JP2021107366A - Cosmetics - Google Patents

Abstract

To provide cosmetics that can suppress the shininess of the skin after a long time has passed since it was applied to the skin, have less secondary adhesion, and keep a uniform bright shade without color unevenness.SOLUTION: There is provided a cosmetic containing the following ingredients (A) to (C): (A) an organic powder having an oil absorption of 3 g/g or more in an oil composition in which the mass ratio of oleic acid to squalane is 1: 2; (B) a silicone film forming agent; and (C) an ester oil, the content of component (A) being 0.1 mass% or more and 20 mass% or less.SELECTED DRAWING: None

Description

The present invention relates to cosmetics.

Attempts have been made to prevent makeup from collapsing and secondary adhesion in cosmetics such as makeup bases and foundations.
For example, Patent Document 1 discloses that a makeup base material containing a fluorine-modified silicone resin having a silanol group in the molecule and having a predetermined structure has excellent long-lasting cosmetic effect and is less likely to be twisted or crumbled. It has excellent long-lasting cosmetic effect and is less likely to wrinkle or crumble.
Patent Document 2 describes a cosmetic containing an acrylic-silicone graft copolymer and / or a trimethylsiloxysilicic acid, a predetermined polyhydric alcohol-modified silicone, and a cosmetic film-forming composition containing a volatile oil agent. It is disclosed that it has an excellent effect of preventing secondary adhesion and a long-lasting makeup, and can form a non-sticky, lightly stretched and flexible makeup film.

Japanese Unexamined Patent Publication No. 9-25218 Japanese Unexamined Patent Publication No. 2006-306860

The cosmetics containing the resins described in Patent Documents 1 and 2 are excellent in makeup durability, but when a long time has passed after being applied to the skin, the shine due to the sebum secreted from the skin becomes remarkable. In addition, there is a problem that the color tone tends to be dull after a long period of time, and secondary adhesion of cosmetics also occurs, which makes it difficult to remake makeup.
An object of the present invention is to provide a cosmetic that can suppress the shine of the skin after a long period of time after being applied to the skin, has less secondary adhesion, has no color unevenness, and maintains a uniform and bright color. be.

The present inventors have found that a cosmetic containing a predetermined amount of organic powder having a predetermined oil absorbing ability, a silicone-based film forming agent, and an ester oil can solve the above-mentioned problems.
That is, the present invention has the following components (A) to (C);
(A) Organic powder having a composition oil having a mass ratio of oleic acid and squalane of 1: 2 and having an oil absorption of 3 g / g or more (B) Silicone-based film forming agent (C) Ester oil is contained in the component (A). ) Is 0.1% by mass or more and 20% by mass or less.

According to the cosmetic of the present invention, it is possible to suppress the shine of the skin after a long time has passed since it was applied to the skin. In addition, it is possible to suppress secondary adhesion of cosmetics, and it is possible to maintain a uniform and bright color without uneven color.

[Cosmetics]
The cosmetic of the present invention has the following components (A) to (C);
(A) Organic powder having a composition oil having a mass ratio of oleic acid and squalane of 1: 2 and having an oil absorption of 3 g / g or more (B) Silicone-based film forming agent (C) Ester oil is contained in the component (A). ) Is a cosmetic containing 0.1% by mass or more and 20% by mass or less.
Since the cosmetic of the present invention has the above-mentioned structure, it is possible to suppress the shine when a long time has passed after applying it to the skin, it is possible to suppress the secondary adhesion of the cosmetic, and the color is uniform and bright without unevenness. Has the effect of being able to sustain.

The reason why the cosmetic of the present invention exerts the above effect is not clear, but it is presumed as follows.
Sebum contains oleic acid and hydrocarbon oil in a ratio of about 3: 7. The component (A) used in the cosmetic of the present invention is an oil absorbent, and since the oil absorption amount of the composition oil having a mass ratio of oleic acid and squalane of 1: 2 is 3 g / g or more, the sebum trapping performance is high. It is thought that it is possible to suppress the shine of the skin when a long time has passed after applying it to the skin.
The component (B) forms a film when the cosmetic is applied to the skin, and the component (A) and the powder component such as a coloring pigment described later are fixed in the film to prevent the secondary adhesion of the cosmetic. Has the effect of In addition, the component (C) acts as a plasticizer, and when used in combination with the component (A) and the component (B), the effect of preventing secondary adhesion of the cosmetic is enhanced, and the component (A), the component (B) and other powders are used. It is considered that a cosmetic that suppresses the aggregation of body components and maintains a uniform and bright color without uneven color can be obtained.
The mechanism of action of the present invention is not limited to the above.

The cosmetic of the present invention can be in the form of a solid, powder, liquid, milky liquid, paste, creamy, gel, sheet or the like, and is preferably milky or creamy.
The cosmetic preparation can be applied as an emulsified type, an oil-based type, or a powder type, and is preferably a water-in-oil type or an oil-in-water type emulsified cosmetic, and is an oil from the viewpoint of making-up cosmetics. It is more preferable that it is a medium-water emulsified cosmetic.

The cosmetic of the present invention is preferably a skin cosmetic from the viewpoint of the effectiveness of the effect of the invention, and specific examples thereof include face powder, white powder, makeup base, foundation, concealer; blusher, eye shadow, mascara, eye liner, and the like. Makeup cosmetics such as eyebrow, overcoat, lipstick; UV protection cosmetics such as sunscreen emulsion, sunscreen cream; skin care cosmetics such as skin care emulsion, skin care cream, BB cream, beauty liquid, etc. Can be done. Among these, makeup cosmetics are preferable from the viewpoint of suppressing secondary adhesion of cosmetics and maintaining a uniform and bright color without uneven color, such as face powder, white powder, makeup base, liquid foundation, and cream foundation. Is more preferable, and a makeup base, a liquid foundation, and a cream foundation are more preferable.
The cosmetic can be used alone or in layers of powder foundations such as liquid foundations, powder foundations, and white powders.

<Component (A): Organic powder>
The component (A) used in the cosmetic of the present invention is an organic powder having a composition oil having a mass ratio of oleic acid and squalane of 1: 2 and having an oil absorption amount of 3 g / g or more. By containing the component (A), the cosmetic of the present invention can suppress the shine of the skin when a long time has passed after being applied to the skin.
From the viewpoint of suppressing the shine of the skin when a long time has passed after application, the oil absorption amount of the component (A) is preferably 6 g / g or more, more preferably 10 g / g or more. The upper limit of the oil absorption amount is not particularly limited, but is usually 50 g / g or less.

In the present specification, the oil absorption amount of the component (A) is measured by the following method with reference to the oil absorption amount measuring method of the pigment defined in JIS K5101-13-2: 2004.
First, 0.2 g of the powder as the component (A) is taken on a glass plate, and a composition oil having a mass ratio of oleic acid and squalane of 1: 2 is dropped little by little using a pipette, and a pallet knife is used each time. Knead the powder and squalane. When the composition oil with a mass ratio of powder, oleic acid, and squalane of 1: 2 changes to a hard paste, knead it drop by drop, and the last drop of the oil causes the paste to soften rapidly and begin to flow. Is the end point of the oil absorption amount. The total amount (g) of the amount of the composition oil dropped when the end point is reached is taken as the oil absorption amount per 0.2 g of the powder, and is converted into the oil absorption amount (g / g) per 1 g of the powder. In the JIS method, oil is used as the oil for boiling, but in this method, a composition oil having a mass ratio of oleic acid and squalane of 1: 2 is used because of its similarity to sebum.
At the end point, the paste was rapidly softened by dropping the last drop of the composition oil having a mass ratio of oleic acid and squalane of 1: 2, and more than half of the paste was placed on the pallet knife, and the flat surface of the pallet knife was placed. Is tilted 90 ° with respect to the ground, and the paste falls within 10 seconds (if it does not fall within 10 seconds, it is not considered as the end point).

The component (A) can be used without particular limitation as long as it is an organic powder having the predetermined oil absorption amount. From the viewpoint of being contained in cosmetics and achieving the oil absorption amount, the component (A) is a structural unit derived from monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 or more and 10 or less carbon atoms. It is preferable to contain a polymer containing (a-1). The polymer containing the structural unit has an amide group, and the carboxy group in oleic acid contained in sebum is easily adsorbed, so that the effect of capturing sebum is high. Therefore, it is considered to be excellent in the effect of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin.

Here, "monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 or more and 10 or less carbon atoms" is defined as 1 bonded to the terminal amino group of (meth) acrylamide having only one (meth) acrylic group. It means a compound in which one or two hydrogen atoms are substituted with one or two hydrocarbon group-containing groups having 1 or more and 10 or less carbon atoms. In addition, in this specification, "(meth) acrylamide" means methacrylamide or acrylamide.
From the viewpoint of achieving the oil absorption, the (meth) acrylamide is monofunctional (meth) in which one hydrogen atom bonded to a terminal amino group is replaced with one hydrocarbon group-containing group having 1 to 10 carbon atoms. ) It is preferably acrylamide.

Further, the "hydrocarbon group-containing group having 1 or more and 10 or less carbon atoms" means a group having 1 or more and 10 or less carbon atoms containing at least one hydrocarbon group, and may be partitioned by, for example, an ether group. , Hydrocarbon groups having 1 or more and 10 or less carbon atoms can be mentioned.
Examples of the hydrocarbon group-containing group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxyalkyl group and the like. Among these, at least one selected from the group consisting of an alkyl group, an alkenyl group, and an alkoxyalkyl group is preferable from the viewpoint of suppressing the shine of the skin after a long time has passed since the cosmetic was applied to the skin, and the alkyl group is preferable. Is more preferable.

The hydrocarbon group-containing group has 1 or more and 10 or less carbon atoms, and is preferably 2 or more, more preferably 3 or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. Preferably, 4 or more is more preferable, 9 or less is preferable, 8 or less is more preferable, and 6 or less is further preferable.
The total number of carbon atoms of the hydrocarbon group-containing groups is 1 or more, preferably 2 or more, and preferably 3 or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. Is more preferable, and 4 or more is further preferable. The total number of carbon atoms may be 20 or less, preferably 10 or less, more preferably 9 or less, further preferably 8 or less, and even more preferably 6 or less.

Specific examples of (meth) acrylamide having a hydrocarbon-containing group having 1 or more and 10 or less carbon atoms forming the structural unit (a-1) include methyl (meth) acrylamide, ethyl (meth) acrylamide, and n-propyl (. Meta) acrylamide, isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, isobutyl (meth) acrylamide, t-butyl (meth) acrylamide, n-hexyl (meth) acrylamide, n-octyl (meth) acrylamide, 2- Ethylhexyl (meth) acrylamide, n-decyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, din-propyl (meth) acrylamide, diisopropyl (meth) acrylamide, din-butyl (meth) acrylamide, Examples thereof include diisobutyl (meth) acrylamide, dit-butyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
Among the above, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin, methyl acrylamide, ethyl acrylamide, n-propyl acrylamide, isopropyl acrylamide, n-butyl acrylamide, isobutyl acrylamide, t- One or more selected from the group consisting of butyl acrylamide, n-hexyl acrylamide, n-octyl acrylamide, 2-ethylhexyl acrylamide, n-decyl acrylamide, dimethyl acrylamide, diethyl acrylamide, and N-butoxymethyl acrylamide is preferable.

式中、Ｒ^１は炭素数１以上１０以下のアルキル基を示し、Ｒ^２は水素原子又はメチル基を示す。
Ｒ^１は、炭素数１以上１０以下の直鎖又は分岐鎖のアルキル基が挙げられ、化粧料を肌に塗布後、長時間経過した際の肌のテカリを抑える観点から、分岐鎖のアルキル基が好ましい。
Ｒ^１の炭素数は、２以上が好ましく、３以上がより好ましく、４以上が更に好ましく、そして、１０以下が好ましく、８以下がより好ましく、６以下が更に好ましい。
Ｒ^２は、水素原子であることが好ましい。 As the structural unit (a-1), the structural unit represented by the following formula (I) is more preferable from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin.

In the formula, R ¹ represents an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, and R ² represents a hydrogen atom or a methyl group.
Examples of R ¹ include straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms, and from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin, the branched-chain alkyl groups. Is preferable.
The carbon number of R ¹ is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less.
R ² is preferably a hydrogen atom.

