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    • 专利摘要:
    The present invention provides a composition comprising: 30 to 99% by weight of t-butyl acrylate and / or t-butyl methacrylate designated as monomer A; 1 to 28% by weight of acrylic acid and / or methacrylic acid designated as monomer B; And 0 to 60% by weight of a radical copolymerizable monomer or a radical copolymerizable monomer mixture designated as monomer C (at least one of the monomers C produces a homopolymer having a glass transition temperature of less than 30 캜) Values of 10 to 60 (the total weight percent is 100%). The radical polymerization is carried out in the presence of an alkanethiol having a carbon chain length of C14 to C22. The present invention also provides a composition comprising: 30 to 99% by weight of t-butyl acrylate and / or t-butyl methacrylate designated as monomer A; 1 to 28% by weight of acrylic acid and / or methacrylic acid designated as monomer B; And 0 to 60% by weight of a radical copolymerizable monomer or a radical copolymerizable monomer mixture designated as monomer C (at least one monomer C produces a homopolymer having a glass transition temperature of less than 30 캜) Values of 10 to 60 (the sum of the weight percentages being 100). This radical polymerization is carried out in the presence of an alkanethiol having a carbon chain length of C10 to C22, followed by hydrogen peroxide treatment. The invention also relates to the use of these acrylate polymers as film-forming agents and their use in cosmetic preparations.
    公开号:KR20030051790A
    申请号:KR10-2003-7006315
    申请日:2001-11-09
    公开日:2003-06-25
    发明作者:빌마 엠. 다우쉬；카트린 짜이츠；탄야 슈나이더；막시밀리안 앙겔；베른트 데포촐리；클라우디아 우드
    申请人:바스프 악티엔게젤샤프트；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION [0002] Acrylate polymers based on t-butyl acrylate and / or t-butyl methacrylate {ACRYLATE POLYMERS BASED ON TERT-BUTYL ACRYLATE AND / OR TERT-BUTYL METHACRYLATE}
    [1] The present invention relates to a novel polymer based on t-butyl acrylate and / or t-butyl methacrylate, a process for its preparation and its use, in particular its use in cosmetic preparations.
    [2] EP 379 082 A1
    [3] A) 75 to 99% by weight of t-butyl acrylate and / or t-butyl methacrylate,
    [4] B) from 1 to 25% by weight of acrylic acid and / or methacrylic acid and
    [5] C) t-butyl acrylate and / or t-butyl methacrylate based copolymer having a K value of 10 to 50, obtainable by free radical polymerization of 0 to 10% by weight of an additional free radical copolymerizable monomer, Wherein the carboxyl groups of the copolymer are not neutralized or are partially or fully neutralized with an amine.
    [6] EP 696 916 B1
    [7] A) 30 to 72% by weight of t-butyl acrylate or t-butyl methacrylate as monomer A and mixtures thereof,
    [8] B) from 10 to 28% by weight of acrylic acid or methacrylic acid or mixtures thereof as monomer B and
    [9] C) 0 to 60% by weight of free radical copolymerizable monomers or free radical copolymerizable monomer mixtures as monomer C, or by free radical polymerization of one or more monomers C to produce a homopolymer having a glass transition temperature of less than 30 DEG C Butyl acrylate or t-butyl methacrylate based copolymer having a K value of 10 to 50, wherein the carboxyl group of the copolymer is not neutralized, partially or completely neutralized.
    [10] The polymer is suitable as a film forming agent in cosmetic compositions. Disadvantages of known polymers are mainly due to their strong intrinsic odor, which often becomes worse during storage and / or formulation of cosmetic compositions. For this reason, the known products can only be used within a limited range. In cosmetic formulations, attempts have been made to remove the intrinsic odor of polymers using perfume oils. Apart from the fact that it is not always possible to completely remove the intrinsic odor, the use of flavor oils causes an undesirable allergic reaction in individual cases. This limits the use of known polymers in cosmetic compositions. In addition, the polymer should be less irritating than prior art products and therefore suitable for use in antiallergic cosmetic preparations.
    [11] It is an object of the present invention to provide a process for the preparation of t-butyl acrylate and / or t-butyl methacrylate based on t-butyl acrylate and / or t-butyl methacrylate which is suitable for a wide range of applications, in particular for cosmetic compositions, To provide an improved polymer. In this regard, there is a growing interest in polymers that do not create the inherent odor of cosmetic formulations, especially after storage. In addition, properties such as the ability to be washed away from hair, compatibility with other cosmetic ingredients, especially solubility in aqueous formulations, texture and setting of treated hair, are desirable. It is also desired to provide polymers that are less irritating than prior art products.
    [12] The present inventors have found that this object
    [13] A) 30 to 99% by weight of t-butyl acrylate and / or t-butyl methacrylate as monomer A,
    [14] B) 1 to 28% by weight of acrylic acid and / or methacrylic acid as monomer B and
    [15] C) from 0 to 60% by weight of a free radical copolymerizable monomer or a free radical copolymerizable monomer mixture as monomer C, wherein at least one of the monomers C is a homopolymer having a glass transition temperature of less than 30 DEG C, Is achieved by an acrylate polymer with a K value of 10 to 60, which can be obtained by free radical polymerization in the presence of an alkanethiol of C < 22 >, provided that the sum of the weight percentages is 100.
    [16] The present inventors have found that this object
    [17] A) 30 to 99% by weight of t-butyl acrylate and / or t-butyl methacrylate as monomer A,
    [18] B) 1 to 28% by weight of acrylic acid and / or methacrylic acid as monomer B and
    [19] C) 0 to 60% by weight of a free radical copolymerizable monomer or a free radical copolymerizable monomer mixture as monomer C, at least one of which produces a homopolymer having a glass transition temperature of less than 30 DEG C, Is achieved by an acrylate polymer with a K value of 10 to 60, obtainable by free radical polymerization in the presence of an alkanethiol of C22 followed by hydrogen peroxide treatment, provided that the sum of the weight percentages is 100.
    [20] In contrast to the products of the prior art, in particular the polymers according to EP 696 916, the polymers obtainable in this way are odorless and are characterized in that no odor is produced as individual substances or after they are stored in cosmetic preparations. At the same time, the polymers obtainable in this way exhibit good film-forming properties and good miscibility with conventional cosmetic ingredients.
    [21] Acrylate polymers are prepared by free radical polymerization of monomers A, B and optionally C by known methods. In this connection, conventional polymerization techniques are used, such as suspension, emulsion or solution polymerization methods.
