CN100594879C - Glossy liquid composition comprising block polymer - Google Patents
Glossy liquid composition comprising block polymer Download PDFInfo
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- CN100594879C CN100594879C CN03825357A CN03825357A CN100594879C CN 100594879 C CN100594879 C CN 100594879C CN 03825357 A CN03825357 A CN 03825357A CN 03825357 A CN03825357 A CN 03825357A CN 100594879 C CN100594879 C CN 100594879C
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Abstract
The invention relates to a liquid cosmetic composition comprising a sufficient amount of non-elastomer, filmogenic, linear ethylenic sequenced polymer such that the average glossiness of the depositedcomposition when it is spread over a support is 30%-100% .
Description
The present invention relates to be used for the skin (comprising scalp) of people face and health and people's lip or the cosmetic of covering (as hair, eyelashes, eyebrow or fingernail) or the liquid cosmetic composition of nursing, described compositions comprises acceptable medium on the cosmetics that contain specific block polymer.
Many cosmetic compositions are after being applied to keratin material (skin, lip or covering), and the gloss characteristic of sedimentary thin film is extremely important.The example that can mention comprises lip pomade, nial polish or some hair product and some mascara.
Cosmetic product prescription known use high viscosity of teacher and high refractive index also have good pigment or the oil of filler (if existing in the compositions) dispersing characteristic can improve gloss characteristic.
From this angle, the prescription teacher has obtained various raw materials, as butyrous polymer, as polybutene, Indopol H100, the H300 and the H1500 that sell of Amoco company particularly, this product has very high viscosity, but weak point is all very thickness, and pigment-dispersing is relatively poor, and its weak point has limited their use.
The object of the present invention is to provide the new way of the good cosmetic product of a kind of allotment cosmetic product, particularly gloss.
Specifically, product of the present invention can obtain successive deposit on skin or lip, this deposit has good covering power, show the very outward appearance of light that satisfies consumer demand, and be not moved and shift, have good adhesive force, this product is non-oleaginous, and can not make the skin, hair or the lip that scribble this product dry during using or after using.Product of the present invention has good stable and can all evenly use attractive in appearancely simultaneously.
A theme of the present invention be used for skin and/or lip and/or obducent nursing or cosmetic the light fluid composition arranged, described compositions comprises block polymer, described block polymer can overcome the known deficiency that the light compositions is arranged.The inventor is unexpected to find to use that the specific block polymer of capacity can be had good adhesion simultaneously that the light compositions arranged.
Compositions of the present invention can be in particular have nursing and/or a treatment characteristic be used for human body, lip or obducent hair products or cosmetic product.The particularly lip pomade or the lip pomade that adds lustre to, eye shadow, tattoo product, mascara, eyeliner, nial polish, the product that is used for artificial tanning, optional nursing or protection cream or hair dyeing or the hair products that are colored.
More particularly, the present invention relates to liquid cosmetic composition, described compositions comprises acceptable organic liquid medium and the linear olefinic block polymer of stiff film forming on the cosmetics, when having the described block polymer of capacity in the described compositions, under 20 °, record described compositions launches to obtain on carrier sedimental average gloss and be preferably greater than or equal 30%.
Of the present invention another themes as liquid cosmetic composition, described compositions comprises acceptable organic liquid medium on the cosmetics and does not contain the linear olefinic block polymer of film forming of styrene units, when having the described block polymer of capacity in the described compositions, under 20 °, record described compositions launches to obtain on carrier sedimental average gloss and be preferably greater than or equal 30%.
Term " fluid composition " is meant under 25 ℃, normal pressure to possess the compositions of the container shapes poured into.
Preferred compositions of the present invention is leave-on composition (leave-in).
The average gloss of compositions
Term " average gloss " is meant and makes moon gloss of gloss meter conventional determining according to the methods below.
Use automatic coating machine that described compositions is deployed on the Leneta board contrast card Form 1A Penopac with coating thick between 50 μ m and the 150 μ m.This coating has covered the white background of this card at least.Under 30 ℃, make deposit dry 24 hours, and used the gloss of Byk Gardner board microTri-Gloss gloss meter under under white background, measuring 20 ° then.
At least replication 3 times (between 0 and 100), then with the meansigma methods of at least three measured values as average gloss.
The average gloss of the described compositions that records under 20 ° is preferably greater than or equals 30, more preferably more than or equal to 35, even more preferably more than or equal to 40, even more preferably more than or equal to 45, even more preferably more than or equal to 50%, even more preferably more than or equal to 55, even more preferably more than or equal to 60, even more preferably more than or equal to 65, even more preferably more than or equal to 70 or even more preferably about or equal 75%.For some compositions of the present invention (as nial polish), the gloss that records under 20 ° can be more than or equal to 70, perhaps even be 80%.
The average gloss that is deployed in the described compositions on the carrier that preferably records under 60 ° is more than or equal to 50, more preferably more than or equal to 60, more preferably more than or equal to 65, more preferably more than or equal to 70, more preferably more than or equal to 75, more preferably more than or equal to 80, more preferably more than or equal to 85, perhaps even more preferably more than or equal to 90%.
The following average gloss that is determined under 60 °.Can use gloss meter to measure gloss in the mode of routine according to the methods below.
Use automatic coating machine that described compositions is deployed on the Leneta board contrast card Form 1A Penopac with coating thick between 50 μ m and the 150 μ m.This coating has covered the white background of this card at least.Under 30 ℃, make deposit dry 24 hours, and used Byk Gardner board microTri-Gloss gloss meter under white background, to measure 60 ° of following gloss then.
At least replication 3 times (between 0 and 100), then with the meansigma methods of at least three measured values as average gloss.
According to an embodiment, the average gloss of the described compositions that records under 20 ° is preferably greater than or equals 35, is preferably 40,45 or 50%, and/or the average gloss of the described compositions that records under 60 ° is preferably greater than or equals 65,70 or 75%.In this embodiment, preferred described compositions is a liquid lipstick.
According to an embodiment, the average gloss of the described compositions that records under 20 ° is preferably greater than or equals 60, is preferably 65,70 or 75%, and/or the average gloss of the described compositions that records under 60 ° is preferably greater than or equals 80,85 or 90%.In this embodiment, preferred described compositions is a nial polish.
The invention still further relates to cosmetic composition, described compositions comprises organic liquid medium and at least a block polymer as described below.
The invention still further relates to a kind of method of making up for skin and/or lip and/or covering, described method comprises compositions as defined above is applied on skin and/or lip and/or the covering.
Compositions of the present invention can be applied to the inboard and the covering (as fingernail, eyelashes, hair, eyebrow or chaeta) of skin (face, scalp and health), mucosa (as lip), palpebra inferior.
The invention still further relates to that the block polymer of capacity makes the deposit of described compositions have the purposes of gloss and/or adhesive force in cosmetic composition.
The invention still further relates to as defined above, compositions improves the glossy cosmetic use that skin and/or lip and/or covering apply some make up.
Preferred described compositions comprises a small amount of routine and is used to give glossy oil, and these oil are generally the oil of viscosity.
Preferred compositions of the present invention comprises less than 30%, preferably less than 25%, less than 20%, and more preferably less than 15% at least a gloss oil arranged.
Term " oil " is meant arbitrary proportion and water unmixing and is the chemical compound of liquid down in room temperature (25 ℃) and normal pressure (760mmHg).
It is 650 to 10000g/mol that term " has gloss oil " and be meant preferred molal weight scope, and is preferably 750 to 7500g/mol oil.
