CN101151016A - Use of a water-in-water emulsion polymers in the form of a thickener for cosmetic preparations - Google Patents

Use of a water-in-water emulsion polymers in the form of a thickener for cosmetic preparations Download PDF

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CN101151016A
CN101151016A CNA2006800103251A CN200680010325A CN101151016A CN 101151016 A CN101151016 A CN 101151016A CN A2006800103251 A CNA2006800103251 A CN A2006800103251A CN 200680010325 A CN200680010325 A CN 200680010325A CN 101151016 A CN101151016 A CN 101151016A
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acid
polymer
copolymer
methyl
vinyl
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P·穆克吉
K·马斯奥尔
C·伍德
M·劳本德
I·加西亚·卡斯特罗
V·温德尔
H·沃尔玛
A·伦奥考特
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BASF SE
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BASF SE
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212—Face masks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/046—Aerosols; Foams
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/91—Graft copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/26—Optical properties
    • A61K2800/262—Transparent; Translucent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/28—Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06—Lipsticks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/001—Preparations for care of the lips
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/002—Aftershave preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q9/00—Preparations for removing hair or for aiding hair removal
    • A61Q9/02—Shaving preparations

Abstract

The invention relates to the use of polymers, optionally in the form of an aqueous dispersion, obtainable by polymerisation of ethylenically unsaturated anionic monomers for modifying the rheology of aqueous or alcoholic or aqueous/alcoholic cosmetic or dermatological compositions. Said polymers are producible by radical emulsion polymerisation of water-soluble inorganic monomers in the aqueous phase in the presence of at least one type of group a) and b) stabilising polymer. The emulsion polymers are particularly suitable for thickeners in water and alcohol-based cosmetic and dermatological preparations.

Description

The water-in-water type emulsion polymer of thickening agent form is used for the purposes of cosmetic formulations
---suitable form with aqueous dispersion exists---is used to improve the purposes of the rheological property of the cosmetics of aqueous, alcohol or water/alcohol or skin composition if the present invention relates to the polymer of the unsaturated anionic monomer of olefin type.
Polymer is widely used in cosmetics.Its effect in cosmetic hair is to influence the performance of hair, especially makes hair fixing, improves its cardability and gives comfortable sense of touch.
Thereby use dried and wet cardability, touch sense, gloss and the outward appearance of regulator, and give antistatic performance to improve hair.Preferred use have the polar functional group of bigger affinity, usually be the polymer of Cationic functional groups that this polymer is owing to its structure is elecrtonegativity water miscible having in hair surface.The structure of various hair treatment polymer and model of action are described in Cosmetic ﹠amp; Among the Toiletries 103 (1988) 23.The commercial regulator polymer of standard has, for example cationic hydroxyethyl-cellulose; Based on the cation type polymer of N-vinyl pyrrolidone, as the copolymer of N-vinyl pyrrolidone and quaternary ammonium N-vinyl imidazole; Acrylamide and diallyldimethylammonium chloride or silicone.
In the cosmetic hair preparation, the combination of heterogeneity---for example the comfortable sense of touch of typing, hair and have the thickening effect of polymer simultaneously---by force often has difficulties.
This point is particularly important in gel preparation.In addition, conventional styling polymer demonstrates the incompatibility with the thickening agent polymer, causes becoming turbid in the cosmetic formulations and precipitating.The shortcoming that typical thickeners often has is that because crosslinked, it can not form and be fit to the fixedly film of hair.Though this class thickening agent has been guaranteed the denseness of gel, after gel is dry on hair, it is no longer needed, thereby may destroy the application performance (typing effect, moisture sensitivity) of preparation.
Thickening agent is widely used in pharmaceutics and the cosmetic field to increase the viscosity of aqueous formulation.Often the example of the thickening agent that uses is fatty acid polyglycol ethylene glycol ester, fatty acid polyethylene glycol di, Marlamid, ethoxylized fatty alcohol, ethoxylated glycerol fatty acid ester, cellulose ether, sodium alginate, polyacrylic acid and neutral salt.
Carboxylic polymer is known thickening agent.It comprises the homopolymer and the copolymer of monoethenoid unsaturated carboxylic acid, for example acrylic acid, methacrylic acid, maleic acid, maleic anhydride and itaconic acid.These polymer often take place crosslinked at least on less degree.This base polymer for example is described among US 2,798,053, US 3,915,921, US 3,940,351, US 4,062,817, US 4,066,583, US 4,267,103, US 5,349,030 and the US 5,373,044.
Ever-present shortcoming is the dependency and the hydrolytic instability thereof of its pH value when these polymer are used as thickening agent.In addition, often need a large amount of polymer in order to obtain needed thickening effect, and stability of formulation is lower when electrolyte exists.
Naturally occurring material for example casein, alginate, methylcellulose, hydroxyethyl-cellulose, hydroxypropyl cellulose and carbomethoxy cellulose also is used as thickening agent.The weak point of these materials especially is the sensitivity to the microorganism factor, thereby needs to add antimicrobial.
DE-A 10338828 discloses the aqueous dispersion of water-soluble anionic polymer, described dispersion by the unsaturated anionic monomer of olefin type in aqueous medium, in the presence of at least a stabilizing agent, make by radical polymerization, wherein used stabilizing agent is at least a following water-soluble polymer:
(a) vinyl acetate and/or the propionate graft polymers on Polyethylene Glycol, one or both ends are by alkyl, carboxyl or amino-terminated Polyethylene Glycol, the copolymer of alkyl ployalkylene glycol acrylate or alkyl ployalkylene glycol methacrylate and acrylic acid and/or methacrylic acid, molal weight M NBe 1000 to 100000 ployalkylene glycol, one or both ends are by alkyl, carboxyl or amino-terminated and molal weight M NIt is 1000 to 100000 ployalkylene glycol
With
(b) copolymer of the vinyl alkyl ethers of hydrolysis and maleic anhydride, described hydrolyzed copolymer is existed by the form of alkali metal hydroxide or the neutral salt of ammonium class alkali with free carboxyl group with to small part, and/or a kind of cation-modified potato starch, anion-modified potato starch, the potato starch of degraded and water soluble starch of maltodextrin of being selected from.
Aqueous dispersion is as the thickening agent of water-based system, and described water-based system is paper-coating composition, color-printed cream, cosmetic formulations and leather treatment composition thing for example.These polymer are at cosmetic gel preparation, cosmetic cleaning composites, and for example the purposes in shampoo or the cosmetics for skin preparation is not seen description.
The aqueous dispersion of the anionic polymer of water solublity and/or water-swellable is disclosed among the undocumented application DE-A 102,004 038 983.7 equally, described anionic polymer can be by the unsaturated anionic monomer of olefin type in aqueous medium, in the presence of at least a stabilizing agent, make by radical polymerization, wherein polymerization process is carried out in the presence of at least a following water-soluble polymer:
(a) vinyl acetate and/or propionate (i) Polyethylene Glycol or (ii) one or both ends by alkyl, carboxyl or amino-terminated Polyethylene Glycol or the graft polymers on the polypropylene glycol, ployalkylene glycol, one or both ends are by alkyl, carboxyl or amino-terminated ployalkylene glycol
With
(b) water solubility copolymer of following substances:
(b1) nonionic monoethenoid unsaturated monomer,
(b2) cation monoene type unsaturated monomer and, if suitable
(b3) anion monoethenoid unsaturated monomer, wherein the branch rate of the cationic monomer of copolymerization is higher than monomeric minute rate of anionic,
Described water-soluble polymer used as stabilizers.These polymer are at cosmetic gel preparation, cosmetic cleaning composites, and for example the purposes in shampoo or the cosmetics for skin preparation is not seen description.
An object of the present invention is to find to improve rheological property, the polymer of thickening power especially, described polymer height is suitable for cosmetic applications, and especially has the excellent application performance energy at skin and cosmetic hair field.These performances comprise: have the good thickening effect clarity when also being useful on gel during except low raw material consumption in wide pH value scope; For water-insoluble and/or be difficult to stablize component for example (being total to) emulsifying and the Stabilization of the material of silicone and enzyme, hydrolysis and/or oxidation-sensitive; With the used for cosmetic conventional polymer, for example compatibility of cationic polymer; Good adding in cosmetic formulations; With the compatibility of high level of surfactant, for example compatibility in cosmetic cleaning composites such as shampoo.
Especially for gel, preparation needs the transparency (clarity) of maximum possible.
Cosmetic formulations is normally aqueous, alcohol in essence or water-alcohol is blended.Thereby be starved of to provide and in wide pH value scope, regulate the thickening agent of the rheological property of alcohol radical or water-base preparation.
If described purpose can be improved aqueous, alcohol by the polymer---suitable form with aqueous dispersion exists---that uses the unsaturated anionic monomer of olefin type or the cosmetics of water/alcohol or the rheological property of skin composition realize, described polymer can obtain by monomeric radical polymerization in aqueous medium, each comfortable at least a group polymer and at least a group b that is selected from a) that be selected from of polymerization process wherein) carry out under polymer exists, wherein organize a) and be constructed as follows:
A1) vinyl acetate and/or propionate (i) Polyethylene Glycol or (ii) one or both ends by alkyl, carboxyl or amino-terminated Polyethylene Glycol or the graft polymers on the polypropylene glycol,
A2) ployalkylene glycol,
A3) one or both ends are by alkyl, carboxyl or amino-terminated ployalkylene glycol,
A4) alkyl ployalkylene glycol (methyl) acrylate and (methyl) acrylic acid copolymer, and group b) be constructed as follows:
B1) copolymer of the vinyl alkyl ethers of partial hydrolysis and maleic anhydride at least, it can be at least in part exists with the form of salt,
B2) be selected from cation-modified starch, anion-modified starch, the starch of degraded and the water soluble starch of maltodextrin,
B3) be selected from following anionic copolymer:
The homopolymerization of-anionic monomer and copolymer,
If-anionic and copolymer cationic and---suitable---neutral monomer, wherein monomeric minute rate of the anionic of copolymerization greater than the branch rate of cationic monomer and
-at least a anionic monomer and at least a monomeric copolymer that is selected from ester, styrene, N-vinyl pyrrolidone, N-caprolactam, N-vinyl imidazole, N-vinyl formamide, acrylamide, Methacrylamide, vinyl acetate and the propionate of anionic monomer and monohydric alcohol
B4) if the cationic copolymer of nonionic monoethenoid unsaturated monomer and cation monoene type unsaturated monomer and---suitable---anion monoethenoid unsaturated monomer, wherein in each situation the quantity of cation group greater than the quantity of anionic group,
Be sometimes referred to as " emulsion polymer of the present invention " or " W/W polymer " or " W/W emulsion polymer " if be suitable for the W/W emulsion polymer of the unsaturated anionic monomer of olefin type of the present invention below---suitable exist---with the aqueous dispersion form.The group a) and the group b) polymer below be also referred to as " stabilizing agent ".
Preferred W/W emulsion polymer and polymer a) and polymer b)---being also referred to as stabilizing agent---for water miscible.Water-soluble polymer is interpreted as meaning under 20 ℃ and normal pressure herein, dissolves the amount of 1g at least and can generate the polymer of settled solution in the complete demineralized water of 1L.
The unsaturated anionic monomer of olefin type that is fit to is the unsaturated C of for example monoethenoid 3To C 5Carboxylic acid is as acrylic acid, methacrylic acid, ethylacrylic acid .beta.-methylacrylic acid, maleic acid, fumaric acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide group methyl propane sulfonic acid, vinylphosphonic acid, itaconic acid and/or these sour alkali metal salts or ammonium salts.The preferred anionic monomer that uses comprises acrylic acid, methacrylic acid, maleic acid and acrylamido-2-methyl propane sulfonic acid.Be preferably based on the aqueous dispersion of polymerizing acrylic acid thing especially.The anionic monomer separately polymerization form homopolymer or in mixture each other polymerization form copolymer.The example is the copolymer of acrylic acid homopolymer or acrylic acid and methacrylic acid and/or maleic acid.
But the monomeric polymerization of anionic also can be carried out in the presence of other olefin type unsaturated monomer.These monomers can be nonionic or also can have positive charge.The example of this class comonomer is acrylamide, Methacrylamide, monobasic C 1-C 22(methyl) acrylate, the C of alcohol 3-C 22Alkyl vinyl ether, C 6-C 16The amino propyl ester of alkene, derivatives of poly (iso) butene, vinyl acetate, propionate, (methyl) propenoic acid dialkyl amino ethyl ester, (methyl) propenoic acid dialkyl, diallyldimethylammonium chloride, N-vinyl formamide, vinyl imidazole and quaternized vinyl imidazole and partially or even wholly neutralization or quaternised dialkyl aminoalkyl (methyl) acrylamide.
By for example having (methyl) acrylate, the C of the monohydric alcohol of 4 to 22 carbon atoms with hydrophobic monomer 3-C 22Alkyl vinyl ether, C 6-C 16The copolymerization of alkene or derivatives of poly (iso) butene can improve the cosmetics of W/W emulsion polymer thickening or the skin-use preparation toleration (salt-stable) to salt.
The alkalescence monomer, (methyl) propenoic acid dialkyl aminoalkyl ester for example, as acrylic acid dimethylamino ethyl ester or dimethylaminoethyl methacrylate, can free alkali or part or all of neutral form or with a kind of C that for example uses 1To C 18The quaternised form of alkyl halide is used for polymerization.The amount that is used to prepare the comonomer of anionic polymer for example can be the polymer that makes generation to be water miscible and to have negative charge.Based on the used whole monomer meters of polymerization process, the amount of nonionic and/or cationic comonomer is for example 0 to 99 weight %, preferred 5 to 75 weight %.
Preferably copolymer is, for example the copolymer of the acrylamide of the acrylic acid of 25 to 90 weight % and 75 to 10 weight %.Especially preferably can not exist under other monomeric situation by acrylic acid by acrylate homopolymer that radical polymerization obtained, with can be at pentaerythritol triallyl ether, N, N '-divinyl ethylene-urea, methylene diallyl amide, have the dihydroxylic alcohols and the C of 2 to 8 carbon atoms 3To C 5The ester of carboxylic acid, the trimethylolpropane triacrylate of ethoxylation, the trimethylol-propane trimethacrylate of ethoxylation, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the triallyl ammonio methacrylate, the allyl ether that contains at least two allylic saccharides, have under the existence of mixture of the vinyl ethers of two vinyls or triallylamine and above-claimed cpd the acrylic acid that the copolymerization by acrylic acid and/or methacrylic acid makes and/or the copolymer of methacrylic acid at least.
Thus, polymerization process can be carried out in the presence of at least a cross-linking agent.The situation of the W/W polymer of Sheng Chenging anionic monomer polymerization when not having cross-linking agent is compared thus, has higher molal weight.In addition, adding cross-linking agent in polymer can cause the dissolubility of polymer in water to descend.According to the cross-linked dosage of copolymerization, polymer becomes water-insoluble, but in water swellable.Polymer in water fully the dissolving and swelling between have fluidic transition (fluidtransition).Because its swellability in water, cross linked polymer has high water absorbability.
Spendable cross-linking agent has the chemical compound of two olefin type unsaturated double-bonds at least for all at intramolecularly.This compounds is used for for example preparing the cross linked polyacrylate as high water absorbency polymer, and referring to EP-A 858 478, page 4 30 walks to page 5 43 row.The example of cross-linking agent is a triallylamine; Pentaerythritol triallyl ether; Methylene diallyl amide; N, N '-divinyl ethylene-urea; The containing at least two allylic allyl ethers or contain the vinyl ethers of at least two vinyls of polyhydric alcohol, described polyhydric alcohol is sorbitol, 1,1 for example, 4-butanediol, trimethylolpropane, glycerol, diethylene glycol; The containing at least two allylic allyl ethers or contain the vinyl ethers of at least two vinyls of sugar, described sugar is sucrose, glucose, mannose for example; Have 2 to 4 carbon atoms and by acrylic or methacrylic the acid dihydroxylic alcohols of esterification, for example ethylene glycol dimethacrylate, glycol diacrylate, butanediol dimethylacrylate, butanediol diacrylate fully; Molecular weight is the diacrylate or the dimethylacrylate of 300 to 600 Polyethylene Glycol; The trimethylolpropane triacrylate of ethoxylation or the trimethylol-propane trimethacrylate of ethoxylation; 2,2-two (methylol) butanols trimethyl acrylic ester; Pentaerythritol triacrylate; Tetramethylol methane tetraacrylate and triallyl ammonio methacrylate.If use cross-linking agent in the preparation process of anionic dispersion, the amount of used cross-linking agent is under the then various situations, 0.0005 to 5.0 weight % for example, and preferred 0.001 to 1.0 weight % is based on the used whole monomer meters of polymerization process.The preferred cross-linking agent that uses is pentaerythritol triallyl ether, N, N '-divinyl ethylene-urea, sugar for example sucrose, glucose, mannose contain at least two allylic allyl ethers, the trimethylolpropane triacrylate of triallylamine and/or ethoxylation, and the mixture of above-claimed cpd.
Polymerization process also can be carried out in the presence of at least a chain-transferring agent.This process generates polymer phase prepared when not having chain-transferring agent than having the more polymer of low molar mass.The example of chain-transferring agent is the chemical compound that contains the sulfur of bonding scheme, for example dodecyl mercaptans, sulfo-diethylene glycol, ethylthioethanol, di-n-butyl sulfur, di-n-octyl sulfur, diphenyl sulfide, diisopropyl disulfide, 2 mercapto ethanol, 1,3-mercaprol, 3-sulfydryl the third-1,2-glycol, 1,4-Mercaptobutanol., TGA, 3-mercaptopropionic acid, dimercaptosuccinic acid, thiacetic acid. and thiourea, aldehyde, organic acid be formic acid, sodium formate or ammonium formate, alcohol isopropyl alcohol and phosphide sodium hypophosphite for example especially for example for example.In polymerization process, single chain-transferring agent can be used, also two or more chain-transferring agents can be used.If use chain-transferring agent in polymerization process, then its consumption for example is 0.01 to 5.0 weight %, and preferred 0.2 to 1 weight % is based on the total monomer meter.In polymerization process, chain-transferring agent preferably uses with at least a cross-linking agent.By changing the amount and the ratio of chain-transferring agent and cross-linking agent, the rheological property of the polymer that may command generates.In polymerization process, chain-transferring agent and/or cross-linking agent can be in water-based polymer medium for example the time be introduced in beginning, perhaps can be according to the progress of polymerization process with monomer or be metered in the polyblend respectively.
In polymerization process, can use the initiator that under reaction condition, forms free radical usually.Suitable polymerization initiator is, for example peroxide, hydroperoxide, hydrogen peroxide, sodium peroxydisulfate or potassium peroxydisulfate, oxidation reduction catalyst and azo-compound for example 2,2-azo two (N, N-two methylene isobutyl amidines) dihydrochloride, 2,2-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2-azo two (2, the 4-methyl pentane nitrile) and 2,2-azo two (2-amidine propane) dihydrochloride.Initiator uses with amount conventional in the polyreaction.The preferred azo initiator that uses is as initiators for polymerization.But polyreaction also can be by using high-energy ray for example electron beam initiation or use UV light radiation initiation.
The concentration of anionic polymer is in the aqueous dispersion of preferred water soluble anion W/W emulsion polymer, for example, and 1 to 70 weight %, 5 to 50 weight % in most cases, preferred 10 to 25 weight %, preferred especially 15 to 20 weight %.
According to the present invention, comprise two kinds of inhomogeneous above-mentioned polymer (a) and (b) in the aqueous dispersion at least, be used for being stabilized in the anionic polymer that polymerization process forms.Stabilizing agent in the aqueous dispersion (a) and amount (b) are that for example 1 to 40 weight % in most cases is 5 to 30 weight % and preferred 10 to 25 weight %.The viscosity of aqueous dispersion for example pH value be 2.5 o'clock between 200 to 100000mPas, preferred 200 to 20000mPas, preferred 200 to 10000mPas (in the Brookfield viscometer, at 20 ℃, rotor 6, recording under the 100rpm condition).
Being suitable for the molecular weight Mw that the not crosslinked anionic polymer of purposes of the present invention generally has is 10000 to 15000000, and preferred 50000 to 10000000g/mol.Molecular weight is determined with polyacrylic acid standard or use FFF (field flow fractionation (FFF)) according to for example conventional method well known by persons skilled in the art such as SEC (size exclusion chromatography (SEC)).
The molecular weight of cross linked polymer can not be determined in this way.The molecular weight of cross linked polymer depends on the amount of used cross-linking agent and the degree of branching of polymer, may exceed the scope of the not cross linked polymer of being given.
Group is polymer a)
The stabilizing agent of group (a) comprises a1) vinyl acetate and/or propionate (i) Polyethylene Glycol or (ii) one or both ends by alkyl, carboxyl or amino-terminated Polyethylene Glycol or the graft polymers on the polypropylene glycol, the copolymer of alkyl ployalkylene glycol (methyl) acrylate and methacrylic acid, and ployalkylene glycol and one or both ends are by alkyl, carboxyl or amino-terminated ployalkylene glycol.
Ployalkylene glycol is described in for example WO 03/046024, and page 4 37 walks to the 8th page of 9 row.Wherein said ployalkylene glycol can be directly as the stabilizing agent of group (a), or by graft modification, for example vinyl acetate and/or the propionate of grafting 10 to 1000, preferred 30 to 300 weight portions on the ployalkylene glycol of 100 weight portions.The preferred molecular weight M that uses NBe 1000 to 100000 Polyethylene Glycol as the grafting base, grafting vinyl acetate thereon.
The stabilizing agent of suitable group (a) also comprises a2) copolymer of alkyl ployalkylene glycol acrylate or alkyl ployalkylene glycol methacrylate and acrylic acid and/or methacrylic acid.Described copolymer is by at first adding to for example C with acrylic acid and/or methacrylic acid with oxirane and/or expoxy propane 1To C 18Product esterification on the alcohol, then these esters and acrylic acid and/or methacrylic acid copolymerization are made, used copolymer comprises for example alkyl ployalkylene glycol (methyl) the acrylic ester copolymer unit of 5 to 60 weight %, preferred 10 to 35 weight % and (methyl) acrylic acid copolymer unit of 95 to 40 weight %, preferred 90 to 65 weight % usually.Its molecular weight M wMost cases is 2000 to 50000, preferred 5000 to 20000.These copolymers can free acidic-group or all or part of neutral form be used for the preparation of dispersion.Carboxyl in the copolymer is preferably with sodium hydroxide or ammonia neutralization.
Other suitable stabilizing agent (a) is above-mentioned a3) ployalkylene glycol and a4) one or both ends are by alkyl, carboxyl or amino-terminated ployalkylene glycol.More than the molal weight M that has of indicated polymer nFor example be 100 to 100000, preferred 300 to 80000, preferred especially 600 to 50000, especially 1000 to 50000.
Advantageously, used group (a) polymer is molal weight M nBe that 100 to 100000 ployalkylene glycol, one or both ends are by alkyl, carboxyl or amino-terminated and molal weight M nIt is 100 to 100000 ployalkylene glycol.
This base polymer is described in for example above-mentioned WO that quotes 03/046024 page 4 37 and walks to the 8th page of 9 row.Preferably ployalkylene glycol is, for example, and the block copolymer of Polyethylene Glycol, polypropylene glycol and oxirane and expoxy propane.Block copolymer can comprise oxirane and the expoxy propane with any amount and random order copolymerization.The OH end group of ployalkylene glycol, if suitable, can be at one end or two ends by alkyl, carboxyl or amino-terminated, methyl especially is suitable as end group in this case.
The stabilizing agent of the preferred especially group (a) that adopts is the copolymer of oxirane and expoxy propane.Especially preferred molal weight M nBe 500 to 20000g/mol and the amount of ethylene oxide unit be the oxirane of 10 to 80 moles of % and the block copolymer of expoxy propane.
The stabilizing agent of the preferred especially group (a) that adopts is that general formula is (EO) x(PO) y(EO) zBlock copolymer.The OH end group of these ployalkylene glycols, if suitable, can be at one end or two ends by alkyl, carboxyl or amino-terminated, wherein methyl especially is suitable as end group.The molal weight of preferred ployalkylene glycol is between 300 to 20000, and preferred 900 to 9000g/mol, and the amount of ethylene oxide unit is 10 to 90 weight %.The commercially available acquisition of this class ployalkylene glycol, for example Pluronic Series of products.
Pluronic The PE series of products are low foaming non-ionic surface active agent, and it is made by expoxy propane and oxirane copolymerization.Shown in following general formula (I), Pluronic The PE series of products are that polypropylene glycol forms the segmental block polymer of middle element:
Figure A20068001032500141
Particularly preferred Pluronic PE series of products for example,
Pluronic PE 3100、Pluronic PE 4300、Pluronic PE 6100、
Pluronic PE 6120、Pluronic PE 6200、Pluronic PE 6400、
Pluronic PE 7400、Pluronic PE 8100、Pluronic PE 9200、
Pluronic PE 9400、Pluronic PE 10100、Pluronic PE 10300、
Pluronic PE 10400, Pluronic PE 10500, Pluronic PE 10500 solution, Pluronic PE 3500.
Following table has provided the Pluronic that is suitable as a) The series of products overview.
Pluronic Quantity Polypropylene glycol block molecule amount (g/mol) Quantity The branch rate (%) of molecule inner injection ethylene glycol
PE 3100 PE 3500 PE 4300 PE 6100 PE 6120 PE 6200 PE 6400 PE 6800 PE 7400 PE 8100 PE 9200 PE 9400 PE 10100 PE 10300 PE 10400 PE 10500 3 3 4 6 6 6 6 6 7 8 9 9 10 10 10 10 850 850 1100 1750 1750 1750 1750 1750 2100 2300 2750 2750 3250 3250 3250 3250 1 5 3 1 12 2 4 8 4 1 2 4 1 3 4 5 10 50 30 10 12 20 40 80 40 10 20 40 10 30 40 50
In a preferred embodiment of the invention, the mixture of above-mentioned ployalkylene glycol as polymer a).Preferably mixture is, the mixture of for example different Pluronic products, and wherein blended weight ratio is between 5: 1 to 1: 5, preferably between 2: 1 to 1: 2, especially between 1.3: 1 to 1: 1.3.What be used for that W/W emulsion polymer of the present invention has the good especially suitability for preparation is to comprise Pluronic PE 4300 and Pluronic The mixture of PE 6200, or by its mixture of forming.
The amount of polymer that is used to prepare the group (a) of dispersion is for example 1 to 39.5 weight %, preferred 5 to 30 weight %, and preferred especially 10 to 25 weight % are based on total dispersion meter.
Group (b) polymer
The group b that is fit to) polymer is selected from:
B1) copolymer of the vinyl alkyl ethers of partial hydrolysis and maleic anhydride at least, this copolymer can exist to the form of small part with salt,
B2) be selected from the water soluble starch of cationic modified starch, anion-modified starch, degradable starch and maltodextrin,
B3) be selected from following anionic copolymer:
Monomeric homopolymer of-anionic and copolymer,
If-anionic monomer and cationic monomer and---suitable---and copolymer neutral monomer, wherein monomeric minute rate of the anionic of copolymerization greater than the branch rate of cationic monomer and
-at least a anionic monomer and at least a monomeric copolymer that is selected from ester, styrene, N-vinyl pyrrolidone, N-caprolactam, N-vinyl imidazole, N-vinyl formamide, acrylamide, Methacrylamide, vinyl acetate and the propionate of anionic monomer and monohydric alcohol
B4) if nonionic monoethenoid unsaturated monomer and cation monoene type unsaturated monomer and---suitable---and cationic copolymer anion monoethenoid unsaturated monomer, the quantity of cation group is greater than the quantity of anionic group under the wherein various situations.
The polymer of suitable group (b) is:
B1) copolymer of the vinyl alkyl ethers of partial hydrolysis and maleic anhydride at least, this copolymer can be at least in part exist with the form of alkali metal salts or ammonium salt.Alkyl preferably has 1 to 4 carbon atom in the vinyl alkyl ethers.This copolymer can by make vinyl alkyl ethers and maleic anhydride copolymerization and then make anhydride group partly or entirely be hydrolyzed to carboxyl and, if suitable, this carboxyl of partly or entirely neutralizing forms salt and makes.The polymer of particularly preferred group (b) is the vinyl methyl ether of at least partly or entirely hydrolysis and the copolymer of maleic anhydride, and this copolymer exists with the form of its alkali metal salts or ammonium salt at least in part.
B2) be selected from the starch of cationic modified starch, anion-modified starch, degradable starch and maltodextrin.Starch can by big beans, Semen Pisi sativi class, Fructus Hordei Vulgaris, Herba bromi japonici, foxtail millet for example wax millet, Rhizoma Solani tuber osi, corn for example starch maize or Glutinous Semen Maydis, Maninot esculenta crantz., rice for example wax rice, rye (Secale cereale L.) or Semen Tritici aestivi obtain.Preferred starch is water miscible starch, especially water miscible potato starch.The example of cation-modified potato starch is for being purchased product A mylofax 15 and Perlbond 970.The anion-modified potato starch that is fit to is Perfectamyl A 4692.The modification of indication herein is essentially the carboxylated of potato starch.C*Pur 1906 is a kind of example of potato starch of enzymic degradation, and Maltodextrin C 01915 is a kind of example of potato starch of Hydrolyze method degraded.Among the starch of pointing out, preferably use maltodextrin.
B3) be selected from following anionic copolymer:
B3-1) homopolymer and the copolymer that comprises or constitute by the anionic monomer,
B3-2) if anionic monomer and cationic monomer and---suitable---and copolymer neutral monomer, wherein monomeric minute rate of the anionic of copolymerization greater than the branch rate of cationic monomer and
B3-3) at least a anionic monomer and at least a monomeric copolymer that is selected from ester, styrene, N-vinyl pyrrolidone, N-caprolactam, N-vinyl imidazole, N-vinyl formamide, acrylamide, Methacrylamide, vinyl acetate and the propionate of anionic monomer and monohydric alcohol.
Used group (b3-1) polymer is, for example, and the unsaturated C of olefin type 3To C 5Carboxylic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide group methyl propane sulfonic acid, vinylphosphonic acid and their part or all of at least a homopolymer and/or these monomeric at least a copolymers with alkali metal base and/or the neutral salt of ammonium alkali.Be used to prepare existing description of example of the olefin type unsaturated carboxylic acid of aqueous dispersion.Thereby these anionic monomers also can be used to prepare the polymer (b) of stabilizer blend similarly.Preferably, the mixture of acrylic acid, methacrylic acid, acrylamide group methyl propane sulfonic acid and/or its arbitrary proportion here is suitable.
Particularly suitable be the copolymer of methacrylic acid and acrylamide group methyl propane sulfonic acid, wherein, in a preferred embodiment, the mol ratio that is used to prepare the monomer methacrylic acid of copolymer and acrylamide group methyl propane sulfonic acid between 9: 1 to 1: 9, preferred 9: 1 to 6: 4.
Group (b3-2) polymer that in the stabilizer blend other is fit to is the copolymer of following substances:
(i) the unsaturated C of at least a olefin type 3To C 5Carboxylic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide group methyl propane sulfonic acid, vinylphosphonic acid and/or its alkali metal salt and/or ammonium salt,
(ii) at least a be selected from part or all of neutral dialkyl aminoalkyl (methyl) acrylate, part or all of quaternised dialkyl aminoalkyl (methyl) acrylate, quaternized or in and the cationic monomer of dialkyl aminoalkyl (methyl) acrylamide, dialkyl diallyl ammonium halide and the quaternised N-vinyl imidazole of form and, if it is suitable
(iii) at least a neutral monomer,
Wherein monomeric minute rate of the anionic of copolymerization is greater than the branch rate of cationic monomer.Address before the example of anionic monomer (i).
The cationic monomer that is fit to (ii) is, (methyl) propenoic acid dialkyl aminoalkyl ester for example, for example acrylic acid dimethylamino ethyl ester, dimethylaminoethyl methacrylate, acrylic acid diethylamino ethyl ester, diethyl aminoethyl methacrylate, acrylic acid dimethylamino propyl ester, the amino propyl ester of dimethylaminoethyl acrylate methyl base, acrylic acid diethylamino propyl ester and methacrylic acid diethylamino propyl ester; Dialkyl diallyl ammonium halide, for example dimethyl diallyl ammonium chloride and diethyl diallyl ammonium chloride; The N-vinyl imidazole; Quaternised N-vinyl imidazole and dialkyl aminoalkyl acrylamide, for example dimethyl aminoethyl acrylamide or dimethyl aminoethyl Methacrylamide.
Alkalescence monomer for example acrylic acid dimethylamino ethyl ester or dimethylaminoethyl methacrylate, form that both can free alkali also can be partly or entirely with acid---for example hydrochloric acid, sulphuric acid, formic acid and p-methyl benzenesulfonic acid---, and neutral form is used.In addition, alkaline monomer can by with C 1To C 18Alkyl halide and/or C 1To C 18Alkyl C 1To C 18Alkaryl halogenation thing reaction and partly or entirely quaternized, and be used for polymerization with this form.The example is with chloromethane all quaternised (methyl) acrylic acid dimethylamino ethyl ester, for example acrylic acid dimethylamino ethyl ester methochloride or dimethylaminoethyl methacrylate methochloride.The polymer of group (b) also can comprise the vinylamine unit as the cationic source group.If this base polymer can suitable, with at least a anionic water-soluble monomer polymerization, then make the polymer hydrolysis partly to eliminate the formoxyl generation unitary polymer of vinylamine-containing and to make by for example making the N-vinyl formamide.
Available neutral monomer (iii) is, for example the anionic monomer---C especially 3To C 5Carboxylic acid---with the ester of monohydric alcohol with 1 to 20 carbon atom, acrylic acid methyl ester. for example, methyl methacrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, 2-EHA, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-BMA, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate, and acrylamide, Methacrylamide, acrylonitrile, methacrylonitrile, the N-vinyl pyrrolidone, the N-vinyl imidazole, the N-vinyl formamide, vinyl acetate, propionate and styrene.
Be suitable as in the ampholyte copolymer of component (b3-2), monomeric minute rate of the anionic of copolymerization is always greater than the branch rate of cationic monomer.Thereby these copolymers always have negative charge.
In addition, the copolymer of suitable group (b3-3) is the copolymer of following material:
(i) at least a anionic monomer and
The (ii) at least a monomer that is selected from ester, styrene, N-vinyl pyrrolidone, N-caprolactam, N-vinyl imidazole, N-vinyl formamide, acrylamide, Methacrylamide, vinyl acetate and the propionate of olefin type unsaturated acids and monohydric alcohol
The copolymer of acrylic acid, acrylic acid methyl ester. and N-vinylpyrrolidone copolymers or methacrylic acid, acrylamide group methyl propane sulfonic acid, acrylic acid methyl ester. and vinyl imidazole for example.
Polymer (b3) can comprise the suitable monomer of any ratio of copolymerized form, and ampholyte copolymer just is configured to and makes it always have negative charge.The average molar mass M of the group of stabilizer blend (b) polymer wFor, for example be up to 1,500,000, in most cases be up to 1,200,000, preferably between 1000 to 1,000,000, most applications especially (is determined by light scattering method) between 2000 to 70000 between 1500 to 100000.
B4) if nonionic monoethenoid unsaturated monomer and cation monoene type unsaturated monomer and---suitable---and cationic copolymer anion monoethenoid unsaturated monomer, wherein the quantity of cation group is greater than the quantity of anionic group.
Can use the polymer of the copolymer of following substances as group (b4):
(b4-1) water miscible, non-ionic monoethenoid unsaturated monomer,
(b4-2) water miscible, cationic monoethenoid unsaturated monomer and, if suitable,
(b4-3) water miscible, anionic monoethenoid unsaturated monomer,
Wherein the branch rate of the cationic monomer of copolymerization is greater than monomeric minute rate of anionic.
The example of water miscible nonionic monomers (b1) is acrylamide, Methacrylamide, N-vinyl formamide, N-vinyl pyrrolidone and N-caprolactam.The monomer that is suitable for use as group (b1) in principle is at least the monoethenoid unsaturated monomer of 100g/l for all dissolubility non-ionic, when temperature is 20 ℃ in water.Especially preferably can dissolve each other and form the monomer (b1) of clear aqueous solution, for example acrylamide or N-vinyl formamide with arbitrary proportion and water.
