CN1700900A - Compositions containing block polymers and film-forming agent - Google Patents

Compositions containing block polymers and film-forming agent Download PDF

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CN1700900A
CN1700900A CN 03825321 CN03825321A CN1700900A CN 1700900 A CN1700900 A CN 1700900A CN 03825321 CN03825321 CN 03825321 CN 03825321 A CN03825321 A CN 03825321A CN 1700900 A CN1700900 A CN 1700900A
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compositions
block
polymer
monomer
methyl
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X·布林
V·德拉波特里
V·费拉里
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LOreal SA
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LOreal SA
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Abstract

The invention relates to a cosmetic composition comprising, in a cosmetically-acceptable organic liquid medium, at least one film-forming linear ethylene block polymer and another film-forming agent. The aforementioned film-forming agent can be dissolved or dispersed in the organic liquid medium. The inventive composition can contain an aqueous phase, in which case the film-forming agent can be dissolved or dispersed in the aqueous phase. The invention also relates to the way in which the combination of one such block polymer and a film-forming agent can be used to improve the performance of said composition on keratinous materials.

Description

The compositions that comprises block polymer and film former
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 acceptable medium on the cosmetics that contain the film forming block polymer that is used in combination with other film former.
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.
Can improve adhesive force by ethereal oil is combined with film forming polymer (for example silicones), particularly the adhesive force of lip pomade.But the adhesion properties that obtains still is worse than the adhesive force of consumer's expectation.
The sedimental cosmetics of (particularly dressing effect) have lasting demand for obtain having good adhesive force on keratin material.
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 unexpected discovery of the inventor obtains cosmetic composition by specific block polymer is combined with known film former, and the sedimental adhesive force that said composition obtains on keratin material is better than comprising the adhesive force of the conventional composition of film former.
More particularly, the invention provides a kind of cosmetic composition, described compositions comprises organic liquid medium, the linear olefinic block polymer of at least a film forming and at least a other film former.
The invention provides a kind of cosmetic composition specifically, described compositions comprises organic liquid medium, the linear olefinic block polymer of at least a film forming and at least a other film former that are dissolved in the described organic liquid medium.
The present invention also provides a kind of cosmetic composition, and described compositions comprises organic liquid medium, the linear olefinic block polymer of at least a film forming and at least a other water-soluble film forming agents.
The present invention also provides a kind of cosmetic composition, and described compositions comprises organic liquid medium, the linear olefinic block polymer of at least a film forming and the particulate aqueous dispersion of at least a film forming polymer.
The present invention also provides a kind of cosmetic composition, and described compositions comprises organic liquid medium, the linear olefinic block polymer of at least a film forming and the particulate nonaqueous dispersion of at least a film forming polymer.
The linear olefinic block polymer of described film forming is preferably stiff polymer.The linear olefinic block polymer of described film forming does not preferably contain styrene units.
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 cosmetic use of the adhesive force of cosmetics on skin and/or lip and/or epidermis derivant.
Particularly when described compositions is eyelashes application composition or mascara, after such compositions is applied to eyelashes, can obtain having the cosmetic thin film of good adhesive force, for example particularly water-fast when shower or shower, and the friction of particularly anti-finger and/or tear, antiperspirant or sebum.
The invention provides the purposes of film former 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 on lip and/or epidermis derivant, obtain having the sedimentary compositions of good adhesive force.
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 at room temperature (25 ℃) and normal pressure (10 5Pa) under, the mixture unmixing in organic 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 more than or equal to 5% condition of described mixture (polymer and main organic liquid) gross weight 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 300000, is 35000 to 200000 as weight average molecular weight, and more preferably 45000 to 150000.
The number-average molecular weight of preferred described block polymer (Mn) is less than or equal to 70000, is 10000 to 60000 as number-average molecular weight, and more preferably 12000 to 50000.
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:
Figure A0382532100241
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 " scope is ... extremely ... " scope of numerical value comprises 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:
Figure A0382532100251
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 20 ℃ monomer.This second 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 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 represents one or more substituent groups that are selected from hydroxyl and halogen (Cl, Br, I or F) to replace 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,
-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/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,
-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/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:
-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,
-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 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,
-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 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: poly-(isobornyl acrylate/methyl methacrylate/acrylic acid 2-ethyl is own
Ester) preparation of copolymer
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 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 ℃.
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 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 76500, and number-average molecular weight is 22000, and polydispersity index I is 3.48.
Embodiment 2: poly-(isobornyl acrylate/isobornyl methacrylate/acrylic acid 2-ethyl
Own ester) 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.
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 ℃.
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/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 103900, and number-average molecular weight is 21300, and promptly polydispersity sex index I is 4.89.
Embodiment 3: poly-(isobornyl acrylate/isobutyl methacrylate/Isobutyl 2-propenoate) is poly-
The preparation of compound
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 Isobutyl 2-propenoate, 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 whole subsequently cooling down at 90 ℃.
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 75 ℃ are-20 ℃ polyisobutyl acrylate second block and the polymer of mid-block, and described mid-block is isobornyl acrylate/isobutyl methacrylate/Isobutyl 2-propenoate atactic polymer.
The weight average molecular weight of this polymer is 144200, and number-average molecular weight is 49300, and polydispersity sex index I is 2.93.
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
-mid-block, described mid-block are isobornyl acrylate/isobutyl methacrylate/2-EHA random copolymer.
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.
Compositions of the present invention comprises preferred 0.1% to 60% weight, preferred 0.5% to 50% weight, more preferably the polymer active material (or polymer solids) of 1% to 40% weight.
Film former
Compositions of the present invention also comprises at least a film former, and described film former can be the organic or inorganic polymer.When described film former was organic polymer, it was not the linear olefinic block polymer of aforesaid film forming.
In one embodiment, described film forming organic polymer is at least a following polymer that is selected from:
-be dissolved in the film forming polymer of described organic liquid medium, when described organic liquid medium comprised at least a oil, this film forming polymer was in particular lipophilic polymer,
-be scattered in the film forming polymer of described organic liquid solvent medium, particularly, preferably be scattered in silicone oil or the alkyl oil with the polymer of the nonaqueous dispersion form of polymer beads; In one embodiment, the nonaqueous dispersion of described polymer comprises by its lip-deep at least a stabilizing agent stable polymer granule, and this nonaqueous dispersion often is called as " NAD (nonaqueous dispersion) ",
The particulate aqueous dispersion of-film forming polymer is commonly referred to " latex "; In the case, described compositions also must comprise water except comprising organic liquid medium,
-water-soluble, film-forming polymers; In the case, described compositions also must comprise water except comprising liquid medium.
In one embodiment, described film former is the film forming organic polymer that is dissolved in described organic liquid medium.
I/ is dissolved in the polymer of described organic liquid medium
When the organic liquid medium of described compositions comprised at least a oil, described film former can be and is dissolved in described oil bodying thing.In the case, this film former is called " lipophilic polymer ".Described lipophilic polymer can be any chemical type, and can specifically be selected from:
A) following monomeric fat-soluble, amorphous homopolymer and copolymer: alkene, cycloolefin, butadiene, isoprene, styrene, vinyl ethers, ester or amide or contain linear, branching or ring-type C 4-C 50(methyl) the acrylic acid ester or the amide of alkyl are preferably unbodied.Preferred fat-soluble homopolymer and copolymer derive from and are selected from following monomer: (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylic acid isopentyl ester, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) acrylic acid methyl ester., (methyl) tert-butyl acrylate, (methyl) tridecyl acrylate and (methyl) acrylic acid stearyl or its mixture.The example that can mention comprises: alkyl acrylate/acrylic acid cycloalkyl ester copolymer of the commodity Giovarez AC-5099 ML by name that sells by Phoenix Chem., and vinylpyrrolidone copolymer is (as C 2-C 30(as C 3-C 22) olefin copolymer) and combination.As the example that can be used for VP copolymer of the present invention, that can mention has VP/ vinyl laurate, VP/ stearic acid vinyl ester, butylated polyvinyl pyrrolidone (PVP), VP/ hexadecene, VP/ melene or a VP/ acrylic acid/lauryl methacrylate copolymer.
The concrete fat-soluble copolymer that can mention has:
I) have polysiloxane backbone, acrylic compounds grafted chain or have the polysiloxanes-acrylic compounds graft polymers of acrylic backbone, polysiloxane-grafted chain, as by 3M with the trade name product sold of SA70.5 and at patent US 5,725,882, US 5,209, and 924, US 4,972,037, US 4,981,903, US 4,981, and 902, US 5,468,477/US5,219,560 and EP 0 388 582 in the product described;
Ii) belong to a kind of in above-mentioned and have the lipophilic polymer of fluorin radical, particularly those are at patent US 5,948, the polymer of describing in 393, and at patent EP 0 815836 and US 5, the copolymer of (methyl) alkyl acrylate/(methyl) perfluoroalkyl acrylate of describing in 849,318;
The iii) polymerization of the olefinic type monomers by comprising one or more ethylene linkages, preferred conjugated bonds (or diene) or polymer or the copolymer that copolymerization obtains.As the polymer or the copolymer that obtain by olefinic type monomers polymerization or copolymerization, available have vinyl-based, acrylic compounds or a methacrylic copolymer.
In one embodiment, described film former is for comprising the block copolymer of at least a block of being made up of styrene or styrene derivative unit (as methyl styrene, chlorostyrene or 1-chloro-4-methyl-benzene).The copolymer that comprises at least a styrene block can be diblock or triblock copolymer, or even is star or radial segmented copolymer.The described copolymer that comprises at least a styrene block also can comprise the combination as ring-alkylated styrenes (AS) block, ethylene/butylene (EB) block, ethylene/propene (EP) block, butadiene (B) block, isoprene (I) block, acrylate (A) block, methacrylate (MA) block or these blocks.The copolymer that comprises at least a block of being made up of styrene or styrene derivative unit can be triblock copolymer, specifically can be polystyrene/polyisoprene or polystyrene/polybutadiene class, as " LuvitolHSB " and polystyrene/(ethylene-propylene copolymer) class or polystyrene/(ethylene-butene copolymer) class of BASF sale or production, as " the Gelled Permethyl 99A " of Shell Chemical Co. sale or " Kraton " that produce or Penreco sale or production.Also can use styrene-methacrylate copolymer.
