Radical copolymer composition and method for producing the same, as well as cosmetics or cosmetic raw materials containing the radical copolymer composition.

Abstract

[Problem] To provide a monomer composition and a production method therefor, with which there are no safety concerns in the case of use as a cosmetic ingredient or the like and a decline in the quality of gelling or the like is not caused. [Solution] A radical copolymer composition which contains a) radical polymerisable monomers that include in the molecule a radical-copolymerisable organic group and an organosilicon-containing organic group, and b) a radical copolymer of radical polymerisable monomers other than component a), wherein the total concentration of a polymerisation inhibitor in relation to the total mass of the radical copolymer and the polymerisation inhibitor is 50 mass ppm or less; and a production method for said radical copolymer composition.

Description

[Technical Field]

[0001] The present invention relates to a radical copolymer composition, a method for producing the same, and a cosmetic or cosmetic raw material containing the radical copolymer composition. [Background technology]

[0002] To improve the water resistance and sebum resistance of cosmetics, particularly makeup cosmetics, and thus enhance their longevity, it is known that polymers prepared from monomer compositions containing radically polymerizable groups are used as film-forming agents. In particular, organopolysiloxanes containing radically polymerizable organic groups can impart water repellency and slipperiness to cosmetics. However, there have been problems with compatibility with the cosmetic ingredients into which they are formulated.

[0003] To solve these problems, copolymers having a carbosiloxane dendrimer structure or a siloxane macromonomer structure have been proposed. For example, Patent Document 1 proposes a copolymer based on an unsaturated monomer having a specific carbosiloxane dendrimer structure, and it has been shown that it can be used as a film-forming agent with excellent blending stability with cosmetic raw materials such as UV absorbers, as well as excellent water resistance and sebum resistance.

[0004] On the other hand, producing monomers with complex structures, such as carbosiloxane dendrimer structures and siloxane macromonomer structures, requires a multi-step process. In particular, some raw materials in the upstream process are highly reactive, so measures are generally taken to prevent the raw materials from reacting and gelling during storage and in the process by adding polymerization inhibitors.

[0005] For example, Patent Document 2 describes a silicone monomer composition containing a silicone monomer having a polymerizable group and a polymerization inhibitor having a specific structure of 5 to 400 ppm with respect to the silicone monomer. Further, Patent Document 3 describes that in order to increase the stability of a cosmetic composition over time, a polymerization inhibitor of 10 ppm to 20% by mass is contained with respect to the total mass of the composition.

[0006] However, some polymerization inhibitors have been pointed out to have suspicions of mutagenicity, etc. When directly contacting the human body like in cosmetics, it is preferable that the content is reduced as much as possible from the perspective of safety. Therefore, it is desirable to separate the polymerization inhibitor from the monomer composition. However, particularly in raw materials such as organopolysiloxanes containing a radically polymerizable organic group, it has been difficult to remove the polymerization inhibitor by means such as distillation. Specifically, in order to distill, it is necessary to heat the monomer composition, but unintended polymerization and gelation may occur, and there has been a problem that the amount of the polymerization inhibitor cannot be reduced to a certain amount or less.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] The present invention has been made to solve the above problems of the prior art, and an object thereof is to provide a radical copolymer composition and a method for producing the same, which have no concerns about safety when used in raw materials for cosmetics, etc., and do not cause a decrease in quality such as gelation.

Means for Solving the Problems

[0009] The inventors of this invention have diligently studied the above problems and arrived at the present invention. That is, the object of the present invention is a) Radical polymerizable monomers having a radically polymerizable organic group and an organosilicon-containing organic group within the molecule, and b) Radical polymerizable monomers other than component a) This is achieved by a radical copolymer composition comprising a radical copolymer, wherein the total concentration of the polymerization inhibitor relative to the total mass of the radical copolymer and polymerization inhibitor is 50 ppm by mass or less. The present invention also relates to a method for producing the radical copolymer composition of the present invention, comprising the step of contacting an adsorbent selected from the group consisting of activated carbon and alumina with a liquid containing a radical polymerizable monomer. The present invention also relates to a cosmetic or cosmetic raw material comprising the radical copolymer composition of the present invention. [Effects of the Invention]

[0010] According to the radical copolymer composition of the present invention, the content of polymerization inhibitors is reduced to an extremely low level, so there are no safety concerns even when used in applications that come into direct contact with the human body, such as cosmetics, or as a raw material for such applications.

[0011] Furthermore, since the method for producing the radical copolymer composition of the present invention does not involve a heating step such as distillation, it does not cause unintended reactions such as gelation, even with a low content of polymerization inhibitors, and can provide a high-quality radical copolymer composition. [Brief explanation of the drawing]

[0012] [Figure 1] A schematic diagram shows the separation apparatus for the polymerization inhibitor in the method for producing the radical copolymer composition of the example. [Modes for carrying out the invention]

[0013] [Radical polymerizable monomers having a radically polymerizable organic group and an organosilicon-containing organic group within the molecule] The radical copolymer composition of the present invention includes a radical polymerizable monomer having a radical polymerizable organic group and an organosilicon-containing organic group in its molecule, as a component constituting the radical copolymer ("component a").

[0014] Examples of organosilicon-containing organic groups contained in radical polymerizable monomers include carbosiloxane dendrimer structures and branched or linear siloxane structures. Carbosiloxane dendrimer structures are preferred.

[0015] The carbosiloxane dendrimer structure is a chemical structure in which a single silicon atom is highly branched radially. Radical polymerizable monomers having a carbosiloxane dendrimer structure include those with the following general formula (1):

[0016] [ka] (1)

[0017] {In the formula, Y is an organic group that can be radically polymerized, R 1 These are alkyl groups, aryl groups, or trimethylsiloxy groups. X 1 The silylalkyl group represented by the following general formula (2) when i=1 is:

[0018] [ka] (2)

[0019] (In the formula, R 1 This is the same group as defined for general formula (1), R 2 This is an alkylene group with 2 to 10 carbon atoms. R 3is a group selected from the group consisting of an alkoxy group, a hydroxyl group, an alkyl group, an aryl group, and a trimethylsiloxy group, X i+1 is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group, and i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, a is an integer of 0 to 3, b and c are 0 or 1.) The monomer represented by {} is preferred.

[0020] The radically polymerizable organic group is not particularly limited as long as it is an organic group capable of radical reaction, and examples include a (meth)acryloxy group-containing organic group, a (meth)acrylamide group-containing organic group, a styryl group-containing organic group, and an alkenyl group having 2 to 10 carbon atoms. It is preferably an organic group containing a (meth)acryloyl group. Examples of the radically polymerizable organic group include an organic group represented by the following general formula.

[0021]

Chemical formula

[0022] (In the formula, R 4 and R 6 are a hydrogen atom or a methyl group, R 5 and R 8 are an alkylene group having 1 to 10 carbon atoms, R 7 is an alkyl group having 1 to 10 carbon atoms. b is an integer of 0 to 4, and c is 0 or 1.).

[0023] Examples of such radically polymerizable organic groups include acryloxymethyl group, 3-acryloxypropyl group, methacryloxymethyl group, 3-methacryloxypropyl group, 4-vinylphenyl group, 3-vinylphenyl group, 4-(2-propenyl)phenyl group, 3-(2-propenyl)phenyl group, 2-(4-vinylphenyl)ethyl group, 2-(3-vinylphenyl)ethyl group, vinyl group, allyl group, methallyl group, and 5-hesenyl group.

[0024] In general formulas (1) and (2), R 1 The group is an alkyl group, an aryl group, or a trimethylsiloxy group, of which methyl and phenyl groups are preferred, and methyl groups are particularly preferred.