The molal weight scope is that 650 to 10000g/mol oil can be selected from:
-lipophilic polymer, as
-polybutene, as Indopol H-100 (molal weight or MM=965g/mol), Indopol H-300 (MM=1340g/mol) and the Indopol H-1500 (MM=2160g/mol) that sells or produce from Amoco company,
-Parleam, sell or the Viseal20000 (MM=6000g/mol) of production and the Rewopal PIB1000 (MM=1000g/mol) that Witco company sells or produces as Panalane H-300E (MM=1340g/mol), Synteal company that Amoco company sells or produces
-poly decene and hydrogenated polydecene, as the Puresyn 10 (MM=723g/mol) and the Puresyn150 (MM=9200g/mol) of sale of Mobil Chemicals company or production,
-vinylpyrrolidone copolymer, as the Antaron V-216 (MM=7300g/mol) of vinyl pyrrolidone/cetene copolymer, the sale of ISP company or production,
-ester, as:
-total carbon atom number order is the straight-chain fatty acid ester of 35-70, as four n-nonanoic acid pentaerythritol esters (MM=697.05g/mol),
-hydrogenant ester, as poly-three isostearic acid 2-glyceride (polyglyceryl-2triisostearate) (MM=965.58g/mol),
-aromatic ester, as 1,2,4-benzenetricarboxylic acid ester in three last of the ten Heavenly stems (MM=757.19g/mol),
-C
24-C
28The ester of branched fatty alcohol or fatty acid, as describing among the patent application EP-A-0 955 039 those, citric acid three (Isoeicosane) ester (MM=1033.76g/mol) particularly, four different n-nonanoic acid pentaerythritol esters (MM=697.05g/mol), three glyceryl isostearates (MM=891.51g/mol), three (2-decyl tetradecylic acid) glyceride (MM=1143.98g/mol), four isostearic acid pentaerythritol esters (MM=1202.02g/mol), poly-four isostearic acid 2-glyceride (polyglyceryl-2tetraisostearate) (MM=1232.04g/mol) or four (2-decyl tetradecylic acid) pentaerythritol ester (MM=1538.66g/mol)
-silicone oil, as phenyl polysiloxane, as the Belsil PDM1000 (MM=9000g/mol) of Wacker company,
The oil of-plant origin, as Oleum sesami (820.6g/mol),
-and composition thereof.
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, and 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 forced to stretch (as stretching 30% with respect to initial length), if stop coaction, 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 is derived 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 derived 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 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 meant 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 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 should be understood that more than or equal to 5% of described mixture (polymer and main organic liquid) gross weight:
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 is derived from one type monomer or derived from the monomer of number of different types.
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:
Except as otherwise noted, the Tg value of first and second blocks of indication is theory T g value otherwise in the present patent application.
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.
In the present invention, statement " ... with ... between " scope of numerical value do not comprise two end points, " ... extremely ... " and the scope of " scope is ... extremely ... " numerical value comprise two end points.
A) Tg is greater than or equal to 40 ℃ block
Tg such as scope that Tg is greater than or equal to 40 ℃ block are 40 to 150 ℃, preferably are greater than or equal to 50 ℃, be 50 ℃ to 120 ℃ as the Tg scope, and more preferably be greater than or equal to 60 ℃, and be 60 ℃ to 120 ℃ as scope.
Tg is greater than or equal to 40 ℃ block and can be homopolymer or copolymer.
Tg is greater than or equal to 40 ℃ block and can all or part of glass transition temperature derived from one or more homopolymer prepared therefrom be greater than or equal to 40 ℃ monomer.
At this block is under the situation of homopolymer, and this block is greater than or equal to 40 ℃ monomer 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 (Tg of the corresponding homopolymer of this kind monomer is greater than or equal to 40 ℃).
At first block is under the situation of copolymer, and this block can be all or part of derived from one or more monomers, selects these monomeric character and concentration to make the Tg of the copolymer that obtains be greater than or equal to 40 ℃.Described copolymer can comprise as following monomer:
The Tg of-homopolymer prepared therefrom is greater than or equal to 40 ℃ monomer, is 40 ℃ to 150 ℃ as the Tg scope, preferably is greater than or equal to 50 ℃, be 50 ℃ to 120 ℃ as scope, and more preferably be greater than or equal to 60 ℃, as scope be 60 ℃ to 120 ℃ and
The Tg of-homopolymer prepared therefrom is lower than 40 ℃ monomer, the Tg that this monomer is selected from its homopolymer as described below is that the Tg of monomer between 20 ℃ and 40 ℃ and/or its homopolymer is less than or equal to 20 ℃ monomer, as the Tg scope is-100 ℃ to 20 ℃, preferably be lower than 15 ℃, particularly scope is-80 ℃ to 15 ℃, and more preferably being lower than 10 ℃, is-50 ℃ to 0 ℃ as scope.
The glass transition temperature of corresponding homopolymer is greater than or equal to 40 ℃ monomer and is preferably selected from following monomer (these monomers also are known as principal monomer):
-Shi CH
2=C (CH
3)-COOR
1Methacrylate, R wherein
1Representative comprises the unsubstituted straight or branched alkyl of 1 to 4 carbon atom, as methyl, ethyl, propyl group or isobutyl group, perhaps R
1Represent C
4-C
12Cycloalkyl;
-Shi CH
2=CH-COOR
2Acrylate, R wherein
2Represent C
4-C
12The cycloalkyl (as isobornyl acrylate) or the tert-butyl group;
(methyl) acrylamide of-following formula:
R wherein
7And R
8Can be identical or different, represent the C of hydrogen atom or straight or branched separately
1-C
12Alkyl, as normal-butyl, the tert-butyl group, isopropyl, isohesyl, iso-octyl or different nonyl, or R
7Represent H and R
8Represent 1,1-dimethyl-3-oxo butyl, and R ' represents H or methyl.The monomeric example that can mention has: N-butyl acrylamide, N tert butyl acrylamide, N-N-isopropylacrylamide, N,N-DMAA and N, N-dibutyl acrylamide;
-and composition thereof.
Particularly preferred principal monomer is methyl methacrylate, (methyl) Isobutyl 2-propenoate and (methyl) isobornyl acrylate and composition thereof.
B) Tg is less than or equal to 20 ℃ block
Tg such as scope that Tg is less than or equal to 20 ℃ block are-100 ℃ to 20 ℃, preferably are less than or equal to 15 ℃, and particularly scope is-80 ℃ to 15 ℃, and more preferably is less than or equal to 10 ℃, are-50 ℃ to 0 ℃ as scope.
Tg is less than or equal to 20 ℃ block and is can be homopolymer or copolymer.
Tg is less than or equal to 20 ℃ block and can all or part of glass transition temperature derived from one or more homopolymer prepared therefrom be less than or equal to 20 ℃ monomer.
At this block is under the situation of homopolymer, and this block is less than or equal to 20 ℃ monomer derived from the glass transition temperature of homopolymer prepared therefrom.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, methacrylic acid and methacrylate and composition thereof of preferred first block and second block.
Preferred first and second blocks are separately all derived from least a monomer that is selected from acrylic acid, acrylate, methacrylic acid and methacrylate and composition thereof.
But described block can comprise the compositing monomer of a small amount of at least a other blocks separately.
Therefore, first block can comprise the compositing monomer of at least a second block, and vice versa.
Except above-mentioned various monomers, first and/or second block also can comprise one or more other monomers that are known as " other monomers " that are different from above-mentioned principal monomer separately.
Select other monomers and various other monomeric property quality and quantities, make the block at their places have required glass transition temperature.
