Monomer compositions and methods for producing the same, as well as cosmetics or cosmetic raw materials containing the monomer composition.

Abstract

[Problem] To provide a monomer composition that poses no concern about safety when used as a raw material of a cosmetic, etc. and does not trigger a decrease in quality such as gelation, and a method for producing the same. [Solution] A monomer composition including a radical polymerizable monomer having an organic group capable of radical polymerization and an organic silicon-containing organic group in the molecule, wherein the total concentration of polymerization inhibitor to the total mass of the radical polymerizable monomer and polymerization inhibitor is 130 mass ppm or less, and a method for producing the same.

Description

[Technical Field]

[0001] This invention relates to monomer compositions, methods for producing the same, and cosmetics or cosmetic ingredients containing the monomer 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 over time of a cosmetic composition, it contains a polymerization inhibitor of 10 ppm to 20% by mass based on the total mass of the composition.

[0006] However, some polymerization inhibitors have been pointed out to have suspicions such as mutagenicity. 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, especially 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 is a problem that the amount of the polymerization inhibitor cannot be reduced to less than a certain amount.

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 monomer composition and a method for producing the same that 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] As a result of intensive studies on the above problems, the present inventors have reached the present invention. That is, an object of the present invention is a monomer composition containing a radically polymerizable monomer having a radically polymerizable organic group and an organosilicon-containing organic group in the molecule, wherein the total concentration of the polymerization inhibitor relative to the total mass of the radically polymerizable monomer and the polymerization inhibitor is 130 ppm by mass or less, which is achieved by the monomer composition. The present invention also relates to a method for producing the monomer composition of the present invention, which includes a step of bringing a liquid containing a radically polymerizable monomer into contact with an adsorbent selected from the group consisting of activated carbon and alumina. The present invention also relates to a cosmetic or a cosmetic raw material containing the monomer composition of the present invention.

Advantages of the Invention

[0010] According to the monomer composition of the present invention, since the content of the polymerization inhibitor is extremely low and reduced, there is no concern about safety even when used as a raw material for applications that directly contact the human body such as cosmetics.

[0011] In addition, the method for producing the monomer composition of the present invention does not include a heating step such as distillation, so even though the content of the polymerization inhibitor is low, it does not cause gelation or the like due to an unintended reaction, and a high-quality monomer composition can be provided.

Brief Description of the Drawings

[0012] [Figure 1] Schematically shows a separation device for a polymerization inhibitor in the method for producing the monomer composition of the example.

Embodiments for Carrying Out the Invention

[0013] [Radically Polymerizable Monomer Having a Radically Polymerizable Organic Group and an Organosilicon-Containing Organic Group in the Molecule] The monomer composition of the present invention contains a radically polymerizable monomer having a radically polymerizable organic group and an organosilicon-containing organic group in the molecule.

[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 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 0 or 1.) A 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 thereof 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 a radically polymerizable organic group include an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2-propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallyl group, a sorbyl group, and a 5-hexenyl group.)

[0024] In general formulas (1) and (2), R 1 is an alkyl group, an aryl group, or a trimethylsiloxy group, preferably a methyl group and a phenyl group, and particularly preferably a methyl group.)

[0025] In general formula (2), R2 The group is an alkylene group having 2 to 10 carbon atoms, and ethylene, methylethylene, hexylene, 1-methylpentylene, and 1,4-dimethylbutylene groups 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, with alkyl groups having 1 to 10 carbon atoms being examples of alkyl 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 12a 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 1And 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 aThe 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] [Polymerization inhibitor] The monomer 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 polymerizable monomer and polymerization inhibitor is 130 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 110 ppm by mass or less, more preferably 90 ppm by mass or less, and even more preferably 70 ppm by mass or less.

[0042] 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.

[0043] [Method for producing monomer compositions] In one embodiment, the present invention relates to a method for producing a monomer 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.

[0044] The activated carbon used in the method for producing the monomer 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.

[0045] 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.

[0046] 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.

[0047] 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. The circulating method is preferable because it makes it easier to ensure sufficient contact time between the liquid and the adsorbent.

[0048] 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 it can be supplied in amounts of 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), as the supply flow rate of the liquid divided by the mass (g-AD) of the adsorbent. 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.

[0049] 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.

[0050] 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.

[0051] The method for producing the monomer composition of the present invention may include a step of bringing an adsorbent into contact with a liquid containing a radically 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.

[0052] [Cosmetics] In one embodiment, the monomer composition of the present invention can be used as a cosmetic raw material or for cosmetics, and may be included in cosmetic raw materials or cosmetics as a copolymer polymerized with other radical polymerizable monomers. The cosmetic raw material and cosmetics 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. These specific examples are common to the components disclosed in Patent Document 1 (Japanese Patent Application Publication No. 2014-40512), etc.