The structural units represented by the formula (I) include methyl (meth) acrylamide, ethyl (meth) acrylamide, n-propyl (meth) acrylamide, isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, and isobutyl (meth). ) Acrylamide, t-butyl (meth) acrylamide, n-hexyl (meth) acrylamide, n-octyl (meth) acrylamide, 2-ethylhexyl (meth) acrylamide, n-decyl (meth) acrylamide, etc. Can be mentioned.
Among the above, preferably one or more selected from the group consisting of methyl acrylamide, ethyl acrylamide, n-propyl acrylamide, isopropyl acrylamide, n-butyl acrylamide, iso butyl acrylamide, t-butyl acrylamide, and n-hexyl acrylamide is derived. A structural unit derived from at least one selected from the group consisting of isopropylacrylamide, isobutylacrylamide, and t-butylacrylamide, and more preferably a constitution derived from t-butylacrylamide. It is a unit.

The content of the structural unit (a-1) in the polymer is 100 mass by mass of all the monomers constituting the polymer from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. %, The total amount of the monomers forming the structural unit (a-1) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably. Is 75% by mass or more, and may be 100% by mass.
In addition, the content of the polymer containing the constituent unit (a-1) in the component (A) is preferably 50 mass from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. % Or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 85% by mass or more, and it may be 100% by mass.

More specifically, the component (A) is a monofunctional (A) having a hydrocarbon group-containing group having 1 or more and 10 or less carbon atoms from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. A crosslinked polymer containing a structural unit (a-1) derived from meta) acrylamide, or a structural unit (a-) derived from a monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 to 10 carbon atoms. It is preferably a polymer composite containing a polymer containing 1). The polymer complex preferably has a network structure formed by ionic bonds or hydrogen bonds.
When the component (A) is the crosslinked polymer or the polymer complex, the sebum trapping effect based on the amide group of the structural unit (a-1) in the polymer can be obtained, and the component (A) is formed in the component (A). The network structure allows more sebum to be absorbed and retained. As a result, it is considered that the effect of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin is more excellent.

The component (A) is more preferably the following crosslinked polymer (A1), polymer composite (A2), and polymer composite from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. One or more selected from the group consisting of the body (A3).
(A1) A structural unit (a-1) derived from a monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 or more and 10 or less carbon atoms, and a crosslinkability having two or more polymerizable unsaturated groups. Crosslinked polymer (A2) containing a constituent unit (a1-2) derived from a monomer At least, a polymer composite (A2a) in which the following polymer component (A2a) and polymer component (A2b) are composited: 1 carbon number. Polymer having a structural unit (a-1) derived from a monofunctional (meth) acrylamide having a hydrocarbon group-containing group of 10 or less (A2b): A structural unit derived from (meth) acrylic acid (a2-2) ), A polymer other than (A2a) (A3) At least a polymer composite (A3a) in which the following polymer component (A3a) and a metal compound (A3b) are composited: Contains a hydrocarbon group having 1 or more and 10 or less carbon atoms. Polymer (A3b) containing a structural unit (a-1) derived from monofunctional (meth) acrylamide having a group and a structural unit (a3-2) derived from (meth) acrylic acid: metal oxide, One or more metal compounds selected from the group consisting of metal hydroxides and metal chlorides

(Crosslinked polymer (A1))
The crosslinked polymer (A1) (hereinafter, also simply referred to as “component (A1)”) is a structural unit (a-1) derived from a monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 to 10 carbon atoms. ), And a crosslinked polymer containing a structural unit (a1-2) derived from a crosslinkable monomer having two or more polymerizable unsaturated groups. The details of the structural unit (a-1) and its preferred range are the same as described above.

[Constituent unit (a1-2)]
The crosslinked polymer (A1) contains, as a structural unit (a1-2), a structural unit derived from a crosslinkable monomer having two or more polymerizable unsaturated groups. It is considered that the crosslinked polymer (A1) contains a structural unit (a1-2) to form a network structure capable of absorbing and retaining sebum.
Examples of the polymerizable unsaturated group include one or more selected from the group consisting of an allyl group, a vinyl group, and a (meth) acrylic group. From the viewpoint of reactivity with the monomer forming the structural unit (a-1), a vinyl group or a (meth) acrylic group is preferable, and a (meth) acrylic group is more preferable. In addition, in this specification, a "(meth) acrylic group" means a methacrylic group or an acrylic group.

Examples of the crosslinkable monomer having two or more polymerizable unsaturated groups used for forming the structural unit (a1-2) include polyallyl compounds, polyvinyl compounds, polyfunctional (meth) acrylates, and polyfunctional (meth). Examples include acrylamide.

Examples of polyallyl compounds include N, N-diallyl (meth) acrylamide, diallylamine, triallylamine, diallyl phthalate, diallyl malate, diallyl terephthalate, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, tetraallyloxyethane, and penta. Examples thereof include erythritol triallyl ether and poly (meth) allyloxyalkane.

Examples of the polyvinyl compound include divinylbenzene and divinylnaphthalene.

Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1,4-butylene. Glycoldi (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, decaethylene glycol di (meth) acrylate, penta Decaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, glycerin di (meth) acrylate, Glycerin diacrylate methacrylate, trimethylolpropane di (meth) acrylate, diethylene glycol di (meth) acrylate, 2,2'-bis (4- (meth) acryloxipropyroxyphenyl) propane, 2,2'-bis ( Bifunctional (meth) acrylates such as 4- (meth) acryloxidiethoxyphenyl) propane; trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, glycerin tri (meth) acrylate, ethylene oxide-modified tri Examples thereof include 3- to hexafunctional (meth) acrylates such as methylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Examples of polyfunctional (meth) acrylamide include N, N'-methylenebis (meth) acrylamide.
In addition, compounds having an allyl group and a (meth) acrylic group, such as allyl (meth) acrylate, can also be used as the crosslinkable monomer.

The crosslinkable monomer may be used alone or in combination of two or more.
Among the above, as the crosslinkable monomer forming the constituent unit (a1-2), a polyvinyl compound and a polyfunctional compound are used from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. One or more selected from the group consisting of meta) acrylate and polyfunctional (meth) acrylamide is preferable, from the viewpoint of improving sebum capture and the viewpoint of reactivity with the monomer forming the structural unit (a-1). Therefore, polyfunctional (meth) acrylate is more preferable, and bifunctional (meth) acrylate is further preferable.

式中、Ｒ^３、Ｒ^４はそれぞれ独立に水素原子又はメチル基を示し、Ｒ^５は炭素数１以上１０以下のアルキレン基を示す。
Ｒ^３、Ｒ^４は、化粧料を肌に塗布後、長時間経過した際の肌のテカリを抑える観点から、メチル基が好ましい。
Ｒ^５の炭素数は、化粧料を肌に塗布後、長時間経過した際の肌のテカリを抑える観点から、２以上が好ましく、そして、８以下が好ましく、６以下がより好ましく、４以下が更に好ましい。 As (a1-2), the structural unit represented by the following formula (II) is more preferable from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin.

In the formula, R ³ and R ⁴ independently represent a hydrogen atom or a methyl group, and R ⁵ represents an alkylene group having 1 to 10 carbon atoms.
R ³ and R ⁴ are preferably methyl groups from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin.
The number of carbon atoms of R ⁵ may, after coating the cosmetic skin, from the viewpoint of suppressing the shininess of the skin when long time has elapsed, preferably 2 or more, and preferably 8 or less, more preferably 6 or less, 4 or less More preferred.

The structural unit represented by the formula (II) includes ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, and 1,6-butylene. Examples thereof include a structural unit derived from one or more selected from the group consisting of glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate, including ethylene glycol dimethacrylate and 1,3-butylene glycol dimethacrylate. A structural unit derived from one or more selected from the group consisting of methacrylate and 1,6-hexanediol dimethacrylate is preferable, and one selected from the group consisting of ethylene glycol dimethacrylate and 1,6-hexanediol dimethacrylate. The structural unit derived from the above is more preferable.

The mass ratio [(a-1) / (a1-2)] of the structural unit (a-1) in the crosslinked polymer (A1) to the structural unit (a1-2) is in the structural unit (a1-1). From the viewpoint of efficiently capturing sebum by the amide group and forming a flexible network structure capable of absorbing and retaining sebum, 15 or more is preferable, 20 or more is more preferable, 25 or more is further preferable, and 30 or more is further more preferable. preferable. Further, from the viewpoint of forming a crosslinked structure and improving sebum trapping property, 60 or less is preferable, 55 or less is more preferable, 50 or less is further preferable, and 45 or less is further preferable.
In the present specification, the mass ratio of the structural units in the polymer means the mass ratio of the monomers forming each structural unit. For example, the mass ratio of the structural unit (a-1) to the structural unit (a1-2) [(a-1) / (a1-2)] is the mass ratio of the monomer forming the structural unit (a-1). It is a ratio of the mass to the mass of the monomer forming the structural unit (a1-2).

The total content of the structural unit (a-1) and the structural unit (a1-2) in the crosslinked polymer (A1) is determined from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. When the total amount of the monomers forming the crosslinked polymer (A1) is 100% by mass, the total amount of the monomers forming the structural unit (a-1) and the structural unit (a1-2) is 50% by mass. The above is preferable, 60% by mass or more is more preferable, 70% by mass or more is further preferable, and 80% by mass or more is further preferable. The upper limit may be 100% by mass, but from the viewpoint of including the structural unit (a1-3) described later, 99% by mass or less is preferable, 98% by mass or less is more preferable, and 96% by mass or less is further preferable. It is even more preferably 95% by mass or less.

式中、Ｒ^６は炭素数１以上１８以下のアルキル基又は炭素数４以上１４以下のジメチルアミノアルキル基を示し、Ｒ^７は水素原子又はメチル基を示す。 [Constituent unit (a1-3)]
The crosslinked polymer (A1) may further contain a structural unit (a1-3) represented by the following formula (III) from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. preferable.

In the formula, R ⁶ represents an alkyl group having 1 to 18 carbon atoms or a dimethylaminoalkyl group having 4 to 14 carbon atoms, and R ⁷ represents a hydrogen atom or a methyl group.

In R ^6, an alkyl group having 1 to 18 carbon atoms may be either straight or branched chain, in view of the sebaceous capture improvement, linear alkyl groups are preferred. The number of carbon atoms of the alkyl group is 1 or more and 18 or less, preferably 2 or more, preferably 16 or less, more preferably 14 or less, still more preferably 12 or less, from the viewpoint of improving sebum capture.
In R ⁶ , the dimethylaminoalkyl group having 4 or more and 14 or less carbon atoms is a group represented by (CH ₃ ) ₂ N-R ^8- (R ⁸ indicates an alkylene group having 2 or more and 12 or less carbon atoms). be. The ^{alkylene group represented by R 8} may be either a straight chain or a branched chain, but a straight chain alkylene group is preferable from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin.
The carbon number of the dimethylaminoalkyl group is 4 or more and 14 or less, preferably 10 or less, more preferably 6 or less, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. 5 or less is more preferable, and 4 or less is even more preferable.

As the structural unit (a1-3), for example, a (meth) acrylic acid alkyl ester having an alkyl group having 1 or more and 18 or less carbon atoms and a (meth) acrylic having a dimethylaminoalkyl group having 4 or more and 14 or less carbon atoms. Examples thereof include structural units derived from an acid (dimethylamino) alkyl ester.

Specific examples of the structural unit derived from the (meth) acrylic acid alkyl ester having 1 or more and 18 or less carbon atoms in the alkyl group include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, and n (meth) acrylic acid. -Propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n (meth) acrylate -Octyl, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate, (meth) ) A structural unit derived from n-octadecyl acrylate or the like can be mentioned, and one or more of these can be used.
Among the above, methyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic from the viewpoint of suppressing the shine of the skin after a long period of time has passed since the cosmetic was applied to the skin. Isopropyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic One or more selected from the group consisting of 2-ethylhexyl acid acid, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, and n-hexadecyl (meth) acrylate. The structural unit derived from is preferable, methyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, (meth). A structural unit derived from one or more selected from the group consisting of n-octyl acrylate, n-decyl (meth) acrylate, and n-dodecyl (meth) acrylate is more preferable, and methyl methacrylate and ethyl acrylate. , N-butyl acrylate, and n-dodecyl methacrylate are more preferably constituent units derived from one or more selected from the group.