[0025] In general formula (2), R 2 The group is an alkylene group having 2 to 10 carbon atoms, and among these, the ethylene group, methylethylene group, hexylene group, 1-methylpentylene group, and 1,4-dimethylbutylene group are preferred.

[0026] In general formula (2), R 3 The group is selected from the group consisting of alkoxy groups, hydroxyl groups, alkyl groups, aryl groups, and trimethylsiloxy groups. Preferably, the alkyl group has 1 to 10 carbon atoms, and examples include methyl, ethyl, propyl, butyl, and isopropyl groups.

[0027] In general formula (2), X i+1 is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the silylalkyl group mentioned above. i is an integer from 1 to 10, which indicates the number of layers of the silylalkyl group, i.e., the number of repetitions of the silylalkyl group. Therefore, when the number of layers is 1, the radical polymerizable monomer has the general formula:

[0028] [ka]

[0029] (In the formula, Y, R 1 , R 2 and R 3 R is the same group defined for general formulas (1) and (2), 12 is a hydrogen atom or the R 1 It is the same group as . a is the same number as defined for general formula (1), but the average total number of a in one molecule is 0 to 7. ) is represented by ). When the number of layers is 2, the radical polymerizable monomer is given by general formula:

[0030] [ka]

[0031] (In the formula, Y, R 1 , R 2 , R 3 and R 12 a and a are the same groups defined for general formulas (1) and (2). 1 The number is the same as the number defined for general formula (1), but a and a in one molecule 1 The average sum of the numbers is between 0 and 25. This is shown by ( ).

[0032] Examples of radical polymerizable monomers having a carbosiloxane dendrimer structure of this component include the monomers shown in the following average composition formula.

[0033] [ka] [ka]

[0034] Such carbosiloxane dendrimers can be produced according to the method for producing branched siloxane-silalkylene copolymers described in Japanese Patent Publication No. 11-1530. For example, the general formula is:

[0035] [ka]

[0036] (In the formula, R 1 And Y are the same groups as defined for general formula (1). It can be produced by hydrosilylation reaction of a silicon compound containing a silicon atom bonded to a hydrogen atom, represented by the formula (), with an alkenyl group containing an organosilicon compound. Examples of silicon compounds represented by the above formula include 3-methacryloxypropyltris(dimethylsiloxy)silane, 3-acryloxypropyltris(dimethylsiloxy)silane, and 4-vinylphenyltris(dimethylsiloxy)silane. Examples of alkenyl group containing an organosilicon compound include vinyltris(trimethylsiloxy)silane, vinyltris(dimethylphenylsiloxy)silane, and 5-hexenyltris(trimethylsiloxy)silane. It is preferable to carry out this hydrosilylation reaction in the presence of a transition metal catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex.

[0037] As radical polymerizable monomers having a branched or linear siloxane structure, R a 3SiO 1 / 2 or R a 2R b SiO 1 / 2 M units, R a 2SiO 2 / 2 or R a R b SiO 2 / 2 The D unit is represented by R a SiO 3 / 2 or R b SiO 3 / 2 The T units represented by SiO 4 / 2 Examples of organopolysiloxanes include those containing Q units represented by in any proportion. Here, R a R is an alkyl group, aryl group, aralkyl group, or a group in which some or all of the hydrogen atoms of these groups are replaced with halogen atoms. b This is an organic group that can be radically polymerized. Radical polymerizable monomers having a branched or linear siloxane structure are preferably macromonomers with a relatively large weight-average molecular weight.

[0038] R a The group is an alkyl group, an aryl group, an aralkyl group, or a group in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms. Preferably, the alkyl group has 1 to 10 carbon atoms, and examples include methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, cyclopentyl, and cyclohexyl groups. Examples of aryl groups include phenyl and naphthyl groups. Examples of aralkyl groups include benzyl and phenethyl groups. Examples of groups in which some or all of the hydrogen atoms are substituted with halogen atoms include fluorine-substituted alkyl groups such as trifluoropropyl and heptadecafluorodecyl groups.

[0039] R b This refers to an organic group that can be radically polymerized, and is not particularly limited as long as it is an organic group that can react radically, and can be the same group as the group defined for the carbosiloxane dendrimer structure. That is, examples include (meth)acryloxy group-containing organic groups, (meth)acrylamide group-containing organic groups, styryl group-containing organic groups, and alkenyl groups having 2 to 10 carbon atoms.

[0040] Radical polymerizable monomers having such branched or linear siloxane structures can be synthesized by raw materials and methods well known to those skilled in the art. For example, they can be obtained by reacting an organosiloxane having a silanol group in its molecule with an organic chlorosilane compound in the presence of a base. The organic chlorosilane compound is not particularly limited as long as it has a radically polymerizable organic group, and examples include 3-methacryloxypropyldimethylchlorosilane and 3-methacryloxypropyldichloromethylsilane.

[0041] [a) Radical polymerizable monomers other than component] The radical copolymer composition of the present invention includes a radical polymerizable monomer other than component a) as a component constituting the radical copolymer ("component b"). That is, the radical copolymer contained in the radical copolymer composition of the present invention is a radical copolymer of component a) and component b).

[0042] Component b) is not particularly limited as long as it can copolymerize with component a), and examples include monomers containing a monovalent hydrocarbon group having a carbon-carbon double bond at the end of the molecular chain or a group derived from a monovalent unsaturated carboxylic acid, such as a vinyl group, an allyl group, a (meth)acrylic group, and a (meth)acrylooxy group, as the unsaturated bond. Component b) is preferably an acrylic acid ester monomer or a methacrylic acid ester monomer having 4 to 13 carbon atoms. It is more preferably an acrylic acid ester or a methacrylic acid ester having 4 to 10 carbon atoms.

[0043] Specifically, component b) includes lower alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate; glycidyl (meth)acrylate; n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and (meth)acrylic acid Higher (meth)acrylates such as stearyl, isostearyl (meth)acrylate, and behenyl (meth)acrylate; lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate; higher fatty acid esters such as vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurylate, and vinyl stearate; aromatic vinyl monomers such as styrene, vinyltoluene, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and vinylpyrrolidone; (meth)acrylamide, N-methylol (meth)acrylamide Amide group-containing vinyl monomers such as mid, N-methoxymethyl(meth)acrylamide, isobutoxymethoxy(meth)acrylamide, and N,N-dimethyl(meth)acrylamide; hydroxyl group-containing vinyl monomers such as hydroxyethyl (meth)acrylate and hydroxypropyl alcohol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate (T)Acrylates, hydroxybutyl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether are ether-linked vinyl monomers; (meth)acryloxypropyltrimethoxysilane, polydimethylsiloxane containing a (meth)acrylic group at one end, both ends and / or side chain, and polydimethylsiloxane containing a styryl group at one end are unsaturated group-containing silicone compounds; butadiene; vinyl chloride; vinylidene chloride; (meth)acrylonitrile; dibutyl fumarate; maleic anhydride; dodecyl succinic anhydride;Examples of (meth)acrylic glycidyl ethers include quaternary ammonium salts derived from (meth)acrylic acid such as 2-hydroxy-3-methacrylateoxypropyltrimethylammonium chloride, methacrylic acid esters of alcohols having a tertiary amine group such as diethylamine methacrylate, and their quaternary ammonium salts. b) The radical polymerizable monomers of component may be used individually or in combination of two or more.

[0044] Polyfunctional vinyl monomers can also be used, and examples include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane trioxyethyl(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, and unsaturated group-containing silicone compounds such as styryl group-blocked polydimethylsiloxane.