[0053] (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.

[0054] (B) Alcohol As the alcohol, one or more polyhydric alcohols and / or lower monohydric alcohols can be used. Examples of lower alcohols include ethanol, isopropanol, n-propanol, t-butanol, and sec-butanol, with ethanol being preferred. Examples of polyhydric alcohols include dihydric alcohols such as 1,3-propanediol, 1,3-butylene glycol, 1,2-butylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, dibutylene glycol, pentyl glycol, hexylene glycol, and octylene glycol; trihydric alcohols such as glycerin, trimethylolpropane, and 1,2,6-hexanetriol; polyhydric alcohols of tetrahydric or higher hydration such as pentaerythritol and xylitol; and sugar alcohols such as sorbitol, mannitol, maltitol, maltotriose, sucrose, erythritol, glucose, fructose, starch hydrolysates, maltose, xylitol, and starch hydrolysate-reduced alcohols. Furthermore, in addition to these low molecular weight polyhydric alcohols, other examples include polyhydric alcohol polymers such as diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, and polyglycerin. Among these, ethanol, 1,3-propanediol, 1,3-butylene glycol, sorbitol, dipropylene glycol, glycerin, and polyethylene glycol are particularly preferred.

[0055] A cosmetic raw material or cosmetic containing the monomer composition of the present invention or a copolymer obtained therefrom 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.

[0056] Examples of (C1) silicone-based surfactants include polyglyceryl-modified silicone, diglyceryl-modified silicone, glyceryl-modified silicone, sugar-modified silicone, fluorine polyether-modified silicone, polyether-modified silicone, carboxylic acid-modified silicone, linear silicone-polyether block copolymer (e.g., polysilicone-13), long-chain alkyl-polyether copolymer, polyglyceryl-modified silicone elastomer, diglyceryl-modified elastomer, glyceryl-modified elastomer, and polyether-modified elastomer. Furthermore, among the aforementioned silicones and elastomers, those in which alkyl branching, linear silicone branching, siloxane dendrimer branching, etc., are applied simultaneously with hydrophilic groups as needed can also be suitably used. Commercially available products include SH 3771 M, SH 3772 M, SH 3773 M, SH 3775 M, BY 22-008M, BY 11-030, ES-5373 FORMULATION AID, ES-5612 FORMULATION AID, ES-5300 FORMULATION AID, and ES-5600 SILICONE GLYCEROL EMULSIFIER (all manufactured by Dow-Toray).

[0057] The amount of (C) surfactant in a cosmetic raw material or cosmetic containing the monomer composition of the present invention or a copolymer obtained therefrom 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 per mass of the composition.

[0058] (D) Powder or coloring agent The monomer composition of the present invention or the copolymer obtained therefrom, which is used as a cosmetic raw material or cosmetic, 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, with an average particle size in the range of 1 nm to 20 μm.

[0059] 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.

[0060] Furthermore, it is particularly preferable that some or all of these powders or colorants are treated to be water-repellent. This allows for stable incorporation into the oil phase. Additionally, these powders or colorants can be compounded, or surface-treated with general oils, silicone compounds, fluorine compounds, surfactants, etc.

[0061] 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.

[0062] 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.

[0063] The (D) powder or colorant in the cosmetic raw material or cosmetic containing the monomer composition of the present invention or a copolymer obtained therefrom may be used one or more as needed, and the amount blended is not particularly limited, but it may be blended in the range of 0.1 to 99.5% by mass of the composition or the entire cosmetic, preferably 1 to 99% by mass. In particular, in the case of powder solid cosmetics, the blending amount is preferably in the range of 80 to 99% by mass of the entire cosmetic.

[0064] (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.

[0065] (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.).

[0066] (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.

[0067] 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.

[0068] (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. In the present invention, silicone gums can be used individually or in combination of two or more types as needed. These silicone gums can be incorporated as is, or as a liquid gum dispersion (oil dispersion of silicone gum) dispersed in oily silicone, into cosmetic raw materials or cosmetics containing the monomer composition of the present invention or copolymers obtained therefrom.

[0069] 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.

[0070] 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. It should be noted that if the silicone gum is used as an emulsified composition prepared in advance through an emulsification process (including emulsion polymerization), it is easier to incorporate and can be stably incorporated into cosmetic raw materials or cosmetics containing the monomer composition of the present invention or copolymers obtained therefrom. If the amount of silicone gum included is below the aforementioned lower limit, the gloss-granting effect on skin and hair may be insufficient.

[0071] (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 cosmetic raw materials or cosmetics containing the monomer composition of the present invention or copolymers obtained therefrom. Examples of commercially available aqueous dispersions include BY 29-129 and 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 cosmetic raw materials or cosmetics containing the monomer composition of the present invention or copolymers obtained therefrom.