The copolymer that comprises at least a block of being made up of styrene or styrene derivative unit for example is Kraton G1650 (SEBS), Kraton G1651 (SEBS), KratonG1652 (SEBS), Kraton G1657X (SEBS), Kraton G1701X (SEP), KratonG1702X (SEP), Kraton G1726X (SEB), Kraton D-1101 (SBS), KratonD-1102 (SBS), Kraton D-1107 (SIS), Gelled Permethyl 99A-750, Gelled Permethyl 99A-753-58 (mixture of triblock polymer and radial block polymer), Gelled Permethyl 99A-753-59 (mixture of triblock polymer and radial block polymer), the Versagel 5970 of Penreco and Versagel 5960 (triblock polymer and the star polymer mixture in Fancol ID), and the OS129880 of Lubrizol, OS 129881 and OS 84383 (styrene-methacrylate copolymer).
In one embodiment, described film former is selected from vinyl esters, and (described vinyl is directly connected on the oxygen atom of ester group, and described vinyl esters is connected with on the carbonyl of ester group has the saturated of 1-19 carbon atom, the alkyl of straight or branched) and at least a other monomeric copolymers, described other monomers can be the vinyl esters that is different from already present vinyl esters, alpha-olefin (comprising 8 to 8 carbon atoms), (carbonyl of ester group is connected with has the saturated of 1 to 19 carbon atom for alkyl vinyl ether (described alkyl comprises 2 to 18 carbon atoms) or allyl ester or methyl allyl ester, the straight or branched alkyl).
Can use vinyl-based or allyl ester or methyl allyl esters cross-linking agent these copolymers are partial cross-linked, described cross-linking agent is as being tetraene propoxyl group ethane, divinylbenzene, suberic acid divinyl ester, dodecanedioic acid divinyl ester and octadecane diacid divinyl ester.
The example of these copolymers that can mention comprises following copolymer: the vinyl acetate of the divinyl benzene crosslinked with 0.2%/stearic acid allyl ester, vinyl acetate/vinyl laurate, vinyl acetate/stearic acid vinyl ester, vinyl acetate/vaccenic acid, vinyl acetate/octadecyl vinyl ether, propionate/lauric acid allyl ester, propionate/vinyl laurate, stearic acid vinyl ester/1-vaccenic acid, vinyl acetate/1-dodecylene, stearic acid vinyl ester/ethyl vinyl ether, propionate/cetyl vinyl ethers, stearic acid vinyl ester/allyl acetate, 2,2-dimethyl-octa vinyl acetate/vinyl laurate, 2,2-dimethyl-penten allyl propionate/vinyl laurate, dimethyl propylene vinyl acetate/stearic acid vinyl ester, dimethyl propylene allyl propionate/stearic acid vinyl ester, propionate/stearic acid vinyl ester; Dimethyl propylene vinyl acetate/the vinyl laurate of divinyl benzene crosslinked with 0.2%; The crosslinked vinyl acetate/octadecyl vinyl ether of tetraene propoxyl group ethane with 0.2%; The vinyl acetate of divinyl benzene crosslinked/stearic acid allyl ester with 0.2%; The vinyl acetate of divinyl benzene crosslinked/1-vaccenic acid and with the allyl propionate/stearic acid allyl ester of 0.2% divinyl benzene crosslinked with 0.2%.
The fat-soluble film forming polymer that can mention also can comprise fat-soluble copolymer, specifically is those fat-soluble copolymers that get the copolyreaction of the vinyl esters of self-contained 9 to 22 carbon atoms or alkyl acrylate that alkyl comprises 10 to 20 carbon atoms or alkyl methacrylate.
This fat-soluble copolymer is optional from polyvinyl stearate; With the crosslinked polyvinyl stearate of divinylbenzene, diallyl ether or diallyl phthalate; The copolymer of poly-(methyl) stearyl acrylate ester, polyoxyethylene lauryl vinyl acetate and poly-(methyl) lauryl acrylate that available Ethylene glycol dimethacrylate or dimethacrylate TEG ester are crosslinked.
Fat-soluble as defined above copolymer is known copolymer, and specifically describes in patent application FR-A-2 232 303, and its weight average molecular weight is 2000-500000, is preferably 4000-200000.
As the example that can be used for lipophilic polymer of the present invention, that can mention has polyolefin and a C 2-C 20Olefin copolymer, particularly polybutene.
B) unbodied, liposoluble, preferably do not contain the condensation polymer of any group to the hydrogen effect, particularly have C 4-50The aliphatic polyester of alkyl side chain or the polyester that obtains by the dimeric condensation of fatty acid, or or even as defined among the patent application FR 0 113 920 (unexposed) at room temperature be the segmental polyester of polysiloxane group of solid block, grafting or end group form.
C) unbodied, liposoluble, the polysaccharide that comprises alkyl (ether or ester) side chain particularly has C saturated or unsaturated, straight or branched 1-C 8The alkylcellulose of alkyl is as ethyl cellulose and propyl cellulose.
Described film forming polymer can be selected from cellulose-based polymer especially, as celluloid, cellulose acetate, acetobutyric acid cellulose, cellulose acetopropionate or ethyl cellulose, perhaps be selected from polyurethane, acrylic polymer, polyvinyls, polyvinylbutyrals, alkyd resins, derived from the resin (as aromatic sulfuryl amine-formaldehyde resin (as toluenesulfonamide-formaldehyde resin) and aromatic sulfuryl amine epoxy resin) of the condensation product of aldehyde.
RS1/8sec., RS1/4sec., 1/2sec., RS5sec., RS15sec., RS35sec., RS75sec., RS150sec., AS1/4sec., AS1/2sec., SS1/4sec., SS1/2sec., SS5sec. celluloid that available film-forming polymer can be sold particularly including: Hercules company; " the Santolite MHP " of toluenesulfonamide-formaldehyde resin of Akzo company " Ketjentflex MS80 " or Faconnier company and " Resimpol 80 " of " Santolite MS80 " or PanAmericana company; The alkyd resins of Dainippon company " Beckosol Ode 230-70-E "; Rohm ﹠amp; The polyurethane resin " Trixene PR4127 " of acrylic resin of Haas company " Acryloid B66 " and Baxenden company.
D) dissolve in silicone oil or by the swollen silicones of silicone oil.These resins are partial cross-linked polysiloxane, and according to the degree of cross linking, these polysiloxane can be by dissolving of the silicone oil of the oil phase of described organic liquid medium or swelling.These silicones can be selected from following non-limiting instance: MQ resin or trimethyl silyloxy esters of silicon acis (trimethylsiloxysilicate), polysilsesquioxane or crosslinked dimethyl polysiloxane/vinyl-dimethyl based polysiloxane polymer.
The nonaqueous dispersion of II/ polymer beads
Described compositions also can comprise the film former of the nonaqueous dispersion that is selected from polymer beads.It is spherical that described granule is generally.Before mixing compositions of the present invention, described granule is scattered in the acceptable liquid aliphatic phase of physiology (as alkyl oil or silicone oil) usually.According to an embodiment, these dispersions are commonly referred to the NAD (nonaqueous dispersion) of polymer, and they are different with reticular tissue (network), and reticular tissue is the aqueous dispersion of polymer.These dispersions can be in particular the form of the nano-particle of the polymer in the stabilising dispersions of described fat in mutually.In one embodiment, described nano-particle size is between 5nm and the 600nm.But, can obtain the polymer beads that the diameter maximum can reach 1 μ m.
An advantage of the polymeric dispersions of compositions of the present invention is the glass transition temperature (Tg) that can change polymer or polymeric system (additive of polymer and plasticizer type), hard polymer transition can be become softer polymer thus, thus can according to the purpose purposes, especially sedimentary film adjust the mechanical performance of described compositions.
Preferably the molecular weight of the polymer in can be used for the dispersion of compositions of the present invention is about 2000 to 10000000, Tg for-100 ℃ to 300 ℃, more preferably-50 ℃ to 50 ℃, be preferably-10 ℃ to 100 ℃.
Can use preferably to have and be less than or equal to skin temperature, particularly be less than or equal to the film forming polymer of 40 ℃ low Tg.When the dispersion that will so obtain is applied on the carrier, can form film.
The film forming polymer that can mention has free radical acrylic compounds or vinyl-based homopolymer or copolymer, and preferred Tg is less than or equal to 40 ℃, particularly-10 ℃ to 30 ℃.These polymer use separately or use with form of mixtures.
Term " free radical polyalcohol " is meant by various and contains the polymer that unsaturated bond, especially ethylenically unsaturated monomer (each monomer can carry out homopolymerization (different with polycondensation)) polymerization obtains.Free radical polyalcohol can be vinyl class in polymer or copolymer, especially acrylic polymer especially.
Described vinyl class in polymer can be obtained by the ester of the ethylenically unsaturated monomer that contains at least one acidic group and/or these acid monomers and/or the polymerization of these sour amide.
As the monomer that has acidic-group, spendable have a α, and β-ethylenically unsaturated carboxylic acids is as acrylic acid, methacrylic acid .beta.-methylacrylic acid, maleic acid or itaconic acid.Preferred (methyl) acrylic acid and .beta.-methylacrylic acid, more preferably (methyl) acrylic acid of using.