    [22] Initiators such as peroxo or azo compounds such as dibenzoyl oxide, t-butyl perpivalate, t-butyl per-2-ethylhexanoate, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t) butylperoxy (hexane), alkali metal or ammonium persulfate, azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) Azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2-amidinopropane) salt , 4,4'-azobis (4-cyanovaleric acid), or 2- (carbamoyl azo) isobutyronitrile, hydrogen peroxide or a redox initiator is used to prepare the polymer in a conventional manner. The initiator is usually used in an amount of 10% by weight or less, preferably 0.02 to 5% by weight based on the monomers to be polymerized.
    [23] Emulsion polymerization is generally carried out in the absence of oxygen at temperatures in the range of 20 to 200 캜. The polymerization can be carried out discontinuously or continuously.
    [24] Preferably, at least a portion of the monomer, the initiator and the alkanethiol are metered simultaneously during polymerization and introduced into the reactor. However, it is also possible to introduce and polymerize monomers, alkanethiols and initiators first, where it is essential to carry out the cooling in certain cases.
    [25] Once the polymerization is complete, the post-polymerization can be carried out in a known manner by adding suitable initiators to reduce the residual monomer content. If desired, physical deodorization may be performed in a conventional manner, for example, by introducing water vapor.
    [26] The alkanethiol used is a straight chain and branched chain alkanethiol having a carbon chain length of C10 to C22. Especially preferred are straight chain alkanethiols, and also preferred are alkanethiol having carbon chain lengths C14 to C22, in particular C14 to C18. Examples of the alkanethiol include n-decanethiol, n-dodecanethiol, t-dodecanethiol, n-tetradecanethiol, n-pentadecanethiol, n-hexadecanethiol, n-heptadecanethiol, n-nonadecanethiol, n-eicosanthiol, n-dococanthiol. Particularly preferably straight chain, even alkanethiol.
    [27] The alkanethiol may be used as a mixture.
    [28] The alkanethiol is usually used in an amount of from 0.1 to 5% by weight, especially from 0.25 to 2% by weight, based on the monomers to be polymerized. Generally, the alkanethiol is added to the polymerization together with the monomer.
    [29] If alkane thiol having a carbon chain length of C10 to C13 is used, subsequent hydrogen peroxide treatment is essential to obtain an odor-neutralized polymer. For this hydrogen peroxide treatment which burns the polymerization, 0.01 to 2.0% by weight, especially 0.2 to 1.0% by weight, particularly preferably 0.03 to 0.15% by weight, in particular 0.1 to 1.0% by weight, of hydrogen peroxide, based on the monomers to be polymerized, . It has proven advantageous to carry out the hydrogen peroxide treatment at temperatures of 20 to 100 DEG C, particularly 30 to 80 DEG C. The hydrogen peroxide treatment is generally carried out for 30 minutes to 240 minutes, in particular 45 minutes to 90 minutes.
    [30] If alkane thiol having a carbon chain length of C14 to C22 is used, the hydrogen peroxide treatment may be omitted. However, in another embodiment of the present invention, hydrogen peroxide treatment can be followed even when alkane thiol having carbon chain lengths C14 to C22 is added.
    [31] The polymer should have a K value of 10 to 60, preferably 15 to 50. [ The preferred K value in each case can be determined in a known manner by selection of polymerization conditions such as polymerization temperature and initiator concentration. In certain instances, especially when emulsions and suspension polymerizations are used, modifiers, especially sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid or dodecyl mercaptan, are used to lower the K value . The K value is described in Fikentscher, Cellulosechemie, Vol. 13, p. 58 to 64 (1932)], which is a measure of molecular weight, measured in an ethanol solution at a concentration of 1% by weight at 25 ° C.
    [32] The polymer generally has a glass transition temperature of from 50 to 130 占 폚, especially from 60 to 100 占 폚.
    [33] If the polymer is prepared by emulsion polymerization, the prepared dispersion may be incorporated directly into an aqueous, aqueous-alcoholic or alcoholic cosmetic preparation, such as a hair setting formulation, or the dispersion may be dried, e.g. spray- It can be used and processed as a powder.
    [34] The polymers obtained in this way can be used directly (non-neutralized), partially or fully neutralized forms. In a preferred embodiment, the polymer is partially or fully neutralized.
    [35] The neutralization of the polymer is generally carried out by alkali metal hydroxides or preferably by amines, partially or completely, conveniently from 5 to 100%, preferably from 30 to 95%. Preferably,
    [36] Mono-, di- and triethanolamine, mono-, di- and tri-alkanol radicals in which the alkanol radical may be of 2 to 5 carbon atoms, which may be in etherified form, propanolamine, mono-, di- and triisopropanolamine, 2-amino-2-methylpropanol and di (2-methoxyethyl) amine,
    [37] - alkane diol amines having 2 to 5 carbon atoms, such as 2-amino-2-methylpropane-l, 3-diol and 2-amino-
    [38] - a primary, secondary or tertiary alkylamine having a total of 5 to 10 carbon atoms, such as N, N-diethylpropylamine or 3-diethylamino-1-propylamine.
    [39] Particularly good results are achieved by using 2-amino-2-methylpropanol, triisopropanolamine, 2-amino-2-ethylpropane-1,3-diol and 3-diethylamino-1-propylamine.
    [40] Alkali metal hydroxides suitable for neutralization are mainly sodium hydroxide and potassium hydroxide; In addition, aqueous buffers, such as alkali metal or ammonium carbonate or bicarbonate based buffers, are suitable for neutralization. The neutralizing agent is preferably added to the dispersion as a dilute aqueous solution.
    [41] To modify the properties of the acrylate polymer, one or more additional monomers C may also be incorporated by polymerization, if desired. The monomers or one or more of these monomers produce a homopolymer having a glass transition temperature of less than 30 < 0 > C. These monomers are preferably selected from the group consisting of C 1 -C 18 -alkyl acrylates, C 1 -C 18 -alkyl methacrylates, NC 1 -C 18 -alkyl acrylamides and NC 1 -C 18 -alkyl methacrylamides . Particularly preferably NC 1 -C 4 -alkylacrylamides or -methacrylamides or mixtures of two or more of these monomers, particularly preferably non-branched C 2 - to C 4 -alkyl acrylates themselves or branched NC 3 - to - C 4 - alkyl acrylamides. Suitable C 1 -C 4 -alkyl radicals for said (meth) acrylates and (meth) acrylamides are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl and t- butyl. A particularly preferred monomer B is ethyl acrylate or a mixture of ethyl acrylate and Nt-butyl acrylamide.