[0045] The copolymer contained in the radical copolymer composition of the present invention has an acid value of 5 to 300 mg KOH / g, preferably 35 to 100 mg KOH / g, measured according to JIS 1557-5 with respect to its form before neutralization. The number-average molecular weight of the copolymer is preferably 2,000 to 200,000, more preferably 3,000 to 80,000, for ease of incorporation into cosmetics. Its properties include liquid, gum, paste, solid, and powder forms.

[0046] [Manufacturing method for radical copolymers] The copolymer contained in the radical copolymer composition of the present invention can be produced by polymerizing a monomer composition containing component a) and component b). This production method includes a step of adding a polymerization initiator to the monomer composition and carrying out a polymerization reaction (first step). Subsequently, optionally, the method may include a step of contacting the obtained polymerized product with a palladium catalyst (second step).

[0047] First step In the polymerization reaction carried out in the first step, radical polymerization and ionic polymerization can be used as polymerization methods, but radical polymerization is preferred. In this radical polymerization method, solution polymerization is preferably used. This solution polymerization is carried out by reacting a monomer composition containing components a) and b) in a solvent in the presence of a radical initiator under a temperature of 50 to 150°C for 3 to 20 hours. Examples of solvents used in polymerization reactions include aliphatic hydrocarbons such as hexane, octane, decane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; and organosiloxane oligomers such as octamethyltecyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, and octamethyltrisiloxane.

[0048] As radical initiators, conventionally known compounds generally used in radical polymerization methods are used. Specifically, examples include azobis compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile); and organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, and tert-hexyl peroxy-2-ethylhexanoate. These radical initiators may be used individually or in combination of two or more. The amount of radical initiator used is preferably in the range of 0.1 to 5 parts by mass per 100 parts by mass of the total monomer composition.

[0049] Furthermore, chain transfer agents can be added during polymerization. Specific examples of such chain transfer agents include mercapto compounds such as 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, and polydimethylsiloxane having a mercaptopropyl group; and halogenated compounds such as methylene chloride, chloroform, carbon tetrachloride, butyl bromide, and 3-chloropropyltrimethoxysilane.

[0050] Second process The polymerization product obtained in the first step can be contacted with a palladium catalyst or a nickel catalyst. Contact with a palladium catalyst saturates any unreacted vinyl groups remaining in the polymerization product, reducing irritation and odor when added to cosmetics. Examples of palladium catalysts include, but are not limited to, palladium compounds such as tetrakis(triphenylphosphine)palladium(O) and dichlorobis(triphenylphosphine)palladium(II), carbon-supported palladium, carbon-supported palladium hydroxide, and platinum oxide. A preferred catalyst is carbon-supported palladium. Other metals such as nickel can also be considered as catalysts, but since the polymerization product may contain acidic groups, using nickel as a catalyst is undesirable because nickel gradually dissolves into the reaction system under acidic conditions. On the other hand, palladium, a precious metal, and especially carbon-supported palladium catalysts as heterogeneous catalysts, hardly exhibit such problems and can be suitably used as catalysts in the present invention.

[0051] The temperature at which the polymerization reaction product is brought into contact with the palladium catalyst is 50 to 200°C, preferably 70 to 130°C. The pressure is 1 to 1,000 kg / cm². 2 (Absolute pressure), preferably 2-100 kg / cm² 2 The contact time is 1 to 15 hours, preferably 3 to 10 hours. The reaction can be carried out in a solvent, and the solvent used in the polymerization may be used as is, or the solvent may be replaced. The solvents that can be used are the same as those described in the polymerization reaction.

[0052] Other steps, such as stripping, resettling, and filtration, may be included between the first and second steps. Alternatively, steps such as stripping, resettling, filtration, grinding, and classification may be performed after the second step. Furthermore, the second step may be omitted, and steps such as stripping, resettling, filtration, grinding, and classification may be performed after the first step.

[0053] The presence or absence of unreacted monomers in the copolymer obtained as described above can be determined by: 1The reaction endpoint can be confirmed by the peak integral value (5.5-6.5 ppm) of the ethylenically unsaturated group using 1H-NMR, and the endpoint can be confirmed by the disappearance or reduction of the peak originating from the ethylenically unsaturated group. For example, it can be compared using the ratio of the peak integral value of the ethylenically unsaturated group (remaining unsaturated amount ratio) to the product of the integral value of the methyl group derived from the radical polymerizable monomer (0-0.3 ppm) and the mass % of the radical polymerizable monomer at the time of charging. The remaining unsaturated amount ratio in the copolymer is 0.1 or less, preferably 0.02 or less.

[0054] The copolymer contained in the radical copolymer composition of the present invention can be incorporated into cosmetics as is, or in the form of a composition dissolved in a solvent or dispersed in a dispersion medium.

[0055] [Polymerization inhibitor] The radical copolymer composition of the present invention contains a polymerization inhibitor at a concentration such that the total concentration of the polymerization inhibitor relative to the total mass of the radical copolymer and polymerization inhibitor is 50 ppm by mass or less. Preferably, the total concentration of the polymerization inhibitor relative to the total mass of the radical polymerizable monomer and polymerization inhibitor is 30 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 5 ppm by mass or less.

[0056] The polymerization inhibitor comprises one or more selected from hindered phenol polymerization inhibitors, hydroquinone polymerization inhibitors, and catechol polymerization inhibitors. Examples of hindered phenol polymerization inhibitors include dibutylhydroxytoluene, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol. Examples of hydroquinone polymerization inhibitors include methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, and 2,5-diphenylparabenzoquinone. Examples of catechol-based polymerization inhibitors include catechol, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol. The monomer composition of the present invention particularly contains one or more selected from dibutylhydroxytoluene (BHT), methylhydroquinone (MEHQ), and 4-tert-butylcatechol (TBC). Some of these hindered phenol-based polymerization inhibitors, hydroquinone-based polymerization inhibitors, and catechol-based polymerization inhibitors have been reported to be mutagenic, and it is desirable to reduce their content to mitigate potential risks.

[0057] [Method for producing radical copolymer composition] In one embodiment, the present invention relates to a method for producing a radical copolymer composition, comprising the step of contacting an adsorbent selected from the group consisting of activated carbon and alumina with a liquid containing a radically polymerizable monomer. Generally, the obtained crude monomer composition is purified by distillation or the like, but in that case, unintended polymerization and gelation may occur, and there have been cases where the quality of the monomer composition has been problematic. For this reason, polymerization inhibitors have been used without sufficiently reducing their concentration.

[0058] The activated carbon used in the method for producing the radical copolymer composition of the present invention is not particularly limited and is produced by activating a carbon material by reacting it with a gas or chemical substance at a high temperature. The adsorbent can be used alone, but it can also be used in combination with adsorbents other than alumina and activated carbon, such as zeolite, silica, and aluminum silicate. It is preferable to use activated carbon as the adsorbent.

[0059] Contact between the adsorbent and the liquid containing the radical polymerizable monomer can be carried out without a solvent or in the presence of a solvent. The temperature and pressure for carrying out the step of contacting the adsorbent and the liquid containing the radical polymerizable monomer are not particularly limited, but can be carried out at atmospheric pressure at 0°C to 200°C, preferably 5°C to 150°C, and more preferably 10°C to 100°C.

[0060] The method for contacting the adsorbent with a liquid containing radical polymerizable monomers is not particularly limited, but can be carried out using a fixed-bed method in which the adsorbent is filled into a container and the liquid containing radical polymerizable monomers is continuously supplied; a batch method in which stirring and mixing and solid-liquid separation are performed in batch operations, respectively; a mobile-bed method in which the adsorbent is used as a mobile bed and the liquid containing radical polymerizable monomers is passed through it; or a fluidized-bed method in which the solid layer of the adsorbent is fluidized with the liquid containing radical polymerizable monomers. The step of contacting the adsorbent with a liquid containing radical polymerizable monomers is particularly preferably carried out using a fixed-bed method, and it is more preferable to continuously supply the liquid containing radical polymerizable monomers to a fixed bed of activated carbon.

