JP2014198678A - Resin-coated particles for cosmetics and process for producing same, and cosmetics - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-coated particles for cosmetics excellent in water resistance and to provide cosmetics comprising the resin-coated particles for cosmetics.SOLUTION: Metallic oxide particles, a layer derived from a coupling agent which coats the surface of the metallic oxide particles, and a resin layer which coats the layer of derived from the coupling agent are contained. The coupling agent is at least one selected from the group consisting of an aluminium-containing organic compound represented by a specific general formula, a zirconium-containing organic compound and a titanium-containing organic compound represented by a specific general formula. The resin layer comprises a segment derived from silicone macro-monomer represented by the following general formula (in the above formula, Rrepresents a hydrogen atom or a methyl group; Rrepresents an alkylene group of carbon numbers 2-4; Ris mutually the same or different, and represents an alkyl group or phenyl group of carbon numbers 1-4; and r represents a positive integer).

Description

  The present invention relates to a resin-coated particle for cosmetics containing metal oxide particles, a method for producing the same, and a cosmetic containing the resin-coated particles for cosmetics, and in particular, a resin-coated particle for cosmetics excellent in water resistance and its The present invention relates to a production method and a cosmetic material excellent in water resistance.

  In general, metal oxide particles represented by titanium oxide, zinc oxide, etc. are widely used in the cosmetics field such as basic cosmetics, suncut materials, nail color, nail coat, foundation, mascara, eyeliner, etc. Yes. When using metal oxide particles in the field of cosmetics, for the purpose of blocking the surface activity of the metal oxide particles and for imparting water resistance, sebum resistance, etc. to the particles, alumina treatment, silica treatment, oil treatment, It is common to use particles obtained by subjecting metal oxide particles to surface treatment such as metal soap treatment, coating treatment with organopolysiloxane, coating treatment with a polymer such as acrylic resin.

  For example, when an organopolysiloxane having a reactive site in the molecule is used as a surface treatment agent and the metal oxide particles are coated with this surface treatment agent, the organopolysiloxane forms a chemical bond with the surface of the metal oxide particles. To do. Therefore, in addition to modifying the surface of the metal oxide particles and simultaneously blocking the surface activity of the metal oxide particles, it is possible to suppress the detachment of the surface treatment agent from the surface of the metal oxide particles. As a result, it is possible to suppress a change in properties of the cosmetic using the coated metal oxide particles.

  Patent Document 1 discloses a surface-treated powder obtained by surface-treating a powder such as zinc oxide, titanium oxide, or extender pigment with an acrylic / silicone copolymer having a hydrolyzable silyl group.

  In Patent Document 2, the surface of metal oxide fine particles is coated with silica, and the outside thereof is coated with a polymer such as a (meth) acrylic polymer, and in an aqueous medium, By conducting emulsion polymerization using a polymerizable monomer having a reactive group capable of reacting with a functional group introduced on the surface of the silica-coated metal oxide fine particles and a radical initiator in the presence of the silica-coated metal oxide fine particles. A production method for producing the polymer-coated metal oxide fine particles is disclosed.

  Patent Document 3 discloses composite polymer particles containing a metal oxide coated with silicone and / or a fluorine compound, a metal oxide coated with silicone and / or a fluorine compound, a monomer component, and a crosslinking agent. A production method is disclosed in which the composite polymer particles are produced by dispersing and mixing the particles, followed by suspension polymerization.

International Publication No. 2002 / 1003.6 JP 2008-266283 A JP 2009-1828 A

  However, the particles obtained by subjecting metal oxide particles to surface treatment with a conventional surface treatment agent may have poor water resistance.

  Furthermore, since the method for producing composite polymer particles described in Patent Document 2 is a method of emulsion polymerization of a polymerizable monomer in an aqueous medium, for example, a segment derived from a poorly water-soluble monomer such as a silicone macromonomer is used. There is a problem that it is difficult to be contained in the polymer, and it is difficult to impart functions such as water resistance derived from the silicone macromonomer to the composite polymer particles.

  Moreover, since the manufacturing method of the composite polymer particle of patent document 3 is a method of manufacturing the said composite polymer particle by suspension polymerization in water, the average particle diameter of the composite polymer particle obtained becomes large. Therefore, when the composite polymer particle obtained by the manufacturing method of Patent Document 3 is used for cosmetics, there arises a problem that transparency when the cosmetics are applied to the skin is lowered.

  This invention is made | formed in view of the said conventional subject, The objective is to provide the cosmetics containing the resin-coated particle for cosmetics excellent in water resistance, and the resin-coated particle for cosmetics. Another object of the present invention is to provide a method for producing cosmetic resin-coated particles, which is excellent in water resistance and capable of easily obtaining resin-coated particles for cosmetics having a small average particle diameter.

  In order to solve the above problems, the resin-coated particles for cosmetics of the present invention include metal oxide particles, a layer derived from a surface treatment agent that coats the surface of the metal oxide particles, and a layer derived from the surface treatment agent. And the surface treatment agent is represented by the following general formula:

(In the formula, R ¹ represents an alkyl group having 8 to 20 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ³ represents an alkoxy group having 1 to 6 carbon atoms, m Represents an integer of 0 to 2, n represents an integer of 1 to 3, and m + n = 3)
An aluminum-containing organic compound, a zirconium-containing organic compound, and the following general formula

(In the above formula, R ⁴ represents an optionally substituted alkoxy group having 1 to 15 carbon atoms, R ⁵ represents an alkyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, or Represents an alkenyl group having 2 to 24 carbon atoms, X represents a carbon atom or a phosphorus atom, a represents 1 when X represents a carbon atom, and a represents 2 when X represents a phosphorus atom. P represents an integer of 1 to 3, q represents an integer of 1 to 3, and p + q = 4)
And at least one selected from the group consisting of titanium-containing organic compounds represented by the formula:

(In the above formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkylene group having 2 to 4 carbon atoms, and R ⁸ are the same or different from each other and represent an alkyl group or phenyl group having 1 to 4 carbon atoms. And r represents a positive integer)
It contains the segment derived from the silicone macromonomer represented by these.

  According to the above configuration, the resin layer covering the metal oxide particles through the layer derived from the surface treatment agent includes a segment derived from the silicone macromonomer represented by the general formula, The water resistance of the resin layer can be increased. Moreover, according to the said structure, between the said metal oxide particle and the said resin layer, the aluminum containing organic compound represented by the said general formula, the zirconium containing organic compound, and the titanium containing organic represented by the said general formula Since the layer derived from the surface treatment agent that is at least one selected from the group consisting of compounds is present, the amount of the resin layer attached to the surface in contact with the resin layer can be increased. By these, the resin-coated particle for cosmetics excellent in water resistance can be provided.

  In order to solve the above-mentioned problem, the method for producing resin-coated particles for cosmetics according to the present invention is a method for producing the resin-coated particles for cosmetics, which includes a monomer component containing the silicone macromonomer and a dispersant. Is dissolved in a non-aqueous solvent, and the metal oxide particles coated with the layer derived from the surface treatment agent are dispersed in the non-aqueous solvent, and then the monomer component is polymerized.

  According to the method, the monomer component and the dispersant are dissolved in a non-aqueous solvent, and the metal oxide particles coated with the surface treatment agent-derived layer are dispersed in the non-aqueous solvent. Thus, since the monomer component is polymerized, cosmetic resin-coated particles having a small average particle diameter can be easily obtained.

  The cosmetic of the present invention is characterized by including the resin-coated particles for cosmetics of the present invention.

  According to the said structure, since the resin-coated particle | grains for cosmetics of this invention excellent in water resistance are included, the cosmetics excellent in water resistance can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the cosmetics containing the resin-coated particle for cosmetics excellent in water resistance and the resin-coated particle for cosmetics can be provided. Moreover, according to this invention, the manufacturing method of the resin coating particle for cosmetics which can obtain easily the resin coating particle for cosmetics which is excellent in water resistance and a small average particle diameter can be provided.