    [42] In a preferred embodiment, the acrylate polymer
    [43] A) 30 to 72% by weight, in particular 50 to 72% by weight, in particular 60 to 70% by weight, of monomers A,
    [44] B) from 10 to 28% by weight, in particular from 12 to 25% by weight, in particular from 15 to 23% by weight, of monomers B and
    [45] C) from 0 to 60% by weight, in particular from 3 to 38% by weight, in particular from 7 to 25% by weight, of monomer C,
    [46] In another preferred embodiment, the acrylate polymer comprises
    [47] A) t-Butyl acrylate as monomer A,
    [48] B) methacrylic acid as monomer B and
    [49] C) Ethyl acrylate as monomer C or a mixture of ethyl acrylate and N-t-butyl-acrylamide.
    [50] The acrylate polymers according to the invention are characterized by good film-forming properties. The present invention therefore provides the use of acrylate polymers as film formers.
    [51] The acrylate polymers according to the invention are also suitable for use in cosmetic preparations. In this case, especially partially or fully neutralized acrylate polymers are suitable.
    [52] Skin cosmetic preparations may be mentioned as cosmetic preparations, especially for skin care and / or cleansing. These are especially day and night cream in the form of W / O or O / W skin creams, eye creams, face creams, wrinkle creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, It is a lotion. They can also be used in skin cosmetic preparations such as facial tonics, face masks, deodorants and other cosmetic lotions and decorative cosmetics such as concealing sticks, step makeups, mascara and eye irrigation, , Kohl pencil, eyeliner, makeup, foundation, ball lotion and powder and eyebrow pencil.
    [53] The acrylate polymers according to the present invention may also be used in nose-strips, anti-acne compositions, colourants, shaving compositions, depilatories, personal care compositions, foot care compositions and baby products for pore cleaning.
    [54] Acrylate polymers may be formulated as aqueous or aqueous-alcoholic solutions, O / W and W / O emulsions in cosmetic preparations such as shampoos, creams, foams, sprays (pump sprays or aerosols), gels, gel sprays, lotions or mousses And the like.
    [55] The use of acrylate polymers in hair cosmetic formulations is particularly preferred. Hair cosmetic preparations include hair treatment, hair lotion, hair rinse, hair emulsion, hair-cleaved hair liquid, permanent wave neutralizing agent, hot-oil treatment agent, Mention may be made of a conditioner, a curl relaxer, a styling wrap lotion, a setting lotion, a shampoo, a hair wax, a pomade, a hair foam, a hair coloring agent or a hair spray. Especially preferred is a hair styling setting composition which is in the form of a spray formulation and / or a hair foam of an acrylate polymer.
    [56] The acrylate polymers according to the invention are distinguished by a high miscibility with nonpolar propellants in spray formulations, especially hydrocarbons such as n-propane, isopropane, n-butane, isobutane, n-pentane and mixtures thereof in hair cosmetic preparations . They have good hair setting action and are characterized by virtually preventing the hair from sticking together.
    [57] In addition to deodorization, acrylate polymers give excellent results on performance properties in hair cosmetic preparations. They are dissolved in alcohols such as ethanol or isopropanol and in mixtures with these alcohols and water and a clear solution is prepared. The transparency of the solution is maintained even when the solution is used with propellants such as dimethyl ether in standard spray formulations. The hair setting composition according to the present invention can be thoroughly washed from the hair. The hair treated with this increased flexibility and good natural tactile sensation. At the same time, the setting action is also excellent, which in principle means that the required amount of film former in the hair spray formulation can be reduced. Since the odor of the acrylate polymer is eliminated, addition of odor removing perfume oil can be omitted if necessary. For these reasons, acrylate polymers are particularly suitable as film formers in hair cosmetic preparations.
    [58] The acrylate polymer is generally used as a part or fully neutralized acrylate polymer in an amount of from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, in particular from 2 to 10% by weight, based on the cosmetic preparation.
    [59] The use of acrylate polymers, preferably in cosmetic preparations, in particular hair spray preparations, is provided which comprises the following components:
    [60] - from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, in particular from 2 to 6% by weight, of partially or completely neutralized acrylate polymers
    [61] -1 to 99.9% by weight, preferably 5 to 50% by weight, in particular 10 to 20% by weight, of water
    [62] From 0 to 95% by weight, preferably from 20 to 60% by weight, especially from 25 to 50% by weight, of conventional organic solvents such as primary ethanol, isopropanol and dimethoxymethane and additionally acetone, Butanol, 2-methoxypropan-1-ol, n-pentane, n-hexane, cyclohexane, n-heptane, n-octane or dichloromethane or mixtures thereof
    [63] Such as n-propane, isopropane, n-butane, isobutane, 2,2-dimethylbutane, n-propane, - pentane, isopentane, dimethyl ether, difluoroethane, fluorotrichloromethane, dichlorodifluoromethane or dichlorotetrafluoroethane, HCF 152 A or mixtures thereof.
    [64] Among the above compounds, propellants (propellant gases) used are mainly hydrocarbons, especially propane, n-butane, n-pentane and mixtures thereof and also dimethyl ether and difluoroethane. If appropriate, one or more of the chlorinated hydrocarbons may be used simultaneously in the propellant mixture, but only a small amount, for example up to 20% by weight, based on the propellant mixture.
    [65] The hair cosmetic preparations according to the invention are particularly suitable for pump spray formulations without the addition of propellants or for aerosol sprays with conventional compressed gases such as nitrogen, compressed air or carbon dioxide as a propellant.
    [66] Water-containing standard spray formulations, for example, have the following composition:
    [67] A 100% neutralized acrylate polymer with 2 to 10 wt% 2-amino-2-methylpropanol
    [68] 10 to 76% by weight of ethanol
    [69] 2 to 20% by weight of water
    [70] 10 to 60% by weight of dimethyl ether and / or propane / n-butane and / or propane / isobutane.
    [71] In order to target the properties of a hair cosmetic preparation, it may be advantageous to use the acrylate polymer according to the invention as a mixture with other hair setting polymers.
