or the condensation polymer type, polymer of natural origin and composition thereof.The film forming polymer that can mention specifically comprises acrylic polymer, polyurethane, polyester, polyamide, polyureas and cellulose-based polymer (as celluloid).

Described polymer can be used in combination with one or more auxiliary film former.This film former can be selected from any chemical compound that can finish required function well known by persons skilled in the art, and particularly optional self-plasticization agent and coalescent.

Compositions of the present invention can comprise at least a wax.For the present invention, term " wax " is meant in room temperature (25 ℃) and is down solid lipophilic cpd, and this chemical compound shows reversible solid phase/liquid phase state to be changed, and fusing point is greater than or equal to 30 ℃ and reach as high as 120 ℃.

Can adopt differential scanning calorimetry (DSC) to measure the fusing point of wax, as DSC 30 calorimeters of Mettler company sale.

Described wax can be alkyl wax, fluorine wax and/or silicone wax, and can be plant-derived, mineral, animal and/or synthetic source.Particularly the fusing point of described wax is higher than 25 ℃, and more preferably is higher than 45 ℃.

The wax that can be used for compositions of the present invention that can mention has: Cera Flava, Brazil wax, candelilla wax, paraffin, microwax, ceresine (ceresin) or ceresine (ozokerite), synthetic wax are (as Tissuemat E or Fischer-Tropsch wax and silicone wax the alkyl or the alkoxyl diformazan siloxanes of 16 to 45 carbon atoms (as comprise).

Described hard fat class Substance Properties and amount depend on required mechanical performance and texture.As guidance, described compositions can comprise and accounts for 0% to 50% of its gross weight, and the more preferably wax of 1%-30%.

Compositions of the present invention also can comprise the dyestuff that one or more are selected from water-soluble dye and powder dye, as pigment well known to those skilled in the art, Concha Margaritifera and leidosome.The amount scope of described coloring agent in described compositions is 0.01% to 50% of described composition weight, preferred 0.01% to 30%.

Be to be understood that term " pigment " is meant white or coloured, inorganic or the organic granular of Any shape, this granule is insoluble to physiological medium also can be painted with described compositions.

Be to be understood that term " Concha Margaritifera " is meant the claimed flare pellet of Any shape, particularly by some molluscan shell or by synthetic preparation.

Described pigment can be white or coloured, inorganic and/or organic pigment.The inorganic pigment that can mention has optional surface-treated titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, ferrum oxide (iron oxide black, iron oxide yellow or iron oxide red), chromium oxide, manganese violet (manganeseviolet), ultramarine, chromic oxide gel and barba hispanica (ferric blue) and metal dust (as aluminium powder or copper powder).

The organic pigment that can mention has white carbon black, D﹠amp; The pigment of C type, barium, strontium, calcium or aluminum color lake based on cochineal carmine base.

Also can mention pigment with effect, as comprising the granule of inorganic or organic, natural or synthetic base material (as glass, acrylic resin, polyester, polyurethane, polyethylene terephthalate, pottery or aluminium oxide), described base material is not coated with or scribbles metallics (as aluminum, gold, silver, platinum, copper or bronze) or metal-oxide (as titanium dioxide, ferrum oxide or chromium oxide) and composition thereof.

Described pearlescent pigment optional from the white pearlescent pigment Muscovitum or the bismuthyl chloride of titanium (as scribble), coloured pearlescent pigment (as scribble the odenite of the oxide of ferrum, particularly scribble barba hispanica or chromium oxide odenite, scribble the above-mentioned type organic pigment odenite and based on the pearlescent pigment of bismuthyl chloride).Also can use coated interference pigment, particularly liquid crystal pigment or multi-layer pigments.

Described water-soluble dye for example is beet root juice (beetroot juice) and methylene blue.

Compositions of the present invention also can comprise one or more fillers, and concrete content range is 0.01% to 50% of a described composition total weight, and preferable range is 0.01% to 30%.Be to be understood that term " filler " is meant colourless or white, the inorganic or synthetic granule of Any shape, no matter described compositions prepares under what temperature, this granule is insoluble to the medium of described compositions.These fillers are used in particular for improving the texture of mobile or described compositions.