  The resin-coated particles for cosmetics of the present invention include metal oxide particles, a layer derived from a surface treatment agent that covers the surface of the metal oxide particles, and a resin layer that covers the layer derived from the surface treatment agent. The surface treatment agent is at least one selected from the group consisting of an aluminum-containing organic compound represented by a specific general formula, a zirconium-containing organic compound, and a titanium-containing organic compound represented by a specific general formula, The resin layer has the following general formula

(In the above formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkylene group having 2 to 4 carbon atoms, and R ⁸ are the same or different from each other and represent an alkyl group or phenyl group having 1 to 4 carbon atoms. And r represents a positive integer)
The segment derived from the silicone macromonomer represented by these is included.

  Moreover, it is preferable that the average particle diameter of the resin coating particle for cosmetics of this invention is 0.15 micrometer or more and 1.5 micrometers or less. When the average particle diameter of the resin-coated particles for cosmetics is less than 0.15 μm, the coating of the metal oxide particles with the resin layer tends to be incomplete, and the surface activity of the metal oxide particles is sealed with the resin layer. Is likely to be insufficient, and the characteristic change of the resin-coated particles for cosmetics may easily occur. On the other hand, when the average particle size of the resin-coated particles for cosmetics is larger than 1.5 μm, the cosmetic resin-coated particles including the cosmetic resin-coated particles are applied to the skin because the particle size of the resin-coated particles for cosmetics is large. When applied, the transparency may be reduced.

  The resin-coated particles for cosmetics of the present invention are preferably obtained by polymerization in a non-aqueous solvent. Thereby, the resin-coated particles for cosmetics which are excellent in the ultraviolet protection index of cosmetics containing the resin-coated particles for cosmetics and have a small average particle diameter (particularly 1.5 μm or less) can be easily realized.

[Metal oxide particles]
The metal oxide particles are not particularly limited as long as they are metal oxide particles. Examples of the metal oxide include iron oxide, lead oxide, titanium oxide, zinc oxide, molybdenum oxide and the like. Specific examples of the metal oxide particles include iron oxide pigments such as mica-like iron oxide and iron black; lead oxide pigments such as red lead and yellow lead; oxidation of titanium white, titanium yellow, titanium black and the like Examples thereof include particles comprising titanium pigments; zinc oxide pigments such as cobalt oxide and zinc yellow; molybdenum oxide pigments such as molybdenum red and molybdenum white. 1 type may be used for the said metal oxide particle, and 2 or more types may be used together.

[Layer derived from surface treatment agent]
The layer derived from the surface treatment agent covers the metal oxide particles. The layer derived from the surface treatment agent can be formed by treating the surface of the metal oxide particles with a surface treatment agent.

  The layer derived from the surface treatment agent preferably directly covers the metal oxide particles. That is, the metal oxide particles are preferably in a bare state not covered with silica or the like. When the amount of silica used to coat the metal oxide particles is large, the metal oxide particles coated with silica have a problem that the ultraviolet absorption ability is lowered as compared with the bare metal oxide particles. is there.

  The aluminum-containing organic compound as the surface treatment agent has the following general formula:

(In the formula, R ¹ represents an alkyl group having 8 to 20 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ³ represents an alkoxy group having 1 to 6 carbon atoms, m Represents an integer of 0 to 2, n represents an integer of 1 to 3, and m + n = 3)
It is an aluminum containing organic compound represented by these.

The alkyl group represented by R ¹ is a long-chain alkyl group having 8 to 20 carbon atoms. When the number of carbon atoms of the alkyl group represented by R ¹ is less than 8, the hydrophobicity of the layer derived from the surface treatment agent becomes low, so the compatibility between the layer derived from the surface treatment agent and the resin constituting the resin layer is high. As a result, the amount of adhesion of the resin layer to the layer derived from the surface treatment agent may decrease. When the alkyl group represented by R ¹ has more than 20 carbon atoms, the hydrophobicity of the layer derived from the surface treatment agent becomes high and the polymerization of the monomer used to form the resin layer is difficult to proceed. May decrease. The alkyl group represented by R ¹ may be linear or branched. Specific examples of the alkyl group represented by R ¹ include an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, and an n-hexadecyl group. And linear alkyl groups such as n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group; branched alkyl groups which are structural isomers of these linear alkyl groups. The number of carbon atoms of the alkyl group represented by R ¹ is preferably in the range of 12-20, and more preferably in the range of 12-18. Moreover, it is preferable that the alkyl group represented by R < ¹ > is a linear alkyl group from a viewpoint of making the compatibility with the resin which comprises the layer derived from a surface treating agent, and a resin layer favorable.

R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R ² is more preferably a linear alkyl group, and most preferably a methyl group.

The substituent represented by R ³ is an alkoxy group having 1 to 6 carbon atoms. Specific examples of the group represented by R ³ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n- A pentyloxy group, an isopentyloxy group, an n-hexyloxy group, an isohexyloxy group, and the like can be given. Further, from the viewpoint of improving the stability of the aluminum-containing organic compound, the group represented by R ³ is preferably a branched alkoxy group having 3 to 6 carbon atoms. The sum (m + n) of m and n is 3. M is 0 to 2, and n is 1 to 3. A preferred combination of R ^{1 to} R ³ , m and n is as follows: R ¹ is a linear alkyl group having 12 to 20; R ² is a linear alkyl group having 1 to ³ carbon atoms; and R ³ is 3 to 6 carbon atoms. A branched alkoxy group, wherein m is 2 and n is 1. A particularly preferable aluminum-containing organic compound is acetooctadecyloxyaluminum diisopropylate in which R ¹ is an n-octadecyl group, R ² is a methyl group, R ³ is an isopropoxy group, m is 2, and n is 1. This aluminum-containing organic compound is available from Ajinomoto Fine Techno Co., Ltd. as an aluminum-based coupling agent under the trade name “Plenact (registered trademark) AL-M”.

  Further, as the zirconium-containing organic compound as the surface treatment agent, the following general formula

(In the above formula, R ⁹ represents an optionally substituted alkoxy group having 1 to 15 carbon atoms, R ¹⁰ represents an alkyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, or Represents an alkenyl group having 2 to 24 carbon atoms, Y represents a carbon atom or a phosphorus atom, b represents 1 when Y represents a carbon atom, and b represents 2 when Y represents a phosphorus atom. , S represents an integer of 1 to 3, t represents an integer of 1 to 3, and s + t = 4)
A zirconium-containing organic compound represented by the formula is preferred.

The substituent represented by R ⁹ is an alkoxy group having 1 to 15 carbon atoms. Specific examples of the substituent represented by R ⁹ include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, etc. A straight-chain alkoxy group of the above-mentioned linear alkoxy group such as isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, isopentyloxy group, isohexyloxy group, dimethylpropyloxy group, etc. A certain branched alkoxy group is mentioned. Furthermore, the C1-C15 alkoxy group represented by R < ⁹ > may have a substituent. One or more substituents may be present at the substitutable position of the alkoxy group having 1 to 15 carbon atoms. As said substituent, a C1-C4 lower alkoxy group is mentioned, for example. The lower alkoxy group may have a vinyl group at a substitutable position, for example, as an allyloxy group.

The substituent represented by R ¹⁰ may be an alkyl group having 1 to 24 carbon atoms. When the substituent represented by R ¹⁰ is an alkyl group having more than 24 carbon atoms, the hydrophobicity of the surface treatment agent-derived layer is increased, and the polymerization of the monomer used to form the resin layer is difficult to proceed. The adhesion amount of the resin layer may decrease. This alkyl group may be linear or branched. Specific examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl. Group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group Group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group and the like, and branched alkyl groups which are structural isomers of these linear alkyl groups Is mentioned. Carbon number of the alkyl group is preferably 1 to 22, and more preferably 1 to 20. In addition, when the alkyl group is a branched alkyl group, the lower limit of the carbon number of the alkyl group is 3. Moreover, it is preferable that the said alkyl group is a linear alkyl group from a viewpoint which makes the compatibility with the resin which comprises the layer derived from a surface treating agent, and the resin layer favorable.