    [72] Suitable hair cosmetic polymers are, for example, anionic polymers. These anionic polymers are mono- and copolymers of acrylic acid and methacrylic acid, or salts thereof, copolymers of acrylic acid and acrylamide and salts thereof, which are different from the acrylate polymers according to the invention; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes (e.g. Luviset P.U.R.) and polyureas. Particularly suitable polymers are copolymers of ethyl acrylate and methacrylic acid (e.g. Luvimer TM MAE), copolymers of Nt-butyl acrylamide, ethyl acrylate, acrylic acid (Ultrahold 8, Strong ), Copolymers of vinyl acetate, crotonic acid and optionally other vinyl esters (e.g., Luviset (TM) grades), maleic anhydride copolymers optionally reacted with alcohols, anionic polysiloxanes such as vinyl (For example Luviskol TM VBM) or ternary copolymers of t-butyl acrylate, methacrylic acid and dimethicone copolyols (for example, methyl methacrylate, methyl methacrylate, For example, Luviflex (R) Silk).
    [73] Other suitable hair cosmetic polymers may also include polymers such as copolymers of a neutral polymer such as polyvinylpyrrolidone, N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and N- Cellulose derivatives, polyaspartic acid salts and derivatives.
    [74] The acrylate polymers may be formulated in cosmetic preparations using other conventional adjuvants. Other conventional adjuvants may include the following: surfactants, oily bodies, emulsifiers, co-agents, over-emulsifiers, milky waxes, bodying agents, thickeners, fats, waxes, silicone compounds, Preservatives, perfume oils, dyes, stabilizers, pH adjusting agents, control substances such as panthenol, pitantriol, collagen, vitamins and proteinaceous substances, solubilizing agents, glitter substances, complexing agents and the like.
    [75] Suitable anionic surfactants are, for example, alkyl sulphates, alkyl ether sulphates, alkyl sulphonates, alkyl aryl sulphonates, alkyl succinates, alkyl sulphosuccinates, N-alcoyl sarcosinates, acyl taurates, Alkyl ether carboxylates, alpha-olefinsulfonates, especially alkali metal salts and alkaline earth metal salts such as sodium, potassium, magnesium, calcium and ammonium and triethanolamine salts, such as, for example, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, . The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates may have from 1 to 10 ethylene oxide or propylene oxide units, preferably from 1 to 3 ethylene oxide units, in the molecule.
    [76] Suitable compounds are, for example, sodium lauryl sulphate, ammonium lauryl sulphate, sodium lauryl ether sulphate, ammonium lauryl ether sulphate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulphate Sodium dodecylbenzenesulfonate, and triethanolamine dodecylbenzenesulfonate.
    [77] Suitable amphoteric surfactants include, for example, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines, alkyl glycinates, alkyl carboxy glycinates, alkyl amphoacetates or amphopropionates, Acetate or amphodipropionate.
    [78] For example, cocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine or sodium cocopropopropionate can be used.
    [79] Suitable non-ionic surfactants are, for example, reaction products of ethylene oxide and / or propylene oxide with an alkylphenol of an alkyl chain of 6 to 20 carbon atoms, which may be an aliphatic alcohol or a straight chain or branched chain. The amount of alkylene oxide is about 6 to 60 moles per mole of alcohol. Also suitable are alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkylpolyglycosides or sorbitan ether esters.
    [80] The composition may also comprise conventional cationic surfactants such as quaternary ammonium compounds such as cetyltrimethylammonium chloride.
    [81] If the acrylate polymers according to the invention are used in shampoo formulations, they generally contain anionic surfactants as basic surfactants and amphoteric and nonionic surfactants as co-surfactants.
    [82] The cosmetic preparations generally contain from 2 to 50% by weight, preferably from 5 to 40% by weight, particularly preferably from 8 to 30% by weight, of a surfactant.
    [83] Suitable oil bodies are, for example, Guerbet alcohols based on fatty alcohols of 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C 6 -C 22 -fatty acids with straight chain C 6 -C 22 -fatty alcohols, Esters of branched C 6 -C 13 -carboxylic acids with straight-chain C 6 -C 22 -fatty alcohols, esters of straight-chain C 6 -C 22 -fatty acids with branched chain alcohols, especially 2-ethylhexanol, Esters of straight chain or branched C 6 -C 22 -fatty alcohols of acids, in particular polyfunctional alcohols, such as dioctyl malate, linear and / or branched chain fatty acids (for example propylene glycol, dimerdiol or trimertryol) and Esters with alcohols and / or guerbet alcohols, C 6 -C 10 -fatty acid based triglycerites, C 6 -C 18 -fatty acid based liquid mono- / di- / triglyceride mixtures, C 6 -C 22 -fatty alcohols and ( Or) aromatic carboxylic acids of Guerbet alcohol, especially esters with benzoic acid, vegetable oils, Jiswae primary alcohols, substituted cyclohexane, linear and branched C 6 -C 22-ester (such as a alcohol-fatty alcohol carbonates, Guerbet carbonates, benzoic acid and linear and (or) a branched C 6 -C 22 For example, Finsolv (TM) TN), dialkyl ethers of 6 to 22 carbon atoms per alkyl group, linear or branched, symmetrical or asymmetric, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and / Or naphthenic hydrocarbons.
    [84] Suitable emulsifiers are, for example, one or more non-ionogenic surfactants selected from the group consisting of:
    [85] (1) an alkyl (meth) acrylate having 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with a straight chain fatty alcohol having 8 to 22 carbon atoms, Adducts with phenols;
    [86] (2) C 12/ 18 -fatty acid mono-and diesters of 1 to 30 moles of the addition product of ethylene oxide with glycerol;
    [87] (3) glycerol mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and sorbitan mono- and diesters and their ethylene oxide adducts;
    [88] (4) alkyl mono- and oligoglycosides having 8 to 22 carbon atoms and their ethoxylated analogs;
    [89] (5) addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
    [90] (6) polyols and in particular polyglycerol esters, such as polyglycerol polypyrinolate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Mixtures of two or more of these classes of materials are also suitable;
    [91] (7) addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
    [92] (8) a mixture of linear, branched, unsaturated or saturated C 6/22 -fatty acids, ricinolic acid and 12-hydroxystearic acid with glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols such as sorbitol, , Partial esters based on alkyl glucosides (e.g., methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g., cellulose);
    [93] (9) mono-, di- and trialkylphosphates, and mono-, di- and / or tri-PEG alkylphosphates and their salts;
    [94] (10) wool wax alcohol;
    [95] (11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives thereof;
    [96] (12) Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohols according to German Patent 1165574 and / or mixed esters of fatty acids, methyl glycoses and polyols having 6 to 22 carbon atoms, preferably glycerol or polyglycerol , And
    [97] (13) Polyalkylene glycols.