The ester of acid monomer is preferably selected from (methyl) acrylic acid ester (being also referred to as (methyl) acrylate), for example: (methyl) alkyl acrylate, particularly (methyl) acrylic acid C 1-C 20And preferred C 1-C 6Arrcostab; (methyl) aryl acrylate, particularly (methyl) acrylic acid C 6-C 10Aromatic ester; (methyl) acrylic acid hydroxy alkyl ester, particularly (methyl) acrylic acid C 2-C 6Hydroxy alkyl ester.(methyl) alkyl acrylate that can mention comprises (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) 2-EHA and (methyl) lauryl acrylate.(methyl) acrylic acid hydroxy alkyl ester that can mention comprises (methyl) 2-(Acryloyloxy)ethanol and (methyl) acrylic acid 2-hydroxypropyl acrylate.(methyl) aryl acrylate that can mention comprises benzyl acrylate or phenyl acrylate.
Particularly preferred (methyl) acrylate is (methyl) alkyl acrylate.
The preferred free radical polyalcohol that uses is (methyl) acrylic acid and (methyl) alkyl acrylate, particularly C 1-C 4The copolymer of Arrcostab.More preferably can use acrylic acid methyl ester., optional and acrylic acid copolymer.
The amide of the acid monomer that can mention comprises various (methyl) acrylamide, particularly N-alkyl (methyl) acrylamide, especially C 2-C 12Alkyl acrylamide is as N-ethyl acrylamide, N tert butyl acrylamide, N-octyl acrylamide and N-two (C 1-C 4) alkyl (methyl) acrylamide.
Described vinyl-based film forming polymer also can be obtained by the polymerization of the amide of the ester of the monomer that contains ethylenic unsaturated bond and at least one acidic-group and/or these acid monomers and/or these acid monomers.
The available monomer that has acidic-group is α, and β-ethylenically unsaturated carboxylic acids is as acrylic acid, methacrylic acid .beta.-methylacrylic acid, maleic acid or itaconic acid.Preferred (methyl) acrylic acid and .beta.-methylacrylic acid, more preferably (methyl) acrylic acid of using.
The ester of acid monomer is preferably selected from (methyl) acrylic acid ester (being also referred to as (methyl) acrylate), especially (methyl) alkyl acrylate, particularly (methyl) acrylic acid C 1-C 30And preferred C 1-C 20Arrcostab; (methyl) aryl acrylate, particularly (methyl) acrylic acid C 6-C 10Aromatic ester and (methyl) acrylic acid hydroxy alkyl ester, particularly (methyl) acrylic acid C 2-C 6Hydroxy alkyl ester.
(methyl) alkyl acrylate that can mention is methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, methacrylic acid 2-Octyl Nitrite, lauryl methacrylate and cyclohexyl methacrylate.
(methyl) acrylic acid hydroxy alkyl ester that can mention is 2-(Acryloyloxy)ethanol and acrylic acid 2-hydroxypropyl acrylate, hydroxyethyl methylacrylate and methacrylic acid 2-hydroxypropyl acrylate.
(methyl) aryl acrylate that can mention is benzyl acrylate or phenyl acrylate.
Preferred especially (methyl) acrylate is (methyl) alkyl acrylate.
According to the present invention, the alkyl of described ester can be fluoridized or perfluorinate, that is to say that the part or all of hydrogen atom of alkyl is replaced by fluorine atom.
The example of the amide of the acid monomer that can mention has (methyl) acrylamide, especially N-alkyl (methyl) (C particularly 2-C 12Alkyl) acrylamide.N-alkyl (methyl) acrylamide that can mention is N-ethyl acrylamide, N tert butyl acrylamide, uncle's N-octyl acrylamide and N-undecyl acrylamide.
Described vinyl film forming polymer also can obtain by being selected from vinyl esters and cinnamic monomeric homopolymerization or copolymerization.Specifically, can be with these monomers and above-mentioned various acid monomer and/or its ester and/or its amide polymerization.
The example of the vinyl esters that can mention is vinyl acetate, vinyl neodecanoate, new vinyl acetate acid, vinyl benzoate and p t butylbenzoic acid vinyl acetate.
The styrene monomer that can mention is styrene and α-Jia Jibenyixi.
Polymer in the dispersion of the present invention can be selected from but be not limited to following polymer or copolymer: polyurethane, polyurethane-polyacrylic class, polyureas, polyureas-polyurethane, polyester-polyurethane, polyethers-polyurethane, polyester, polyesteramide, the polyester of band aliphatic chain, alkyd resins; Acrylic compounds and/or vinyl class in polymer or copolymer; Acrylic compounds-polysiloxane copolymer; Polyacrylamide; Polysiloxane polymer is as polysiloxane polyurethane or polysiloxanes acrylic compounds and fluoropolymer polymer and composition thereof.
Polymer in the oil dispersion can account for 0.1% to 60%, preferred 2% to 40% and more preferably 4% to 25% of composition weight, calculates with solids or active substance.For being solid stabilizing agent at ambient temperature, the amount representation polymer of solids and the total amount of stabilizing agent in the dispersion.
The use amount of the fat-soluble or polymer dispersion in the compositions of the present invention can account for 0.01% to 20% of composition total weight in appropriate circumstances, and for example 1% to 10%, calculate with active substance.
III) aqueous dispersion of polymer particles
According to another embodiment, the aqueous dispersion of the optional auto polymerization composition granule of described film forming polymer, in this case, compositions of the present invention comprises water.
The aqueous dispersion that comprises one or more film forming polymers can particularly be obtained by emulsion polymerisation or by the polymer dispersed that will make in advance by the world knowledge preparation of those skilled in the art according to its grasp.
The film forming polymer that can be used for compositions of the present invention that can mention has the synthetic polymer that obtains by polycondensation or radical polymerization, polymer of natural origin and composition thereof.
In these condensation polymers, that also can mention has anion, cation, nonionic or amphotenic polkyurethanes, polyurethane-polyacrylic class, polyurethane-polyethylene base ketopyrrolidine, polyester-polyurethane, polyethers-polyurethane, polyureas, polyureas-polyurethane and composition thereof.
Described polyurethane can for example be aliphatic, alicyclic or aromatic polyurethane, polyureas-polyurethane or polyurea copolymers, and these polyurethane comprise following one or more:
-at least a the block that comes from aliphatic and/or alicyclic and/or the aromatic polyester of straight or branched, and/or
-at least aly come from block aliphatic and/or alicyclic and/or aromatic-polyether, and/or
-at least a replacement or not replacement, branching or nonbranched polysiloxane block, as polydimethylsiloxane or PSI, and/or
-at least aly contain fluorine-based block.
Polyurethane as definition in the present invention also can derive from branching or nonbranched polyester or alkyd resins, these polyester or alkyd resins contain reactive hydrogen atom (by with vulcabond and organic difunctional coreactivity chemical compound (as dihydro, diaminourea or hydroxyl amino chemical compound) sudden reaction modification), also contain carboxylic acid group or carboxylate group, sulfonic acid or sulfonate group or can neutral tertiary amine or quaternary ammonium group.
The polyester, polyamide and the epoxy ester resin that also have polyester, polyesteramide, band aliphatic chain that can mention.
Can be in accordance with known methods, obtain polyester by aliphatic series or aromatic diacid and aliphatic series or aromatic diol or with the polyhydric alcohol polycondensation.Succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid or decanedioic acid can be used as aliphatic diacid.P-phthalic acid, M-phthalic acid or derivatives thereof (as phthalate anhydride) can be used as aromatic diacid.Ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 4, (4,4-N-(1-methylpropylidene)-bisphenol) can be used as aliphatic diol to 4-N-(1-methyl propylidene) xenol.Glycerol, tetramethylolmethane, Sorbitol, trimethylolpropane can be used as polyhydric alcohol.
Polyesteramide can be according to the method that is similar to polyester, is obtained by diacid and diamidogen or amino alcohol polycondensation.Ethylenediamine, 1,6-hexamethylene diamine, m-diaminobenzene. or p-phenylenediamine (PPD) can be used as diamidogen.Monoethanolamine can be used as hydrogen base alcohol.
As the monomer of spendable band anionic group in polycondensation process, that can mention for example has dihydromethyl propionic acid, trimellitic acid or derivatives thereof (as trimellitic anhydride), pentanediol-3-sulfonate sodium and 5-sulfo group-1, a 3-disodium terephthalate.The polyester of band aliphatic chain can obtain by use the glycol of band aliphatic chain in polycondensation process.Epoxy ester resin can obtain but ω-diepoxy end has the polycondensation of the fatty acid of condensation group by at α.
Free radical polyalcohol can be acrylic compounds and/or vinyl class in polymer or copolymer especially.The preferred anionic free radical polyalcohol.As the monomer of the band anionic group that can be used for radical polymerization, that can mention has acrylic acid, methacrylic acid .beta.-methylacrylic acid, maleic anhydride or a 2-acrylamido-2-methyl propane sulfonic acid.
Acrylic polymer can be obtained by the monomeric copolymerization of ester that is selected from acrylic or methacrylic acid and/or amide.The example of the esters monomer that can mention has methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, methacrylic acid 2-Octyl Nitrite and lauryl methacrylate.The monomeric example of the amide-type that can mention has N tert butyl acrylamide and uncle's N-octyl acrylamide.
The preferred acrylic polymer that uses the copolymerization by the ethylenically unsaturated monomer that contains hydrophilic group (preferred nonionic) to obtain is as 2-(Acryloyloxy)ethanol, acrylic acid 2-hydroxypropyl acrylate, hydroxyethyl methylacrylate and methacrylic acid 2-hydroxypropyl acrylate.
Vinyl class in polymer can be obtained by the monomeric homopolymerization or the copolymerization that are selected from vinyl esters, styrene or butadiene.The example of the vinyl esters that can mention has vinylacetate, vinyl neodecanoate, new vinyl acetate acid, vinyl benzoate and p t butylbenzoic acid vinyl acetate.
Also can use acrylic compounds/polysiloxane copolymer or even celluloid/acrylic copolymer.