Water miscible, cationic monoethenoid unsaturated monomer (b4-2) is, (methyl) propenoic acid dialkyl aminoalkyl ester for example, for example acrylic acid dimethylamino ethyl ester, dimethylaminoethyl methacrylate, acrylic acid diethylamino ethyl ester, diethyl aminoethyl methacrylate, acrylic acid dimethylamino propyl ester, the amino propyl ester of dimethylaminoethyl acrylate methyl base, acrylic acid diethylamino propyl ester and methacrylic acid diethylamino propyl ester; Dialkyl diallyl ammonium halide, for example dimethyl diallyl ammonium chloride and diethyl diallyl ammonium chloride; The N-vinyl imidazole; Quaternised N-vinyl imidazole.
Alkalescence monomer for example acrylic acid dimethylamino ethyl ester or dimethylaminoethyl methacrylate, form that both can free alkali also can be partly or entirely with acid---for example hydrochloric acid, sulphuric acid, formic acid and p-methyl benzenesulfonic acid---, and neutral form is used.In addition, alkaline monomer can by with C 1To C 18Alkyl halide and/or C 1To C 18Alkyl C 1To C 18Alkaryl halogenation thing reaction and partly or entirely quaternized, and be used for polymerization with this form.The example is with chloromethane all quaternised (methyl) acrylic acid dimethylamino ethyl ester, for example acrylic acid dimethylamino ethyl ester methochloride or dimethylaminoethyl methacrylate methochloride.The polymer of group (b4) also can comprise the vinylamine unit as cation group.This base polymer can be by for example making the N-vinyl formamide, if suitable, with at least a anionic water-soluble monomer polymerization, then make the polymer hydrolysis partly eliminate formoxyl and generate the unitary polymer of vinylamine-containing and make.
The polymer of group (b4) if suitable, also can comprise at least a anion monoethenoid unsaturated monomer (b4-3) of copolymerized form.The monomeric example of this class is the anionic monomer of the preceding formation water-soluble polymer of having addressed, for example acrylic acid, methacrylic acid, vinyl sulfonic acid, vinylphosphonic acid, maleic acid, fumaric acid .beta.-methylacrylic acid, itaconic acid, and these sour alkali metal salt and ammonium salts.
The example of the copolymer of group (b4) is the copolymer of following substances:
(b4-1) acrylamide, Methacrylamide, N-vinyl formamide, N-vinyl pyrrolidone and/or N-caprolactam,
(b4-2) propenoic acid dialkyl aminoalkyl ester, methacrylic acid dialkyl aminoalkyl ester, partly or entirely neutral (methyl) propenoic acid dialkyl aminoalkyl ester, season
(methyl) propenoic acid dialkyl aminoalkyl ester of ammoniumization, dialkyl diallyl ammonium halide, N-vinyl imidazole and quaternised N-vinyl imidazole and, if suitable,
(b4-3) acrylic acid, methacrylic acid, vinyl sulfonic acid, vinylphosphonic acid, maleic acid, fumaric acid .beta.-methylacrylic acid, itaconic acid, and these sour alkali metal salt and ammonium salts.Polymer (b4) comprises, for example
(b4-1) at least a non-ionic monomer of 2 to 90 moles of %, preferred 20 to 80 moles of % and preferred especially 35 to 70 moles of %
(b4-2) at least a cationic monomer of 2 to 90 moles of %, preferred 20 to 80 moles of % and preferred especially 35 to 70 moles of %
With
(b4-3) anionic monomer of at least a copolymerized form of 0 to 48.9 mole of %, preferred 0 to 30 mole of % and preferred especially 0 to 10 mole of %, wherein the branch rate of cationic monomer unit is greater than the branch rate of anionic monomer unit.
The independent example of polymer (b4) is the copolymer of acrylamide and acrylic acid dimethylamino ethyl ester methochloride, the copolymer of acrylamide and dimethylaminoethyl methacrylate methochloride, the copolymer of acrylamide and acrylic acid dimethylamino propyl ester methochloride, the copolymer of Methacrylamide and dimethylaminoethyl methacrylate methochloride, acrylamide, acrylic acid dimethylamino ethyl ester methochloride and acrylic acid copolymer, acrylamide, the copolymer of dimethylaminoethyl methacrylate methochloride and methacrylic acid, and acrylamide, acrylic acid dimethylamino ethyl ester methochloride and acrylic acid copolymer.
Polymer (b) also can characterize by the K value.It for example has 15 to 200, preferred 30 to 150 and preferred especially 45 to 110 K value (according to H.Fikentscher, Cellulose-Chemie, 13 volumes, 58-64 page or leaf and 71-74 page or leaf (1932) are that 0.1 weight %, pH value are to record in the sodium-chloride water solution of 7 3% weight concentration at 25 ℃, polymer concentration).
Group (b) polymer that the used aqueous dispersion of the present invention comprises is for example 0.5 to 15 weight %, preferred 1 to 10 weight %.The ratio of the polymer of the polymer of group (a) and group (b) is in 1: 5 to 5: 1 scope for example in the used dispersion of the present invention, preferably in 1: 2 to 2: 1 scope.
In a preferred embodiment of the invention, the aqueous dispersion of anionic polymer preferably includes the combination of following material as stabilizing agent
(a) graft polymers of at least a vinyl acetate on Polyethylene Glycol, molecular weight M NBe 1000 to 100000
With
The copolymer of (b1) vinyl alkyl ethers of at least a partial hydrolysis at least---preferred vinyl methyl ether---and maleic anhydride, it can be at least in part exists with the form of salt.In another embodiment preferred of the present invention, use the combination of following polymer:
(a) copolymer of alkyl ployalkylene glycol acrylate or alkyl ployalkylene glycol methacrylate and acrylic acid and/or methacrylic acid
With
(b1) copolymer of the vinyl methyl ether of at least a hydrolysis and maleic anhydride, described copolymer are with the form of free carboxyl group and exist with the form of using sodium hydroxide solution, potassium hydroxide solution or the formed salt of ammonia at least in part.
Other is used to prepare being combined as of stabilizing agent of anionic polymer aqueous dispersion, for example mixture of following substances:
(a) molecular weight M NBe 300 to 50000 polypropylene glycol, Polyethylene Glycol and/or oxirane and the block copolymer and/or the molecular weight M of expoxy propane NBe 300 to 50000, at one end or two ends by C 1To C 4The block copolymer of alkyl-blocked polypropylene glycol, Polyethylene Glycol and/or oxirane and expoxy propane
With
(b2) maltodextrin.
In another preferred embodiment of the present invention, the combination that the aqueous dispersion of anionic polymer preferably includes following material is as stabilizing agent:
(a) block copolymer of at least a oxirane and expoxy propane
With
(b3) copolymer of at least a methacrylic acid and acrylamide group methyl propane sulfonic acid, overall is the copolymer of electronegative acrylic acid methyl ester., acrylamide group methyl propane sulfonic acid and quaternised vinyl imidazole, acrylamide group methyl propane sulfonic acid, acrylic acid, acrylic acid methyl ester. and cinnamic copolymer, polyacrylic acid, polymethylacrylic acid and polyacrylamide base methyl propane sulfonic acid.
In another preferred embodiment of the present invention, the combination that the aqueous dispersion of anionic polymer preferably includes following material is as stabilizing agent:
(a) block copolymer of at least a oxirane and expoxy propane
With
(b4) copolymer of at least a acrylamide and acrylic acid dimethylamino ethyl ester methochloride.
In the copolymer (b4),, also can comprise the acrylic acid of the copolymerized form that is up to 5 moles of % if suitable.
Component in stabilizer blend (a) and weight ratio (b) can change in big scope.This scope for example can be 50: 1 to 1: 10.Preferably, (a): ratio (b) was at least 1.5: 1, especially selected 7: 1 to 10: 1.
The granularity of anionic W/W polymer in the stabilized aqueous dispersion is 0.1 to 200 μ m, preferred 0.5 to 70 μ m.Granularity can be determined by for example optical microscope, light scattering or freeze-fraction ultramicroscope.Aqueous dispersion is for example preparing in 0.5 to 9, preferred 1 to 5 the pH value scope.Be lower than at 9 o'clock at pH value, the dispersion that the content of anionic polymer is about 5 to 35 weight % has relatively low viscosity.If but its content that is diluted to anionic polymer were lower than 4 weight %, the viscosity of mixture would then significantly increase.
---there is---thickening agent as cosmetic formulations in anionic W/W emulsion polymer as suitable form with aqueous dispersion.
The W/W emulsion polymer that exists with the aqueous dispersion form can carry out drying by simple mode, generates polymer powders redispersible.
Based on the rheological property improver of conventional homo-polypropylene acid esters especially thickening agent,, preferably obtain with powder type because its preparation method (preferred sedimentation polymerization) obtains with solid forms usually.Have to solid is transformed into problem in the liquid medium once more so often have.This usually by pH value less than 7, usually be less than 4 o'clock, under violent and/or long-term the stirring with solvent, preferably water makes the polymer beads moistening gradually and realizes.Usually, in order to prepare the liquid preparation of thickening, at first the thickening agent with routine is dissolved in the acid medium, adds other component again.The homo-polypropylene acid esters thickening agent that adds based on prior art in alkaline medium is impossible.Medium thickens after adding thickening agent immediately, and pulverous thickening agent forms insoluble or insoluble,practically granule, thereby can not form predetermined viscosity by this way.When adding basic component for example during nertralizer in the aqueous formulation that contains anionic polymer, its viscosity increases.
Suitable nertralizer is acceptable and be conventional nertralizer on cosmetic field or the Dermatology.In and the time can use the alkali metal bases, for example sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate and alkaline-earth metal bases, for example calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate, and ammonia or amine.Suitable amine is, for example C 1-C 6Alkylamine, preferred n-propylamine and n-butylamine; Dialkylamine, preferred diethyl propylamine and dipropyl methylamine; Trialkylamine, preferred triethylamine and triisopropylamine; C 1-C 6The alkyl diethanolamine, preferable methyl or ethyldiethanolamine; And two C 1-C 6AEOA.Neutralization for the polymer that contains acidic-group, 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-ethyl the third-1 have been proved, 3-glycol, diethyl amino propylamine, triisopropanolamine and triethanolamine are specially adapted to cosmetic formulations, especially are suitable for skin and hair-treatment composition.The neutralization that contains the polymer of acidic-group also can be undertaken by the mixture that uses two or more alkali, for example uses the mixture of sodium hydroxide solution or potassium hydroxide solution and 2-amino-2-methyl-1-propanol to carry out.
The degree of thickening effect can be decided by selecting suitable nertralizer.For example use AMP higher than the viscosity of using NaOH to produce.
Other nertralizer that is fit to is disclosed in W003/099253, and p.2I.1 extremely p.3, I.6, its full content is hereby incorporated by reference.
According to the purposes of planning, degree of neutralization can be 5 to 95%, and preferred 30 to 95% or be higher than 99%.In addition, nertralizer also can be higher than normal amount adding.
The use of W/W emulsion polymer has caused the new probability of the cosmetic formulations of multiple preparation thickening.The W/W emulsion polymer can add when any pH value to be treated in the preparation of thickening.
W/W emulsion polymer and dispersion thereof can be advantageously by only using small shearing force to be dissolved in the acid medium or being dissolved in the alkaline medium.
Particularly advantageously, W/W emulsion polymer and dispersion thereof can be added in the basic formulations.Even the homo-polypropylene acid esters thickening agent of prior art adds, also can only add very little amount, and need to use high shearing force or long mixing time.
Because the good solubility of W/W emulsion polymer and dispersion thereof only needs small shearing force, for example can use anchor agitator or dasher as agitator.Need not use the complex device that produces high shear force.Owing to need not depend on high shear force, the probability of polymer chain degraded has reduced, and has avoided the decline of viscosity thus.
Use a very big advantage of W/W emulsion polymer to be that it can add in any stage of preparation cosmetic formulations.Thereby the W/W emulsion polymer can for example only add when the process of preparation preparation finishes.This thus mean that other component can add in the low viscosity preparation, thereby do not need high shearing force.Thereby make adding solid-state, the mechanical instability component become more easy.
Compare with the thickening agent of routine, the thickening effect that activates the W/W emulsion polymer neither needs high temperature, does not also need high shear force or adds emulsifying agent, has simplified its use greatly.
Being suitable for the advantage that polymer of the present invention and dispersion thereof also have is, because its low viscosity, thereby be easy to handle and allotment, and can be dissolved in very soon in the medium for the treatment of thickening.Therefore this caused the short relatively processing time.
The W/W emulsion polymer dispersion can directly add cosmetic formulations for example hair fixing preparation, the preparation that is used for cleaning skin or hair or shampoo, also can carry out the dispersion drying of routine well known by persons skilled in the art, for example spray drying or lyophilization is so that the W/W emulsion polymer can Powderedly use and handle.Consider above-mentioned reason, it is favourable adding the W/W emulsion polymer with dispersive form.
According to the present invention, use W/W emulsion polymer can prepare the gel with the high polar solvent of high concentration that is used for all administration forms and the form of supply.
Cosmetics and skin-use preparation
Above-mentioned emulsion polymer---if suitable form with aqueous dispersion exists---especially is suitable as the thickening agent in the cosmetic formulations particularly according to the present invention.
This class cosmetic formulations is, for example water, water-alcohol or alcoholic solution, O/W, W/O, W/O/W and PIT emulsion, aqueous dispersion preparation, the preparation of Pickering, thickness preparation.Important dosage form is Emulsion, infusion, spray (spraying of pump formula or aerosol), gel, gel spray, lotion, oil preparation, oleogel agent or mousse, and above-mentioned preparation correspondingly uses other conventional auxiliary agent preparation.The preferred cosmetic composition within the meaning of the present invention be shampoo, gel, latex, aqueous formulation, thickness preparation, cosmetics oil and oleogel agent, mascara (mascara), imitative shine (self-tanning) compositions, facial-care compositions, body care composition, solarization after preparation, forming hair compositions, hair setting composition, hair-care agent and the decoration compositions that applies some make up.In a single day the cosmetics and the skin-use preparation that contain the W/W emulsion polymer exist monohydric alcohol or polyol component or water promptly to become the improved system of rheology.
This makes can prepare clear gel agent, anhydrous hydrophilic gel with stable water sensitivity active component, can make the oxidation-sensitive material stable, can prepare low drip or not drip hair colorant preparation, disinfecting gel preparation, do not contain the gel rubber system preparation of antiseptic or have the height polar solvent of high concentration such as the gel preparation of glycerol etc.
For the administration form of cosmetics and Dermatology field utmost point wide region and supply form also is like this.
Except being used for the W/W polymer of thickening, cosmetic composition preferably also comprises the acceptable additive commonly used in this class preparation of cosmetics, for example emulsifying agent and co-emulsifier, solvent, surfactant, the oil body, antiseptic, aromatic oil, cosmetics care substance and active component, for example AHA acid, fruit acid, ceramide, phytantriol (phytantriol), collagen, vitamin and provitamin be vitamin A for example, E and C, retinal, bisabolol, pantothenylol, natural and synthetic light protective agent, natural materials, opacifier, cosolvent, repellent, bleach, coloring agent, the color and luster agent, tanning agent (as dihydroxy acetone), little pigment (micropigment) is titanium oxide or zinc oxide for example, super fat (superfatting) agent, pearlescent waxes, consistency modifiers, thickening agent, solubilizing agent, chelating agent, fat, wax, silicone compounds, hydrotrote, dyestuff, stabilizing agent, the pH value regulator, reflective agent, protein and protein hydrolysate are (as Semen Tritici aestivi, Semen Armeniacae Amarum or Semen Pisi sativi protein), ceramide, protein hydrolysate, salt, gel former, consistency modifiers, silicone, wetting agent (as 1, the 2-pentanediol), stuffing (refatting) agent and other conventional formulation.In addition, particularly also can exist other other polymer to obtain performance required under the various situations.
It also is favourable providing compositions of the present invention with liquid form, so that available its soaks the cloth of various materials and embossing.Those skilled in the art knows how to produce the cloth that this mode is soaked.
For preventing the adverse effect of UV ray, also can in cosmetic formulations, add the UV light protective agent.
The invention still further relates to the cosmetic composition that contains the W/W emulsion polymer, if the suitable form with aqueous dispersion of described emulsion polymer exists.Especially preferred cosmetic composition is shampoo and gel.
Above-mentioned W/W emulsion polymer---if suitable form with aqueous dispersion exists---is suitable for preparing the cosmetic hair preparation, as agent for treatment of hair, hair lotion, hair rinse agent, hair emulsion, end fluids, permanent wave nertralizer, " hot oil processing " preparation, regulator, typing lotion or hair jelly.According to application, the cosmetic hair preparation can spray, infusion, gel, gel spray or mousse form are used.
The W/W emulsion polymer especially is fit to thickening and contains the oxidation hair dyestuff of hydrogen peroxide, thereby prepares the not even hair-dyeing agent of drip of heavy-gravity low drip.
In addition, because its thickening effect, the W/W emulsion polymer especially can be used in the nonaqueous alcohol medium, is used for stablizing material such as vitamin C oxidation-sensitive and/or the hydrolysis sensitivity.
The W/W emulsion polymer is advantageously used in the preparation of subtilisin, lecithin and coenzyme Q10.
The compositions of aqueous, alcohol or water/alcohol
Preferred compositions is to contain the compositions of aqueous, alcohol or water/alcohol that at least a content is the W/W emulsion polymer of 0.01 to 20 weight %, preferred especially 0.05 to 10 weight %, preferred extremely especially 0.1 to 7 weight %, and described amount is in this group and thing.
Waterborne compositions be interpreted as the water that contains at least 40 weight %, preferred at least 50 weight %, especially at least 60 weight % and simultaneously the content of alcohol less than the compositions of 20 weight %.
The alcohol compositions be interpreted as one or more alcohol of containing at least 40 weight %, preferred 50 weight %, especially at least 60 weight % and simultaneously content of water less than the compositions of 20 weight %.
Water/alcohol compositions is interpreted as water that contains at least 20 weight % and the compositions that contains the alcohol of at least 20 weight % simultaneously.
A preferred embodiment of the present invention is the water/alcohol compositions that contains the alcohol of the water of at least a W/W polymer and preferred at least 50 weight % and preferred at least 40 weight %.
Another embodiment of the present invention is the alcohol compositions that comprises the water of at least a W/W polymer and maximum 10 weight %, preferred maximum 5 weight %, preferred especially maximum 2 weight %, especially maximum 1 weight %.This low water or substantially anhydrous preparation can be polymer-thickened by W/W.
Because the W/W polymer can be used as the thickening agent that its liquid phase mainly comprises the preparation that contains the OH based compound, thereby it is applicable to that purposes of the present invention is clearly.These chemical compounds that contain the OH base are mainly water and alcohol.
The W/W polymer that is fit to purposes of the present invention is particularly suitable for improving the rheological property of alcohol preparation.Alcohol suitable in these preparations is generally all alcohol that exist with liquid form when STP.These alcohol are for example methanol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, 3-methyl isophthalic acid-butanols (isoamyl alcohol), hexanol, Hexalin or glycol, for example ethylene glycol, propylene glycol and butanediol, polyhydric alcohol is glycerol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., ployalkylene glycol Polyethylene Glycol for example for example, and number-average molecular weight is up to the alkyl ether of these polyhydric alcohol of about 3000.
Be fit to polyhydric alcohol of the present invention and can advantageously be selected from dual functional at least alcohol.Polyhydric alcohol especially advantageously is selected from following each group:
Ethylene glycol, molal weight is up to about 2000 Polyethylene Glycol, propylene glycol-1,2, molal weight is up to about 2000 polypropylene glycol-1,2, propylene glycol-1,3, molal weight is up to about 2000 polypropylene glycol-1,3, butanediol-1,2, molal weight is up to about 2000 polytetramethylene glycol-1,2, butanediol-1,3, molal weight is up to about 2000 polytetramethylene glycol-1,3, butanediol-1,4, molal weight is up to about 2000 polytetramethylene glycol-1,4, butanediol-2,3, molal weight is up to about 2000 polytetramethylene glycol-2,3, glycerol, diglycerol, triglycerin, four glycerol and five glycerol, wherein said low polyglycereol is made of the glycerol unit by the condensation of one or more ether bridge, and is for example as follows:
Preferred cosmetics acceptable alcohol, particularly ethanol, glycerol and/or isopropyl alcohol, or contain ethanol, glycerol and/or isopropyl alcohol, special preferably glycerine and/or ethanol.
The W/W polymer both can be used as the thickening agent of compositions alcohol, substantially anhydrous, also can be used as aqueous, substantially do not have alcohol compositions and the thickening agent of water/alcohol compositions.
In a preferred embodiment, compositions of the present invention comprises:
A) the W/W emulsion polymer of 0.05-20 weight %
B) water of 20-99.95 weight % and/or alcohol
C) other component of 0-79.5 weight %.
Other component is interpreted as the conventional additives in the cosmetics, and for example propellant, anti-foaming agent, interfacial activity chemical compound are surfactant, emulsifying agent, foam formation agent and solubilizing agent.Used interfacial activity chemical compound can be anionic property, cationic, amphoteric or neutral.Other conventional component can also be, for example antiseptic, aromatic oil, opacifier, active component, UV filtering agent, care substance such as pantothenylol, collagen, vitamin, protein hydrolysate, α-and beta-hydroxycarboxylic acids, protein hydrolysate, stabilizing agent, pH value regulator, dyestuff, viscosity modifier, gel former, dyestuff, salt, wetting agent, fatting agent and other conventional additives.
The cosmetic hair preparation
In the cosmetic hair preparation, the W/W polymer can be used in combination with known form regulator polymer (styling and conditioner polymer).
Suitable conventional cosmetic hair polymer is for example anionic polymer.The homopolymer that this anionoid type polymer is acrylic acid and methacrylic acid or its salt and the copolymer of copolymer, acrylic acid and acrylamide and its salt, multi-hydroxy carboxy acid's the dispersible polyester of sodium salt, water solublity or water, polyurethane (Luviset P.U.R.) and polyureas.Particularly suitable polymer is that the copolymer of tert-butyl acrylate, ethyl acrylate, methacrylic acid is (as Luvimer 100P), N tert butyl acrylamide, ethyl acrylate, acrylic acid copolymer (Ultrahold 8, strong), if the copolymer of vinyl acetate .beta.-methylacrylic acid and suitable other vinyl acetate is (as Luviset Series of products), if copolymer-maleic anhydride is suitable and pure reaction; Anion polysiloxane, for example carboxy-functionalized; The copolymer of vinyl pyrrolidone, tert-butyl acrylate, methacrylic acid is (as Luviskol VBM).
Extremely particularly preferred anionic polymer is an acid number more than or equal to the copolymer of 120 acrylate and tert-butyl acrylate, ethyl acrylate, methacrylic acid.
Other cosmetic hair polymer that is fit to is called the cation type polymer of polyquaternary ammonium salt (Polyquaternium), for example copolymer (Luviquat of vinyl pyrrolidone/N-vinyl imidazole salt for the INCI name FC, Luviquat HM, Luviquat MS, Luviquat Care), use the copolymer (Luviquat of the quaternised N-vinyl pyrrolidone/dimethylaminoethyl methacrylate of dithyl sulfate PQ11), the copolymer (Luviquat of N-caprolactam, N-vinyl pyrrolidone/N-vinyl imidazole salt Hold), cationic cellulose derivative (polyquaternary ammonium salt-4 and polyquaternary ammonium salt-10), acrylamide copolymer (polyquaternary ammonium salt-7).
Other cosmetic hair polymer that is fit to also can be a neutral polymer, for example the copolymer of polyvinyl pyrrolidone, N-vinyl pyrrolidone and vinyl acetate and/or propionate, polysiloxanes, Vinylcaprolactam homopolymer and and N-vinylpyrrolidone copolymers, poly-Ethylenimine and salt, polyvinylamine and salt thereof, cellulose derivative, polyaspartic acid salts and derivant thereof.
For forming certain performance, also can comprise instrumentality in the preparation based on silicone compounds.Suitable silicone compounds is that for example amino dimethicone of silicone compounds (amodimethicone) of for example poly-alkylsiloxane, poly-aryl siloxanes, poly-aralkyl siloxanes, polyether siloxane, organic siliconresin or dimethicone copolyol (CTFA) and aminofunctional (CTFA).
The W/W emulsion polymer is suitable for for example preparing hair style preparation, especially limpid, transparent gel and gel spray.
In a preferred embodiment, these preparations contain:
A) the W/W emulsion polymer of 0.1-10 weight %
B) water of 20-99.9 weight % and/or alcohol
C) propellant of 0-70 weight %
D) other component of 0-20 weight %
Propellant is a propellant commonly used in hair jelly or the aerosol infusion.Preferably propane/butane mixture, pentane, dimethyl ether, 1,1-Difluoroethane (HFC-152a), carbon dioxide, nitrogen or compressed air.
The preparation of the preferred aerosol hair of a kind of the present invention infusion contains:
A) the W/W emulsion polymer of 0.1-10 weight %
B) water of 55-94.8 weight % and/or alcohol
C) propellant of 5-20 weight %
D) emulsifying agent of 0.1-5 weight %
E) other component of 0-10 weight %
Emulsifying agent is all emulsifying agents commonly used in the hair infusion.Suitable emulsifying agent can be nonionic, cationic or anionic.
The example of nonionic emulsifier (INCI name) is laureth class (laureths), for example laureth-4; Ceteth class (ceteths), for example ceteth-1, Polyethylene Glycol cetyl ether; Ceteareth class (ceteareths), for example ceteareth-25; The polyethylene glycol fatty acid glyceride; Hydroxylated lecithin; The lactyl ester of fatty acid; Alkyl polyglycoside (alkyl polyglycosides).
The example of cationic emulsifier is that cetyl dimethyl-2-ethoxy Ammonium biphosphate, cetyl trimethyl ammonium chloride (cetyltrimonium chloride), cetyl trimethylammonium bromide, cocoyl trimethyl ammonium methyl sulfate (cocotrimonium methylsulfate), quaternary ammonium salt-1 are to x (INCI).
Anion emulsifier can be selected from; for example alkyl sulfate, alkyl ether sulfate, alkylsulfonate, alkylaryl sulfonates, alkyl succinate, salts of alkyl sulfosuccinates salt, N-alkoyl sarcosinate, acyl taurine salt (acyl taurates), acyl-hydroxyethyl sulfonate (acylisethionates), alkylphosphonic, alkyl ether phosphate, alkyl ether carboxy acid salt, alpha-alkene sulfonate, the especially salt of its alkali metal and alkaline-earth metal such as sodium, potassium, magnesium, calcium salt and ammonium salt and triethanolamine salt.Described alkyl ether sulfate, alkyl ether phosphate and alkyl ether carboxy acid salt's intramolecularly can have 1 to 10 oxirane or propylene oxide units, preferred 1 to 3 ethylene oxide unit.
Because its thickening effect, the W/W emulsion polymer can be used as gel former unique in the cosmetic formulations.In addition, they also are suitable for being used in combination with other gel former.
The preparation of the present invention that is suitable as transparent hair style gel can for example have following component:
A) the W/W emulsion polymer of 0.1-10 weight %
B) water of 60-99.85 weight % and/or alcohol
C) other gel former of 0-10 weight %
D) other component of 0-20 weight %
Other gel former that can adopt is a gel former commonly used in the cosmetics.These comprise lightly crosslinked polyacrylic acid, and for example carbomer (Carbomer) (INCI); Cellulose derivative, for example hydroxy propyl cellulose, hydroxy ethyl cellulose, cation-modified cellulose; Polysaccharide, for example xanthan gum (xanthum gum), caprylic/capric triglyceride, sodium acrylate copolymer; Polyquaternium-32 (Polyquaternium-32) (with) liquid paraffin (Paraffinum Liquidum) (INCI); Sodium acrylate copolymer (with) liquid paraffin (with) PPG-1 tridecyl alcohol polyethers-6 (Trideceth-6); Acrylamido oxypropyl trimethyl ammonium chloride/acrylamide copolymer; Stearyl alcohol polyethers-10 (Steareth-10) allyl ether acrylates copolymer; Polyquaternary ammonium salt-37 (with) liquid paraffin (with) PPG-1 tridecyl alcohol polyethers-6; Polyquaternary ammonium salt-37 (with) the propylene glycol dicaprate dicaprylate (with) PPG-1 tridecyl alcohol polyethers-6; Polyquaternary ammonium salt-7; Polyquaternary ammonium salt-44.
One embodiment of the present invention are the C that contains the W/W emulsion polymer, is at least 30 weight % 1-C 4If alcohol and---suitable---alcohol alcohol molten, film forming hair fixing copolymer substantially anhydrous basic cosmetic formulations, especially hair gel.
With aqueous or water/alcohol gel phase ratio, based on C 1-C 4The gel of alcohol can satisfy the hair gel other/replenish requirement.If for example plan preparation typing gel, then like this also can use the molten styling polymer of alcohol.
Preferred 0.01 to the 20 weight % of the consumption of W/W emulsion polymer, preferred especially 0.05 to 10 weight %, preferred extremely especially 0.1 to 7 weight %.If use hair fixing copolymer, then preferred 0.1 to the 20 weight % of consumption, preferred especially 0.5 to 15 weight %, preferred extremely especially 1 to 10 weight %.Preferred 50 to the 99 weight % of consumption, preferred especially 70 to the 98 weight % of alcohol.Under various situations, weight % is based on total restatement of preparation.
In this case, the molten polymer of alcohol be interpreted as finger 25 ℃, at least a alcohol with 1 to 4 carbon atom the polymer of solubilized at least 5 weight %.The liquid alcohol that is fit to alcohol, substantially anhydrous basic hair gel is for being in a liquid state in room temperature (20 ℃) and having the monobasic or the polyhydric alcohol of 1 to 4 carbon atom.These especially are the conventional lower alcohol that is used for cosmetic use, for example ethanol, isopropyl alcohol, glycerol, ethylene glycol or propylene glycol.Monohydric alcohol, the especially ethanol and the isopropyl alcohol that especially preferably have 2 to 4 carbon atoms.The hair gel is preferably substantially anhydrous, and in order to improve the dissolubility of other component, it also can comprise low amounts of water, although pure content is apparently higher than water content.The substantially anhydrous water content that means is not higher than 10 weight %, preferably is not higher than 5 weight %.It should be noted that when styling polymer exists alcohol gel of the present invention has good adjusting function, high typing degree, rapid draing and gratifying cooling effect.
Preparation of the present invention can be applied to wet sending out or dried sending out.This product both had been applicable to that straight hair also was applicable to curly hair.
The W/W emulsion polymer also can be advantageously used in the hair washing preparation.
Preferred hair washing preparation contains:
A) the W/W emulsion polymer of 0.05-10 weight %
B) water of 25-94.95 weight %
C) surfactant of 5-50 weight %
D) regulator of 0-5 weight %
E) setting agent of 0-5 weight %
F) other components of cosmetics of 0-10 weight %
In the hair washing preparation, can use all aniones, neutrality, both sexes or cationic surfactant commonly used in shampoo.
Suitable anion surfactant is; for example alkyl sulfate, alkyl ether sulfate, alkylsulfonate, alkylaryl sulfonates, alkyl succinate, salts of alkyl sulfosuccinates salt, N-alkoyl sarcosinate, acyl taurine salt, acyl-hydroxyethyl sulfonate, alkylphosphonic, alkyl ether phosphate, alkyl ether carboxy acid salt, alpha-alkene sulfonate, the especially salt of its alkali metal and alkaline-earth metal such as sodium, potassium, magnesium, calcium salt and ammonium salt and triethanolamine salt.Described alkyl ether sulfate, alkyl ether phosphate and alkyl ether carboxy acid salt's intramolecularly can have 1 to 10 oxirane or propylene oxide units, preferred 1 to 3 ethylene oxide unit.
What be suitable for has, for example sodium lauryl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, Zetesol AP, sodium N-lauroyl sarcosinate, oleyl sodium succinate, lauryl 2-Sulfosuccinic acid ammonium, dodecylbenzene sodium sulfonate, DBSA triethanolamine.
Suitable amphoteric surfactant is, for example alkyl betaine, alkylamidoalkyl CAB, alkyl sulfobetaines, glycine alkyl ester, carboxyl glycine alkyl ester, both sexes alkyl acetate or both sexes alkyl propionates, both sexes oxalic acid Arrcostab or both sexes dipropionic acid Arrcostab.
For example, can use cocoyl dimethyl sulfopropyl betaine, lauryl betaine, cocamidopropyl betaine or cocos nucifera oil both sexes sodium propionate.
Suitable non-ionic surface active agent is for example to have the product of aliphatic alcohol or alkyl phenol and the oxirane and/or the expoxy propane of 6 to 20 carbon atoms in the alkyl chain of straight or branched.The amount of alkylene oxide is about 6 to 60 moles of every mol of alcohol.The fatty acid ester that alkyl amine oxide, list or dialkyl group alkanolamide, Polyethylene Glycol are arranged, alkyl polyglycoside or sorbic acid ether-ether that other is fit to.
In addition, the hair washing preparation also can comprise conventional cationic surfactant, and quaternary ammonium compound for example is as the cetyl trimethyl ammonium chloride.
In the hair washing preparation,, conventional regulator and emulsion polymer of the present invention can be used in combination in order to obtain certain effect.These regulators comprise that for example the INCI name is called the cation type polymer of polyquaternary ammonium salt, especially copolymer (the Luviquat of vinyl pyrrolidone/N-vinyl imidazole salt FC, Luviquat HM, Luviquat MS, Luviquat Care), use the copolymer (Luviquat of the quaternised N-vinyl pyrrolidone/dimethylaminoethyl methacrylate of dithyl sulfate PQ11), the copolymer (Luviquat of N-caprolactam/N-vinyl pyrrolidone/N-vinyl imidazole salt Hold); Cationic cellulose derivative (polyquaternary ammonium salt-4 and polyquaternary ammonium salt-10), acrylamide copolymer (polyquaternary ammonium salt-7).In addition, the protein hydrolysate based on silicone compounds can be used as the adjusting material, for example poly-alkylsiloxane, poly-aryl siloxanes, poly-aralkyl siloxanes, polyether silicone or organic siliconresin.Other silicone compounds that is fit to is for example amino dimethyl polysiloxane of silicone compounds (CTFA) of dimethicone copolyol (CTFA) and aminofunctional.
The cosmetics for skin preparation
Skin cosmetic composition of the present invention, especially those are used for the compositions of nursing skin, can exist and use by various forms.For example, it can be oil-in-water type (O/W) emulsion or complex emulsions, as W/O/W (W/O/W) type.The preparation such as aqueous dispersion, hydrogel or the Pickering emulsion that do not contain emulsifying agent also are favourable embodiment.
The denseness of preparation can be from ointment preparation, the preparation that can flow to easily mobile, sprayable product.Thereby, can be made into Emulsion, lotion or spray.During use, cosmetic composition of the present invention can be applied to skin with cosmetics and skin product mode commonly used with suitable amount.
Thereby the salt content of skin surface is enough to reduce the viscosity of preparation of the present invention can disperse and infiltrate preparation easily.
Cosmetics for skin preparation of the present invention especially exists with the form of W/O or O/W skin cream, day cream and late frost, eye cream, facial cream, crease-proof cream, mimic creams, water replenishing cream, fair complexion cream, vitamin cream, skin lotion, nursing lotion and moisturizing lotion.
Other favourable cosmetics for skin preparation is face's nourishing agent, facial film, deodorizer and other cosmetics lotion and the preparation that is used to decorate cosmetics, for example hides rod, stage cosmetic, mascara, eye shadow, lip pomade, eye shadow chalk, eyeliner, cosmetics, end powder, kermes, XIANGFEN and eyebrow pencil.
In addition, compositions of the present invention can be used for nasal region pore cleaning, be used for acne-removing composition, repellant, shaving compositions, defeathering compositions, privates care composition, foodcare compositions and be used for Baby Care.
Except that W/W emulsion polymer and suitable carriers, cosmetics for skin preparation of the present invention also comprises other active component and/or auxiliary agent commonly used in the cosmetics that reach the following stated as mentioned above.