[0061] In the fixed-bed method, the liquid containing the radical polymerizable monomer can be passed through the fixed bed of the adsorbent only once, or the liquid containing the radical polymerizable monomer can be circulated by supplying the outlet liquid from the fixed bed of the adsorbent back to the inlet. However, the circulating method makes it easier to ensure sufficient contact time between the liquid and the adsorbent. preferable.

[0062] In a fixed-bed system, the supply flow rate of the liquid containing the radical polymerizable monomer can be appropriately determined according to the type and concentration of the polymerization inhibitor and adsorbent. The supply flow rate of the liquid containing the radical polymerizable monomer is not particularly limited, but the supply flow rate of the liquid divided by the mass (g-AD) of the adsorbent can be 0.1 g / (min·g-AD) to 100 g / (min·g-AD), preferably 0.5 g / (min·g-AD) to 50 g / (min·g-AD), and more preferably 1.0 g / (min·g-AD) to 10 g / (min·g-AD). It is preferable to set the supply flow rate within an appropriate range so that sufficient contact time with the adsorbent is ensured and the polymerization inhibitor can be properly removed.

[0063] In a fixed-bed system, the number of cycles for circulating a liquid containing radically polymerizable monomers can be appropriately determined according to the type and concentration of polymerization inhibitors and adsorbents. The number of cycles is not particularly limited, but is preferably 0.1 to 20 times / h, more preferably 0.5 to 15 times / h, and more preferably 1 to 10 times / h. By setting the number of cycles within the above range, the concentration of polymerization inhibitors in the liquid becomes more uniform, and the polymerization inhibitors can be appropriately removed, which is preferable.

[0064] In batch processes, the stirring time of the liquid containing the radical polymerizable monomer can be appropriately determined depending on the type and concentration of the polymerization inhibitor and adsorbent. The stirring time of the liquid containing the radical polymerizable monomer is not particularly limited, but can be 0.5 to 30 hours, preferably 1 to 20 hours, and more preferably 3 to 10 hours.

[0065] The method for producing the radical copolymer composition of the present invention may include a step of bringing an adsorbent into contact with a liquid containing a radical polymerizable monomer, followed by adding a polymerization inhibitor that does not pose risks such as mutagenicity, preferably a polymerization inhibitor other than BHT, MEHQ, and TBC, such as a cinnamic acid derivative such as tetra(di-t-butylhydroxyhydrocinnamate)pentaerythrityl, alpha-tocopherol, or propyl gallate.

[0066] [Cosmetics] In one embodiment, the radical copolymer composition of the present invention can be used as a cosmetic raw material or cosmetic. When incorporating the radical copolymer of the present invention into a cosmetic, it can be in the form of a solution dissolved in a solvent, a dispersion in a dispersion medium, or a solid such as a powder, granules, or block. The amount of radical copolymer incorporated into the cosmetic raw material or cosmetic of the present invention is not particularly limited, and for example, it can contain 0.1 to 90% by mass of radical copolymer based on the total mass of the cosmetic raw material or cosmetic. Specifically, the amount of radical copolymer incorporated can be appropriately changed depending on the type of cosmetic raw material or cosmetic, for example, in the range of 0.1 to 50% by mass, 0.5 to 20% by mass, or 1 to 10% by mass.

[0067] The cosmetic raw materials and cosmetics of the present invention may be compositions comprising at least one selected from the group consisting of (A) oils, (B) alcohols, (C) surfactants, (D) powders or colorants, (E) gelling agents or thickeners, (F) organically modified clay minerals, (G) silicone resins, (H) silicone gums, (I) silicone elastomers, (J) organically modified silicones, (K) UV protection components, and (L) water-soluble polymers.

[0068] (A) Oils Examples of oils include animal oils, vegetable oils, and synthetic oils commonly used in cosmetics. The oil may be solid, semi-solid, or liquid, and may be non-volatile, semi-volatile, or volatile. The oil is used to provide lubrication to the skin and hair, to soften the skin, and to give a moist feeling. Furthermore, the oil can also be used to dilute copolymers to obtain copolymer compositions. It is particularly preferable that the oil is liquid at 5-100°C and is at least one selected from (A1) silicone-based oils and (A2) organic-based oils. The type and viscosity of these oils can be appropriately selected depending on the type and application of the cosmetic. These oils are incorporated into the cosmetic raw materials or cosmetics of the present invention simultaneously with the monomer composition described above.

[0069] (A1) Silicone-based oil Silicone-based oils are generally hydrophobic, and their molecular structure can be linear, cyclic, or branched. The viscosity of silicone-based oils at 25°C is typically 0.65 to 100,000 mm². 2 The range is / s, from 0.65 to 10,000 mm. 2 A range of / s is preferred. Furthermore, the silicone-based oil agent may and preferably be volatile.

[0070] Specific examples of silicone-based oils include cyclic organopolysiloxanes, linear organopolysiloxanes, and branched organopolysiloxanes. Among these, volatile linear organopolysiloxanes, branched organopolysiloxanes, and cyclic organopolysiloxanes are preferred.

[0071] By including at least one of these silicone-based oils in the cosmetic composition or cosmetic ingredient of the present invention, its long-term stability can be improved, and the refreshing feel characteristic of silicone oils can be achieved. Particularly preferred are decamethylcyclopentasiloxane, linear organopolysiloxane with a low viscosity range of 2 to 6 mPa·s, 1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane (also known as "caprylyl methicone"), and tritrimethylsiloxymethylsilane (also known as "M3T") from among the above-mentioned silicone-based oils.

[0072] (A2) Organic oil Typical organic oils include (A2-1) hydrocarbon oils, (A2-2) fatty acid ester oils, higher alcohols, higher fatty acids, oils and fats, and fluorinated oils. While not particularly limited in this invention, organic oils are preferably liquid at 5-100°C. Furthermore, hydrocarbon oils and / or fatty acid ester oils are preferred. These may be used alone or in combination, and can also be used in combination with silicone oils. By combining appropriate oils, the long-term stability of the composition and / or cosmetic can be enhanced, and the desired feel for each cosmetic can be imparted. By incorporating silicone oils, the refreshing feel characteristic of silicone oils can be imparted. Furthermore, by using highly volatile oils, a refreshing feel can be imparted to the skin. Moreover, by using hydrocarbon oils and / or fatty acid ester oils in combination with silicone oils, a moisturizing feeling (also called a "moist feel") and a smooth feel can be imparted to the skin and hair.

[0073] In addition to the above, oils and fats, higher alcohols, higher fatty acids, and fluorinated oils may be used as oiling agents, and two or more of these may be used in combination. For example, two or more of the oiling agents listed below may be used in combination. The following are more specific examples of other oiling agents that can be used in the present invention. Specifically, the use of one or more selected from oils and fats, higher alcohols, higher fatty acids, and fluorinated oils is an example.

[0074] (B) Alcohol As the alcohol, one or more polyhydric alcohols and / or lower monohydric alcohols can be used. Among these, ethanol, 1,3-propanediol, 1,3-butylene glycol, sorbitol, dipropylene glycol, glycerin, and polyethylene glycol are particularly preferred.

[0075] The radical copolymer composition of the present invention, or a cosmetic raw material or cosmetic containing the same, may contain (C) a surfactant as an optional component. Depending on the purpose, (C) the surfactant may be one or more surfactants selected from the group consisting of (C1) silicone surfactants, (C2) anionic surfactants, (C3) cationic surfactants, (C4) nonionic surfactants, (C5) amphoteric surfactants, and (C6) semipolar surfactants.