No matter described filler can be any type of lamellar, sphere or the rectangular inorganic or organic filler of crystal form (as lobate, cube, hexagon, oblique side etc.).That can mention has: Pulvis Talci, Muscovitum, quartz, Kaolin, polyamide (Nylon ^) powder (Orgasol ^, derive from Atochem), poly--Beta-alanine powder and polyethylene powders, polytetrafluorethylepowder powder (Teflon ^), the polymer microbody ball of lauroyl lysine, starch, boron nitride, hollow is (as the microbody ball of polyvinylidene chloride/acrylonitrile, as Exapancel ^(Nobel Industrie)), acrylic acid copolymer (Polytrap ^, derive from Dow Corning company) and the silicones microballon (as Tospearls ^, derive from Toshiba), elastic organo-polysilane granules, sedimentary calcium carbonate, magnesium carbonate, magnesium bicarbonate, hydroxyapatite, hollow silica microsphere (Silica Beads ^, derive from Maprecos), pottery or glass microcapsule and derived from the metallic soap (as zinc stearate, manganese stearate, lithium stearate, Dodecanoic acid, zinc salt and myristic acid magnesium) of the organic carboxyl acid that contains 8 to 22 carbon atoms (preferred 12 to 18 carbon atoms).

That compositions of the present invention can be in particular is bar-shaped, suspension, dispersion liquid, solution, gel, emulsion form, particularly oil-in-water (O/W) emulsion, Water-In-Oil (W/O) emulsion or complex emulsions (W/O/W or polyhydric alcohol/O/W or O/W/O emulsion), perhaps with the form of the dispersion of emulsifiable paste, paste, mousse, capsule, particularly (particularly soft paste specifically is that 25C, shear rate are 200s for ion or nonionic liposome, two-phase or multiphase lotion, spraying, powder, paste ^-1Following, the dynamic viscosity of mensuration after 10 minutes is about 0.1 to 40Pa.s soft paste in cone and plate viscometer).Described compositions can be anhydrous composition, as can be anhydrous soft paste.

Those skilled in the art at first consider the character of used component according to its conventional knowledge, their dissolubility in carrier particularly, and next considers the purpose purposes of described compositions, can select dosage form that is fit to and preparation method thereof.

Compositions of the present invention can be cosmetic composition, as is used for product (foundation cream), lipstick, eye shadow, lip pomade, plaster for covering (concealer), kermes, mascara, eyeliner, eyebrow cosmetic product, liner, eyeliner, fingernail product (as nial polish), health cosmetic product or the hair cosmetic product (hair dyeing oil or pomade) of the colour of skin.

Compositions of the present invention also can be product, particularly sunscreen product or the dye product (as from pitch-dark product) that is used for face or body skin nursing.

Of the present inventionly also provide a kind of cosmetics external member, described external member comprises:

I) defined the container of at least one compartment, described container close by a closing element and

Ii) place the aforesaid compositions in the described compartment.

Described container can any suitable form.Described container can be specially bottle, pipe, jar, case, box, pouch or carton form.

Described closing element can be the movably form of stopper, lid, pipe cap, the band that can tear off or valve protection cap, particularly comprises the type of object that invests on this container and the covering pipe cap that is associated with this object.Also can be the element of optionally closing this container, particularly pump, valve or disk valve.

Described container can combine with spreader, and described spreader particularly comprises the brush form that keeps the mane arrangement by the tinsel of distortion.The brush of this distortion is specifically seen and is set forth in US 4 887 622.Described spreader also can be and comprises a plurality of combs that are coated with brush element that particularly obtain by molding.This comb is set forth in FR 2 796 529 as seeing.Described in FR 2 722 380, described spreader also can be the form of exquisite brush.Described spreader can foam or the form of elastomer block, felt or scraper.Described in US 5 492 426, described spreader can be nothing fixing (silk wadding or sponge) or is firmly fixed on the rod that has closing element.Described in FR 2 761 959, described spreader is parts of container.

Described product can directly or indirectly be contained in the container.For example described product can be placed on the impregnated carrier (the particularly impregnated carrier of cleaning piece or mat form), subsequently independent or a plurality of impregnated carriers that contain described product be placed box or pouch.This carrier that has mixed described product is for example seen and is set forth in patent application WO 01/03538.

Described closing element can link to each other with container by spiral.Perhaps, being connected except that by the spiral of closing element and container also connects by bayonet coupling mechanism especially, by buckle fastening (snap-fastening), folder, welding, bonding or magnetic attraction connection.Term " buckle is fastening " refers in particular to and relates to any system that realizes connection by following operation: the strain by part (particularly closing element) makes beadlet or band by bayonet socket, makes this part return to the position that strain does not take place subsequently.

Described container can to small part by the thermoplastic manufacturing.The example of the thermoplastic that can mention comprises polypropylene and polyethylene.

Perhaps, described container is by non-thermoplastic material manufacturing, particularly glass or metal (or alloy).

Described container can have inflexible wall or deformable wall, particularly with the pipe or the form of cast bottle.