These preferably include emulsifying agent, antiseptic, and aromatic oil, the cosmetic active component is phytantriol, vitamin A, E and C, retinal, bisabolol, pantothenylol for example, natural and synthetic light protective agent, bleach, coloring agent, color and luster agent, tanning agent, collagen, protein hydrolysate, stabilizing agent, the pH value regulator, dyestuff, salt, thickening agent, gel former, consistency modifiers, silicone, wetting agent, regulator, fatting agent and other conventional additives.
If want to form specific performance properties, also can in compositions, add other polymer.For forming certain character, for example improve the cohesive that touches sense, diffusion, water-resistance and/or active component and auxiliary agent such as pigment, also can comprise adjusting material in the compositions in addition based on silicone compounds.Suitable silicone compounds is for example poly-alkylsiloxane, poly-aryl siloxanes, poly-aralkyl siloxanes, polyether siloxane or organic siliconresin.
Other possible component of the present composition is described under the following relevant key word.
Oil, fat and wax
Skin and composition of hair cosmetics also preferably contain oil, fat or wax.The component of cosmetic composition oil phase and/or fat phase advantageously is selected from lecithin and fatty acid triglycercide, promptly chain length be 8 to 24, the triglyceride of the alkyl carboxylic acid of saturated and/or undersaturated, the side chain of 12 to 18 carbon atoms and/or straight chain especially.Fatty acid glyceryl ester can for example advantageously be selected from synthetic, semisynthetic and natural oil, for example olive oil, Oleum helianthi, soybean oil, Oleum Arachidis hypogaeae semen, Oleum Brassicae campestris, almond oil, Petiolus Trachycarpi oil, Oleum Cocois, Oleum Ricini, wheat germ oil, Oleum Vitis viniferae, artichoke plant oil, evening primrose oil, nut wet goods.Other polar oil component is selected from the ester of the alcohol of saturated and/or undersaturated, side chain that the alkyl carboxylic acid of saturated and/or undersaturated, side chain that chain length is 3 to 30 carbon atoms and/or straight chain and chain length are 3 to 30 carbon atoms and/or straight chain, and the ester that is selected from the alcohol of saturated and/or undersaturated, side chain that aryl carboxylic acid and chain length are 3 to 30 carbon atoms and/or straight chain.This class ester can advantageously be selected from isopropyl myristate, isopropyl palmitate, isopropyl stearate, acid isopropyl, n-butyl stearate, the just own ester of lauric acid, oleic acid ester in the positive last of the ten Heavenly stems, the different monooctyl ester of stearic acid, stearic acid ester in the different ninth of the ten Heavenly Stems, isononyl isononanoate, Palmic acid 2-Octyl Nitrite, lauric acid 2-Octyl Nitrite, stearic acid 2-hexyl ester in the last of the ten Heavenly stems, Palmic acid 2-octyl group dodecyl ester, the oleyl alcohol oleate, oleyl alcohol savoy acid esters (oleylerucate), the erucyl alcohol oleate, erucyl alcohol savoy acid esters, dicaprylyl carbonate (cetiol CC) and cocoyl glyceride (cocoglyceride) (Myritol 331), butanediol dicaprylate/dicaprate and dibutyl adipate, and this class ester is synthetic, semisynthetic and natural mixture, for example Jojoba oil (jojoba oil).
In addition, one or more oil ingredients can advantageously be selected from hydrocarbon and chloroflo, silicone oil, dialkyl ether, saturated or undersaturated side chain or the straight chain alcohol of side chain and straight chain.
Any mixture of this class oil and wax component also can be advantageously used in purpose of the present invention.If suitable, also can advantageously use wax, cetin for example is as fat component unique in the oil phase.
According to the present invention, oil ingredient advantageously is selected from isostearic acid 2-Octyl Nitrite, octyldodecanol, different n-nonanoic acid isotridecyl ester, Isoeicosane, coconut oil 2-Octyl Nitrite, benzoic acid C12-15 Arrcostab, caprylic/capric triglyceride, dicaprylyl ether.
Favourable according to the present invention is mixture, and the mixture of benzoic acid C12-15 Arrcostab, isostearic acid 2-Octyl Nitrite and different n-nonanoic acid isotridecyl ester of mixture, benzoic acid C12-15 Arrcostab and the different n-nonanoic acid isotridecyl ester of benzoic acid C12-15 Arrcostab and isostearic acid 2-Octyl Nitrite.
According to the present invention, be 5 to 50mN/m oil for polarity, especially preferably use fatty acid triglycercide, especially soybean oil and/or almond oil.
Paraffin oil in the hydro carbons, squalane, Squalene, especially polyisobutylene---it also can be hydrogenated---can be used for purpose of the present invention.
In addition, oil phase can advantageously be selected from Guerbet alcohol.It is according to following reaction equation
By oxidation alcohol is aldehyde, makes aldehyde generation aldol condensation, elimination of water and hydrogenation pi-allyl aldehyde from aldol and make.Guerbet alcohol is uniform liquid and non-stimulated substantially to skin at low temperatures.It can be advantageously used for the fat in the cosmetic formulations, super fat and stuffing component.
It is known that Guerbet alcohol is used for cosmetics itself.Such material in most of the cases can characterize by following formula:
R wherein 1And R 2Be generally the alkyl of straight chain.
According to the present invention, Guerbet alcohol advantageously is selected from following group, wherein
R 1=propyl group, butyl, amyl group, hexyl, heptyl or octyl group, and
R 2=hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl or myristyl.
The preferred Guerbet alcohol of the present invention is 2-butyl capryl alcohol (commercially available acquisition, for example Isofol 12 (Condea)) and 2-hexyldecanol (commercially available acquisition, for example Isofol 16 (Condea)).
According to the present invention, also can advantageously use mixture, for example mixture (commercially available acquisition, for example Isofol of 2-butyl capryl alcohol and 2-hexyldecanol according to Guerbet alcohol of the present invention 14 (Condea)).
Any mixture of such oil and wax component also can be advantageously used in purpose of the present invention.In polyolefin, poly decene is preferred material.
Oil ingredient also can advantageously contain ring-type or linear silicone oil, or is all become by these line of oils, but also preferably uses other oil phase component of certain content except that these one or more silicone oils in addition.
Low-molecular-weight silicone or silicone oil are usually by following general formula definition:
Figure A20068001032500353
The silicone of higher molecular weight or silicone oil are usually by following general formula definition:
Figure A20068001032500361
Wherein silicon atom can be replaced by identical or different alkyl and/or aryl, it is passed through radicals R with general term herein 1To R 4Describe.Be restricted to 4 but not isoplastic number is also nonessential.The value of m can be taken as 2 to 200000.
The ring-type silicone that the present invention advantageously uses is usually with following general formula definition:
Wherein silicon atom can be replaced by identical or different alkyl and/or aryl, it is passed through radicals R with general term herein 1To R 4Describe.Be restricted to 4 but not isoplastic number is also nonessential.N at locating desirable 3/2 to 20.The reason of n being considered fractional value is can have the odd number siloxy in endless-chain.
Advantageously select Silicone DC 556 as silicone oil.Other silicone oil, for example dimethyl polysiloxane, hexamethyl cyclotrisiloxane, phenyl dimethyl polysiloxane, ring dimethyl siloxane (for example decamethyl cyclopenta siloxanes), hexamethyl cyclotrisiloxane, polydimethylsiloxane (polydimethylsiloxane), poly-(methyl phenyl siloxane), cetyl dimethyl polysiloxane, Shan Yu oxygen base polydimethylsiloxane also can be advantageously used in purpose of the present invention.The mixture that other is favourable, and the mixture of ring dimethyl siloxane and isostearic acid 2-Octyl Nitrite for ring dimethyl siloxane and different n-nonanoic acid isotridecyl ester.
But also can advantageously select with the above-claimed cpd structural similarity, its organic side chain---for example polyethoxylated and/or poly-propenoxylated---silicone oil that is deutero-.These comprise that for example, polysiloxanes gathers alkyl-copolyether, as cetyl dimethyl polysiloxane copolyol.
According to the present invention, ring dimethyl siloxane (octamethylcy-clotetrasiloxane) is advantageously used for silicone oil.
The component that is advantageously used for fat and/or wax can be selected from vegetable wax, animal wax, mineral wax and petrochemistry wax.For example, candelilla wax, horse west palm wax, Japan wax, alfa wax, cork wax, guaruma wax, Fructus Oryzae Germinatus oil wax, sugarcane wax, berry wax, ouricury wax, montan wax, Jojoba wax, tallow, Cera Flava, shellac wax, spermaceti, lanoline (lanocerin), uropygium oils and fats, ceresine (ceresin), Linesless charcoal (ceresine (earth wax)), paraffin and microwax are favourable.
Other preferred fat and/or wax component are the wax and the synthetic wax of chemical modification, for example Syncrowax HRC (glycerol San behenic acid ester) and Syncrowax AW1C (C 18-36And brown coal ester type waxes, Sa Suoer wax (sasol waxes), hydrogenant Jojoba wax fatty acid); The Cera Flava of synthetic or modification is (as dimethicone copolyol Cera Flava and/or C 30-50The alkyl Cera Flava); Ricinoleic acid cetyl ester, for example Tegosoft CR; Polyolefin-wax; Polyethylene glycol wax; And the fat of chemical modification, for example hydrogenant vegetable oil (as castor oil hydrogenated and/or hydrogenant coconut oil fat acid glyceride); Triglyceride, for example hydrogenant Semen sojae atricolor glyceride; Three hydroxyl stearins, fatty acid, fatty acid ester and diol ester, for example stearic acid C 20-40Arrcostab, hydroxyl stearoyl stearic acid C 20-40Arrcostab and/or montanic acid glycol ester.Other is favourable also comprises the organo-silicon compound that some and specified fat and/or wax component have similar physical character, for example stearoxyl trimethyl silane.
According to the present invention, fat in the compositions and/or wax component can be used separately, also can be used as mixture and use.
Any mixture of described oil and wax component also can be advantageously used in purpose of the present invention.
Oil phase advantageously is selected from isostearic acid 2-Octyl Nitrite, octyldodecanol, different n-nonanoic acid isotridecyl ester, butanediol dicaprylate/dicaprate, coconut oil 2-Octyl Nitrite, benzoic acid C 12-15Arrcostab, caprylic/capric triglyceride, dicaprylyl ether.
Particularly advantageous is the mixture or the benzoic acid C of octyldodecanol, caprylic/capric triglyceride, dicaprylyl ether, dicaprylyl carbonate, cocoyl glyceride 12-15The mixture of Arrcostab and isostearic acid 2-Octyl Nitrite, benzoic acid C 12-15The mixture of Arrcostab and butanediol dicaprylate/dicaprate, and benzoic acid C 12-15The mixture of Arrcostab, isostearic acid 2-Octyl Nitrite and different n-nonanoic acid isotridecyl ester.
Among the hydro carbons, paraffin oil, cycloalkanes, squalane, Squalene, Parleam and poly decene are advantageously used in purpose of the present invention.
Oil ingredient also can advantageously be selected from phospholipid.Phospholipid is the phosphate ester of acidylate glycerol.Of paramount importance among the phosphatidylcholine is lecithin for example, and it characterizes by following general formula:
Wherein, R ' and R " are generally the unbranched aliphatic hydrocarbyl that has 15 or 17 carbon atoms and be up to 4 cis-double bondss.
According to the present invention, can be advantageously used in paraffin oil of the present invention for Merkur Weissoel Pharma 40, from Shell ﹠amp from Merkur Vaseline; The Shell Ondina of DEA Oil 917, Shell Ondina 927, Shell Oil 4222, Shell Ondina 933, and Pionier 6301S, Pionier 2071 (Hansen ﹠amp; Rosenthal).
The oil ﹠ fat component of suitable cosmetics compatibility is recorded in Karl-Heinz Schrader, Grundlagen und Rezepturen der Kosmetika[Fundamentals andformulations of cosmetics], the 2nd edition, Verlag H ü thig, Heidelberg, the 319-355 page or leaf, its full content is included this description in by the mode of quoting as proof.
Regulator
In a preferred embodiment, also comprise regulator in the cosmetic composition.
Suitable regulator is, for example be recited in International CosmeticIngredient Dictionary and Handbook (the 4th volume, editor: R.C.Pepe, J.A.Wenninger, G.N.McEwen, The Cosmetic, Toiletry, andFragrance Association, the 9th edition, 2002) the 4th joint key word " hair conditioner (Hair Conditioning Agents) ", " wetting agent (Humectants) ", " skin conditioner (Skin-Conditioning Agents) ", " skin conditioner-emollient (Skin-Conditioning Agents-Emollient) ", " skin conditioner-wetting agent (Skin-Conditioning Agents-Humectant) ", " skin conditioner-mix agent (Skin-Conditioning Agents-Miscellaneous) ", chemical compound under " skin conditioner-occlusive agent (Skin-Conditioning Agents-Occlusive) " and " skin protectant (SkinProtectants) ", and be recited in whole chemical compounds under EP-A 934 956 (11-13 page or leaf) " water solublity regulator (water soluble conditioning agent) " and " oil-soluble regulator (the oil soluble conditioning agent) ".Other favourable regulator is called the compounds represented of polyquaternary ammonium salt (being specially polyquaternary ammonium salt-1 to polyquaternary ammonium salt-56) by for example INCI.
Suitable regulator comprises, for example polyquaternary ammonium salt chemical compound, cationic cellulose derivative, chitosan derivatives and polysaccharide.The regulator favourable according to the present invention also can be selected from the chemical compound shown in the following table 1.
Table 1: the regulator of Shi Yonging advantageously
The INCI title CAS number Polymer type Example (trade (brand) name)
Polyquaternary ammonium salt-2 CAS 63451-27-4 Urea, N, N '-two [3-(dimethylamino) propyl group] and 1,1, the polymer of-oxygen base two (2-ethyl chloride) Mirapol A-15
Polyquaternary ammonium salt-5 CAS 26006-22-4 Acrylamide, Beta-methyl acryloyl group ethyl triethyl group ammonium methyl sulfate
Polyquaternary ammonium salt-6 CAS 26062-79-3 N, N-dimethyl-N-2-acrylic-2-acrylic chlorination ammonium Merquat100
Polyquaternary ammonium salt-7 CAS 26590-05-6 N, N-methyl-N-2-acrylic-2-acrylic chlorination ammonium, 2-acrylamide MerquatS
Polyquaternary ammonium salt-10 CAS 53568-66-4， 55353-19-0， 54351-50-7， 68610-92-4， 81859-24-7 The quaternary ammonium salt of hydroxyethyl-cellulose Celquat SC-230M， Polymer JR 400
Polyquaternary ammonium salt-11 CAS 53633-54-8 Vinyl pyrrolidone/dimethylaminoethyl methacrylate copolymer/dithyl sulfate product Gafquat 755N
Polyquaternary ammonium salt-16 CAS 29297-55-0 Vinyl pyrrolidone/vinyl first imidazolitm chloride quinoline copolymer Luviquat HM552
Polyquaternary ammonium salt-17 CAS 90624-75-2 Mirapol AD-1
Polyquaternary ammonium salt-19 CAS 110736-85-1 Quaternised water-soluble poval
Polyquaternary ammonium salt-20 CAS 110736-86-2 Dispersible quaternised polyvinyl octadecyl ether in the water
Polyquaternary ammonium salt-21 Polysiloxanes-poly dimethyl dimethyl second AbilB 9905
Acid ammonium copolymer
Polyquaternary ammonium salt-22 CAS 53694-17-0 Dimethyl diallyl ammonium chloride/acrylic copolymer Merquat280
Polyquaternary ammonium salt-24 CAS 107987-23-5 The polyquaternary ammonium salt of hydroxyethyl-cellulose Quartisoft LM-200
Polyquaternary ammonium salt-28 CAS 131954-48-8 Vinyl pyrrolidone/methacryl amido-oxypropyl trimethyl ammonium chloride copolymer Gafqua t HS-100
Polyquaternary ammonium salt-29 CAS 92091-36-6， 148800-30-2 Also use the quaternised chitosan of chloropropylene oxide with propylene oxide reaction LexquatCH
Polyquaternary ammonium salt-31 CAS 136505-02-7， 139767-67-7 The polyquaternary ammonium salt that DMAPA-acrylate/acrylic acid/propylene nitrogen copolymer and dithyl sulfate reaction make HypanQT 100
Polyquaternium-32 CAS 35429-19-7 N, N, N-trimethyl-2-([82-methyl isophthalic acid-oxo-2-acrylic) oxygen base] polymer of ethyl ammonium chloride and 2-acrylamide
Polyquaternary ammonium salt-37 CAS 26161-33-1
Polyquaternary ammonium salt-44 The quaternary ammonium copolymer of vinyl pyrrolidone and quaternised imidazoline
According to the present invention, other favourable regulator is cellulose derivative and quaternised guar derivative, and particularly melon that hydroxypropyl ammonium chloride is (as Jaguar Excel , Jaguar C162 (Rhodia), CAS 65497-29-2, CAS 39421-75-5).Non-ionic poly-N-vinyl ketopyrrolidine/polyvinyl acetate ester copolymer is (as Luviskol VA 64 (BASF)), anionic acrylate copolymer is (as Luviflex Soft (BASF)) and/or amphoteric amide/acrylate/methacrylate copolymer (as Amphomer (National Starch)) also can be advantageously used for regulator according to the present invention.Other possible regulator is quaternised silicone.
Thickening agent
Except that the W/W emulsion polymer, also can comprise other thickening agent according to cosmetic composition of the present invention.Suitable thickening agent is crosslinkable polyacrylic acid and derivant thereof, polysaccharide---for example xanthan gum, guar gum, agar, alginate or methylcellulose, cellulose derivative---as carboxymethyl cellulose or hydroxyl carboxymethyl cellulose, and the monoesters of the Polyethylene Glycol of higher molecular weight and fatty acid or diester, aliphatic alcohol, monoglyceride and fatty acid, polyvinyl alcohol and polyvinyl pyrrolidone.
The thickening agent that is fit to also has polyacrylate, for example Carbopol (Noveon), Ultrez (Noveon), Luvigel EM (BASF), Capigel 98 (Seppic), Synthalene (Sigma); Aculyn from Rohm und Haas Grade products, for example Aculyn 22 (acrylate and copolymer) and Aculyn with methacrylic acid b-oxide (20 EO unit) of stearyl 28 (acrylate and copolymers) with methacrylic acid b-oxide (25 EO unit) of Shan Yu base.
The thickening agent that is fit to also has, for example aerosil grade products (hydrophilic Silicon stone), polyacrylamide, the pure and mild polyvinyl pyrrolidone of polyvinyl, the fatty glyceride of surfactant such as ethoxylation, fatty acid and polyhydric alcohol for example tetramethylolmethane or trimethylolpropane ester, have alcohol ethoxylate that narrow homologue distributes or alkyl oligoglycosides and electrolyte for example sodium chloride and ammonium chloride.The particularly preferred thickening agent that is used to prepare gel is Ultrez 21, Aculyn 28, Luvigel EM and Capigel 98.
Especially for the compositions of higher concentration, in order to regulate denseness, also can add the material that reduces preparation viscosity, for example propylene glycol or glycerol.These materials only produce minimal effect to the character of product.
In an embodiment preferred of the present invention, except that the W/W emulsion polymer, do not comprise other thickening agent in the cosmetic formulations.
Antiseptic
Aqueous cosmetic composition of the present invention also can comprise antiseptic.Must protect accumulation reliably for the higher compositions of water content with bacteriological protection.The topmost antiseptic that is used for this purpose is the conjugate of urea condensation compound, p-Hydroxybenzoate, phenyl phenol and methyl dibromo glutaronitrile, and the acid antiseptic that contains benzoic acid, salicylic acid and sorbic acid.
Compositions with the surfactant of high score rate or polyhydric alcohol and low moisture content is adding preservative agent and make preparation not also.
Compositions of the present invention can comprise one or more antiseptic.The favourable antiseptic that is used for the object of the invention is, for example (for example trade mark is Glydant to formaldehyde donor for DMDM Hydantoin for example, its commercially available acquisition (Lonza)), butyl carbamic acid iodo propyl ester is (as Glycacil-L , Glycacil-S (Lonza), Dekaben LMB (Jan Dekker)), parabens (alkyl paraben, for example P-hydroxybenzoic acid first, second, third and/or butyl ester), dehydroactic acid (Euxyl  K 702 (Sch ü lke﹠amp; Mayr)), phenyl phenol, ethanol, benzoic acid.So-called anticorrosion auxiliary agent, for example Sensiva SC50, glycine, Semen sojae atricolor etc. are also preferably used.
Following table has provided the conventional preservatives that also can be present in the cosmetic composition of the present invention.
E200 sorbic acid E227 calcium bisulfite
E201 sodium sorbate E228 Potassium acid sulfite
E202 potassium sorbate E230 biphenyl (phenylbenzene)
E203 calcium sorbate E231 o-phenyl phenol
E210 benzoic acid E232 o-Phenylphenol Sodium salt tetrahydrate
E211 sodium benzoate E233 Apl-Luster
E212 Potassium Benzoate E235 natamycin
E213 calcium benzoate E236 formic acid
E214 ethylparaben E237 sodium formate
E215 nipagin A sodium salt E238 calcium formate
E216 P-hydroxybenzoic acid n-propyl E239 hexamethylenetetramine
E217 P-hydroxybenzoic acid n-propyl sodium salt E249 potassium nitrite
E218 methyl parahydroxybenzoate E250 sodium nitrite
E219 Sodium Methyl Hydroxybenzoate salt E251 Chile saltpeter
E220 sulfur dioxide E252 potassium nitrate
E221 sodium sulfite E280 propanoic acid
E222 sodium sulfite E281 sodium propionate
E223 sodium sulfite E282 calcium propionate
E224 two potassium sulfite E283 potassium propionates
E226 calcium sulfite E290 carbon dioxide
Favourable in addition antiseptic or anticorrosion auxiliary agent commonly used in cosmetics is, for example dibromo dicyanobutane (2-bromo-2-bromomethyl glutaronitrile), phenyl phenol, butyl carbamic acid 3-iodo-2-propynyl ester, 2-bromo-2-nitro the third-1,3-glycol, imidazolidinyl urea, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-chloroacetamide, alkyldimethylbenzylammonium chloride, benzyl alcohol, salicylic acid and Salicylate.
Preferred especially used antiseptic is butyl carbamic acid iodo propyl ester, parabens (P-hydroxybenzoic acid first, second, third and/or butyl ester) and/or phenyl phenol.
For stable alcohols, especially alcoholic acid compositions, often do not need antiseptic.Therefore, contain the W/W emulsion polymer and do not need antiseptic as the preferred cosmetic formulations based on alcohol or water/alcohol of thickening agent.
In addition, the W/W emulsion polymer is particularly suitable for the disinfecting gel of preparation based on alcohol (ethanol, propanol, the Polyethylene Glycol that is in a liquid state when the STP are as PEG-8).
Chelating agent
Because raw material and compositions itself mainly prepare, thereby may comprise the ferrum of trace in the end product in steel systeming equipment.In order to prevent that these impurity from by with the reaction of dyestuff and aromatic oil component product quality being had a negative impact, adding chelating agent for example edetate, nitrilotriacetic acid salt, imino group succinate or phosphate.
UV photoprotection filtering agent
For the component of stable existence in the present composition for example dyestuff and aromatic oil,, can add the UV light protective agent, for example benzophenone derivative to prevent the photogenic variation of UV.The all acceptable UV light protective agents of cosmetics that is that are suitable for this purpose.
The example that can be present in the UV light protective agent in the present composition is:
Numbering Material CAS number (=acid)
1 The 4-amino benzoic Acid 150-13-0
2 3-(4 '-trimethyl amino) benzylidene camphane-2-ketone methylsulfuric acid ester 52793-97-2
3 3,3,5-trimethylcyclohexyl salicylate (homosaligenin) 118-56-9
4 2-hydroxyl-4-methoxyl group benzophenone (oxybenzone) 131-57-7
5 2-Phenylbenzimidazole-5-sulfonic acid and potassium salt, sodium salt and triethanolamine salt 27503-81-7
6 3,3 '-(1,4-penylene two methines) two (7,7-dimethyl-2-oxo bicyclo-[2.2.1] heptan-1-methanesulfonic acid) and salt thereof 90457-82-2
7 Two (polyethoxy) amino benzoic Acid ethoxyethyl group esters of poly-4- 113010-52-9
8 4-dimethylaminobenzoic acid 2-Octyl Nitrite 21245-02-3
9 The 2-Ethylhexyl salicylate 118-60-5
Figure A20068001032500441
Numbering Material CAS number (=acid)
30 2,2 '-(1, the 4-phenylene) is two-1H-benzimidazole-4,6-disulfonic acid and sodium salt thereof 180898-37-7
31 2, two [4-(2-the ethyl hexyl oxy)-2-hydroxyl] phenyl-6-(4-methoxyphenyl) (1,3,5)-triazine of 4- 187393-00-6
32 3-(4-methylbenzene methylene) Camphora 36861-47-9
33 Two (polyethoxy) para-amino benzoic acid ethoxyethyl group esters of poly-4- 113010-52-9
34 2,4 dihydroxy benzophenone 131-56-6
35 2,2 '-dihydroxy-4,4 '-dimethoxy benzophenone-5,5 '-disodium sulfonate 3121-60-6
36 Benzoic acid, 2-[4-(diethylamino)-2-(2-hydroxybenzoyl)], hexyl ester 302776-68-7
37 2-(2H-benzotriazole-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethyl silyl) the oxygen base] disiloxanyl] propyl group] phenol 155633-54-8
38 1,1-[(2,2 '-dimethyl propoxyl group) carbonyl-4,4-diphenyl-1,3-butadiene 363602-15-7
The light protective agent that is applicable to the present composition also has among the EP-A 1084696 [0036] to the pointed chemical compound of [0053] paragraph, and its full content is included in herein by the mode of quoting as proof.Be applicable to the specified whole UV photoprotection filtering agents under " Ultraviolet filters for cosmetic compositions " in the German Cosmetics Directive appendix 7 (to § 3b) that are of purposes of the present invention.
The UV photoprotection filtering agent of pointing out that can be used for the present composition is also non exhaustive.
Antioxidant
Usually preferably also contain a certain amount of antioxidant.According to the present invention, spendable antioxidant is all antioxidants conventional or that be applicable to cosmetic use.Antioxidant advantageously is selected from aminoacid (for example glycine, histidine, tyrosine, tryptophan) and derivant thereof; Imidazoles (for example urocanic acid) and derivant thereof; Peptide, D for example, L-carnosine, D-carnosine, L-carnosine and derivant (as anserine) thereof; Carotenoid; Carotene (as alpha-carotene, beta-carotene, γ-lycopene) and derivant thereof; Chlorogenic acid and derivant thereof; Thioctic acid and derivant thereof (as dihydrolipoic acid); Aurothioglucose; Propylthiouracil and other thio-alcohol (as thioredoxin, glutathion, cysteine, cystine, cystamine and glycosyl thereof, n-acetyl group, methyl, ethyl, propyl group, amyl group, butyl and lauryl, palmityl, oil base, γ-Ya oil base, cholesteryl and glyceryl ester) and salt thereof; Thiodipropionate dilauryl; Thio-2 acid distearyl ester; Thio-2 acid and derivant thereof (ester, ether, peptide, lipoid, nucleotide, nucleoside and salt thereof); Sulfo group oxime (sulfoximine) chemical compound of extremely low tolerance dose (as pmol to μ mol/kg) (as fourth thionine sulfo group oxime, homocysteine sulfo group oxime, fourth thionine sulphur ketone (buthionine sulfone), amyl group-, hexyl-, heptyl thionine sulfo group oxime); And (metal) chelating agen (as α-hydroxy fatty acid, Palmic acid, phytic acid, lactoferrin), alpha-hydroxy acid (as citric acid, lactic acid, maleic acid), humic acid, bile acid, bile extract, bilirubin, biliverdin, EDTA, EGTA and derivant thereof; Unsaturated fatty acid and derivant thereof (as gamma-Linolenic acid, linoleic acid, oleic acid); Folic acid and derivant thereof; Furfurylidene sorbitol and derivant thereof; Ubiquinone and pantothenylol and derivant thereof; Vitamin C and derivant thereof (as sodium L-ascorbate-2-phosphate, Magnesium L-Asacorbic Acid 2-O-Phosphate, the vitamin C acetas); Vitamin E and derivant thereof (as vitamin E acetate); Vitamin A and derivant thereof (vitamin A palmitate); Benzoic acid cypress ester, rutinic acid and the derivant thereof of benzoin resin; Alpha-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, Butylated hydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxy butyrophenone, uric acid and derivant thereof; Mannose and derivant thereof; Zinc and derivant thereof are (as ZnO, ZnSO 4), selenium and derivant thereof (as selenomethionine); Stilbene and derivant thereof (as Stilbene oxide, anti-Stilbene oxide) and the derivant (salt, ester, ether, sugar, nucleotide, nucleoside, peptide and lipoid) that is fit to these specified active components of the present invention.
Preferred 0.001 to the 30 weight % of the amount of above-mentioned antioxidant in the compositions (one or more chemical compounds), preferred especially 0.05 to 20 weight %, especially 0.1 to 10 weight % are based on total restatement of compositions.
If vitamin E and/or its derivant are one or more antioxidants, can advantageously be made into the concentration of 0.001 to 10 weight %, based on total restatement of compositions.
If vitamin A, or vitamin A derivative, or the carotene or derivatives thereof is one or more antioxidants, can advantageously be made into the concentration of 0.001 to 10 weight %, based on total restatement of compositions.
Buffer agent
Buffer agent is guaranteed pH value stable of waterborne compositions of the present invention.Preferred citrate, lactate and the phosphate buffer used.
Dissolution accelerator
Use the purpose of dissolution accelerator to be to form the clear solution of nursing oil or aromatic oil and it is remained in the clear solution at low temperatures.Chang Yong dissolution accelerator is the non-ionic surface active agent of ethoxylation the most, the Oleum Ricini of for example hydrogenant and ethoxylation.
Antibacterial
In addition, also can use antibacterial.It generally includes all antiseptic suitable, that have specific resisting gram-positive bacteria effect, and for example triclosan (2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether), hibitane (1,1 '-hexamethylene two [5-(4-chlorophenyl) biguanide] and TTC (3,4,4 '-neko).Quaternary ammonium compound is suitable in principle equally.Multiple essence also has antibiotic property.Multiple quintessence oil and characteristic component thereof, for example Oleum Caryophylli (acetaminol), Oleum menthae (menthol) or thyme oil (thymol) also demonstrate tangible antibacterial effect.
The antibacterial effect material uses with the concentration of about 0.1 to 0.3 weight % usually.
Dispersant
---for example dandruff active component or silicone oil---is scattered in the compositions and remains in the suspension for a long time if purpose is to make undissolved active component; it is favourable using dispersant and thickening agent; described dispersant or thickening agent be aluminium-magnesium silicate, bentonite, fatty acyl group derivant, polyvinyl pyrrolidone or hydrocolloid for example, for example xanthan gum or carbomer.
Except that above-mentioned substance, if compositions of the present invention comprises---suitable---other additive commonly used in cosmetics, for example other conventional component of spice, dyestuff, antibiotic substance, fatting agent, chelating agent and screening agent, pearling agent, plant extract, vitamin, active component, antibacterial, pigment, softening agent, humidification and/or moistening material or cosmetics or skin-use preparation, for example alcohol, polyhydric alcohol, polymer, the organic acid that is used to regulate pH value, foam stabiliser, electrolyte, organic solvent or silicone derivative with color effect.
The fatty acid glyceride of ethoxylation
If the oil of the ethoxylation of cosmetic composition of the present invention comprises---suitable---fatty acid glyceride that is selected from ethoxylation, preferred especially PEG-10 olive oil glyceride, PEG-11 American Avocado Tree oil glyceride, PEG-11 cupu oil glyceride, PEG-13 Oleum helianthi glyceride, the PEG-15 glyceryl isostearate, PEG-9 coconut oil fat acid glyceride, the PEG-54 castor oil hydrogenated, the PEG-7 castor oil hydrogenated, the PEG-60 castor oil hydrogenated, (the PEG-26 Jojoba fat acid of Jojoba oil b-oxide, PEG-26 Jojoba alcohol), glycerin polyether-5 cocos nucifera oil acid esters, PEG-9 coconut oil fat acid glyceride, the PEG-7 glyceryl cocoate, PEG-45 palm-kernel oil glyceride, the PEG-35 Oleum Ricini, olive oil PEG-7 ester, PEG-6 caprylic/capric glyceride, PEG-10 olive oil glyceride, PEG-13 Oleum helianthi glyceride, the PEG-7 castor oil hydrogenated, hydrogenated palm kernel oil glyceride PEG-6 ester, PEG-20 Semen Maydis oil glyceride, PEG-18 glyceryl oleate cocos nucifera oil acid esters, the PEG-40 castor oil hydrogenated, the PEG-40 Oleum Ricini, the PEG-60 castor oil hydrogenated, PEG-60 Semen Maydis oil glyceride, the PEG-54 castor oil hydrogenated, PEG-45 palm-kernel oil glyceride, the PEG-80 glyceryl cocoate, PEG-60 almond oil glyceride, PEG-60 Radix Oenotherae erythrosepalae glyceride, PEG-200 hydrogenating glycerol cetylate, the PEG-90 glyceryl isostearate.
Preferred ethyoxyl carburetion is PEG-7 glyceryl cocoate (glyceryl cocoate), PEG-9 cocos nucifera oil fat acid glyceride (cocoglyceride), PEG-40 castor oil hydrogenated, PEG-200 hydrogenating glycerol cetylate.
The ethoxylated glycerol fatty acid ester is that various purposes are used for the watersoluble cleaning preparation.Fatty acid glyceride with low ethoxyquin degree (3-12 ethylene oxide unit) usually as fatting agent to improve the sensation on the skin of dry back, to have the fatty acid glyceride that is about 30 to 50 ethoxyquin degree dissolution accelerator as apolar substance such as aromatic oil.The fatty acid glyceride of height ethoxyquin is as thickening agent.The common trait of all these materials is in the process on being applied to skin, and behind dilute with water, it produces special sensation on skin.
Active component
The active component of having found many kinds of different solubilities can add in cosmetics of the present invention or the skin composition equably.These active components are bigger than the substantivity on skin and hair in the cleaning formulation that contains surfactant of routine in described compositions.
According to the present invention, active component (one or more chemical compounds) can advantageously be selected from aspirin, atropine, azulenes, hydrocortisone and derivant thereof, as hydrocortisone-17 valerate; The vitamin of B and D series, especially vitamin B 1, vitamin B 12, vitamin D; Vitamin A and derivant thereof, for example vitamin A palmitate; Vitamin E or derivatives thereof, for example alpha-tocopherol acetate; Vitamin C and derivant thereof, for example vitamin C glucosides; And nicotiamide, pantothenylol, bisabolol, polydocanol, unsaturated fatty acid, for example essential fatty acid (so-called vitaminF), especially gamma-Linolenic acid, oleic acid, eicosapentaneoic acid, docosahexenoic acid (docosahexaenoic acid) and derivant thereof; Chloromycetin, caffeine, prostaglandins, thymol, Camphora, squalene; The extract in plant and animal source or other products, for example evening primrose oil, borage oil or blackcurrant seed oil, fish oil, cod-liver oil and ceramide and class ceramide chemical compound, incense extract, green tea extract, Flos nymphaeae (Nymphaea teragona Georgi) extract, licorice extract, Radix Hamamelidis Mollis; Dandruff active component (as selenium sulfide, 2-mercaptopyridine zinc oxide, pears ketone (piroctone), pyrrone (olamine), climbazole (climbazole), pyridine ketone ethanolamine salt (octopirox), polydocanol and derivant thereof); The complexation active component for example contains the active component of gamma oryzanol and calcium salt such as calcium pantothenate, calcium chloride, calcium acetate.
From stuffing material for example purcellin oil, Eucerit And Neocerit Middle selection active component also is favourable
One or more active components also can particularly advantageously be selected from the NO synthase inhibitor, if compositions especially of the present invention is to be used for the treatment of and to prevent intrinsic and/or external skin aging symptom and be used for the treatment of and pre-ultraviolet radiation preventing during to the adverse effect of skin and hair.Preferred NO synthase inhibitor is the nitro arginine.
One or more active components also advantageously are selected from the bile acid ester that contains catechin, catechin, and be selected from from the plant of the bile acid ester that contains a certain amount of catechin or catechin or aqueous or the organic extract that plant part obtains the leaf that described plant or plant part be Camellia for example---especially tea (green tea) class---.Particularly advantageous is its typical component (as polyphenol and catechin, caffeine, vitamin, sugar, mineral, aminoacid, lipoid).