The substituent represented by R ¹⁰ may be an alkoxy group having 1 to 24 carbon atoms. When the substituent represented by R ¹⁰ is an alkoxy group having more than 24 carbon atoms, the hydrophobicity of the layer derived from the surface treatment agent is increased, and the polymerization of the monomer used to form the resin layer is difficult to proceed. The adhesion amount of the resin layer may decrease. This alkoxy group may be linear or branched. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, and n-octyloxy group. N-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group Group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, n-henicosyloxy group, n-docosyloxy group, n-tricosyloxy group, n-tetracosyl group Examples thereof include linear alkoxy groups such as oxy groups and branched alkoxy groups that are structural isomers of these linear alkoxy groups. Carbon number of the alkoxy group is preferably 1 to 22, more preferably 1 to 20. In addition, when the said alkoxy group is a branched alkoxy group, the minimum of the carbon number of the said alkoxy group is 3. Moreover, it is preferable that the said alkoxy group is a linear alkoxy group from a viewpoint which makes compatibility with the resin which comprises the layer derived from a surface treating agent, and the resin layer favorable.

The substituent represented by R ¹⁰ may be an alkenyl group having 1 to 24 carbon atoms. When the substituent represented by R ¹⁰ is an alkenyl group having more than 24 carbon atoms, the hydrophobicity of the layer derived from the surface treatment agent is increased, and the polymerization of the monomer used to form the resin layer is difficult to proceed. The adhesion amount of the resin layer may decrease. This alkenyl group may be linear or branched. Specific examples of the alkenyl group include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl. Group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, henicocenyl group, dococenyl group, tricocenyl group, tetracocenyl group and the like. These alkenyl groups may be linear alkenyl groups or branched alkenyl groups that are structural isomers of linear alkenyl groups (for example, isopropenyl and the like). The carbon number of the alkenyl group is preferably 1 to 22, more preferably 1 to 20. When the alkenyl group is a branched alkenyl group, the lower limit of the carbon number of the alkenyl group is 3. Furthermore, the position of the carbon-carbon double bond in the alkenyl group is not particularly limited. Moreover, it is preferable that the said alkenyl group is a linear alkenyl group from a viewpoint of making the compatibility with the resin which comprises the layer derived from a surface treating agent, and the resin layer favorable.

  Y represents a carbon atom or a phosphorus atom. b is 1 when Y represents a carbon atom, and 2 when Y represents a phosphorus atom. s represents an integer of 1 to 3, t represents an integer of 1 to 3, and the sum (s + t) of s and t is 4.

  Specific examples of the zirconium-containing organic compound represented by the above general formula include zirconium tributoxy systemate, zirconium dibutoxybis (acetylacetonate), zirconium, in which Y in the general formula represents a carbon atom. Tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis (ethyl acetoacetate), zirconium (IV) 2,2 (bis-2-propenolate methyl) butanolate, trisneodecanolate-O (“KEN-REACT ( (Registered trademark) NZ 01 ", which is commercially available from KENRICH PETROCHEMICALS, INC.). Examples of the zirconium-containing organic compound in which Y in the general formula represents a phosphorus atom include zirconium (bispropanolatemethyl) butanoate tris (dioctyl) phosphate.

  Furthermore, as the zirconium-containing organic compound that can be used in the present invention, product names A, C, C-1, F, M, M-1, S, APG, CPG, CPM, FPM, MPG, manufactured by Enomoto Kasei Co., Ltd. The following general formulas such as MPM and tetrapropyl zircoaluminate

(In the above formula, u represents an integer of 1 to 18, and Z represents a hydrogen atom, an amino group, a carboxyl group, a thiol group, or a (meth) acryloyl group).
The zircoaluminum compound represented by these is also mentioned. Here, the (meth) acryloyl group in this specification means a methacryloyl group or an acryloyl group.

  The titanium-containing organic compound as the surface treatment agent has the following general formula:

(In the above formula, R ⁴ represents an optionally substituted alkoxy group having 1 to 15 carbon atoms, R ⁵ represents an alkyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, or Represents an alkenyl group having 2 to 24 carbon atoms, X represents a carbon atom or a phosphorus atom, a represents 1 when X represents a carbon atom, and a represents 2 when X represents a phosphorus atom. P represents an integer of 1 to 3, q represents an integer of 1 to 3, and p + q = 4)
It is a titanium containing organic compound represented by these.

The substituent represented by R ⁴ is an alkoxy group having 1 to 15 carbon atoms. Specific examples of the substituent represented by R ⁴ include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, etc. A straight-chain alkoxy group of the above-mentioned linear alkoxy group such as isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, isopentyloxy group, isohexyloxy group, dimethylpropyloxy group, etc. A certain branched alkoxy group is mentioned. Furthermore, the C1-C15 alkoxy group represented by R < ⁴ > may have a substituent. One or more substituents may be present at the substitutable position of the alkoxy group having 1 to 15 carbon atoms. As said substituent, a C1-C4 lower alkoxy group is mentioned, for example. The lower alkoxy group may have a vinyl group at a substitutable position, for example, as an allyloxy group.

Substituents represented by R ⁵ may be an alkyl group having 1 to 24 carbon atoms. When the substituent represented by R ⁵ is an alkyl group having more than 24 carbon atoms, the hydrophobicity of the layer derived from the surface treatment agent is increased, and the polymerization of the monomer used to form the resin layer is difficult to proceed. The adhesion amount of the resin layer may decrease. This alkyl group may be linear or branched. Specific examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl. Group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group Group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group and the like, and branched alkyl groups which are structural isomers of these linear alkyl groups Is mentioned. Carbon number of the alkyl group is preferably 1 to 22, and more preferably 1 to 20. In addition, when the alkyl group is a branched alkyl group, the lower limit of the carbon number of the alkyl group is 3. Moreover, it is preferable that the said alkyl group is a linear alkyl group from a viewpoint which makes the compatibility with the resin which comprises the layer derived from a surface treating agent, and the resin layer favorable.

The substituent represented by R ⁵ may be an alkoxy group having 1 to 24 carbon atoms. When the substituent represented by R ⁵ is an alkoxy group having more than 24 carbon atoms, the hydrophobicity of the layer derived from the surface treatment agent is increased, and the polymerization of the monomer used for forming the resin layer is difficult to proceed. The adhesion amount of the resin layer may decrease. This alkoxy group may be linear or branched. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, and n-octyloxy group. N-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group Group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, n-henicosyloxy group, n-docosyloxy group, n-tricosyloxy group, n-tetracosyl group Examples thereof include linear alkoxy groups such as oxy groups and branched alkoxy groups that are structural isomers of these linear alkoxy groups. Carbon number of the alkoxy group is preferably 1 to 22, more preferably 1 to 20. In addition, when the said alkoxy group is a branched alkoxy group, the minimum of the carbon number of the said alkoxy group is 3. Moreover, it is preferable that the said alkoxy group is a linear alkoxy group from a viewpoint which makes compatibility with the resin which comprises the layer derived from a surface treating agent, and the resin layer favorable.

The substituent represented by R ⁵ may be an alkenyl group having 1 to 24 carbon atoms. When the substituent represented by R ⁵ is an alkenyl group having more than 24 carbon atoms, the hydrophobicity of the layer derived from the surface treatment agent is increased, and the polymerization of the monomer used for forming the resin layer is difficult to proceed. The adhesion amount of the resin layer may decrease. This alkenyl group may be linear or branched. Specific examples of the alkenyl group include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl. Group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, henicocenyl group, dococenyl group, tricocenyl group, tetracocenyl group and the like. These alkenyl groups may be linear alkenyl groups or branched alkenyl groups that are structural isomers of linear alkenyl groups (for example, isopropenyl and the like). The carbon number of the alkenyl group is preferably 1 to 22, more preferably 1 to 20. When the alkenyl group is a branched alkenyl group, the lower limit of the carbon number of the alkenyl group is 3. Furthermore, the position of the carbon-carbon double bond in the alkenyl group is not particularly limited. Moreover, it is preferable that the said alkenyl group is a linear alkenyl group from a viewpoint of making the compatibility with the resin which comprises the layer derived from a surface treating agent, and the resin layer favorable.

  X represents a carbon atom or a phosphorus atom. a is 1 when X represents a carbon atom, and 2 when X represents a phosphorus atom. p represents an integer of 1 to 3, q represents an integer of 1 to 3, and the sum (p + q) of p and q is 4.