This other monomers are as being selected from following monomer:
A) hydrophilic monomer, as:
-comprise at least one carboxylic acid or sulfonic acid functional group's ethylenically unsaturated monomer, if any acrylic acid, methacrylic acid, butenoic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamido propane sulfonic acid, vinyl benzoic acid, vinylphosphonic acid and salt thereof;
-comprise the ethylenically unsaturated monomer of at least one tertiary amine functional group, if any 2-vinylpyridine, 4-vinylpridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylamino-propyl Methacrylamide and salt thereof;
-Shi CH
2=C (CH
3)-COOR
6Methacrylate,
R wherein
6Representative comprises the straight or branched alkyl of 1 to 4 carbon atom, as methyl, ethyl, propyl group or isobutyl group, the alkyl of described alkyl for being replaced by one or more substituent groups that are selected from hydroxyl (as being methacrylic acid 2-hydroxypropyl acrylate and methacrylic acid 2-hydroxyl ethyl ester) and halogen atom (Cl, Br, I or F) (as being trifluoroethyl methacrylate);
-Shi CH
2=C (CH
3)-COOR
9Methacrylate,
R
9Represent C
6-C
12The straight or branched alkyl, the one or more hetero atoms that are selected from O, N and S of wherein optional insertion, described alkyl is replaced by one or more substituent groups that are selected from hydroxyl and halogen (Cl, Br, I or F);
-Shi CH
2=CHCOOR
10Acrylate,
R
10The straight or branched C that representative is replaced by one or more substituent groups that are selected from hydroxyl and halogen (Cl, Br, I or F)
1-C
12Alkyl (as being acrylic acid 2-hydroxypropyl acrylate and acrylic acid 2-hydroxyl ethyl ester), perhaps R
10Represent the C of 5-30 oxygen ethylene repeating unit
1-C
12Alkyl-O-POE (polyoxyethylene), as methoxyl group-POE, or
R
10Representative comprises the polyoxyethylene group of 5 to 30 oxygen ethylene unit,
B) comprise the ethylenically unsaturated monomer of one or more silicon atoms, as methacryloxypropyl trimethoxy silane and methacryloxypropyl three (trimethylsiloxy) silane;
-and composition thereof.
Particularly preferred other monomers are acrylic acid, methacrylic acid and trifluoroethyl methacrylate and composition thereof.
According to an embodiment, the monomer of each self-contained at least a being selected from (methyl) acrylate of first and second blocks of described block polymer and at least a other monomers (as (methyl) acrylic acid) of choosing wantonly and composition thereof.
According to another embodiment, first and second blocks of described block polymer separately all derived from the monomer of at least a being selected from (methyl) acrylate and optional at least a other monomers as ((methyl) acrylic acid) and composition thereof.
According to an embodiment preferred, described block polymer is a non-siloxane polymer, i.e. the polymer of silicon atoms not.
This or these other monomeric content is less than or equal to 30% weight of the first and/or second block gross weight usually, as is 1% to 30% weight, is preferably 5% to 20% weight, more preferably 7% to 15% weight.
Can obtain described block polymer by free radical solution polymerization according to following preparation method:
-partially polymerized solvent is introduced in the reactor that is fit to, and heat until the temperature (being generally between 60 ℃ and 120 ℃) that is fit to polyreaction,
-in case reach this temperature, in the presence of partially polymerized initiator, the compositing monomer of first block is introduced,
-through after being 90% time T corresponding to maximum conversion rate, introduce the compositing monomer and the remaining initiator of second block,
-this mixture is continued reaction a period of time T ' (scope is 3 to 6 hours), subsequently this mixture is cooled to room temperature,
-obtain being dissolved in the polymer in the polymer solvent.
First embodiment
According to first embodiment, the Tg described in described block polymer comprises as above a) is greater than or equal to 40 ℃ first block and as above b) described in Tg be less than or equal to 20 ℃ second block.
Preferred Tg is greater than or equal to 40 ℃ first block for be greater than or equal to the copolymer of 40 ℃ monomer (as above-mentioned monomer) derived from the glass transition temperature of homopolymer prepared therefrom.
It is the homopolymer that the glass transition temperature of homopolymer prepared therefrom is less than or equal to 20 ℃ monomer (as above-mentioned monomer) that preferred Tg is less than or equal to 20 ℃ second block.
The content range that preferred Tg is greater than or equal to 40 ℃ block is 20% to 90% of a described polymer weight, more preferably 30% to 80%, more more preferably 50% to 70%.The content range that preferred Tg is less than or equal to 20 ℃ block is 5% to 75% of a described polymer weight, is preferably 15% to 50%, and more preferably 25% to 45%.
Therefore, according to first kind of scheme variant, polymer of the present invention can comprise:
-Tg is greater than or equal to 40 ℃, be 70 ℃ to 110 ℃ first block as the Tg scope, described first block is methyl methacrylate/acrylic copolymer,
-Tg is less than or equal to 20 ℃, be 0 ℃ to 20 ℃ second block as the Tg scope, described second block be the acrylic acid methyl ester. homopolymer and
-mid-block, described mid-block are methyl methacrylate/acrylic acid/methyl acrylate copolymer.
According to second kind of scheme variant, polymer of the present invention can comprise:
-Tg is greater than or equal to 40 ℃, be 70 ℃ to 100 ℃ first block as scope, described first block is methyl methacrylate/acrylic acid/trifluoroethyl methacrylate copolymer,
-Tg is less than or equal to 20 ℃, be 0 ℃ to 20 ℃ second block as scope, described second block be the acrylic acid methyl ester. homopolymer and
-mid-block, described mid-block are methyl methacrylate/acrylic acid/acrylic acid methyl ester ./trifluoroethyl methacrylate random copolymer.
According to the third scheme variant, polymer of the present invention can comprise:
-Tg is greater than or equal to 40 ℃, be 85 ℃ to 115 ℃ first block as scope, described first block is isobornyl acrylate/isobutyl methacrylate copolymer,
-Tg is less than or equal to 20 ℃, is-85 ℃ to-55 ℃ second block as scope, described second block be the 2-EHA homopolymer and
-mid-block, described mid-block are isobornyl acrylate/isobutyl methacrylate/2-EHA random copolymer.
According to the 4th kind of scheme variant, polymer of the present invention can comprise:
-Tg is greater than or equal to 40 ℃, be 85 ℃ to 115 ℃ first block as scope, described first block is isobornyl acrylate/methylmethacrylate copolymer,
-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: the preparation of poly-(methyl methacrylate/acrylic acid/acrylic acid methyl ester .) polymer
In the reactor with 1 liter of 100g butyl acetate adding, in 1 hour, temperature is increased to 90 ℃ from room temperature (25 ℃) subsequently.
Under 90 ℃, in 1 hour, add 180g methyl methacrylate, 30g acrylic acid, 40g butyl acetate, 70g isopropyl alcohol and 1.8g 2 subsequently, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane (
141, derive from Akzo Nobel).
This mixture was kept 1 hour down at 90 ℃.
Subsequently still under 90 ℃, in 1 hour with 90g acrylic acid methyl ester., 70g butyl acetate, 20g isopropyl alcohol and 1.2g 2, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane adds in the said mixture.
This mixture was kept 3 hours down at 90 ℃, use 105g butyl acetate and 45g isopropanol subsequently, and with this mixture cooling.
Obtain the solution that comprises 40% polymer active material in butyl acetate/isopropanol mixture.
Poly-(methyl methacrylate/acrylic acid) first block, the Tg that obtain comprising Tg and be 100 ℃ are 10 ℃ polymethyl acrylate second block and the polymer of mid-block, and described mid-block is methyl methacrylate/acrylic acid/polymethyl acrylate atactic polymer.