On behalf of a class, catechin can be considered to the chemical compound of hydrogenation flavone or anthocyanidin, the derivant of representative " catechin " (catechol, 3,3 ', 4 ', 5,7-flavane amylalcohol, 2-(3, the 4-dihydroxy phenyl) benzodihydropyran-3,5,7-triol).Epicatechin ((2R, 3R)-3,3 ', 4 ', 5,7-flavane amylalcohol) also be the favourable active component that is used for the object of the invention.
Favourable in addition is the plant extract that contains a certain amount of catechin, especially extract from green tea, the extract of plant of theaceae leaf for example, the utmost point be in particular old tea (Camelliasinenis), Folium camelliae assamicae (C.assamica), Dali tea (C.taliensis) and C.inawadiensis tea kind and with the extract of the leaf of the Hybrid of for example Flos Camelliae Japonicae (Camellia japonica).
Preferred active ingredient also has polyphenol and is selected from the catechin of (-)-catechin, (+)-catechin, (-)-Catechin 3-gallate, (-)-gallocatechin gallate, (+)-Biao bitter edible plant element, (-)-epicatechin, (-)-epicatechin gallate, (-)-Biao Gallate bitter edible plant element, (-)-epigallocatechin gallate.
Flavone and derivant thereof (also being generically and collectively referred to as flavone usually) also are the favorable activity components that is used for the object of the invention.Its available following basic structure formula (having provided substituting group position) characterizes:
Figure A20068001032500501
Some even more important flavone that also can be preferably used for compositions of the present invention are listed in the table below 2.
Table 2 The OH substituting group position
3 5 7 8 2’ 3’ 4’ 5’
Flavone - - - - - - - -
Flavonol + - - - - - - -
Chrysin - + + - - - - -
Galangin - + + - - - - -
Apigenin - + + - - - + -
Fisetin + - + - - + + -
Luteolin - + + - - + + -
Kaempferol + + + - - - + -
Tricetin + + + - - + + -
Morin + + + - + - + -
3,7-dihydroxy-2-(3,4,5-trihydroxy-phenyl)-chromen-4-one + - + - - + + +
Gossypetin + + + + - + + -
Myricetin + + + - - + + +
Occurring in nature, flavone exist with glycosylated form usually.
According to the present invention, flavonoid is preferably selected from the material of following general formula:
Figure A20068001032500511
Z wherein 1To Z 7Be independently from each other H, OH, alkoxyl and hydroxy alkoxy base, wherein alkoxyl and hydroxy alkoxy base can be the groups with 1 to 18 carbon atom of side chain or straight chain, and wherein Gly is selected from monoglycosides and oligoglycosides group.
According to the present invention, flavonoid also can advantageously be selected from the material of following general formula:
Figure A20068001032500512
Z wherein 1To Z 6Be independently from each other H, OH, alkoxyl and hydroxy alkoxy base, wherein alkoxyl and hydroxy alkoxy base can be the groups with 1 to 18 carbon atom of side chain or straight chain, and wherein Gly is selected from monoglycosides and oligoglycosides group.
Preferably, described structural formula can be selected from the material of following general formula:
Figure A20068001032500513
Z wherein 1To Z 6As above definition, and Gly independently of one another 1, Gly 2And Gly 3Be monoglycosides group or oligoglycosides group independently of one another.Gly 2And Gly 3Also can be separately or saturated by hydrogen atom jointly.
Preferably, Gly 1, Gly 2And Gly 3Be independently from each other hexose-based (hexosyl) group, especially rhamanopyranosyl and glucityl.But other hexose-based, for example allose base (allosyl), altrose base (altrosyl), galactosyl, gulose base (gulosyl), idose base (idosyl), mannose group and talose base (talosyl) are if suitablely also can advantageously use.
According to the present invention, also can advantageously use pentose base (pentosyl) group.
Advantageously, Z 1To Z 5Be independently from each other H, OH, methoxyl group, ethyoxyl and 2-hydroxyl-oxethyl, flavone glycoside is corresponding to following general formula:
Figure A20068001032500521
Flavone glycoside particularly advantageously is selected from the material of following structure:
Figure A20068001032500522
Gly wherein 1, Gly 2And Gly 3Be monoglycosides and oligoglycosides group independently of one another.Gly 2And Gly 3Also can be separately or saturated by hydrogen atom jointly.
Preferably, Gly 1, Gly 2And Gly 3Be independently from each other the hexose group, especially rhamanopyranosyl and glucityl.But other hexose group, for example allose base, altrose base, galactosyl, gulose base, idose base, mannose group and talose base are if suitablely also can advantageously use.
According to the present invention, also can advantageously use the pentose group.
Particularly advantageous for the object of the invention is from alpha-glucosyl rutin, selects one or more flavone glycosides in alpha-glucosyl myricetin, alpha-glucosyl isoquercitrin, the different Tricetin of alpha-glucosyl and the alpha-glucosyl quercimentin.
Other favourable active component is sericoside, pyridoxol, vitamin K, biotin and aromatic substance.
In addition, active component (one or more chemical compounds) but also the utmost point advantageously be selected from the hydrophilic active component, especially following material:
'alpha '-hydroxy acids, for example lactic acid or salicylic acid and salt thereof are as sodium lactate, calcium lactate, lactic acid TEA, urea, allantoin, serine, sorbitol, glycerol, lactoprotein, pantothenylol, chitosan.
The active component of enumerating that can be used for the present composition and the conjugate of active component are also nonrestrictive certainly.Active component can be used separately or be used in combination arbitrarily each other.
Preferred 0.001 to the 30 weight % of the amount of this active component (one or more chemical compounds) in the present composition, preferred especially 0.05 to 20 weight %, especially 1 to 10 weight % are based on total restatement of compositions.
Enumerate and other active component that can be used for the present composition is recorded among DE 103 18 526A1 the 12nd page to 17 pages, and its full content is included in herein by the mode of quoting as proof.
Pearlescent waxes
Suitable pearlescent waxes is, for example alkylene glycol ester, especially diglycol stearate; Marlamid, especially fatty acid distribution of coconut oil diglycollic amide; Partial glyceride, especially glycerol monostearate; The ester of polyacid base, the randomly tartaric ester of the carboxylic acid that replaces of hydroxyl and ester, the especially long-chain of aliphatic alcohol with 6 to 22 carbon atoms; Lipoid material for example has aliphatic alcohol, aliphatic ketone, fatty aldehyde, aliphatic ether and aliphatic carbonate ester, especially laurone and the distearyl ether of at least 24 carbon atoms of total; Fatty acid, for example stearic acid, hydroxy stearic acid Huo behenic acid; Olefin epoxide with 12 to 22 carbon atoms with have the aliphatic alcohol of 12 to 22 carbon atoms and/or have the open-loop products of the polyhydric alcohol of 2 to 15 carbon atoms and 2 to 10 hydroxyls; And the mixture of above-mentioned substance.
The present composition also can comprise luminescent substance and/or other effector substance (as color fringe).
Emulsifying agent
In a kind of preferred embodiment of the present invention, cosmetic composition of the present invention is an emulsion form.This emulsion prepares by known method.Except that the W/W emulsion polymer, also can comprise aliphatic alcohol, fatty acid ester in the emulsion---especially fatty acid triglycercide, fatty acid, lanoline and derivant thereof, natural or synthetic oil or wax and emulsifying agent when water exists.Type according to emulsion is specifically selected additive, the preparation process of suitable emulsion is described in for example Schrader, Gfundlagen und Rezepturen der Kosmet ika[cosmetics principle and preparation], H ü thig Buch Verlag, Heidelberg, the 2nd edition, 1989, third part, its content is clearly included this description in by the mode of quoting as proof.
Suitable emulsion---as skin cream, generally include by suitable emulsifier system oil phase or fat mutually in emulsified water.
The branch rate of emulsifier system is preferably about 4 to 35 weight % in such emulsion, based on total restatement of emulsion.Preferably about 20 to the 60 weight % of the branch rate of fat phase.Preferably, the branch rate of water is about 20 to 70%, and various situations are all based on total restatement of emulsion.
The emulsifying agent that is fit to is, for example at least aly is selected from following nonionic source surfactant:
(1) 2 to 30mol oxirane and/or 0 to 5mol expoxy propane in linear fatty alcohols with 8 to 22 carbon atoms, have the fatty acid of 12 to 22 carbon atoms and have addition product on the alkyl phenol of 8 to 15 carbon atoms on the alkyl;
The C12/18 fatty-acid monoester and the diester of (2) 1 to 30mol the addition product of oxirane on glycerol;
(3) saturated and undersaturated monoglyceride and diester and sorbitan monoester and diester and ethylene oxide adduct thereof with fatty acid of 6 to 22 carbon atoms;
(4) on alkyl, have the alkyl monoglycosides of 8 to 22 carbon atoms and the analog of oligosaccharide acid anhydride and ethoxylation thereof;
(5) 15 to 60mol the addition product of oxirane on oil, for example addition product on Oleum Ricini and/or castor oil hydrogenated;
(6) polyhydric alcohol, especially polyglycerin ester, for example polyglycerol polyricinoleate, polyglycereol gather-12-hydroxy stearic acid ester or polyglycereol two godied oils (polyglycerol dimerate).The mixture of two or more chemical compounds of this class material is suitable equally;
(7) 2 to 15mol the addition product of oxirane on Oleum Ricini and/or castor oil hydrogenated;
(8) based on straight chain, side chain, unsaturated or saturated C 6/ 22Fatty acid, castor oil acid, and 12-hydroxy stearic acid and glycerol, polyglycereol, tetramethylolmethane, dipentaerythritol, sugar alcohol (as sorbitol), alkyl polyglucoside (as methylglycoside, butyl glycoside, Plantacare APG 1200G), and the partial ester of polyglycosides (as cellulose);
(9) single, two and trialkyl phosphates, and single-, two-and/or three-PEG alkyl phosphate and salt thereof;
(10) wool wax alcohol;
(11) polysiloxanes-poly-alkyl-copolyether and corresponding derivative thereof;
(12) mixed ester of the aliphatic alcohol of tetramethylolmethane, fatty acid, citric acid and DE-C1165574 and/or have the mixed ester of fatty acid, methyl monosaccharide and the polyhydric alcohol---preferably glycerine or polyglycereol---of 6 to 22 carbon atoms; With
(13) ployalkylene glycol.
Oxirane and/or expoxy propane are products known, commercially available acquisition at the sorbitan monoester and the addition compound product on diester or the Oleum Ricini of the monoglyceride of aliphatic alcohol, fatty acid, alkyl phenol, fatty acid and diester, fatty acid.These are mixture of the same clan, and its average degree of alkoxylation is corresponding with the ratio of the amount of the substrate of carrying out additive reaction with oxirane and/or expoxy propane.The C of the addition compound product of oxirane on glycerol 12To C 18Fatty-acid monoester and diester are known in DE-C 2024051 as the fatting agent of cosmetic composition.C 8To C 18Alkyl monoglycosides and oligoglycosides, its preparation method and its purposes can be known from prior art.Its preparation process is especially undertaken by glucose or oligosaccharide and reaction with primary alconol of 8 to 18 carbon atoms.As for the glucosides ester, wherein the ring-type glycosyl is bonded to the monoglycosides of aliphatic alcohol and oligomeric degree by glycosidic bond to be up to preferred about 8 oligoglycosides all is suitable.Oligomeric herein degree is the assembly average based on the homologue distribution of this class handicraft product routine.
In addition, zwitterionic surfactant can be used as emulsifying agent.The amphion surface activity is to be used to describe the term that intramolecularly has the surface active cpd of a quaternary ammonium group and at least one carboxylation and/or sulfonation group at least.Particularly suitable zwitterionic surfactant is so-called betanin, N-alkyl-N for example, and N-dimethylglycine ammonium is as cocoyl alkyl dimethyl glycine ammonium; N-acylamino-propyl group-N, N-dimethylglycine ammonium is as cocos nucifera oil acylamino-propyl-dimethyl glycine ammonium; And the 2-alkyl-3-carboxy methyl-3-hydroxyethyl imidazoline and the hydroxyethyl carboxyl methylglycine cocos nucifera oil acylamino-ethyl ester that have 8 to 18 carbon atoms in each comfortable alkyl or the acyl group.
Preferred especially known CTFA name is called the fatty acid amide derivant of cocamidopropyl betaine (cocamidopropyl betaine).The same emulsifying agent that is fit to is an amphoteric surfactant.Amphoteric surfactant is interpreted as meaning those and removes C at intramolecularly 8To C 18Outside alkyl or the acyl group, also comprise at least one free amino group and at least one-COOH and/or-SO 3H also can form the surface active cpd of inner salt.The examples of amphoteric surfactants that is fit to is for having N-alkyl glycine, N-alkyl propanoic acid, N-alkyl amino butanoic acid, N-alkyl imino dipropionic acid, N-hydroxyethyl-N-alkylamidoalkyl propyl group glycine, N-alkyl taurine, N-alkyl sarcosine, 2-alkyl aminopropionic acid and the p dialkylaminobenzoic acid of 8 to 18 carbon atoms on each comfortable alkyl.Particularly preferred amphoteric surfactant is N-coco alkyl amino propionic acid ester, cocoamidoethyl alanine ester and C 12To C 18The acyl group sarcosine.
Except that amphoteric emulsifier, quaternised emulsifying agent also is fit to, the quaternized type of preferred especially ester, the ester salt of preferable methyl-quaternised difatty acid triethanolamine.
Aromatic oil
If suitable, cosmetic composition of the present invention can comprise aromatic oil.The mixture of for example natural and synthetic perfume of the aromatic oil that can mention.Natural perfume material is for extracting from flower (Bulbus Lilii, Garden lavender, Flos Rosae Rugosae, jasmine, orange blossom oil, Cananga odorata), stem and leaf (Flos Pelargonii, Herba Pogostemonis, Folium Citri grandis), fruit (Fructus Foeniculi, coriander, umbrella flower Fructus Foeniculi, Juniperus rigida Sieb.et Zucc.), peel (bergamot, Fructus Citri Limoniae, Citrus), root (Semen Myristicae, the Radix Angelicae Dahuricae, Herba Apii graveolentis, Elettaria cardamomum (L.) Maton, the Radix Aucklandiae, Rhizoma Iridis Tectori, Rhizoma Acori Graminei), forest (Masson Pine, sandalwood, lignum-vitae, Cupressus funebris Endl., amboyna (rose wood)), medicinal herbs and herbage (tarragon, lemon grass (Cymbopogon citratus), Salvia japonica Thunb., Herba thymi vulgaris), needle and branch (PiceameyeriRehd. Et Wils., fir, pinaster, Pinus mugo), resin and face cream (galbanum, elemi, Benzoinum, Myrrha, Olibanum, opopanax (opoponax)).What be fit to also has zoogenous material, for example Zibethum and castoreum.Typical synthetic perfume chemical compound is ester, ether, aldehyde, ketone, pure and mild hydrocarbon products.The flavor compounds of esters is, for example which ester, benzyl formate, phenylglycine ethyl methyl ester, allyl cyclohexyl propionate, styralyl propionate and benzyl salicylate in benzyl acetate, phenoxyethyl isobutanoate, cyclohexyl-acetic acid 4-tertiary butyl ester, linalyl acetate, acetic acid dimethyl benzyl methyl ester, ethyl phenyl acetate, the benzoic acid.Described ether comprises, for example benzylisoeugenol; Described aldehyde comprises for example having linear chain alkanal, citral, citronellal, citronellyl oxy-aldehyde, cyclamen aldehyde, hydroxycitronellal, lilestralis and the bourgeonal of 8 to 18 carbon atoms; Described ketone comprises, for example ionone, cc-isomethylionene and methyl Cupressus funebris Endl. base ketone; Described alcohol comprises anethole, citronellol, acetaminol, isoeugenol, geraniol, linalool, the pure and mild terioneol of phenylethyl; Described hydrocarbon mainly comprises terpene and face cream.But preferred use can produce the mixture of the different spice of pleasant abnormal smells from the patient together.The quintessence oil of low volatility---it is mostly as aromatised fraction---also is suitable as aromatic oil, for example sage oil, chamomile oil, Oleum Caryophylli, melissa oil, Oleum menthae, Cortex Cinnamomi leaf oil, linden concrete, cade oil, vetiver oil, Olibanum oil, galbanum oil, labolanum oil and lavandin oil.Preferred use separately or use following substances: oleum bergamottae, dihydromyrcenol, lilestralis, lyral, citronellol, phenylethyl alcohol, jasmonal H, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene with form of mixtures Forte, imperial saliva furan (ambroxan), indole, hedione, sandelice, tangerine oil, Fructus Citri tangerinae oil, orange oil, glycolic acid pi-allyl pentyl ester, cyclovertal, lavandin oil, clary sage oil, β-damascone, geranium oil Bourbon, salicylic acid cyclohexyl, Vertofix Coeur, Iso-E-Super , Fixolide NP, synthetic oak moss (evernyl), methyl ionone γ (iraldeingamma), phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat.
Pigment
If suitable, also comprise pigment in the cosmetic composition of the present invention.
Pigment is present in the product with insoluble form, can 0.01 to 25 weight %, especially preferably the amount with 5 to 15 weight % exists.Preferred granularity is 1 to 200 μ m, 3 to 150 μ m especially, preferred especially 10 to 100 μ m.Pigment is largely insoluble coloring agent in application media, can be that inorganic matter also can be an Organic substance.It also can be inorganic-organic hybrid pigment.The preferred inorganic pigment that uses.The advantage of inorganic pigment is that it has good fast light, weather-proof and heat resistance.Inorganic pigment can be a natural origin, for example by Chalk, ocher, umber, terre verte, burnt sienna or graphite system.Pigment can be white pigments, for example titanium dioxide or zinc oxide; Mineral black, for example iron oxide black; Color pigment, for example ultramarine or iron oxide red; Luminous pigment, metal effect pigments, pearlescent pigment and fluorescence or phosphorescent pigment, wherein preferred at least a pigment are pigment chromatic, non-white race.
Metal-oxide, hydroxide and hydrous oxide, mixed dyes of Fe, the silicate of sulfur-bearing, metal sulfide, the metal cyanides of complexation, metal sulfate, chromate and molybdate, with and metal itself (bronze powder pigment) all be suitable.Specially suitable is titanium dioxide (CI77891), Black Rouge (CI 77499), iron oxide yellow (CI 77492), red and Brown Ferric Oxide (CI 77491), manganese violet (CI 77742), ultramarine (thiosilicic acid sodium aluminum, CI 77007, alizarol saphirol 29), chromium oxide hydrate (C177289), barba hispanica (ferric ferrocyanide, CI 77510), carmine (alkermes).
Be preferably based on micaceous pearly-lustre and color pigment especially, itself and metal-oxide or metal oxychloride for example titanium dioxide or bismuth oxychloride and, if it is suitable, other material that gives color for example ferrum oxide, barba hispanica, ultramarine, carmine etc. applies together, and color can be decided by the thickness that changes layer.These pigment are with for example Rona , Colorona , Dichrona And Timiron (Merck) trade mark is sold.
Organic pigment is, for example natural pigment sepia, Resina garciniae, bone black, Vandyke brown, indigo, chlorophyll and other vegetable pigment.Synthetic organic pigment is, for example AZOpigments, anthraquinone class, indigo-blue, two  piperazines, quinacridone, phthalocyanine, isoindolinone (isoindolinone), perylene and purple cyclic ketones (perinone), metal complex, alkali blue and diketopyrrolo-pyrrole (Diketopyrrolopyrrole) pigment.
In one embodiment, compositions of the present invention comprises at least a particulate matter of 0.01 to 10 weight %, preferred especially 0.05 to 5 weight %.The material that is fit to is for example to be solid-state and to be the material of particle shape in room temperature (25 ℃).For example, Silicon stone, silicate, aluminate, clay, Muscovitum, salt---especially inorganic metal salt, metal oxides such as titanium dioxide, mineral and polymer beads all are suitable.
Granule with insoluble, preferably the form with stable dispersion is present in the compositions, can solid forms after being administered to application surface and solvent evaporated under the deposition.
Preferred particulate matter is Silicon stone (silica gel, silicon dioxide) and slaine, especially inorganic metal salt, special preferred silica.Slaine is, for example alkali metal or alkaline-earth halide are as sodium chloride or potassium chloride; Alkali metal or alkali earth metal sulfate are as sodium sulfate or magnesium sulfate.
Polymer
Cosmetic composition of the present invention also can comprise other polymer.
The polymer that is fit to is that for example the INCI name is called the cation type polymer of polyquaternary ammonium salt, as the copolymer (Luviquat of vinyl pyrrolidone/N-vinyl imidazole salt FC, Luviquat HM, Luviquat MS, Luviquat Care, Luviquat UltraCare), with the quaternised N-vinyl pyrrolidone of dithyl sulfate/dimethylaminoethyl methacrylate copolymer (Luviquat PQ11), the copolymer (Luviquat of N-caprolactam/N-vinyl pyrrolidone/N-vinyl imidazole salt Hold); Cationic cellulose derivative (polyquaternary ammonium salt-4 and-10); Acrylamide copolymer (polyquaternary ammonium salt-7) and chitosan.Cationic (quaternised) polymer that is fit to also has Merquat (based on the polymer of dimethyl diallyl ammonium chloride), Gafquat (reacting formed quaternary ammonium polymer), polymer JR (hydroxyethyl-cellulose that has cation group) and based on the cation type polymer of plant by polyvinyl pyrrolidone and quaternary ammonium compound, as Guar beans polymer (guar polymer), be Jaguar such as trade mark from Rhodia Grade products.
Other polymer that is fit to also has neutral polymer, for example other copolymer, polymine and salt thereof, polyvinylamine and salt thereof, cellulose derivative, polyaspartic acid salts and the derivant thereof of the copolymer of polyvinyl pyrrolidone, N-vinyl pyrrolidone and vinyl acetate and/or propionate and/or (methyl) stearyl acrylate base ester, poly-first siloxanes, Vinylcaprolactam homopolymer and itself and N-vinyl pyrrolidone.These comprise, for example Luviflex Swing (polyvinyl acetate of partial hydrolysis and the copolymer of Polyethylene Glycol, BASF) or Kollicoat IR.
Suitable copolymers also has (methyl) acrylamide copolymer of record among the W0 03/092640, especially as example 1 to 50 (table 1,40 pages reach thereafter) and described those copolymers of example 51 to 65 (table 2,43 pages), its full content is included in herein by the mode of quoting as proof.
Suitable polymers also has nonionic, water solublity or water-dispersible polymer and oligomer, for example Vinylcaprolactam homopolymer such as Luviskol Plus (BASF), or polyvinyl pyrrolidone and copolymer thereof are especially with the vinyl esters copolymer of vinyl acetate for example, as Luviskol VA 37 (BASF); Polyamide, as the polyamide based on itaconic acid and aliphatic diamine, it for example is described among the DE-A-43 33 238.
Suitable polymers also has both sexes or amphoteric ion polymer, for example trade mark Amphomer by name The copolymer of the octyl acrylamide/methyl methacrylate of (National Starch)/t-butylaminoethyl methacrylate/methacrylic acid 2-hydroxypropyl acrylate, and amphoteric ion polymer for example is disclosed among German patent application DE 39 29 973, DE 21 50 557, DE 28 17 369 and the DE 3,708 451.Acrylamido oxypropyl trimethyl ammonium chloride.Acrylic or methacrylic acid copolymer and alkali metal salt thereof and ammonium salt are preferred amphoteric ion polymer.Other amphoteric ion polymer that is fit to is methacryl ethyl betanin/methacrylate copolymer, and its trade mark is called Amersette (AMERCHOL) and hydroxyethyl methylacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid copolymer (Jordapon ).
The polymer that is fit to is non-ionic in addition, contain siloxanes, water solublity or water dispersible polymers, as polyethers first siloxanes, for example Tegopren (Goldschmidt) or Belsil (Wacker).
In addition, biopolymer also is suitable, also promptly by the raw material acquisition of natural reproducible and the polymer of being constructed by natural unibody construction segment, as cellulose derivative, chitin, chitosan, DNA, hyaluronic acid and RNA derivant.
Other compositions of the present invention comprises the chitosan (poly-(D-glucamine)) and/or the chitosan derivatives of at least a other water-soluble polymer, especially different molecular weight.
Anionic polymer
Other polymer that is suitable for the present composition is the copolymer that contains the carboxylic acid group.These copolymers are for containing the polyeletrolyte of the dissociable group of anionic of relatively large quantity on main chain and/or side chain.It can with copolymer A) form PEC (simplexes).
In a preferred embodiment, in the present composition used PEC contain excessive generation anionic/anionic group.
Except that at least a above-mentioned copolymer A), PEC also comprises at least a polymer that contains acidic-group.
PEC preferably with about 50: 1 to 1: 20, especially preferably contain copolymer A with 20: 1 to 1: 5 weight ratio) and contain the polymer of acidic-group.
The carboxy-containing acid group's who is fit to polymer can be by for example α, and the radical polymerization of β-olefin type unsaturated monomer obtains.Herein, used monomer ml) each intramolecularly comprises the α of at least one free redical polymerization, β-olefin type unsaturated double-bond and the anionic and/or anionic group of at least one generation.
The carboxy-containing acid group's who is fit to polymer contains carboxylic acid group's polyurethane in addition.Preferably, described monomer is selected from monoethenoid unsaturated carboxylic acid, sulfonic acid, phosphonic acids and composition thereof.
Monomer m1) comprise have 3 to 25, the undersaturated monocarboxylic acid of monoethenoid and the dicarboxylic acids of preferred 3 to 6 carbon atoms, also can its salt or the form of anhydride use.The example is acrylic acid, methacrylic acid, ethylacrylic acid, α-Lv Daibingxisuan .beta.-methylacrylic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconate, equisetic acid and fumaric acid.Described monomer also comprise have 4 to 10, monoethenoid unsaturated dicarboxylic such as the monoesters of maleic acid, for example monomethyl maleate of preferred 4 to 6 carbon atoms.Described monomer also comprises monoethenoid unsaturated sulfonic acid and phosphonic acids, for example vinyl sulfonic acid, allyl sulphonic acid, acrylic acid sulphur ethyl ester, methacrylic acid sulphur ethyl ester, acrylic acid sulphur propyl ester, methacrylic acid sulphur propyl ester, 2-hydroxyl-3-propenyloxy group propyl sulfonic acid, 2-hydroxy-3-methyl propenyloxy group propyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinyl phosphonate and pi-allyl phosphonic acids.Described monomer also comprises the salt of above-mentioned acid, especially sodium, potassium and ammonium salt, and with the salt of above-mentioned amine.Described monomer can use separately or use with each other mixture.The weight fraction of being given all is the form in acid.
Preferably, monomer m1) is selected from acrylic acid, methacrylic acid, ethylacrylic acid, α-Lv Daibingxisuan .beta.-methylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconate, equisetic acid and its mixture, preferred especially acrylic acid, methacrylic acid and composition thereof.
Above-mentioned monomer m1) can use separately in all cases or use with the form of any mixture.
The comonomer of polymer that is applicable to the preparation carboxy-containing acid group in principle is above-mentioned as copolymer A) the given compound a of component) to d), condition is included in the mole fraction of anionic group of generation in carboxy-containing acid group's the polymer of copolymerization and anionic group greater than the mole fraction that generates cationic group and cation group.
In a preferred embodiment, carboxy-containing acid group's polymer comprises at least a monomer that exists with copolymerized form that is selected from above-mentioned cross-linking agent.
In addition, carboxy-containing acid group's polymer preferably includes at least a monomer m2 that exists with copolymerized form that is selected from following general formula (VI) chemical compound):
Figure A20068001032500611
Wherein
R 1Be hydrogen or C 1-C 8Alkyl,
Y 1Be O, NH or NR 3, and
R 2And R 3Be C independently of one another 1-C 30Alkyl or C 5-C 8Cycloalkyl, wherein alkyl can or contain heteroatomic group at interval by the hetero atom of maximum four the non-conterminous O of being selected from, S and NH.
Preferably, R among the formula VI 1Be hydrogen or C 1-C 4Alkyl, especially hydrogen, methyl or ethyl.Preferably, R among the formula VI 2Be C 1-C 8Alkyl, preferable methyl, ethyl, normal-butyl, isobutyl group, the tert-butyl group or formula-CH 2-CH 2-NH-C (CH 3) 3Group.If R 3Be alkyl, then it is preferably C 1-C 4Alkyl, for example methyl, ethyl, n-pro-pyl, normal-butyl, isobutyl group or the tert-butyl group.
Suitable monomer m2) is (methyl) acrylic acid methyl ester., the ethylacrylic acid methyl ester, (methyl) ethyl acrylate, the ethyl propylene acetoacetic ester, (methyl) tert-butyl acrylate, the ethyl propylene tert-butyl acrylate, (methyl) acrylic acid n-octyl, (methyl) acrylic acid 1,1,3,3-tetramethyl butyl ester, (methyl) EHA, (methyl) acrylic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) acrylic acid n-undecane base ester, (methyl) tridecyl acrylate, (methyl) acrylic acid myristyl ester, (methyl) acrylic acid pentadecyl ester, (methyl) acrylic acid cetyl ester, (methyl) acrylic acid heptadecyl ester, (methyl) acrylic acid nonadecyl ester, (methyl) acrylic acid Semen arachidis hypogaeae alcohol ester, (methyl) acrylic acid docosyl ester, (methyl) acrylic acid lignocerenyl ester, (methyl) acrylic acid ceryl alcohol ester, (methyl) acrylic acid melissin ester, (methyl) acrylic acid Petiolus Trachycarpi grease, (methyl) acrylic acid grease, the inferior grease of (methyl) acrylic acid, (methyl) acrylic acid linaethol, (methyl) stearyl acrylate base ester, (methyl) acrylic acid Lauryl Ester and composition thereof.
Suitable monomer m2) also is acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-(normal-butyl) (methyl) acrylamide, N-(tert-butyl group) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, piperidyl (methyl) acrylamide and morpholinyl (methyl) acrylamide, N-(n-octyl) (methyl) acrylamide, N-(1,1,3, the 3-tetramethyl butyl) (methyl) acrylamide, N-ethylhexyl (methyl) acrylamide, N-(n-nonyl) (methyl) acrylamide, N-(positive decyl) (methyl) acrylamide, N-(n-undecane base) (methyl) acrylamide, N-(tridecyl) (methyl) acrylamide, N-myristyl (methyl) acrylamide, N-pentadecyl (methyl) acrylamide, N-palmityl (methyl) acrylamide, N-heptadecyl (methyl) acrylamide, N-nonadecyl (methyl) acrylamide, N-larane base (methyl) acrylamide, N-docosyl (methyl) acrylamide, N-lignocerenyl (methyl) acrylamide, N-cerul (methyl) acrylamide, N-melissin base (methyl) acrylamide, N-Petiolus Trachycarpi oil base (methyl) acrylamide, N-oil base (methyl) acrylamide, inferior oil base (methyl) acrylamide of N-, N-Caulis et Folium Lini base (methyl) acrylamide, N-stearyl (methyl) acrylamide and N-lauryl (methyl) acrylamide.
In addition, carboxy-containing acid group's polymer preferably comprises at least a monomer m3 that is selected from the copolymerized form of following general formula VII chemical compound):
Wherein
The order of alkylene oxide unit is arbitrarily,
K and I are 0 to 1000 integer independently of one another, and wherein K and I sum are at least 5,
R 4Be H, C 1-C 30Alkyl or C 5-C 8Cycloalkyl,
R 5Be H or C 1-C 8Alkyl,
Y 2Be O or NR 6, R wherein 6Be H, C 1-C 30Alkyl or C 5-C 8Cycloalkyl.
Preferably, k is 1 to 500 integer among the formula VII, especially is 3 to 250.I is preferably 0 to 100 integer.R 5Be preferably H, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl or n-hexyl, especially H, methyl or ethyl.R among the formula VII 4Be preferably H, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, n-pentyl, n-hexyl, octyl group, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl.Y among the formula VII 2Be preferably O or NH.
Suitable polyether acrylate VII) is for example above-mentioned α, the condensation polymer of β-olefin type unsaturated monocarboxylic and/or dicarboxylic acids and chloroacid, amide and anhydride and Aethoxy Sklerol.Suitable Aethoxy Sklerol can be at an easy rate by oxirane, 1,2 epoxy prapane and/or chloropropylene oxide and a kind of trigger molecule such as water or short chain alcohol R 4-OH reaction makes.Alkylene oxide can use separately, use in succession or use with mixture.Polyether acrylate VII) when being used to prepare polymer of the present invention, can use separately or use with mixture.Suitable polyether acrylate II) has carbamate (methyl) acrylate of alkylene oxide group in addition.This compounds is described in DE 198 38 851 (component e2)), its full content is included this description in by the mode of quoting as proof.
Preferably the anionic polymer of carboxy-containing acid group's polymer is, for example, and the homopolymer of acrylic acid and methacrylic acid and salt thereof and copolymer.It also comprises acrylic acid cross linked polymer, is called the material of carbomer as the INCI name.The commercially available acquisition of acrylic acid this cross-linked homopolymer, for example the commodity Carbopol of Noveon The cross-linked polyacrylate polymer of also preferred hydrophobically modified, for example the commodity Carbopol of Noveon Ultrez.
The example of the anionic polymer that other is fit to is the copolymer of acrylic acid and acrylamide and salt thereof, the sodium salt of polyhydroxycarboxyliacid acid, the polyester of water solublity or water dispersible, polyurethane and polyureas.Particularly suitable polymer is the copolymer of (methyl) acrylic acid and polyether acrylate, and wherein polyether chain is with C 8-C 30Alkyl is a terminal.It comprises, acrylate/behenyl alcohol polyethers-25 methacrylate copolymer for example, and it can trade (brand) name Aculyn Obtain by Rohm und Haas.Particularly suitable polymer also has the copolymer of tert-butyl acrylate, ethyl acrylate, methacrylic acid (as Luvimer 100P, Luvimer Pro55); The copolymer of ethyl acrylate and methacrylic acid is (as Luvimer MAE); N tert butyl acrylamide, ethyl acrylate, acrylic acid copolymer (Ultrahold 8, Ultrahold Strong); If the copolymer of vinyl acetate .beta.-methylacrylic acid and suitable other vinyl acetate (Luviset for example Grade products); If copolymer-maleic anhydride is suitable and alcohol, anionic polysiloxanes such as carboxylic functional polysiloxanes, tert-butyl acrylate, metering system acid reaction (Luviskol for example VBM); The C of acrylic acid and methacrylic acid and hydrophobic monomer such as methacrylic acid 4-C 30Arrcostab, C 4-C 30Alkyl vinyl ester, C 4-C 30Alkyl vinyl ether and hyaluronic copolymer.The example of anionic polymer also has vinyl acetate/.beta.-methylacrylic acid copolymer, as commercially available commodity Resyn (National Starch) and Gafset (GAF), and vinyl pyrrolidone/vinyl acrylate copolymer, as commercially available commodity Luviflex (BASF).Other polymer that is fit to is trade mark Luviflex by name The vinyl pyrrolidone of VBM-35 (BASF)/acrylate trimer and contain the polyamide of sodium sulfonate or contain the polyester of sodium sulfonate.