Specific examples of the titanium-containing organic compound represented by the general formula include, for example, isopropyl titanium triisostearate (a titanium-containing organic compound represented by the general formula, wherein R ⁴ is an isopropoxy group. , R ⁵ is an n-heptadecyl group, X is a carbon atom, a is 1, p is 1, and q is 3. Isopropyl titanium triisostearate is commercially available from Kenrich Petrochemicals under the trade name “KEN-REACT® KR TTS”. 1 type may be used for a surface treating agent and it may use 2 or more types together.

The amount of the layer derived from the surface treatment agent (corresponding to the amount of the surface treatment agent used to prepare the layer derived from the surface treatment agent) is the surface area of the metal oxide particles (specific surface area of the metal oxide particles). And 0.0015 to 0.0080 g per m ^{2 (} calculated from the weight). For example, when titanium oxide particles having a specific surface area of 20.5 m ² / g are used as the metal oxide particles, the amount of the layer derived from the surface treatment agent is 0.3075 to 0.164 g per gram of the metal oxide particles. It is preferable that By using the surface treatment agent in this range, it is possible to enhance the adhesion of the resin layer formed on the surface treatment agent-derived layer. When the amount of the layer derived from the surface treatment agent is below the above range, the adhesiveness of the resin layer formed on the layer derived from the surface treatment agent is lowered, and the resulting resin-coated particles for cosmetics are obtained. May cause problems with water resistance. Moreover, when the amount of the layer derived from the surface treatment agent exceeds the above range, an effect corresponding to the addition amount of the surface treatment agent cannot be obtained.

  The surface treatment agent-derived layer can be formed by a known surface treatment method in which metal oxide particles are treated with a surface treatment agent. Examples of the surface treatment method include a direct method in which metal oxide particles are directly treated with a surface treatment agent, and the direct method is simple. Examples of the direct method include a dry method, a wet method (slurry method), and a spray method. The surface treatment method is most preferably a wet method. Thereby, the process of forming a resin layer can be easily performed by a dispersion polymerization method.

  Examples of the dry method include a direct method called an integral blend method, a master batch method, and a dry concentrate method. In the dry method, the metal oxide particles and the surface treatment agent are mixed in a dry state (a state without a medium such as a solvent) to perform surface treatment of the metal oxide particles. In this method, after the surface treatment agent is added, the surface treatment can be performed by high-speed stirring under a heating condition using a Henschel mixer, a super mixer, or the like having a shearing force. The temperature conditions at the time of the surface treatment may be any conditions that allow the treatment reaction with the surface treatment agent to proceed, and may be heated as necessary. Further, if the metal oxide particles are dried before the surface treatment as necessary, the efficiency of the treatment can be improved.

  The wet method performs surface treatment with a surface treatment agent in a state where metal oxide particles are dispersed in a solvent. Also in this case, it may be heated as necessary, and the metal oxide particles may be dried before the surface treatment. In addition, the wet method is a method in which the surface treatment of the metal oxide particles proceeds in a state where the metal oxide particles are dispersed in a solvent. Therefore, in order to improve the surface treatment efficiency of the metal oxide particles, It is preferable to loosen the aggregation state of the metal oxide particles before. Examples of the method for loosening the aggregation state of the metal oxide particles include a pulverization process by stirring, dispersion, etc., a pulverization process using shearing force by various mixers, a dispersion process by adding various dispersing agents, emulsifiers, and the like. .

  Specifically, the wet method can be performed, for example, by the following procedure. That is, first, a metal oxide particle is dispersed in a solvent to prepare a dispersion, and then a surface treatment agent is added to the dispersion. After the addition, a dispersion medium such as glass beads, steel beads, and zirconia beads is added to the dispersion as necessary. The surface treatment of the metal oxide particles can be performed by putting a dispersion liquid containing a dispersion medium into a disperser and mixing the dispersion liquid in the disperser. Examples of the disperser include a ball mill; a bead mill such as “DYNO (registered trademark) -MILL” (Dyno mill) and a DSP-mill; a roll mill; a sand mill; an attritor; a kneader; and a high-pressure jet mill such as a nanomizer.

  As the solvent used in the wet method, both an aqueous solvent and a non-aqueous solvent can be used, but a non-aqueous solvent is preferable. Examples of the non-aqueous solvent include paraffin hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane and dodecane; isoparaffin hydrocarbons such as isohexane, isooctane and isododecane; alkyl naphthene hydrocarbons such as liquid paraffin. A dialkyl silicone oil such as dimethyl silicone oil, an alkylphenyl silicone oil such as methylphenyl silicone oil (phenylmethylsilicone oil), a silicone oil such as cyclic polydialkylsiloxane, and cyclic polyalkylphenylsiloxane. Of these, taking into consideration the environmental impact of the working environment, alkyl naphthenic hydrocarbons such as liquid paraffin; dialkyl silicone oils such as dimethyl silicone oil, and alkyl phenyls such as methyl phenyl silicone oil (phenyl methyl silicone oil) Silicone oils such as silicone oil, cyclic polydialkylsiloxane, and cyclic polyalkylphenylsiloxane are preferred as the solvent. The said solvent may use 1 type and may use 2 or more types together. In order to efficiently disperse the metal oxide particles and the surface treatment agent, the silicone oil is a silicone oil having a kinematic viscosity measured by a measuring method defined in JIS K 2283 of 100 cSt (centistokes) or less. Is preferred.

[Resin layer]
The resin layer covers a layer derived from the surface treatment agent, and includes a segment derived from the silicone macromonomer. By including a segment derived from a silicone macromonomer in the resin layer, a resin layer excellent in water resistance and lipid resistance is provided.

[Silicone macromonomer]
The silicone macromonomer has the following general formula

(In the above formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkylene group having 2 to 4 carbon atoms, and R ⁸ are the same or different from each other and represent an alkyl group or phenyl group having 1 to 4 carbon atoms. And r represents a positive integer)
Is a silicone macromonomer represented by

Examples of the alkylene group having 2 to 4 carbon atoms represented by R ⁷ include an ethylene group, a trimethylene group, a tetramethylene group, and positional isomers thereof. Moreover, as a C1-C4 alkyl group represented by R < ⁸ >, a methyl group, an ethyl group, a propyl group, a butyl group, those positional isomers, etc. are mentioned. Moreover, r is preferably an integer of 3 to 500, and more preferably an integer of 10 to 250.

Specific examples of the silicone macromonomer include α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane (in the general formula, R ⁶ is a methyl group, and R ⁷ is a propylene group). Yes, R ⁸ is a methyl group; for example, trade names “Silaplane (registered trademark) FM-0711”, “Silaplane (registered trademark) FM-0721”, “Silaplane (registered trademark)” manufactured by JNC Corporation FM-0725 ") and the like. The silicone macromonomer may be used alone or in combination of two or more.

  The number average molecular weight of the silicone macromonomer is preferably in the range of 500 to 40000, and more preferably in the range of 1000 to 20000.

  The ratio of the amount of segments derived from the silicone macromonomer to the total amount of the resin layer (the ratio of the amount of the silicone macromonomer used for forming the resin layer to the total amount of raw materials used in the resin layer) (Corresponding) is more preferably in the range of 5 to 60% by weight.

[Vinyl monomers other than silicone macromonomers]
The resin layer only needs to contain a segment derived from the silicone macromonomer, but a vinyl monomer having a segment derived from the silicone macromonomer and at least one ethylenically unsaturated group other than the silicone macromonomer. It is preferable that it consists of a polymer containing the structural unit derived from.

  As the vinyl monomer having at least one ethylenically unsaturated group other than the silicone macromonomer, a monofunctional vinyl monomer having one ethylenically unsaturated group can be used. Examples of the monofunctional vinyl monomer having one ethylenically unsaturated group include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, n -Styrenes such as methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene and derivatives thereof; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride; acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl benzoate and vinyl butyrate; methyl acrylate, vinyl Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α- Methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate; Acrylic acid or methacrylic acid derivatives (α-methylene) such as rilonitrile, methacrylonitrile, acrylamide, methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate Fatty acid having an ethylenically unsaturated group such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl nitrogen-containing compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, and N-vinyl pyrrolidone Monomers having a double bond in the molecule such as a ring compound and vinyl naphthalene salt. These monofunctional vinyl monomers having one ethylenically unsaturated group may be used singly or in combination of two or more.