Specific examples of the structural unit derived from the (meth) acrylic acid (dimethylamino) alkyl ester having 4 or more and 14 or less carbon atoms of the dimethylaminoalkyl group include dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth). Examples of structural units derived from acrylate, dimethylaminobutyl (meth) acrylate, dimethylaminohexyl (meth) acrylate, dimethylaminooctyl (meth) acrylate, dimethylaminodecyl (meth) acrylate, dimethylaminododecyl (meth) acrylate, etc. And one or more of these can be used.
Among the above, from the viewpoint of suppressing the shine of the skin after a long time has passed since the cosmetic was applied to the skin, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, A structural unit derived from one or more selected from the group consisting of dimethylaminohexyl (meth) acrylate and dimethylaminooctyl (meth) acrylate is preferable, and dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, And a structural unit derived from one or more selected from the group consisting of dimethylaminobutyl (meth) acrylate is more preferable, and one selected from the group consisting of dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate. The structural unit derived from the above is more preferable, and the structural unit derived from one or more selected from the group consisting of dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate is further preferable, and the structural unit derived from dimethylaminoethyl acrylate is more preferable. Is even more preferable.

The mass ratio [(a-1) / (a1-3)] of the structural unit (a-1) and the structural unit (a1-3) in the crosslinked polymer (A1) is long after the cosmetic is applied to the skin. From the viewpoint of suppressing the shine of the skin over time, 3 or more is preferable, 3.3 or more is more preferable, 3.5 or more is further preferable, 3.8 or more is more preferable, and 100 or less is preferable. 70 or less is more preferable, 50 or less is further preferable, and 20 or less is further preferable.

The crosslinked polymer (A1) may contain structural units other than the structural unit (a-1), the structural unit (a1-2) and the structural unit (a1-3) as long as the effects of the present invention are not impaired. good.
However, the total content of the structural unit (a-1), the structural unit (a1-2) and the structural unit (a1-3) in the crosslinked polymer (A1) has elapsed for a long time after the cosmetic was applied to the skin. From the viewpoint of suppressing the shine of the skin, when the total amount of the monomers forming the crosslinked polymer (A1) is 100% by mass, the structural unit (a-1), the structural unit (a1-2) and the structural unit ( The total amount of the monomers forming a1-3) is preferably 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, and 100% by mass. It may be.

The crosslinked polymer (A1) can be produced by using known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among the above, suspension polymerization is preferable from the viewpoints of reaction efficiency, ease of polymerization, and obtaining a crosslinked polymer in a powder state.
In suspension polymerization, for example, a solution (oil phase) containing the monomer, a polymerization initiator, and an organic solvent forming each of the constituent units is mixed with a solution (aqueous phase) containing a dispersant and water. This can be done by preparing a suspension, substituting with nitrogen, and heating and stirring the suspension.

The reaction form is preferably a radical polymerization reaction from the viewpoint of ease of production.
Examples of the radical polymerization initiator used in the radical polymerization reaction include peroxide-based polymerization initiators such as benzoyl peroxide and lauroyl peroxide; 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile and other azo-based polymerization initiators; and the like. From the viewpoint of carrying out suspension polymerization, an oil-soluble polymerization initiator is preferable, and an oil-soluble azo-based polymerization initiator is more preferable.
The amount of the polymerization initiator used can be appropriately selected depending on the type and concentration of the monomer used, the type of the initiator, the polymerization temperature, etc., but is usually preferably 0.01% by mass with respect to all the monomers used. It is 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less.

The polymerization temperature can be appropriately selected depending on the type of solvent and polymerization initiator, and is usually selected in the range of 40 to 120 ° C. The monomer concentration in the reaction system is not particularly limited, but is preferably in the range of 1 to 60% by mass from the viewpoint of production efficiency and ease of reaction control.
After the polymerization, the organic solvent is removed and then freeze-dried to obtain a powdered crosslinked polymer (A1).

(Polymer complex (A2))
The polymer complex (A2) (hereinafter, also simply referred to as “component (A2)”) is at least a polymer complex in which the following polymer component (A2a) and polymer component (A2b) are composited.
(A2a): Polymer having a structural unit (a-1) derived from monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 to 10 carbon atoms (A2b): Derived from (meth) acrylic acid. Polymers other than (A2a), including the structural unit (a2-2)

[Polymer component (A2a)]
The polymer component (A2a) is a polymer having a structural unit (a-1) derived from monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 or more and 10 or less carbon atoms. The details of the structural unit (a-1) and its preferred range are the same as described above.

The content of the structural unit (a-1) in the polymer component (A2a) is the total mass forming the polymer component (A2a) from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. When the amount of the polymer is 100% by mass, the total amount of the polymers forming the structural unit (a-1) is preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass or more. Even more preferably, 95% by mass or more is even more preferable, and it may be 100% by mass.

≪Constructive unit (a2-3) ≫
The polymer component (A2a) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 or more and 10 or less carbon atoms from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. It is preferable to include the structural unit (a2-3) from which it is derived.
The alkyl group may be either a straight chain or a branched chain, but a linear alkyl group is preferable from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. The number of carbon atoms of the alkyl group is 1 or more and 10 or less, preferably 2 or more, and preferably 9 or less, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. 8 or less is more preferable, and 6 or less is further preferable.
Specific examples of the structural unit derived from the (meth) acrylic acid alkyl ester having an alkyl group having 1 or more and 10 or less carbon atoms include methyl methacrylate, ethyl (meth) acrylic acid, and n-propyl (meth) acrylic acid. , (Meta) isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate , 2-Ethylhexyl (meth) acrylate, n-decyl (meth) acrylate and the like, one or more of the constituent units.
Among the above, a structural unit derived from an acrylic acid alkyl ester having an alkyl group having 1 or more and 10 or less carbon atoms is preferable from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. , Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, and acrylate A structural unit derived from one or more selected from the group consisting of 2-ethylhexyl is more preferable, from methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl ester of acrylate, and n-hexyl acrylate. A structural unit derived from one or more selected from the group consisting of ethyl acrylate, n-propyl acrylate, and n-butyl acrylate is more preferable. Even more preferable.

When the polymer component (A2a) contains the structural unit (a2-3), the mass ratio of the structural unit (a-1) to the structural unit (a2-3) in the polymer component (A2a) [(a-1) / (A2-3)] is preferably 3 or more, more preferably 5 or more, further preferably 10 or more, and 15 or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. More preferably, 40 or less is preferable, 30 or less is more preferable, 25 or less is further preferable, and 20 or less is further preferable.

The polymer component (A2a) may contain a structural unit other than the structural unit (a-1) and the structural unit (a2-3) as long as the effects of the present invention are not impaired.
However, the total content of the structural unit (a-1) and the structural unit (a2-3) in the polymer component (A2a) is from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. Therefore, when the total amount of the monomers forming the polymer component (A2a) is 100% by mass, the total amount of the constituent units (a-1) and the monomers forming the constituent units (a2-3) is 80. By mass% or more is preferable, 85% by mass or more is more preferable, 90% by mass or more is further preferable, 95% by mass or more is further preferable, and 100% by mass may be used.

The polymer component (A2a) preferably does not contain a structural unit derived from (meth) acrylic acid. Specifically, the content of the structural unit derived from (meth) acrylic acid in the polymer component (A2a) is (1) when all the monomers forming the polymer component (A2a) are 100% by mass. The amount of (meth) acrylic acid is preferably 5% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and may be 0% by mass.
In addition, in this specification, "(meth) acrylic acid" means methacrylic acid or acrylic acid.

The weight average molecular weight of the polymer component (A2a) is preferably 50,000 g / mol or more, more preferably 100,000 g / mol or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. It is preferable, and more preferably 200,000 g / mol or more. Further, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin and from the viewpoint of handleability, 1,000,000 g / mol or less is preferable, and 800,000 g / mol or less is more preferable. , 700,000 g / mol or less is more preferable.
The weight average molecular weight of the polymer component (A2a) can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and specifically, can be measured by the method described in Examples.

The polymer component (A2a) can be produced by using known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among the above, solution polymerization is preferable from the viewpoint of reaction efficiency and easiness of polymerization. Solution polymerization can be carried out, for example, by heating and stirring the monomer and the polymerization initiator forming the respective structural units in an organic solvent.

[Polymer component (A2b)]
The polymer component (A2b) is a polymer other than the component (A2a), which contains a structural unit (a2-2) derived from (meth) acrylic acid.

≪Constructive unit (a2-2) ≫
The polymer component (A2b) contains a structural unit derived from (meth) acrylic acid as a structural unit (a2-2). When the polymer component (A2b) contains the structural unit (a2-2), the amide group in the polymer component (A2a) and the carboxy group in the polymer component (A2b) are hydrogen-bonded to absorb and retain sebum. It is considered that a polymer composite (A2) having a possible network structure can be formed.
The (meth) acrylic acid used for forming the structural unit (a2-2) is acrylic acid or methacrylic acid, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. , Acrylic acid is preferable.

The content of the constituent unit (a2-2) in the polymer component (A2b) is the total amount of the polymer component (A2b) formed from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. When the amount of the monomer is 100% by mass, the total amount of the monomers forming the structural unit (a2-2) is preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass or more. More preferably, 60% by mass or more is even more preferable. The upper limit may be 100% by mass, but when the structural unit (a2-4) described later is included, 99% by mass or less is preferable, 90% by mass or less is more preferable, and 80% by mass or less is further preferable. 70% by mass or less is even more preferable.

≪Constructive unit (a2-4) ≫
The polymer component (A2b) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 or more and 24 or less carbon atoms from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. Can include a structural unit (a2-4) derived from.
The alkyl group may be either a straight chain or a branched chain, but a linear alkyl group is preferable from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. The number of carbon atoms of the alkyl group is 1 or more and 24 or less, preferably 4 or more, more preferably 8 or more, and more preferably 12 or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. The above is more preferable, and 22 or less is preferable, 20 or less is more preferable, and 18 or less is further preferable.
Specific examples of the structural unit derived from the (meth) acrylic acid alkyl ester having an alkyl group having 1 or more and 24 or less carbon atoms include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, and (meth) acrylic acid. n-propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylate n-octyl, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, One or more of the structural units derived from octadecyl (meth) acrylate and the like can be mentioned.
Among the above, a structural unit derived from an acrylic acid alkyl ester having an alkyl group having 1 or more and 24 or less carbon atoms is preferable from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. A structural unit derived from one or more selected from the group consisting of dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, and octadecyl acrylate is more preferable.

When the polymer component (A2b) contains the structural unit (a2-4), the mass ratio of the structural unit (a2-2) to the structural unit (a2-4) in the polymer component (A2b) [(a2-2) / (A2-4)] is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1 or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. , 10 or less is preferable, 8 or less is more preferable, and 5 or less is further preferable.

The polymer component (A2b) may contain structural units of the polymer other than the structural unit (a2-2) and the structural unit (a2-4) as long as the effects of the present invention are not impaired.
However, the total content of the structural unit (a2-2) and the structural unit (a2-4) in the polymer component (A2b) is from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. Therefore, when the total amount of the monomers forming the polymer component (A2b) is 100% by mass, the total amount of the constituent units (a2-2) and the monomers forming the constituent units (a2-4) is 80. By mass% or more is preferable, 85% by mass or more is more preferable, 90% by mass or more is further preferable, 95% by mass or more is further preferable, and 100% by mass may be used.

The weight average molecular weight of the polymer component (A2b) is preferably 5,000 g / mol or more, more preferably 6,000 g / mol or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. It is preferable, and more preferably 8,000 g / mol or more. Further, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin, and from the viewpoint of handleability, 500,000 g / mol or less is preferable, 400,000 g / mol or less is more preferable, and 300. More preferably, it is 000 g / mol or less.
The weight average molecular weight of the polymer component (A2b) can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and specifically, can be measured by the method described in Examples.

The polymer component (A2b) can be produced by the same method as the polymer component (A2a). Further, a commercially available poly (meth) acrylic acid or the like can also be used as the polymer component (A2b).

The mass ratio [(A2a) / (A2b)] of the polymer component (A2a) and the polymer component (A2b) constituting the polymer complex (A2) is the value of the skin when a long time has passed after the cosmetic was applied to the skin. From the viewpoint of suppressing shine, 1 or more is preferable, 2 or more is more preferable, 4 or more is further preferable, 6 or more is more preferable, 100 or less is more preferable, 70 or less is more preferable, 50 or less is further preferable, and 35 or less. The following is even more preferable.