[0076] The amount of (C) surfactant in the radical copolymer composition of the present invention or in cosmetic raw materials or cosmetics containing the same is not particularly limited, but in order to stabilize the emulsion or dispersion, it can be added in a range of 0.05 to 90% by mass in the emulsion composition or dispersion composition, preferably 0.1 to 50% by mass, and more preferably 0.5 to 25% by mass, based on the mass of the composition.

[0077] (D) Powder or coloring agent The radical copolymer composition of the present invention, or a cosmetic raw material or cosmetic containing the same, may further contain powders or colorants, particularly any powder used in cosmetics (including powders and pigments used as colorants). Any powder or colorant used in ordinary cosmetics can be used, regardless of its shape (spherical, rod-shaped, needle-shaped, plate-shaped, sheet-shaped, irregular shape, spindle-shaped, bowl-shaped, raspberry-shaped, etc.), particle size (fuzzy, fine particles, pigment grade, etc.), or particle structure (porous, non-porous, secondary aggregation, etc.). However, when these powders and / or colorants are incorporated as pigments, it is preferable to incorporate one or more types selected from inorganic pigment powders, organic pigment powders, and resin powders, each with an average particle size in the range of 1 nm to 20 μm.

[0078] The powders or colorants specifically include inorganic powders, organic powders, surfactant metal salt powders (metal soaps), colored pigments, pearl pigments, metal powder pigments, and silicone elastomer powders, and composites thereof can also be used. These powders or colorants include those that function as UV protection components.

[0079] Furthermore, it is particularly preferable that some or all of these powders or colorants are treated to be water-repellent by known methods. This allows for stable incorporation into the oil phase. In addition, these powders or colorants can be compounded with each other, or they can be used if they have been surface-treated with general oils, silicone compounds, fluorine compounds, surfactants, etc.

[0080] The above-mentioned powder or colorant is preferably treated with other powder dispersants or surface treatment agents, and in particular, it may be dispersed or surface treated with novel powder treatment agents and treatment methods proposed in International Publication No. 2009 / 022621, Japanese Patent Publication No. 2011-148784, Japanese Patent Publication No. 2011-149017, Japanese Patent Publication No. 2011-246704, Japanese Patent Publication No. 2011-246705, Japanese Patent Publication No. 2011-246706, International Publication No. 2009 / 022621, International Publication No. 2011 / 049246, International Publication No. 2011 / 049248, Japanese Patent Application No. 2011-286973, etc., or it may be made into a slurry by treating it with these novel powder treatment agents and the oil. These novel treatment agents exhibit superior performance in areas such as improved texture and dispersion stability. Therefore, when used in combination with the radical copolymer composition of the present invention, further improvements in the functionality, texture, and storage stability of cosmetics can be expected.

[0081] Furthermore, some or all of these powders or colorants can be subjected to a hydrophilic treatment. This allows for the incorporation of powders or colorants related to the aqueous phase.

[0082] Furthermore, these powders or colorants can be partially or entirely subjected to hydrophobic and / or hydrophilic treatment. This allows the powder itself to be imparted with emulsifying properties. A commercially available example is the MZY-500SHE manufactured by Teika Corporation.

[0083] The radical copolymer composition of the present invention, or a cosmetic raw material or cosmetic containing the same, may contain one or more of the (D) powders or colorants as needed. The amount of these ingredients is not particularly limited, but can be included in a range of 0.1 to 99.5% by mass of the composition or the entire cosmetic, preferably 1 to 99% by mass. In particular, for powder solid cosmetic compositions, the amount of these ingredients is preferably in the range of 80 to 99% by mass of the entire cosmetic.

[0084] (E) Gelling agent or thickener As gelling agents, oil-soluble ones are preferred, and specifically include metal soaps such as aluminum stearate, magnesium stearate, and zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid and α,γ-di-n-butylamine; dextrin fatty acid esters such as dextrin palmitate, dextrin stearate, and dextrin 2-ethylhexanoate palmitate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; and benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol. These can be used individually or in combination of two or more as needed.

[0085] (F) Organically modified clay minerals Examples of organically modified clay minerals include dimethylbenzylddecylammonium montmorillonite clay, dimethyldioctadecylammonium montmorillonite clay, dimethylalkylammonium hectorite, benzyldimethylstearylammonium hectorite, and distearyldimethylammonium chloride-treated aluminum magnesium silicate. Commercially available products of these include Benton 27 (benzyldimethylstearylammonium chloride-treated hectorite: manufactured by National Red Co.) and Benton 38 (distearyldimethylammonium chloride-treated hectorite: manufactured by National Red Co.).

[0086] (G) Silicone resin The silicone resin is an organopolysiloxane having a highly branched, network, or cage-like structure, and is liquid or solid at room temperature. Any silicone resin commonly used in cosmetics is acceptable, as long as it does not contradict the purpose of the present invention. Examples of solid silicone resins include MQ resins, MDQ resins, MTQ resins, MDTQ resins, TD resins, TQ resins, and TDQ resins, which consist of any combination of triorganosiloxy units (M units) (organo groups consisting only of methyl groups, methyl groups and vinyl or phenyl groups), diorganosiloxy units (D units) (organo groups consisting only of methyl groups, methyl groups and vinyl or phenyl groups), monoorganosiloxy units (T units) (organo groups consisting of methyl groups, vinyl groups, or phenyl groups), and siloxy units (Q units). Furthermore, examples include trimethylsiloxysilicate, polyalkylsiloxysilicate, dimethylsiloxy unit-containing trimethylsiloxysilicate, and alkyl(perfluoroalkyl)siloxysilicate. These silicone resins are oil-soluble, and those that can dissolve in (A) are particularly preferred.

[0087] Silicone resins, when applied to skin, hair, etc., form a uniform film and provide protection against drying and low temperatures. Furthermore, silicone resins with these branched units adhere firmly to skin, hair, etc., and can give the skin, hair, etc., a glossy and translucent appearance.

[0088] (H) Silicone gum In this invention, 1,000,000 mm 2Ultra-high viscosity organopolysiloxanes, also known as silicone gums, with viscosity levels of 1 / s or higher can also be used as silicone oils. Silicone gums are linear diorganopolysiloxanes with an ultra-high degree of polymerization, and are also called silicone raw rubber or organopolysiloxane gum. Silicone gums are distinguished from the aforementioned silicone-based oils by their high degree of polymerization, which allows them to possess a measurable degree of plasticity. Examples of such silicone raw rubbers include substituted or unsubstituted organopolysiloxanes having dialkylsiloxy units (D units), such as dimethylpolysiloxane, methylphenylpolysiloxane, aminopolysiloxane, and methylfluoroalkylpolysiloxane, or those having a micro-crosslinked structure thereof. A representative example is the general formula: R 10 (CH3)2SiO{(CH3)2SiO} s {(CH3)R 11 SiO} t Si(CH3)2R 10 (In the formula, R 11 The group is selected from vinyl groups, phenyl groups, alkyl groups having 6 to 20 carbon atoms, aminoalkyl groups having 3 to 15 carbon atoms, perfluoroalkyl groups having 3 to 15 carbon atoms, and quaternary ammonium base-containing alkyl groups having 3 to 15 carbon atoms, with terminal group R 10 The group is selected from alkyl groups having 1 to 8 carbon atoms, phenyl groups, vinyl groups, aminoalkyl groups having 3 to 15 carbon atoms, and hydroxyl groups and alkoxy groups having 1 to 8 carbon atoms. There are also groups represented by s=2,000 to 6,000, t=0 to 1,000, and s+t=2,000 to 6,000. Among these, dimethylpolysiloxane raw rubber with a degree of polymerization of 3,000 to 20,000 is preferred. Amino-modified methylpolysiloxane raw rubber having a 3-aminopropyl group, N-(2-aminoethyl)3-aminopropyl group, etc., in the side chain or terminal of the molecule is also preferred. In addition, in the present invention, one or more types of silicone gum can be used in combination as needed. These silicone gums can be used as is, or as a liquid gum dispersion (oil dispersion of silicone gum) dispersed in oily silicone, and incorporated into the radical copolymer composition of the present invention or cosmetic raw materials or cosmetics containing the same.