  The vinyl monomer preferably includes a crosslinkable monomer having two or more ethylenically unsaturated groups. That is, the resin layer is preferably made of a polymer including a segment derived from the silicone macromonomer and a structural unit derived from a crosslinkable monomer having two or more ethylenically unsaturated groups. Thereby, since a resin layer is bridge | crosslinked, a resin layer becomes difficult to peel from a metal oxide particle, and a chemically stable resin layer can be formed.

  As the crosslinkable monomer, a known crosslinkable monomer having two or more ethylenically unsaturated groups can be used. Examples of the crosslinkable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and pentadecaethylene glycol di (meth). Acrylate, pentacontaector ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, allyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol di (meth) acrylate phthalate , Caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol diacrylate, polyester acrylate, urethane acrylate and other (meth) acrylate crosslinkable monomers; divinylbenzene, divinylnaphthalene And aromatic divinyl monomers which are derivatives thereof. In the present specification, “(meth) acrylate” means methacrylate or acrylate, and “(meth) acryl” means methacryl or acryl. These crosslinkable monomers may be used alone or in combination of two or more.

  Ratio of the amount of structural units derived from the crosslinkable monomer to the total amount of the resin layer (ratio of the amount of the crosslinkable monomer used to form the resin layer to the total amount of raw materials used for the resin layer) Is more preferably in the range of 5 to 50% by weight.

  The amount of the resin layer is preferably in the range of 20 to 350 parts by weight and more preferably 30 to 250 parts by weight with respect to 100 parts by weight of the metal oxide particles. When the amount of the resin layer is less than 20 parts by weight with respect to 100 parts by weight of the metal oxide particles, the coating of the metal oxide particles and the layer derived from the surface treatment agent by the resin layer becomes insufficient, and the cosmetic The water resistance of the resin-coated particles for use may be inferior. When the amount of the resin layer is more than 350 parts by weight with respect to 100 parts by weight of the metal oxide particles, the resin layer does not cover the metal oxide particles when the cosmetic resin-coated particles are viewed from one direction. A part (part only of a resin layer) generate | occur | produces notably, and the ultraviolet-absorbing ability of the said resin-coated particle for cosmetics and the cosmetics containing it may fall.

[Method for producing resin-coated particles for cosmetics]
The method for producing the resin-coated particles for cosmetics of the present invention is not particularly limited, but a method for obtaining the resin-coated particles for cosmetics by polymerization in a non-aqueous solvent is preferred. Is more preferable. The production method of the present invention is a method for producing the resin-coated particles for cosmetics of the present invention, wherein the monomer component containing the silicone macromonomer and the dispersant are dissolved in a non-aqueous solvent, and the surface treatment agent is used. This is a method of polymerizing the monomer component after dispersing the metal oxide particles coated with a layer derived from the non-aqueous solvent.

  When obtaining resin-coated particles for cosmetics by emulsion polymerization in an aqueous medium such as water, it is difficult to contain a segment derived from a poorly water-soluble monomer such as a silicone macromonomer in the resin layer. In particular, there is a problem that it is difficult to impart functions such as water resistance derived from a silicone macromonomer that is hardly water-soluble to cosmetic resin-coated particles.

  Further, when the resin-coated particles for cosmetics are obtained by suspension polymerization in an aqueous medium such as water, the average particle size of the resin-coated particles for cosmetics tends to be large, and the average particle size is 1.5 μm or less. It is difficult to obtain resin-coated particles. Therefore, when cosmetics containing the resin-coated particles for cosmetics are applied to the skin, this causes a decrease in transparency. Furthermore, suspension polymerization in water tends to cause aggregation of the metal oxide particles coated with the layer derived from the surface treatment agent, so that the UV protection index of cosmetics containing resin-coated particles for cosmetics is reduced. It can be a cause.

  On the other hand, in the production method of the present invention, the monomer component and the dispersant are dissolved in a non-aqueous solvent, and the metal oxide particles coated with the layer derived from the surface treatment agent are contained in the non-aqueous solvent. Since the monomer component is polymerized in a dispersed state, the average particle diameter is small (especially 1.5 μm or less) while suppressing aggregation of the metal oxide particles coated with the surface treatment agent-derived layer. Resin-coated particles for cosmetics can be easily obtained. Therefore, resin-coated particles for cosmetics that can realize cosmetics excellent in transparency and ultraviolet blocking ability when blended in cosmetics can be easily obtained.

  In the production method of the present invention, the dissolution of the dispersant in the non-aqueous solvent, the dispersion of the metal oxide particles in the non-aqueous solvent, and the dissolution of the monomer component in the non-aqueous solvent may be performed at the same time or separately. The order of implementation in the case of carrying out separately is not particularly limited, but after first dissolving the dispersant in the non-aqueous solvent, and then dispersing the metal oxide particles in the non-aqueous solvent in which the dispersant is dissolved, It is preferable to dissolve the monomer in the non-aqueous solvent.

  Regarding the non-aqueous solvent, one or more of the various solvents mentioned as the non-aqueous solvent used in the wet method can be used, and the preferred non-aqueous solvent also includes the non-aqueous solvent used in the wet method and It is the same. As the usage-amount of the said non-aqueous solvent, 650-3200 weight part is preferable with respect to 100 weight part of monomer components, for example, More preferably, it is 650-1500 weight part.

  The dispersing agent may be a dispersing agent obtained by polymerizing the silicone macromonomer and a vinyl monomer other than the silicone macromonomer, and in the presence of the silicone macromonomer and a chain transfer agent. A dispersant (reactive dispersant) having an ethylenically unsaturated group obtained by polymerizing a vinyl monomer other than the silicone macromonomer may be used, or the silicone macromonomer itself (reactive dispersant) may be used. It may be a polymer of the silicone macromonomer or a polymer of vinyl monomers other than the silicone macromonomer. The vinyl monomer other than the silicone macromonomer is the same as described in the section [Vinyl monomer other than silicone macromonomer]. The polymerization of the silicone macromonomer and the vinyl monomer other than the silicone macromonomer can be performed in the same manner as the polymerization of the monomer component except that metal oxide particles are not used. The chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, tert-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan; α-methylstyrene dimer; 2 , 6-di-tert-butyl-4-methylphenol, styrenated phenol, and the like; allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrachloride; These may use 1 type and may use 2 or more types together.

  When the dispersant is a reactive dispersant, it is copolymerized with a monomer constituting the resin layer and is taken in as a segment in the resin layer. Therefore, when the dispersant is a reactive dispersant, it functions as a part of the monomer component. Therefore, when the dispersant is a reactive dispersant, the structural unit derived from the silicone macromonomer contained in the resin layer may be derived from the reactive dispersant.

  The amount of the dispersant used is preferably in the range of 20 to 400 parts by weight with respect to 100 parts by weight of the monomer component. When the usage-amount of the said dispersing agent is less than 20 weight part, the dispersion stability in a non-aqueous solvent may fall. When the amount of the dispersing agent used is more than 400 parts by weight, the particle size becomes small, the viscosity in the nonpolar solvent increases, and as a result, the dispersion stability in the nonpolar solvent may decrease. The amount of the dispersant used is more preferably in the range of 40 to 200 parts by weight with respect to 100 parts by weight of the monomer component.

  The polymerization of the monomer component is preferably performed in an inert atmosphere. The inert atmosphere is preferably a nitrogen gas atmosphere. The polymerization temperature and the polymerization time are not particularly limited, but the polymerization temperature is preferably in the range of 40 to 120 ° C., and the polymerization time is preferably in the range of 0.5 to 50 hours. The polymerization temperature is more preferably 40 to 80 ° C., and the polymerization time is more preferably in the range of 1 to 24 hours.

  A polymerization initiator may be used for the polymerization of the monomer component. The polymerization initiator is not particularly limited. For example, benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy Organic peroxides such as 2-ethylhexanoate and di-t-butyl peroxide; azobisisobutyronitrile, azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) An azo compound such as The polymerization initiator is preferably used in the range of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the monomer component. The polymerization initiator can be used by dissolving in a monomer component.