Described container can comprise distribution or be convenient to distribute the instrument of described compositions.For example described container can have deformable wall, makes described compositions extrude to push the normal pressure that produces by the elasticity (or non-resilient) of chamber wall in the Bedpan.Perhaps, particularly when described product when being bar-shaped, product can be displaced by piston mechanism.Be under the situation bar-shaped, particularly cosmetic stick (for example lip pomade, foundation cream etc.), described container can comprise and can replace this excellent mechanism, particularly have sliding track mechanism at described opening direction, perhaps has threaded bar, perhaps has helical groove.Such mechanism for example sees and is set forth in patent FR 2 806 273 or FR 2 775 566.The type mechanism that is used for fluid product sees and is set forth in patent FR 2 727 609.

Described container also can by the carton that has the base that has defined at least one cell that contains described compositions with can form to the lid (the particularly lid that links to each other with base) that small part covers described base.This carton is set forth in patent application WO 03/018423 or patent FR 2 791 042 as seeing.

Described container can be equipped with the water trap of the gap area that is positioned at container.This water trap makes wiping spreader and the close-connected rod of spreader become possibility.This for example see be set forth in patent FR 2 792 618.

Compositions can be normal pressure (under the room temperature) or pressurization (particularly by propellant (aerosol)) in container.Under latter event, described container is equipped with valve (valve types that is used for aerosol).

The content of foregoing invention or patent application is combined in the present patent application by reference.

Following examples are for example understood compositions of the present invention in the mode of indefiniteness.

Embodiment 7: liquid lipstick

Component	The % quality
Component	The % quality	The polymer of embodiment 4	????50.0
Silicon dioxide (Aerosil R972 ^，Degussa)	????5.0	The polymer of embodiment 4	????50.0
Silicon dioxide (Aerosil R972 ^，Degussa)	????5.0	With ethylene/propene/styrol copolymer and butylene/ethylene/styrene copolymer (Versagel ^MD 970, Penreco) agglomerative Fancol ID	????7.0 ?
Parleam	????2.1		????7.0 ?
Parleam	????2.1	Octyldodecanol	????0.9
Silicone DC 556 (DC 556,20cSt, Dow Corning)	????2.1	Octyldodecanol	????0.9
Silicone DC 556 (DC 556,20cSt, Dow Corning)	????2.1	Fancol ID	????28.3

Vinyl pyrrolidone/1-eicosylene copolymer (Antaron V-220 ^，ISP)	????1.2
	????1.2	Pigment	????3.0
Spice	In right amount	Pigment	????3.0

The viscosity of said preparation is far above the viscosity of the preparation that does not contain gellant.Also can use foam applicator to apply like a dream, and obtain uniform deposit.

Embodiment 8: sunscreen composition

Component	% weight
Component	% weight	Glycerol	???6
Propylene glycol	???6	Glycerol	???6
Propylene glycol	???6	Acrylate/acrylic acid C ₁₀-C ₃₀Alkyl ester copolymer PEMULEN TR-2 (Noveon)	???0.3
Polypropylene acyl group dimethyl taurine ammonium polymer (HOSTACERIN AMPS, Clariant)	???0.3 ?		???0.3
	???0.3 ?	Hexamethylene siloxanes (DOW CORNING 246 FLUID, Dow Corning)	???6
Xanthan gum RHODICARE XC (Rhodia)	???0.1		???6
Xanthan gum RHODICARE XC (Rhodia)	???0.1	Terephthalylidene dicamphor sulfonic acid (MEXORYL SX, Chimex)	???1.5
Triethanolamine	In right amount		???1.5
Triethanolamine	In right amount	2-cyano group-3, and 3-diphenylacrylate-2-Octyl Nitrite (UVINUL N539, BASF)	???10
PAROSOL 1789 (Parsol 1789, Roche Vitamines)	???2.5		???10
PAROSOL 1789 (Parsol 1789, Roche Vitamines)	???2.5	2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole trisiloxanes (MEXORYL XL, Chimex)	???1.5 ?
Benzoic acid C ₁₂-C ₁₅Arrcostab (FINSOLV TN, Witco)	???4		???1.5 ?
Benzoic acid C ₁₂-C ₁₅Arrcostab (FINSOLV TN, Witco)	???4	The polymer of embodiment 3	???1
Triethanolamine	???0.35	The polymer of embodiment 3	???1
Triethanolamine	???0.35	Antiseptic and chelating agen	In right amount
Water	Add to 100	Antiseptic and chelating agen	In right amount

Embodiment 9: nial polish

The polymer of embodiment 1	(23.8g in active substance)
The polymer of embodiment 1	(23.8g in active substance)	Butyl acetate	?24.99g
Isopropyl alcohol	?10.71g	Butyl acetate	?24.99g
Isopropyl alcohol	?10.71g	Hexanediol	?2.5g