[0089] Because silicone gum has an ultra-high degree of polymerization, it has excellent persistence on the skin and hair and forms a highly breathable protective film. For this reason, it is an ingredient that can particularly give shine and luster to the skin and hair, and impart a firm and resilient texture to the skin and hair during and after use.

[0090] The amount of silicone gum included is, for example, in the range of 0.05 to 30% by mass of the total cosmetic composition, preferably in the range of 1 to 15% by mass. Silicone gum is easier to incorporate if it is used as an emulsified composition prepared in advance through an emulsification process (including emulsion polymerization), and can be stably incorporated into the radical copolymer composition of the present invention or a cosmetic raw material containing it, or a cosmetic raw material containing a cosmetic, or a cosmetic. If the amount of silicone gum included is below the lower limit, the gloss-granting effect on the skin and hair may be insufficient.

[0091] (I) Silicone elastomer Silicone elastomers can be incorporated into cosmetic raw materials or cosmetics in any form depending on their purpose, but it is particularly preferable to incorporate them as crosslinkable organopolysiloxanes, in addition to the silicone elastomer powder described in "(D) Powder" above. Silicone elastomer powders can also be used in the form of aqueous dispersions in the radical copolymer composition of the present invention or cosmetic raw materials or cosmetics containing the same. Examples of commercially available aqueous dispersions include BY 29-129, PF-2001 PIF Emulsion from Dow-Toray. Incorporating these aqueous dispersions (=suspendions) of silicone elastomer powders is extremely useful in that it can further improve the feel of the radical copolymer composition of the present invention or cosmetic raw materials or cosmetics containing the same.

[0092] As the crosslinkable organopolysiloxane, it is preferable that it has a structure in which organopolysiloxane chains are three-dimensionally crosslinked by reaction with a crosslinkable component, and that it does not have hydrophilic parts such as polyoxyalkylene units, and is non-emulsifying. Such a crosslinkable organopolysiloxane can be used without restriction regardless of its physical form such as dilution and properties or manufacturing method, but particularly preferred examples include the α,ω-diene crosslinked silicone elastomer described in U.S. Patent No. 5,654,362 (commercial products include DOWSIL 9040 Silicone Elastomer Blend, DOWSIL 9041 Silicone Elastomer Blend, DOWSIL 9045 Silicone Elastomer Blend, DOWSIL 9046 Silicone Elastomer Blend, manufactured by Dow Chemical Company, USA). Furthermore, crosslinkable organopolysiloxanes that are fluid at room temperature can also be suitably used, such as DOWSIL 3901 LIQUID SATIN BLEND (manufactured by Dow Chemical Company, USA).

[0093] (J) Organic modified silicone Organically modified silicones are preferably lipophilic. Specifically, in addition to the above, examples include amino-modified silicones, aminopolyether-modified silicones, epoxy-modified silicones, carboxyl-modified silicones, amino acid-modified silicones, carbinol-modified silicones, acrylic-modified silicones, phenol-modified silicones, amide-alkyl-modified silicones, aminoglycol-modified silicones, and alkoxy-modified silicones. These organically modified silicones may have, in addition to polysiloxane bonds as the main chain, alkylene chains, aminoalkylene chains, or polyether chains to the extent that the compound is not hydrophilic, and the organic modification group may be present on one or both of the side chains or terminals of the polysiloxane chain. When using a cosmetic raw material or cosmetic containing the monomer composition of the present invention or a copolymer obtained therefrom for use as a hair cosmetic, amino-modified silicones, carbinol-modified silicones, aminopolyether-modified silicones, or aminoglycol-modified silicones can be suitably used, and amino-modified silicones having 3-aminopropyl groups, N-(2-aminoethyl)3-aminopropyl groups, etc., can be given as examples of common examples.

[0094] The following describes particularly preferred higher alkyl-modified silicones, alkyl-modified silicone resins, and polyamide-modified silicone resins as organically modified silicones. Higher alkyl-modified silicones are waxy at room temperature and are useful components as raw materials for cosmetics. Therefore, they can be suitably used in the radical copolymer composition of the present invention or in cosmetic raw materials or cosmetics containing the same. Examples of such higher alkyl-modified silicone waxes include methyl long-chain alkylpolysiloxanes with trimethylsiloxy groups sealed at both ends of the molecular chain, dimethylpolysiloxane-methyl long-chain alkylsiloxane copolymers with trimethylsiloxy groups sealed at both ends of the molecular chain, and long-chain alkyl-modified dimethylpolysiloxanes. Examples of commercially available products include AMS-C30 Cosmetic Wax and 2503 Cosmetic Wax (manufactured by Dow Chemical Company, USA).

[0095] In the radical copolymer composition of the present invention, or cosmetic raw materials or cosmetics containing the same, the higher alkyl-modified silicone wax is preferably melted at 60°C or higher, from the viewpoint of cosmetic retention effect and high-temperature stability.

[0096] Alkyl-modified silicone resins are ingredients that impart sebum resistance, moisturizing properties, and a fine feel to the skin to cosmetics, and waxy forms at room temperature are preferably used. For example, silsesquioxane resin wax described in Japanese Patent Publication No. 2007-532754 is a preferred example. Examples of commercially available products include SW-8005 C30 RESIN WAX (manufactured by Dow Chemical Company, USA).

[0097] Examples of polyamide-modified silicones include siloxane-based polyamide compounds described in U.S. Patent No. 5981680 (Japanese Patent Publication No. 2000-038450) and Japanese Patent Publication No. 2001-512164, and commercially available products include 2-8178 Gellant and 2-8179 Gellant (manufactured by Dow Chemical Company, USA). Such polyamide-modified silicones also function as thickeners / gelling agents for oily raw materials, particularly silicone oils.

[0098] (K) Ultraviolet protection ingredient UV protection components include inorganic UV protection components and organic UV protection components. If the radical copolymer composition of the present invention or a cosmetic raw material or cosmetic containing the same is for sunscreen use, it is preferable that it contains at least one inorganic or organic, particularly organic, UV protection component. The radical copolymer of the present invention has excellent compatibility with generally poorly soluble organic UV protection components, such as diethylamino hydroxybenzoyl hexyl benzoate known as "Ubinal A", bis-ethylhexyloxyphenol methoxyphenyl triazine known as "Tinosorb S", 2-ethylhexyl ester of 2-cyano-3,3-diphenylpropane-2-enoate known as "Octocrylene", and other cinnamic acid-based UV absorbers, and can improve formulation stability.

[0099] In the radical copolymer composition of the present invention, or in cosmetic raw materials or cosmetics containing the same, suitably usable ultraviolet protection components are at least one selected from the group consisting of fine particle titanium dioxide, fine particle zinc oxide, 2-ethylhexyl paramethoxycinnamate, 4-tert-butyl-4'-methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, 2-ethylhexyl ester of 2-cyano-3,3-diphenylpropa-2-enoic acid, and other benzophenone-based ultraviolet absorbers. These ultraviolet protection components are suitable for use because they are widely used, readily available, and have high ultraviolet protection effects. In particular, it is preferable to use inorganic and organic ultraviolet protection components in combination, and it is even more preferable to use an ultraviolet protection component corresponding to UV-A and an ultraviolet protection component corresponding to UV-B in combination.