The polymer of natural origin (optional modification) can be selected from lac resin, callitris quadrivalvis Latreille glue,
Figure A0382532100481
Saqima resin, Canarium luzonicum Elemi,   resin, cellulose derivative and composition thereof.
What also can mention is to carry out the polymer that radical polymerization obtains by one or more free radical monomers in its surface in already present at least a polymer beads inside and/or part, and wherein said at least a polymer is selected from polyurethane, polyureas, polyester, polyesteramide and/or alkyd resins.The so-called heteropolymerization thing of these polymer.
When using aqueous dispersion of polymer particles, the solid content of described aqueous dispersion can be about 5% to 60% weight, preferred 30% to 50% weight.
The particle diameter of the polymer beads in aqueous dispersion can be between 10nm and the 500nm, between preferred 20nm and the 150nm, such particle diameter can obtain having remarkable glossy film.But also can use the granule that reaches as high as 1 micron grain size.
The aqueous dispersion of available film forming polymer comprises: the acrylic compounds dispersion, and as the Neocryl XK-90 of Avecia-Neoresins company , Neocryl A-1070 , Neocryl A-1090 , Neocryl BT-62 , Neocryl A-1079 With Neocryl A-523 , the Dow Latex 432 of Dowing Chemical company , Daitosol 5000 AD of Daito Kasey Kogyo company Or the Syntran 5760 of Daitosol 5000 SJ, Interpolymer company; The perhaps aqueous dispersion of polyurethane is as the Neorez R-981 of Avecia-Neoresins company With Neorez R-974 , the Avalure UR-405 of Goodrich company , Avalure UR-410 , Avalure UR-425 , Avalure UR-450 , Sancure 875 , Sancure 861 , Sancure 878 With Sancure 2060 , the Impranil 85 of Bayer company And the Aquamere H-1511 of Hydromer company Sulfonic polyester is as the Eastman AQ  of Eastman Chemical Products company; And the vinyl dispersion, as Mexomere PAM.
The IV water-soluble polymer
Comprise in described compositions under the situation of water, described film forming polymer can be water-soluble polymer.Therefore described water-soluble polymer is dissolved in the aqueous phase of described compositions.
The water-soluble, film-forming polymers that can mention has following cationic polymer:
(1) acrylic polymer or copolymer are as polyacrylate or polymethacrylates; (1) Zu copolymer also can comprise one or more derived from the unit that is selected from following comonomer: acrylamide and Methacrylamide, acrylic or methacrylic acid or its ester, vinyl lactam (vinylactam) (as vinyl pyrrolidone or caprolactam) or vinyl esters that acrylamide, Methacrylamide, N-[2-(2-methyl-4-oxopentyl), nitrogen-atoms are replaced by low alkyl group.
The copolymer of (1) group that therefore, can mention has:
-by the copolymer of dimethyl sulfate or quaternised acrylamide of dimethyl halogenide and dimethylaminoethyl methacrylate, as the commodity of selling with the title of Hercofloc by Hercules company,
The copolymer of-acrylamide and methacryloxyethyl trimethyl ammonium chloride for example has description in patent application EP-A-080976, by the commodity of Ciba Geigy company with the title sale of BinaQuatP 100,
The copolymer of-acrylamide and methacryloxyethyl trimethyl methylsulfuric acid ammonium, as the commodity of selling with the title of Reten by Hercules company,
-quaternized or not quaternised vinyl pyrrolidone/acrylic acid dialkylaminoalkyl ester or methacrylic acid dialkylaminoalkyl ester copolymer, for example by the commodity of ISP company, as " Gafquat 734 ", " Gafquat 755 " or " Copolymer 845,958 and 937 " with the title sale of " Gafquat ".The detailed description of these polymer is referring to French Patent (FRP) 2 077 143 and 2 393 573,
-dimethylaminoethyl methacrylate/caprolactam/vinyl pyrrolidone terpolymer is as the commodity of being sold with the title of Gaffix VC 713 by ISP company; With
-quaternised vinyl pyrrolidone/dimethylamino-propyl methacrylamide copolymer is as the commodity of being sold with the title of " Gafquat HS 100 " by ISP company;
(2) quaternised polysaccharide specifically is a United States Patent (USP) 3,589,578 and US 4,031,307 in describe those, as contain the guar gum of trialkyl ammonium cation group.Be specially the commodity of selling with the title of Jaguar C13S, Jaguar C 15, Jaguar C 17 by Meyhall company;
(3) copolymer of quaternised vinyl pyrrolidone and vinyl imidazole;
(4) chitosan or its salt;
(5) cationic cellulose derivative, as cellulose or grafting contain the copolymer of cellulose derivative of the water-soluble monomer of quaternary ammonium, specifically in U.S. Pat 4,131, description is arranged in 576, hydroxy alkyl cellulose (as methylol, ethoxy or hydroxypropyl cellulose) for example, concrete grafting methacryloxyethyl trimethyl ammonium, methacrylamido oxypropyl trimethyl ammonium, dimethyldiallylammonium salt.Corresponding to the product of this definition more specifically example the commodity of being sold with the title of " Celquat L 200 " and " Celquat H 100 " by National Starch company are arranged.
The water-soluble, film-forming polymers that can mention has following amphiphilic polymers:
(1) polymer that obtains by monomer and alkaline monomeric copolymerization derived from the vinyl compound that has carboxyl, described vinyl compound specifically is acrylic acid, methacrylic acid, maleic acid, α-Lv Daibingxisuan, the vinyl compound of the replacement of self-contained at least one the alkaline atom of described alkaline monomer derived for example specifically is methacrylic acid dialkylaminoalkyl ester, acrylic acid dialkylaminoalkyl ester, dialkylaminoalkyl Methacrylamide and acrylamide.These chemical compounds are at United States Patent (USP) 3,836, description are arranged in 537;
(2) contain derived from following unitary polymer:
A) at least a nitrogen-atoms that is selected from is by the monomer of AAM and Methacrylamide,
B) at least a acidic comonomer that contains one or more pendant carboxylic groups and
C) at least a as comprise primary, the alkaline comonomer of secondary, uncle and substituent acrylate of quaternary amine and methacrylate, and with dimethyl sulfate or the quaternised dimethylaminoethyl methacrylate of dithyl sulfate;
(3) all or part of crosslinked alkyl polyaminoamide derived from polyaminoamide;
(4) contain the unitary polymer of amphion;
(5) derived from the polymer of chitosan;
(6) derived from the polymer of the N-carboxylation alkylation thing of chitosan, as N-carboxymethyl chitosan or the N-carboxylic butyl chitosan of selling with the title of " EValsan " by Jan Dekker company;
(7) by using N, N-dialkylaminoalkyl amine (as N, the N-dimethylaminopropylamine) half amideization or use N, N-dioxane hydramine half esterization is carried out partially modified (C 1-C 5) the alkyl vinyl ether/maleic anhydride copolymer.These copolymers also can contain other vinyl comonomer, as caprolactam.
Described water-soluble, film-forming polymers is preferably selected from:
-protein, the protein of plant source for example is as Semen Tritici aestivi and soybean protein; Zoogenous protein, for example keratin (as keratin hydrolyzate and sulfonation keratin);
-anion, cation, both sexes or non-ionic chitin or chitosan polymer;
-cellulosic polymer is as hydroxyethyl-cellulose, hydroxypropyl cellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethyl cellulose and cellulosic quaternary ammonium derivative;
-acrylic polymer or copolymer are as polyacrylate or polymethacrylates;
-polyvinyl is as the copolymer of copolymer, vinyl pyrrolidone and the vinylacetate of copolymer, vinylacetate and the .beta.-methylacrylic acid of polyvinyl pyrrolidone, methyl vinyl ether and maleic anhydride;
The copolymer of-vinyl pyrrolidone and caprolactam; Polyvinyl alcohol;
The polymer of the natural origin of-optional modification, as:
Radix Acaciae senegalis, guar gum, xanthan derivatives, karaya;
Alginate and carrageenin;
Glucoamino polysaccharide, hyaluronic acid and derivant thereof;
Lac resin, sandarac gum, Agate fat, Canarium luzonicum Elemi and   fat;
DNA (deoxyribonucleic acid);
Mucopolysaccharide (as hyaluronic acid) and chondroitin sulfate and composition thereof.
Remove under the situation of striping at the more or less obvious water of needs, especially can use these polymer.
In order to improve the film property of oiliness or waterborne polymeric, can in polymeric system, add known coalescent.
According to an embodiment of the invention, the optional self-contained polymer that is contained the monomer-grafted organic main chain of non-silicone of polysiloxanes of described film forming polymer.In appropriate circumstances, these polymer can be fat-soluble, fat dispersibility, water solublity maybe can be scattered in the polymer in the aqueous medium.
The polymer that comprises the monomer-grafted organic main chain of non-silicone that is contained polysiloxanes is made of organic main chain that the organic monomer that does not contain polysiloxanes forms, wherein at described main chain with choose wantonly at an one end at least and be grafted with at least one polysiloxanes macromole.
Hereinafter, it has been generally acknowledged that term " polysiloxanes macromole " is meant any monomer that contains polysiloxane-based polymer chain in its structure.
But constitute described graft polysiloxane polymer main chain the optional self-contained ethylenic unsaturated bond of non-silicone organic monomer free redical polymerization monomer polycondensation-polymeric monomer (forming the monomer of polyamide, polyester or polyurethane) as those but and those monomers of the monomer (of ring-opening polymerisation such as oxazoline or caprolactone class).
The polymer that comprises the monomer-grafted organic main chain of non-silicone that is contained polysiloxanes of the present invention can obtain according to any method well known by persons skilled in the art, specifically, by following (i) and the reaction (ii) obtain: (i) on polysiloxane chain through suitable functionalized raw material polysiloxanes macromole, (ii) one or more non-silicone organic compound, they by can with described polysiloxanes with functional group reactions and to form the functional group of covalent bond suitably functionalized; The exemplary of this reaction be on the end of described polysiloxanes with vinyl and main chain in reaction between two keys of band ethylenically unsaturated monomer.