DC RED 7 color lakes	????1g
DC RED 7 color lakes	????1g	With the Strese Hofmann's hectorite. of stearyl dimethyl benzyl ammonium chloride modification (Bentone 27V, Elementis)	????1.3g

Embodiment 10: mascara composition

Cera Flava	8g
Cera Flava	8g	Paraffin	3g
Brazil wax	6g	Paraffin	3g
Brazil wax	6g	With the Strese Hofmann's hectorite. of distearyl dimethyl benzyl ammonium chloride modification (Bentone38V, Elementis)	5.3g
Propylene carbonate	1.7g		5.3g
Propylene carbonate	1.7g	Filler	1g
Pigment	5g	Filler	1g
Pigment	5g	The polymer of embodiment 2	12g is in active substance
Fancol ID	Add to 100	The polymer of embodiment 2	12g is in active substance

Embodiment 11: mascara composition

Cera Flava	??8g
Cera Flava	??8g	Paraffin	??3g
Brazil wax	??6g	Paraffin	??3g
Brazil wax	??6g	With the Strese Hofmann's hectorite. of distearyl dimethyl benzyl ammonium chloride modification (Bentone 38V, Elementis)	??5.3g ?
Propylene carbonate	??1.7g		??5.3g ?
Propylene carbonate	??1.7g	Filler	??lg
Pigment	??5g	Filler	??lg
Pigment	??5g	The polymer of embodiment 4	12g is in active substance
Fancol ID	Add to 100	The polymer of embodiment 4	12g is in active substance

Embodiment 12: nial polish

The polymer of embodiment 5	23.8g, in active substance
The polymer of embodiment 5	23.8g, in active substance	Butyl acetate	??24.99g
Isopropyl alcohol	??10.71g	Butyl acetate	??24.99g
Isopropyl alcohol	??10.71g	Hexanediol	??2.5g
????DC?RED?7?Lake	??1g	Hexanediol	??2.5g

With the Strese Hofmann's hectorite. of stearyl dimethyl benzyl ammonium chloride modification (Bentone 27V, Elementis)	? 1.3g
	? 1.3g	Ethyl acetate	Add to 100g

Embodiment 13: mascara composition

Cera Flava	8g
Cera Flava	8g	Paraffin	3g
Brazil wax	6g	Paraffin	3g
Brazil wax	6g	With the Strese Hofmann's hectorite. of distearyl dimethyl benzyl ammonium chloride modification (Bentone38V, Elementis)	5.3g
Propylene carbonate	1.7g		5.3g
Propylene carbonate	1.7g	Filler	1g
Pigment	5g	Filler	1g
Pigment	5g	The polymer of embodiment 6	12g is in active substance
Fancol ID	Add to 100g	The polymer of embodiment 6	12g is in active substance

Claims

1. cosmetic composition is characterized in that the gellant that described compositions is included in the linear olefinic block polymer of at least a non-resilient film forming in the acceptable organic liquid medium on the cosmetics and is used for described organic liquid medium.

2. a cosmetic composition is characterized in that described compositions is included at least a linear olefinic block polymer of film forming of styrene units and the gellant that is used for described organic liquid medium of not containing in the acceptable organic liquid medium on the cosmetics.

3. claim 1 or 2 cosmetic composition is characterized in that described block polymer for deriving from the monomeric ethylenic polymer of aliphatic olefinic, and described olefinic type monomers comprises carbon-to-carbon double bond and at least one ester group-COO-or acylamino--CON-.

4. each cosmetic composition during aforesaid right requires, it is characterized in that described polymer in room temperature (25 ℃), do not change pH, activity substance content is at least under 1% weight, the water insoluble or water of described polymer and contain the mixture of the straight or branched low-grade monobasic alcohol of 2 to 5 carbon atoms.

5. each cosmetic composition during aforesaid right requires, it is characterized in that described block polymer comprises by interconnected first and second blocks of mid-block, described mid-block comprises the compositing monomer of at least a first block and the compositing monomer of at least a second block.

6. each cosmetic composition is characterized in that described block polymer comprises first and second blocks with different glass transition temperature (Tg) during aforesaid right required.

7. each compositions is characterized in that described first and second blocks are interconnection by the mid-block of glass transition temperature between the glass transition temperature of first and second blocks during aforesaid right required.

8. each cosmetic composition is characterized in that described block polymer is included in inconsistent first and second blocks in the described organic liquid medium during aforesaid right required.

9. each cosmetic composition during aforesaid right requires, the polydispersity index I that it is characterized in that described block polymer is greater than 2.

10. the compositions of claim 6 is characterized in that first block of described polymer is selected from:

A) Tg is greater than or equal to 40 ℃ block,

B) Tg is less than or equal to 20 ℃ block,

C) Tg is the block between 20 ℃ and 40 ℃, and

Described second block be selected from be different from described first block a), b) or the c) block of class.