    [98] Fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters of fatty acids and / or propylene oxide, and adducts of sorbitan mono- and diesters with or with castor oil are known, commercially available Products. These are homologous mixtures in which the degree of average degree of alkoxylation corresponds to the ratio of the amount of ethylene oxide and / or propylene oxide to the substrate on which the addition reaction is carried out. The C 12/ 18 -fatty acid mono-and diesters of the addition product of ethylene oxide to glycerol are known from German Patent No. 2024051 as re-fizzing agents for cosmetic preparations. C 8/18 -alkyl mono- and oligoglycosides , processes for their preparation and their uses are known from the prior art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. For glycosidic esters, monoglycosides in which the cyclic sugar radical is bonded to the fatty alcohol with a glycoside, and also oligomeric glycosides with degree of oligomerization of up to about 8 are suitable. The degree of oligomerization in this specification is a statistical average based on the homologous distribution that is typical for the technical grade product.
    [99] A zwitterionic surfactant may be used as the emulsifier. Zwitterionic surfactants are terms used to refer to a surfactant compound having at least one quaternary ammonium group in the molecule and at least one carboxylate and at least one sulfonate group. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinates having in each case alkyl or acyl groups having 8 to 18 carbon atoms, such as cocoalkyldimethyl Ammonium glycinate, N-acylaminopropyl-N, N-dimethyl ammonium glycinate such as cocoamylaminopropyldimethyl ammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazole Zolin and cocasyl aminoethyl hydroxyethyl carboxymethyl glycinate. Particularly preferred is a fatty acid amide derivative known as CTFA designation cocamidopropyl betaine. Amphoteric surfactants are also suitable emulsifiers. The amphoteric surfactant is, apart from the C 8/18 -alkyl or acyl group in the molecule, a surfactant compound containing at least one free amino group and at least one -COOH- or -SO 3 H- group and capable of forming an internal salt As used herein. Examples of suitable amphoteric surfactants include, in each case, N-alkyl glycine, N-alkyl propionic acid, N-alkylaminobutyric acid, N-alkyl iminodipropionic acid, N-hydroxyethyl- N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid. Particularly preferred amphoteric surfactants are N-coco alkylaminopropionate, cocacylaminoethylaminopropionate and C 12/18 -acyl sarcosine. In addition to amphoteric emulsifiers, quaternary emulsifiers are also suitable, of which the quaternary ester type, preferably the methyl-quaternary di-fatty acid triethanolamine ester salts, are particularly preferred.
    [100] As over-embrittlement agents, for example, substances such as lanolin and lecithin, polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used, the latter acting as a foam stabilizer do.
    [101] Examples of suitable milky waxes are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglycerides; Esters of polyhydric acids, esters of polyhydric acids, esters of polyhydric acids, esters of polyhydric acids, polyhydric carboxylic acids and polyhydric alcohols, especially long chain esters of tartaric acid; Fatty substances such as fatty alcohols having a total carbon number of 24 or more, fatty ketones, fatty aldehydes, fatty esters and fatty carbonates, especially lauro- and distearyl ethers; A ring-opening of a fatty acid such as stearic acid, hydroxystearic acid or behenic acid, an olefin epoxide having 12 to 22 carbon atoms and a polyol having 12 to 22 carbon atoms and / or a hydroxyl group having 2 to 15 carbon atoms and / or 2 to 10 carbon atoms Products, and mixtures thereof.
    [102] Suitable boarding agents are mainly fatty alcohols or hydroxy fatty alcohols of 12 to 22 carbon atoms, preferably 16 to 18 carbon atoms, and also partial glycerides, fatty acids or hydroxy fatty acids. Preferably a mixture of alkyl oligoglucosides and / or fatty acid N-methyl glucamides of the same chain length and / or polyglycerol poly-12-hydroxy stearate. Suitable thickening agents are, for example, polyethylene glycols mono- and diesters of polysaccharides, in particular xanthan gum, guar gum, agar, alginates and Tylose, carboxymethylcellulose and hydroxyethylcellulose and also of relatively high molecular weight fatty acids, Polyacrylates (for example, Carbopols (R) or Synthalens (R) from Goodrich), polyacrylamides, polyvinyl alcohols and polyvinyl pyrrolidones, surfactants such as Ethoxylated fatty acid glycerides, polyols of fatty acids such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates or alkyloligosaccharides with narrow homologous distribution and electrolytes such as sodium chloride and ammonium chloride.
    [103] Typical examples of fats are glycerides and suitable waxes are, among others, waxes, waxes, candelilla waxes, montan waxes, paraffin waxes or microcrystalline waxes optionally mixed with hydrophilic waxes such as cetylstearyl alcohol or partial glycerides. Stabilizers which may be used are metal salts of fatty acids, such as magnesium, calcium, aluminum and / or zinc stearate or ricinoleate.
    [104] Suitable silicone compounds include, for example, dimethylpolysiloxane, methylphenylpolysiloxane, cyclic silicone and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and (Or) alkyl-modified silicone compounds.
    [105] In order to improve the flow properties, a cooling agent such as ethanol, isopropyl alcohol or a polyol may be used. Suitable polyols in the present invention are preferably 2 to 15 carbon atoms and have 2 or more hydroxyl groups. A typical example would be:
    [106] - glycerol;
    [107] Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having an average molecular weight of from 100 to 1000 daltons; A technical grade diglycerol mixture of a self-condensation degree of from 1.5 to 10, for example a technical grade diglycerol mixture of a diglycerol content of from 40 to 50% by weight;
    [108] Methylol compounds, such as, in particular, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
    [109] Lower alkyl glucosides, especially those in which the alkyl radical has from 1 to 8 carbon atoms, such as methyl and butyl glucoside;
    [110] Sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol;
    [111] Sugars having 5 to 12 carbon atoms, such as glucose or sucrose;
    [112] - Amino sugars, such as glucamine.
    [113] Examples of suitable preservatives are phenoxyethanol, formaldehyde solutions, parabens, pentanediol or sorbic acid, and other classes of materials described in Appendix 6, Part A and B of the Cosmetics Directive.