The polymer that comprises the monomer-grafted organic main chain of non-silicone that is contained polysiloxanes of the present invention is preferably selected from patent US 4,693,935, US 4,728,571 and US4,972,037 and patent application EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578 in those polymer of describing.These copolymers are for by containing ethylenically unsaturated monomer and have the copolymer that the monomeric radical polymerization of vinyl ends obtains, or the polyolefin by containing functional group and have can and the copolymer that obtains of the polysiloxanes macromolecular reaction of the functional end-group of described functional group reactions.
Be suitable for implementing graft polysiloxane polymer of the present invention and specifically comprise the graft polysiloxane polymer that contains with the lower part:
A) the lipotropy monomer (A) of at least a low polar free redical polymerization of 0% to 98% weight, described monomer contains ethylenic unsaturated bond;
B) at least a hydrophilic polar monomer (B) that contains ethylenic unsaturated bond of 0% to 98% weight, described monomer can with (A) class monomer copolymerization;
C) at least a polysiloxanes macromole (C) of 0.01% to 50% weight with following general formula:
X(Y) nSi(R) 3-mZ m?????(I)
Wherein:
X representative can with the monomer (A) and (B) vinyl of copolymerization;
Y represents divalent group key;
R represents hydrogen, C 1-C 6Alkyl, alkoxyl or C 6-C 12Aryl;
On behalf of number-average molecular weight, Z be at least 500 monovalence polysiloxane unit;
N be 0 or 1 and m be 1 to 3 integer; Wherein percent is based on monomer (A), (B) and total weight (C).
The number-average molecular weight scope of these polymer is 10,000 to 2,000,000, and preferred glass transition temperature T g or crystalline melting point Tm are at least-20 ℃.
The example of the lipotropy monomer (A) that can mention has the C of acrylic or methacrylic acid 1-C 18Alcohol ester; The C of methacrylic acid 12-C 30Alcohol ester; Styrene; Polystyrene macromolecular; Vinylacetate; Propionate; α-Jia Jibenyixi; T-butyl styrene; Butadiene; Cyclohexadiene; Ethylene; Propylene; Vinyltoluene; Acrylic or methacrylic acid and 1, the ester of 1-dihydro perfluoroalkane alcohol or its homologue; The ester of acrylic or methacrylic acid and ω-hydroxyl fluorine alkanol (hydrofluoroalkanol); The ester of acrylic or methacrylic acid and fluoroalkyl sulfonamido alcohol; The ester of acrylic or methacrylic acid and fluoroalkyl alcohol; Ester or its mixture of acrylic or methacrylic acid and fluorine ether alcohol.Preferred monomer (A) is selected from n-BMA, isobutyl methacrylate, tert-butyl acrylate, the methacrylate tert-butyl ester, methacrylic acid 2-Octyl Nitrite, methyl methacrylate, acrylic acid 2-(N-methyl PFO sulfonamido) ethyl ester and acrylic acid 2-(N-butyl PFO sulfonamido) ethyl ester and composition thereof.
The example of the polar monomer that can mention (B) has acrylic acid, methacrylic acid, N,N-DMAA, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, (methyl) acrylamide, N tert butyl acrylamide, maleic acid, maleic anhydride and half ester thereof, (methyl) acrylic acid hydroxy alkyl ester, diallyldimethylammonium chloride, vinyl pyrrolidone, vinyl ethers, maleimide, vinylpyridine, vinyl imidazole, heterocycle vinyl polar compound, styrene sulfonate, 1-propenol-3, vinyl alcohol, caprolactam or its mixture.Preferred monomer (B) is selected from acrylic acid, N,N-DMAA, dimethylaminoethyl methacrylate, quaternised dimethylaminoethyl methacrylate, vinyl pyrrolidone and composition thereof.
Preferred especially product sold KP 561 of Shin Etsu company or KP 562, monomer (A) is selected from C like this 18-C 22The ester of pure and mild methacrylic acid.
The polysiloxanes macromole (C) of formula (I) is preferably selected from those chemical compounds corresponding to following general formula (II):
Wherein:
R 1For hydrogen or-COOH (being preferably hydrogen);
R 2For hydrogen, methyl or-CH 2COOH (being preferably methyl);
R 3Be C 1-C 6Alkyl, alkoxyl, alkylamino, C 6-C 12Aryl or hydroxyl (being preferably methyl);
R 4Be C 1-C 6Alkyl, alkoxyl, alkylamino, C 6-C 12Aryl or hydroxyl (being preferably methyl);
Q is 2 to 6 integer (being preferably 3);
P is 0 or 1;
R is all numbers of 5 to 700;
M is 1 to 3 integer (being preferably 1).
The preferred polysiloxanes macromole that uses following formula:
N is that 5 to 700 number and 1 is the integer between 0 and 3.
One embodiment of the invention are used and can be carried out the copolymer that radical polymerization obtains as raw material by following monomeric mixture:
A) tert-butyl acrylate of 60% weight;
B) acrylic acid of 20% weight;
C) the polysiloxanes macromole of the following formula of 20% weight:
N is that 5 to 700 number and 1 is the integer between 0 and 3, and percetage by weight is calculated based on each total monomer weight.
Another specific embodiment of the present invention is used and can be carried out the copolymer that radical polymerization obtains as raw material by following monomeric mixture:
A) tert-butyl acrylate of 80% weight;
B) the polysiloxanes macromole of the following formula of 20% weight:
N is that 5 to 700 number and 1 is the integer between 0 and 3, and wherein wt percent calculates based on each total monomer weight.
The graft polysiloxane copolymer that another particular type that is suitable for implementing the graft polysiloxane polymer that contains the organic main chain of non-silicone of the present invention obtains for the reactive extrusion molding of polysiloxanes macromole that can be by having reactive terminal functional group and polyolefin polymers, wherein said polyolefin polymers comprise can with the macromolecular functional end-group reactive activity of described polysiloxanes group, to form covalent bond with described polysiloxane-grafted on described polyolefinic main chain.These polymer and preparation method thereof have description in patent application WO 95/00578.
Described active polyolefin be preferably selected from polyethylene or derive self-contained can with the polymer of the vinyl monomer of the macromolecular functional end-group reactive activity of described polysiloxanes functional group, described vinyl monomer such as propylene, styrene, ring-alkylated styrenes, butylene, butadiene, (methyl) acrylate, vinyl esters or equivalent.They specifically are to be selected from ethylene or ethene derivatives and to be selected from following monomeric copolymer: contain the monomer of carboxylic acid functional, as (methyl) acrylic acid; The monomer that contains the anhydride functional group is as maleic anhydride; The monomer that contains acid chloride functional groups is as (methyl) acryloyl chloride; The monomer that contains ester functional group is as (methyl) acrylate; The monomer that contains the isocyanate functional group.
Described polysiloxanes macromole is preferably selected from and contains the polysiloxanes that is selected from following functional group at the terminal of polysiloxane chain or at the end near this chain: alcohol, mercaptan, epoxide group, primary amine and secondary amine more particularly are those polysiloxanes macromole corresponding to following general formula:
T-(CH 2) 6-Si-[-(OSiR 5R 6) t-R 7] y?????????(III)
Wherein T is selected from NH 2, NHRN, epoxy, OH or SH functional group; R 5, R 6, R 7, and RN independently represent C 1-C 6Alkyl, phenyl, benzyl, C 6-C 12Alkyl phenyl or hydrogen; S is that 2 to 100 number, t are that 0 to 1000 number and y are 1 to 3 number.Their number-average molecular weight is preferably 5,000 to 300,000, and more preferably 8,000 to 200,000, and more especially 9,000 to 40,000.
According to an embodiment preferred, described film forming polymer can be called the polymer of " Silicone Plus " available from the commodity of MinnesotaMining and Manufacturing company.For example commodity are called the graft copolymer of (isobutyl methacrylate-methyl FOSEA copolymer)-poly-(dimethyl siloxane) of SA 70-5 IBMMF.
Another preferred form according to the present invention, described film forming polymer the have been selected from grafting polysiloxane polymer of non-silicone organic monomer.In appropriate circumstances, these polymer can be fat-soluble, fat dispersibility, water solublity maybe can be scattered in the aqueous medium.
Described contained grafting graft polysiloxane polymer of polysiloxane backbone of non-silicone organic monomer or various polymer contain polysiloxane (or (/SiO-) n) main chain, on the main chain and choose on its at least one end at least one organic group of polysiloxane compound not of grafting wantonly.
The polymer that contains polysiloxane backbone and grafting non-silicone organic monomer of the present invention can obtain available from commodity or according to any method well known by persons skilled in the art, obtain by following monomer (i) and reaction (ii) specifically: (i) on one or more these silicon atoms, carry out suitably functionalized raw material polysiloxanes, (ii) non-silicone organic compound, they itself by can with described polysiloxanes with functional group reactions and to form the functional group of covalent bond suitably functionalized; The exemplary of this reaction is/Si-H group and vinyl CH 2Reaction between the hydrosilylation reactions between=CH-or mercapto functional group-SH and these vinyls.
Be suitable for implementing example and the concrete preparation method thereof that contains the polymer of polysiloxane backbone and grafting non-silicone organic monomer of the present invention and specifically describe in patent application EP-A-0582 152, WO 93/23009 and WO 95/03776, the description of these patent applications is attached in the description of the invention in full by non-limiting quoting.
According to a particularly preferred embodiment according to the invention, the polysiloxane polymer that contains polysiloxane backbone and grafting non-silicone organic monomer of use is by following monomer (i) and free-radical polymerized obtaining (ii): (i) at least a non-silicone hydrophobicity organic monomer that contains the non-silicone anion organic monomer of ethylenic unsaturated bond and/or contain ethylenic unsaturated bond; (ii) on its chain, contain at least a, and preferred several can form the polysiloxanes of functional group's (especially sulfydryl) of covalent bond with the monomeric ethylenic unsaturated bond reaction of described non-silicone.