11. the compositions of claim 10 is characterized in that Tg is greater than or equal to 40 ℃ all or part of glass transition temperature that derives from one or more homopolymer prepared therefrom of block and is greater than or equal to 40 ℃ monomer.

12. each compositions during aforesaid right requires, the glass transition temperature that it is characterized in that corresponding homopolymer are greater than or equal to 40 ℃ monomer and are selected from following monomer:

-Shi CH ₂=CH-COOR ₂Acrylate, R wherein ₂Represent C ₄-C ₁₂Cycloalkyl, as isobornyl acrylate, or the tert-butyl group;

(methyl) acrylamide of-following formula:

R wherein ₇And R ₈Can be identical or different, represent the C of hydrogen atom or straight or branched separately ₁-C ₁₂Alkyl, as normal-butyl, the tert-butyl group, isopropyl, isohesyl, iso-octyl or different nonyl, or R ₇Represent H and R ₈Represent 1,1-dimethyl-3-oxo butyl, and R ' represents H or methyl;

-and composition thereof.

13. the compositions of claim 11 or 12, the glass transition temperature that it is characterized in that corresponding homopolymer are greater than or equal to 40 ℃ monomer and are selected from methyl methacrylate, (methyl) Isobutyl 2-propenoate, (methyl) isobornyl acrylate and composition thereof.

14. the compositions of claim 10 is characterized in that Tg is less than or equal to 20 ℃ all or part of glass transition temperature that derives from homopolymer prepared therefrom of block and is less than or equal to 20 ℃ monomer.

15. the compositions of claim 14, the glass transition temperature that it is characterized in that corresponding homopolymer are less than or equal to 20 ℃ monomer and are selected from following monomer:

-C ₄-C ₁₂Alkyl vinyl ether;

-N-(C ₄-C ₁₂) alkyl acrylamide, as the N-octyl acrylamide;

-and composition thereof.

16. the compositions of claim 14 or 15, the glass transition temperature that it is characterized in that corresponding homopolymer are less than or equal to 20 ℃ monomer and are selected from and comprise 1 to 10 carbon atom, the alkyl acrylate except that the tert-butyl group on the alkyl chain.

17. the compositions of claim 10 is characterized in that Tg is that all or part of glass transition temperature that derives from homopolymer prepared therefrom of block between 20 ℃ and 40 ℃ is the monomer between 20 ℃ and 40 ℃.

18. the compositions of claim 10 is characterized in that Tg is that Tg that all or part of Tg that derives from corresponding homopolymer of block between 20 ℃ and 40 ℃ is greater than or equal to 40 ℃ monomer and corresponding homopolymer is less than or equal to 20 ℃ monomer.

19. the compositions of claim 17 or 18 is characterized in that Tg is that all or part of the deriving from of block between 20 ℃ and 40 ℃ is selected from following monomer: methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, butyl acrylate and 2-EHA and composition thereof.

20. each compositions among the claim 10-19, it is characterized in that described compositions comprises block polymer, described block polymer comprises at least a first block and at least a second block, the glass transition temperature of described first block (Tg) is greater than or equal to 40 ℃, and the glass transition temperature of described second block is less than or equal to 20 ℃.

21. each compositions is characterized in that all or part of glass transition temperature that derives from one or more homopolymer prepared therefrom of described first block is greater than or equal to 40 ℃ monomer during aforesaid right required.

22. the compositions of claim 21 is characterized in that described first block is that the glass transition temperature that derives from homopolymer prepared therefrom is greater than or equal to 40 ℃ monomeric copolymer.

23. the compositions of claim 21 or 22, the glass transition temperature that it is characterized in that corresponding homopolymer are greater than or equal to 40 ℃ monomer and are selected from following monomer:

(methyl) acrylamide of-following formula:

R wherein ₇And R ₈Identical or different, represent the C of hydrogen atom or straight or branched separately ₁-C ₁₂Alkyl, as normal-butyl, the tert-butyl group, isopropyl, isohesyl, iso-octyl or different nonyl, or R ₇Represent H and R ₈Represent 1,1-dimethyl-3-oxo butyl, and R ' represents H or methyl;

-and composition thereof.

24. each compositions among the claim 21-23, the glass transition temperature that it is characterized in that corresponding homopolymer are greater than or equal to 40 ℃ monomer and are selected from methyl methacrylate, isobutyl methacrylate and (methyl) isobornyl acrylate and composition thereof.

25. each compositions among the claim 21-24 is characterized in that the proportion of described first block is the 20%-90% of described polymer weight, is preferably 30%-80%, and 50%-70% more preferably.