The weight average molecular weight of this polymer is 52000, and number-average molecular weight is 18000, and promptly polydispersity sex index I is 2.89.
Embodiment 2: the preparation of poly-(isobornyl acrylate/isobutyl methacrylate/2-EHA) polymer
In the reactor with 1 liter of 100g Fancol ID adding, in 1 hour, temperature is increased to 90 ℃ from room temperature (25 ℃) subsequently.
Under 90 ℃, in 1 hour, add 120g isobornyl acrylate, 90g isobutyl methacrylate, 110g Fancol ID and 1.8g 2 subsequently, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane (
141, derive from Akzo Nobel).
This mixture was kept 1 hour 30 minutes down at 90 ℃.
Subsequently still under 90 ℃, in 30 minutes with 90g 2-EHA, 90g Fancol ID and 1.2g 2, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane adds in the said mixture.
This mixture was kept 3 hours down at 90 ℃, with postcooling.
Obtain the solution that comprises 50% polymer active material in Fancol ID.
Poly-(isobornyl acrylate/isobutyl methacrylate) first block, the Tg that obtain comprising Tg and be 80 ℃ are-70 ℃ polyacrylic acid 2-Octyl Nitrite second block and the polymer of mid-block, and described mid-block is isobornyl acrylate/isobutyl methacrylate/2-EHA atactic polymer.
The weight average molecular weight of this polymer is 77000, and number-average molecular weight is 19000, and promptly polydispersity sex index I is 4.05.
Embodiment 3: the preparation of poly-(isobornyl acrylate/isobornyl methacrylate/2-EHA) polymer
In the reactor with 1 liter of 100g Fancol ID adding, in 1 hour, temperature is increased to 90 ℃ from room temperature (25 ℃) subsequently.
Under 90 ℃, in 1 hour, add 105g isobornyl acrylate, 105g isobornyl methacrylate, 110g Fancol ID and 1.8g 2 subsequently, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane (
141, derive 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 4: the preparation of poly-(isobornyl acrylate/isobutyl methacrylate/Isobutyl 2-propenoate) polymer
In the reactor with 1 liter of 100g Fancol ID adding, in 1 hour, temperature is increased to 90 ℃ from room temperature (25 ℃) subsequently.
Under 90 ℃, in 1 hour, add 120g isobornyl acrylate, 90g isobutyl methacrylate, 110g Fancol ID and 1.8g 2 subsequently, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane (
141, derive 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 down at 90 ℃, with postcooling.
Obtain the solution that comprises 50% polymer active material in Fancol ID.
Poly-(isobornyl acrylate/isobutyl methacrylate) first block, the Tg that obtain comprising Tg and be 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.
Embodiment 5: the preparation of poly-(methyl methacrylate/acrylic acid methyl ester ./acrylic acid) polymer
In the reactor with 1 liter of 100g butyl acetate adding, in 1 hour, temperature is increased to 90 ℃ from room temperature (25 ℃) subsequently.
Under 90 ℃, in 1 hour, add 50.4g methyl methacrylate, 21g acrylic acid, 138.6g acrylic acid methyl ester., 40g butyl acetate, 70g isopropyl alcohol and 1.8g 2 subsequently, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane (
141, derive from AkzoNobel).
This mixture was kept 1 hour down at 90 ℃.
Subsequently still under 90 ℃, in 1 hour with 90g methyl methacrylate, 70g butyl acetate, 20g isopropyl alcohol and 1.2g 2, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane adds in the said mixture.
This mixture was kept 3 hours down at 90 ℃, subsequently with 105g butyl acetate and 45g isopropanol and cooling.
Obtain the solution that comprises 40% polymer active material in butyl acetate/isopropanol mixture.
Obtaining comprising Tg is poly-(acrylic acid methyl ester ./methyl methacrylate/acrylic acid) first block of 35 ℃, the polymer that gathers (methyl methacrylate) second block and mid-block that Tg is 100 ℃, and described mid-block is methyl methacrylate/acrylic acid/polymethyl acrylate atactic polymer.
Embodiment 6: the preparation of poly-(isobornyl acrylate/isobornyl methacrylate/Isobutyl 2-propenoate) polymer
In the reactor with 1 liter of 100g Fancol ID adding, in 1 hour, temperature is increased to 90 ℃ from room temperature (25 ℃) subsequently.
Under 90 ℃, in 1 hour, add 105g isobornyl acrylate, 105g isobornyl methacrylate, 110g Fancol ID and 1.8g 2 subsequently, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane (
141, derive 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 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-20 ℃ polyisobutyl acrylate second block and the polymer of mid-block, and described mid-block is isobornyl acrylate/isobornyl methacrylate/Isobutyl 2-propenoate atactic polymer.
The weight average molecular weight of this polymer is 151000, and number-average molecular weight is 41200, and promptly polydispersity sex index I is 3.66.
Embodiment 7: the preparation of poly-(isobornyl methacrylate/isobutyl methacrylate/Isobutyl 2-propenoate) polymer
In the reactor with 1 liter of 100g Fancol ID adding, in 1 hour, temperature is increased to 90 ℃ from room temperature (25 ℃) subsequently.
Under 90 ℃, in 1 hour, add 120g isobornyl methacrylate, 90g isobutyl methacrylate, 110g Fancol ID and 1.8g 2 subsequently, two (the 2-ethyl hexanoyl peroxides)-2 of 5-, the 5-dimethylhexane (
141, derive 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 down at 90 ℃, with postcooling.
Obtain the solution that comprises 50% polymer active material in Fancol ID.
Poly-(isobornyl methacrylate/isobutyl methacrylate) first block, the Tg that obtain comprising Tg and be 95 ℃ are-20 ℃ polyisobutyl acrylate second block and the polymer of mid-block, and described mid-block is isobornyl methacrylate/isobutyl methacrylate/Isobutyl 2-propenoate atactic polymer.
The weight average molecular weight of this polymer is 100700, and number-average molecular weight is 20800, and promptly polydispersity sex index I is 4.85.
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.
Preferred compositions of the present invention comprises 0.1% to 60% weight, preferred 0.5%-50% weight, the more preferably block polymerization active substances (polymer solids) of 1%-40% weight.
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 hydrophilic C
2Ether and C
2-C
4Aldehyde.
The content range of the mixture of water or water and hydrophilic organic solvent in compositions of the present invention can be 0.1% to 99% of described composition total weight, is preferably 10% to 80%.
Compositions of the present invention comprises acceptable organic liquid medium on the cosmetics (acceptable toleration, toxicity and sensation).
According to a particularly preferred embodiment, the organic liquid medium of described compositions comprises at least a organic solvent, and this organic solvent is the polymer solvent of aforesaid block polymer or a kind of polymer solvent wherein.Preferred described organic solvent is for accounting for the liquid of major part (by weight) in the organic liquid medium of described cosmetic composition.
According to an embodiment, described organic liquid medium comprises and at least aly at room temperature (is generally 25 ℃) and is the lipoid material of liquid.This liquid aliphatic class material can derive from animal, plant, mineral or synthetic.
Can be used for of can mentioning, of the present inventionly at room temperature have for the lipoid material of liquid (so-called " oil "): zoogenous alkyl oil, as perhydro-squalene; Plant source alkyl oil, as contain liquid triglyceride (as triheptin or tricaprylin), Oleum Helianthi, Semen Maydis oil, soybean oil, Oleum Vitis viniferae, Oleum sesami, almond oil, macadimia nut oil, Oleum Ricini, American Avocado Tree oil, three sad/decanoins, Jojoba oil or 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 or the different stearyl ester of isostearic acid; The ester of hydroxylation is as the fatty alkyl ester of 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 enanthic acid, sad or capric acid; Polyol ester is as two sad propylene glycol esters, two enanthic acid DOPCP or 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 or 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 and dichlorodiethyl ether; Alkane is as decane, heptane, dodecane, Fancol ID and cyclohexane extraction; The cyclophane compounds of group is as toluene and dimethylbenzene; Aldehyde is as benzaldehyde and acetaldehyde; And composition thereof.