According to the present invention, the described anionic monomer that contains ethylenic unsaturated bond is preferably selected from one or more unsaturated carboxylic acids linear or branching, optional part or be neutralized the form of salify fully, these unsaturated carboxylic acids can be more particularly acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid and .beta.-methylacrylic acid.Suitable salt is specially alkali metal, alkaline-earth metal and ammonium salt.Should note equally, in final graft polysiloxane polymer, the anion organic group that is obtained by at least a unsaturated carboxylic acid anionoid monomer radical polymerization (homopolymerization) can be become salt form by alkali (sodium hydroxide, ammonia etc.) post neutralization (post-neutralize) after reaction.
According to the present invention, the described hydrophobic monomer that contains ethylenic unsaturated bond is preferably selected from one or more acrylic acid chain triacontanol esters and/or methacrylic acid chain triacontanol ester.Described alkanol is preferably C 1-C 18And be more particularly C 1-C 22Alkanol.Preferred monomer is selected from (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylic acid isopentyl ester, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) acrylic acid methyl ester., (methyl) tert-butyl acrylate, (methyl) tridecyl acrylate, (methyl) acrylic acid stearyl or its mixture.
Being particularly suitable for implementing a class that contains the polysiloxane polymer of polysiloxane backbone and grafting non-silicone organic monomer of the present invention is to contain the unitary polysiloxane polymer of following formula I V in its structure:
Figure A0382532100591
Wherein said group G 1Identical or different, represent hydrogen, C 1-C 10Alkyl or phenyl; Group G 2Identical or different, represent C 1-C 10Alkylidene; G 3The polymer residue that representative is obtained by at least a polymerization (homopolymerization) that contains the anionic monomer of ethylenic unsaturated bond; G 4The polymer residue that representative is obtained by at least a polymerization (homopolymerization) that contains the hydrophobic monomer of ethylenic unsaturated bond; M and n equal 0 or 1; A is 0 to 50 integer; B can be the integer between 10 and 350; C is the integer between 0 and 50; Condition is that among parameter a and the c is not 0.
Above Chinese style (IV) unit preferably has at least one and more preferably all following features:
-G 1Group is represented alkyl, preferable methyl;
-n is non-vanishing, and G 2Group is represented bivalence C 1-C 3Group, preferred propylidene;
-G 3Representative derives from least a polymeric groups that contains the monomeric polymerization of carboxylic acids (homopolymerization) of ethylenic unsaturated bond, preferred acrylic acid and/or methacrylic acid;
-G 4Representative derives from least a (methyl) acrylic acid C 1-C 10The polymeric groups of the monomeric polymerization of alkyl esters (homopolymerization), preferred (methyl) Isobutyl 2-propenoate or methyl methacrylate.
Example corresponding to the polysiloxane polymer of formula (IV) specifically has polydimethylsiloxane (PDMS), is grafted with the mixed polymer unit of poly-(methyl) acrylic compounds and poly-(methyl) alkyl-acrylates thereon by sulfo-propylidene class connection chain.
Other example corresponding to the polysiloxane polymer of formula (IV) specifically has polydimethylsiloxane (PDMS), is grafted with the polymer unit of poly-(methyl) Isobutyl 2-propenoate class thereon by sulfo-propylidene class connection chain.
These polymer comprise the polymer of the group that contains at least one following formula:
Wherein
A, b and c can be identical or different, 1 to 100,000 the number of respectively doing for oneself; End group can be identical or different, respectively is selected from C 1-C 20Straight chained alkyl, C 3-C 20Branched alkyl, C 3-C 20Aryl, C 1-C 20Straight chain alkoxyl and C 3-C 20Branched alkoxy.
These polymer are at United States Patent (USP) 4,972, and 037,5,061,481,5,209,924,5,849,275 and 6,033,650, description is arranged among WO 93/23446 and the WO 95/06078.
Be particularly suitable for implementing the another kind of polysiloxane polymer that contains polysiloxane backbone and grafting non-silicone organic monomer of the present invention and be the unitary polysiloxane polymer of formula V under in its structure, containing:
Group G wherein 1And G 2Definition as above; G 5Representative is by the polymerization (homopolymerization) of the unsaturated hydrophobic monomer of at least a olefinic, or the polymer residue that obtains of the combined polymerization of unsaturated anionic monomer of at least a olefinic and the unsaturated hydrophobic monomer of at least a olefinic; N equals 0 or 1; A is 0 to 50 integer; B can be the integer between 10 and 350; Condition is that a is not 0.
Above the formula V unit preferably has at least one and more preferably all following features:
-G 1Group is represented alkyl, preferable methyl;
-n is non-vanishing, and G 2Group is represented bivalence C 1-C 3Group, preferred propylidene.
It is about 10,000 to 1,000,000 that number-average molecular weight with polysiloxane polymer of polysiloxane backbone and grafting non-silicone organic monomer of the present invention is preferably, and more preferably from about 10,000 to 100,000.
Described compositions can comprise 2% to 60% weight, more preferably 5% to 60%, the solid of the film forming polymer of preferred 2% to 30% weight.More particularly, the total amount of described polymer should be enough on skin and/or lip to form and can move and the adhesive film that can not peel off or crack with skin and/or lip.
When the glass transition temperature of described polymer is too high with respect to the purpose purposes, can be used in combination plasticizer, to reduce the glass transition temperature of used mixture.The plasticizer that the optional self-application of described plasticizer field is commonly used especially can be used as the chemical compound of the solvent of described polymer.
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%
Compositions of the present invention can comprise emulsifying surfactant, and its amount is specially 2% to 30% of described composition total weight, and more preferably 5% to 15%.These surfactants can be selected from anion and non-ionic surface active agent.But list of references " encyclopedia of chemical technology; Kirk-Othmer " (the 22nd volume, the 333-432 page or leaf, the third edition, 1979, Wiley) in about in the 347-377 page or leaf of surfactant, particularly described list of references about the definition of the performance and the function (emulsification) of anion and non-ionic surface active agent.
The surfactant that is preferred in the compositions of the present invention is selected from:
-non-ionic surface active agent: fatty acid, aliphatic alcohol, polyethoxylated or bound to polyglycerol (polyglycerolated) aliphatic alcohol is (as the fatty acid ester of polyethoxylated stearyl alcohol or polyethoxylated cetyl stearyl alcohol, sucrose, alkyl glucose ester (C particularly 1-C 6The polyoxyethylene fatty ester of alkyl glucose) and composition thereof,
-anion surfactant: with amine, ammonia or the neutral C of alkali metal salt 16-C 30Fatty acid and composition thereof.
According to an embodiment, preferred use can obtain the surfactant of oil-in-water or water bag wax emulsion.
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 (being called oil).This liquid aliphatic class material can derive from animal, plant, mineral or synthetic.
The oil that can be used among the present invention that can mention has: 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.
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 gel is generally high molecular polydimethylsiloxane (PDMS) or cellulose gel or polysaccharide.Described pasty masses is generally Hydrocarbon, as lanoline and derivant or PDMS.
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%.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 also can comprise the coloring agent that one or more are selected from water-soluble dye and coloured powdery agent, 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 (SilicaBeads , 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).
Compositions of the present invention can be in particular bar-shaped, suspension, dispersion liquid, solution, gel, emulsion form, oil-in-water (O/W) emulsion particularly, Water-In-Oil (W/O) emulsion or complex emulsions (W/OW or polyhydric alcohol/O/W or O/W/O emulsion), perhaps with emulsifiable paste, paste, mousse, the form of the dispersion of capsule, particularly ion or nonionic liposome, two-phase or multiphase lotion, spraying, powder, paste (particularly soft paste, it specifically is 25 ℃, shear rate is under the 200s-1, and 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.
Compositions of the present invention also can be hair product, especially for keeping hair style or making the product of Hair styling.Described hair composition is preferably shampoo, gel, hair style fixative, style keeping liquid, fixing composition and Hairstyling composition (for example lacquer (lacquers) or spraying).
According to an embodiment, the invention provides a kind of coating composition that is used for keratin fiber (for example eyelashes, eyebrow and hair), described compositions comprises linear olefinic block polymer of organic liquid medium, at least a water and at least a film forming and the particulate dispersion of aforesaid film forming polymer.
The preferred described film forming polymer that is scattered in water is selected from the mixture of polyurethane, polyurethane-acrylate class, polyacrylic, poly-(methyl) acrylate, polyvinyl pyrrolidone, polyurethane-polyethylene base ketopyrrolidine, polyester-polyurethane, polyethers-polyurethane, polyureas, polyurea/polyurethane and above-mentioned substance.
Preferred described compositions comprises at least a second kind of film former that is selected from water-soluble polymer, for example the polymer of the modification of cationic cellulose derivative and/or optional natural origin, for example Radix Acaciae senegalis.
Preferred described compositions comprises wax, and more preferably described compositions comprises surfactant.
This compositions can exist in a variety of forms, for example exists with emulsion, the aqueous dispersion of biphase water bag wax or wax Bao Shui or the form of not having an aqueous dispersion.
Preferred described compositions is the compositions that is used to apply eyelashes.
Of the present inventionly also provide a kind of cosmetics assembly, described assembly 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 FR2 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 4: liquid lipstick
Component The % quality
The polymer of embodiment 2 ??50.0
Silicon dioxide (Aerosil R 972 ，Degussa) ??5.0
Agglomerative Fancol ID (the Vetsagel of ethylene/propene/styrol copolymer and butylene/ethylene/styrene copolymer MD?970，Penreco) ??7.0
Parleam ??2.1
Octyldodecanol ??0.9
Phenyl front three siloxanes (DC 556,20cSt, Dow Corning) ??2.1
Fancol ID ??28.3
Vinyl pyrrolidone/1-eicosylene copolymer (Antaron V-220 ，ISP) ??1.2
Pigment ??3.0
Spice In right amount
Can use the foam applicator coating like a dream, and the uniform deposit that obtains having good adhesion.