In addition, the anionic polymer that is fit to comprises, for example Balance CR (NationalStarch; Acrylate copolymer), Balance 0/55 (National Starch; Acrylate copolymer), Balance 47 (National Starch; Octyl acrylamide/acrylate/metering system acid butyl amino ethyl ester copolymer), Aquaflex FX 64 (ISP; Isobutene ./ethyl maleimide/ethoxy maleimide copolymer), Aquaflex SF-40 (ISP/National Starch; VP/ caprolactam/DMAPA acrylate copolymer), Allianz LT-120 (ISP/Rohm ﹠amp; Haas; Acrylate/C1-2 succinate/hydroxy acrylate copolymer), Aquarez HS (Eastman; Polyester-1), Diaformer Z-400 (Clariant; Methacryl ethyl betanin/methacrylate copolymer), Diaformer Z-711 (Clariant; Methacryloyl ethyl n-oxide/methacrylate copolymer), Diaformer Z-712 (Clariant; Methacryloyl ethyl n-oxide/methacrylate copolymer), Omnirez 2000 (ISP; The mono ethyl ester of poly-(methyl vinyl ether/maleic acid) in the ethanol), Amphomer HC (National Starch; Acrylate/octyl acrylamide copolymer), Amphomer 28-4910 (National Starch; Octyl acrylamide/acrylate/metering system acid butyl amino ethyl ester copolymer), Advantage HC 37 (ISP; The trimer of caprolactam/vinyl pyrrolidone/dimethylaminoethyl methacrylate), Advantage LC55 and LC80 or LCA and LCE, Advantage Plus (ISP; VA/ maleic acid butyl ester/isobornyl acrylate copolymer), Aculyne 258 (Rohm ﹠amp; Haas; Acrylate/hydroxy ester acrylate copolymer), Luviset P.U.R. (BASF, polyurethane-1), Luviflex Silk (BASF), Eastman AQ 48 (Eastman), Styleze CC-10 (ISP; The VP/DMAPA acrylate copolymer), Styleze 2000 (ISP; VP/ acrylate/methacrylic acid Lauryl Ester copolymer), DynamX (National Starch; Polyurethane-14 AMP-acrylate copolymer), Resyn XP (National Starch; Acrylate/octyl acrylamide copolymer), Fixomer A-30 (Ondeo Nalco; Polymethylacrylic acid (with) the acrylamide group methyl propane sulfonic acid), Fixate G-100 (Noveon; AMP-acrylate/allyl methacrylate copolymer).
The carboxy-containing acid group's who is fit to polymer is described in US 3,405 in addition, the vinyl pyrrolidone in 084, (methyl) acrylic acid C 1-C 10Arrcostab, cycloalkyl ester and aryl ester and acrylic acid trimer.The carboxy-containing acid group's who is fit to polymer is described in vinyl pyrrolidone, (methyl) acrylic acid tertiary butyl ester and (methyl) the acrylic acid trimer among EP-A-0 257 444 and the EP-A-0480 280 in addition.The carboxy-containing acid group's who is fit to polymer is described in addition and comprises the copolymer of at least a (methyl) acrylate, (methyl) acrylic acid and N-vinyl pyrrolidone and/or N-caprolactam with copolymerized form among the DE-A-42 23 066.The full content of these documents is included this description at this in by the mode of quoting as proof.
Above-mentioned carboxy-containing acid group's polymer prepares by known method, for example by polymerisation in solution, sedimentation polymerization, suspension polymerization or emulsion polymerisation, as above-mentioned copolymer A) as described in the part.
The carboxy-containing acid group's who is fit to polymer also has carboxy-containing acid group's polyurethane.
Disclose among the EP-A-636361 and contained band hydroxy-acid group and/or the polysiloxane block of sulfonic acid group and the suitable block copolymer of polyurethane/polyurea block.The polyurethane that contains silicone that is fit to also is recorded among WO 97,/25 021 and the EP-A-751 162.
Suitable polyurethane also is described in DE-A-42 25 045, and its full content is included this description at this in by the mode of quoting as proof.
The acidic-group of carboxy-containing acid group's polymer can partly or entirely be neutralized.Then some acidic-group exists to remove protonated form at least, and anti-charge ion is preferably from alkali metal ion such as Na +, K +, ammonium ion, or its organic derivative etc.
Propellant (propellant gas)
If compositions of the present invention will then need propellant as the aeroge spray.Suitable propellant (propellant gas) is conventional propellant, for example n-propane, different propane, normal butane, iso-butane, 2,2-dimethylbutane, pentane, isopentane, dimethyl ether, Difluoroethane, fluoro trichloromethane, dichlorodifluoromethane or dichlorotetra-fluoroethane, HFC 152 A or its mixture.Main use hydro carbons, especially propane, normal butane, pentane or its mixture, and dimethyl ether and Difluoroethane.If suitable, in propellant mixture, can use one or more specified chlorohydrocarbons jointly, but can only use slightly, for example be up to 20 weight % based on the propellant mixture meter.
Cosmetic hair preparation of the present invention also is suitable for pump formula spray agent and need not to add propellant, and for example nitrogen, compressed air or carbon dioxide are used as the aeroge spray as propellant also can to use conventional Compressed Gas.
Surfactant
Compositions of the present invention also can comprise surfactant.Spendable surfactant has anion, cation, nonionic and/or amphoteric surfactant.
The favourable anion surfactant that is used for the object of the invention is
Acylamino acid and salt thereof, for example
-acyl glutamate, especially acyl glutamic acid sodium,
-sarcosinate, for example myristoyl-N-methylaminoacetic acid, TEA Hamposyl L salt, sodium lauroyl sarcosine and cocos nucifera oil acylsarcosine sodium,
Sulfonic acid and salt thereof, for example
-acyl-hydroxyethyl sulfonate, for example cocoyl sodium isethionate (sodium cocoylisethionate) or Ammonium cocoyl isethionate,
-sulfosuccinate, for example dioctyl sodium sulphosuccinate, laureth disodium sulfosuccinate, lauryl disodium sulfosuccinate, endecatylene amide MEA disodium sulfosuccinate, PEG-5 lauryl citrate disodium sulfosuccinate and derivant thereof
And sulfuric ester, for example
-alkyl ether sulfate, the laureth sulfate of sodium, ammonium, magnesium, MI PA, TIPA for example, myristyl alcohol polyethers sodium sulfate (sodium myreth sulfate) and C 12-13Alkanol polyethers sodium sulfate (sodium C 12-13Pareth sulfate),
-alkyl sulfate, for example lauryl sulfate of sodium, ammonium and TEA.
Other favourable anion surfactant is
-aurate, for example lauroyl sodium aurate and methyl cocoyl sodium aurate,
-ether carboxylic acid, for example laureth-13 carboxylic acid sodium and PEG-6 coconut oleoyl amine carboxylic acid sodium, PEG-7 olive oil carboxylic acid sodium
-phosphate ester and salt, for example oleth-10 p hydroxycinnamic acid alite and two lauryl alcohol polyethers-4 phosphate esters,
-alkylsulfonate, for example coconut oil monoglyceride sodium sulfate, C 12-14Alkene sodium sulfonate, lauryl sulfoacetate sodium and PEG-3 coconut oleoyl amine magnesium sulfate,
-acyl glutamate, palmityl aspartic acid two-TEA salt and octyl group/decyl sodium glutamate for example,
-acyl group peptide, for example palmityl lactoalbumin hydrolysate, cocoyl hydrolyzed soybean protein sodium salt and cocoyl hydrolytic collagen matter sodium/potassium salt,
And carboxylic acid and derivant thereof, for example
Lauric acid, sodium stearate, alkanoic acid magnesium (magnesium alkanolate) and Zinc Undecenoate, carboxylate, for example CSL, laureth-6 citrate and PEG-4 lauramide carboxylic acid sodium,
-alkylaryl sulfonates.
The favourable cationic surfactant that is used for the object of the invention is the quaternary ammonium type surfactant.The quaternary ammonium type surfactant comprises the N atom of at least one and 4 alkyl or aryl covalent bonds.For example alkyl betaine, alkylamide propyl-betaine and alkylamide propyl hydroxyl sulfo betaine are favourable.
Other favourable cationic surfactant that is used for the object of the invention also has
-alkylamine,
-alkyl imidazole and
-ethoxylated amine,
Reach especially its salt.
The favourable amphoteric surfactant that is used for the object of the invention is acyl group/dialkyl group ethylene diamine, for example acyl group both sexes sodium acetate, acyl group both sexes disodium beclomethasone, alkyl both sexes oxalic acid disodium, acyl group both sexes hydroxypropyl sodium sulfonate, acyl group both sexes oxalic acid disodium, acyl group both sexes sodium propionate and N-coconut fatty acid amido-ethyl-N-ethoxy glyceric acid sodium salt.
Other favourable amphoteric surfactant is the N-alkyl amino acid, for example aminocarbonyl propyl alkyl glutamine, alkyl aminopropionic acid, alkylimide dipropionic acid and lauryl both sexes carboxylic acid glycinate.
The favourable active nonionic surfactant that is used for the object of the invention is
-alkanolamide, coconut oleoyl amine MEA/DEA/MIPA for example,
-usefulness oxirane, glycerol, sorbitan or the formed ester of other pure esterification carboxylic acid,
-ether, for example ethoxylated alcohol, ethoxylation lanoline, ethoxylation polysiloxanes, propoxylation POE ether, alkyl polyglycoside---for example Laurel glycosides, the last of the ten Heavenly stems, glycosides and cocos nucifera oil glucoside, HLB value were at least 20 glucosides (as Belsil SPG 128V (Wacker)).
Other favourable non-ionic surface active agent is the alkohol and amine oxide, for example cocamidopropyl propylamine oxide.
In alkyl ether sulfate, especially be preferably based on the sodium alkylether sulphate of diethoxyization or triethoxy lauryl alcohol and myristyl alcohol.It obviously is being better than alkyl sulfate aspect sensitivity, thickening properties, low-temperature solubility and especially skin and the mucosa adaptability of the water hardness.Lauryl ether sulfate is compared with the myristyl ether sulfate has better foam performance, but is being inferior to it aspect the gentle degree.
The average higher especially relatively alkyl ether carboxy acid salt of gentle degree in fact belongs to the gentleest surfactant, but demonstrates relatively poor foaminess and viscosity.It often is used in combination with alkyl ether sulfate and amphoteric surfactant.
The esters of 2-Sulfosuccinic acid (sulfosuccinate) is gentle and surfactant that be easy to foam, but because it is difficult to by thickening, can only preferably use with other anion surfactant and amphoteric surfactant, and, only be preferred for the product of neutrality or comfort cushioning because it is low water-disintegrable.
Amido propyl betaine has excellent skin and eyes mucosa adaptability.When being used in combination with anion surfactant, its mildness can obtain collaborative the improvement.The preferred cocamidopropyl betaine of using.
Both sexes acetate/both sexes diacetin has extraordinary skin and mucosa adaptability as amphoteric surfactant and can have regulating effect and the nursing efficacy of raising additive.It is used to optimize the alkyl ether sulfate preparation in the mode similar to betanin.The most preferred cocos nucifera oil both sexes sodium acetate and cocos nucifera oil both sexes oxalic acid disodium.
The alkyl polyglycoside gentleness has good universality, but foam performance is relatively poor.Given this, preferably it is used in combination with anion surfactant.
Polysorbate
In addition, according to the present invention, can advantageously in compositions, add Polysorbate reagent.
The Polysorbate that can be advantageously used in the object of the invention is
-polyoxyethylene (20) sorbitan monolaurate (Tween 20, CAS No.9005-64-5)
-polyoxyethylene (4) sorbitan monolaurate (Tween 21, CAS No.9005-64-5)
-polyoxyethylene (4) sorbitan monostearate (Tween 61, CAS No.9005-67-8)
-polyoxyethylene (20) sorbitan tristearate (Tween 65, CAS No.9005-71-4)
-polyoxyethylene (20) sorbitan monoleate (Tween 80, CAS No.9005-65-6)
-polyoxyethylene (5) sorbitan monoleate (Tween 81, CAS No.9005-65-5)
-polyoxyethylene (20) sorbitan trioleate (Tween 85, CAS No.9005-70-3).
Particularly advantageously be, especially
-polyoxyethylene (20) sorbitan monopalmitate (Tween 40, CAS No.9005-66-7)
-polyoxyethylene (20) sorbitan monostearate (Tween 60, CAS No.9005-67-8).
According to the present invention, it advantageously uses separately or uses with the form of mixtures of two or more Polysorbate with the concentration of 0.1 to 5 weight %, especially 1.5 to 2.5 weight %, and described concentration is based on total restatement of compositions.
In one embodiment of the present invention, compositions of the present invention comprise copolymer a) and comprise under the various situations based on its amount of compositions meter be lower than 1 weight %, preferably be lower than the oligomer b of 0.1 weight %) and especially do not contain oligomer b).
Containing copolymer cosmetic composition of the present invention a) can be advantageously used in from skin surface and remove excessive oil or lipid.Especially, these compositionss comprise based on the compositions meter be lower than 1 weight %, preferably be lower than the oligomer b of 0.1 weight %), particularly do not contain oligomer b).
The imitative product that shines
The imitative normally O/W type emulsion of product of shining of the commercialization of standard.In this class material, water is stable by emulsifying agent commonly used in the cosmetics.Required pass through that carbomer carries out further stable is disadvantageous.Itself and imitative solarization agent especially cause the destruction of change of preparation yellow skin and abnormal smells from the patient owing to chemical reaction with the common use of dihydroxy acetone (DHA).A kind of alternative articles for use of carbomer are xanthan gum.Although what it provided is stable product, often have to be received in the uncomfortable sticking sense on the skin.
Compositions of the present invention can exist and use in a variety of forms.Thereby it can be, for example oil-in-water (O/W) type emulsion or complex emulsions, for example W/O/W (W/O/W) type.The preparation that does not contain emulsifying agent, for example aqueous dispersion, hydrogel or Pickering emulsion also are favourable embodiment.
The denseness of preparation can be from unguentum to flowable preparation until low viscous sprayable product.Therefore can be made into Emulsion, lotion or spray.During use, cosmetic composition of the present invention is applied on the skin with cosmetics and skin product mode capacity ground commonly used.
Not only the uniform colour of skin can be obtained by using, and the color that presents the local skin of the different colours of skin owing to natural cause or pathological change can be changed.
The imitative solarization agent that the present invention advantageously uses is, especially glyceraldehyde, hydroxypropanone-aldehyde, γ-dialdehyde, Erythrulose, 5-hydroxyl-1,4-naphthoquinone (juglone) and be present in 2-hydroxyl-1 in the lawsonia, the 4-naphthoquinone.
When being used for the object of the invention, preferred extremely especially 1,3-dihydroxy acetone (DHA)---a kind of intravital trivalent sugar of people that is present in.6-oxo-D-fructose and 1,2,3-indantrione monohydrate also can be used as imitative solarization agent of the present invention.When being used for purpose of the present invention, imitatively shining agent and also can be understood that to make skin to have the material of the color beyond the brown shade.
In a kind of preferred embodiment of the present invention, comprise two or more imitative materials that shines with the concentration of 0.1 to 10 weight %, preferred especially 0.5 to 6 weight % in these compositionss, various situations are all based on total restatement of compositions.
Preferably, these compositionss comprise 1, and the 3-dihydroxy acetone is as imitative solarization agent.More preferably contain organic and/or inorganic photoprotection filtering agent in the compositions.Also can comprise inorganic and/or organic and/or improved inorganic pigment in the said composition.
Also can be present in the conventional component in the present composition and favourable component sees above and DE 10321147, the [0024] to [0132] section.
The invention still further relates to said composition and be used to change the skin of multi-cell organism---especially human and animal's skin---cosmetic use of color, especially also be used to make the color even in the different zone of skin color.
With another advantage of the preparation of W/W emulsion polymer thickening is that the wetting agent with high score rate for example O/W and the W/O/W emulsion of glycerol can stably be provided.
Another advantage of using the W/W emulsion polymer to improve the rheological property of cosmetics or skin-use preparation is and can obtains thickening effect in the pH value scope of from 4 to 11, especially from 6 to 10 broad.Compare with the commercial thickening agent of standard, can make viscosity obtain successive increase, and the commercial thickening agent of standard in most of the cases can only make viscosity change with relatively large degree step evolution ground.Thereby can more easily form viscosity more suitable for for example body lotion or lotion.
Following examples will be carried out the example explanation to the present invention, but be not limited to this.
Embodiment
The K value of polymer is according to H.Fikentscher, the Cellulose-Chemie[cellulose chemistry], the 13rd volume, 58-64 page or leaf and 71-74 page or leaf (1932) are determined when its concentration is 0.1 weight % in 25 ℃, the sodium-chloride water solution of 3 weight % concentration.
The temperature that each leisure of the viscosity of dispersion has in the Brookfield viscometer of No. 4 spindles 20rpm and 20 ℃ records.Unless point out in addition, data are represented with weight %.
The group of using used as stabilizers in an embodiment a) and b) polymer have following composition:
Stabilizing agent 1: molecular weight M NBe 6000 the graft polymers of vinyl acetate on Polyethylene Glycol, polymer concentration 20%
Stabilizing agent 2: the vinyl methyl ether that exists with the free carboxyl group form of hydrolysis and the copolymer of maleic acid, polymer concentration 35%
Stabilizing agent 3: molal weight M WBe 1500 the methacrylic acid methyl macrogol ester and the copolymer of methacrylic acid, polymer concentration 40%
Stabilizing agent 4: molecular weight M NIt is 600 polypropylene glycol
Stabilizing agent 5: molecular weight M NIt is 900 polypropylene glycol
Stabilizing agent 6: molecular weight M NBe 1000 and at one end by the polypropylene glycol of a methyl blocking
Stabilizing agent 7: molecular weight M NIt is the block copolymer of 1000 poly alkylene glycol
Stabilizing agent 8: maltodextrin (C-PUR01910,100% concentration)
Stabilizing agent 9: molecular weight M NBe 2000 and at one end by the polypropylene glycol of a methyl blocking
Stabilizing agent 10: molecular weight M NBe the quaternised acrylamide of 500-6000 and the copolymer of DMAEMA
Stabilizing agent 11: mol ratio is 80: 20 the methacrylic acid and the copolymer of acrylamide group methyl propane sulfonic acid
Stabilizing agent 12: mol ratio is 70: 30 the methacrylic acid and the copolymer of acrylamide group methyl propane sulfonic acid
Stabilizing agent 13: mol ratio is 60: 40 the methacrylic acid and the copolymer of acrylamide group methyl propane sulfonic acid
Stabilizing agent 14:Pluronic PE 4300: the oxirane of general formula (I) (on seeing) and the block copolymer of expoxy propane, wherein the quality of polypropylene glycol block is about 1100g/mol, and in each block copolymer the about 30 weight % of the amount of Polyethylene Glycol
Stabilizing agent 15:Pluronic PE 6200: the oxirane of general formula (I) (on seeing) and the block copolymer of expoxy propane, wherein the quality of polypropylene glycol block is about 1750g/mol, and in each block copolymer the about 20 weight % of the amount of Polyethylene Glycol
The copolymer of the acrylamide of stabilizing agent 16:50 mole % and the acrylic acid dimethylamino ethyl ester methochloride of 50 moles of %, the K value is 82.6
The acrylamide of stabilizing agent 17:50 mole %, the acrylic acid dimethylamino ethyl ester methochloride of 45 moles of % and acrylic acid copolymer of 5 moles of %, the K value is 45.1
The acrylamide of stabilizing agent 18:60 mole %, the acrylic acid dimethylamino ethyl ester methochloride of 38 moles of % and acrylic acid copolymer of 2 moles of %, the K value is 78.0.
In an embodiment, used following polymerization initiator:
Azostarter VA-044 : 2,2 '-azo two (N, N '-dimethylene isobutyl amidine) dihydrochloride
Azostarter V-70 : 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile)
Azostarter V-65 : 2,2 '-azo two (2, the 4-methyl pentane nitrile)
Embodiment 1
The 250ml capacity have a Teflon agitator and an a kind of four-necked bottle that is used for the equipment (a device for working under nitrogen) of under nitrogen, working, under the situation that feeds nitrogen, will
90.0g stabilizing agent 1,
51.4g stabilizing agent 2 Hes
28.6g complete demineralized water
At first add and stir with the speed of 300rpm.In 5 to 10min process, in this solution, drip 30g acrylic acid,, add 0.03g 2,2 '-azo two (N, N '-dimethylene isobutyl amidine) dihydrochloride (Azostarter VA-044 mixture heated to 50 ℃ ) and make mixture at 50 ℃ of polymerization 5h.Then reactant mixture is used 0.05g Azostarter VA-044 Handle and carry out post polymerization 1h at 60 ℃.Generate solid content thus and be 33% aqueous dispersion.Its pH is 4, and viscosity is 5950mPas.The K value of polymer is 120.7.By in dispersion, adding entry, make the aqueous solution of 2% concentration, this aqueous solution is that 7 o'clock viscosity is 2640mPas at pH.
The particle size distribution of discrete particles is 3 to 8 μ m in the polymeric dispersions.
Embodiment 2
In embodiment 1 described equipment, will
90.0g stabilizing agent 1,
51.4g stabilizing agent 2 Hes
28.6g complete demineralized water
At first add, and the speed with 300rpm stirs under the situation that feeds nitrogen.In 5 to 10min process, in this solution, drip the mixture of 30g acrylic acid and 0.09g triallyl amine crosslinker, and the gained mixture is heated to 40 ℃ in 5 to 10min process.Then add 0.03g 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile) (Azostarter V-70 ) and make mixture at 40 ℃ of polymerization 5h.Then, add 0.05g Azostarter V-70 And this dispersion is heated to 50 ℃ carries out the 1h post polymerization.Generate the aqueous dispersion that viscosity is 2700mPas thus.Its pH is 4.By adding entry in hydrotropism's dispersion, make the aqueous solution of 2% concentration.This aqueous solution is that 7 o'clock viscosity is 39000mPas at pH.The particle size distribution of discrete particles is 5 to 60 μ m in the polymeric dispersions.
Embodiment 3
Repeat embodiment 2, difference is to add at first in polymerization unit
12g stabilizing agent 4,
51.4g stabilizing agent 2 Hes
106.6g complete demineralized water and do not use triallylamine.The aqueous emulsion that to be created on pH value thus and to be 4 o'clock viscosity be 2240mPas.
Embodiment 4
In the equipment that embodiment 1 is given, at first add
1.5g stabilizing agent 5,
16.5g stabilizing agent 4
18.0g stabilizing agent 8 Hes
104.0g complete demineralized water,
With mixture continuous stirring under 300rpm, and in 5 to 10min process, add 30g acrylic acid continuously.Hydrochloric acid by adding 30g 32% concentration adjusts to 3 with the pH value of reactant mixture from 4.5, and this emulsion is heated to 50 ℃ temperature.Add 0.03g AzostarterVA-044 After make emulsion at 50 ℃ of polymerization 5h, then add 0.05g Azostarter VA-044 and make this mixture at 50 ℃ of post polymerization 1h again.Generate the aqueous dispersion that viscosity is 208mPas thus.
Embodiment 5
Repeat embodiment 1, difference is at first to add in polymerization unit
45g stabilizing agent 3,
51.4g stabilizing agent 2 Hes
73.6g the mixture of complete demineralized water.Generate the aqueous emulsion that viscosity is 3650mPas thus.The particle size distribution of discrete particles is 3 to 10 μ m in the polymeric dispersions.
Embodiment 6
In the equipment that embodiment 1 is given, will
90.0g stabilizing agent 1,
51.4g stabilizing agent 2 Hes
28.6g complete demineralized water
At first add, and the speed with 300rpm stirs under the situation that feeds nitrogen.In 5 to 10min process, in this solution, drip the mixture of 30g acrylic acid and 0.22g pentaerythritol triallyl ether (70% concentration) cross-linking agent, and this mixture is heated to 40 ℃ in 5 to 10min process.Then add 0.03g Azostarter V-70 And make mixture at 40 ℃ of polymerization 5h.Then, add 0.05g Azostarter VA-044 And this dispersion is heated to 50 ℃ carries out the 1h post polymerization.Generate the aqueous dispersion that viscosity is 2900mPas thus.By adding entry and adjusting its pH value is 7, makes viscosity and for 10000mPas concentration be 2% aqueous solution.The particle size distribution of discrete particles is 5 to 70 μ m in the polymeric dispersions.
Embodiment 7
The 250ml capacity have a Teflon agitator and an a kind of four-necked bottle that is used for the equipment of under nitrogen, working, under the situation that feeds nitrogen, will
90.0g stabilizing agent 1,
18.0g stabilizing agent 8 Hes
62.0g complete demineralized water
At first add and stir with the speed of 200rpm.In 5 to 10min process, in this solution, drip 30g acrylic acid,, add 0.03g Azostarter VA-044 mixture heated to 50 ℃ And make mixture at 50 ℃ of polymerization 5h.Then reactant mixture is used 0.05gAzostarter VA-044 Handle and carry out post polymerization 1h at 60 ℃.Generate solid content thus and be 33% aqueous dispersion.Its pH is 2, and viscosity is 10500mPas.Make the solution of 2% concentration by adding water, aqueous solution is that 7 o'clock viscosity is 2000mPas at pH.The particle size distribution of discrete particles is 5 to 40 μ m in the polymeric dispersions.
Embodiment 8
In embodiment 1 described equipment, will
90.0g stabilizing agent 1,
51.4g stabilizing agent 2 Hes
28.6g complete demineralized water
At first add, and the speed with 300rpm stirs under the situation that feeds nitrogen.In 5 to 10min process, in this solution, drip the mixture of 30g acrylic acid and 0.09g triallyl amine crosslinker, and this emulsion is heated to 50 ℃ in 5 to 10min process.Then add 0.03gAzostarter V-65 And make mixture at 50 ℃ of polymerization 5h.Then, add 0.05gAzostarter VA-044 And this dispersion is heated to 60 ℃ carries out the 1h post polymerization.Generate the aqueous dispersion that viscosity is 3700mPas thus.Its pH is 4.By adding entry in hydrotropism's dispersion, make the aqueous solution of 2% concentration.This aqueous solution is that 7 o'clock viscosity is 29000mPas at pH.The particle size distribution of discrete particles is 5 to 30 μ m in the polymeric dispersions.
Embodiment 9
In embodiment 1 described equipment, will
90.0g stabilizing agent 1,
45.7g stabilizing agent 2 Hes
34.3g complete demineralized water
At first add, and the speed with 300rpm stirs under feeding nitrogen situation.In the 5th to 10min process, in this solution, drip the mixture of 30g acrylic acid and 0.09g triallyl amine crosslinker, and the gained mixture is heated to 40 ℃ in 5 to 10min process.Then add 0.03g Azostarter V-70 And make mixture at 40 ℃ of polymerization 5h.Then, add 0.05g Azostarter VA-044 And this dispersion is heated to 50 ℃ carries out the 1h post polymerization.Generate the aqueous dispersion that viscosity is 2300mPas thus.By adding entry and adjusting its pH to 7, making viscosity is the aqueous solution of 2% concentration of 32000mPas.
Embodiment 10
In embodiment 1 described equipment, will
18.0g stabilizing agent 9,
18.0g stabilizing agent 8 Hes
90.0g complete demineralized water
At first add, under the situation that feeds nitrogen,, and in 5 to 10min process, add 30g acrylic acid continuously this mixture continuous stirring under 300rpm.Hydrochloric acid by adding 30g 32% concentration adjusts to 3 with the pH value of reactant mixture from 4.5, and this emulsion is heated to 50 ℃ temperature.Add 0.03g Azostarter VA-044 After make emulsion at 50 ℃ of polymerization 5h, then add 0.05g Azostarter VA-044 Make this mixture at 50 ℃ of repolymerization 1h.Generate the aqueous dispersion that viscosity is 320mPas thus.
Embodiment 11
In embodiment 1 described equipment, will
63.0g stabilizing agent 7,
9.0g stabilizing agent 8
400g water and
45g acrylic acid
At first add, and the speed with 100rpm stirs under the situation that feeds nitrogen.In this solution, add 0.45g sodium peroxydisulfate and 14.4g water, make initial polymerization carry out 15min at 25 ℃.Then, in 25 ℃ of processes, add 135g acrylic acid and 27g stabilizing agent 8 at 2h.Simultaneously, in the process of 7h, add the 0.18g ascorbic acid.Then with this mixture post polymerization 1h again.Generating viscosity thus is that 800mPas, pH value are 1.5 aqueous dispersion.To make pH be that 7 concentration is 2% dispersion by adding water and sodium hydroxide solution.This dispersion viscosity is 5000mPas.
Embodiment 12
The 2L capacity have a Teflon agitator and an a kind of four-necked bottle that is used for the equipment of under nitrogen, working, feeding under the nitrogen situation, will
257.0g stabilizing agent 1,
449.0g stabilizing agent 2 Hes
102.5g deionized water
At first add and feeding under the nitrogen situation, under 200rpm speed, stirring 10min.In the process of 10min, in this solution, drip 60g acrylic acid, reactant mixture is heated to 60 ℃ and add the solution of the trimethylene propane triacrylate of 90g acrylic acid and 1.5g ethoxylation in the process of 3.5h.When adding acrylic acid/trimethylolpropane triacrylate solution, the interpolation that began four hours is dissolved in the 0.15g Azostarter VA-044 in the 40g water The process of solution.After the interpolation process finishes, with mixture at 60 ℃ of restir 30min.At last, add 0.225g VA-044 again Make polymerization process proceed 1h at 60 ℃.Behind the cool to room temperature, obtaining polymer content is that 15 weight %, viscosity are that 5350mPa*s and pH value are 4.5 aqueous dispersion.Add suitable quantity of water and sodium hydroxide solution, make solid content and be 2 weight %, pH value and be 7, viscosity is the dispersion of 10900mPa*s.
Embodiment 13
In embodiment 12 described equipment, under the situation that feeds nitrogen, will
257.0g stabilizing agent 1,
449.0g stabilizing agent 2 Hes
102.5g deionized water
At first add, and under the situation that feeds nitrogen, mixture is stirred 10min under 200rpm speed.In the process of 10min, in this solution, drip 60g acrylic acid and 0.015gVA-044 , reactant mixture is heated to 60 ℃ and add the trimethylolpropane triacrylate solution of 90g acrylic acid and 1.5g ethoxylation in the process of 3.5h.When adding acrylic acid/trimethylene propane triacrylate solution, the interpolation that began four hours is dissolved in the 0.135g Azostarter VA-044 in the 40g water The process of solution.After the interpolation process finishes, with mixture at 60 ℃ of restir 30min.At last, add 0.225gVA-044 again Make polymerization process proceed 1h at 60 ℃.Behind the cool to room temperature, obtaining polymer content is that 15 weight %, viscosity are that 5550mPa*s and pH value are 4.5 aqueous dispersion.Add suitable quantity of water and sodium hydroxide solution, make solid content and be 2 weight %, pH value and be 7, viscosity is the dispersion of 10300mPa*s.
Embodiment 14
In embodiment 12 described equipment, under the situation that feeds nitrogen, will
257.0g stabilizing agent 1,
449.0g stabilizing agent 2 Hes
102.5g deionized water
At first add, and under the situation that feeds nitrogen, mixture is stirred 10min under 200rpm speed.In the process of 10min, in this solution, drip 60g acrylic acid and 0.015gVA-044 , reactant mixture is heated to 60 ℃ and add the solution of 90g acrylic acid and 1.5g triallylamine in the process of 3.5h.When adding acrylic acid/triallyl amine aqueous solution, the interpolation that began four hours is dissolved in the 0.135g AzostarterVA-044 in the 40g water The process of solution.After the interpolation process finishes, with mixture at 60 ℃ of restir 30min.At last, add 0.225g VA-044 again Make polymerization process proceed 1h at 60 ℃.Behind the cool to room temperature, obtaining polymer content is that 15 weight %, viscosity are that 10250mPa*s and pH value are 4.5 aqueous dispersion.Add suitable quantity of water and sodium hydroxide solution, make solid content and be 2 weight %, pH value and be 7, viscosity is the dispersion of 28500mPa*s.
Embodiment 15
In embodiment 12 described equipment, under the situation that feeds nitrogen, will
257.0g stabilizing agent 1,
449.0g stabilizing agent 2 Hes
102.5g deionized water
At first add, and under the situation that feeds nitrogen, mixture is stirred 10min under 200rpm speed.In the process of 10min, in this solution, drip 60g acrylic acid and 0.015gVA-044 , reactant mixture is heated to 60 ℃ and add the solution of 75g acrylic acid, 15g methyl methacrylate and 1.5g triallylamine in the process of 3.5h.When adding acrylic acid/triallyl amine aqueous solution, the interpolation that began four hours is dissolved in the 0.135g Azostarter VA-044 in the 40g water The process of solution.After the interpolation process finishes, with mixture at 60 ℃ of restir 30min.At last, add 0.225g VA-044 again Make polymerization process proceed 1h again at 60 ℃.Behind the cool to room temperature, obtaining polymer content is that 15 weight %, viscosity are that 5800mPa*s and pH value are 4.5 aqueous dispersion.Add suitable quantity of water and sodium hydroxide solution, make solid content and be 2 weight %, pH value and be 7, viscosity is the dispersion of 17500mPa*s.
Embodiment 16
In embodiment 12 described equipment, under the situation that feeds nitrogen, will
257.0g stabilizing agent 1,
449.0g stabilizing agent 2 Hes
102.5g deionized water
At first add, and under the situation that feeds nitrogen, mixture is stirred 10min under 200rpm speed.In the process of 10min, in this solution, drip 60g acrylic acid and 0.015gVA-044 , reactant mixture is heated to 60 ℃ and add the solution of 82.5g acrylic acid, 7.5g methyl methacrylate and 1.5g triallylamine in the process of 3.5h.When adding acrylic acid/triallyl amine aqueous solution, the interpolation that began four hours is dissolved in the 0.135g Azos arter VA-044 in the 40g water The process of solution.After the interpolation process finishes, with mixture at 60 ℃ of restir 30min.At last, add 0.225g VA-044 again Make polymerization process proceed 1h again at 60 ℃.Behind the cool to room temperature, obtaining polymer content is that 15 weight %, viscosity are that 21900mPa*s and pH value are 4.5 aqueous dispersion.Add suitable quantity of water and sodium hydroxide solution, make solid content and be 2 weight %, pH value and be 7, viscosity is the dispersion of 23650mPa*s.
Embodiment 17
The 250ml capacity have a Teflon agitator and an a kind of four-necked bottle that is used for the equipment of under nitrogen, working, feeding under the nitrogen situation, will
87.5g (8.75%) stabilizing agent 14,
87.5g (8.75%) stabilizing agent 15,
25g (2.5%) K value be 74.2 stabilizing agent 11,
442.8g complete demineralized water
At first add, and stir with the speed of 200rpm.In 5 to 10min process, in this solution, drip 174g acrylic acid and 1.134g pentaerythritol triallyl ether mixture, reactant mixture is heated to 40 ℃, add the 0.2g AzostarterVA-044 that is dissolved in the 20g water And make mixture at 40 ℃ of polymerization 4h.Then with the reactant mixture 0.3g Azostarter VA-044 that is dissolved in the 20g water Handle and carry out post polymerization 1h at 40 ℃.Generate solid content thus and be 37.5% aqueous dispersion.
Embodiment 18
The 250ml capacity have a Teflon agitator and an a kind of four-necked bottle that is used for the equipment of under nitrogen, working, feeding under the nitrogen situation, will
87.5g (8.75%) stabilizing agent 14,
87.5g (8.75%) stabilizing agent 15,
20g (2%) K value be 92.3 stabilizing agent 12,
409.0g complete demineralized water
At first add, and stir with the speed of 200rpm.In 5 to 10min process, in this solution, drip 174g acrylic acid and 1.05g pentaerythritol triallyl ether mixture,, add the 0.2g AzostarterVA-044 that is dissolved in the 20g water gained mixture heated to 40 ℃ And make mixture at 40 ℃ of polymerization 4h.Then with the reactant mixture 0.3g Azostarter VA-044 that is dissolved in the 20g water Handle and carry out post polymerization 1h at 40 ℃.Generate solid content thus and be 37.1% aqueous dispersion.
Embodiment 19
The 250ml capacity have a Teflon agitator and an a kind of four-necked bottle that is used for the equipment of under nitrogen, working, feeding under the nitrogen situation, will
87.5g (8.75%) stabilizing agent 14,
87.5g (8.75%) stabilizing agent 15,
20g (2%) K value be 84.1 stabilizing agent 13,
359.5g complete demineralized water
At first add, and stir with the speed of 200rpm.In 5 to 10min process, in this solution, drip the mixture of 174g acrylic acid and 1.05g pentaerythritol triallyl ether,, add the 0.2g AzostarterVA-044 that is dissolved in the 20g water gained mixture heated to 40 ℃ And make mixture at 40 ℃ of polymerization 4h.Then with the reactant mixture 0.3g Azostarter VA-044 that is dissolved in the 20g water Handle and carry out post polymerization 1h at 40 ℃.Generate solid content thus and be 37.5% aqueous dispersion.