    [114] There is no need to add a perfume oil to eliminate the odor of the polymer. Nonetheless, in certain instances, the cosmetic formulation may comprise a perfume oil. Mixtures of natural and synthetic flavors may be mentioned as spice oils. Natural spices include flowers (lilies, lavenders, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, parsley, petit grains), fruits (aniseed, coriander, cumin, juniper), fruit bark (bergamot, Lemongrass, lemongrass, lemongrass, lemongrass, lemongrass), root (mace, angelica, celery, cardamom, costus, iris and calmus), wood (pine tree, sandalwood, Extracts from leaves and branches (spruce, fir, pine, dwarf-pine), resin and balms (galbanum, elemi, benzoin, myrrh, olivanum, opopanax). Animal raw materials such as sibbet and casterole are also suitable. Typical synthetic perfume compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon types. The ester-type perfume compound may be, for example, benzyl acetate, phenoxyethyl isobutyrate, pt-butylcyclohexyneacetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl Methylphenyl glycidate, allyl cyclohexyl propionate, styrally propionate, and benzyl salicylate. The ether includes, for example, benzyl ethyl ether, and the aldehyde includes, for example, straight chain alkanols having 8 to 18 carbon atoms, citral, strontium, citroneloxyacetaldehyde, cyclamaldehyde, hydroxycitronel, Containing ketones include, for example, ionone, alpha -isomethylionone, and methyl cedryl ketone, and the alcohols include anethole, citronellol, yuzenol, isoethanol, Oleyl, phenylethyl alcohol and terpineol, and the hydrocarbons mainly include terpenes and balsams. However, it is preferable to use a mixture of various fragrances so that a good odor is produced together. Essential oils of lower volatility, which are mostly used as perfume ingredients, are also suitable as perfume oils, such as, for example, sage oil, camomile oil, clove oil, balms oil, mint oil, cinnamon leaf oil, lime flower oil, Oil, betibeur oil, olivanum oil, galbanum oil, ravudumum oil and lavadin oil.
    [115] Benzyl acetone, cyclamenaldehyde, linalool, bovine bran forte, ambroxol, benzyl alcohol, benzyl alcohol, benzyl acetal, benzyl acetal, benzaldehyde, linalool, lauryl, citronellol, phenylethyl alcohol, , Clary sage oil, beta-damascone, geranium oil bourbon, cyclohexyl salicylate, cyclohexanol salicylate, cyclodextrin, lauric acid, , Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iridane gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, Romillat, Irotyl and Floramat are preferably used alone or as a mixture.
    [116] Dyes which can be used are substances which are certified as suitable for cosmetics and are described, for example, in "Kosmetische Farbemittel" [Cosmetic Colorants] from the Farbstoffkommission der Deutschen Forschungsgemeinschaft [Dyes Commission of the German Research Council], Verlag Chemie, Weinheim, 1984 , pp. 81-106. These dyes are generally used in a concentration of 0.001 to 0.1% by weight based on the total mixture.
    [117] Other suitable polymers include, for example, cationic polymers, copolymers of the INCI designation Polyquaternium, such as N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat TM FC, Luviquat TM HM, Luviquat (Luviquat < (R) >), N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts copolymer (Luviquat (R) PQ11), cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymer (Polyquaternium-7) And guar hydroxypropyltrimethylammonium chloride (INCI: hydroxypropyl guar hydroxypropyl trimonium chloride). Polyethyleneimine and its salts, polyvinylamine and its salts are also suitable polymers.
    [118] The total amount of adjuvants and additives may be from 1 to 50% by weight, preferably from 5 to 40% by weight, based on the composition.
    [119] The present invention also provides a process for preparing an acrylate polymer in which an alkanethiol, in particular a linear alkanethiol having a carbon chain length of C14 to C22, is used. In the present invention, alkanethiols are generally used together with monomers to be polymerized. The alkanethiol is used in an amount of from 0.1 to 5% by weight based on the monomers generally polymerized in the present invention.
    [120] The present invention also provides a process for preparing an acrylate polymer, wherein an alkanethiol, in particular a linear alkanethiol having a carbon chain length of C10 to C22, is used and the hydrogen peroxide treatment is carried out when the polymerization is complete.
    [121] The acrylate polymers obtainable by the process according to the invention are characterized by little or no inherent odor.
    [122] The process according to the invention is generally suitable for preparing acrylate polymers, especially those described in claims 1 and 2.
    [123] In addition, the process according to the invention is also suitable for preparing other acrylate polymers.
    [124] Suitable acrylate polymers are all polymers comprising one or more monomers based on acrylate.
    [125] Examples of suitable non-limiting representative monomers are, for example, acrylic acid and its salts, esters and amides. The salt may be derived from any desired non-toxic metal, ammonium or substituted ammonium counterion.
    [126] The esters can be prepared from C 10-40 straight chain, C 3-40 branched chain or C 3-40 carbocyclic alcohol by reaction with polyhydric alcohols having 2 to about 8 hydroxyl groups such as ethylene glycol, hexylene glycol, glycerol and 1, 2,6-hexanetriol, from aminoalcohols or from alcohol ethers such as methoxyethanol and ethoxyethanol or polyethylene glycol.
    [127] Also suitable are N, N-dialkylaminoalkyl acrylates and methacrylates of the following formula (I) and N-dialkylaminoalkyl acrylamides and -methacrylamides.
    [128]
    [129] In the above formula, R 1 is H or alkyl having 1 to 8 carbon atoms,
    [130] R 2 is H or methyl,
    [131] R < 3 > is alkylene of 1 to 24 carbon atoms optionally substituted with alkyl,
    [132] R 4 and R 5 are C 1 -C 40 alkyl radicals,
    [133] Z is nitrogen when x is 1 and oxygen when x is zero.
    [134] The amide can be unsubstituted, N-alkyl or N-alkylamino-mono-substituted, or N, N-dialkyl-substituted or N, N-dialkylamino- Straight chain, C3-C40 branched or C3-C40 carbocyclic unit. The alkylamino group may also be quaternized.
    [135] Preferred monomers of formula I are N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, N, Diethylaminoethyl (meth) acrylate.
    [136] Monomers which can be used are substituted acrylic acids and their salts, esters and amides wherein the substituents of the carbon atoms are at the 2 or 3 position of the acrylic acid and are each independently selected from the group consisting of C1-C4 alkyl, -CN, -COOH, Preferred are methacrylic acid, ethacrylic acid and 3-cyanoacrylic acid. These salts, esters and amides of substituted acrylic acid can be selected from those mentioned above for the salts, esters and amides of acrylic acid.