[0100] (L) Water-soluble polymer On the other hand, the radical copolymer composition of the present invention or the cosmetic raw material or cosmetic containing the same may be an aqueous or emulsion-type composition containing a large amount of water-soluble components, and (L) water-soluble polymers may be added depending on the dosage form, and are preferred. One or more water-soluble polymers can be used as the water-soluble polymer, and examples include natural water-soluble polymers, semi-synthetic water-soluble polymers, and synthetic water-soluble polymers. Other cationic water-soluble polymers that can be suitably incorporated into hair cosmetics include quaternary nitrogen-modified polysaccharides (e.g., cationically modified cellulose, cationically modified hydroxyethylcellulose, cationically modified guar gum, cationically modified locust bean gum, cationically modified starch, etc.), dimethyldiallylammonium chloride derivatives (e.g., dimethyldiallylammonium chloride-acrylamide copolymer, polydimethylmethylenepiperidinium chloride, etc.), and vinylpyrrolidone derivatives (e.g., vinylpyrrolidone-dimethylaminoethyl methacrylic acid copolymer salt, vinylpyrrolidone-methacrylamidopropyltrimethylammonium chloride copolymer, vinylpyrrolidone-methylvinylimidazolium chloride copolymer, etc.).

[0101] The radical copolymer composition of the present invention, or cosmetic raw materials or cosmetics containing the same, may contain other components commonly used in cosmetics, to the extent that they do not interfere with the effects of the present invention: organic resins, humectants, preservatives, antibacterial agents, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin beautifying ingredients (whitening agents, cell activators, skin roughness improving agents, blood circulation promoters, skin astringents, anti-seborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, inclusion compounds, etc. Specific examples of these are common to those specifically disclosed in paragraphs 0100-0113 of Japanese Patent Application Publication No. 2011-149017, but are not limited thereto.

[0102] The radical copolymer composition of the present invention, or a cosmetic raw material or cosmetic containing the same, may be formulated with natural plant extracts, seaweed extracts, or herbal medicine components depending on its purpose. Two or more of these components may be formulated. These specific examples are common to, but not limited to, those specifically disclosed in paragraph 0115 of Japanese Patent Application Publication No. 2011-149017, etc.

[0103] The radical copolymer composition of the present invention, or a cosmetic raw material or cosmetic containing the same, may contain, depending on its purpose, a solvent other than water, such as purified water or mineral water, such as light isoparaffin, ethers, LPG, N-methylpyrrolidone, or next-generation chlorofluorocarbons.

[0104] Furthermore, the radical copolymer composition of the present invention, or the cosmetic raw material or cosmetic composition containing the same, may contain at least one selected from the group consisting of acrylic silicone dendrimer copolymer and alkyl-modified silicone resin wax. These are film-forming components, similar to the copolymers contained in the radical copolymer composition of the present invention, but they are not components that also possess cleaning properties, so it is preferable to incorporate them to the extent that they do not impair the technical effects of the present invention.

[0105] As acrylic silicone dendrimer copolymers, vinyl polymers having a carbosiloxane dendrimer structure in their side chains, as described in Japanese Patent No. 4009382 (Japanese Patent Publication No. 2000-063225), are particularly preferred examples. Commercially available examples include FA 4001 CM Silicone Acrylate and FA 4002 ID Silicone Acrylate from Dow-Toray.

[0106] As an alkyl-modified silicone resin wax, for example, the silsesquioxane resin wax described in Japanese Patent Publication No. 2007-532754 is preferred.

[0107] The radical copolymer composition of the present invention, or a cosmetic raw material or cosmetic containing the same, may be in any form: liquid, emulsion, cream, solid, paste, gel, powder, multilayer, mousse, or spray.

[0108] The copolymer contained in the radical copolymer composition of the present invention can form a film on the skin or hair that has water resistance and sebum resistance while also having excellent cleanability, and it is possible to design cosmetics that provide these functional films.

[0109] The radical copolymer composition of the present invention, or cosmetic raw materials or cosmetics containing the same, can be used in specific products such as skin cosmetics including skin cleansing products, skincare products, makeup products, antiperspirant products, and UV protection products; hair cosmetics including hair cleansing products, hair styling products, hair coloring products, hair tonic products, hair rinse products, hair conditioner products, and hair treatment products; bath cosmetics; and hair growth agents, hair tonics, analgesics, bactericides, anti-inflammatory agents, cooling agents, and anti-aging agents. In particular, when used as skin cosmetics and hair cosmetics, the radical copolymer composition of the present invention comes into direct contact with the human body. Therefore, it has been necessary to remove as much as possible ingredients that pose health risks, such as polymerization inhibitors that may be mutagenic. The radical copolymer composition of the present invention meets these requirements and has been able to significantly reduce the amount of polymerization inhibitors compared to conventional products. [Examples]

[0110] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

[0111] [Measurement of polymerization inhibitor concentration] 0.25 g of the sample was diluted 20-fold in tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd., for high-performance liquid chromatography, stabilizer-free) and 20 μL was injected into a high-performance liquid chromatography system (SHIMAZU Prominence-iLC-2030C3D) equipped with a reversed-phase column (Waters, Atlantis T3-3 μm (3.0 × 100 mm)). The column oven temperature was set to 40°C. A mixed solvent of water / methanol / tetrahydrofuran was used as the mobile phase at a flow rate of 0.45 mL / min. The BHT concentration in the sample was calculated using a calibration curve created from the peak area values ​​of a standard sample with a known concentration, the peak area value of the measured sample, and the dilution factor. The BHT concentration relative to the total mass of copolymer and BHT excluding the solvent was calculated by dividing the BHT concentration in the sample by the non-volatile content concentration of the sample. The BHT concentrations described in the Examples and Comparative Examples refer to the BHT concentration relative to the total mass of copolymer and BHT.

[0112] [Measurement of non-volatile content concentration] A 1.0 g sample was weighed into an aluminum dish and placed in an oven heated to 150°C. After 3 hours, it was removed and the weight of the remaining substance was measured. The non-volatile content concentration was calculated using the following formula.

[0113] Non-volatile content concentration = sample weight after heating / initial sample weight

[0114] [Production of radical polymerizable monomers] Radical polymerizable monomers having the following structure, used in the examples and comparative examples, were prepared by the following method. Note that Me in the figure represents a methyl group.

[0115] [ka]

[0116] 688 g of 1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]-3-vinyltrisiloxane and 0.12 g of a toluene solution containing 5% by mass of 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complex (hereinafter referred to as platinum catalyst) were placed in a flask. The solution was heated to 70°C and bubbling was performed with nitrogen gas containing 2% by volume of oxygen. While maintaining the solution temperature at 70°C, 136 g of a methaculoxypropyltris(dimethylsiloxy)silane solution containing 500 ppm by mass of BHT was added dropwise over 2 hours. After maintaining the solution temperature at 70°C for 2 hours, it was maintained at 120°C for 2 hours. Next, simple distillation was performed at 120°C and 1 kPa for 5 hours, and the liquid in the flask was collected. The BHT concentration of the collected material was measured to be 160 ppm by mass.

[0117] [Manufacturing of monomer compositions] The apparatus shown in Figure 1 was used as the separation device for the polymerization inhibitor used in Preparation Example 1.

[0118] The end 17 of the first resin tube was placed in beaker 18 containing a magnetic stirrer, and the other end 16 was connected to the suction port of the diaphragm pump 14. The end 15 of the second resin tube was connected to the discharge port of the diaphragm pump, and the other end 13 was connected to the inlet of the activated carbon immobilized filter 11 (Osaka Gas Chemical Co., Ltd. SC050X AKJ: activated carbon load 1.45g). The end 12 of the third resin tube was connected to the outlet of the filter, and the other end 19 was placed above beaker 18.