Further, the molar ratio of the structural unit (a-1) in the polymer component (A2a) contained in the polymer composite (A2) to the structural unit (a2-2) in the polymer component (A2b) [(a). -1) / (a2-2)] is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. 5 or more is more preferable, 100 or less is preferable, 60 or less is more preferable, 33 or less is further preferable, and 20 or less is further preferable.

The polymer complex (A2) is at least a composite of the polymer component (A2a) and the polymer component (A2b), and may contain components other than the polymer component (A2a) and the polymer component (A2b). However, from the viewpoint of obtaining the effects of the present invention, the total content of the polymer component (A2a) and the polymer component (A2b) in the polymer composite (A2) is preferably 50% by mass or more, more preferably 70% by mass. % Or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and it may be 100% by mass.

(Method for producing polymer complex (A2))
The method for producing the polymer complex (A2) can be produced by mixing the polymer component (A2a) and the polymer component (A2b) in a solvent. From the viewpoint of efficiently forming and complexing hydrogen bonds between the polymer component (A2a) and the polymer component (A2b), the method for producing the polymer composite (A2) is to dissolve the polymer component (A2a) in an organic solvent. It is preferable to have a step of mixing the polymer solution A and the polymer solution B in which the polymer component (A2b) is dissolved in an organic solvent, and then removing the organic solvent. By this method, a polymer complex can be easily produced.

(Polymer solution A)
The polymer solution A is obtained by dissolving the polymer component (A2a) in an organic solvent. The organic solvent for dissolving the polymer component (A2a) is not particularly limited as long as the polymer component (A2a) can be dissolved, and an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, or the like may be used. Can be done. The concentration of the polymer solution A is not particularly limited, but is preferably 5 to 40% by mass from the viewpoint of solubility and production efficiency.

(Polymer solution B)
The polymer solution B is obtained by dissolving the polymer component (A2b) in an organic solvent. The organic solvent that dissolves the polymer component (A2b) is not particularly limited as long as it can disperse the polymer component (A2b), and the same solvent as the organic solvent used for the polymer solution A can be used.
The concentration of the polymer solution B is also not particularly limited, but is preferably 5 to 40% by mass from the viewpoint of solubility and production efficiency.

The polymer solution A and the polymer solution B are blended so that the polymer component (A2a) and the polymer component (A2b) have a desired mass ratio, and then stirred and mixed by a known stirring device, then reprecipitated, filtered, and dried under reduced pressure. The organic solvent in the mixed solution is removed by the above method, and if necessary, a pulverization treatment is carried out to obtain a preferably powdery polymer composite (A2).

(Polymer complex (A3))
The polymer complex (A3) (hereinafter, also simply referred to as “component (A3)”) is at least a polymer complex in which the following polymer component (A3a) and a metal compound (A3b) are composited.
(A3a): A structural unit (a-1) derived from a monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 to 10 carbon atoms, and a structural unit derived from (meth) acrylic acid (meth). Polymer (A3b) containing a3-2): One or more metal compounds selected from the group consisting of metal oxides, metal hydroxides and metal chlorides.

[Polymer component (A3a)]
The polymer component (A3a) is derived from a structural unit (a-1) derived from monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 or more and 10 or less carbon atoms, and (meth) acrylic acid. It is a polymer containing a structural unit (a3-2). The details of the structural unit (a-1) and its preferred range are the same as described above.

≪Constructive unit (a3-2) ≫
The polymer component (A3a) contains a structural unit derived from (meth) acrylic acid as a structural unit (a3-2). When the component (A3a) contains the structural unit (a3-2), the carboxy group in the structural unit (a3-2) and the metal atom in the component (A3b) described later are ionically bonded to form a network structure. It is considered that a polymer complex (A3) having a network structure capable of forming and absorbing and retaining sebum can be formed.
The (meth) acrylic acid used for forming the structural unit (a3-2) is acrylic acid or methacrylic acid, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. , Acrylic acid is preferable. "(Meta) acrylic acid" means methacrylic acid or acrylic acid.

The mass ratio [(a-1) / (a3-2)] of the structural unit (a-1) and the structural unit (a3-2) in the polymer component (A3a) is long after the cosmetic is applied to the skin. From the viewpoint of suppressing the shine of the skin over time, 7 or more is preferable, 7.3 or more is more preferable, 7.5 or more is further preferable, 7.8 or more is further preferable, and 50 or less is preferable. 33 or less is more preferable, 25 or less is further preferable, 19 or less is further preferable, and 15 or less is further preferable.
The total content of the structural unit (a-1) and the structural unit (a3-2) in the polymer component (A3a) is determined from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. When the total amount of the monomers forming the polymer component (A3a) is 100% by mass, the total amount of the constituent units (a-1) and the monomers forming the constituent unit (a3-2) is 50% by mass. The above is preferable, 60% by mass or more is more preferable, 70% by mass or more is further preferable, and 80% by mass or more is further preferable. The upper limit may be 100% by mass, but from the viewpoint of including the structural unit (a3-3) described later, 99% by mass or less is preferable, 98% by mass or less is more preferable, and 96% by mass or less is further preferable. 94% by mass or less is even more preferable, and 92% by mass or less is even more preferable.

≪Constructive unit (a3-3) ≫
The polymer component (A3a) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 or more and 10 or less carbon atoms from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. It is preferable to include a structural unit (a3-3) derived from.
The alkyl group may be either a straight chain or a branched chain, but a linear alkyl group is preferable from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. The number of carbon atoms of the alkyl group is 1 or more and 10 or less, and from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin, 2 or more is preferable, 3 or more is more preferable, and 4 The above is more preferable, and 9 or less is preferable, 8 or less is more preferable, and 6 or less is further preferable.
Specific examples of the structural unit derived from the (meth) acrylic acid alkyl ester having an alkyl group having 1 or more and 10 or less carbon atoms include methyl methacrylate, ethyl (meth) acrylic acid, and n-propyl (meth) acrylic acid. , (Meta) isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate , 2-Ethylhexyl (meth) acrylate, n-decyl (meth) acrylate and the like, one or more of the constituent units.
Among the above, acrylic acid having an alkyl group having 1 or more and 10 or less carbon atoms as a constituent unit (a3-3) from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. Alkyl esters are preferred, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-hexyl acrylate, n-octyl acrylate. , And a structural unit derived from one or more selected from the group consisting of 2-ethylhexyl acrylate, more preferably, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl ester of acrylate, and acrylic acid. A constituent unit derived from one or more selected from the group consisting of n-hexyl is more preferable, and derived from one or more selected from the group consisting of ethyl acrylate, n-propyl acrylate, and n-butyl acrylate. The structural unit to be used is even more preferable, and the structural unit derived from n-butyl acrylate is even more preferable.

When the polymer component (A3a) contains the structural unit (a3-3), the mass ratio of the structural unit (a-1) to the structural unit (a3-3) in the polymer component (A3a) [(a-1) / (A3-3)] is preferably 3 or more, more preferably 3.3 or more, and even more preferably 3.5 or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. 4, or more is more preferable, and 20 or less is preferable, 15 or less is more preferable, 12 or less is further preferable, and 9 or less is further preferable.

The polymer component (A3a) contains a structural unit of a polymer other than the structural unit (a-1), the structural unit (a3-2) and the structural unit (a3-3) within a range that does not impair the effects of the present invention. You may.
However, the total content of the structural unit (a3-1), the structural unit (a3-2), and the structural unit (a3-3) in the polymer component (A3a) has elapsed for a long time after the cosmetic was applied to the skin. From the viewpoint of suppressing the shine of the skin, the structural unit (a-1), the structural unit (a3-2) and the structural unit (when the total amount of the monomers forming the polymer component (A3a) is 100% by mass). The total amount of the monomers forming a3-3) is preferably 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, and 100% by mass. It may be.

The weight average molecular weight of the polymer component (A3a) is preferably 100,000 g / mol or more, more preferably 200,000 g / mol or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. It is preferable, and more preferably 250,000 g / mol or more. Further, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin and from the viewpoint of handleability, 1,000,000 g / mol or less is preferable, and 800,000 g / mol or less is more preferable. , 700,000 g / mol or less is more preferable.
The weight average molecular weight of the polymer component (A3a) can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and specifically, can be measured by the method described in Examples.

The polymer component (A3a) can be produced in the same manner as the polymer component (A2a).

[Metallic compound (A3b)]
The metal compound (A3b) (hereinafter, also simply referred to as “component (A3b)”) is one or more metal compounds selected from the group consisting of metal oxides, metal hydroxides, and metal chlorides. By combining the component (A3b) with the polymer component (A3a), the carboxy group of the structural unit (a3-2) in the polymer component (A3a) and the metal atom in the component (A3b) form an ionic bond. It is considered that a polymer complex (A3) capable of forming a network structure and absorbing and retaining sebum can be obtained.
The component (A3b) is preferably a solid at room temperature (25 ° C.), and more preferably has no deliquescent property, from the viewpoint of compounding with the polymer component (A3a).

The metal in the component (A3b) is preferably one or more selected from the group consisting of alkali metals, alkaline earth metals, transition metals belonging to Group 4 to Group 12 of the periodic table (long cycle), and aluminum. ..
Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, and one or more selected from the group consisting of sodium and potassium is preferable.
Examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, barium and radium, and one or more selected from the group consisting of magnesium, calcium and barium is preferable.
Periodic Table (Long Period) Transition metals belonging to Groups 4 to 12 include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, rhodium, palladium, silver, zinc, and so on. Cadmium and the like can be mentioned. Among these, one or more selected from the group consisting of titanium, manganese, iron, cobalt, nickel, copper, zirconium, and zinc is preferable, and one or more selected from the group consisting of titanium, manganese, iron, and zinc is preferable. More preferred, zinc is even more preferred.

Among the above, as the metal in the component (A3b), an alkaline earth metal is preferable from the viewpoint of exhibiting excellent sebum capture property by combining with the polymer component (A3a), and the periodic table (long cycle) Group 4 is preferable. One or more selected from the group consisting of transition metals belonging to Group 12 and aluminum, and more preferably one selected from the group consisting of magnesium, calcium, barium, titanium, manganese, iron, zinc, and aluminum. As described above, one or more selected from the group consisting of calcium, zinc, and aluminum is more preferable, and zinc is even more preferable.

Examples of the metal oxide used as the component (A3b) include magnesium oxide, calcium oxide, manganese oxide, iron oxide, zinc oxide, and aluminum oxide. Among these, zinc oxide is preferable from the viewpoint of exhibiting excellent sebum trapping property by compounding with the polymer component (A3a).
Examples of the metal hydroxide used as the component (A3b) include magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide and the like. Among these, one or more selected from the group consisting of calcium hydroxide and aluminum hydroxide is preferable from the viewpoint of exhibiting excellent sebum trapping property by compounding with the polymer component (A3a).
Examples of the metal chloride used as the component (A3b) include iron chloride and aluminum chloride.

As the component (A3b), one or more of the above metal compounds can be used. One or more selected from the group consisting of zinc oxide, calcium hydroxide, aluminum hydroxide, and aluminum chloride as the component (A3b) from the viewpoint of exhibiting excellent sebum trapping property by compounding with the polymer component (A3a). Is preferable, and zinc oxide is more preferable.

From the viewpoint of easily producing a complex with the polymer component (A3a), the component (A3b) is preferably a surface of the metal compound hydrophobized with a surface treatment agent. As the hydrophobizing treatment, a silicone treatment such as a dimethicone treatment, a hydrogen dimethicone treatment, or an alkylsilane treatment is preferable from the viewpoint of easily producing a complex with the polymer component (A3a). Examples of the surface treatment agent used for the silicone treatment include dimethylsiloxane, polydimethylsiloxane, trimethoxycaprylylsilane, and triethoxycaprylylsilane.

The average primary particle size of the component (A3b) is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 5 nm or more, from the viewpoint of exhibiting sebum trapping property by combining with the polymer component (A3a) and from the viewpoint of handleability. It is 10 nm or more, more preferably 15 nm or more, and preferably 100 nm or less, more preferably 60 nm or less, still more preferably 40 nm or less from the viewpoint of transparency when blended in cosmetics.
The average primary particle size of the component (A3b) is an average primary particle size measured by a laser diffraction / scattering method or the like, and can be measured by various commercially available particle size distribution measuring devices.