[0072] 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 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).

[0073] (J) Organic modified silicone Organically modified silicones are preferably lipophilic. Specifically, in addition to the above, examples include amino-modified silicones, amino-polyether-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, amino-glycol-modified silicones, and alkoxy-modified silicones. Furthermore, particularly preferred organically modified silicones include higher alkyl-modified silicones, alkyl-modified silicone resins, and polyamide-modified silicone resins.

[0074] (K) Ultraviolet protection ingredient UV protection components include inorganic UV protection components and organic UV protection components. If the cosmetic raw material or cosmetic containing the monomer composition of the present invention or a copolymer obtained therefrom is for sunscreen use, it is preferable that it contains at least one inorganic or organic, particularly organic, UV protection component. In particular, it is preferable to use inorganic and organic UV protection components in combination, and it is even more preferable to use a UV protection component that corresponds to UV-A and a UV protection component that corresponds to UV-B.

[0075] (L) Water-soluble polymer On the other hand, the cosmetic raw material or cosmetic containing the monomer composition of the present invention or a copolymer obtained therefrom 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 is preferable. One or more water-soluble polymers can be used as the water-soluble polymer.

[0076] Cosmetic raw materials or cosmetics containing the monomer composition of the present invention or copolymers obtained therefrom may contain other ingredients 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.

[0077] The monomer composition of the present invention or the copolymer obtained therefrom may contain cosmetic raw materials or cosmetics, which may be blended with natural plant extracts, seaweed extracts, or herbal medicine components depending on their purpose. Two or more of these components may be blended. Specific examples of these components are common to, but not limited to, those specifically disclosed in paragraph 0115 of Japanese Patent Application Publication No. 2011-149017, etc.

[0078] The monomer composition of the present invention or the copolymer obtained therefrom may contain, depending on its purpose, a solvent other than water, such as purified water or mineral water, such as light isoparaffins, ethers, LPG, N-methylpyrrolidone, or next-generation chlorofluorocarbons.

[0079] Furthermore, cosmetic raw materials or cosmetics containing the monomer composition of the present invention or copolymers obtained therefrom may contain at least one selected from the group consisting of acrylic silicone dendrimer copolymers and alkyl-modified silicone resin waxes. These are film-forming components, similar to the copolymers obtained from the monomer composition of the present invention, but they are not components that also have cleaning properties, so it is preferable to incorporate them to the extent that they do not impair the technical effects of the present invention.

[0080] 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.

[0081] As an alkyl-modified silicone resin wax, for example, the silsesquioxane resin wax described in Japanese Patent Publication No. 2007-532754 is preferred.

[0082] The monomer composition of the present invention or the copolymer obtained therefrom may be used as a cosmetic raw material or cosmetic in any of the following forms: liquid, emulsion, cream, solid, paste, gel, powder, multilayer, mousse, or spray.

[0083] The copolymer obtained from the monomer composition of the present invention can form a film on the skin or hair that has water resistance and sebum resistance, as well as excellent cleanability, and it is possible to design cosmetics that provide these functional films.

[0084] Cosmetics containing the monomer composition of the present invention or copolymers obtained therefrom include, but are not limited to, skin cosmetics such as skin cleansing products, skincare products, makeup products, antiperspirant products, and UV protection products; hair cosmetics such as 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, disinfectants, anti-inflammatory agents, cooling agents, and skin anti-aging agents. In particular, when used as skin cosmetics and hair cosmetics, the monomer composition of the present invention or copolymers obtained therefrom come 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 monomer composition of the present invention meets this requirement and has been able to significantly reduce the content of polymerization inhibitors compared to conventional products. Furthermore, specific examples of skin cosmetics and hair cosmetics are common to the various cosmetics disclosed in Patent Document 1 (Japanese Patent Publication No. 2014-40512) and other documents mentioned above. In addition, the monomer composition according to the present invention or the copolymer obtained therefrom can be used to replace part or all of it in the composition of a cosmetic product containing an acrylic copolymer having an organosilicon-containing organic selected from known carbosiloxane dendrimer structures and branched or linear siloxane structures. [Examples]

[0085] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

[0086] [Measurement of polymerization inhibitor concentration] A 0.25 g 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, and the peak area value and dilution factor of the sample being measured.

[0087] [Manufacturing example] The radical polymerizable monomer having the structure shown below, used in the examples, was prepared by the following method. Note that Me in the figure represents a methyl group.

[0088] [ka]

[0089] 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. After heating to a temperature of 70°C, 136 g of a methacrylateoxypropyltris(dimethylsiloxy)silane solution containing 500 ppm by mass of BHT was added dropwise over 2 hours while maintaining the temperature at 70°C. The temperature was maintained at 70°C for 2 hours, then 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 in the obtained solution was measured to be 160 ppm by mass.