[0119] [Preparation Example 1] In the apparatus shown in Figure 1, 145 g of the radical polymerizable monomer produced by the above method was placed in a beaker and stirred at room temperature using a magnetic stirrer. The ratio of activated carbon mass to liquid mass was 0.005. The liquid in the beaker was supplied to a filter at a flow rate of 11.0 g / min (7.59 g / (min·g-AD)), and the discharged liquid was returned to the beaker and circulated. The number of circulation cycles, which is the value obtained by dividing the circulation flow rate by the total liquid volume, was 2.3 times / h. After circulating for 8 hours, a 1 g sample was taken from the beaker and the BHT concentration was analyzed. The BHT concentration was 31.1 ppm by mass.

[0120] [Comparative Preparation Example 1] Without separating the polymerization inhibitor, the radical polymerizable monomer was used directly. The BHT concentration was 160 ppm by mass.

[0121] [Comparative Preparation Example 2] 300 g of the radical polymerizable monomer produced by the above method was placed in a flask, and the pressure was reduced to 2.0 kPa using a vacuum pump. The mixture was then heated with a mantle heater until the liquid temperature reached 125°C. After simple distillation under these conditions for 3 hours, 1 g of the liquid in the flask was taken and the BHT concentration was measured to be 145.2 ppm by mass.

[0122] [Comparative Preparation Example 3] The procedure was the same as in Comparative Preparation Example 2, except that the simple distillation time was set to 6 hours. The BHT concentration was 139.2 ppm by mass.

[0123] [Comparative Preparation Example 4] The procedure was the same as in Comparative Preparation Example 2, except that the simple distillation time was set to 9 hours. The BHT concentration was 134.2 ppm by mass.

[0124] [Example 1] 290 g of radical polymerizable monomer with a BHT concentration of 31.1 ppm by mass, obtained according to Preparation Example 1, was placed in a beaker and stirred at room temperature using a magnetic stirrer. The solution was supplied to a filter using a diaphragm pump, and the discharged liquid was returned to the beaker, circulating for 3 hours. 74.2 g of the radical polymerizable monomer solution was mixed with 9.3 g of butyl acrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) and 102.1 g of methyl methacrylate (Mitsubishi Chemical, Acryester M) to obtain a monomer mixture. In addition, 4.1 g of 2,2'-azobis(isobutyrate)dimethyl (Fujifilm Wako Pure Chemical Industries, Ltd., V-601) was dissolved in 68 g of 2-propanol to obtain a catalyst solution. 175 g of 2-propanol was placed in a 1 L flask, and after raising the temperature to 65°C, the monomer mixture and catalyst solution obtained above were added dropwise at a constant flow rate over 3 hours at the same temperature. Next, the temperature was raised to 75°C and aged at the same temperature for 12 hours. After adding 336g of isododecane (Maruzen Petroleum, Marcazole R), 2-propanol was removed from the solution at 20kPa and 120°C until the non-volatile content concentration was 40% by mass. A 1g sample was taken and the BHT concentration was analyzed. The BHT concentration was below the detection limit (5 ppm by mass), and BHT could not be detected.

[0125] [Comparative Example 1] The procedure was carried out in the same manner as in Example 1, except that the radical polymerizable monomer with a BHT concentration of 160 ppm by mass, obtained in Comparative Preparation Example 1, was used instead of the radical polymerizable monomer with a BHT concentration of 31.1 ppm by mass, obtained in Preparation Example 1. The BHT concentration was 75.0 ppm by mass.

[0126] [Comparative Example 2] The procedure was carried out in the same manner as in Example 1, except that a radical polymerizable monomer with a BHT concentration of 145.2 ppm by mass, obtained in Comparative Preparation Example 2, was used instead of a radical polymerizable monomer with a BHT concentration of 31.1 ppm by mass, obtained in Preparation Example 1. The BHT concentration was 63.0 ppm by mass.

[0127] [Comparative Example 3] The procedure was carried out in the same manner as in Example 1, except that the radical polymerizable monomer with a BHT concentration of 139.2 ppm obtained in Comparative Preparation Example 3 was used instead of the radical polymerizable monomer with a BHT concentration of 31.1 ppm obtained in Preparation Example 1. The BHT concentration was 60.3 ppm.

[0128] [Comparative Example 4] The procedure was carried out in the same manner as in Example 1, except that a radical polymerizable monomer with a BHT concentration of 134.2 ppm, obtained in Comparative Preparation Example 4, was used instead of the radical polymerizable monomer with a BHT concentration of 31.1 ppm, obtained in Preparation Example 1. The BHT concentration was 58.3 ppm, obtained in Comparative Preparation Example 4.

[0129] Table 1 Experimental conditions and BHT concentrations for Example 1 and Comparative Examples 1 to 4 [Table 1]

[0130] As can be seen from Table 1, which summarizes the results of the examples and comparative examples, it was found that the method of the present invention can produce copolymers in which the total concentration of polymerization inhibitor relative to the total mass of the radical copolymer and polymerization inhibitor is 50 ppm by mass or less. On the other hand, it was found that in the simple distillation method used in Comparative Examples 2 to 4, the BHT concentration exceeded 50 ppm by mass even after prolonged processing. [Explanation of symbols]

[0131] 11. Activated carbon immobilized filter 12 End of the third resin tube 13 The other end of the second resin tube 14. Diaphragm pump 15 End of the second resin tube 16 The other end of the first resin tube 17 End of the first resin tube 18 beakers 19 The other end of the third resin tube

Claims

1. A step of contacting an adsorbent selected from the group consisting of activated carbon and alumina with a liquid containing a radically polymerizable monomer having a radically polymerizable organic group in the molecule and an organosilicon-containing organic group selected from a carbosiloxane dendrimer structure and a branched or linear siloxane structure, A step of continuously supplying a liquid containing the radical polymerizable monomer to the fixed bed of the adsorbent, and The process includes circulating the liquid containing the radical polymerizable monomer by supplying the outlet liquid of the fixed bed of the adsorbent back to the inlet, a) A radically polymerizable monomer having a radically polymerizable organic group within the molecule and an organosilicon-containing organic group selected from a carbosiloxane dendrimer structure and a branched or linear siloxane structure, and b) Radical polymerizable monomers other than component a) A method for producing a radical copolymer composition comprising a radical copolymer, wherein the total concentration of the polymerization inhibitor, dibutylhydroxytoluene (BHT), relative to the total mass of the radical copolymer and the polymerization inhibitor, dibutylhydroxytoluene (BHT), is 5 ppm by mass or less.

2. a) The radical polymerizable monomer of the component is the following general formula (1): 【Chemistry 1】 （１） {During the ceremony, Y is an organic group that can be radically polymerized, R １ These are alkyl groups, aryl groups, or trimethylsiloxy groups. X １ When i = 1, the silylalkyl group is represented by the following general formula (2): 【Chemistry 2】 （２） (In the formula, R １ This is the same group as defined for general formula (1), R ２ This is an alkylene group having 2 to 10 carbon atoms. R ３ This group is selected from the group consisting of alkoxy groups, hydroxyl groups, alkyl groups, aryl groups, and trimethylsiloxy groups. X ｉ＋１ is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the silylalkyl group, and i is an integer from 1 to 10 indicating the hierarchy of the silylalkyl group. a is an integer between 0 and 3. b and c are either 0 or 1. The method for producing the radical copolymer composition according to claim 1, which is represented as}.

3. A method for producing a radical copolymer composition according to claim 1 or claim 2, wherein the radical polymerizable organic group includes a (meth)acryloyl group.

4. A method for producing a radical copolymer composition according to any one of claims 1 to 3, which is a cosmetic raw material or a cosmetic.

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