A commercially available metal compound can also be used as the component (A3b). Examples of commercially available zinc oxide products used as the component (A3b) include fine particle zinc oxide MZ series, MZX series, and MZY series manufactured by TAYCA CORPORATION.

The mass ratio [(A3a) / (A3b)] of the polymer component (A3a) and the component (A3b) constituting the polymer complex (A3) is the shine of the skin when a long time has passed after applying the cosmetic to the skin. From the viewpoint of suppressing the above, 1 or more is preferable, 3 or more is more preferable, 5 or more is further preferable, 70 or less is more preferable, 65 or less is more preferable, 60 or less is further preferable, and 55 or less is further preferable.

The molar ratio [(a3-2) / (A3b)] of the structural unit (a3-2) in the polymer component (A3a) contained in the polymer composite (A3) to the component (A3b) is a cosmetic. From the viewpoint of suppressing the shine of the skin when a long time has passed after application to the skin, 1 or more is preferable, 1.5 or more is more preferable, 1.8 or more is further preferable, and 5 or less is preferable, 4.5 or less. The following is more preferable, and 4 or less is further preferable.

The polymer complex (A3) is at least a composite of the polymer component (A3a) and the component (A3b), and may contain other components. However, from the viewpoint of obtaining the effects of the present invention, the total content of the polymer component (A3a) and the component (A3b) in the polymer complex (A3) is preferably 50% by mass or more, more preferably 70% by mass. As described above, it is more preferably 80% by mass or more, still more preferably 90% by mass or more, and may be 100% by mass.

In the polymer complex (A3), whether or not the polymer component (A3a) and the component (A3b) are compounded can be confirmed by infrared absorption (IR) spectrum measurement. Specifically, the peak intensity ratio [polymer component (A3a) / polymer composite] of the IR spectrum of the polymer component (A3a) alone and the IR spectrum of the polymer composite (A3) at a wave number of 1730 cm- ^{1 obtained by the following method.} If the body (A3)] exceeds 1, it can be determined that the component (A3a) and the component (A3b) are compounded.
The IR spectra of the polymer component (A3a) alone used for the polymer composite (A3) and the polymer composite (A3) are measured by the total reflection method (ATR method), respectively. In each IR spectrum, the vertical axis represents the Abs, The peak intensity at a wavenumber of 1650 cm ^-1 (P1) and peak intensity at a wavenumber of 1730 cm ^-1 (P2), the intensity ratio of the (P2) with respect to (P1) [(P2) / (P1)] is calculated.
The strength ratio of the polymer component (A3a) alone is (S1), the strength ratio of the polymer composite (A3) is (S2), and the ratio of (S1) to (S2) [(S1) / (S2)] is set. , The peak intensity ratio [polymer component (A3a) / polymer composite (A3)].
The peak of wave number 1650 cm ^-1 in the IR spectrum is the peak of COO ⁻ derived from the polymer component (A3a) (bonded to the metal atom in the component (A3b)), and the peak of ^{wave number 1730 cm -1 is.} , The peak of the carboxy group (those not bonded to the metal atom in the component (A3b)) derived from the polymer component (A3a).
The peak intensity ratio [polymer component (A3a) / polymer complex (A3)] is more preferably 1.1 or more from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. 1.2 or more is more preferable. Further, 2.5 or less is preferable, 2.3 or less is more preferable, and 2.1 or less is further preferable.
The peak intensity ratio [polymer component (A3a) / polymer complex (A3)] can be specifically measured by the method described in Examples.

The polymer complex (A3) can be produced by mixing the polymer component (A3a) and the component (A3b) in a dispersion medium. The polymer component (A3a) was dissolved in an organic solvent from the viewpoint of efficiently forming a network structure by ionic bonds between the carboxy group in the polymer component (A3a) and the metal atom in the component (A3b) to form a complex. It has a step of stirring and mixing a polymer solution A and a dispersion liquid B in which a component (A3b) is dispersed in an organic solvent to prepare a mixed liquid, dispersing the mixed liquid in water, and then removing the dispersion medium. Is preferable. By this method, the polymer complex (A3) can be easily produced.

The average particle size of the component (A) is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.1 μm or more, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. It is 0.5 μm or more, preferably 60 μm or less, more preferably 20 μm or less, still more preferably 10 μm, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin and from the viewpoint of handleability. It is as follows.
The average particle size of the component (A) is a median diameter (D50) measured by a laser diffraction / scattering type particle size distribution measuring device, and can be specifically measured by the method described in Examples.

<Content of component (A)>
The content of the component (A) in the cosmetic is 0.1% by mass or more, preferably 0.5% by mass, from the viewpoint of suppressing the shine of the skin when a long time has passed after applying the cosmetic to the skin. % Or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and even after a long time has passed since the cosmetic was applied to the skin, the secondary adhesion of the cosmetic was suppressed and the color unevenness was observed. From the viewpoint of maintaining a uniform and bright color without any problem, it is 20% by mass or less, preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 10% by mass or less.

<Component (B): Silicone film forming agent>
As the component (B) used in the cosmetics of the present invention, those usually used in cosmetics can be used, but those solid at 25 ° C. are preferable.
As the silicone-based film-forming agent of the component (B), the secondary adhesion of the cosmetic is suppressed even after a long time has passed since the application to the skin, and the viewpoint of maintaining a uniform and bright color without uneven color and the finish. From the viewpoint of goodness, one or more selected from the group consisting of trimethylsiloxysilicic acid (B1), fluorine-modified silicone resin (B2), and acrylic silicone resin (B3) is preferable.

(Trimethylsiloxysilicic acid (B1))
The trimethylsiloxysilicic acid (B1) (hereinafter, also referred to as "component (B1)") is not limited as long as it is used in ordinary cosmetics, and is a compound having a crosslinked structure having a siloxane structure as a main skeleton. [(CH ₃ ) ₃ SiO _1/2 ] _a [SiO ₂ ] _b (a is 1 to 3 and b is 0.5 to 8) is preferable.
Ingredient (B1) is a weight average from the viewpoint of suppressing secondary adhesion of cosmetics even after a long time has passed since application to the skin, maintaining a uniform and bright color without uneven color, and from the viewpoint of good finish. Those having a molecular weight of 1,000 to 10,000 are preferable, those having a molecular weight of 2,000 to 9,000 are more preferable, and those having a molecular weight of 3,000 to 6,000 are even more preferable. The properties may be liquid, gum-like, paste-like, solid-like, etc. at 25 ° C., but even when a long time has passed after application to the skin, secondary adhesion of cosmetics is suppressed and color unevenness occurs. From the viewpoint of maintaining a uniform and bright color without any problem and from the viewpoint of good finish, a solid state is preferable. Further, from the viewpoint of compoundability, the component (B1) may be a solution diluted with a solvent or a dispersion liquid. As the solvent to be diluted or dispersed, at least one selected from the group consisting of dimethylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and isododecane is preferable, and volatile dimethylpolysiloxane and decamethylcyclopentasiloxane are used. More preferably, one or more selected from the group consisting of. Volatile means having a flash point of 35 to 87 ° C.

Commercially available products of the component (B1) are those previously dissolved in a solvent, such as KF-7312J (50% by mass% decamethylcyclopentasiloxane solution), KF-9021 (50% by mass% decamethylcyclopentasiloxane solution), and X21. -5249 (50 mass% decamethylcyclopentasiloxane solution) (above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), SS4267 (35 mass% dimethylpolysiloxane solution), SR1000 (above, Momentive Performance Materials Japan LLC) , BY11-018 (30 mass% cyclopentasiloxane solution) (manufactured by Dow Toray Co., Ltd.), BEALSIL TMS 803 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) and the like can be used.

(Fluorine-modified silicone resin (B2))
The fluorine-modified silicone resin (B2) (hereinafter, also referred to as “component (B2)”) includes the following general formula (1):
R ¹ _a SiO _{(4-a) / 2} (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 or more and 8 or less carbon atoms, a phenyl group, a hydroxyl group, or -R ^2- Rf (R ² represents a divalent alkylene group having 2 or more and 6 or less carbon atoms, and Rf is a group represented by showing a perfluoroalkyl group having 1 to 8 carbon atoms), optionally selected a group represented by a hydroxyl group and -R 2 ^-Rf from the functional groups as an essential, a is the average number 1.0 ≦ a ≦ 1.8.)
Those having a structure represented by are preferable.
The fluorine-modified silicone resin has a silanol group in the molecule from the viewpoint of adhesion to the skin, and the ratio of the OH group in the silanol group is 0.1% by mass or more and 5% by mass or less with respect to the resin mass. It is preferably present, and more preferably 0.5% by mass or more and 5% by mass or less.

The component (B2) is preferably a solid at 25 ° C., and may be a solution diluted with a solvent or a dispersion from the viewpoint of compoundability. As the solvent to be diluted or dispersed, it is preferable to use it by dissolving it in cyclic silicone, dimethylpolysiloxane or the like. As the cyclic silicone, one or more selected from the group consisting of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) is preferable.
Examples of the fluorine-modified silicone resin (B2) include XS66-B8226, XS66-C1191, XS66-B8636 (above, Momentive), which have INCI names of "Trifluoropropyldimethyl / Trimethylsilicite". Commercially available products such as (manufactured by the company) can be used.

(Acrylic silicone resin (B3))
Examples of the acrylic silicone resin (B3) (hereinafter, also referred to as “component (B3)”) include a vinyl polymer having a carbosiloxane dendrimer structure in the side chain, an acrylic-silicone graft copolymer, and the like.
Examples of the vinyl-based polymer having a carbosiloxane dendrimer structure in the side chain include a silicone dendrimer / acrylic copolymer and the like, and are described in, for example, JP-A-11-1530 and JP-A-2000-63225. It can be manufactured according to a manufacturing method.
The number average molecular weight of the vinyl polymer having a carbosiloxane dendrimer structure suppresses the secondary adhesion of cosmetics even after a long time has passed since it was applied to the skin, and from the viewpoint of maintaining a uniform and bright color without uneven color. From the viewpoint of good finish, it is preferably 3,000 or more and 2,000,000 or less, and more preferably 5,000 or more and 800,000 or less.
The component (B3) is preferably solid at 25 ° C. Further, the vinyl-based polymer having a carbosiloxane dendrimer structure can be blended in a solid state, but can also be used by being dissolved in a solvent. Examples of the solvent include silicone oil and hydrocarbon oil, and preferably one or more selected from the group consisting of dimethylpolysiloxane, decamethylcyclopentasiloxane, and isododecane.

As the vinyl-based polymer having a carbosiloxane dendrimer structure in the side chain, a silicone dendrimer / acrylic copolymer is preferable, and the cosmetic labeling name "(Acrylate / polytrimethylsiloxy methacrylate) copolymer" (INCI name "Acrylates / Polytimethylymethylmetrycopolymer") ) Is more preferable, and commercially available products such as FA4001CM (30% by mass decamethylcyclopentasiloxane solution) and FA4002ID (40% by mass isododecane solution) (all manufactured by Dow Toray Co., Ltd.) previously dissolved in a solvent should be used. Can be done.

The acrylic-silicone graft copolymer is a radical polymer of an organopolysiloxane compound having a radically polymerizable group at one end of the molecular chain and a radically polymerizable monomer mainly composed of acrylate and / or methacrylate. This is, for example, those described in JP-A-2-25411, JP-A-2-132141, etc., and the acrylics described in JP-A-3-162442, JP-A-2003-104825, etc. Silicone-based graft copolymers can be used.

As the acrylic-silicone graft copolymer, the cosmetic labeling name "(Acrylate / Dimethicone) Copolymer" (INCI name "Acrylates / Dimethicone Composer") is preferable, and KP545 (30 mass% decamethylcyclopenta) previously dissolved in a solvent is preferable. Commercial products such as siloxane solution), KP549 (40% by mass methyltrimethicone solution), and KP550 (40% by mass isododecane solution) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.) can be used.