  The polymerization of the monomer component may be performed under ultrasonic irradiation. Ultrasonic irradiation is a method of irradiating ultrasonic waves by filling a generally used ultrasonic cleaning device with a medium such as warm water and immersing a container containing a mixed solution for reaction, or generating internal irradiation type ultrasonic waves. Using an apparatus or the like, it can be carried out by a method of irradiating ultrasonic waves by inserting an ultrasonic vibrator into a container containing a mixed solution to be subjected to reaction. The ultrasonic oscillation frequency is preferably 16 kHz or more, and more preferably in the range of 20 to 500 kHz. Further, the output of the ultrasonic wave is preferably 10 to 1000 W per 1 L of the medium irradiated with the ultrasonic wave. For dispersion polymerization under ultrasonic irradiation, a mechanical stirring device such as a magnetic stirrer can be used in combination.

  After the polymerization, the obtained resin-coated particles for cosmetics may be washed. The washing method is not particularly limited, but after forming the resin-coated particles for cosmetics, using a high-speed centrifuge or the like, the supernatant is removed by applying a very high centrifugal acceleration to remove the supernatant, and a new nonpolar solvent is added. In addition, the resin-coated particles for cosmetics are dispersed in a nonpolar solvent, and this operation is repeated several times to remove impurities, the method of removing impurities by washing with a cross-flow filtration method, and cosmetics Examples include a method of coagulating and precipitating particles in a solvent by adding a solvent as a particle coagulant to the resin-coated particles, separating the resin-coated pigment particles using a filter, and washing with a washing solvent. It is done.

[Cosmetics]
The cosmetic of the present invention includes the resin-coated particles for cosmetics of the present invention.

  By including the resin-coated particles for cosmetics of the present invention, the cosmetic of the present invention can be expected to improve the feeling of use (feel against the skin) and sebum resistance, in addition to improving the water resistance.

  The content of the resin-coated particles for cosmetics in the cosmetic can be appropriately set according to the type of cosmetic, but is preferably 0.1 to 50% by weight, and more preferably 0.3 to 30% by weight. If the content of the resin-coated particles for cosmetics is less than 0.1% by weight based on the total amount of the cosmetic, a clear effect due to the inclusion of the resin-coated particles for cosmetics may not be recognized. On the other hand, if the content of the resin-coated particles for cosmetics exceeds 50% by weight, a remarkable effect commensurate with the increase in content may not be recognized, which is not preferable in terms of production cost.

  The cosmetic is not particularly limited as long as it has an effect due to the inclusion of the resin-coated particles for cosmetics. For example, pre-shave lotion, body lotion, lotion, cream, milky lotion, body shampoo, antiperspirant, etc. Cosmetics for soaps, soaps, scrubs, etc .; packs; shave creams; funerals; foundations; lipsticks; lip balms; blusher; blusher cosmetics; nail polish cosmetics; Hairdressing products; aromatic cosmetics; toothpaste; bath preparations; sunscreen products; suntan products; body powders such as body powders and baby powders.

  Moreover, in these cosmetics, the additive generally used can be mix | blended according to the objective in the range which does not impair the effect of this invention. Examples of such additives include water, lower alcohols (alcohols having 5 or less carbon atoms), oils and waxes, hydrocarbons (such as petroleum jelly and liquid paraffin), higher fatty acids (fatty acids having 12 or more carbon atoms such as stearic acid). ), Higher alcohols (alcohols having 6 or more carbon atoms such as cetyl alcohol), sterols, fatty acid esters (octyldodecyl myristate, oleate, cetyl 2-ethylhexanoate, etc.), metal soaps, humectants, surfactants, High molecular compounds, coloring materials (red iron oxide, yellow iron oxide, black iron oxide, etc.), titanium oxide, zinc oxide, clay minerals (talc, mica, etc.), fragrances, antiseptic / bactericides, antioxidants, ultraviolet rays Other cosmetic resin-coated particles such as absorbents, silicone-based particles, and polystyrene particles, and special compounding additives are included.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples.

  First, a method for measuring the average particle diameter of resin-coated particles for cosmetics and the amount of the resin layer in the following Examples and Comparative Examples, and a method for measuring the weight average molecular weight of the dispersant used in the following Examples and Comparative Examples Will be explained.

[Measurement method of average particle diameter of resin-coated particles for cosmetics]
In the following examples and comparative examples, the Z-average particle size of the resin-coated particles for cosmetics is measured using the dynamic light scattering method as follows, and the measured Z-average particle size is coated with the resin for cosmetics. The average particle size of the particles was used.

  That is, first, resin-coated particles for cosmetics obtained in the following examples and comparative examples are dispersed in silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KF-96L-2cs”, kinematic viscosity 2 cSt). A silicone oil dispersion having a solid content concentration of 0.1% by weight was prepared. This silicone oil dispersion having a solid content concentration of 0.1% by weight was irradiated with laser light, and the intensity of scattered light scattered from the resin-coated particles for cosmetics was measured over time in microseconds. Then, the Z-average particle diameter of the cosmetic resin-coated particles was determined by a cumulant analysis method for calculating the average particle diameter by applying the detected scattering intensity distribution resulting from the cosmetic-coated resin particles to a normal distribution. .

  The measurement of the Z average particle diameter can be easily performed with a commercially available particle diameter measuring apparatus. In the following Examples and Comparative Examples, the Z average particle size was measured using a particle size measuring device (trade name “Zetasizer Nano ZS”) manufactured by Malvern Instruments Ltd. (Malvern Instruments Ltd.). Usually, a commercially available particle size measurement apparatus is equipped with data analysis software, and the data analysis software can automatically calculate the Z-average particle size by analyzing the measurement data.

[Method for measuring the amount of resin layer in resin-coated particles for cosmetics]
The resin-coated particles for cosmetics are weighed. The weighed resin-coated particles for cosmetics are placed in a platinum cell in a thermogravimetric analyzer (manufactured by SII Nanotechnology, TG / DTA6200 type). The resin-coated particles for cosmetics in the platinum cell are heat-treated at a rate of 10 ° C./min from room temperature to 800 ° C. in a nitrogen atmosphere to thermally decompose the resin and obtain particles. The extracted particles are weighed. By substituting the weighed value A of the resin-coated particles for cosmetics and the weighed value B of the heat-treated particles into the following equation, the amount of the resin layer relative to 100 parts by weight of the metal oxide particles is calculated.

Resin ratio (% by weight) = (Weighing value A−Weighing value B) × 100 / Weighing value A
Resin layer amount (parts by weight) = resin ratio / (100-resin ratio) × 100
[Method for measuring weight average molecular weight of dispersant]
The weight average molecular weight of the dispersant in terms of polystyrene (PS) was measured using gel permeation chromatography (GPC), and this was defined as the weight average molecular weight of the dispersant.

  Specifically, 4 mg of a dispersant sample was dissolved in 4 mL of tetrahydrofuran (THF) (permeation time: 6.0 ± 0.5 hr (complete dissolution)) and filtered through a non-aqueous 0.45 μm chromatographic disk. Measure using a chromatograph under the following conditions. The polystyrene-converted weight average molecular weight of the sample is determined from a standard polystyrene calibration curve that has been measured and prepared in advance.

GPC device: manufactured by Tosoh Corporation, trade name “Gel Permeation Chromatograph HLC-8320”
Analytical column: manufactured by Tosoh Corporation, trade name “TSKgel SuperMultipore HZ-H” (inner diameter 4.6 mm × length 15 cm), 2 guard columns: manufactured by Tosoh Corporation, trade name “TSKgel guardcolumn SuperMP (HZ) -H” ( (Inner diameter 4.6 mm x length 2 cm), 1 column temperature: 40 ° C
Mobile phase: Tetrahydrofuran (THF)
Mobile phase flow rate: 0.2 mL / min
Detection: RI (differential refractive index detector)
Sample concentration: 0.5 g / mL THF
Injection volume: 20 μl
Measurement time: 25 minutes Standard polystyrene for calibration curve: trade name “Shodex (registered trademark)” manufactured by Showa Denko KK (weight average molecular weights: 5620,000, 3120,000, 1250,000, 442000, 131000, 54000, 20000, 7590, 3450, 1320 )
In the calibration curve creation method, the standard polystyrene for calibration curve is grouped into A and B, and the standard polystyrene for calibration curve of each group is dissolved in THF to a concentration of about 1% by weight (0.1 g / L). Then, 20 μL of the obtained solution is injected into the column. A calibration curve (linear equation) is created from these retention times and used for molecular weight distribution measurement.