Embodiment 5: sunscreen composition
Component % weight
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 polymeric ammonium salts (HOSTACERIN AMPS, ??0.3
???Clariant)
Hexamethylene siloxanes (DOW CORNING 246 FLUID, Dow Corning) ???6
Xanthan gum RHODICARE XC (Rhodia) ???0.1
Terephthalylidene dicamphor sulfonic acid (MEXORYL SX, Chimex) ???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
2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole trisiloxanes (MEXORYL XL, Chimex) ???1.5
Benzoic acid C 12-C 15Arrcostab (FINSOLV TN, Witco) ???4
The polymer of embodiment 1 ???1
Triethanolamine ???0.35
Antiseptic and chelating agen In right amount
Water Add to 100
Embodiment 6-11: mascara Emulsion
Mascara composition according to the present invention and below the prior art for preparing:
The prior art compositions of embodiment 6 does not contain block polymer or the particulate aqueous dispersion of film forming polymer.
The compositions of embodiment 10 comprises the particulate aqueous dispersion of film forming polymer, but does not contain block polymer.
The compositions of embodiments of the invention 7-9 and embodiment 11 comprises block polymer and the particulate aqueous dispersion of film forming polymer.
Embodiment 6 (contrast) Embodiment 7 (invention) Embodiment 8 (invention) Embodiment 9 (invention) Embodiment 10 (contrast) Embodiment 11 (invention)
Candelilla wax ?20 ?5 ?5 ?5 ?5
Comprise 38%AS polyurethane aqueous dispersion body (Avalure UR-450, Goodrich) ?8.3(AS *)
Ethyl acrylate/methyl methacrylate in comprising the aqueous dispersion of 50%AS (80/20) copolymer (Daltosol 5000AD, DAITO) ?10(AS)
(Syntran 5760, Interpolymer) for acrylic compounds in comprising the aqueous dispersion of 40%AS and styrene/acrylic analog copolymer ?8.7(AS) ?17.42(AS) ?6.37(AS)
The block polymer of embodiment 3 ?10(AS) ?10(AS) ?10(AS) ?15(AS)
Stearic acid ?5.8
Triethanolamine stearate ?2.9
Iron oxide black ?8
Hydroxyethyl-cellulose ?0.9
Radix Acaciae senegalis ?3.4
Water, antiseptic Add to 100
*AS: active substance
Adopt following method to measure the dry distilling branch of each compositions, external loading and adhesive force.
Adopt gravimetric method the Caucasian's of curling hair sample (30 hairs that 1cm is long, between distance be 1cm) on carry out external loading and measure.
Mascara is made up on described sample, apply 10 at every turn, apply altogether 3 times, be spaced apart 2 minutes at every turn, after each 10 coatings, collect described product.
At room temperature, weigh then samples dried 10 minutes.
Carry out this mensuration with 6 samples.
Loading is the amount that is deposited in the material on the sample, equals to be coated with the difference of quality and the quality of the sample that is not coated with cosmetics of the sample of cosmetics.
Average load is the meansigma methods that 6 samples are measured.
Go up mensuration solid content, the i.e. nonvolatile matter of described compositions or dry distilling part at Mettler Toledo HG 53 balances (halogen moisture analyzer (HalogenMoisture Analyzer)).(2-3g) places on the aluminum boat with the eyelashes sample, and heats 60 minutes down at 120 ℃.The mensuration that dry distilling divides is equivalent to monitor sample mass over time.Therefore final solid content is last quality (after 60 minutes) and the ratio of initial quality: SC=(final quality/initial quality) * 100.
The adhesion of thin film that is formed by compositions of the present invention is by the time dependent test evaluation of resistance to water, and this method is deployed in the thin film of compositions on the glass plate and places water-bearing media to stir.Method is as follows:
Under room temperature (25 ℃), be on the glass plate of 10cm * 10cm compositions to be launched at surface area, obtaining thickness is that 300 μ m (before the drying), surface area are the layer of 9cm * 9cm, making it subsequently is that 30 ℃, relative humidity are 50% time drying 24 hours in temperature.After the drying, it is 19cm, 2 liters crystallizer that this plate is placed diameter, and 1 premium on currency is housed in the crystallizer, and on the RCT basic heating magnetic stirring apparatus of the IKA labortechnik company that this crystallizer is placed.Subsequently slick columniform PTFE magnetic stirring bar (length is 6cm, and diameter is 1cm) is placed on this thin film.Stir speed (S.S.) is arranged on position 5.By thermometer water temperature is adjusted in 20 ℃ or 40 ℃.t 0, stir beginning at=0 o'clock.Write down and begin on this thin film slave plate to separate or peel off, the time the when diameter of perhaps observing the hole that magnetic stirring bar produces is 6cm.
The resistance to water of thin film is corresponding to measurement time t.
The result who obtains is as follows:
Embodiment 6 (contrast) Embodiment 7 (invention) Embodiment 8 (invention) Embodiment 9 (invention) Embodiment 10 (contrast) Embodiment 11 (invention)
The solid content that records (%) ?38.8 ?43.8 ?45.2 ?44.9 ?41.6 ?41.8
External loading (mg) ?11.90±1.34 ?12.5±1.42 ?10.18±1.54 ?7.43±0.65 ?11.17±0.74
Adhesive force ?55” ?1’24” ?2’24” ?6’26” ?38’ ?19’
Discovery contains the embodiment 7-9 of particulate aqueous dispersion of film forming polymer and block polymer and 11 compositions table of the present invention reveals good adhesive force, and the adhesive force of compositions of embodiment 10 that does not more contain block polymer is good.In addition, compositions of the present invention makes the eyelashes after the cosmetic dense, because it has high solid content and high external loading.
Mascara below produced according to the present invention:
Brazil wax ?4.7
Cera Flava ?8.2
Rice bran wax ?2.2
Modification Strese Hofmann's hectorite. (" Bentone 38VR " derives from Elementis) ?5.5
Paraffin ?2.2
Pulvis Talci ?1
Vinyl acetate/stearic acid allyl ester copolymer (Mexomere PQ derives from Chimex) ?6.7
The block polymer of embodiment 1 ?10
Polyoxyethylene lauryl vinyl acetate (Mexomere PP derives from Chimex company) ?0.7
Sulfonated polyester (Eastman AQ 55S derives from Eastman) ?0.1
Antiseptic ?0.2
Propylene carbonate ?1.8
Water ?7
Pigment ?5.2
Fancol ID Add to 100
According in the description as described above assay method measure solid content, external loading and adhesive force.
The result who obtains is as follows:
The solid content that records (%) ??45.4
External loading (mg) ??8.9±0.9
Adhesive force Greater than 1 day (24h)
This mascara has on eyelashes in the good thickness (loading), also shows good adhesive force.

Claims (107)

1. cosmetic composition, described compositions comprise organic liquid medium, at least a linear olefinic block polymer of film forming that does not contain styrene units and at least aly dissolve in or be scattered in other film former in the described organic liquid medium.
2. cosmetic composition, described compositions comprises organic liquid medium, at least a water, at least a linear olefinic block polymer of film forming and at least a other film former that dissolve in or be scattered in described aqueous phase that do not contain styrene units.
3. claim 1 or 2 cosmetic composition is characterized in that described block polymer is the non-elastomeric blocks polymer.
4. each cosmetic composition during aforesaid right requires 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-.
5. 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.
6. 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.
7. 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.
8. 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.
9. 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.
10. each cosmetic composition during aforesaid right requires, the polydispersity index I that it is characterized in that described block polymer is greater than 2.
11. the compositions of claim 7 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.
12. the compositions of claim 11 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.
13. 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=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 12Cycloalkyl, as isobornyl acrylate, or the tert-butyl group;
(methyl) acrylamide of-following formula:
Figure A038253210003C1
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.
14. the compositions of claim 12 or 13, 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.
15. the compositions of claim 11 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.
16. the compositions of claim 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 following 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.
17. the compositions of claim 15 or 16, 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.
18. the compositions of claim 11 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 ℃.
19. the compositions of claim 11 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.
20. the compositions of claim 18 or 19 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.
21. each compositions among the claim 11-20, 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 ℃.
22. 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.
23. the compositions of claim 22 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.
24. the compositions of claim 22 or 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 following 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 12Cycloalkyl, as isobornyl acrylate, or the tert-butyl group;
(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.
25. each compositions among the claim 22-24, 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.
26. each compositions among the claim 22-25 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.
27. each compositions among the claim 21-26 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.
28. each compositions among the claim 21-27 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.
29. the compositions of claim 27 or 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 following 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.
30. each compositions among the claim 27-29, 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.
31. each compositions among the claim 21-30 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.
32. each compositions among the claim 11-20, 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 ℃.
33. 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 ℃.
34 claim 32 or 33 compositions 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.
35. each compositions among the claim 32-34 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.
Each compositions among the 36 claim 32-35 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.
37. each compositions among the claim 32-35 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.
38. each compositions among the claim 32-37 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.
39. each compositions in claim 37 and 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 following 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 12Cycloalkyl, as isobornyl acrylate, or the tert-butyl group;
(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.
40. each compositions among the claim 36-39, 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.
41. each compositions among the claim 37-40 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.
42. each compositions among the claim 32-41 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.
43. each compositions among the claim 32-41 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.
44. the compositions of claim 42 or 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 following 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.
45. each compositions among the claim 42-44, 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.
46. each compositions among the claim 42-45, 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.
47. 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 6-8.
48. 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.
49. the compositions of claim 47 or 48 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, acryloyl hydrogen base 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,
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 be 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
B) comprise the ethylenically unsaturated monomer of one or more silicon atoms, as methacryloxypropyl trimethoxy silane and methacryloxypropyl three (trimethylsiloxy) silane;
-and composition thereof.