Embodiment 20
The 250ml capacity have a Teflon agitator and an a kind of four-necked bottle that is used for the equipment of under nitrogen, working, feeding under the nitrogen situation, will
87.5g (8.75%) stabilizing agent 14,
87.5g (8.75%) stabilizing agent 15,
24g (2.4%) stabilizing agent 11,
398.13g complete demineralized water
At first add, and stir with the speed of 200rpm.In 5 to 10min process, in this solution, drip the mixture of 172.3g acrylic acid, 1.74g octadecyl vinyl ether and 1.05g pentaerythritol triallyl ether, with gained mixture heated to 40 ℃, add the 0.2g Azostarter VA-044 that is dissolved in the 20g water And make mixture at 40 ℃ of polymerization 5h.Then with the reactant mixture 0.3g Azostarter VA-044 that is dissolved in the 20g water Handle and carry out post polymerization 1h at 40 ℃.Generate solid content thus and be 37.5% aqueous dispersion.
Embodiment 21
The 250ml capacity have a Teflon agitator and an a kind of four-necked bottle that is used for the equipment of under nitrogen, working, feeding under the nitrogen situation, will
87.5g (8.75%) stabilizing agent 14,
87.5g (8.75%) stabilizing agent 15,
24g (2.4%) stabilizing agent 12,
509.0g complete demineralized water
At first add, and stir with the speed of 200rpm.In 5 to 10min process, in this solution, drip the mixture of 165.3g acrylic acid, 17.4g hexene-1 and 1.05g pentaerythritol triallyl ether,, add the 0.2g Azostarter VA-044 that is dissolved in the 20g water gained mixture heated to 40 ℃ And make mixture at 40 ℃ of polymerization 5h.Then with the reactant mixture 0.3g Azostarter VA-044 that is dissolved in the 20g water Handle and carry out post polymerization 1h at 40 ℃.Generate solid content thus and be 37.5% aqueous dispersion.
Embodiment 22
An anchor agitator and a kind of glass reactor that is used for the equipment of working under nitrogen are being housed, under the constant agitation speed conditions that feeds nitrogen and 200rpm, at first add the complete demineralized water of 489g, the 175g ethylene oxide content be 20% and the molal weight of polypropylene glycol block be the oxirane (EO) of 1750g/mol and the block copolymer of expoxy propane (PO), and 120g contains the acrylamide group methyl propane sulfonic acid of 59 weight portions, 20 parts by weight of acrylic methyl ester, 20% concentration of aqueous solution of the cinnamic copolymer of 20 parts by weight of acrylic and 1 weight portion.Under agitation then (200rpm) drips the mixture of 174g acrylic acid and 1.5g pentaerythritol triallyl ether (70% concentration) in the process of 5min, and the emulsion that generates is heated to 40 ℃.Add the solution be dissolved in the 0.2g AzostarterVA-044 in the 10g water and with after the 10g water flushing measuring equipment, reactant mixture is heated to 40 ℃ and keep 4h under this temperature.Then, be metered into the solution of the 0.3g Azostarter VA-044 that is dissolved in the complete demineralized water of 10g, stir with at 40 ℃ of post polymerization 1h again with the flushing of the complete demineralized water of 10g and with reactant mixture then.Generating viscosity thus is the milky dispersion of 18800mPas.A kind of aqueous solution of 0.5% concentration is that 7 o'clock viscosity is 26600mPas at pH.
Embodiment 23
An anchor agitator and a kind of glass reactor that is used for the equipment of working under nitrogen are being housed, under the constant agitation speed conditions that feeds nitrogen and 200rpm, the copolymer that at first adds the oxirane of the expoxy propane of the complete demineralized water of 489g, 175g 20.3 weight portions and 14.2 weight portions, and 120g contains the aqueous solution of 20% concentration of cinnamic copolymer of acrylamide group methyl propane sulfonic acid, 20 parts by weight of acrylic methyl ester, 20 parts by weight of acrylic and 1 weight portion of 59 weight portions.Under agitation then (200rpm) drips the mixture of 174g acrylic acid and 1.5g pentaerythritol triallyl ether (70% concentration) in the process of 5min, and the emulsion that generates is heated to 40 ℃.Add the solution be dissolved in the 0.2gAzostarter VA-044 in the 10g water and with after the flushing of 10g water, with reactant mixture be heated to 40 ℃ and under this temperature polymerization 4h.Then, be metered into the solution of the 0.3g Azostarter VA-044 that is dissolved in the complete demineralized water of 10g,, and reactant mixture stirred with at 40 ℃ of post polymerization 1h again with the flushing of the complete demineralized water of 10g.Generating viscosity thus is the milky dispersion of 19600mPas.A kind of aqueous solution of 0.5% concentration is that 7 o'clock viscosity is 22400mPas at pH.
Embodiment 24
Repeat embodiment 22, difference in polymer reactor, at first add the complete demineralized water of 359g, 87.5g ethylene oxide content be 20% and the molal weight of polypropylene glycol block be the oxirane (EO) of 1750g/mol and the block copolymer of expoxy propane (PO), the aqueous solution of 10% concentration of the copolymer of the copolymer of the oxirane of the expoxy propane of 87.5g20.3 weight portion and 14.2 weight portions and 250g90 mole % methacrylic acid and 10 moles of % acrylamide group methyl propane sulfonic acid sodium salts.Generate the white dispersion that viscosity is 1000mPas thus.A kind of 0.5% concentration of aqueous solution prepared therefrom is that 7 o'clock viscosity is 30000mPas at pH.
Embodiment 25
Repeat embodiment 24, unique difference is to replace with the copolymer that consists of 10 moles of % methacrylic acids and 90 moles of % acrylamide group methyl propane sulfonic acid sodium salts the copolymer of 90 moles of % methacrylic acids and 10 moles of % acrylamide group methyl propane sulfonic acid sodium salts.Generate the aqueous dispersion that viscosity is 1500mPas thus.It is that 7 o'clock viscosity is 25000mPas at pH that this dispersion a kind of is diluted to 0.5% aqueous solution.
Embodiment 26
Repeat embodiment 24, unique difference is to replace with the copolymer that consists of 50 moles of % methacrylic acids and 50 moles of % acrylamide group methyl propane sulfonic acid sodium salts the copolymer of 90 moles of % methacrylic acids and 10 moles of % acrylamide group methyl propane sulfonic acid sodium salts.Generate the aqueous dispersion that viscosity is 1200mPas thus.It is that 7 o'clock viscosity is 35000mPas at pH that this dispersion a kind of is diluted to 0.5% aqueous solution.
Embodiment 27
Repeat embodiment 24, unique difference is to replace with the copolymer that consists of 80 moles of % methacrylic acids and 20 moles of % acrylamide group methyl propane sulfonic acid sodium salts the copolymer of 90 moles of % methacrylic acids and 10 moles of % acrylamide group methyl propane sulfonic acid sodium salts.Generate the aqueous dispersion that viscosity is 1300mPas thus.It is that 7 o'clock viscosity is 33000mPas that this dispersion a kind of is diluted to 0.5% aqueous solution pH.
Embodiment 28
Repeat embodiment 24, unique difference is to replace with the copolymer that consists of 70 moles of % methacrylic acids and 30 moles of % acrylamide group methyl propane sulfonic acid sodium salts the copolymer of 90 moles of % methacrylic acids and 10 moles of % acrylamide group methyl propane sulfonic acid sodium salts.Generate the aqueous dispersion that viscosity is 1100mPas thus.It is that 7 o'clock viscosity is 29000mPas at pH that this dispersion a kind of is diluted to 0.5% aqueous solution.
Embodiment 29
An anchor agitator and a kind of glass reactor that is used for the equipment of working under nitrogen are being housed, under the lasting stirring state that feeds nitrogen and 200rpm, at first add the complete demineralized water of 359g, 87.5g ethylene oxide content be 20% and the molal weight of polypropylene glycol block be the oxirane (EO) of 1750g/mol and the block copolymer of expoxy propane (PO), 87.5g the copolymer of the oxirane of the expoxy propane of 20.3 weight portions and 14.2 weight portions, and 10% concentration of aqueous solution of the copolymer of 80 moles of % methacrylic acids of 250g and 20 moles of % acrylamide group methyl propane sulfonic acid sodium salts.
Under agitation then (200rpm) drips the mixture of 174g acrylic acid and 1.5g pentaerythritol triallyl ether (70% concentration) in the process of 5min, and the emulsion that generates is heated to 50 ℃.Add the solution be dissolved in the 0.2g Azostarter VA-044 in the 10g water and with after the 10g water flushing measuring equipment, with reactant mixture be heated to 50 ℃ and under this temperature polymerization 4h.Then, be metered into the solution that is dissolved in the 0.3gAzostarter VA-044 in the complete demineralized water of 10g, with the complete demineralized water of 10g flushing measuring equipment, and with reactant mixture 50 ℃ of stirrings to carry out post polymerization 1h again.Generating viscosity thus is the milky dispersion of 1600mPa s.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 29000mPas at pH.
Embodiment 30
An anchor agitator and a kind of glass reactor that is used for the equipment of working under nitrogen are being housed, under the constant agitation speed conditions that feeds nitrogen and 200rpm, at first add the complete demineralized water of 359g, 87.5g ethylene oxide content be 20% and the molal weight of polypropylene glycol block be the oxirane (EO) of 1750g/mol and the block copolymer of expoxy propane (PO), 87.5g the copolymer of the oxirane of the expoxy propane of 20.3 weight portions and 14.2 weight portions, and 10% concentration of aqueous solution of the copolymer of 80 moles of % methacrylic acids of 250g and 20 moles of % acrylamide group methyl propane sulfonic acid sodium salts.
Under agitation then (200rpm) drips the mixture of 174g acrylic acid and 1.5g pentaerythritol triallyl ether (70% concentration) in the process of 5min, and the emulsion that generates is heated to 35 ℃.Add the solution be dissolved in the 0.2g Azostarter V-70 in the 10g water and with after the 10g water flushing measuring equipment, with reactant mixture be heated to 50 ℃ and under this temperature polymerization 4h.Then, be metered into the solution that is dissolved in the 0.3gAzostarter V-70 in the complete demineralized water of 10g, with the complete demineralized water of 10g flushing measuring equipment, and with reactant mixture 35 ℃ of stirrings to carry out post polymerization 1h again.Generating viscosity thus is the milky dispersion of 1400mPas.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 32000mPas at pH.
Embodiment 31
Repeat embodiment 22, difference be at first to add the 87.5g ethylene oxide content be 20% and the molal weight of polypropylene glycol block be copolymer, the 53.4g molal weight M of the oxirane of the expoxy propane of solution, 87.5g 20.3 weight portions of the block copolymer of the oxirane (EO) of 1750g/mol and expoxy propane (PO) and 14.2 weight portions wBe 50000 polyacrylic 45% concentration of aqueous solution and the complete demineralized water of 555.7g.Generate the aqueous dispersion that viscosity is 2000mPas thus.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 26000mPas at pH.
Embodiment 32
Repeat embodiment 22, difference be at first to add the 87.5g ethylene oxide content be 20% and the molal weight of polypropylene glycol block be the copolymer of the oxirane of the expoxy propane of solution, 87.5g 20.3 weight portions of the block copolymer of the oxirane (EO) of 1750g/mol and expoxy propane (PO) and 14.2 weight portions, 20% concentration of aqueous solution and the complete demineralized water of 555.7g of 120g polyacrylamide base methyl propane sulfonic acid.Generate the aqueous dispersion that viscosity is 1900mPas thus.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 28000mPas at pH.
Embodiment 33
Repeat embodiment 32, unique difference is initial charging, the polyacrylamide base methyl propane sulfonic acid molal weight M of same amount w20% concentration of aqueous solution that is 40000 polymethylacrylic acid replaces.Generate the aqueous dispersion that viscosity is 1900mPas thus.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 36000mPas at pH.
Embodiment 34
Repeat embodiment 27, unique difference is to replace pentaerythritol triallyl ether as cross-linking agent with 10% concentration of aqueous solution of the trimethylolpropane triacrylate of 1.75g ethoxylation.Generate the aqueous dispersion that viscosity is 900mPas thus.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 34000mPas at pH.
Embodiment 35
Repeat embodiment 27, unique difference is to replace pentaerythritol triallyl ether as cross-linking agent with 10% concentration of aqueous solution of 4.35g triallylamine.Generate the aqueous dispersion that viscosity is 1000mPas thus.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 38000mPas at pH.
Embodiment 36
Repeat embodiment 22, difference be with the 87.5g ethylene oxide content be 20% and the molal weight of polypropylene glycol block be 60 moles of % methacrylic acids of copolymer, 250g of oxirane of the expoxy propane of solution, 87.5g 20.3 weight portions of the block copolymer of the oxirane (EO) of 1750g/mol and expoxy propane (PO) and 14.2 weight portions and 20 moles of % acrylamide group methyl propane sulfonic acid sodium salts and 20 moles of % with 10% concentration of aqueous solution of the copolymer of the quaternised vinyl imidazoles of chloromethane and the complete demineralized water of 359g as charging at first.Generate the dispersion that viscosity is 2000mPas thus.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 20000mPas at pH.
Embodiment 37
Repeat embodiment 22, difference be with the 87.5g ethylene oxide content be 20% and the molal weight of polypropylene glycol block be the solution of the block copolymer of the oxirane (EO) of 1750g/mol and expoxy propane (PO), 87.5g the copolymer of the oxirane of the expoxy propane of 20.3 weight portions and 14.2 weight portions, 250g is by 20 moles of % acrylic acid methyl ester .s, 69 moles of % acrylamide group methyl propane sulfonic acid sodium salts, 10 moles of %, 10% concentration of aqueous solution and the initial charging of the complete demineralized water conduct of 359g of the copolymer of the quaternised vinyl imidazole of chloromethane and 1 mole of % styrene formation.Generate the dispersion that viscosity is 900mPas thus.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 22000mPas at pH.
Embodiment 38
Repeat embodiment 22, difference is with 175g molal weight M wBe that 10% concentration of aqueous solution of the copolymer that is made of 80 moles of % methacrylic acids and 20 moles of % acrylamide group methyl propane sulfonic acid sodium salts of the solution, 250g of 1500 Polyethylene Glycol and the complete demineralized water of 359g are as initial charging.Generate the dispersion that viscosity is 2500mPas thus.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 34000mPas at pH.
Embodiment 39
An anchor agitator and a kind of glass reactor that is used for the equipment of working under nitrogen are being housed, under the constant agitation speed conditions that feeds nitrogen and 200rpm, at first add the complete demineralized water of 479.8g, 106.7g ethylene oxide content be 20% and the molal weight of polypropylene glycol block be the oxirane (EO) of 1750g/mol and the block copolymer of expoxy propane (PO), 53.3g the copolymer of the oxirane of the expoxy propane of 20.3 weight portions and 14.2 weight portions and 110g are by the acrylamide group methyl propane sulfonic acid of 59 weight portions, 20 parts by weight of acrylic methyl ester, 20% concentration of aqueous solution of the copolymer that the styrene of 20 parts by weight of acrylic and 1 weight portion constitutes.
Under agitation then (200rpm), in the process of 5min, drip 139.2g acrylic acid and 69.55g mixture, and the emulsion that generates is heated to 40 ℃ with quaternised dimethylaminoethyl methacrylate of dithyl sulfate and 1.5g pentaerythritol triallyl ether (70% concentration).Add the solution be dissolved in the 0.2g Azostarter VA-044 in the 10g water and with after the 10g water flushing measuring equipment, reactant mixture is heated to 40 ℃ and keep 4h under this temperature.Then, be metered into the solution that is dissolved in the 0.3gAzostarter VA-044 in the complete demineralized water of 10g, wash measuring equipment with the complete demineralized water of 10g, and reactant mixture is carried out post polymerization at 40 ℃ of restir 1h.Generating viscosity thus is the milky dispersion of 1850mPas.A kind of 0.5% concentration of aqueous solution of this dispersion is that 7 o'clock viscosity is 12150mPas at pH.
Embodiment 40
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 600.59g distilled water, 160g ethylene oxide content and be 40% and the molal weight of polypropylene glycol block be the oxirane (EO) of 1750g/mol and the block copolymer (Pluronic of expoxy propane (PO) -PE 6400) and 89.41g stabilizing agent 16.
Then under room temperature and stirring (200rpm), in the process of 10min, drip 150g acrylic acid.Add after the 0.2g Azostarter V-65, to be heated to internal temperature be 40 ℃ and keep this temperature with reactant mixture.After the 1h, add 0.3g AzostarterV-65 again and after 5h, add 0.4g Azostarter VA-044.Generating viscosity thus is 650mPas (spindle 4, milky dispersion 20rpm).
A kind of aqueous solution of counting 2 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 550mPas (spindle 4,20rpm).
Embodiment 41
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 575.55g distilled water, 160g ethylene oxide content and be 40% and the molal weight of polypropylene glycol block be the oxirane (EO) of 1750g/mol and the block copolymer (Pluronic of expoxy propane (PO) PE 6400) and 89.41g stabilizing agent 16.
Then under room temperature and stirring (200rpm), in the process of 10min, drip 175g acrylic acid.Add after the 0.3g Azostarter VA-044, to be heated to internal temperature be 40 ℃ and keep this temperature and finish until polymerization process with reactant mixture.Generating viscosity thus is 1550mPas (spindle 4, milky dispersion 20rpm).The particle size distribution of discrete particles is that the granularity of 5 to 10 μ m and indivedual larger particles is up to 50 μ m.
A kind of aqueous solution of counting 2 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 600mPas (spindle 4,20rpm).
Embodiment 42
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 560.59g distilled water, 175g ethylene oxide content and be 40% and the molal weight of polypropylene glycol block be the oxirane (EO) of 1750g/mol and the block copolymer (Pluronic of expoxy propane (PO) PE 6400) and 89.41g stabilizing agent 16.
Then under room temperature and stirring (200rpm), in the process of 10min, drip 175g acrylic acid and 0.875g triallylamine.Add after the 0.3g Azostarter VA-044, to be heated to internal temperature be 40 ℃ and keep this temperature and finish until polymerization process with reactant mixture.Generating viscosity thus is 4000mPas (spindle 4, milky dispersion 20rpm).The particle size distribution of dispersed polymeres is that the granularity of 5 to 10 μ m and indivedual larger particles is up to 40 μ m.
A kind of aqueous solution of counting 1 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 11600mPas (spindle 4,20rpm).
Embodiment 43
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 560.59g distilled water, 175g ethylene oxide content and be 30% and the molal weight of polypropylene glycol block be the oxirane (EO) of 1100g/mol and the block copolymer (Pluronic of expoxy propane (PO) PE 4300) and 89.41g stabilizing agent 16.Then under room temperature and stirring (200rpm), in the process of 10min, drip 175g acrylic acid and 0.875g triallylamine.Add after the 0.3gAzostarter VA-044, to be heated to internal temperature be 40 ℃ and keep this temperature and finish until polymerization process with reactant mixture.Generating viscosity thus is 6700mPas (spindle 5, milky dispersion 20rpm).
A kind of aqueous solution of counting 1 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 11500mPas (spindle 6,20rpm).
Embodiment 44
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 560.59g distilled water, 175g ethylene oxide content and be 30% and the molal weight of polypropylene glycol block be the oxirane (EO) of 1100g/mol and the block copolymer (Pluronic of expoxy propane (PO) PE 4300) and 89.41g stabilizing agent 16.Then under room temperature and stirring (200rpm), in the process of 10min, drip 173.55g acrylic acid and 1.75g triallylamine.Add after the 0.3gAzostarter VA-044, mixture heated is 40 ℃ and keeps this temperature and finish until polymerization process to internal temperature.Generating viscosity thus is 16000mPas (spindle 4, milky dispersion 20rpm).The granularity of dispersed polymeres particle is 5 to 10 μ m.
A kind of aqueous solution of counting 1 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 21000mPas (spindle 6,20rpm).
Embodiment 45
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 515.88g distilled water, 175gEO content and be 30% and the molal weight of polypropylene glycol block be the EO of 1100g/mol and the block copolymer (Pluronic of PO PE 4300) and 134.12g stabilizing agent 16.Then under room temperature and stirring (200rpm), in the process of 10min, drip 173.55g acrylic acid and 1.75g triallylamine.Add after the 0.3g Azostarter VA-044, to be heated to internal temperature be 40 ℃ and keep this temperature and finish until polymerization process with reactant mixture.Generate milky thixotropic dispersion thus.The granularity of this dispersion is 8 to 20 μ m.
A kind of aqueous solution of counting 1 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 34000mPas (spindle 6,20rpm).
Embodiment 46
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 552.38g distilled water, 175gEO content and be 30% and the molal weight of polypropylene glycol block be the EO of 1100g/mol and the block copolymer (Pluronic of PO PE 4300) and 97.32g stabilizing agent 17.Then under room temperature and stirring (200rpm), in the process of 10min, drip 173.55g acrylic acid and 1.75g triallylamine.Add after the 0.3g Azostarter VA-044, to be heated to internal temperature be 40 ℃ and keep this temperature and finish until polymerization process with reactant mixture.Generating viscosity thus is 42000mPas (spindle 4, milky dispersion 20rpm).The granularity of dispersed polymeres particle is 5 to 10 μ m.
A kind of aqueous solution of counting 1 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 13000mPas (spindle 6,20rpm).
Embodiment 47
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 560.59g distilled water, 175gEO content and be 30% and the molal weight of polypropylene glycol block be the EO of 1100g/mol and the block copolymer (Pluronic of PO PE 4300) and 89.41g stabilizing agent 16.Then under room temperature and stirring (200rpm), in the process of 10min, drip 173.25g acrylic acid and 1.75g N, N '-divinyl ethylidene-urea.Add after the 0.3g Azostarter VA-044, to be heated to internal temperature be 40 ℃ and keep this temperature and finish until polymerization process with reactant mixture.Generating viscosity thus is 4950mPas (spindle 4, milky dispersion 20rpm).The granularity of this dispersion is 5 to 10 μ m.
A kind of aqueous solution of counting 1 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 3000mPas (spindle 6,100rpm).
Embodiment 48
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 556.5g distilled water, 175g EO content and be 30% and the molal weight of polypropylene glycol block be the EO of 1100g/mol and the block copolymer (Pluronic of PO PE 4300) and 93.2g stabilizing agent 18.Then under room temperature and stirring (200rpm), in the process of 10min, drip 172.5g acrylic acid and 1.25g pentaerythritol triallyl ether (70% concentration).Add after the 0.3g AzostarterVA-044, to be heated to internal temperature be 40 ℃ and keep this temperature and finish until polymerization process with reactant mixture.Generating viscosity thus is the milky dispersion of 13000mPas (spindle 5,20rpm, 30 ℃).The granularity of dispersed polymeres particle is 15 to 35 μ m in this dispersion.
A kind of aqueous solution of counting 0.25 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 12000mPas (spindle 7,10rpm).
Embodiment 49
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 556.5g distilled water, 175g EO content and be 30% and the molal weight of polypropylene glycol block be the EO of 1100g/mol and the block copolymer (Pluronic of PO PE 4300) and 93.2g stabilizing agent 18.Then under room temperature and stirring (200rpm), in the process of 10min, drip 174g acrylic acid and 1.0g pentaerythritol triallyl ether (70% concentration).Add after the 0.2g Azostarter VA-044, to be heated to internal temperature be 40 ℃ and keep this temperature and finish until polymerization process with reactant mixture.When polyreaction finishes, add 0.4g Azostarter VA-044 to carry out post polymerization.Generating viscosity thus is 68000mPas (spindle 4, milky dispersion 2.5rpm).The granularity of this dispersion is 6 to 30 μ m.
A kind of aqueous solution of counting 0.5 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 33000mPas (spindle 7,20rpm).
Embodiment 50
An anchor agitator and a kind of 2L glass reactor that is used for the equipment of working under nitrogen are being housed, feeding under the nitrogen situation, at first add 560.39g distilled water, 175gEO content and be 30% and the molal weight of polypropylene glycol block be the EO of 1100g/mol and the block copolymer (Pluronic of PO PE 4300) and 89.41g stabilizing agent 16.Then under room temperature and stirring (200rpm), in the process of 10min, drip 174g acrylic acid and 1.0g pentaerythritol triallyl ether (70% concentration).Add after the 0.2g Azostarter VA-044, to be heated to internal temperature be 40 ℃ and keep this temperature and finish until polymerization process with reactant mixture.When actual polymerisation process finishes, add 0.4g Azostarter VA-044 and carry out post polymerization.Generating viscosity thus is 15400mPas (spindle 4, milky dispersion 10rpm).The granularity of this dispersion is 6 to 30 μ m.
A kind of aqueous solution of counting 0.5 weight % concentration based on polyacrylic acid with triethanolamine with its pH value adjust to viscosity after 7 be 30000mPa s (spindle 7,20rpm).
The Application Example of cosmetic formulations
Following quantitative data is represented with weight %, unless point out in addition.The amount of the copolymer that the present invention is used is represented with the weight % of solid polymer.If polymer uses with the form of dispersion, then the polymer of described aequum must be the form use with the dispersion of respective amount.The % weight portion of polymer is derived from the data of preparation embodiment.If polymer uses with the solution form, situation similarly.In following examples, replace used paraffin oil or except that used paraffin oil, also can advantageously use for example mixture of the isoalkane described in the patent application DE 102004018753.
The preferred especially isoalkane mixture that uses 1H-NMR spectrum counts 25 to 70% at the area integral in 0.6 to 1.0ppm zone based on total integral area based on tetramethylsilane meter chemical shift δ.This isoalkane mixture and preparation method thereof is described among the undocumented patent application DE 102005022021.5.
Above-mentioned isoalkane mixture also can be advantageously to use with the mixture of 2-Methylpentadecane or with the form of the mixture of liquid paraffin, the weight ratio under the various situations is 10: 1 to 1: 10, rather than uses paraffin refined wax oil.
In following Application Example, if mention the polymer of example 2 to 50, then should be understood to mean polymer and any suitable mixture thereof of above-mentioned preparation embodiment 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50.
Application Example 1: the Hairstyling composition that is used for the hair gel
INCI
0.50% Carbopol 940 carbomers
The polymer of 3.00% embodiment 1
0.10% phytantriol
0.50% pantothenylol
An amount of aromatic oil
An amount of antiseptic
Add to 100% water
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the salubrious gel of superperformance under the various situations.
Application Example 2: hair shampoo or bath gels
INCI
The polymer of 0.50% embodiment 18
40.00% Texa pon The sulfuric ester sodium salt of NSO laureth-(1-4)
5.00% Tego Betain The L7 cocamido propyl betaine
5.00% Plantacare 2000 decyl glucoside
1.00% propylene glycol
An amount of citric acid
An amount of antiseptic
1.00% sodium chloride
Add to 100% water
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the hair shampoo or the bath gels of superperformance under the various situations.
Application Example 3: skin cream
According to following formulation water/bloom emulsion:
Weight of additive %
Cremophor A 6 ceteareth-6 and stearyl alcohol 2.0
Chremophor A 25 ceteareth-25 2.0
LanetteO cetearyl alcohol 2.0
Imwitor 960 K glyceryl stearate SE 3.0
Paraffin oil 5.0
Jojoba oil 4.0
Luvitol EHO cetearyl alcohol caprylate 3.0
ABIL 350 dimethyl polysiloxanes 1.0
Amerchol L 101 mineral oil and lanolin alcohol 3.0
Veegum Ultra Magnesiumaluminumsilicate 0.5
1,2-propylene glycol propylene glycol 5.0
Abiol Imidazolidinyl urea 0.3
Phenoxyethanol 0.5
D-panthenol USP 1.0
The polymer 0.5 of embodiment 1
Water adds to 100
This embodiment can repeat with the polymer of embodiment 1 to 50.All obtain having the skin creams of superperformance under the various situations.
Application Example 4: bath gels
According to following formulation the bath gels preparation:
Weight of additive %
Texapon The sulfuric ester sodium salt 40.0 of NSO laureth-(1-4)
Tego Betain L7 cocamido propyl betaine 5.0
Plantacare 2000 decyl glucoside 5.0
Spice 0.2
The polymer 0.2 of embodiment 17
Euxyl K100 benzyl alcohol, 0.1
Methylchloroisothiazandnone,
Methylisothiazolinone
D-panthenol USP 0.5
Citric acid (pH 6-7) is an amount of
NaCl 2.0
Water adds to 100
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the bath gels of superperformance under the various situations.
Application Example 5: hair gelling thickener
The 0.50% usefulness triethanolamine pH that neutralizes is the polymer of 7.5 embodiment 1
3.00％Luviskol K 90 P
0.50% pantothenylol
An amount of aromatic oil
An amount of antiseptic
Add to 100% water
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having desalination (freshening) gel of superperformance under the various situations.
Application Example 6: wetting agent preparation
Preparation A
Weight of additive %
A) Cremophor A6 ceteareth-6 and stearyl alcohol 2.0
Cremophor A25 ceteareth-25 2.0
Paraffin oil (high viscosity) 10
Lannette 0 cetearyl alcohol 2.0
Stearic acid 3.0
The Nip-Nip methyl parahydroxybenzoate/
Propyl p-hydroxybenzoate 70: 30 0.5
Abiol Imidazolidinyl urea 0.5
B) polymer 3.0 of embodiment 18
Water adds to 100.0
All be heated to 80 ℃ with biphase, phase a) is stirred to phase b) in, homogenize also stirs up to cooling, then with the NaOH aqueous solution of 10% concentration pH value is adjusted to 6.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the wetting agent preparation of superperformance under the various situations.
Application Example 7:O/W skin water replenishing cream
Weight of additive %
Glyceryl monostearate 2.0
Spermol 3.0
Paraffin oil, inferior liquid 15.0
Vaseline 3.0
Caprylic/capric triglyceride 4.0
Octyldodecanol 2.0
Hydrogenated coconut fat 2.0
Phosphoric acid cetyl 0.4
The polymer 3.0 of embodiment 17
Glycerol 3.0
Sodium hydroxide is an amount of
Aromatic oil is an amount of
Antiseptic is an amount of
Water adds to 100
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the O/W skin water replenishing cream of superperformance under the various situations.
Application Example 8:0/W washing liquid
Weight of additive %
Stearic acid 1.5
Arlacel-60 1.0
Arlacel-80 1.0
Paraffin oil, inferior liquid 7.0
Spermol 1.0
Polydimethylsiloxane 1.5
Glycerol 3.0
The polymer 0.5 of embodiment 1
Aromatic oil is an amount of
Antiseptic is an amount of
Water adds to 100
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the O/W washing liquid of superperformance under the various situations.
Application Example 9:W/O Emulsion
Weight of additive %
PEG-7 castor oil hydrogenated 4.0
Wool wax alcohol 1.5
Cera Flava 3.0
Triglyceride, liquid 5.0
Vaseline 9.0
Ceresine 4.0
Paraffin oil, inferior liquid 4.0
Glycerol 2.0
The polymer 2.0 of embodiment 18
Magnesium sulfate * 7H2O 0.7
Aromatic oil is an amount of
Antiseptic is an amount of
Water adds to 100
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the W/O Emulsion of superperformance under the various situations.
Application Example 10: skin care hydrogel
Weight of additive %
The polymer 3.0 of embodiment 17
Sorbitol 2.0
Glycerol 3.0
PEG400 5.0
Ethanol 1.0
Aromatic oil is an amount of
Antiseptic is an amount of
Water adds to 100
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the skin care hydrogel of superperformance under the various situations.
Application Example 11: aqueous dispersion gel
Weight of additive %
The polymer 3.0 of embodiment 1
Sorbitol 2.0
Glycerol 3.0
PEG400 5.0
Triglyceride, liquid 2.0
Ethanol 1.0
Aromatic oil is an amount of
Antiseptic is an amount of
Water adds to 100
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the aqueous dispersion gel of superperformance under the various situations.
Application Example 12: liquid soap
Weight of additive %
Coco-nut oil fatty acid, potassium salt 15
Potassium oleate 3
Glycerol 5
The polymer 2 of embodiment 18
Tristerin 1
Diglycol stearate 2
Special additive, chelating agent, spice are an amount of
Water adds to 100
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the liquid soap of superperformance under the various situations.
Application Example 13: contain TiO 2And ZnO 2The shading emulsion
Phase A
6.00 PEG-7 castor oil hydrogenated
2.00 PEG-45/ dodecyl glycol copolymer
3.00 isopropyl myristate
8.00 Jojoba (Buxus Chinensis) oil
4.00 octyl methoxycinnamate (Uvinu l MC 80)
2.00 4 methyl benzylidene camphor (Uvinul MBC 95)
3.00 titanium dioxide, dimethicone
1.00 dimethicone
5.00 zinc oxide, dimethicone
Phase B
2.00 the polymer of embodiment 17
0.20 EDTA-disodium
5.00 glycerol
An amount of antiseptic
58.80 distilled water
Phase C
An amount of aromatic oil
Preparation:
Phase A is heated to 85 ℃ respectively with B mutually.Be stirred among the phase A phase B and homogenize.Be cooled to about 40 ℃, add phase C and carry out of short duration homogenize once more.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the shading emulsion of superperformance under the various situations.
Application Example 14:O/W type facial milk cleanser
Phase A
1.50 ceteareth-6
1.50 ceteareth-25
2.00 tristerin
2.00 spermol
10.00 mineral oil
Phase B
5.00 propylene glycol
An amount of antiseptic
1.0 the polymer of embodiment 1
66.30 distilled water
Phase C
0.20 carbomer
10.00 cetearyl alcohol caprylate
Phase D
0.40 tetrahydroxypropyl ethylenediamine
Phase E
An amount of aromatic oil
0.10 bisabolol
Preparation:
Phase A is heated to 80 ℃ respectively with B mutually.Phase B homogenize is stirred among the phase A, carries out of short duration back homogenize.C prepares serosity by phase, is stirred among the phase AB, with phase D neutralization and back homogenize.Be cooled to about 40 ℃, add phase E and carry out homogenize once more.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the facial milk cleanser of superperformance under the various situations.
Application Example 15: health maintenance frost
Weight of additive %
Cremophor A6 ceteareth-6 and stearyl alcohol 2.0%
Cremophor A 25 ceteareth-25 2.0%
Fructus Vitis viniferae (Vitis Vinifera) seed oil 6.0%
Tristerin SE 3.0%
Cetearyl alcohol 2.0%
Dimethicone 0.5%
Luvitol EHO cetearyl alcohol caprylate 8.0%
Oxynex 2004 propylene glycol, BHT,
Ascorbyl palmitate, tristerin, citric acid 0.1%
Antiseptic is an amount of
1,2-propylene glycol USP 3.0%
Glycerol 2.0%
EDTA BD 0.1％
D-panthenol USP 1.0%
Water adds to 100
The polymer 1.5% of embodiment 18
Tocopherol acetas 0.%
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the health maintenance frost of superperformance under the various situations.
In following Application Example, all quantity are all in weight %.
Application Example 16: liquid make-up
Phase A
1.70 tristerin
1.70 spermol
1.70 ceteareth-6
1.70 ceteareth-25
5.20 caprylic/capric triglyceride
5.20 mineral oil
Phase B
An amount of antiseptic
4.30 propylene glycol
2.50 the polymer of embodiment 17
59.50 distilled water
Phase C
An amount of aromatic oil
Phase D
2.00 ferrum oxide
12.00 titanium dioxide
Preparation:
Phase A is heated to 80 ℃ separately from each other with B mutually.Then by using agitator that phase B is mixed among the phase A.All be cooled to 40 ℃, add phase C and D mutually.Carry out homogenize once more.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the liquid make-up of superperformance under the various situations.
Application Example 17: do not have oily cosmetics
Phase A
0.35 Veegum
5.00 butanediol
0.15 xanthan gum
Phase B
53.0 distilled water
An amount of antiseptic
0.2 Polvsorbate -20
1.6 tetrahydroxypropyl ethylenediamine
Phase C
1.0 Silicon stone
2.0 PA-12
4.15 Muscovitum
6.0 titanium dioxide
1.85 ferrum oxide
Phase D
4.0 stearic acid
1.5 tristerin
7.0 Laurel acid benzyl ester
5.0 Isoeicosane
An amount of antiseptic
Phase E
1.0 distilled water
0.5 pantothenylol
0.1 imidazolidinyl urea
5.0 the polymer of embodiment 1
Preparation:
With butanediol wetting phase A, add among the phase B and uniform mixing.AB to 75 ℃ of heating phase.With the efflorescence of phase C raw material, join among the phase AB and carry out good homogenize.Mixed phase D raw material is heated to 80 ℃ and add among the phase ABC.It is even that mixed process proceeds to each material.With each substance transfer in the container that has propeller mixer.Mixed phase E raw material adds among the phase ABCD and mix homogeneously.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the nothing oil cosmetics of superperformance under the various situations.