    [137] Particularly suitable monomers are acrylic acid, methacrylic acid, ethyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl Acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate Methyl ethyl ketone, methyl methacrylate, methyl methacrylate, methyl methacrylate, ethyl methacrylate, ethyl methacrylate, ethyl methacrylate, ethyl methacrylate, Hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, Methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl methacrylate, 2-methoxyethyl methacrylate, Hydroxyethyl methacrylate, glyceryl monoacrylate, glyceryl monomethacrylate, polyalkylene glycol (meth) acrylate, unsaturated sulfonic acid such as acrylamidopropanesulfonic acid;
    [138] Acrylamide, N-methylacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butyl acrylamide, Nt-butyl acrylamide, N-octyl acrylamide, N-octadecyl acrylamide, N-phenyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-dodecyl methacrylamide, (Meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminomethyl (Meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl Dimethylaminohexyl (meth) acrylate, N, N-dimethylaminooctyl (meth) acrylate, N, N-dimethylamino Propyl] methacrylamide, N - [(3-dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) butyl] methacrylamide , N- [8- (dimethylamino) propyl] methacrylamide, N- [2- (dimethylamino) - [3- (diethylamino) propyl] acrylamide;
    [139] Of these, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, Acrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, Nt-butyl acrylamide, N-octylacrylamide, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, Particular preference is given to hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkylene glycol (meth) acrylate, unsaturated sulfonic acids such as acrylamidopropanesulfonic acid or diethylsulfate.
    [140] The process according to the invention is particularly suitable for the preparation of mono- and copolymers of acrylic acid and acrylamide and salts thereof, copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example Luvimer TM 100 P) , Copolymers of ethyl acrylate and methacrylic acid (e.g. Luviflex TM Soft), copolymers of Nt-butyl acrylamide, ethyl acrylate, acrylic acid (Ultrahold Strong TM), acrylic acid and methacrylic acid Hydrophobic monomers of acrylic acid, for example C 4 -C 30 -alkyl esters of (meth) acrylic acid, C 4 -C 30 -alkyl vinyl esters, C 4 -C 30 -alkyl vinyl ethers and copolymers with hyaluronic acid And additional polymers, such as the trade name Amerhold DR-25, Ultrahold TM, Acronal TM, Acudyne TM, Lovocryl TM, Versatyl TM, Amphomer TM TM 28-4910 , LV-71), Placise (registered trademark) L53, Advantage Plus (registered trademark), Balance Table) (0/55), it is suitable for the production of the known ones to Acudyne (R) 255.
    [141] The following list is the INCI / CTFA designation and manufacturer of acrylate polymers suitable for the process according to the invention:
    [142] INCI / CTFApolymermanufacturer Acrylate copolymerAmerhold DR-25Amerchol Styrene / acrylate copolymerAcronal 290 D, 296 DBASF (BASF) Acrylate / acrylamide copolymerUltrahold 8BASF Acrylate / acrylamide copolymerUltrahold StrongBASF Acrylate copolymerLuviflex SoftBASF Acrylate copolymerLuvimer 100P, 36D, 30EBASF Methacryloylethyl betaine / acrylate copolymerDiaformerClariant Acrylate / diacetone acrylamide copolymerPlascize L-53Goo Chemical Vinyl caprolactam / PVP / dimethylaminoethyl methacrylate copolymerCopolymer VC 713 (= Advantage HC)ISP Vinyl caprolactam / PVP / dimethylaminoethyl methacrylate copolymerH 2 OLD (R) EP-1ISP VA / butyl maleate / isobornyl acrylateAdvantage PlusISP PVP / DMAPA acrylate copolymerStyleeze CC-10ISP PVP / vinylcaprolactam / DMAPA acrylate copolymerAquaflex SF-40ISP Octyl acrylamide / acrylate / butylaminoethyl methacrylate copolymerAmphomer 28-4910National Starch (National Starch) Octyl acrylamide / acrylate / butylaminoethyl methacrylate copolymerAmphomer LV-71National Starch Acrylate / octyl acrylamide copolymerVersatyl 42National Starch Octyl acrylamide / acrylate copolymerVersatyl 90National Starch Acrylate copolymerBalance 0/55National Starch Octyl acrylamide / acrylate / butylaminoethyl methacrylate copolymerLovocryl 47National Starch Acrylate / hydroxy ester acrylateAcudyneRohm & Hass
    [143] The polymerization method may be carried out by solution polymerization, emulsion polymerization, inverse emulsion polymerization, suspension polymerization, inverse suspension polymerization or precipitation polymerization, but there is no limitation on the method that can be used. In solution polymerization, water or a conventional organic solvent may be used as the solvent.
    [144] Example 1 Preparation of acrylate polymer E5 (emulsion polymerization)
    [145] (Monomer B), 490 g of t-butyl acrylate (Monomer A), 70 g of ethyl acrylate (< RTI ID = 0.0 > An emulsion was prepared from monomer C) and 3 g of t-dodecyl mercaptan. This emulsion was introduced into a polymerization reactor containing 750 g of water at a temperature of about 75 to 85 DEG C during a polymerization time of about 2 to 4 hours and metered in. 1.1 g of sodium persulfate dissolved in 14.9 g of water, which is a polymerization initiator, was added at the beginning of the emulsion feed. When the polymerization was completed, 3.6 g of hydrogen peroxide (50% concentration) was metered in at 60 to 70 캜.
    [146] The preparation of the other Examples (E1 to E4 and E6 to E9) and Comparative Example C1 (according to EP 696 916) to C5 was carried out according to Example 1. The types and amounts of the corresponding amounts of monomers A, B and C, alkanethiol and, if appropriate, hydrogen peroxide are listed in the table below.