As the component (B), a film is formed on the skin to suppress the shine of the skin after a long time has passed since application, and the secondary adhesion of cosmetics is suppressed to maintain a uniform and bright color without uneven color. It is preferable to contain at least one selected from the group consisting of trimethylsiloxysilicic acid, a fluorine-modified silicone resin, and a vinyl-based polymer having a carbosiloxane dendrimer structure in the side chain, from the viewpoint of allowing the mixture to be obtained and the quality of the finish. It is more preferable to contain at least one selected from the group consisting of trimethylsiloxysilicic acid and a fluorine-modified silicone resin.

The content of the component (B) in the cosmetics is from the viewpoint of suppressing the shine of the skin after a long time has passed since application, and from the viewpoint of suppressing the secondary adhesion of the cosmetics and maintaining a uniform and bright color without uneven color. From the viewpoint of good finish, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 2% by mass or more, and more preferably. Is 25% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, still more preferably 10% by mass or less.

Further, in the cosmetic of the present invention, the mass ratio [(A) / (B)] of the component (A) to the component (B) is determined from the viewpoint of suppressing the shine of the skin when a long time has passed after application. From the viewpoint of suppressing the next adhesion, maintaining a uniform and bright color without uneven color, and from the viewpoint of good finish, it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more. It is more preferably 0.5 or more, preferably 20 or less, more preferably 10 or less, still more preferably 5 or less.

<Component (C): Ester oil>
The ester oil of the component (C) is not particularly limited as long as it is used in ordinary cosmetics, but a non-volatile ester oil is preferable. Here, the non-volatile means that it does not have a flash point at 35 to 87 ° C., and is preferably liquid or paste-like and has fluidity at 25 ° C.

As the ester oil, any of monoester oil, diester oil, triester oil, and tetraester oil can be used.
Examples of the monoester oil include isononyl isononanoate, isodecyl isononanoate, isotolideyl isononanoate, tricyclodecanemethyl isononanoate, hexyl laurate, octyldodecyl malate, cetyl 2-ethylhexanoate, and 2-ethylhexanoate 2-ethylhexanoate. Hexyldecyl, isopropyl myristate, 2-hexyldecyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, ethyl isostearate, isopropyl isostearate, isobutyl isostearate, 2-hexyldecyl isostearate, hydroxysteer Examples thereof include 2-ethylhexyl acid acid, octyldodecyl oleate, oleyl oleate, octyldodecyl ricinoleate, octyl paramethoxysilicate and propylene carbonate.
Diester oils include di2-hetylhexyl succinate, bisethoxydiglycol succinate, di (caprylic acid / capric acid) propanediol, neopentyl glycol diisononanoate, neopentyl glycol dicaprate, glyceryl diisostearate, polyglyceryl diisostearate. , Propanediol diisostearate, diisostearyl malate, di lauroyl glutamate (phytosteryl / octyldodecyl), di lauroyl glutamate (cholesteryl / behenyl / octyldodecyl), di lauroyl glutamate (octyldodecyl / phytosteryl / behenyl), di2-ethyl Examples thereof include neopentyl glycol hexanoate and neopentyl glycol dioctanoate.
Examples of the triester oil include trimethyl propane triisostearate, glyceryl triisostearate, diglyceryl triisostearate, jojoba oil, trimethylolpropane tri-2-hetylhexanoate, glyceryl tri2-ethylhexanoate, and tri (capril /). Capric acid) Glyceryl, glyceryl trioctanoate, tritridecyl trimeritate, macadamia nut oil, olive oil, sunflower oil, jojoba oil, avocado oil, sunflower oil and the like.
Examples of the tetraester oil include pentaerythrityl tetraoctanoate, diglyceryl tetraisostearate, dipentaerythrityl tetraisostearate, and pentaerythrit tetraisostearate.

As the component (C), one kind or two or more kinds can be used.
Among the above, monoester oil and diester as the component (C) from the viewpoint of suppressing secondary adhesion of cosmetics even after a long time has passed after application to the skin and maintaining a uniform and bright color without color unevenness. One or more selected from the group consisting of oil and triester oil is preferable, monoester oil is more preferable, and one or more selected from the group consisting of octyl paramethoxycinnamate and isononyl isononanoate is more preferable, and paramethoxy It is even more preferable to include octyl silicate.

The content of the component (C) in the cosmetics is preferably from the viewpoint of suppressing the secondary adhesion of the cosmetics even after a long time has passed since the application to the skin, and maintaining a uniform and bright color without uneven color. 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 2% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass. % Or less, more preferably 10% by mass or less, still more preferably 7% by mass or less.

Further, in the cosmetic of the present invention, the mass ratio [(A) / (C)] of the component (A) to the component (C) suppresses the secondary adhesion of the cosmetic even after a long time has passed since it was applied to the skin. However, from the viewpoint of maintaining a uniform and bright color without uneven color, it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, still more preferably 0.4 or more. Further, it is preferably 15 or less, more preferably 10 or less, and further preferably 4 or less.

<Component (D): Coloring pigment>
The cosmetic of the present invention preferably contains a coloring pigment as the component (D) from the viewpoint of making a makeup cosmetic.
The coloring pigment may be any pigment usually used in cosmetics, for example, white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide and barium sulfate; Colored inorganic pigments such as chromium oxide, chromium hydroxide, navy blue, ultramarine; titanium oxide-coated mica, titanium oxide-coated bismuth oxychloride, iron oxide-coated mica titanium, iron oxide mica, navy blue-treated mica titanium, carmine-treated mica titanium, oxychloride Bright powders such as bismuth and fish scale foil; organic pigments such as red 201, red 202, red 205, red 226, red 228, orange 203, orange 204, blue 404, and yellow 401. Red No. 3, Red No. 104, Red No. 106, Orange No. 205, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1 and other rake pigments such as zirconium, barium or aluminum lake; Fine particle titanium oxide coated mica Composite pigments such as titanium, fine particle zinc oxide-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide; and the like, and one or more of these can be used. ..

When the cosmetic of the present invention contains the component (D), the content thereof is preferably 0.1% by mass or more, more preferably 1% by mass or more in the cosmetic from the viewpoint of imparting a desired hue. From the viewpoint of dispersibility in cosmetics and economic efficiency, it is preferably 50% by mass or less, more preferably 30% by mass or less.

<Component (E): Volatile oil>
The cosmetic of the present invention can contain a volatile oil as a component (E) from the viewpoint of making a water-in-oil emulsified cosmetic and from the viewpoint of obtaining a uniform finish when applied to the skin. As used herein, a volatile oil is an oil having a flash point of 35 to 87 ° C.
Examples of the volatile oil include volatile silicone oil and volatile hydrocarbon oil.
Examples of the volatile silicone oil include linear dimethylpolysiloxane (1 to 2 cs); branched siloxanes such as methyltrimethicone, tris (trimethylsilyl) methylsilane, and tetrakis (trimethylsilyl) silane; octamethylcyclotetrasiloxane and decamethyl. Cyclic dimethylsiloxane such as cyclopentasiloxane and dodecamethylcyclohexasiloxane; and the like.
Of these, from the viewpoint of obtaining a uniform finish when applied to the skin, one or more selected from the group consisting of linear dimethylpolysiloxane and cyclic dimethylpolysiloxane is preferable, and linear dimethylpolysiloxane is contained. Is more preferable.

Examples of the volatile hydrocarbon oil include paraffinic hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; isoparaffinic hydrocarbon oils such as isodecane, isododecane, and hydrogenated polyisobutene; cyclodecane, cyclododecane, and the like. Cyclic paraffin hydrocarbon oil can be mentioned. Of these, a hydrocarbon oil having 8 or more and 16 or less carbon atoms is preferable, a hydrocarbon oil having 10 or more and 16 or less carbon atoms is more preferable, and a hydrocarbon oil having 12 or more and 16 or less carbon atoms is further preferable.

As the component (E), one kind or two or more kinds can be used. Among the above, the component (E) preferably contains a volatile silicone oil, and more preferably contains a linear dimethylpolysiloxane, from the viewpoint of obtaining a uniform finish when applied to the skin.

When the cosmetic of the present invention contains the component (E), the content thereof is determined in the cosmetic from the viewpoint of making it a water-in-oil emulsified cosmetic and from the viewpoint of obtaining a uniform finish when applied to the skin. It is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less.

<Component (F): Nonionic surfactant>
The cosmetic of the present invention is a nonionic surfactant as a component (F) from the viewpoint of making a water-in-oil emulsified cosmetic, obtaining a uniform finish when applied to the skin, and improving makeup durability. Can be contained.
The nonionic surfactant is not limited as long as it is used in ordinary cosmetics, and for example, sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, and sucrose. Fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, Polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxyethylene phytostanol ether, polyoxyethylene phytosterose ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, alkyl glyceryl ether-modified silicone, Examples thereof include polyethylene-modified silicone, polyoxyalkylene / alkyl co-modified silicone, polyoxyalkylene / fluoroalkyl co-modified silicone, and one or more of these can be used.

Among the above, the component (F) preferably contains a polyether-modified silicone from the viewpoint of obtaining a uniform finish when applied to the skin and improving the durability of makeup.
Examples of the polyether-modified silicone include SH3771M, SH3772M, SH3773M, SH3775M, SH3749, DC5200 (all manufactured by Dow Toray Co., Ltd.), KF-6011, KF-6012, KF-6013, KF-6015, KF-6016. , KF6017, KF-6004 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be used.

The HLB (hydrophilic-lipophilic balance)> value of the nonionic surfactant is preferably set from the viewpoint of obtaining a uniform finish when applied to the skin and improving the durability of makeup. It is 1 or more, more preferably 2 or more, and preferably 7 or less, more preferably 6 or less.
In the present specification, the HLB value indicates the molecular weight of the hydrophilic group portion in the total molecular weight of the surfactant, and is determined by the formula of Griffin.
The HLB of a mixed surfactant composed of two or more types of nonionic surfactants is obtained as follows. The HLB of the mixed surfactant is a phase-added average of the HLB values of each nonionic surfactant based on the blending ratio.
HLB = Σ (HLBx × Wx) / ΣWx of mixed surfactant
HLBx indicates the HLB value of the nonionic surfactant X.
Wx indicates the weight (g) of the nonionic surfactant X having a value of HLBx.

When the cosmetic of the present invention contains the component (F), the content thereof is from the viewpoint of making a water-in-oil emulsified cosmetic, from the viewpoint of obtaining a uniform finish when applied to the skin, and improving the durability of makeup. From the viewpoint, in cosmetics, it is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and preferably 8% by mass or less, more preferably 6% by mass or less, still more preferably 4% by mass. % Or less.

<Water>
The cosmetic of the present invention may further contain water from the viewpoint of improving the feeling of use. When the cosmetic of the present invention contains water, the content thereof is preferably 1% by mass or more, more preferably 10% by mass or more, and preferably 70 in the cosmetic, from the viewpoint of improving usability. It is mass% or less, more preferably 60 mass% or less, still more preferably 45 mass% or less.

In addition to the above-mentioned ingredients, the cosmetics of the present invention include other ingredients usually used in cosmetics, such as oils, powders, water-soluble polymers, antioxidants, fragrances, pigments, preservatives, and thickeners. It can contain a pH adjuster, a blood circulation promoter, a cold sensation agent, an antiperspirant, a bactericidal agent, a skin activator, a moisturizer, a refreshing agent and the like.
The cosmetic of the present invention can be produced according to a conventional method.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to the scope of the Examples. In this example, various measurements and evaluations were carried out by the following methods.

<Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) under the following conditions.
(GPC measurement conditions)
Column: Used by connecting two "α-M" (manufactured by Tosoh Corporation) in series Eluent: 60 mM phosphoric acid, 50 mM lithium bromide / N, N-dimethylformamide solution Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI
Measurement sample: 1 mg / mL N, N-dimethylformamide solution, 100 μL
Calibration curve: Polystyrene molecular weight 8.42 million, 1.09 million, 964,000 (manufactured by Tosoh Corporation), polystyrene molecular weight 30,000 (manufactured by Nishio Kogyo Co., Ltd.), polystyrene molecular weight 5,400,500 (manufactured by Tosoh Co., Ltd.)

<Measurement of average particle size>
The average particle size (median diameter: D50) of the component (A) is a relative refractive index using water as a dispersion medium using a laser diffraction / scattering type particle size distribution measuring device "LA-920" manufactured by Horiba Seisakusho Co., Ltd. Measured as 1.200-0.000i.