Except above-mentioned block polymerization beyond the region of objective existence, described compositions also can comprise other polymer (as film forming polymer).According to the present invention, term " film forming polymer " is meant self or in the presence of auxiliary film former, can forms the polymer that is attached to the continuous films on the carrier (particularly keratin material).
The film forming polymer that can be used for compositions of the present invention that can mention has the synthetic polymer free radical type or the condensation polymer type, polymer of natural origin and composition thereof.The film forming polymer that can mention specifically comprises acrylic polymer, polyurethane, polyester, polyamide, polyureas and cellulose-based polymer (as celluloid).
Described polymer can be used in combination with one or more auxiliary film former.This film former can be selected from any chemical compound that can finish required function well known by persons skilled in the art, and particularly optional self-plasticization agent and coalescent.
Compositions of the present invention can comprise at least a wax.For the present invention, term " wax " is meant in room temperature (25 ℃) and is down solid lipophilic cpd, and this chemical compound changes through reversible solid phase/liquid phase state, and fusing point is greater than or equal to 30 ℃ and reach as high as 120 ℃.
Can adopt differential scanning calorimetry (DSC) to measure the fusing point of wax, as DSC 30 calorimeters of Mettler company sale.
Described wax can be alkyl wax, fluorine wax and/or silicone wax, and can be plant-derived, mineral, animal and/or synthetic source.Particularly the fusing point of described wax is higher than 25 ℃, and more preferably is higher than 45 ℃.
The wax that can be used for compositions of the present invention that can mention has: Cera Flava, Brazil wax, candelilla wax, paraffin, microwax, ceresine (ceresin) or ceresine (ozokerite), synthetic wax are (as Tissuemat E or Fischer-Tropsch wax and silicone wax the alkyl or the alkoxyl diformazan siloxanes of 16 to 45 carbon atoms (as comprise).
Described hard fat class Substance Properties and amount depend on required mechanical performance and texture texture.As guidance, described compositions can comprise and accounts for 0% to 50% of its gross weight, and the more preferably wax of 1%-30%.
Compositions of the present invention also can comprise the dyestuff that one or more are selected from water-soluble dye and powder dye, as pigment well known to those skilled in the art, Concha Margaritifera and leidosome.The amount scope of described dyestuff 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, based on the cochineal carmine or based on the color lake of barium, strontium, calcium or aluminum.
Also can mention pigment with effect, as comprising granule natural or synthetic, inorganic or organic substrate (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 of titanium or bismuthyl chloride (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) or methylene blue.
Compositions of the present invention 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
Powder (
Derive from Atochem), poly--Beta-alanine powder and polyethylene powders, polytetrafluorethylepowder powder
The polymer microbody ball of lauroyl lysine, starch, boron nitride, hollow (as the microbody ball of polyvinylidene chloride/acrylonitrile, as
(Nobel Industrie)) or acrylic acid copolymer (
Derive from Dow Corning company) and the silicones microballon (as
Derive from Toshiba), elastic organo-polysilane granules, sedimentary calcium carbonate, magnesium carbonate, magnesium bicarbonate, hydroxyapatite, hollow silica microsphere (Silica
Derive from Maprecos), glass or ceramic microcapsule and derived from the metallic soap (as zinc stearate, manganese stearate, lithium stearate, Dodecanoic acid, zinc salt or 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 suspension, dispersion liquid, solution, gel, emulsion form, particularly oil-in-water (O/W) emulsion, Water-In-Oil (W/O) emulsion or complex emulsions (W/O/W or polyhydric alcohol/O/W or O/W/O emulsion), perhaps with the form of the dispersion of emulsifiable paste, paste, mousse, capsule, (particularly soft paste specifically is that 25 ℃, shear rate are 200s for particularly ion or nonionic liposome, two-phase or multiphase lotion, spraying, powder, paste
-1Down, the dynamic viscosity of measuring after 10 minutes in cone and plate viscometer is about ointment of 0.1 to 40Pa.s).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), cosmetic lipstick, eye shadow, liquid lipstick, covering product (concealer products), mascara, eyeliner, eyebrow cosmetic product, 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 health and facial skin nursing.
Of the present invention another themes as the cosmetics external member, and described external member comprises:
I) defined the container of at least one compartment, described container close by a closing element and
Ii) place the aforesaid compositions in the described compartment.
Described container can any suitable form.Described container can be specially bottle, pipe, jar, case, box, pouch or carton form.
Described closing element can be the movably form of stopper, lid, pipe cap, the band that can tear off or valve protection cap, particularly comprises the type of object that invests on this container and the covering pipe cap that is associated with this object.Also can be the element of optionally closing this container, particularly pump, valve or disk valve.
Described container can combine with spreader, and described spreader particularly comprises the brush form that keeps the mane arrangement by the tinsel of distortion.The brush of this distortion is specifically seen and is set forth in US 4 887 622.Described spreader also can be and comprises a plurality of combs that are coated with brush element that particularly obtain by molding.This comb is set forth in FR 2 796 529 as seeing.Described in FR 2 722 380, described spreader also can be the form of exquisite brush.Described spreader can foam or the form of elastomer block, felt or scraper.Described in US 5 492 426, described spreader can be nothing fixing (silk wadding or sponge) or is firmly fixed on the rod that has closing element.Described in FR 2 761 959, described spreader can be securely fixed on the 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 (click-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 or 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.
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 8-12: lip pomade
| Embodiment | 8 | 9 | 10 | 11 | 12 |
| The polymer of embodiment 2 | 90.7 | ||||
| The polymer of embodiment 3 | 90.7 |
| The polymer of embodiment 4 | 90.7 | ||||
| The polymer of embodiment 6 | 90.7 | ||||
| The polymer of embodiment 7 | 90.7 | ||||
| Parleam | 2.1 | 2.1 | 2.1 | 2.1 | 2.1 |
| Octyldodecanol | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 |
| Silicone DC 556 (DC 556,20 cSt, Dow Corning) | 2.1 | 2.1 | 2.1 | 2.1 | 2.1 |
| Vinyl pyrrolidone/1-eicosylene copolymer (Antaron V-220, ISP) | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 |
| Pigment | 3 | 3 | 3 | 3 | 3 |
Step
1. in three-roll grinder, the pigment composition in oil phase is ground three times, obtain the ground pigment composition in oil phase.
2. in beaker, take by weighing ground material and other components that described compositions needs.
3. at room temperature use the Rayneri blender that this mixture was stirred 45 minutes.
4. with said preparation cast molding in Fancol ID-anti-leak cooling box.
Gloss is measured
1. use mechanical applicator to prepare the thin film that wet-film thickness is 50 and/or 150 μ m.Deposit is coated on the Leneta board contrast card Form 1A Penopac.
2. be adjusted in and make film drying 24 hours under 30 ℃.
3. be to use Byk Gardner micro-Tri-Gloss gloss meter to measure each serial sedimental gloss under 20 ° and 60 ° taking measurement of an angle.
The glossiness that obtains the results are shown in following table:
The deposit of 150 μ m
The deposit of 50 μ m
Taking measurement of an angle is that to obtain thickness under 20 ° be that the average gloss of thin film of 50 μ m or 150 μ m is greater than 40%.