    [147] The odor analysis of the prepared acrylate polymers was carried out by four test panels. To this end, the acrylate polymer prepared according to this example was dried, dissolved in ethanol at 30% and then compounded as a 3% strength aqueous solution and 100% neutralized with 2-amino-2-methylpropanol. The evaluation of odor properties was according to the following classification:
    [148] "1" No smell
    [149] "2" Weak, unpleasant odor
    [150] "3" strong, unpleasant odor
    [151] Example No.Composition (% by weight)Additive substanceAddition amount (% by weight)The amount (% by weight) of H 2 O 2 smellt-BAMAAEAt-BAA C1701812-Mercaptoethanol0.3-2 C2721810-n-butanethiol0.15-3 C3721810-n-butanethiol0.150.403 C4651520-1-octanethiol0.450.503 E1651520-Decanethiol0.500.30One E26520510Decanethiol0.500.40One E3651520-Decanethiol0.500.50One C565151010n-dodecanethiol0.45-2 C6702010-t-dodecanethiol0.40-2 E465151010n-dodecanethiol0.450.30One E5702010-n-dodecanethiol0.400.25One E6672310-n-dodecanethiol0.430.50One E7672310-n-dodecanethiol0.40.11One E850202010n-dodecanethiol0.350.40One E9672310-n-octadecanethiol0.500.20One E10602020-n-octadecanethiol0.500.50One Table Explanation t-BA = t-butyl acrylate MAA = methacrylic acid AA = acrylic acid EA = ethyl acrylate t-BAA = Nt-butyl acrylamide
    [152] Blending Example ingredientINCIFormulation 1 Aerosol Hair SprayFormulation 2 Aerosol Hair SprayFormulation 3 Aerosol Hair SprayFormulation 4 aerosol hair spray Data (wt%) The acrylate polymer of Example 1, 100% neutralized with AMPAcrylate copolymer4.02.04.05.0 Amino-2-methylpropanol (AMP)Aminomethyl propanol0.950.470.931.18 waterwater--7.1513.82 Dow Corning 190 polyether or Wacker DMC 6031Dimethicone Copol0.1 0.01Luvitol EHOCetearyl octanoate0.1 Dow Corning 344 fluid or Wacker CM 040Cyclomethicone 0.05D-Panthenol USPPanthenol 0.1 Abil B 8843 or Wacker DMC 6032Dimethicone copolyol 0.1 Anhydrous ethanolAlcohol54.7547.23 80.00 Ethanol 96%Alcohol 42.77Propane / butanePropane / butane40.050.0 Dimethyl etherDimethyl ether 45.0
    权利要求:
    Claims (15)
    [1" claim-type="Currently amended] - from 30 to 99% by weight of t-butyl acrylate and / or t-butyl methacrylate as monomer A,
    - from 1 to 28% by weight of acrylic acid and / or methacrylic acid as monomer B, and
    - 0 to 60% by weight of a free radical copolymerizable monomer or a free radical copolymerizable monomer mixture (at least one of the monomers C producing a homopolymer having a glass transition temperature of less than 30 캜) as monomer C being)
    Is obtained by free radical polymerization in the presence of an alkane thiol having a carbon chain length of C14 to C22.
    [2" claim-type="Currently amended] - from 30 to 99% by weight of t-butyl acrylate and / or t-butyl methacrylate as monomer A,
    - from 1 to 28% by weight of acrylic acid and / or methacrylic acid as monomer B, and
    - 0 to 60% by weight of a free radical copolymerizable monomer or a free radical copolymerizable monomer mixture (at least one of the monomers C producing a homopolymer having a glass transition temperature of less than 30 캜) as monomer C being)
    Is obtained by free radical polymerization in the presence of an alkane thiol having a carbon chain length of C10 to C22, followed by hydrogen peroxide treatment.
    [3" claim-type="Currently amended] 3. The acrylate polymer according to claim 1 or 2, wherein a straight chain alkanethiol is used.
    [4" claim-type="Currently amended] The acrylate polymer according to claim 1 or 2, wherein from 0.1 to 5% by weight, based on the monomer to be polymerized, of alkane thiol is used.
    [5" claim-type="Currently amended] The composition of claim 1 or 2, wherein said monomer C is selected from the group consisting of C 1 -C 18 -alkyl acrylate, C 1 -C 18 -methacrylate, NC 1 -C 18 -alkyl acrylamide and NC 1 -C 18- ≪ / RTI > methacrylamide.
    [6" claim-type="Currently amended] 6. The method according to any one of claims 1 to 5,
    A) 30 to 72% by weight of monomer A,
    B) from 10 to 28% by weight of monomer B, and
    C) 0 to 60% by weight of monomer C (sum of said weight% being 100) is used.
    [7" claim-type="Currently amended] 7. The method according to any one of claims 1 to 6,
    A) t-butyl acrylate is used as monomer A,
    B) methacrylic acid is used as monomer B,
    C) acrylate polymers in which a mixture of ethyl acrylate or ethyl acrylate and N-t-butyl acrylamide is used as monomer C.
    [8" claim-type="Currently amended] Use of the acrylate polymer according to any one of claims 1 to 7 as a film forming agent.
    [9" claim-type="Currently amended] Use of an acrylate polymer according to any one of claims 1 to 8 in a cosmetic preparation.
    [10" claim-type="Currently amended] 11. Use according to claim 9 in the preparation of hair cosmetics.
    [11" claim-type="Currently amended] And performing polymerization in the presence of an alkanethiol having a carbon chain length of C14 to C22.
    [12" claim-type="Currently amended] a) performing polymerization in the presence of an alkanethiol having a carbon chain length of C10 to C22,
    b) performing a hydrogen peroxide treatment.
    [13" claim-type="Currently amended] 13. The method according to claim 11 or 12, wherein from 0.1 to 5% by weight of the alkanethiol is used, based on the amount of monomer to be polymerized.
    [14" claim-type="Currently amended] 13. The process according to claim 12, wherein the treatment is carried out with 0.01 to 2% by weight of hydrogen peroxide based on the amount of monomer to be polymerized.
    [15" claim-type="Currently amended] Use of an alkanethiol of carbon chain length C14 to C22 for the preparation of acrylate polymers.
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    同族专利:
    公开号 | 公开日
    WO2002038638A1|2002-05-16|
    CA2428309C|2010-01-12|
    KR100827902B1|2008-05-07|
    AT299900T|2005-08-15|
    US7015294B2|2006-03-21|
    EP1335943A1|2003-08-20|
    CA2428309A1|2002-05-16|
    EP1335943B1|2005-07-20|
    JP2004514000A|2004-05-13|
    AU2183002A|2002-05-21|
    CN1473168A|2004-02-04|
    CN1197887C|2005-04-20|
    JP4267913B2|2009-05-27|
    ES2246351T3|2006-02-16|
    JP4855377B2|2012-01-18|
    US20040042994A1|2004-03-04|
    JP2008115399A|2008-05-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-11-10|Priority to DE10055776.7
    2000-11-10|Priority to DE10055776
    2001-11-09|Application filed by 바스프 악티엔게젤샤프트
    2001-11-09|Priority to PCT/EP2001/012976
    2003-06-25|Publication of KR20030051790A
    2008-05-07|Application granted
    2008-05-07|Publication of KR100827902B1
    优先权:
    申请号 | 申请日 | 专利标题
    DE10055776.7|2000-11-10|
    DE10055776|2000-11-10|
    PCT/EP2001/012976|WO2002038638A1|2000-11-10|2001-11-09|Acrylate polymers based on tert-butyl acrylate and/or tert-butyl methacrylate|
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