26. each compositions among the claim 20-25 is characterized in that all or part of glass transition temperature that derives from one or more homopolymer prepared therefrom of described second block is less than or equal to 20 ℃ monomer.

27. each compositions among the claim 20-26 is characterized in that described second block is that the glass transition temperature that derives from homopolymer prepared therefrom is less than or equal to 20 ℃ monomeric homopolymer.

28. the compositions of claim 26 or 27, the glass transition temperature that it is characterized in that corresponding homopolymer are less than or equal to 20 ℃ monomer and are selected from following monomer:

-C ₄-C ₁₂Alkyl vinyl ether;

-N-(C ₄-C ₁₂) alkyl acrylamide, as the N-octyl acrylamide;

-and composition thereof.

29. each compositions among the claim 26-28, the glass transition temperature that it is characterized in that corresponding homopolymer are less than or equal to 20 ℃ monomer and are selected from and comprise 1 to 10 carbon atom, the alkyl acrylate except that the tert-butyl group on the alkyl chain.

30. each compositions among the claim 20-29 is characterized in that it is the 5%-75% of described polymer weight that Tg is less than or equal to the proportion of 20 ℃ second block, 15%-50% more preferably, and even 25%-45% more preferably.

31. each compositions among the claim 10-19, it is characterized in that described compositions comprises block polymer, described block polymer comprises at least a first block and at least a second block, the glass transition temperature of described first block (Tg) is between 20 ℃ and 40 ℃, and the glass transition temperature of described second block is less than or equal to 20 ℃ or glass transition temperature and is greater than or equal to 40 ℃.

32. each compositions during aforesaid right requires is characterized in that Tg is that all or part of glass transition temperature that derives from one or more homopolymer prepared therefrom of first block between 20 ℃ and 40 ℃ is the monomer between 20 ℃ and 40 ℃.

33. the compositions of claim 31 or 32 is characterized in that Tg is that first block between 20 ℃ and 40 ℃ is that Tg that the Tg that derives from corresponding homopolymer is greater than or equal to 40 ℃ monomer and corresponding homopolymer is less than or equal to 20 ℃ monomeric copolymer.

34. each compositions among the claim 31-33 is characterized in that Tg is that first block between 20 ℃ and 40 ℃ derives from and is selected from following monomer: methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, butyl acrylate and 2-EHA and composition thereof.

35. each compositions among the claim 31-34 is characterized in that Tg is that the proportion of first block between 20 ℃ and 40 ℃ is the 10%-85% of described polymer weight, 30%-80% more preferably, and even 50%-70% more preferably.

36. each compositions among the claim 31-34 it is characterized in that the Tg of described second block is greater than or equal to 40 ℃, and all or part of glass transition temperature that derives from one or more homopolymer prepared therefrom is greater than or equal to 40 ℃ monomer.

37. each compositions among the claim 31-36 is characterized in that the Tg of described second block is greater than or equal to 40 ℃, and is greater than or equal to 40 ℃ monomeric homopolymer for the glass transition temperature that derives from homopolymer prepared therefrom.

38. each compositions in claim 36 and 37, the glass transition temperature that it is characterized in that corresponding homopolymer are greater than or equal to 40 ℃ monomer and are selected from following monomer:

(methyl) acrylamide of-following formula:

-and composition thereof.

39. each compositions among the claim 35-38, the glass transition temperature that it is characterized in that corresponding homopolymer are greater than or equal to 40 ℃ monomer and are selected from methyl methacrylate, isobutyl methacrylate, (methyl) isobornyl acrylate and composition thereof.

40. each compositions among the claim 36-39 is characterized in that the proportion that Tg is greater than or equal to 40 ℃ second block is the 10%-85% of described polymer weight, is preferably 20%-70%, and 30%-70% more preferably.

41. each compositions among the claim 31-40 it is characterized in that the Tg of described second block is less than or equal to 20 ℃, and all or part of glass transition temperature that derives from one or more homopolymer prepared therefrom is less than or equal to 20 ℃ monomer.

42. each compositions among the claim 31-40 is characterized in that the Tg of described second block is less than or equal to 20 ℃, and is less than or equal to 20 ℃ monomeric homopolymer for the glass transition temperature that derives from homopolymer prepared therefrom.

43. the compositions of claim 41 or 42, the glass transition temperature that it is characterized in that corresponding homopolymer are less than or equal to 20 ℃ monomer and are selected from following monomer:

-C ₄-C ₁₂Alkyl vinyl ether;

-N-(C ₄-C ₁₂) alkyl acrylamide, as the N-octyl acrylamide;

-and composition thereof.