[0090] [Manufacturing of monomer compositions] The apparatus shown in Figure 1 was used as the separation apparatus for polymerization inhibitors to produce the monomer compositions in Examples 1 to 5.

[0091] 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.

[0092] [Example 1] In the apparatus shown in Figure 1, 145 g of the radical polymerizable monomer produced according to the manufacturing example was placed in a beaker and stirred at room temperature using a magnetic stirrer. The ratio of activated carbon mass to liquid mass was 0.01. The liquid in the beaker was supplied to a filter at a flow rate of 5.6 g / min (3.86 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 3 hours, a 1 g sample was taken from the beaker and the BHT concentration was analyzed. The BHT concentration was 61.6 ppm by mass.

[0093] [Example 2] The procedure was the same as in Example 1, except that 290 g of radical polymerizable monomer was used. Specifically, the ratio of activated carbon mass to liquid mass was 0.005, and the circulation rate was 1.2 times / h. The BHT concentration was 128.6 ppm by mass.

[0094] [Example 3] The procedure was carried out in the same manner as in Example 2, except that the circulation flow rate was set to 11.0 g / min (7.59 g / (min·g-AD)). Specifically, the ratio of activated carbon mass to liquid mass was 0.005, and the circulation rate was 2.3 times / h. The BHT concentration was 57.7 ppm by mass.

[0095] [Example 4] The procedure was carried out in the same manner as in Example 3, except that the circulation time was set to 8 hours. Specifically, the ratio of activated carbon mass to liquid mass was 0.005, and the circulation rate was 2.3 times / hour. The BHT concentration was 31.1 ppm by mass.

[0096] [Example 5] The procedure was the same as in Example 4, except that the temperature of the liquid in the beaker was maintained at 40°C using a constant temperature bath. Specifically, the ratio of activated carbon mass to liquid mass was 0.005, and the circulation rate was 2.3 times / h. The BHT concentration was 41.1 ppm by mass.

[0097] [Example 6] 40 g of radical polymerizable monomer prepared according to the manufacturing example and 8.1 g of activated alumina particles (ST-1000, manufactured by Union Showa Co., Ltd.) were placed in a beaker and stirred at room temperature for 6 hours using a magnetic stirrer. The ratio of activated alumina mass to liquid mass was 0.20. When 1 g of the liquid in the beaker was taken and the BHT concentration was measured, the BHT concentration was 49.9 ppm by mass.

[0098] [Example 7] 40 g of radical polymerizable monomer prepared according to the manufacturing example and 4.0 g of activated alumina particles (ST-1000, manufactured by Union Showa Co., Ltd.) were placed in a beaker and stirred at room temperature for 6 hours using a magnetic stirrer. The ratio of activated alumina mass to liquid mass was 0.10. When 1 g of the liquid in the beaker was taken and the BHT concentration was measured, the BHT concentration was 104.4 ppm by mass.

[0099] [Comparative Example 1] 300 g of radical polymerizable monomer produced according to the manufacturing example 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.

[0100] [Comparative Example 2] The procedure was the same as in Comparative Example 1, except that the simple distillation time was set to 6 hours. The BHT concentration was 139.2 ppm by mass.

[0101] [Comparative Example 3] The procedure was the same as in Comparative Example 1, except that the simple distillation time was set to 9 hours. The BHT concentration was 134.2 ppm by mass.

[0102] Table 1 Experimental conditions and BHT concentrations for Examples 1 to 5 [Table 1]

[0103] Table 2 Experimental conditions and BHT concentrations for Examples 6 and 7 [Table 2]

[0104] Table 3 Experimental conditions and BHT concentrations for Comparative Examples 1 to 3 [Table 3]

[0105] As can be seen from Tables 1 to 3, which summarize the results of each example, it was found that the method of the present invention can produce monomer compositions in which the total concentration of polymerization inhibitor relative to the total mass of radical polymerizable monomer and polymerization inhibitor is 130 ppm by mass or less. On the other hand, it was found that in the simple distillation method used in the comparative example, the BHT concentration exceeded 130 ppm by mass even after prolonged processing. [Explanation of Symbols]

[0106] 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 method for producing a monomer composition, wherein the total concentration of the polymerization inhibitor, dibutylhydroxytoluene (BHT), relative to the total mass of the radical polymerizable monomer and the polymerization inhibitor, dibutylhydroxytoluene (BHT), is 90 ppm by mass or less.

2. The radical polymerizable monomer is of 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 monomer composition according to claim 1, which is represented as}.

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

4. A method for producing a monomer composition according to any one of claims 1 to 3, for use as a raw material for cosmetics.

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