Taking measurement of an angle is that to obtain thickness under 60 ° be that the average gloss of thin film of 50 μ m is greater than 65%.Taking measurement of an angle is that to obtain thickness under 60 ° be that the average gloss of thin film of 150 μ m is greater than 70%.
Embodiment 13: nial polish
Embodiment 14: nial polish
Claims (74)
1. liquid cosmetic composition, described compositions comprises acceptable organic liquid medium and the linear olefinic block polymer of non-resilient film forming on the cosmetics, when having the described polymer of capacity in the described compositions, the sedimental average gloss that described compositions is launched to obtain on carrier under 20 ° is more than or equal to 30%
The polydispersity index I of described block polymer is greater than 2, and described block polymer comprises at least a first block and at least a second block, each self-contained at least a monomer that is selected from acrylic acid, acrylate, methacrylic acid and methacrylate and composition thereof of first block and second block wherein
First block of wherein said 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.
2. the liquid cosmetic composition of claim 1, wherein the linear olefinic block polymer of film forming does not contain styrene units.
3. the cosmetic composition of claim 1, it is characterized in that described polymer 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.
4. the cosmetic composition of claim 1, it is characterized in that described block polymer comprises first and second blocks that link together by 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.
5. the compositions of claim 1 is characterized in that described first and second blocks link together by the mid-block of glass transition temperature between the glass transition temperature of first and second blocks.
6. the cosmetic composition of claim 1 is characterized in that described block polymer is included in inconsistent first and second blocks in the described organic liquid medium.
7. the compositions of claim 1 is characterized in that Tg is greater than or equal to 40 ℃ all or part of glass transition temperature derived from one or more homopolymer prepared therefrom of block and is greater than or equal to 40 ℃ monomer.
8. the compositions of claim 1, 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, perhaps R
1Represent C
4-C
12Cycloalkyl;
-Shi CH
2=CH-COOR
2Acrylate, R wherein
2Represent C
4-C
12Cycloalkyl, or the tert-butyl group;
-and composition thereof.
9. claim 7 or 8 compositions, 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 and (methyl) isobornyl acrylate and composition thereof.
10. the compositions of claim 1 is characterized in that Tg is less than or equal to 20 ℃ all or part of glass transition temperature derived from homopolymer prepared therefrom of block and is less than or equal to 20 ℃ monomer.
11. the compositions of claim 10, 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;
-and composition thereof.
12. the compositions of claim 10 or 11, 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.
13. the compositions of claim 1 is characterized in that Tg is that all or part of glass transition temperature derived from homopolymer prepared therefrom of block between 20 ℃ and 40 ℃ is the monomer between 20 ℃ and 40 ℃.
14. the compositions of claim 1 is characterized in that Tg is that Tg that all or part of Tg derived 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.
15. the compositions of claim 13 or 14 is characterized in that Tg is that block between 20 ℃ and 40 ℃ is all or part of derived from being selected from following monomer: methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, butyl acrylate and 2-EHA and composition thereof.
16. the compositions of claim 1, 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 Tg of described first block is greater than or equal to 40 ℃, and the glass transition temperature of described second block is less than or equal to 20 ℃.
17. the compositions of claim 1 is characterized in that all or part of glass transition temperature derived from one or more homopolymer prepared therefrom of described first block is greater than or equal to 40 ℃ monomer.
18. the compositions of claim 17 is characterized in that described first block is for being greater than or equal to 40 ℃ monomeric copolymer derived from the glass transition temperature of homopolymer prepared therefrom.
19. the compositions of claim 17 or 18, 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, perhaps R
1Represent C
4-C
12Cycloalkyl;
-Shi CH
2=CH-COOR
2Acrylate, R wherein
2Represent C
4-C
12Cycloalkyl, or the tert-butyl group;
-and composition thereof.
20. the compositions of claim 17, 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.
21. the compositions of claim 17, the proportion that it is characterized in that described first block is the 20%-90% of described polymer weight.
22. the compositions of claim 16 is characterized in that all or part of glass transition temperature derived from one or more homopolymer prepared therefrom of described second block is less than or equal to 20 ℃ monomer.
23. the compositions of claim 16 is characterized in that described second block is for being less than or equal to 20 ℃ monomeric homopolymer derived from the glass transition temperature of homopolymer prepared therefrom.
24. the compositions of claim 22 or 23, 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;
-and composition thereof.
25. the compositions of claim 22, 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.
26. the compositions of claim 1 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.
27. the compositions of claim 1, 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 Tg of described first block 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 ℃.
28. the compositions of claim 1 is characterized in that Tg is that all or part of glass transition temperature derived from one or more homopolymer prepared therefrom of first block between 20 ℃ and 40 ℃ is the monomer between 20 ℃ and 40 ℃.
29. the compositions of claim 27 or 28 is characterized in that Tg is that Tg that first block between 20 ℃ and 40 ℃ is greater than or equal to 40 ℃ monomer and corresponding homopolymer for the Tg derived from corresponding homopolymer is less than or equal to 20 ℃ monomeric copolymer.
30. the compositions of claim 27, it is characterized in that Tg be first block between 20 ℃ and 40 ℃ derived from being selected from following monomer: methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, butyl acrylate and 2-EHA and composition thereof.
31. the compositions of claim 27 is characterized in that Tg is that the proportion of first block between 20 ℃ and 40 ℃ is the 10%-85% of described polymer weight.
32. the compositions of claim 27 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 derived from one or more homopolymer prepared therefrom is greater than or equal to 40 ℃ monomer.
33. the compositions of claim 27 is characterized in that the Tg of described second block is greater than or equal to 40 ℃, is greater than or equal to 40 ℃ monomeric homopolymer for the glass transition temperature derived from homopolymer prepared therefrom.
34. each compositions in claim 32 and 33, 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, perhaps R
1Represent C
4-C
12Cycloalkyl;
-Shi CH
2=CH-COOR
2Acrylate, R wherein
2Represent C
4-C
12Cycloalkyl, or the tert-butyl group;
-and composition thereof.
35. the compositions of claim 31, 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.
36. the compositions of claim 32 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.
37. the compositions of claim 27 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 derived from one or more homopolymer prepared therefrom is less than or equal to 20 ℃ monomer.
38. the compositions of claim 27 is characterized in that the Tg of described second block is less than or equal to 20 ℃, and for be less than or equal to 20 ℃ monomeric homopolymer derived from the glass transition temperature of homopolymer prepared therefrom.
39. the compositions of claim 37 or 38, 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;
-and composition thereof.
40. the compositions of claim 37, 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.
41. the compositions of claim 37 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.
42. the cosmetic composition of claim 1 is characterized in that described first block and/or second block comprise at least a other monomers.
43. the compositions of claim 1 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.
44. the compositions of claim 42 or 43 is characterized in that described other monomers are selected from:
A) hydrophilic monomer:
-comprise at least one carboxylic acid or sulfonic acid functional group's ethylenically unsaturated monomer;
-comprise the ethylenically unsaturated monomer and the salt thereof of at least one tertiary amine functional group;
-Shi CH
2=C (CH
3)-COOR
6Methacrylate,
R wherein
6Representative comprises the straight or branched alkyl of 1 to 4 carbon atom, the alkyl of described alkyl for being replaced by one or more substituent groups that are selected from hydroxyl and halogen atom;
-Shi CH
2=C (CH
3)-COOR
9Methacrylate,
R
9Represent C
6-C
12The straight or branched alkyl, described alkyl is replaced by one or more substituent groups that are selected from hydroxyl and halogen;
-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
1-C
12Alkyl, perhaps R
10Represent the C of 5-30 oxygen ethylene repeating unit
1-C
12Alkyl-O-polyoxyethylene, 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;
-and composition thereof.