44. each compositions among the claim 41-43, the glass transition temperature that it is characterized in that corresponding homopolymer are less than or equal to 20 ℃ monomer and are selected from and comprise 1 to 10 carbon atom, the alkyl acrylate except that the tert-butyl group on the alkyl chain.

45. each compositions among the claim 41-44, it is characterized in that the proportion that glass transition temperature is greater than or equal to 40 ℃ block is the 20%-90% of described polymer weight, 30%-80% more preferably, and even 50%-70% more preferably.

46. each cosmetic composition in each or its above-mentioned dependent claims is characterized in that described first block and/or second block comprise at least a other monomers among the claim 5-8.

47. each compositions during aforesaid right requires is characterized in that described other monomers are selected from hydrophilic monomer and comprise ethylenically unsaturated monomer of one or more silicon atoms and composition thereof.

48. the compositions of claim 46 or 47 is characterized in that described other monomers are selected from:

A) hydrophilic monomer, as:

-comprise at least one carboxylic acid or sulfonic acid functional group's ethylenically unsaturated monomer, as acrylic acid, methacrylic acid, butenoic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamido propane sulfonic acid, vinyl benzoic acid, vinylphosphonic acid and salt thereof;

-comprise the ethylenically unsaturated monomer of at least one tertiary amine functional group, as 2-vinylpyridine, 4-vinylpridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylamino-propyl Methacrylamide and salt thereof;

-Shi CH ₂=C (CH ₃)-COOR ₆Methacrylate,

R wherein ₆Representative comprises the straight or branched alkyl of 1 to 4 carbon atom, as methyl, ethyl, propyl group or isobutyl group, the alkyl of described alkyl for being replaced by one or more substituent groups that are selected from hydroxyl and halogen atom (Cl, Br, I or F), the example that hydroxyl replaces has methacrylic acid 2-hydroxypropyl acrylate and methacrylic acid 2-hydroxyl ethyl ester, and the example that halogen atom replaces has trifluoroethyl methacrylate;

-Shi CH ₂=C (CH ₃)-COOR ₉Methacrylate,

-Shi CH ₂=CHCOOR ₁₀Acrylate,

R ₁₀The straight or branched C that representative is replaced by one or more substituent groups that are selected from hydroxyl and halogen (Cl, Br, I or F) ₁-C ₁₂Alkyl (as being acrylic acid 2-hydroxypropyl acrylate and acrylic acid 2-hydroxyl ethyl ester), perhaps R ₁₀Representative has the C of 5-30 oxygen ethylene repeating unit ₁-C ₁₂Alkyl-O-POE (polyoxyethylene), as methoxyl group-POE, or

R ₁₀Representative comprises the polyoxyethylene group of 5 to 30 oxygen ethylene unit; With

-and composition thereof.

49. each compositions in claim 46 and 47 is characterized in that each self-contained at least a other monomer that are selected from acrylic acid, (methyl) acrylic acid and trifluoroethyl methacrylate of first and second blocks and composition thereof.

50. each compositions in claim 46 and 47 is characterized in that the monomer of each self-contained at least a being selected from (methyl) acrylate of first and second blocks and optional at least a other monomers as (methyl) acrylic acid, and composition thereof.

51. each compositions in claim 46 and 47 is characterized in that first and second blocks all derive from for example (methyl) acrylic acid of the monomer of at least a being selected from (methyl) acrylate and optional at least a other monomers separately, and composition thereof.

52. each compositions among the claim 46-51 is characterized in that described other one or more monomers account for 1% to 30% of the first and/or second block gross weight.

53. each compositions in claim 6 or its above-mentioned dependent claims, it is characterized in that difference between the glass transition temperature (Tg) of described first and second block is greater than 10 ℃, be preferably greater than 20 ℃, very preferably greater than 30 ℃, and more preferably greater than 40 ℃.

54. the compositions of claim 9, the polydispersity index that it is characterized in that described block polymer more than or equal to 2.5, are preferably greater than or equal 2.8.

55. the compositions of claim 54, the polydispersity index that it is characterized in that described block polymer is between 2.8 and 6.

56. each compositions is characterized in that the weight average molecular weight (Mw) of described block polymer is less than or equal to 300000 during aforesaid right required.

57. the compositions of claim 56 is characterized in that weight average molecular weight (Mw) scope is 35000 to 200000, and more preferably 45000 to 150000.

58. the compositions of claim 57 is characterized in that weight average molecular weight (Mw) is less than or equal to 70000.

59. each compositions among the claim 56-58 is characterized in that weight average molecular weight (Mw) scope is 10000 to 60000, and more preferably 12000 to 50000.

60. each compositions is characterized in that described compositions comprises 0.1% to 60% weight during aforesaid right required, preferred 5% to 50% weight, and the more preferably polymer active material of 10% to 40% weight.