Application Example 18: eyeliner
Phase A
40.6 distilled water
0.2 EDTA-disodium
An amount of antiseptic
Phase B
0.6 xanthan gum
0.4 Veegum
3.0 butanediol
0.2 Tween-20
Phase C
15.0 ferrum oxide/aluminium powder/Silicon stone is (as the Sicopearl FantasticoGold of BASF )
Phase D
10.0 distilled water
30.0 the polymer of embodiment 18
Preparation:
Premixing phase B.Use propeller mixer that phase B is sneaked among the phase A, make the thickening agent swelling.With phase D wetting phase C, add among the phase AB and mix homogeneously.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the eyeliner of superperformance under the various situations.
Application Example 19: flash of light gel
Phase A
32.6 distilled water
0.1 EDTA-disodium
25.0 carbomer (2% concentration of aqueous solution)
0.3 antiseptic
Phase B
0.5 distilled water
0.5 triethanolamine
Phase C
10.0 distilled water
9.0 the polymer of embodiment 17
1.0 polyquaternary ammonium salt-46
5.0 ferrum oxide
Phase D
15.0 distilled water
1.0 D-panthenol 50P (pantothenylol and propylene glycol)
Preparation:
Use propeller mixer, press to the thorough mixed phase A of definite sequence raw material.Then phase B is added phase A.Slowly stir up to each material mix homogeneously.Thoroughly homogenize phase C is even until pigment distribution.Add among the phase AB phase C and D mutually and mix homogeneously.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the flash of light gel of superperformance under the various situations.
Application Example 20: waterproof mascara
Phase A
46.7 distilled water
3.0 Lutrol E 400(PEG-8)
0.5 xanthan gum
An amount of antiseptic
0.1 imidazolidinyl urea
1.3 tetrahydroxypropyl ethylenediamine
Phase B
8.0 Carnauba wax
4.0 Cera Flava
4.0 Isoeicosane
4.0 polyisobutylene
5.0 stearic acid
1.0 tristerin
An amount of antiseptic
2.0 Laurel acid benzyl ester
Phase C
10.0 ferrum oxide/aluminium powder/Silicon stone is (as the Sicopearl FantasticoGold of BASF )
Phase E
8.0 polyurethane-1
2.0 the polymer of embodiment 1
Preparation:
Phase A is heated to 85 ℃ independently of one another with B mutually.Keeping this temperature adds phase C among the phase A and carries out homogenize and distribute equably up to pigment.Phase B is joined phase AC and homogenize 2-3 minute.Then add phase E and slowly stirring.Make each material cool to room temperature.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the waterproof mascara of superperformance under the various situations.
Application Example 21: shading gel
Phase A
1.00 PEG-40 castor oil hydrogenated
8.00 octyl methoxycinnamate (the Uvinul MC 80 of BASF )
5.00 octocrylene (the Uvinul N539 of BASF )
0.80 Xin Sanqinzong (octyl triazone) (the Uvinul T150 of BASF )
2.00 PAROSOL 1789 (the Uvinul BMBM of BASF )
2.00 tocopherol acetas
An amount of aromatic oil
Phase B
2.50 the polymer of embodiment 18
0.30 acrylate/C 10-30 alkylol acrylamide acid esters cross-linked copolymer
0.20 carbomer
5.00 glycerol
0.20 EDTA-disodium
An amount of antiseptic
72.80 distilled water
Phase C
0.20 sodium hydroxide
Preparation:
Mixed phase A component.Make phase B swelling and under the homogenize condition, be stirred among the phase A.With phase C neutralization and homogenize once more.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the shading gel of superperformance under the various situations.
Application Example 22: shading washing liquid
Phase A
6.00 the octyl methoxycinnamate (Uvinnl of BASF MC 80)
2.50 the 4 methyl benzylidene camphor (Uvinul of BASF MBC 95)
1.00 the Xin Sanqinzong (Uvinul of BASF T 150TM)
2.00 the PAROSOL 1789 (Uvinul of BASF BMBM)
2.00 PVP/ hexadecene copolymer
5.00 PPG-3 myristicin
0.50 dimethicone
0.10 BHT, ascorbyl palmitate, citric acid, tristerin, propylene glycol
2.00 spermol
2.00 Phosphoric acid monohexadecyl ester potassium
Phase B
2.50 the polymer of embodiment 17
5.00 propylene glycol
0.20 EDTA-disodium
An amount of antiseptic
63.92 distilled water
Phase C
5.00 mineral oil
0.20 carbomer
Phase D
0.08 sodium hydroxide
Phase E
An amount of aromatic oil
Phase A is heated to about 80 ℃ respectively with B mutually.Phase B homogenize is stirred among the phase A, carries out of short duration back homogenize.C prepares serosity by phase, is stirred among the phase AB, with phase D neutralization and back homogenize.Be cooled to about 40 ℃, add phase E and carry out homogenize once more.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the shading washing liquid of superperformance under the various situations.
Application Example 23: peelable facial film
Phase A
57.10 distilled water
6.00 polyvinyl alcohol
5.00 propylene glycol
Phase B
20.00 ethanol
4.00 PEG-32
An amount of aromatic oil
Phase C
5.00 polyquaternary ammonium salt-44
2.70 the polymer of embodiment 1
0.20 allantoin
Preparation:
Heating phase A also stirs up to dissolving at least 90 ℃.At 50 ℃ of dissolving phase B and being stirred among the phase A.At about 35 ℃, the ethanol of replenish lost.Phase C is added and stirring.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the peelable facial film of superperformance under the various situations.
Application Example 24: facial film
Phase A
3.00 ceteareth-6
1.50 ceteareth-25
5.00 cetearyl alcohol
6.00 cetearyl alcohol caprylate
6.00 mineral oil
0.20 bisabolol
3.00 tristerin
Phase B
2.00 propylene glycol
5.00 pantothenylol
2.80 the polymer of embodiment 18
An amount of antiseptic
65.00 distilled water
Phase C
An amount of aromatic oil
0.50 tocopherol acetas
Preparation:
Phase A is heated to about 80 ℃ respectively with B mutually.Phase B homogenize is stirred among the phase A, carries out of short duration back homogenize.Be cooled to about 40 ℃, add phase C and carry out homogenize once more.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the facial film of superperformance under the various situations.
Application Example 25: body wash infusion
Phase A
1.50 ceteareth-25
1.50 ceteareth-6
4.00 cetearyl alcohol
10.00 cetearyl alcohol caprylate
1.00 dimethicone
Phase B
3.00 the polymer of embodiment 17
2.00 pantothenylol
2.50 propylene glycol
An amount of antiseptic
74.50 distilled water
Phase C
An amount of aromatic oil
Preparation:
Phase A is heated to about 80 ℃ respectively with B mutually.Be stirred among the phase A phase B and homogenize.Be cooled to about 40 ℃, add phase C and carry out of short duration homogenize once more.Bottling: 90% active component and 10% propane/butane, 3.5bar (20 ℃).
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the body wash infusion of superperformance under the various situations.
Application Example 26: be used for dry and sensitive-skinned facial tonic
Phase A
2.50 PEG-40 castor oil hydrogenated
An amount of aromatic oil
0.40 bisabolol
Phase B
3.00 glycerol
1.00 ethoxy cetyl dimethyl ammonium phosphate
5.00 Radix Hamamelidis Mollis (Hamamelis Virginiana) distillation
0.50 pantothenylol
0.50 the polymer of embodiment 1
An amount of antiseptic
87.60 distilled water
Preparation:
A is up to clarification for the dissolving phase.Phase B is stirred among the phase A.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the facial tonic of superperformance under the various situations.
Application Example 27: the unguentum of washing one's face with Exfoliating Scrub effect
Phase A
70.00 distilled water
3.00 the polymer of embodiment 18
1.50 carbomer
An amount of antiseptic
Phase B
An amount of aromatic oil
7.00 Cortex cocois radicis acyl hydrolyzed protein potassium
4.00 cocamido propyl betaine
Phase C
1.50 triethanolamine
Phase D
13.00 the polyethylene (Luwax of BASF A)
Preparation:
Make phase A swelling.B is up to clarification for the dissolving phase.Phase B is stirred among the phase A.Neutralize with phase C.Then be stirred among the phase D.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the unguentum of washing one's face of superperformance under the various situations.
Application Example 28: facial soap with soap dish
Phase A
25.0 cocos nucifera oil fat acid potassium
20.0 cocos nucifera oil acyl both sexes base oxalic acid disodium
2.0 lauramide DEA
1.0 glycol stearate
2.0 the polymer of embodiment 17
50.0 distilled water
An amount of citric acid
Phase B
An amount of antiseptic
An amount of aromatic oil
Preparation:
Phase A is heated to 70 ℃ also to be stirred until all substances mix homogeneously.With Fructus Citri Limoniae acid for adjusting pH value to 7.0 to 7.5.Make each material be cooled to 50 ℃ and add the B phase.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the facial soap with soap dish of superperformance under the various situations.
Application Example 29: transparent soap
4.20 sodium hydroxide
3.60 distilled water
2.0 the polymer of embodiment 1
22.60 propylene glycol
18.70 glycerol
5.20 coconut oleoyl amine DEA
10.40 coco amine oxide
4.20 sodium lauryl sulfate salt
7.30 myristic acid
16.60 stearic acid
5.20 tocopherol
Preparation:
Mix all components.At 85 ℃ of molten mixtures up to clarification.Pour in the mould immediately.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the transparent soap of superperformance under the various situations.
Application Example 30:O/W type peeling frost
Phase A
3.00 ceteareth-6
1.50 ceteareth-25
3.00 tristerin
5.00 cetearyl alcohol, cetearyl alcohol sulfuric ester sodium salt
6.00 cetearyl alcohol caprylate
6.00 mineral oil
0.20 bisabolol
Phase B
2.00 propylene glycol
0.10 EDTA-disodium
3.00 the polymer of embodiment 18
An amount of antiseptic
59.70 distilled water
Phase C
0.50 tocopherol acetas
An amount of aromatic oil
Phase D
10.00 polyethylene
Preparation:
Phase A is heated to about 80 ℃ respectively with B mutually.Be stirred among the phase A phase B and homogenize.Be cooled to about 40 ℃, add phase C and carry out of short duration homogenize once more.Then be stirred among the phase D.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the peeling frost of superperformance under the various situations.
Application Example 31: the infusion of shaving
6.00 ceteareth-25
5.00 poloxamer 407
52.00 distilled water
1.00 triethanolamine
5.00 propylene glycol
1.00 PEG-75 lanolin oil
5.00 the polymer of embodiment 17
An amount of antiseptic
An amount of aromatic oil
25.00 the sulfuric ester sodium salt of laureth-(1-4)
Preparation:
Each material is weighed together, then stir until dissolving.Bottling: 90 parts of active substances and 10 parts of propane/butane mix of 25: 75.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the infusion of shaving of superperformance under the various situations.
Application Example 32: use face cream after shaving
Phase A
0.25 acrylate/C10-30 alkylol acrylamide acid esters cross-linked copolymer
1.50 tocopherol acetas
0.20 bisabolol
10.00 caprylic/capric triglyceride
An amount of aromatic oil
1.00 PEG-40 castor oil hydrogenated
Phase B
1.00 pantothenylol
15.00 alcohol
5.00 glycerol
0.05 hydroxyethyl-cellulose
1.92 the polymer of embodiment 1
64.00 distilled water
Phase C
0.08 sodium hydroxide
Preparation:
The component of mixed phase A.Phase B homogenize is stirred among the phase A, carries out of short duration back homogenize.Also carry out homogenize once more with phase C neutralization.
This embodiment can repeat with the polymer of other embodiment 1 to 50.Use face cream after all obtaining having the shaving of superperformance under the various situations.
Application Example 33: health maintenance frost
Phase A
2.00 ceteareth-6
2.00 ceteareth-25
2.00 cetearyl alcohol
3.00 tristerin SE
5.00 mineral oil
4.00 Jojoba (Buxus Chinensis) oil
3.00 cetearyl alcohol caprylate
1.00 dimethicone
3.00 mineral oil, lanolin alcohol
Phase B
5.00 propylene glycol
0.50 Veegum
1.00 pantothenylol
1.70 the polymer of embodiment 18
6.00 polyquaternary ammonium salt-44
An amount of antiseptic
60.80 distilled water
Phase C
An amount of aromatic oil
Preparation:
Phase A is heated to about 80 ℃ respectively with B mutually.Homogenize phase B.Phase B homogenize is stirred among the phase A, and carries out of short duration back homogenize.Be cooled to about 40 ℃, add phase C and carry out of short duration homogenize once more.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the health maintenance frost of superperformance under the various situations.
Application Example 34: toothpaste
Phase A
34.79 distilled water
3.00 the polymer of embodiment 17
0.30 antiseptic
20.00 glycerol
0.76 sodium monofluorophosphate
Phase B
1.20 sodium carboxymethyl cellulose
Phase C
0.80 aromatic oil
0.06 glucide
0.10 antiseptic
0.05 bisabolol
1.00 pantothenylol
0.50 tocopherol acetas
2.80 Silicon stone
1.00 sodium lauryl sulfate salt
7.90 dehydration dicalcium phosphate
25.29 dicalcium phosphate dihydrate
0.45 titanium dioxide
Preparation:
Dissolving phase A.Spray among the phase A phase B and dissolving.Adding phase C also stirred 45 minutes under room temperature, decompression.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the toothpaste of superperformance under the various situations.
Application Example 35: collutory
Phase A
2.00 aromatic oil
4.00 PEG-40 castor oil hydrogenated
1.00 bisabolol
30.00 alcohol
Phase B
0.20 glucide
5.00 glycerol
An amount of antiseptic
5.00 poloxamer 407
0.5 the polymer of embodiment 1
52.30 distilled water
Preparation:
Dissolve phase A and B mutually respectively up to clarification.Phase B is stirred among the phase A.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the collutory of superperformance under the various situations.
Application Example 36: dental adhesive
Phase A
0.20 bisabolol
1.00 beta-carotene
An amount of aromatic oil
20.00 cetearyl alcohol caprylate
5.00 Silicon stone
33.80 mineral oil
Phase B
5.00 the polymer of embodiment 18
35.00 PVP (aqueous solution of 20% concentration)
Preparation:
A thoroughly mixes with phase.Stir phase B in phase A.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the dental adhesive of superperformance under the various situations.
Application Example 37:O/W type skin care frost
Phase A
8.00 cetearyl alcohol
2.00 ceteareth-6
2.00 ceteareth-25
10.00 mineral oil
5.00 cetearyl alcohol caprylate
5.00 dimethicone
Phase B
3.00 the polymer of embodiment 17
2.00 pantothenylol, propylene glycol
An amount of antiseptic
63.00 distilled water
Phase C
An amount of aromatic oil
Preparation:
Phase A is heated to about 80 ℃ respectively with B mutually.Phase B homogenize is stirred among the phase A, and carries out of short duration back homogenize.Be cooled to about 40 ℃, add phase C and homogenize once more.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the skin care frost of superperformance under the various situations.
Application Example 38:W/O type skin care frost
Phase A
6.00 PEG-7 castor oil hydrogenated
8.00 cetearyl alcohol caprylate
5.00 isopropyl myristate
15.00 mineral oil
2.00 PEG-45/ dodecanediol copolymer
0.50 magnesium stearate
0.50 aluminium stearate
Phase B
3.00 glycerol
3.30 the polymer of embodiment 1
0.70 magnesium sulfate
2.00 pantothenylol
An amount of antiseptic
48.00 distilled water
Phase C
1.00 tocopherol
5.00 tocopherol acetas
An amount of aromatic oil
Preparation:
Phase A is heated to about 80 ℃ respectively with B mutually.Be stirred among the phase A phase B and homogenize.Be cooled to about 40 ℃, add phase C and carry out of short duration homogenize once more.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the skin care frost of superperformance under the various situations.
Application Example 39: lipblock
Phase A
10.00 cetearyl alcohol caprylate
5.00 polybutene
Phase B
0.10 carbomer
Phase C
2.00 ceteareth-6
2.00 ceteareth-25
2.00 tristerin
2.00 spermol
1.00 dimethicone
1.00 benzophenone-3
0.20 bisabolol
6.00 mineral oil
Phase D
8.00 the polymer of embodiment 18
3.00 pantothenylol
3.00 propylene glycol
An amount of antiseptic
54.00 distilled water
Phase E
0.10 triethanolamine
Phase F
0.50 tocopherol acetas
0.10 tocopherol
An amount of aromatic oil
Preparation:
A is up to clarification for the dissolving phase.Add phase B and homogenize.Add phase C and 80 ℃ of fusions.D to 80 ℃ of heating phase.Add among the phase ABC phase D and homogenize.Be cooled to about 40 ℃, add phase E and F mutually, carry out homogenize once more.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the lipblock of superperformance under the various situations.
Application Example 40: gloss
Phase A
5.30 little candle tree (Euphorbia Cerifera) wax
1.10 Cera Flava
1.10 microwax
2.00 cetin
3.30 mineral oil
2.40 Oleum Ricini, ricinoleic acid glyceride, octyl dodecanol, Carnauba wax, candelilla wax
0.40 bisabolol
16.00 cetearyl alcohol caprylate
2.00 hydrogenation cocos nucifera oil glycerol mixed ester
An amount of antiseptic
1.00 the polymer of embodiment 17
60.10 Semen Ricini (Ricinus Communis) oil
0.50 tocopherol acetas
Phase B
0.80 azogeramine 4 aluminum colors form sediment; C.I.14720:1
Phase C
4.00 Muscovitum, titanium dioxide
Preparation:
The phase of weighing A component and fusion.Sneak into phase B component up to homogenize.Add phase C and stirring.Cool to room temperature under agitation.
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the lip pomade of superperformance under the various situations.
Application Example 41: the preparation that is used for aerosol hair infusion:
The polymer of 2.00% embodiment 1
2.00% Luviquat Mono LS (cocoyl trimethyl ammonium methyl sulfate)
67.7% water
10.0 propane/butane 3.5bar (20 ℃)
An amount of aromatic oil
Comparative examples
2.00% Luviquat Hold (polyquaternary ammonium salt-46)
2.00% Luviquat Mono LS (cocoyl trimethyl ammonium methyl sulfate)
67.7% water
10.0 propane/butane 3.5bar (20 ℃)
An amount of aromatic oil
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the lip pomade of superperformance under the various situations.
Application Example 42: aerosol hair infusion:
INCI
The polymer of 4.00% embodiment 18
0.20% Cremophor A 25 ceteareth-25
1.00% Luviquat Mono CP ethoxy cetyl dimethyl ammonium phosphate
5.00% ethanol
1.00% pantothenylol
10.0 propane/butane 3.5bar (20 ℃)
An amount of aromatic oil
Add to 100% water
This embodiment can repeat with the polymer of other embodiment 1 to 50.All obtain having the lip pomade of superperformance under the various situations.
Application Example 43: pump formula infusion:
INCI
The polymer of 2.00% embodiment 17
2.00% Luviflex  Soft (amount of polymers)
1.20% 2-amino-2-methyl-1-propanol
0.20％ CremophorA 25
0.10% Uv-nul  P, 25 PEG-25 para-amino benzoic acid
An amount of antiseptic
An amount of aromatic oil
Add to 100% water
Application Example 44: pump formula spray:
INCI
The polymer of 4.00% embodiment 1
1.00% pantothenylol
0.10% Uvinul MS 40 benzophenone-4
An amount of antiseptic
An amount of aromatic oil
Add to 100% water
Application Example 45: pump formula spray:
INCI
The polymer of 4.00% embodiment 18
1.00% pantothenylol
0.10% Uvinul M 40 benzophenone-3
An amount of antiseptic
An amount of aromatic oil
Add to 100% ethanol
Application Example 46: hair jelly:
INCI
The polymer of 5.00% embodiment 17
0.10%Dow Corning DC 190 silicone oil dimethicone copolyol
35.00% dimethyl ether
5.00% pentane
Add to 100% ethanol
An amount of aromatic oil
Application Example 47: hair jelly VOC 55%:
INCI
The polymer of 1.00% embodiment 1
4.00%Luviset  P.U.R. polyurethanes-1
40.00% dimethyl ether
15.00% ethanol
An amount of aromatic oil
Add to 100% water
Application Example 48: hair gelling thickener:
The 0.50% usefulness triethanolamine pH that neutralizes is the polymer of 7.5 embodiment 17
3.00％ Luviset Clear
0.50% pantothenylol
An amount of aromatic oil
An amount of antiseptic
Add to 100% water
Generating viscosity thus is the clarifying substantially hair gel of 26200mPa*s.
This embodiment can repeat with the polymer of embodiment 1 to 16 and 18 to 50.
Application Example 49: hair gelling thickener:
The 0.50% usefulness triethanolamine pH that neutralizes is the polymer of 7.5 embodiment 17
6.00％ Luviskol K 30
0.10% phytantriol
0.50% pantothenylol
An amount of aromatic oil
An amount of antiseptic
Add to 100% water
Generating viscosity thus is the clarifying substantially hair gel of 29300mPa*s.
This embodiment can repeat with the polymer of embodiment 1 to 16 and 18 to 50.
Application Example 50: hair gelling thickener:
INCI
The 0.50% usefulness triethanolamine pH that neutralizes is the polymer of 7.5 embodiment 17
3.00％ Luvi skol K90
0.50% pantothenylol
0.10% Uvinul MS 40 benzophenone-3
An amount of aromatic oil
An amount of antiseptic
Add to 100% water
Generating viscosity thus is the clarifying substantially hair gel of 29200mPa*s.
This embodiment can repeat with the polymer of embodiment 1 to 16 and 18 to 50.
Application Example 51: hair gelling thickener:
INCI
The 0.50% usefulness triethanolamine pH that neutralizes is the polymer of 7.5 embodiment 17
2.00％Luviskol K90
2.00％Luviskol VA64W
0.50% pantothenylol
An amount of aromatic oil
An amount of antiseptic
Add to 100% water
Generating viscosity thus is the clarifying substantially hair gel of 20500mPa*s.
This embodiment can repeat with the polymer of embodiment 1 to 16 and 18 to 50.
Application Example 52: the gel Emulsion that contains the UV filtering agent
1 2 3 4
Acrylate/C10-30 alkylol acrylamide acid esters cross linked polymer 0.40 0.35 0.40 0.35
The polymer of embodiment 17 1.10 2.50 1.60 0.80
Xanthan gum 0.10 0.10
Cetearyl alcohol 3.00 2.50 3.00 2.50
C12-15 alkanol benzoate 4.00 4.50 4.00 4.50
Caprylic/capric triglyceride 3.00 3.50 3.00 3.50
Uvinul A Plus 2.00 1.50 0.75 1.00
UVASorb K2A 0.20 3.00
Ethylhexyl methoxy cinnamate 3.00 1.00
Two-ethyl hexyl oxy phenol methoxyphenyl triazine 0.30 1.50 2.00
Butyl methoxydibenzoylmethise 0.40 2.00
Phenyl bisbenzimidazole tetrasulfonic acid ester disodium salt 2.50 0.50 2.00
The ethylhexyl triazinone 4.00 3.00 4.00
Octocrylene 0.50 4.00
Diethylhexyl amide-based small triazinone 1.00 2.00
Phenylbenzimidazolesulfonic acid 0.50 3.00
Methylene two-benzotriazole base tetramethyl butyl phenol 2.00 0.50 1.50
Ethylhexyl salicylate 0.30 3.00
The drometrizole trisiloxanes 0.30 0.50
The Terephthalidene Dicamphor Sulfonic Acid 0.40 1.50 1.00
2,6-naphthalenedicarboxylic acid ethylhexyl 3.50 4.00 7.00 9.00
Superfine titanic oxide 1.00 3.00
Super fine zinc oxide 1.00 3.00 4.25
The ring-type dimethicone 5.00 5.50 5.00 5.50
Dimethicone releasing agent (dimethicone polydimethylsiloxane) 1.00 0.60 1.00 0.60
Glycerol 1.00 1.20 1.00 1.20
Sodium hydroxide In right amount In right amount In right amount In right amount
Antiseptic 0.30 0.23 0.30 0.23
Spice 0.20 0.20
Water Add to 100 Add to 100 Add to 100 Add to 100
PH regulator to 6.0
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 53:O/W type sunscreen formulations
1 2 3 4 5 6 7
Glyceryl monostearate SE 0.50 1.00 3.00 1.50
Glyceryl stearate Fructus Citri Limoniae ester 2.00 1.00 2.00 4.00
Stearic acid 3.00 2.00
The PEG-40 stearate 0.50 2.00
Phosphoric acid monohexadecyl ester 1.00
The cetearyl alcohol sulfuric ester 0.75
Stearyl alcohol 3.00 2.00 0.60
Spermol 2.50 1.10 1.50 0.60 2.00
The polymer of embodiment 1 2.50 1.60 0.80 1.40 4.00 1.00
Uvinul A Plus 2.00 1.50 0.75 1.00 2.10 4.50 5.00
UVASorb K2A 0.20
Ethylhexyl methoxy cinnamate 0.30 5.00 6.00 8.00
Two-ethyl hexyl oxy phenol methoxyphenyl triazine 0.40 1.50 2.00 2.50 2.50
Butyl methoxydibenzoylmethise 0.60 2.00 2.00 1.50
Phenyl bisbenzimidazole tetrasulfonic acid ester disodium salt 0.90 0.50 2.00 0.30
The ethylhexyl triazinone 4.00 3.00 4.00 2.00
The two propenyl benzenes of cyanogen are misery 4.00 7.50
Ester
Diethylhexyl amide-based small triazinone 1.00 2.00 1.00 1.00
Phenylbenzimidazolesulfonic acid 0.50 3.00
Methylene two-benzotriazole base tetramethyl butyl phenol 2.00 0.50 1.50 2.50
Ethylhexyl salicylate 0.30 3.00 5.00
The drometrizole trisiloxanes 0.80 0.50 1.00
The Terephthalidene Dicamphor Sulfonic Acid 0.50 1.50 1.00 1.00 0.50
2,6-naphthalenedicarboxylic acid ethylhexyl 3.50 7.00 6.00 9.00
Superfine titanic oxide 1.00 3.00 3.50 1.50
Super fine zinc oxide 2.00 0.25 2.00
C12-15 alkanol benzoate 0.25 4.00 7.00
Dicaprylyl ether 3.50 2.00
Butanediol dicaprylate/dicaprate 5.00 6.00
Cocos nucifera oil fat acid glyceride type 6.00 2.00
Dimethicone 0.50 1.00 2.00
The ring dimethyl siloxane 2.00 0.50 0.50
Adeps Bovis seu Bubali resin 2.00
PVP hexadecene copolymer 0.20 0.50 1.00
Glycerol 3.00 7.50 7.50 5.00 2.50
Xanthan gum 0.15
Vitamin E acetate 0.60 0.23 0.70 1.00
Fucogel 1000 3.00 10.00
Soybean oil 0.50 1.50 1.00
The ethyl hexyl oxy glycine 0.30
DMDM Hydantoin 0.60 0.40 0.20
Glyacil-L 0.18 0.20
Methyl butex 0.15 0.25 0.50
Phenoxyethanol 1.00 0.40 0.40 0.50 0.40
EDTA 0.02 0.05
Ethanol 2.00 1.50 3.00 1.20 5.00
Spice 0.10 0.25 0.30 0.40 0.20
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 54: aqueous dispersion
1 2 3 4 5
Ceteareth-20 1.00 0.50
Spermol 1 1.00
Carbomer sodium 0.20
Acrylate/C10-30 alkylol acrylamide acid esters cross linked polymer 0.50 0.40 0.10 0.50
Xanthan gum 0.15
The polymer of embodiment 18 3.00 2.00 2.50 6.00 0.80
Uvinul A Plus 2.00 1.50 0.75 1.00 2.10
UVASorb K2A 0.20 3.50
Ethylhexyl methoxy cinnamate 0.30 5.00
Two-ethyl hexyl oxy phenol methoxyphenyl triazine 0.40 1.50 2.00 2.50
Butyl methoxydibenzoylmethise 0.30 2.00 2.00
Phenyl bisbenzimidazole tetrasulfonic acid ester disodium salt 0.40 0.50 2.00
The ethylhexyl triazinone 4.00 3.00 4.00
Octocrylene 1.00 4.00
Diethylhexyl amide-based small triazinone 0.30 2.00 1.00
Phenylbenzimidazolesulfonic acid 0.50 3.00
Methylene two-benzotriazole base tetramethyl butyl phenol 2.00 0.50 1.50 2.50
Ethylhexyl salicylate 0.20 3.00
The drometrizole trisiloxanes 0.40 0.50
The Terephthalidene Dicamphor Sulfonic Acid 0.30 1.50 1.00 1.00
2,6-naphthalenedicarboxylic acid ethylhexyl 7.00 9.00
Superfine titanic oxide 1.00 3.00 3.50
Super fine zinc oxide 2.00 4.25
C12-15 alkanol benzoate 2.00 2.50
Dicaprylyl ether 4.00
Butanediol dicaprylate/dicaprate 4.00 2.00 6.00
Dicaprylyl carbonate 2.00 6.00
Dimethicone 0.50 1.00
Phenyl trimethyl polysiloxanes 2.00 0.50
Adeps Bovis seu Bubali resin 2.00 5.00
PVP hexadecene copolymer 0.50 0.50 1.00
Melissyl PVP 0.50 1.00
Ethylhexyl glycerol 1.00 0.80
Glycerol 3.00 7.50 7.50 8.50
Vitamin E acetate 0.50 0.25 1.00
Alpha-glucosyl rutin 0.60 0.25
Fucogel 1000 2.50 0.50 2.00
DMDM Hydantoin 0.60 0.45 0.25
Glvacil-S 0.20
Methyl butex 0.50 0.25 0.15
Phenoxyethanol 0.50 0.40 1.00
EDTA 0.01 0.05 0.10
Ethanol 3.00 2.00 1.50 7.00
Spice 0.20 0.05 0.40
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 55:W/O sunscreen formulations
1 2 3 4 5
Poly-cetyl dimethicone copolyol 2.50 4.00
Polyglycereol-2 dimerization hydroxy stearic acid ester 5.00 4.50
PEG-30 dimerization hydroxy stearic acid ester 5.00
The polymer of embodiment 17 2.00 3.00 2.50 1.70 3.00
Uvinul A Plus 2.00 1.50 0.75 1.00 2.10
UVASorb K2A 0.30 2.00
Ethylhexyl methoxy cinnamate 0.40 5.00
Two-ethyl hexyl oxy phenol methoxyphenyl triazine 0.50 1.50 2.00 2.50
Butyl methoxydibenzoylmethise 0.30 2.00 2.00
Phenyl bisbenzimidazole tetrasulfonic acid ester disodium salt 2.50 0.50 2.00
The ethylhexyl triazinone 0.40 3.00 4.00
Octocrylene 0.40 4.00
Diethylhexyl amide-based small triazinone 1.00 2.00 1.00
Phenylbenzimidazolesulfonic acid 0.50 3.00
Methylene two-benzotriazole base tetramethyl butyl phenol 0.50 0.50 1.50 2.50
Ethylhexyl salicylate 0.30 3.00
The drometrizole trisiloxanes 0.80 0.50
The Terephthalidene Dicamphor Sulfonic Acid 0.50 1.50 1.00 1.00
2,6-naphthalenedicarboxylic acid ethylhexyl 7.00 4.00
Superfine titanic oxide 1.00 3.00 3.50
Super fine zinc oxide 1.00 5.25
Paraffin oil 6.00 12.00 10.00 8.00
C12-15 alkanol benzoate 9.00
Two caprylyl ethers 10.00 7.00
Butanediol dicaprylate/dicaprate 2.00 8.00 4.00
Carbonic acid two decoyl esters 5.00 6.00
Dimethicone 4.00 1.00 5.00
Ring diformazan siloxanes 2.00 25.00 2.00
Adeps Bovis seu Bubali resin 3.00
Vaseline 4.50
PVP hexadecene copolymer 0.50 0.50 1.00
Ethylhexyl glycerol 0.30 1.00 0.50
Glycerol 3.00 7.50 7.50 8.50
MgSO 4 1.00 0.50 0.50
MgCl 2 1.00 0.70
Vitamin E acetate 0.50 0.25 1.00
Ascorbyl palmitate 0.50 2.00
Fucogel 1000 3.50 1.00
DMDM Hydantoin 0.60 0.40 0.20
Methyl butex 0.50 0.25 0.15
Phenoxyethanol 0.50 0.40 1.00
EDTA 0.12 0.05 0.30
Ethanol 3.00 1.50 5.00
Spice 0.20 0.40 0.35
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 56:PIT emulsion
1 2 3 4 5 6 7 8
Glyceryl monostearate SE 0.50 2.00 3.00 5.00 0.50 4.00
Iso stearic acid of glycerine ester 3.50 4.00 2.00
Different spermol polyethers-20 0.50 2.00
Ceteareth-12 5.00 1.00 3.50 5.00
Ceteareth-20 5.00 1.00 3.50
The PEG-100 stearate 2.80 2.30 3.30
Spermol 5.20 1.20 1.00 1.30 0.50 0.30
The spermol cetylate 2.50 1.20 1.50 0.50 1.50
Poly-cetyl dimethicone copolyol 0.50 1.00
Polyglycereol-2 dimerization hydroxy stearic acid ester 0.75 0.30
The polymer of embodiment 1 3.20 5.00 2.50 3.00 2.00 1.70 2.90 3.50
Uvinul A Plus 0.20 1.50 0.75 1.00 2.10 4.50 5.00 2.10
UVASorb K2A 0.30 4.00 1.50
Ethylhexyl methoxy cinnamate 0.40 5.00 6.00 8.00 5.00
Two-ethyl hexyl oxy phenol methoxyphenyl triazine 0.40 1.50 2.00 2.50 2.50 2.50
Butyl methoxydibenzoylmethise 2.00 2.00 2.00 1.50 2.00
Phenyl bisbenzimidazole tetrasulfonic acid ester disodium salt 2.50 0.50 2.00 0.30
The ethylhexyl triazinone 4.00 3.00 4.00 2.00
Octocrylene 2.00 4.00 7.50
Diethylhexyl amide-based small triazinone 1.00 2.00 1.00 1.00 1.00
Phenylbenzimidazolesulfonic acid 0.50 3.00
Methylene two-benzotriazole base tetramethyl butyl phenol 2.00 0.50 1.50 2.50 2.50
Ethylhexyl salicylate 0.30 3.00 5.00
The drometrizole trisiloxanes 0.30 0.50 1.00
The Terephthalidene Dicamphor Sulfonic Acid 0.20 1.50 1.00 1.00 0.50 1.00
2,6-naphthalenedicarboxylic acid ethylhexyl 7.00 10.00 7.50 8.00