45. each compositions in claim 42 and 43 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.
46. each compositions in claim 42 and 43 is characterized in that the monomer of each self-contained at least a being selected from (methyl) acrylate of first and second blocks and at least a other monomers of choosing wantonly, and composition thereof.
47. each compositions in claim 42 and 43 is characterized in that first and second blocks separately all derived from the monomer of at least a being selected from (methyl) acrylate and at least a other monomers of choosing wantonly, and composition thereof.
48. the compositions of claim 42 is characterized in that described other one or more monomers account for 1% to 30% of the first and/or second block gross weight.
49. claim 1 compositions is characterized in that difference between the glass transition temperature Tg of described first and second block is greater than 10 ℃.
50. the compositions of claim 1, the polydispersity index that it is characterized in that described block polymer is more than or equal to 2.5.
51. the compositions of claim 50, the polydispersity index that it is characterized in that described block polymer is between 2.8 and 6.
52. the compositions of claim 1 is characterized in that the weight average molecular weight Mw of described block polymer is less than or equal to 300000.
53. the compositions of claim 52 is characterized in that weight average molecular weight Mw scope is 35000 to 200000.
54. the compositions of claim 53 is characterized in that number-average molecular weight Mn is less than or equal to 70000.
55. each compositions among the claim 52-54, its number-average molecular weight Mn scope is 10000 to 60000.
56. the compositions of claim 1, the average gloss that it is characterized in that the described compositions that records under 20 ° is more than or equal to 35%.
The compositions of 57 claim 1, the average gloss that is deployed in the described compositions on the carrier that it is characterized in that recording under 60 ° is more than or equal to 50%.
58. the compositions of claim 1, the average gloss that it is characterized in that the compositions that records under 20 ° is more than or equal to 35%, and/or the gloss of the compositions that records under 60 ° is more than or equal to 65%.
59. aforesaid right requires 1 compositions, the gloss that it is characterized in that the compositions that records under 20 ° is more than or equal to 60%, and/or the gloss of the compositions that records under 60 ° is more than or equal to 80%.
60. the compositions of claim 1 is characterized in that described compositions comprises the polymer active material of 0.1% to 60% weight.
61. the cosmetic composition of claim 1 is characterized in that described compositions also comprises the dyestuff that one or more are selected from water-soluble dye and powder dye.
62. the cosmetic composition of claim 1, it is characterized in that described compositions is suspension, dispersion liquid, solution, gel, emulsion form, perhaps with the form of the dispersion of emulsifiable paste, mousse, capsule, ion or nonionic liposome, two-phase or multiphase lotion, or paste.
63. the cosmetic composition of claim 1 is characterized in that described compositions is an anhydrous form.
64. the cosmetic composition of claim 1 is characterized in that described compositions is to be used for the compositions that keratin material is made up or nursed.
65. the cosmetic composition of claim 1 is characterized in that described compositions is the lip cosmetic product.
66. the cosmetic composition of claim 1 is characterized in that described compositions is the eye cosmetic product.
67. the cosmetic composition of claim 1 is characterized in that described compositions is the fingernail cosmetic product.
68. a cosmetics external member, described external member comprises:
A) defined the container of at least one compartment, described container cuts out by a closing element; With
B) place the interior compositions of described compartment,
Described compositions is each a compositions among the aforesaid right requirement 1-67.
69. the cosmetics external member of claim 68 is characterized in that described container to small part is formed by at least a thermoplastic.
70. the cosmetics external member of claim 68 is characterized in that described container to small part is formed by at least a non-thermoplastic material.
71. the external member of claim 68 is characterized in that the closed position at described container, described closing element is connected on the described container by spiral.
72. the external member of claim 68 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 fastening, bonding or be welded to connect on described container by buckle.
73. the external member of claim 68 is characterized in that described compositions is at the described indoor basic normal pressure that is.
74. the external member of claim 68 is characterized in that described compositions is pressurized in described container.
75. a cosmetic method that is used for the cosmetic or the nursing of keratin material, described method comprise each cosmetic composition among the claim 1-67 is applied to keratin material.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR02/11949 | 2002-09-26 | ||
| FR0211949 | 2002-09-26 | ||
| FR02/16437 | 2002-12-20 | ||
| FR0216437 | 2002-12-20 | ||
| FR0306121 | 2003-05-21 | ||
| FR03/06121 | 2003-05-21 | ||
| PCT/FR2003/002842 WO2004028488A2 (en) | 2002-09-26 | 2003-09-26 | Glossy liquid composition comprising a sequenced polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1700904A CN1700904A (en) | 2005-11-23 |
| CN100594879C true CN100594879C (en) | 2010-03-24 |
Family
ID=35476661
Family Applications (7)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03825338 Pending CN1700902A (en) | 2002-09-26 | 2003-09-26 | Anti-migration cosmetic composition comprising a block polymer |
| CN 03825334 Pending CN1708279A (en) | 2002-09-26 | 2003-09-26 | Glossy non-transfer composition comprising a block polymer |
| CN 03825414 Pending CN1703194A (en) | 2002-09-26 | 2003-09-26 | Keratin fibre coating composition containing high-dry extract, and block polymer containing same |
| CNB038253275A Expired - Fee Related CN100360110C (en) | 2002-09-26 | 2003-09-26 | Lipstick 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 |
| CNB038253542A Expired - Lifetime CN100360113C (en) | 2002-09-26 | 2003-09-26 | Composition containing block polymer and gelling agent |
Family Applications Before (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03825338 Pending CN1700902A (en) | 2002-09-26 | 2003-09-26 | Anti-migration cosmetic composition comprising a block polymer |
| CN 03825334 Pending CN1708279A (en) | 2002-09-26 | 2003-09-26 | Glossy non-transfer composition comprising a block polymer |
| CN 03825414 Pending CN1703194A (en) | 2002-09-26 | 2003-09-26 | Keratin fibre coating composition containing high-dry extract, and block polymer containing same |