50. each compositions in claim 47 and 48 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.
51. each compositions in claim 47 and 48 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.
52. each compositions in claim 47 and 48 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.
53. each compositions among the claim 47-52 is characterized in that described other one or more monomers account for 1% to 30% of the first and/or second block gross weight.
54. each compositions in claim 7 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 more than 20 ℃, very preferably greater than 30 ℃, and more preferably greater than 40 ℃.
The compositions of 55 claim 10, the polydispersity index that it is characterized in that described block polymer be more than or equal to 2.5, is preferably greater than or equals 2.8.
56. the compositions of claim 55, the polydispersity index that it is characterized in that described block polymer is between 2.8 and 6.
57. 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.
58. the compositions of claim 57 is characterized in that weight average molecular weight (Mw) scope is 35000 to 200000, and more preferably 45000 to 150000.
59. the compositions of claim 58 is characterized in that weight average molecular weight (Mw) is less than or equal to 70000.
60. each compositions among the claim 57-59, its weight average molecular weight (Mw) scope is 10000 to 60000, and more preferably 12000 to 50000.
61. 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.
62. the compositions of claim 1 is characterized in that described film former is the film forming polymer that dissolves in the described organic liquid medium.
63. the compositions of claim 62 is characterized in that described film former is fat-soluble film forming polymer.
64. the compositions of claim 63 is characterized in that described fat-soluble film forming polymer is selected from following monomeric fat-soluble, amorphous homopolymer and copolymer: alkene, cycloolefin, butadiene, isoprene, styrene, vinyl ethers, ester or amide or contain linear, branching or ring-type C 4-50(methyl) the acrylic acid ester or the amide of alkyl are preferably unbodied.
65. the compositions of claim 63, it is characterized in that described fat-soluble film forming polymer is selected from homopolymer and the copolymer that is obtained by following monomer: (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylic acid isopentyl ester, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) acrylic acid methyl ester., (methyl) tert-butyl acrylate, (methyl) tridecyl acrylate and (methyl) acrylic acid stearyl or its mixture, particularly alkyl acrylate/acrylic acid cycloalkyl ester copolymer and vinyl pyrrolidone/dodecylene copolymer.
66. the compositions of claim 63, it is characterized in that described fat-soluble film forming polymer be selected from unbodied, liposoluble, preferably do not contain the condensation polymer of any group to the hydrogen effect, particularly have C 4-50The polyester of alkyl side chain or the polyester that obtains by the dimeric condensation of fatty acid, or or even comprise and at room temperature be the segmental polyester of polysiloxane group of solid block, grafting or end group form.
67. the compositions of claim 63, it is characterized in that described fat-soluble film forming polymer is selected from unbodied, liposoluble, as to comprise alkyl (ether or ester) side chain polysaccharide, particularly ethyl cellulose perhaps contains polysiloxane backbone and acrylic compounds grafting or contains acrylic backbone and polysiloxane-grafted polysiloxanes-polyacrylic graft polymers.
68. the compositions of claim 63 is characterized in that described fat-soluble film forming polymer contains fluorin radical.
69. the compositions of claim 68 is characterized in that described fat-soluble film forming polymer is selected from (methyl) alkyl acrylate/(methyl) perfluoroalkyl acrylate copolymer.
70. the compositions of claim 63 is characterized in that described fat-soluble film forming polymer is selected from the polymerization of the olefinic type monomers by comprising one or more ethylene linkages, preferred conjugated bonds or polymer or the copolymer that copolymerization obtains.
71. the compositions of claim 70 is characterized in that described polymer or copolymer that polymerization or copolymerization by olefinic type monomers obtain are selected from polystyrene/(ethylene/butylene) copolymer.
72. the compositions of claim 63 is characterized in that described fat-soluble film forming polymer is selected from the polymer that comprises the monomer-grafted organic main chain of non-silicone that is contained polysiloxanes.
73. the compositions of claim 63, wherein said at least a fat-soluble film forming polymer is selected from by the grafted polysiloxane polymer of non-silicone organic monomer.
74. the compositions of claim 1 is characterized in that described film former can be scattered in the described organic liquid medium.
75. the compositions of claim 74 is characterized in that described organic liquid medium comprises at least a oil, described film former can be scattered in the described oil, and described film former is the form of the nonaqueous dispersion of polymer beads.
76. the compositions of claim 2 is characterized in that described film former is for being scattered in the film forming polymer of aqueous phase.
77. the compositions of claim 76 is characterized in that the described film forming polymer that is scattered in water is selected from polyurethane, polyurethane-polyacrylic class, polyurethane-polyethylene base ketopyrrolidine, polyester-polyurethane, polyethers-polyurethane, polyureas, polyureas-polyurethane and composition thereof.
78. the compositions of claim 77 is characterized in that the described film forming polymer that is scattered in water is aliphatic, alicyclic or aromatic polyurethane copolymer, polyurea/polyurethane or polyurea copolymers, described polymer comprises the mixture of following one or more:
-at least a the block that comes from aliphatic and/or alicyclic and/or the aromatic polyester of straight or branched, and/or
-at least aly come from block aliphatic and/or alicyclic and/or aromatic-polyether, and/or
-at least a replacement or not replacement, branching or nonbranched polysiloxane block, as polydimethylsiloxane or PSI, and/or
-at least aly contain fluorine-based block.
79. the compositions of claim 76 is characterized in that the described film forming polymer that is scattered in aqueous phase is selected from polyester, polyamide and the epoxy ester resin of polyester, polyesteramide, band aliphatic chain.
80. the compositions of claim 76 is characterized in that the described film forming polymer that is scattered in aqueous phase is selected from acrylic polymer, acrylic copolymer and vinyl class in polymer.
81. the compositions of claim 1 is characterized in that the mummification compound of described film former accounts for 2% to 60% of described composition total weight, and is preferred 5% to 60%, more preferably 2% to 30%.
82. each cosmetic composition is characterized in that described compositions also comprises the coloring agent that one or more are selected from water-soluble dye and coloured powdery agent, as pigment, Concha Margaritifera and leidosome during aforesaid right required.
Each cosmetic composition during 83. 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, paste, mousse or carrier dispersion, particularly ion or nonionic liposome, two-phase or multiphase lotion, spraying, powder or paste, particularly soft paste, no water suspension paste, rod or casting solid.
84. each cosmetic composition is characterized in that described cosmetic composition is an anhydrous form during aforesaid right required.
85. each cosmetic composition during aforesaid right requires is characterized in that described cosmetic composition is to be used for the compositions that keratin material is made up or nursed.
86. each compositions is characterized in that described compositions is the lip cosmetic product during aforesaid right required.
87. each compositions during aforesaid right requires is characterized in that described compositions is the eye cosmetic product.
88. each compositions is characterized in that described compositions is a colour of skin cosmetic product during aforesaid right required.
89. each compositions is characterized in that described compositions is the fingernail cosmetic product during aforesaid right required.
90. a coating composition that is used for keratin fiber, particularly eyelashes and eyebrow, described compositions comprise organic liquid medium, at least a water, the linear olefinic block polymer of at least a film forming and at least a other film former that dissolve in or be scattered in described aqueous phase.
91. each compositions during aforesaid right requires is characterized in that described block polymer is each a block polymer among the claim 1-61.
92. the compositions of claim 90 or 91 is characterized in that described film former is for being scattered in the film forming polymer of described aqueous phase.
93. the compositions of claim 92 is characterized in that the described film forming polymer that is scattered in water is selected from polyurethane, polyurethane-polyacrylic class, polyurethane-polyethylene base ketopyrrolidine, polyester-polyurethane, polyethers-polyurethane, polyureas, polyureas-polyurethane and composition thereof.
94. each compositions among the claim 90-93 is characterized in that described compositions comprises wax.
95. each compositions among the claim 90-94 is characterized in that described compositions comprises surfactant.
96. each compositions among the claim 90-95 is characterized in that described compositions comprises at least a second film former that is selected from water-soluble polymer.
97. each compositions is characterized in that described one or more water-soluble polymers are selected from the polymer of the natural origin of cationic cellulose derivative and/or optional modification, for example Radix Acaciae senegalis during aforesaid right required.
98. each compositions among the claim 90-97 is characterized in that described compositions comprises coloring agent.
99. each compositions among the claim 90-98 is characterized in that described compositions is a mascara.
100. 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 compositions in the described compartment, described compositions is each a compositions in the aforesaid right requirement.
101. the cosmetics external member of claim 100 is characterized in that described container to small part is formed by at least a thermoplastic.
102. the cosmetics external member of claim 100 is characterized in that described container to small part is formed by at least a non-thermoplastic material, particularly glass or metal form.
103. each external member among the claim 100-102 is characterized in that the closed position at described container, described closing element is connected on the described container by spiral.
104. each external member among the claim 100-102 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.
105. each external member among the claim 100-104 is characterized in that described compositions is at the described indoor basic normal pressure that is.
106. each external member among the claim 100-104 is characterized in that described compositions is pressurized in described container.
107. a cosmetic method that is used for the cosmetic or the nursing of keratin material, described method comprise each cosmetic composition among the claim 1-99 is applied to keratin material.
CN 03825321 2002-09-26 2003-09-26 Compositions containing block polymers and film-forming agent Pending CN1700900A (en)

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CN 03825338 Pending CN1700902A (en) 2002-09-26 2003-09-26 Anti-migration cosmetic composition comprising a block polymer
CN03825357A Expired - Fee Related CN100594879C (en) 2002-09-26 2003-09-26 Glossy liquid composition comprising block polymer
CN 03825321 Pending CN1700900A (en) 2002-09-26 2003-09-26 Compositions containing block polymers and film-forming agent
CN 03825414 Pending CN1703194A (en) 2002-09-26 2003-09-26 Keratin fibre coating composition containing high-dry extract, and block polymer containing same
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