<Measurement of peak intensity ratio at wave number 1730 cm- ^{1 in IR spectrum>}
For the polymer complex (A3), the IR spectrum of the component (A3a) alone and the polymer complex (A3) was measured using an infrared spectrophotometer (“Nicolet iS5”, Thermo Fisher Scientific, Inc.). , Each was measured by the total reflection method (ATR method). In each IR spectrum, the vertical axis represents the Abs, The peak intensity at a wavenumber of 1650 cm ^-1 (P1) and peak intensity at a wavenumber of 1730 cm ^-1 (P2), the intensity ratio of the (P2) with respect to (P1) [(P2) / (P1)] was calculated.
Let the strength ratio of the component (A3a) alone be (S1) and the strength ratio of the polymer complex (A3) be (S2), and determine the ratio of (S1) and (S2) [(S1) / (S2)]. rice field. When this ratio exceeds 1, it indicates that the component (A3a) and the component (A3b) in the polymer complex (A3) form a complex.

<Preparation of composition oil for evaluation>
Oleic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and Squalan (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed and mixed so as to have a mass ratio of 1: 2 to prepare a composition oil for evaluation.

<Measurement of oil absorption>
The oil absorption of the powder (component (A) and comparative substance) was measured with reference to the method for measuring the oil absorption of pigments specified in JIS K5101-13-2: 2004. First, 0.2 g of powder is taken on a glass plate, and a composition oil having a mass ratio of oleic acid and squalane of 1: 2 is dropped little by little using a pipette, and each time, powder and squalane are used using a palette knife. Was kneaded. When the composition oil with a mass ratio of powder, oleic acid, and squalane of 1: 2 changes to a hard paste, knead it drop by drop, and the last drop of the oil causes the paste to soften rapidly and begin to flow. Was the end point of the oil absorption. The total amount (g) of the composition oil dropped when the end point was reached was defined as the oil absorption amount per 0.2 g of the powder, and was converted into the oil absorption amount (g / g) per 1 g of the powder.
At the end point, the paste was rapidly softened by dropping the last drop of the composition oil having a mass ratio of oleic acid and squalane of 1: 2, and more than half of the paste was placed on the pallet knife, and the flat surface of the pallet knife was placed. Was tilted 90 ° with respect to the ground, and the paste fell within 10 seconds (if it did not fall within 10 seconds, it was not considered as the end point).

<Evaluation of cosmetics>
(1) No shine due to sebum after 8 hours of application Five specialist panelists applied the water-in-oil emulsified cosmetic (foundation) obtained in each example to the skin, and after 8 hours, the shine due to sebum Difficulty was sensory-evaluated according to the following criteria. The results are shown by the total score of 5 people.
5; There is no shine due to sebum.
4; There is no shine due to sebum.
3; There is not much shine due to sebum.
2; There is some shine due to sebum.
1; There is shine due to sebum.

(2) No secondary adhesion to towels after 8 hours of application Five specialist panelists applied the water-in-oil emulsified cosmetics (foundation) obtained in each example to the skin, and after 8 hours had passed. , The non-color transfer of the foundation when a cotton towel was pressed against the skin was sensoriwise evaluated according to the following criteria. The results are shown by the total score of 5 people.
5; Even if the towel is pressed against the skin after application, the foundation does not adhere at all.
4; Even if the towel is pressed against the skin after application, the foundation does not come on.
3; Even if the towel is pressed against the skin after application, the foundation does not adhere much.
2; When you press the towel against the skin after application, the foundation will come a little.
1; When you press the towel against the skin after application, the foundation will be attached.

(3) Brightness of the skin after 8 hours of application Five specialist panelists applied the water-in-oil emulsified cosmetic (foundation) obtained in each example to the skin, and the brightness of the cosmetic skin after 8 hours of application was applied. The sensory evaluation was performed according to the following criteria. The results are shown by the total score of 5 people.
5; Makeup skin looks bright.
4; Makeup skin looks a little bright.
3; Makeup skin does not look very bright.
2; Makeup skin does not look bright.
1; Makeup skin does not look bright at all.

(4) Uniformity of skin after 8 hours of application Five specialist panelists applied the water-in-oil emulsified cosmetic (foundation) obtained in each example to the skin, and uniformed the skin after 8 hours of application. The sensory evaluation was performed according to the following criteria. The results are shown by the total score of 5 people.
5; Makeup skin looks uniform.
4; Makeup skin looks a little even.
3; Makeup skin does not look very uniform.
2; Makeup skin does not look uniform.
1; Makeup skin does not look even at all.

Production Example 1 (Production of crosslinked polymer A1-1)
The crosslinked polymer A1-1 was produced by the suspension polymerization method shown below.
In a 500 mL beaker, 92.00 g of Nt-butyl acrylamide (TBAA), 3.00 g of ethylene glycol dimethacrylate (EGDMA), 5.00 g of dodecyl methacrylate (LMA), and 230.00 g of ethyl acetate are placed, and polytetrafluoroethylene is placed. The temperature was raised to 43 ° C. while stirring using a stirring blade made of (PTFE) to dissolve the monomer and make it uniform. Next, the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) ("V-65B", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., oil-soluble azo polymerization initiator) 1.00 g Was added and dissolved rapidly to prepare an oil phase solution.
Next, 536.67 g of ion-exchanged water and 2.00 g of sodium N-stearoyl-N-methyltaurine (“NIKKOL SMT”, manufactured by Nikko Chemicals Co., Ltd.) as a dispersant were placed in a 2 L beaker, and the temperature was raised to 43 ° C. An aqueous phase solution was prepared by mixing for 1 minute at a rotation speed of 3500 rpm using a homomixer (“ROBOMICS”, manufactured by Primix Corporation).
The entire amount of the oil phase solution was added to the aqueous phase solution, and the mixture was mixed at a rotation speed of 6500 rpm for 5 minutes using a homomixer to prepare a suspension.
A 2 L glass separable flask to be a reaction vessel is heated in an oil bath at 43 ° C., the entire amount of the suspension is put into the reaction vessel, the pressure inside the reaction vessel is reduced to 400 hPa, held for 30 seconds, and nitrogen is blown into the reaction vessel. The operation of returning to normal pressure was repeated 5 times to perform nitrogen substitution. The temperature inside the reaction vessel was raised to 60 ° C. while stirring the suspension using a PTFE stirring blade, and then the suspension was held at 60 ° C. for 5 hours for polymerization. After that, it was kept at 70 ° C. for 1.5 hours for aging. After cooling, ethyl acetate was removed using an evaporator, and the mixture was freeze-dried to obtain a powdery crosslinked polymer A1-1 having an oil absorption of 15 g and an average particle size (median diameter) of 2 μm.

Production Examples 2-4 (Production of crosslinked polymers A1-2 to A1-4)
Powdered crosslinked polymers A1-2 to A1-4 were produced in the same manner as in Production Example 1 except that the ratio of the monomers used was changed to the mass ratio shown in Table 1. Table 1 shows the ratio of the monomers forming the constituent units in the polymer and the amount of oil absorption.

Comparative Production Example 1 (Production of Non-Crosslink Polymer 1)
240.00 g of TBAA and 751.29 g of ethyl acetate were placed in a 3 L glass separable flask to be a reaction vessel, and the temperature was raised to 45 ° C. with stirring using a PTFE stirring blade to make the temperature uniform. Next, in a 300 mL three-necked flask, 2.37 g of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) ("V-65B", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), ethyl acetate. 92.63 g was added and mixed, and degassed by nitrogen bubbling to prepare an initiator solution. Moreover, 560.00 g of TBAA and 1753.01 g of ethyl acetate were mixed to prepare a monomer solution.
A dropping funnel was attached to the separable flask, and the initiator solution was placed in the dropping funnel. The inside of the reaction vessel including the dropping funnel was depressurized to 746.6 hPa, held for 30 seconds, and the operation of blowing nitrogen and returning to normal pressure was repeated three times to perform nitrogen substitution. After the temperature inside the reaction vessel was raised to 62 ° C., 28.50 g of the initiator solution (corresponding to 30% by mass of the total initiator solution) was added dropwise to the reaction vessel over 30 minutes to initiate polymerization. Then, the entire amount of the monomer solution and the initiator solution is added dropwise to the reaction vessel over 2 hours, and after the addition is completed, the temperature is maintained at 62 ° C. for 3 hours, the temperature is raised to 80 ° C., and the temperature is maintained at 80 ° C. for 2 hours. Polymerization and aging were carried out in. After cooling, the mixture was reprecipitated with about 50 L of acetone, purified, and dried under reduced pressure at 60 ° C. under vacuum for 8 hours to obtain a powdery non-crosslinked polymer 1. The oil absorption of the non-crosslinked polymer 1 is shown in Table 1.

The crosslinked polymer particles 1 for comparison (“MAKIBEADS 150”, manufactured by Daito Kasei Kogyo Co., Ltd., spherical methyl methacrylate crosspolymer, porous, specific surface area of about 150 m ^{2), which is a commercially available comparative substance used in this example.} The oil absorption of / g) is also shown in Table 1.

The components listed in Table 1 are as follows.
TBAA: t-Butylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
EGDMA: Ethylene glycol dimethacrylate ("Ethylene glycol dimethacrylate", manufactured by Tokyo Chemical Industry Co., Ltd.)
LMA: Dodecyl methacrylate ("Dodecyl methacrylate", manufactured by Tokyo Chemical Industry Co., Ltd.)
DMAEA: N, N-dimethylaminoethyl acrylate ("2- (dimethylamino) ethyl acrylate", manufactured by Tokyo Chemical Industry Co., Ltd.)
EA: Ethyl acrylate ("Ethyl acrylate", manufactured by Tokyo Chemical Industry Co., Ltd.)
MMA: Crosslinked polymer particles for comparison with methyl methacrylate 1: "MAKIBEADS 150", manufactured by Daito Kasei Kogyo Co., Ltd., spherical methyl methacrylate crosspolymer, porous, specific surface area of about 150 m ² / g

Production Example 5 (Production of Polymer A2a-1)
228.00 g of Nt-butylacrylamide (TBAA), 12.00 g of ethyl acrylate (EA), and 751.29 g of ethanol were placed in a 1 L glass separable flask to be a reaction vessel, and polytetrafluoroethylene (PTFE) was placed. ) Was used to stir and raise the temperature to 45 ° C. to make it uniform.
Next, in a 300 mL three-necked flask, a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) ("V-65B", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., oil-soluble azo polymerization initiator) ) 2.37 g and 84.21 g of ethanol were added and mixed, and degassed by nitrogen bubbling to prepare an initiator solution. In addition, a monomer solution was prepared by mixing 532.00 g of TBAA, 28.00 g of EA, and 1753.01 g of ethyl acetate.
A dropping funnel was attached to the separable flask, and the initiator solution was placed in the dropping funnel. The inside of the reaction vessel including the dropping funnel was depressurized to 746.6 hPa, held for 30 seconds, and the operation of blowing nitrogen and returning to normal pressure was repeated three times to perform nitrogen substitution. After the temperature inside the reaction vessel was raised to 62 ° C., 25.97 g of the initiator solution (corresponding to 30% by mass of the total initiator solution) was added dropwise to the reaction vessel over 30 minutes to initiate polymerization. Then, the monomer solution and the remaining initiator solution were added dropwise to the reaction vessel over 2 hours, and after the addition was completed, the mixture was held at 62 ° C. for 3 hours for polymerization. After that, the temperature was raised to 80 ° C., and the temperature was maintained at 80 ° C. for 2 hours for aging. After cooling, the mixture was reprecipitated with about 50 L of acetone, purified, and dried under reduced pressure at 60 ° C. under vacuum for 8 hours to obtain polymer A2a-1. Table 2 shows the ratio of the monomers forming the constituent units in the polymer A2a-1 and the weight average molecular weight.

Production Example 6 (Production of Polymer A2a-2)
The polymer A2a-2 was produced in the same manner as in Production Example 5 except that the solvent ethanol was changed to ethyl acetate. Table 2 shows the ratio of the monomers forming the structural units in the polymer and the weight average molecular weight.