| CNB038253275A Expired - Fee Related CN100360110C (en) | 2002-09-26 | 2003-09-26 | Lipstick comprising a block polymer |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03825321 Pending CN1700900A (en) | 2002-09-26 | 2003-09-26 | Compositions containing block polymers and film-forming agent |
| CNB038253542A Expired - Lifetime CN100360113C (en) | 2002-09-26 | 2003-09-26 | Composition containing block polymer and gelling agent |
Country Status (2)
| Country | Link |
|---|---|
| CN (7) | CN1700902A (en) |
| ES (8) | ES2354152T3 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2946873A1 (en) * | 2009-06-18 | 2010-12-24 | Oreal | KERATIN FIBER TREATING COMPOSITION COMPRISING A POLYALCENE SUPRAMOLECULAR POLYMER AND A SEQUENCE POLYMER AND A VOLATILE SOLVENT. |
| FR2992195B1 (en) * | 2012-06-21 | 2014-11-07 | Oreal | COSMETIC COMPOSITION COMPRISING AN OIL, HYDROPHOBIC SILICA AEROGEL PARTICLES AND A HYDROCARBON SEQUENCE COPOLYMER PREFERABLY OBTAINED FROM AT LEAST ONE STYRENE MONOMER |
| CN103865015B (en) * | 2014-03-24 | 2017-01-11 | 合肥工业大学 | High-Tg low-softening-point carboxyl-containing acrylic resin for weather-resisting powder coating |
| CN106999403B (en) * | 2014-12-15 | 2021-07-06 | 株式会社Lg生活健康 | Composition for external application to skin |
| FR3045362B1 (en) * | 2015-12-22 | 2020-11-06 | Oreal | COSMETIC TREATMENT PROCESS OF KERATINIC MATERIALS WITH AN ETHYLENIC POLYMER OF MALEIC ANHYDRIDE |
| FR3045377B1 (en) * | 2015-12-22 | 2020-01-03 | L'oreal | COSMETIC PROCESSING PROCESS FOR KERATINIC MATERIALS |
| CN107595672B (en) * | 2017-01-22 | 2020-10-27 | 广州温雅日用化妆品有限公司 | Chromonic paste compositions and methods of making and using the same |
| CN108753219B (en) * | 2018-04-16 | 2019-06-21 | 大连理工大学 | A kind of amphiphilic styrene-series hot-melt pressure-sensitive adhesive of low form, preparation method and applications |
| CN110052172B (en) * | 2019-03-17 | 2021-08-24 | 浙江工业大学 | Preparation method of cross-linked heat-resistant solvent-resistant homogeneous pore membrane and related block copolymer |
| CN111154415B (en) * | 2020-01-08 | 2021-09-17 | 江苏耐斯数码科技股份有限公司 | Thermal sublimation printing adhesive label |
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| US4030512A (en) * | 1974-12-30 | 1977-06-21 | Societe Anonyme Dite: L'oreal | Hair lacquer or setting lotion containing bi- or tri-sequenced copolymer |
| US5110582A (en) * | 1981-03-25 | 1992-05-05 | Basf Aktiengesellschaft | Hair-setting preparation |
| US6106820A (en) * | 1997-05-12 | 2000-08-22 | Procter & Gamble Company | Cosmetic compositions |
| US6153206A (en) * | 1997-08-27 | 2000-11-28 | Revlon Consumer Products Corporation | Cosmetic compositions |
| EP1082953A1 (en) * | 1999-09-07 | 2001-03-14 | L'oreal | Cosmetic composition containing dispersions of polymer particles in a fatty liquid phase |
| DE10029697A1 (en) * | 2000-06-16 | 2001-12-20 | Basf Ag | Binding composition, useful e.g. in paints and inks, or for pigmentation, comprises radical-polymerized block copolymer and non-magnetic filler |
| EP1192930A1 (en) * | 2000-09-29 | 2002-04-03 | L'oreal | Film-forming cosmetic composition |
| FR2832719B1 (en) * | 2001-11-29 | 2004-02-13 | Oreal | ADHESIVE SEQUENCE ETHYLENIC COPOLYMERS, COSMETIC COMPOSITIONS CONTAINING THEM, AND USE OF SUCH COPOLYMERS IN COSMETICS |
| FR2803743B1 (en) * | 2000-01-14 | 2005-04-15 | Atofina | COSMETIC COMPOSITIONS CONTAINING AQUEOUS DISPERSIONS OF POLYMERS, FILMOGENES IN THE ABSENCE OF ORGANIC SOLVENT |
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| DE69832284T2 (en) * | 1997-03-26 | 2006-08-03 | Avon Products, Inc. | ABRASIVE COSMETICS |
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| WO2000028948A1 (en) * | 1998-11-12 | 2000-05-25 | The Procter & Gamble Company | Cosmetic compositions |
| FR2809306B1 (en) * | 2000-05-23 | 2004-02-06 | Oreal | USE IN COSMETICS OF ETHYLENIC COPOLYMERS SEQUENCES WITH ELASTIC CHARACTER AND COMPOSITIONS CONTAINING THEM |
-
2003
- 2003-09-26 ES ES03780204T patent/ES2354152T3/en not_active Expired - Lifetime
- 2003-09-26 CN CN 03825338 patent/CN1700902A/en active Pending
- 2003-09-26 ES ES03782505T patent/ES2355972T3/en not_active Expired - Lifetime
- 2003-09-26 ES ES03798230T patent/ES2356311T3/en not_active Expired - Lifetime
- 2003-09-26 CN CN 03825334 patent/CN1708279A/en active Pending
- 2003-09-26 CN CN 03825414 patent/CN1703194A/en active Pending
- 2003-09-26 ES ES03798229T patent/ES2361010T3/en not_active Expired - Lifetime
- 2003-09-26 ES ES03798228T patent/ES2362275T3/en not_active Expired - Lifetime
- 2003-09-26 CN CNB038253275A patent/CN100360110C/en not_active Expired - Fee Related
- 2003-09-26 CN CN03825357A patent/CN100594879C/en not_active Expired - Fee Related
- 2003-09-26 ES ES03776945T patent/ES2354975T3/en not_active Expired - Lifetime
- 2003-09-26 ES ES03798231T patent/ES2355374T3/en not_active Expired - Lifetime
- 2003-09-26 CN CN 03825321 patent/CN1700900A/en active Pending
- 2003-09-26 CN CNB038253542A patent/CN100360113C/en not_active Expired - Lifetime
- 2003-09-26 ES ES03292382T patent/ES2353495T3/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4030512A (en) * | 1974-12-30 | 1977-06-21 | Societe Anonyme Dite: L'oreal | Hair lacquer or setting lotion containing bi- or tri-sequenced copolymer |
| US5110582A (en) * | 1981-03-25 | 1992-05-05 | Basf Aktiengesellschaft | Hair-setting preparation |
| US6106820A (en) * | 1997-05-12 | 2000-08-22 | Procter & Gamble Company | Cosmetic compositions |
| US6153206A (en) * | 1997-08-27 | 2000-11-28 | Revlon Consumer Products Corporation | Cosmetic compositions |
| EP1082953A1 (en) * | 1999-09-07 | 2001-03-14 | L'oreal | Cosmetic composition containing dispersions of polymer particles in a fatty liquid phase |
| FR2803743B1 (en) * | 2000-01-14 | 2005-04-15 | Atofina | COSMETIC COMPOSITIONS CONTAINING AQUEOUS DISPERSIONS OF POLYMERS, FILMOGENES IN THE ABSENCE OF ORGANIC SOLVENT |
| DE10029697A1 (en) * | 2000-06-16 | 2001-12-20 | Basf Ag | Binding composition, useful e.g. in paints and inks, or for pigmentation, comprises radical-polymerized block copolymer and non-magnetic filler |
| EP1192930A1 (en) * | 2000-09-29 | 2002-04-03 | L'oreal | Film-forming cosmetic composition |
| FR2832719B1 (en) * | 2001-11-29 | 2004-02-13 | Oreal | ADHESIVE SEQUENCE ETHYLENIC COPOLYMERS, COSMETIC COMPOSITIONS CONTAINING THEM, AND USE OF SUCH COPOLYMERS IN COSMETICS |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1700902A (en) | 2005-11-23 |
| CN100360113C (en) | 2008-01-09 |
| ES2354152T3 (en) | 2011-03-10 |
| CN1700900A (en) | 2005-11-23 |
| ES2356311T3 (en) | 2011-04-06 |
| CN1703194A (en) | 2005-11-30 |
| CN1700904A (en) | 2005-11-23 |
| ES2354975T3 (en) | 2011-03-21 |
| ES2355374T3 (en) | 2011-03-25 |
| CN1700903A (en) | 2005-11-23 |
| ES2362275T3 (en) | 2011-06-30 |
| ES2353495T3 (en) | 2011-03-02 |
| ES2361010T3 (en) | 2011-06-13 |
| CN1708279A (en) | 2005-12-14 |
| ES2355972T3 (en) | 2011-04-01 |
| CN100360110C (en) | 2008-01-09 |
| CN1700901A (en) | 2005-11-23 |
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