Superfine titanic oxide 1.00 3.00 3.50 1.50 3.50
Super fine zinc oxide 0.25 2.00
C12-15 alkanol benzoate 3.50 6.35 0.10
Cocos nucifera oil fat acid glyceride type 3.00 3.00 1.00
Dicaprylyl ether 4.50
Carbonic acid two decoyl esters 4.30 3.00 7.00
Dibutyl adipate 0.50 0.30
The polyphenylene trimethicone 2.00 3.50 2.00
The ring dimethyl siloxane 3.00
The ethyl galactomannan 0.50 2.00
Hydrogenation cocos nucifera oil fat acid glyceride type 3.00 4.00
Abil Wax 2440 1.50 2.00
PVP hexadecene copolymer 1.00 1.20
Glycerol 4.00 6.00 5.00 8.00 10.00
Vitamin E acetate 0.20 0.30 0.40 0.30
Adeps Bovis seu Bubali resin 2.00 3.60 2.00
Butyl carbamic acid iodo propyl ester 0.12 0.20
Fucogel 1000 0.10
DMDM Hydantoin 0.10 0.12 0.13
Methyl butex 0.50 0.30 0.35
Phenoxyethanol 0.50 0.40 1.00
Sensiva SC50 0.30 1.00 0.35
Ethanol 2.00 2.00 5.00
EDTA 0.40 0.15 0.20
Spice 0.20 0.20 0.24 0.16 0.10 0.10
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 57: gel Emulsion
1 2 3 4
Acrylate/C10-30 alkylol acrylamide acid esters cross linked polymer 0.40 0.35 0.40 0.35
Luvigel EM 1.50
The polymer of embodiment 18 0.50 2.00 3.60 3.00
Xanthan gum 0.10 0.13 0.10 0.13
Cetearyl alcohol 3.00 2.50 3.00 2.50
C12-15 alkanol benzoate 4.00 4.50 4.00 4.50
Caprylic/capric triglyceride 3.50 3.00 3.50
Superfine titanic oxide 1.00 1.50
Super fine zinc oxide 1.00 2.00 2.25
Dihydroxy acetone 3.00 5.00
The ring-type dimethicone 5.00 5.50 5.00 5.50
The polydimethylsiloxane releasing agent 1.00 0.60 1.00 0.60
Glycerol 1.20 1.00 1.20
Sodium hydroxide In right amount In right amount In right amount In right amount
Antiseptic 0.30 0.23 0.30 0.23
Spice 0.20 0.20
Water Add to 100 Add to 100 Add to 100 Add to 100
PH regulator to 6.0
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 58:O/W preparation
1 2 3 4 5 6 7
Glyceryl monostearate SE 0.50 1.00 3.00 1.50
Glyceryl stearate Fructus Citri Limoniae ester 2.00 1.00 2.00 4.00
Stearic acid 3.00 2.00
The PEG-40 stearate 0.50 2.00
Phosphoric acid monohexadecyl ester 1.00
The cetearyl alcohol sulfuric ester 0.75
Stearyl alcohol 3.00 2.00 0.60
Spermol 1.10 1.50 0.60 2.00
The polymerization of embodiment 17 2.00 5.00 3.00 2.40 2.00 1.00 1.00
Thing
Dihydroxy acetone 3.00 5.00 4
Superfine titanic oxide 1.00 1.50 1.50
Super fine zinc oxide 1.00 0.25 2.00
C12-15 alkanol benzoate 0.25 4.00 7.00
Dicaprylyl ether 3.50 2.00
Butanediol dicaprylate/dicaprate 5.00 6.00
Cocos nucifera oil fat acid glyceride type 6.00 2.00
Dimethicone 0.50 1.00 2.00
The ring dimethyl siloxane 2.00 0.50 0.50
Adeps Bovis seu Bubali resin 2.00
PVP hexadecene copolymer 0.20 0.50 1.00
Glycerol 3.00 7.50 7.50 5.00 2.50
Xanthan gum 0.15 0.05 0.30
Carbomer sodium 0.15
Vitamin E acetate 0.60 0.23 0.70 1.00
Fucogel 1000 3.00 10.00
Paraffin oil 4.00 8.00 5.00 7.00 3.90 4.00 1.00
The ethyl hexyl oxy glycine 0.30
DMDM Hydantoin 0.60 0.40 0.20
Glyacil-L 0.18 0.20
Methyl butex 0.15 0.25 0.50
Phenoxyethanol 1.00 0.40 0.40 0.50 0.40
EDTA 0.02 0.05
Ethanol 2.00 1.50 3.00 1.20 5.00
Spice 0.10 0.25 0.30 0.40 0.20
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 59:O/W cosmetics
1 2 3 4 5 6 7
Glyceryl monostearate SE 0.50 1.00 3.00 1.50
Glyceryl stearate Fructus Citri Limoniae ester 2.00 1.00 2.00 4.00
Stearic acid 3.00 2.00
The PEG-40 stearate 0.50 2.00
Phosphoric acid monohexadecyl ester 1.00
The cetearyl alcohol sulfuric ester 0.75
Stearyl alcohol 3.00 2.00 0.60
Spermol 1.10 1.50 0.60 2.00
The polymer of embodiment 1 3.00 2.40 0.90 3.00 2.00 3.00 1.00
Superfine titanic oxide 1.00 12.00 9.00 8.50 11.00 9.50 10.00
Iron oxides 1.00 4.00 3.00 5.00 3.40 6.00 4.40
Super fine zinc oxide 1.00 4.00 2.00 3.00
C12-15 alkanol benzoate 0.25 4.00 7.00
Dicaprylyl ether 3.50 2.00
Butanediol dicaprylate/dicaprate 5.00 6.00
Cocos nucifera oil fat acid glyceride type 6.00 2.00
Dimethicone 0.50 1.00 2.00
The ring dimethyl siloxane 2.00 0.50 0.50
Adeps Bovis seu Bubali resin 2.00
The copolymerization of PVP hexadecene 0.20 0.50 1.00
Thing
Glycerol 3.00 7.50 7.50 5.00 2.50
Xanthan gum 0.15 0.05 0.30
Carbomer sodium 0.20
Vitamin E acetate 0.60 0.23 0.70 1.00
Paraffin oil 3.00 5.00 7.00 4.00 3.60 4.20 1.00
The ethyl hexyl oxy glycine 0.30
DMDM Hydantoin 0.60 0.40 0.20
Glyacil-L 0.18 0.20
Methyl butex 0.15 0.25 0.50
Phenoxyethanol 1.00 0.40 0.40 0.50 0.40
EDTA 0.02 0.05
The imino group succinic acid 0.25 1.00
Ethanol 2.00 1.50 3.00 1.20 5.00
Spice 0.10 0.25 0.30 0.40 0.20
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 60: aqueous dispersion
1 2 3 4 5
Ceteareth-20 1.00 0.50
Spermol 1.00
Luvigel EM 2.50
Acrylate/C10-30 alkylol acrylamide acid esters cross linked polymer 0.50 0.40 0.10 0.50
Xanthan gum 0.30 0.15
The polymer of embodiment 18 3.00 2.00 0.90 0.40 3.00
Dihydroxy acetone 3.00 5.00
Uvinul A Plus 1.50 0.75 1.00 2.10
Superfine titanic oxide 1.00 1.00 1.00
Super fine zinc oxide 1.00 1.90 0.25
C12-15 alkanol benzoate 2.50
Dicaprylyl ether 4.00
Butanediol dicaprylate/dicaprate 4.00 2.00 6.00
The dicaprylyl carbonate class 2.00 6.00
Dimethicone 0.50 1.00
The polyphenylene trimethicone 2.00 0.50
Adeps Bovis seu Bubali resin 2.00 5.00
PVP hexadecene copolymer 0.50 0.50 1.00
Melissyl PVP 0.50 1.00
Ethylhexyl glycerol 1.00 0.80
Glycerol 3.00 7.50 7.50 8.50
Paraffin oil 3.00 5.00 7.00 4.00 3.60
Vitamin E acetate 0.50 0.25 1.00
Alpha-glucosyl rutin 0.60 0.25
DMDM Hydantoin 0.60 0.45 0.25
Glyacil-S 0.20
Methyl butex 0.50 0.25 0.15
Phenoxyethanol 0.50 0.40 1.00
EDTA 0.01 0.05 0.10
Ethanol 3.00 2.00 1.50 7.00
Spice 0.20 0.05 0.40
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 61: shine the back aqueous dispersion
1 2 3 4 5
Ceteareth-20 1.00 0.50
Spermol 1.00
Luvigel EM 2.00
Acrylate/C10-30 alkylol acrylamide acid esters cross linked polymer 0.50 0.30 0.40 0.10 0.50
Xanthan gum 0.30 0.15
The polymer of embodiment 17 3.00 0.50 2.00 2.00 3.00
C12-15 alkanol benzoate 2.00 2.50
Dicaprylyl ether 4.00
Butanediol dicaprylate/dicaprate 2.00 6.00
The dicaprylyl carbonate class 2.00 6.00
Dimethicone 0.50 1.00
The polyphenylene trimethicone 0.50
Melissyl PVP 0.50 1.00
Ethylhexyl glycerol 1.00 0.80
Glycerol 7.50 7.50 8.50
Paraffin oil 1.00 3.00 1.50 2.00 1.00
Vitamin E acetate 0.50 0.25 1.00
Alpha-glucosyl rutin 0.60 0.25
EDTA 0.01 0.05 0.10
Ethanol 15.00 10.00 8.00 12.00 9.00
Spice 0.20 0.05 0.40
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 62:W/O emulsion
1 2 3 4 5
Poly-cetyl dimethicone copolyol 2.50 4.00
Polyglycereol-2 dimerization hydroxy stearic acid ester 5.00 4.50
PEG-30 dimerization hydroxy stearic acid ester 5.00
The polymer of embodiment 1 2.00 3.00 3.00 2.20 3.10
Uvinul A Plus 2.00 1.50 0.75 1.00 2.10
Superfine titanic oxide 1.00 3.00 3.50
Super fine zinc oxide 1.00 0.90 0.25
Paraffin oil 4.00 12.00 10.00 2.00 8.00
C12-15 alkanol benzoate 9.00
Two caprylyl ethers 10.00 7.00
Butanediol dicaprylate/dicaprate 2.00 8.00 4.00
Carbonic acid two decoyl esters 6.00
Dimethicone 4.00 1.00 5.00
The ring dimethyl siloxane 2.00 25.00 2.00
Adeps Bovis seu Bubali resin 3.00
Vaseline 4.50
PVP hexadecene copolymer 0.50 0.50 1.00
Ethylhexyl glycerol 0.30 1.00 0.50
Glycerol 3.00 7.50 7.50 8.50
MgSO 4 1.00 0.50 0.50
MgCl 2 1.00 0.70
Vitamin E acetate 0.50 0.25 1.00
Ascorbyl palmitate 0.50 2.00
Fucogel 1000 3.50 7.00
DMDM Hydantoin 0.60 0.40 0.20
Methyl butex 0.50 0.25 0.15
Phenoxyethanol 0.50 0.40 1.00
EDTA 0.12 0.05 0.30
Spice 0.20 0.40 0.35
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 63: the emulsion that solid particle is stable
1 2 3 4 5
Paraffin oil 4.00 6.00 16.00 16.00 6.00
Hot dodecanol 9.00 9.00 5.00
Caprylic/capric triglyceride 9.00 9.00 6.00
C12-15 alkanol benzoate 5.00 8.00
Butanediol dicaprylate/dicaprate 8.00
Two caprylyl ethers 9.00 4.00
Carbonic acid two decoyl esters 9.00
Hydroxyl 28 alkanol hydroxy stearic acid ester 2.00 2.00 2.20 2.50 1.50
Distearyl dimethylammonio Strese Hofmann's hectorite. 0.75 0.50 0.25
Microwax+liquid paraffin 0.35 5.00
Hydroxypropyl emthylcellulose 0.10 0.05
Dimethicone 3.00
The polymer of embodiment 18 3.00 5.00 0.90 1.40 2.00
Titanium dioxide+aluminium oxide+dimethione+water 1.00 3.00
Titanium dioxide+trimethoxy caprylyl silane 1.00 2.00 4.00 2.00 4.00
Zinc oxide (z-Cote HP1) 3.00 2.00
The dimetylsilyl Silicon stone 2.50 6.00 2.50
Boron nitride 1.00
Starch/Polymeric sodium metaphosphate. polymer 2.00
Tapioca 0.50
Sodium chloride 5.00 7.00 8.50 3.00 4.50
Glycerol 1.00
EDTA 1.00 1.00 1.00 1.00 1.00
Vitamin E acetate 5.00 10.00 3.00 6.00 10.00
Ascorbyl palmitate 1.00 1.00 1.00
Methyl butex 0.60 0.20
Propyl p-hydroxybenzoate 0.20
Phenoxyethanol 0.20
Hexamidine dihydroxy ethyl sulfonate 0.40 0.50 0.40
Diazolidinyl urea 0.08
Ethanol 0.23 0.20
Spice 5.00 3.00 4.00
Water 0.20 0.30 0.10
Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 64:PIT emulsion
1 2 3 4 5 6 7 8
Glyceryl monostearate SE 0.50 2.00 3.00 5.00 0.50 4.00
Iso stearic acid of glycerine ester 3.50 4.00 2.00
Different spermol polyethers-20 0.50 2.00
Ceteareth-12 5.00 1.00 3.50 5.00
Ceteareth-20 5.00 1.00 3.50
The PEG-100 stearate 3.00 2.80 2.30 3.30
Spermol 5.20 1.20 1.00 1.30 0.50 0.30
The spermol cetylate 2.50 1.20 1.50 0.50 1.50
Poly-cetyl dimethicone copolyol 0.50 1.00
Polyglycereol-2 dimerization hydroxy stearic acid ester 0.30 0.75 0.30
The polymer of embodiment 17 2.00 5.00 2.00 3.00 2.00 1.60 3.80 4.00
Dihydroxy acetone 3.00 5.00 4.00
Uvinul A Plus 2.00 1.50 0.75 1.00 2.10 4.50 5.00 2.10
Superfine titanic oxide 1.00 1.50 3.50 1.50 1.00
Super fine zinc oxide 1.00 1.00 0.25 2.00 1.50
C12-15 alkanol benzoate 3.50 6.35 0.10
Cocos nucifera oil fat acid glyceride type 3.00 3.00 1.00
Dicaprylyl ether 4.50
Carbonic acid two decoyl esters 4.30 3.00 7.00
Dibutyl adipate 0.50 0.30
The polyphenylene trimethicone 2.00 3.50 2.00
The ring dimethyl siloxane 3.00
The ethyl galactomannan 0.50 2.00
Hydrogenation cocos nucifera oil fat acid glyceride type 3.00 4.00
Abil Wax 2440 1.50 2.00
PVP hexadecene copolymer 1.00 1.20
Glycerol 4.00 6.00 5.00 8.00 10.00
Vitamin E acetate 0.20 0.30 0.40 0.30
Adeps Bovis seu Bubali resin 2.00 3.60 2.00
Butyl carbamic acid iodo propyl ester 0.12 0.20
DMDM Hydantoin 0.10 0.12 0.13
Methyl butex 0.50 0.30 0.35
Phenoxyethanol 0.50 0.40 1.00
Sensiva SC50 0.30 1.00 0.35
Ethanol 2.00 2.00 5.00
EDTA 0.40 0.15 0.20
Spice 0.20 0.20 0.24 0.16 0.10 0.10
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 65:O/W foot emulsion formulations
1 2 3 4
The INCI title Weight % Weight % Weight % Weight %
Water Add to 100 Add to 100 Add to 100 Add to 100
Glycerol 5.00 6.00 4.50 3.50
The polymer of embodiment 1 2.30 3.50 0.40 1.20
Cetearyl glucoside, cetearyl alcohol 8.00 7.00 5.00 8.00
American Avocado Tree (Avocado) oil 5.00 4.50 3.00 6.00
Paraffin oil 6.00 3.00 5.00 5.00
Semen Tritici aestivi (Wheat) germ oil 1.00 1.50 1.00 2.00
Two caprylyl ethers 2.00 2.00 2.50 1.00
Caprylic/capric triglyceride 5.00 7.00 2.50 5.00
Dimethicone 0.10 0.20 0.25 0.15
Pantothenylol 1.00 1.00 1.00 1.00
Tocopherol acetas 1.00 1.00 1.00 1.00
Phenoxyethanol, methyl parahydroxybenzoate, oxybenzene Ethyl formate, butyl p-hydroxybenzoate, propyl p-hydroxybenzoate, p-Hydroxybenzoic acid isobutyl ester 0.60 0.50 0.60 0.50
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 66: triple active health face creams
1 2 3 4 5
The INCI title Weight % Weight % Weight % Weight % Weight % Weight %
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
Glycerol 3.0 5.50 6.00 4.50 5.00 3.5
Glyceryl stearate Fructus Citri Limoniae ester 1.80 2.00 2.50 3.00 1.50 2
Sucrose stearate 1.00 1.20 0.95 2.00 2.20 1.5
Cetearyl alcohol 1.80 2.00 3.00 1.50 2.40 2.8
Ethylhexyl palmitate 6.00 5.00 5.50 3.50 3.00 5.5
Paraffin oil 5.00 5.00 4.00 1.00 2.00 3.5
The different pelargonate of cetearyl alcohol 7.00 3.00 2.50 2.40 3.10 4.6
Phenoxyethanol, methyl butex, ethylparaben, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate 1.00 0.60 0.50 0.70 0.60 0.5
Dimethicone 2.00 1.50 0.20 0.50 1.80 1.4
Xanthan gum 0.25 0.2
The polymer of embodiment 18 1.00 1.50 1.80 0.80 2.00 0.7
Sodium hydroxide, water 0.20 0.15 0.20 0.50 0.20 0.2
Bisabolol 2.00 1.50 0.50 0.20 0.50 1
Water, ascorbic acid phosphoric acid esters sodium salt 1.00 0.50 1.50 2.00 3.00 1.5
RetiSTAR 1.00 0.50 0.90 0.80 0.50 1
Spice 0.05 0.10 0.05 0.10 0.05 0.05
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 67: the male uses lipoid moulding (liposculpt) emulsion
1 2 3 4
Raw material Weight % Weight % Weight % Weight % Weight %
Deionized water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
The polymer of embodiment 17 1.00 1.50 2.00 2.20 1.80
Butanediol 5.00 6.50 5.50 3.50 4.00
Mix parabens 0.20 0.20 0.20 0.20 0.20
Potassium sorbate 0.10 0.10 0.10 0.10 0.10
Stearic acid 1.50 2.00 1.90 2.50 1.00
Crodamol GTCC (caprylic/capric triglyceride) 2.00 5.00 3.00 4.00 2.50
Crodacol C90 (spermol) 0.50 1.50 2.00 1.00 0.50
Crodacol CES (cetearyl alcohol ﹠ dicetyl phosphate ﹠ spermol polyethers 10 phosphate esters) 1.50 2.00 1.80 1.90 2.10
Paraffin oil 2.00 5.00 10.00 7.50 4.00
Water, sodium hydroxide 0.50 0.60 0.80 0.90 0.70
Water, ascorbic acid phosphoric acid esters sodium salt 3.00 5.00 6.00 2.00 1.50
Alcohol 95 3.00 5.00 4.00 6.00 5.50
Spice 0.10 0.05 0.05 0.10 0.15
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 68: Fang Shai ﹠amp; Shine the back frost
1 2 3 4 5
The INCI title Weight % Weight % Weight % Weight % Weight %
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
Pantothenylol 2.0 3 2.5 3.5 3
Cetearyl alcohol (with) dicetyl phosphate (with) spermol polyethers 10 phosphate esters 5.00 6.00 5.50 4.00 4.50
Cocos nucifera oil fat acid glyceride type 6.00 5.00 4.00 1.00 2.00
C12-15 alkanol benzoate 3.00 2.00 1.00 2.50 5.00
Coconut acid ester in the last of the ten Heavenly stems 3.00 4.00 1.00 5.00 5.00
Squalane 2.00 0.50 1.00 1.50 2.00
The polymer of embodiment 1 1.00 2.50 2.00 1.50 0.50
Paraffin oil 5.00 10.00 7.50 6.50 8.00
Water, sodium hydroxide 0.60 1.50 1.20 1.00 0.20
Encircle penta siloxanes 3.00 2.00 1.50 1.00 5.00
Bisabolol 0.20 0.50 0.15 0.30 0.45
Phenoxyethanol, methyl parahydroxybenzoate, oxybenzene butyl formate, ethylparaben, propyl p-hydroxybenzoate, p-Hydroxybenzoic acid isobutyl ester 0.40 0.50 0.70 0.80 1.00
Water, ascorbic acid phosphoric acid esters sodium salt 3.00 2.00 5.00 4.00 3.50
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 69: eye fluid
1 2 3 4 5
The INCI title Weight % Weight % Weight % Weight % Weight %
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
Galactoaraban 0.50 1.00 0.75 0.25 1.20
Water, Hamamelis virginiana (hamamelis virginiana) 10.00 5.00 3.00 2.00 4.50
Nicotiamide 0.20 0.30 0.10 0.50 0.40
Phenoxyethanol, methyl butex, ethylparaben, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate 0.50 0.70 0.80 1.00 0.50
Paraffin oil 2.00 5.00 3.00 4.50 2.50
The polymer of embodiment 18 2.50 3.00 1.50 2.00 2.00
Encircle penta siloxanes, dimethicone/silicon alkoxyl silicic acid vinyl trimethyl cross linked polymer 5.00 2.00 4.00 3.50 4.50
Water, caffeine 2.00 5.00 3.00 4.00 3.00
Water, sodium hydroxide 1.20 2.50 1.80 2.40 1.80
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 70: picotement is sent out (tingling hair) integer gel
1 2 3 4 5
The INCI title Weight % Weight % Weight % Weight % Weight %
Boron sikicate aluminum calcium, CI 77891 (titanium dioxide), Silicon stone, stannum oxide 2.55 2.50 2.30 2.00 3.00
Aluminium oxide, CI 77891 (titanium dioxide), stannum oxide 0.40 0.50 0.55 0.35 0.30
Muscovitum, CI 77499 (iron oxides), CI 77891 (titanium dioxide) 0.05 0.10 0.15 0.20 0.05
The polymer of embodiment 17 4.50 5.50 6.00 6.50 7.00
Isopropyl alcohol 20.00 15.00 25.00 30.00 40.00
Water 30.00 35.00 25.00 20.00 10.00
PVP 2.00 2.50 1.50 1.00 2.50
Propylene glycol, diazolidinyl urea, methyl butex, propyl p-hydroxybenzoate 1.00 0.80 1.00 1.00 1.00
AMP 0.50 0.60 0.80 0.90 1.30
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 71:W/O/W emulsion
1 2 3 4
Additive Weight % Weight % Weight % Weight %
Glyceryl stearate 3.00 5.00 4.50 3.50
The PEG-100 stearate 0.75 1.50 3.00 1.20
Behenyl alcohol 2.00 1.50 2.50 4.00
Caprylic/capric triglyceride 8.00 10.00 6.50 5.00
The cetearyl alcohol ethylhexoate 5.00 4.50 6.00 5.50
C12-15 alkanol benzoate 3.00 4.00 5.00 4.50
The polymer of embodiment 1 5.00 4.50 3.50 3.00
Ethylhexyl methoxy cinnamate 5.00 6.00 7.50 5.50
Two-ethyl hexyl oxy phenol 1.80 2.00 1.50 1.00
Methoxy benzene triazine
The ethylhexyl triazinone 1.50 1.00 0.50 1.20
Magnesium sulfate (MgSO 4) 0.80 1.00 0.50 0.75
EDTA 0.10 0.15 0.05 0.10
Antiseptic 0.50 0.60 0.80 1.00
Spice 0.05 0.10 0.05 0.10
Water, triethanolamine 5.50 5.00 4.50 4.00
Water Add to 100.0 Add to 100.0 Add to 100.0 Add to 100.0
PH adjusts to 6.0
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 72: roll and put formula deodorizer on the skin
The INCI title 1 2 3 4 5
The polymer of embodiment 18 1.5 2 2.5 3 2.2
Water 30 30 30 30 30
Water, sodium hydroxide 0.6 0.8 1 1.4 0.9
The PEG-40 castor oil hydrogenated 2 2.5 3 3.5 3
Bisabolol 0.1 0.1 0.1 0.1 0.1
Farnesol 0.3 0.2 0.3 0.1 0.3
Spice 0.1 0.05 0.2 0.1 0.05
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
Ethanol 25 30 35 30 32
Propylene glycol 3 2 2 3 2.5
Allantoin 0.1 0.1 0.1 0.1 0.1
Aluminium chlorohydrate 5 5.5 7.5 6 5.5
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 73: the back face cream shaves
1 2 3 4 5
Composition ％ ％ ％ ％ ％
Acrylate/C 10-30The alkylol acrylamide acid ester copolymer 0.25 0.30 0.34 0.25 0.40
Tocopherol acetas 1.50 2.00 2.50 0.50 1.00
Bisabolol 0.20 0.50 0.25 0.30 0.35
Caprylic/capric triglyceride 10.00 12.00 11.00 8.00 5.00
Spice 0.05 0.10 0.10 0.15 0.10
The PEG-40 castor oil hydrogenated 1.00 1.50 2.00 2.50 1.50
Pantothenylol 1.00 1.50 2.00 0.80 0.75
Ethanol 15.00 20.00 25.00 23.00 19.00
Glycerol 5.00 4.00 6.00 7.50 8.00
Hydroxyethyl-cellulose 0.05 0.10 0.15 0.20 0.15
The polymer of embodiment 17 3.50 3.00 5.00 1.00 1.50
Distilled water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
Water, sodium hydroxide 2.00 1.50 2.20 0.50 1.20
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 74:W/S preparation
1 2 3 4 5
Composition ％ ％ ％ ％ ％
Cetyl PEG/PPG-10/1 dimethicone 2.50 3.50 3.00 2.00 2.50
The cetyl dimethyl polysiloxane 1.50 1.00 2.50 3.00 4.00
Dimethicone 1.50 2.00 3.00 4.50 0.50
Encircle penta siloxanes, hexamethylene siloxanes 15.00 20.00 25.00 10.00 18.00
Encircle penta siloxanes, caprylyl dimethyl polysiloxane ethyoxyl glucoside 1.50 2.50 5.00 0.50 3.50
The polymer of embodiment 1 1.50 2.00 0.50 1.30 0.80
Phenyl trimethyl polysiloxanes 1.50 2.00 5.00
Sodium chloride 1.00 0.50 0.80 0.70 1.50
Water, triethanolamine 1.00 2.00 0.70 1.10 1.00
Propylene glycol 5.00 10.00 15.00 3.00 4.00
Water 70.00
Phenoxyethanol, methyl butex, ethylparaben, butyl p-hydroxybenzoate, propyl p-hydroxybenzoate 0.50 1.00 0.70
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 75: diminishing (water-reduced) glycerogel, not fatty
1 2 3 4 5
Composition ％ ％ ％ ％ ％
Glycerol 99% Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
The polymer of embodiment 18 0.50 1.00 1.50 2.00 2.00
Urea 10.00 15.00 2.00 5.00 7.00
Phenoxyethanol, ethylhexyl glycerol 1.00 0.55
AMP 0.30 0.60 0.90 1.20 1.20
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 76: disinfectant gel
1 2 3 4 5
Composition ％ ％ ％ ％ ％
Ethanol 50.00 45.00 60.00 55.00 40.00
The polymer of embodiment 17 2.00 2.50 1.50 3.50 4.00
Farnesol 0.50 0.80 0.30 0.40 0.55
Peeling Flos Matricariae chamomillae (Chamomilla Recutita, Matricaria) flower/leaf extract 5.00 3.00 4.00 2.00 6.00
AMP 1.20 1.50 0.90 2.10 2.40
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 77: roll and put formula deodorizer on the skin
1 2 3 4 5
Composition ％ ％ ％ ％ ％
Propylene glycol 50.00 60.00 70.00 65.00 75.00
Aluminium chlorohydrate 20.00 15.00 20.00 20.00 15.00
Allantoin 0.05 0.15 0.10 0.15 0.20
The polymer of embodiment 1 1.00 1.50 1.80 2.00 0.90
AMP 0.40 0.30 0.50 0.60 0.30
Farnesol 0.50 0.30 0.20 0.40 0.25
Phenoxyethanol and benzoic acid and dehydroacetic acid 1.00 0.90 0.80 1.00 1.00
Water Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
This embodiment can repeat with the polymer of other embodiment 1-50.
Application Example 78: the diminishing gel that contains enzyme
1 2 3 4 5 6 7
％ ％ ％ ％ ％ ％ ％
Glycerol 99% Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100 Add to 100
The polymer of embodiment 18 2.50 3.00 1.50 1.00 3.00 1.00 3.00
AMP 1.50 1.80 0.60 0.60 1.80 0.60 1.80
Antiseptic In right amount In right amount In right amount In right amount In right amount In right amount In right amount
Ubiquinone 0.01 0.05 0.1
Subtilisin 0.01 0.01
Plankton extractions, lecithin 0.01 0.01
This embodiment can repeat with the polymer of other embodiment 1-50.

Claims (21)

1. if the polymer of the unsaturated anionic monomer of olefin type---suitable form with aqueous dispersion exists---is used to improve the purposes of the rheological property of the cosmetics of aqueous, alcohol or water/alcohol or skin composition, described polymer can obtain by monomeric radical polymerization in aqueous medium, each comfortable at least a group polymer and at least a group b that is selected from a) that be selected from of polymerization process wherein) carry out under polymer exists, wherein organize a) and be constructed as follows:
A1) vinyl acetate and/or propionate (i) Polyethylene Glycol or (ii) one or both ends by alkyl, carboxyl or amino-terminated Polyethylene Glycol or the graft polymers on the polypropylene glycol,
A2) ployalkylene glycol,
A3) one or both ends are by alkyl, carboxyl or amino-terminated ployalkylene glycol,
A4) alkyl ployalkylene glycol (methyl) acrylate and (methyl) acrylic acid copolymer, and group b) be constructed as follows:
B1) copolymer of the vinyl alkyl ethers of partial hydrolysis and maleic anhydride at least, it can be at least in part exists with the form of salt,
B2) be selected from cation-modified starch, anion-modified starch, the starch of degraded and the water soluble starch of maltodextrin,
B3) be selected from following anionic copolymer:
Monomeric homopolymer of-anionic and copolymer,
If-anionic monomer and cationic monomer and---suitable---and copolymer neutral monomer, wherein monomeric minute rate of the anionic of copolymerization greater than the branch rate of cationic monomer and
-at least a anionic monomer and at least a monomeric copolymer that is selected from ester, styrene, N-vinyl pyrrolidone, N-caprolactam, N-vinyl imidazole, N-vinyl formamide, acrylamide, Methacrylamide, vinyl acetate and the propionate of anionic monomer and monohydric alcohol
B4) if the cationic copolymer of nonionic monoethenoid unsaturated monomer and cation monoene type unsaturated monomer and---suitable---anion monoethenoid unsaturated monomer, wherein in each situation the quantity of cation group greater than the quantity of anionic group.
2. according to the purposes of claim 1, molal weight M wherein nBe that 100 to 100 000 ployalkylene glycol, one or both ends are by alkyl, carboxyl or amino-terminated and molal weight M nBe that 100 to 100 000 ployalkylene glycol is as polymer (a).
3. according to the purposes of claim 1 or 2, molal weight M wherein nThe amount that is 500 to 20 000g/mol and ethylene oxide unit is that the oxirane of 10 to 80 moles of % and the block copolymer of expoxy propane are used as polymer (a).
4. according to the purposes of one of claim 1-3, the unsaturated C of olefin type wherein 3To C 5Carboxylic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide group methyl propane sulfonic acid, vinylphosphonic acid, their part or all of usefulness alkali metal base and/or at least a homopolymer and/or at least a these monomeric copolymers of the neutral salt of ammonium alkali are used as polymer (b).
5. according to the purposes of one of claim 1-3, wherein the copolymer of the vinyl alkyl ethers of part or preferred all hydrolysis and maleic anhydride is as the polymer of group (b), exists with the form of its alkali metal salts or ammonium salt at least in part if this copolymer is suitable.
6. according to claim 1,4 or 5 purposes, wherein molecular weight M nBe 100 to 100 000 the graft polymers of vinyl acetate on Polyethylene Glycol as polymer a), and the vinyl methyl ether of part or preferred all hydrolysis and the copolymer of maleic anhydride---it can exist to the form of small part with its alkali metal salts or ammonium salt---are as polymer b).
7. according to the purposes of claim 1, wherein alkyl ployalkylene glycol (methyl) acrylate and (methyl) acrylic acid copolymer as polymer a), and if part or the preferred all vinyl methyl ether of hydrolysis and the copolymer of maleic anhydride---this copolymer suitable to the form of small part exist---with its alkali metal salts or ammonium salt as polymer b).
8. according to the purposes of claim 1, wherein
Molecular weight M NBe 300 to 50 000 polypropylene glycol, Polyethylene Glycol and/or oxirane and the block copolymer and/or the molecular weight M of expoxy propane NBe 300 to 50 000 and at one end or two ends by C 1To C 4The block copolymer of alkyl-blocked polypropylene glycol, Polyethylene Glycol and/or oxirane and expoxy propane as polymer a)
And
Maltodextrin is as polymer b).
9. according to the purposes of one of claim 1-3, wherein
(i) the unsaturated C of at least a olefin type 3To C 5Carboxylic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide group methyl propane sulfonic acid, vinylphosphonic acid and/or its alkali metal salt and/or ammonium salt,
(ii) at least a be selected from partly or entirely neutral (methyl) propenoic acid dialkyl aminoalkyl ester, partly or entirely quaternised (methyl) propenoic acid dialkyl aminoalkyl ester, quaternized or in and the monomer of dialkyl aminoalkyl (methyl) acrylamide, dialkyl diallyl ammonium halide and the quaternised N-vinyl imidazole of form, with, if it is suitable
(iii) at least a neutral monomer,
Copolymer as polymer b),
Wherein monomeric minute rate of the anionic of copolymerization is greater than the branch rate of cationic monomer.
10. according to the purposes of one of claim 1-3, wherein
(i) at least a anionic monomer and
The (ii) at least a monomer that is selected from ester, styrene, N-vinyl pyrrolidone, N-caprolactam, N-vinyl imidazole, N-vinyl formamide, acrylamide, Methacrylamide, vinyl acetate and the propionate of olefin type unsaturated acids and monohydric alcohol
Copolymer as polymer (b)
11. purposes according to claim 1, the block copolymer of wherein at least a oxirane and expoxy propane is used as polymer a), and at least a acrylic acid copolymer of acrylamide, dimethylaminoethyl acrylate methochloride and 0 to 5 mole of % copolymerized form that contains is as polymer b).
12. purposes according to claim 1, wherein the copolymer of methacrylic acid and acrylamide group methyl propane sulfonic acid is as polymer b), be used for preparing the methacrylic acid of copolymer in the described copolymer and the mol ratio of acrylamide group methyl propane sulfonic acid is 9: 1 to 1: 9, preferred 9: 1 to 6: 4.
13. according to the purposes of one of claim 1-12, the unsaturated C of monoethenoid wherein 3To C 5Carboxylic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide group methyl propane sulfonic acid, vinylphosphonic acid and/or its alkali metal salt and/or ammonium salt are as the anionic monomer.
14., wherein carry out under the monomeric existence that is aggregated in other olefin type unsaturated monomer of anionic according to the purposes of one of claim 1-13.
15. according to the purposes of claim 14, monomeric at least a being selected from (methyl) acrylamide, the monobasic C of being aggregated in of anionic wherein 1-C 22(methyl) acrylate, the C of alcohol 3-C 22Alkyl vinyl ether, C 6-C 16Alkene, derivatives of poly (iso) butene, vinyl acetate, propionate, (methyl) propenoic acid dialkyl amino ethyl ester, (methyl) if the amino propyl ester of propenoic acid dialkyl, diallyldimethylammonium chloride, the suitable quaternised vinyl imidazole of N-vinyl formamide and partly or entirely the monomer of neutralization or quaternised dialkyl aminoalkyl (methyl) acrylamide carry out under existing.
16. according to the purposes of one of claim 1-15, wherein in radical polymerization process, acrylic acid uses not existing under other monomeric situation.
17. according to the purposes of one of claim 1-16, wherein polymerization also can be carried out in the presence of at least a cross-linking agent.
18. purposes according to claim 17, wherein said cross-linking agent is selected from triallylamine, pentaerythritol triallyl ether, the methylene diacrylamine, N, N '-divinyl ethylene-urea, have 2 to 4 carbon atoms and by the acrylic or methacrylic acid dihydroxylic alcohols of esterification fully, the trimethylolpropane triacrylate of ethoxylation, the trimethylol-propane trimethacrylate of ethoxylation, pentaerythritol triacrylate, tetramethylol methane tetraacrylate and/or triallyl ammonio methacrylate, the allyl ether that contains at least two allylic sugar, vinyl ethers with at least two vinyls, or triallylamine, and the mixture of these chemical compounds.
19. a composition of hair cosmetics contains at least a polymer as the unsaturated anionic monomer of the defined olefin type of one of claim 1-18.
20. a skin cosmetic composition contains at least a polymer as the unsaturated anionic monomer of the defined olefin type of one of claim 1-18.
21. a skin composition contains at least a polymer as the unsaturated anionic monomer of the defined olefin type of one of claim 1-18.
CNA2006800103251A 2005-01-28 2006-01-24 Use of a water-in-water emulsion polymers in the form of a thickener for cosmetic preparations Pending CN101151016A (en)

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