[Example 1]
(Preparation of Dispersant A)
Silicone oil as a non-aqueous solvent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KF-96L-1cs”, kinematic viscosity 1 cSt) and 100 parts by weight of lauroyl peroxide (manufactured by NOF Corporation, product) 3.0 parts by weight of the name “Perloyl (registered trademark) L” (hereinafter abbreviated as “LPO”), 9.0 parts by weight of methyl methacrylate (hereinafter referred to as “MMA”) as a monofunctional vinyl monomer, and silicone macromonomer 91 parts by weight (trade name “Silaplane (registered trademark) FM-0721”, number average molecular weight 5850, manufactured by JNC Corporation) was added, and solution polymerization was performed for 20 hours while stirring at 80 ° C. in a nitrogen atmosphere. Dispersant A was obtained. The obtained Dispersant A had a weight average molecular weight of 42,000.

  Dispersant A was subjected to a step of removing the silicone oil used in the production thereof before the production of the following resin-coated particles for cosmetics.

(Preparation of resin-coated particles for cosmetics)
In a glass bead pot containing 600 g of zirconia beads having a diameter of 1 mm, 40 parts by weight of the dispersant A, silicone oil as a non-aqueous solvent (trade name “KF-96L-1cs”, manufactured by Shin-Etsu Chemical Co., Ltd. Viscosity 1 cSt) 100 parts by weight, titanium oxide particles as metal oxide particles (Ishihara Sangyo Co., Ltd., brand “PT-401M”, specific surface area 20.5 m ² / g) 20 parts by weight are added, and dispersant A is added. It was dissolved in silicone oil, and titanium oxide particles were dispersed in silicone oil in which Dispersant A was dissolved by a bead mill at room temperature for 72 hours to obtain 160 parts by weight of titanium oxide particle dispersion. Thereafter, 200 parts by weight of silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KF-96L-1cs”, kinematic viscosity 1 cSt) as a non-aqueous solvent is added to 160 parts by weight of the obtained titanium oxide particle dispersion. 360 parts by weight of a diluted titanium oxide particle dispersion was obtained. To 360 parts by weight of the diluted titanium oxide particle dispersion, 1.0 part by weight of an aluminum coupling agent (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name “Plenact (registered trademark) AL-M”) as a surface treatment agent is added. The mixture was added and stirred at room temperature for 16 hours. Thereby, titanium oxide particles are surface-treated with an aluminum coupling agent, and a titanium oil particle dispersion of titanium oxide particles coated with a layer derived from the aluminum coupling agent (dispersant A is dissolved in silicone oil). was gotten.

  In a reaction vessel, silicone oil (non-aqueous solvent, manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KF-96L-1cs”, kinematic viscosity 1 cSt) 600 parts by weight, LPO 7 parts by weight as a polymerization initiator, 20 parts by weight of methyl methacrylate (hereinafter abbreviated as “MMA”) as a monofunctional vinyl monomer and ethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., hereinafter abbreviated as “EGDMA”) as a crosslinkable monomer 20 It is coated with 30 parts by weight of silicone macromonomer (trade name “Silaplane (registered trademark) FM-0721”, number average molecular weight 5850, manufactured by JNC Corporation) and a layer derived from the above-described aluminum-based coupling agent. Added 360 parts by weight of a silicone oil dispersion of titanium oxide particles, and LPO, MMA, EGDM And silicone macromonomer is dissolved in a silicone oil under a nitrogen atmosphere for 7 hours at 60 ° C., it was dispersed polymer.

  After completion of the dispersion polymerization, the resin-coated particles for cosmetics were settled and separated by centrifugation, and dispersed again in hexane (manufactured by Wako Pure Chemical Industries, Ltd.). This operation was repeated four times, and the resin-coated particles for cosmetics were washed to remove reaction residues such as a polymerization initiator, followed by vacuum drying to obtain resin-coated particles for cosmetics.

  The resin-coated particles for cosmetics had an average particle diameter of 0.40 μm, and the amount of the resin layer was 92 parts by weight with respect to 100 parts by weight of the metal oxide particles.

[Example 2]
Instead of 1.0 part by weight of the aluminum coupling agent, the following structural formula

Zirconium-based surface treatment agent represented by the formula (zirconium (IV) 2,2 (bis-2-propanolate methyl) butanolate, trisneodecanolate-O, manufactured by Kenrich Petrochemicals, Inc., trade name “KEN-REACT” (Registered trademark) NZ 01 ", component concentration 95%) (in the above general formula, R ⁹ is 2,2- (bis-2-propenolatemethyl) butanolate, and R ¹⁰ is a straight chain having 9 carbon atoms.) Cosmetics in the same manner as in Example 1 except that 2 parts by weight are used) which is an alkyl group, Y is a carbon atom, b is 1, s is 1 and t is 3. Resin-coated particles were obtained.

  The obtained resin-coated particles for cosmetics had an average particle diameter of 0.41 μm, and the amount of the resin layer was 101 parts by weight with respect to 100 parts by weight of the metal oxide particles.

Example 3
(Preparation of Dispersant B)
An isoparaffin solvent (trade name “Isopar (registered trademark) G” manufactured by ExxonMobil Co., Ltd.) is used in place of silicone oil as a non-aqueous solvent, and the amount of MMA used is changed to 10.0 parts by weight. Dispersant B was obtained in the same manner as in the preparation of Dispersant A in Example 1, except that the amount used was 90 parts by weight. The obtained Dispersant B had a weight average molecular weight of 40,000.

  Dispersant B was subjected to a step of removing the isoparaffinic solvent used in the production thereof before producing the following resin-coated particles.

(Preparation of resin-coated particles for cosmetics)
As a non-aqueous solvent, an isoparaffin solvent (trade name “Isopar (registered trademark) G” manufactured by ExxonMobil Co., Ltd.) is used instead of silicone oil, a dispersant B is used instead of the dispersant A, and a monofunctional vinyl. Styrene is used instead of methyl methacrylate as a system monomer, 10 parts by weight of EGDMA and 10 parts by weight of divinylbenzene are used as a crosslinkable monomer in place of 20 parts by weight of EGDMA, and the amount of silicone macromonomer used is 20 parts by weight. Resin-coated particles for cosmetics were obtained in the same manner as in Example 2 except for changing.

  The average particle diameter of the resin-coated particles for cosmetics was 0.35 μm, and the amount of the resin layer was 86 parts by weight with respect to 100 parts by weight of the metal oxide particles.

Example 4
Instead of 1.0 parts by weight of aluminum coupling agent, the following structural formula

A monofunctional vinyl monomer using 2 parts by weight of a titanate surface treatment agent represented by the formula (isopropyl titanium triisostearate, manufactured by Kenrich Petrochemicals, trade name “KEN-REACT (registered trademark) KR TTS”) Except that styrene is used instead of methyl methacrylate, 20 parts by weight of divinylbenzene is used instead of 20 parts by weight of EGDMA as a crosslinkable monomer, and the amount of silicone macromonomer is changed to 20 parts by weight. In the same manner as in Example 2, resin-coated particles for cosmetics were obtained.

  The average particle diameter of the resin-coated particles for cosmetics was 0.46 μm, and the amount of the resin layer was 78 parts by weight with respect to 100 parts by weight of the metal oxide particles.

[Comparative Example 1]
Resin-coated particles for cosmetics were obtained in the same manner as in Example 1 except that the aluminum-based coupling agent as the surface treatment agent was not used. The obtained resin-coated particles for cosmetics had an average particle size of 0.35 μm, and the amount of the resin layer was 17 parts by weight with respect to 100 parts by weight of the metal oxide particles.

[Comparative Example 2]
Resin-coated particles for cosmetics were obtained in the same manner as in Example 1 except that no silicone macromonomer was used in the dispersion polymerization. The obtained resin-coated particles for cosmetics had an average particle diameter of 0.68 μm, and the amount of the resin layer was 148 parts by weight with respect to 100 parts by weight of the metal oxide particles.