61. each compositions is characterized in that described at least a gellant is selected from the gellant of polymer form during aforesaid right required.

62. the compositions of claim 60 is characterized in that described polymer gel agent is selected from the crosslinked elasticity polysiloxane with three dimensional structure, as MQ silicones, poly-alkyl silsesquioxane and the resin by hydrosilylation cross-linking.

63. the compositions of claim 62 is characterized in that described polymer gel agent comprises hydrophilic group, for example polyethylene glycol oxide or ethylene oxide/propylene oxide copolymer.

64. the compositions of claim 61 is characterized in that realizing that by molecular mixing agglomerative described reagent is the silicone rubber of following formula:

Wherein:

The selection of n and p makes the viscosity of described silicone rubber greater than 100000mPas, as greater than 500000mPas.

65. the compositions of claim 61 is characterized in that described polymer gel agent is selected from vinyl and/or (methyl) acrylic polymer that amino silicones polymer, its end of having with the triazine radical of wherein amino bonded or pyrimidine radicals have non-silicone polyamide, the polyurethane of ester or Disnalon (Ferrer). functional group and have the side group that can produce hydrogen bond action mutually.

66. the compositions of claim 61 is characterized in that described polymer gel agent is selected from:

-polystyrene-poly siloxanes or polyethylene-polysiloxane copolymer,

-comprise the copolymer of polysiloxane block and another kind of polyvinyl or poly-(methyl) acrylic compounds block or grafted chain,

-polymerization of olefinic type monomers by comprising styrene or ring-alkylated styrenes block or polymer or the copolymer that copolymerization obtains.

67. each compositions among the claim 1-60 is characterized in that described gellant is a pyrogenic silica.

68. cosmetic composition, it is characterized in that described compositions is included in the linear olefinic block polymer of a) at least a film forming in the acceptable organic liquid medium on the cosmetics, and b) at least a gellant that is used for described liquid medium, described gellant is selected from:

-pyrogenic silica,

-polystyrene-poly siloxanes or polyethylene-polysiloxane copolymer,

Each cosmetic composition during 69. aforesaid right requires, wherein said at least a gellant accounts for 0.05% to 35% of described composition total weight, for example 0.5% to 20% or 1% to 10%.

70. each cosmetic composition is characterized in that described compositions also comprises the dyestuff that one or more are selected from water-soluble dye and powder dye, as pigment, Concha Margaritifera and leidosome during aforesaid right required.

Each cosmetic composition during 71. aforesaid right requires, it is characterized in that described compositions is suspension, dispersion liquid, solution, gel, emulsion form, particularly oil-in-water (O/W) emulsion, Water-In-Oil (W/O) emulsion, complex emulsions (W/O/W or polyhydric alcohol/O/W or O/W/O emulsion), it perhaps is the form of emulsifiable paste, rod, paste or mousse or carrier dispersion, particularly ion or nonionic liposome, two-phase or multiphase lotion, spraying, powder or paste, particularly soft paste or do not have water suspension paste.

72. each cosmetic composition during aforesaid right requires is characterized in that described compositions is to be used for the compositions that keratin material is made up or nursed.

73. each cosmetic composition is characterized in that described compositions is the lip cosmetic product during aforesaid right required.

74. each cosmetic composition during aforesaid right requires is characterized in that described compositions is the eye cosmetic product.

75. each cosmetic composition is characterized in that described compositions is a colour of skin cosmetic product during aforesaid right required.

76. each cosmetic composition is characterized in that described compositions is the fingernail cosmetic product during aforesaid right required.

77. a cosmetics external member, described external member comprises:

A) defined the container of at least one compartment, described container cuts out by a closing element; With

B) place the interior compositions of described compartment,

Described compositions is each a compositions in the aforesaid right requirement.

78. the cosmetics external member of claim 77 is characterized in that described container to small part is formed by at least a thermoplastic.

79. the cosmetics external member of claim 77 is characterized in that described container to small part is formed by at least a non-thermoplastic material, particularly glass or metal form.

80. each external member among the claim 77-79 is characterized in that the closed position at described container, described closing element is connected on the described container by spiral.

81. each external member among the claim 77-79 is characterized in that the closed position at described container, described closing element is except that being connected on the described container by spiral, also particularly fastening, bonding or be welded to connect on described container by buckle.

82. each external member among the claim 77-81 is characterized in that described compositions is at the described indoor basic normal pressure that is.

83. each external member among the claim 77-81 is characterized in that described compositions is pressurized in described container.

84. a cosmetic method that is used for the cosmetic or the nursing of keratin material, described method comprise each cosmetic composition among the claim 1-76 is applied to keratin material.