[Comparative Example 3]
Use of 3.0 parts by weight of methyl hydrogen polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., model number “KF99”) instead of 2.0 parts by weight of the zirconium-based coupling agent as a surface treatment agent, titanium oxide particle dispersion After obtaining 160 parts by weight, a surface treatment agent (methyl hydrogen polysiloxane) was added without dilution by adding 200 parts by weight of an isoparaffin solvent, and the mixture was stirred at 140 ° C. for 24 hours, and then isoparaffin-based. Example except that 200 parts by weight of solvent was added to obtain a silicone oil dispersion of titanium oxide particles coated with a layer derived from the surface treatment agent, and 10 parts by weight of silicone macromonomer was used for dispersion polymerization. In the same manner as in No. 3, resin-coated particles for cosmetics were obtained.

  The obtained resin-coated particles for cosmetics had an average particle size of 0.30 μm, and the amount of the resin layer was 22 parts by weight with respect to 100 parts by weight of the metal oxide particles.

[Evaluation of water resistance of resin-coated particles for cosmetics]
1 g of resin-coated particles for cosmetics obtained in each example and each comparative example was pressed on an aluminum dish (diameter 50 mm), and a mixed solution of 1,3-butylene glycol: water = 1: 1 was dropped on the aluminum dish. The time until water droplets were formed and the resin-coated particles for cosmetics completely absorbed the water droplets was measured. When the time until water droplets were completely absorbed was 5.5 hours or more, it was determined that the water resistance was sufficient. When the time until the water droplets were completely absorbed was less than 5.5 hours, the water resistance was judged to be insufficient. Table 1 shows the evaluation results of water resistance of the cosmetic resin-coated particles obtained in each Example and each Comparative Example (measurement results of time until water droplets are completely absorbed).

[Example 5] (Preparation example of powder foundation)
10 g of resin-coated particles for cosmetics obtained in Example 1, 19 g of talc, 11 g of mica, 2 g of zinc oxide, 0.3 g of red iron oxide, 0.5 g of yellow iron oxide, and 0.1 g of black iron oxide were added to a Henschel mixer. And mixed to obtain a powder part. Further, 5 g of cetyl 2-ethylhexanoate, 0.5 g of sorbitan sesquioleate, and 0.1 g of preservative were mixed and dissolved to obtain an oil part. The oil part was added to the powder part and mixed uniformly. The resulting mixture was pulverized and passed through a sieve. A powder foundation was obtained by compression molding the material that passed through the sieve.

[Examples 6 to 8] (Preparation example of powder foundation)
In the same manner as in Example 5 except that the cosmetic resin-coated particles obtained in each of Examples 2 to 4 were used in place of the cosmetic resin-coated particles obtained in Example 1, three types of resin-coated particles were used. A powder foundation was obtained.

[Comparative Examples 4 to 6] (Example of making powder foundation)
In the same manner as in Example 5 except that the resin-coated particles for cosmetics obtained in each of Comparative Examples 1 to 3 were used in place of the resin-coated particles for cosmetics obtained in Example 1, three types of resin-coated particles were used. A powder foundation was obtained.

[Powder Foundation Evaluation Method]
About the powder foundation obtained in Examples 5-8 and Comparative Examples 4-6, the use test was done by ten panelists. Each of the panelists evaluated the cosmetic foundation of the powder foundation, the elongation, the absence of bleeding, and the good feeling of use according to the criteria shown below.

(Evaluation criteria)
5 points: Good 4 points: Slightly good 3 points: Normal 2 points: Slightly bad 1 point: Bad The average score of the evaluation scores of the 10 panelists obtained was determined according to the following criteria.

(Criteria for average score)
Average score obtained is 4.5 or more: ◎ (very good)
The obtained average score is 3.5 or more and less than 4.5: ○ (good)
The obtained average score is 2.5 or more and less than 3.5: Δ (slightly poor)
The average score obtained is 1.5 points or more and less than 2.5 points: x (defect)
The average score obtained is less than 1.5 points: xx (very poor)

  From the results of Table 1, it is derived from at least one surface treatment agent selected from the group consisting of an aluminum-containing organic compound represented by the general formula, a zirconium-containing organic compound, and a titanium-containing organic compound represented by the general formula. Resin coated particles for cosmetics of Examples 1 to 4 and a cosmetic of Examples 5 to 8 using the same, wherein the resin layer contains segments derived from the silicone macromonomer represented by the general formula Is a resin-coated particle for cosmetics of Comparative Example 1 that has good water resistance, good feeling of use, good makeup, stretch, and no bleeding, and does not contain a layer derived from a surface treatment agent, and the same Cosmetics of Comparative Example 4, resin-coated particles for cosmetics of Comparative Example 2 in which the resin layer does not contain a segment derived from silicone macromonomer, cosmetics of Comparative Example 5 using the same, and other surface treatments Compared to a cosmetic resin-coated particles of Comparative Example 3 comprising a layer of origin and cosmetics of Comparative Example 6 using the same it was found to be excellent in good water resistance and usability.

Claims (8)

Including metal oxide particles, a layer derived from a surface treatment agent that covers the surface of the metal oxide particles, and a resin layer that covers the layer derived from the surface treatment agent,
The surface treatment agent has the following general formula

(In the formula, R ¹ represents an alkyl group having 8 to 20 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ³ represents an alkoxy group having 1 to 6 carbon atoms, m Represents an integer of 0 to 2, n represents an integer of 1 to 3, and m + n = 3)
An aluminum-containing organic compound, a zirconium-containing organic compound, and the following general formula

(In the above formula, R ⁴ represents an optionally substituted alkoxy group having 1 to 15 carbon atoms, R ⁵ represents an alkyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, or Represents an alkenyl group having 2 to 24 carbon atoms, X represents a carbon atom or a phosphorus atom, a represents 1 when X represents a carbon atom, and a represents 2 when X represents a phosphorus atom. P represents an integer of 1 to 3, q represents an integer of 1 to 3, and p + q = 4)
Is at least one selected from the group consisting of titanium-containing organic compounds represented by:
The resin layer has the following general formula

(In the above formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkylene group having 2 to 4 carbon atoms, and R ⁸ are the same or different from each other and represent an alkyl group or phenyl group having 1 to 4 carbon atoms. And r represents a positive integer)
A resin-coated particle for cosmetics, comprising a segment derived from a silicone macromonomer represented by the formula:   The resin-coated particles for cosmetics according to claim 1, wherein the layer derived from the surface treatment agent directly covers the metal oxide particles.   The resin-coated particles for cosmetics according to claim 1 or 2, which are obtained by polymerization in a non-aqueous solvent.   The resin-coated particles for cosmetics according to any one of claims 1 to 3, wherein the cosmetic resin-coated particles have an average particle size of 0.15 µm or more and 1.5 µm or less.   The resin layer is made of a polymer including a segment derived from the silicone macromonomer and a structural unit derived from a crosslinkable monomer having two or more ethylenically unsaturated groups. The resin-coated particles for cosmetics according to any one of 4. The zirconium-containing organic compound has the following general formula:

(In the above formula, R ⁹ represents an optionally substituted alkoxy group having 1 to 15 carbon atoms, R ¹⁰ represents an alkyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, or Represents an alkenyl group having 2 to 24 carbon atoms, Y represents a carbon atom or a phosphorus atom, b represents 1 when Y represents a carbon atom, and b represents 2 when Y represents a phosphorus atom. , S represents an integer of 1 to 3, t represents an integer of 1 to 3, and s + t = 4)
The resin-coated particle for cosmetics according to any one of claims 1 to 5, which is a zirconium-containing organic compound represented by formula (1). A method for producing resin-coated particles for cosmetics according to any one of claims 1 to 6,
After the monomer component containing the silicone macromonomer and the dispersant are dissolved in a non-aqueous solvent, and the metal oxide particles coated with the layer derived from the surface treatment agent are dispersed in the non-aqueous solvent, A method for producing resin-coated particles for cosmetics, wherein the monomer component is polymerized.   Cosmetics containing the resin-coated particles for cosmetics according to any one of claims 1 to 6.