Production Example 7 (Production of Polymer A2a-3)
In a 10 L glass separable flask to be a reaction vessel, 760.00 g of Nt-butylacrylamide (TBAA), 40.00 g of ethyl acrylate (EA), 2588.51 g of ethyl acetate, and a polymerization initiator 2 , 2'-azobis (2,4-dimethylvaleronitrile) ("V-65B", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., oil-soluble azo polymerization initiator) 2.37 g is added, and polytetrafluoroethylene (PTFE) is added. ) Was stirred with a stirring blade to make it uniform. The inside of the reaction vessel was depressurized to 746.6 hPa, held for 30 seconds, and the operation of blowing nitrogen to return to normal pressure was repeated three times to perform nitrogen substitution, and then the temperature inside the reaction vessel was raised to 62 ° C. to start polymerization. Then, it was kept at 62 ° C. for 3 hours. After that, the temperature was raised to 80 ° C., and the temperature was maintained at 80 ° C. for 2 hours for aging. After cooling, the mixture was reprecipitated with about 50 L of acetone, purified, and dried under reduced pressure at 60 ° C. under vacuum for 8 hours to obtain polymer A2a-3. Table 2 shows the ratio of the monomers forming the constituent units in the polymer A2a-3 and the weight average molecular weight.

Production Example 8 (Production of Polymer A2a-4)
The polymer A2a-4 was produced in the same manner as in Production Example 5 except that the ratio of the monomers used was changed to the mass ratio shown in Table 2. Table 2 shows the ratio of the monomers forming the structural units in the polymer and the weight average molecular weight.

Regarding the commercially available polymers (polymers A2b-1 to A2b-3) used in the polymer composites shown in Table 3 described later, the ratio of the monomers forming the constituent units in the polymer and the weight average molecular weight are also determined. It is shown in Table 2.

The components listed in Table 2 are as follows.
TBAA: t-Butylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
EA: Ethyl acrylate ("Ethyl acrylate", manufactured by Tokyo Chemical Industry Co., Ltd.)
Polymer A2b-1: Polyacrylic acid ("Polyacrylic acid 9,000", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight average molecular weight 9,000)
Polymer A2b-2: Polyacrylic acid ("Polyacrylic acid 50,000", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight average molecular weight 50,000)
Polymer A2b-3: Polyacrylic acid ("Polyacrylic acid 250,000", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight average molecular weight 250,000)

Production Example 9 (Production of Polymer Complex A2-1)
93.0 g of the polymer A2a-2 obtained in Production Example 6 and 873.0 g of ethanol were placed in a polypropylene disposable cup, mixed and dissolved to prepare a 10 mass% polymer A2a-2 solution. 7.0 g of polymer A2b-2 and 27.0 g of ethanol were placed in another disposable cup, mixed and dissolved to prepare a 10 mass% polymer A2b-2 solution. The entire amounts of the polymer A2a-2 solution and the polymer A2b-2 solution were placed in a 2L polypropylene disposable cup, and the mixture was stirred and mixed for 1 hour using a PTFE stirring blade. The solution was dried under reduced pressure at 60 ° C. under vacuum for 8 hours, and then the obtained polymer composite mass was pulverized with a coffee mill to obtain a powdery polymer composite A2- with an average particle size (median diameter) of 2.1 μm. I got 1. The oil absorption of the polymer complex A2-1 is shown in Table 3.

Production Examples 10-12 (Production of Polymer Complex A2-2 to A2-4)
The polymer complex A2-2 to A2-4 was produced in the same manner as in Production Example 9 except that the component (A2a) and the component (A2b) shown in Table 3 were used in the mass ratios shown in Table 3. The oil absorption of the polymer complex A2-2 to A2-4 is shown in Table 3.

The oil absorption of the polymer A2a-4 obtained in Production Example 8 is also shown in Table 3.

Production Example 13 (Production of Polymer A3a-1)
35.1 g of Nt-butylacrylamide (TBAA), 8.8 g of n-butyl acrylate (BA), 3.1 g of acrylate (AA), ethyl acetate 101 in a 1 L glass separable flask as a reaction vessel. .7 g and 7.1 g of ion-exchanged water were added, and the temperature was raised to 40 ° C. while stirring using a stirring blade made of polytetrafluoroethylene (PTFE) to dissolve the monomer and make it uniform.
Next, put 81.9 g of TBAA, 20.5 g of BA, 7.2 g of AA, 198.9 g of ethyl acetate, 16.6 g of ion-exchanged water, and a stirrer piece in a 500 mL beaker, and 40 while stirring with a magnetic stirrer. The temperature was raised to ° C. to dissolve the monomer and homogenize it to prepare a monomer solution for dropping. In addition, 2,2'-azobis (2,4-dimethylvaleronitrile) ("V-65B", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., oil-soluble azopolymerization), which is a polymerization initiator, is added to 38.3 g of ethyl acetate. An initiator solution in which 0.4 g of the initiator) was dissolved was prepared.
A dropping funnel with a temperature control function was attached to the separable flask, and the dropping monomer solution was placed in the dropping funnel. The inside of the reaction vessel including the dropping funnel was depressurized to 400 hPa, held for 30 seconds, and the operation of blowing nitrogen and returning to normal pressure was repeated 5 times to perform nitrogen substitution. After the temperature inside the reaction vessel was raised to 62 ° C., the dropping monomer solution and the initiator solution were each dropped onto the reaction vessel over 2 hours, then held at 62 ° C. for 4 hours, and then heated to 80 ° C. , 80 ° C. was maintained for 1 hour for polymerization and aging. After cooling, ethanol was added and diluted until the total amount became 1 L. Reprecipitation was carried out with a solution of water / ethanol mixed at a mass ratio of 80/20, the supernatant was removed, the mixture was dried under reduced pressure at 80 ° C. for 12 hours, and pulverized with a coffee mill to obtain polymer A3a-1. The weight average molecular weight of the polymer A3a-1 was 600,000 (g / mol).

Production Examples 14 to 15 (Production of Polymers A3a-2 to A3a-3)
Polymer A3a-2 and polymer A3a-3 were produced in the same manner as in Production Example 13 except that the ratio of the monomers used was changed to the mass ratio shown in Table 4 and the polymerization initiator used was changed to 0.4 g. Manufactured. Table 4 shows the ratio of the monomers forming the structural units in the polymer and the weight average molecular weight.

Production Example 16 (Production and evaluation of polymer complex A3-1)
Put 240.0 g of ethyl acetate and a stirrer piece in a 500 mL beaker, and while stirring with a magnetic stirrer, add 30.0 g of the polymer A3a-1 obtained in Production Example 13 little by little to dissolve the polymer solution. Prepared. Next, 436.5 g of ion-exchanged water and 0.6 g of sodium N-stearoyl-N-methyltaurine (“NIKKOL SMT”, manufactured by Nikko Chemicals Co., Ltd.) as an emulsifier were placed in a 1 L beaker, and a homomixer (ROBOMICS, Primix) was added. Co., Ltd.) was mixed to obtain an emulsion.
In a 50 mL screw tube bottle, 1.1 g of zinc oxide 1 (MZX-304OTS, manufactured by Teika Co., Ltd., zinc oxide treated with triethoxycaprylylsilane) and 30.0 g of ethyl acetate were put into an ultrasonic cleaner (UT-). 205, manufactured by Sharp Co., Ltd., was irradiated with ultrasonic waves for 15 minutes to disperse zinc oxide 1 to obtain a dispersion liquid. This dispersion was added to the polymer solution, stirred at room temperature (25 ° C.) to make it uniform, quickly added to the emulsion in its entirety, and mixed at a rotation speed of 5000 rpm for 5 minutes using a homomixer. This was stirred with a PTFE stirring blade for 3 hours and then filtered through a 255 mesh nylon mesh. Ethyl acetate was removed from the filtrate using an evaporator, and then freeze-dried to obtain a powdery polymer composite A3-1 having an average particle size (median diameter) of 3 μm. Table 4 shows the peak intensity ratio and the oil absorption amount of the polymer complex A3-1 at a wave number of 1730 cm- ^{1 in the IR spectrum.}

Production Examples 17-18 (Production of Polymer Complexes A3-2 and A3-3)
Polymer complexes A3-2 and A3-3 were produced in the same manner as in Production Example 16 except that the components (A3a) and components (A3b) shown in Table 4 were used in the mass ratios shown in Table 4. Table 4 shows the peak intensity ratio and the oil absorption amount of the polymer complexes A3-2 and A3-3 in the IR spectrum at a wave number of 1730 cm- ^1.

The oil absorption of the polymer A3a-1 obtained in Production Example 13 is also shown in Table 4.

The components listed in Table 4 are as follows.
TBAA: t-Butylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
AA: Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
BA: n-Butyl acrylate ("Butyl acrylate", manufactured by Tokyo Chemical Industry Co., Ltd.)
Zinc oxide 1: "MZX-304OTS", manufactured by TAYCA CORPORATION, zinc oxide treated with triethoxycaprylylsilane, average particle size 35 nm
Zinc oxide 2: "MZY-505M", manufactured by TAYCA CORPORATION, silicone-treated zinc oxide, average particle size 25 nm

In the polymer complexes of Production Examples 16 to 18, since the ^{peak intensity ratio [polymer component (A3a) / polymer complex] at 1730 cm-1} in the IR spectrum exceeds 1, the polymer component (A3a) and the component (A3b) ) And are compounded.

Examples 1 to 35, Comparative Examples 1 to 9 (Manufacturing and evaluation of water-in-oil emulsified cosmetics)
The oil phase components shown in Tables 5 to 10 were mixed. The crushed powder phase components shown in Tables 5 to 10 were added thereto and dispersed by a disper. Then, the aqueous phase components shown in Tables 5 to 10 were added, dispersed with a disper, and then stirred with a homomixer to obtain a water-in-oil emulsified cosmetic (foundation) of each example.
The evaluation was performed using the obtained cosmetics. The results are shown in Tables 5-10.

As shown in Tables 5 to 10, the cosmetics of the present invention can suppress the shine of the skin when a long time has passed after being applied to the skin, can suppress the secondary adhesion of the cosmetics, and are uniform without color unevenness. A bright shade can be maintained.

According to the cosmetic of the present invention, it is possible to suppress the shine of the skin after a long time has passed since it was applied to the skin. In addition, it is possible to suppress secondary adhesion of cosmetics, and it is possible to maintain a uniform and bright color without uneven color.

Claims (10)

The following components (A) to (C);
(A) Organic powder having a composition oil having a mass ratio of oleic acid and squalane of 1: 2 and having an oil absorption of 3 g / g or more (B) Silicone-based film forming agent (C) Ester oil is contained in the component (A). ) Is 0.1% by mass or more and 20% by mass or less. The first aspect of claim 1, wherein the component (A) contains a polymer containing a structural unit (a-1) derived from a monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 or more and 10 or less carbon atoms. Cosmetics. The component (A) contains a structural unit (a-1) derived from monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 or more and 10 or less carbon atoms, and two or more polymerizable unsaturated groups. The cosmetic according to claim 2, which is a crosslinked polymer (A1) containing a structural unit (a1-2) derived from a crosslinkable monomer having a crosslinkable monomer. The cosmetic according to claim 2, wherein the component (A) is at least a polymer complex (A2) in which the following polymer component (A2a) and the polymer component (A2b) are composited.
(A2a): Polymer having a structural unit (a-1) derived from monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 to 10 carbon atoms (A2b): Derived from (meth) acrylic acid. Polymers other than (A2a), including the structural unit (a2-2) The cosmetic according to claim 2, wherein the component (A) is at least a polymer complex (A3) in which the following polymer component (A3a) and a metal compound (A3b) are composited.
(A3a): A structural unit (a-1) derived from a monofunctional (meth) acrylamide having a hydrocarbon group-containing group having 1 to 10 carbon atoms, and a structural unit derived from (meth) acrylic acid (meth). Polymer (A3b) containing a3-2): One or more metal compounds selected from the group consisting of metal oxides, metal hydroxides and metal chlorides. Any one of claims 1 to 5, wherein the component (B) is at least one selected from the group consisting of trimethylsiloxysilicic acid (B1), fluorosilicone resin (B2), and acrylic silicone resin (B3). Cosmetics listed in. The cosmetic according to any one of claims 1 to 6, wherein the content of the component (B) is 0.1% by mass or more and 25% by mass or less. The cosmetic according to any one of claims 1 to 7, wherein the content of the component (C) is 0.1% by mass or more and 20% by mass or less. The cosmetic according to any one of claims 1 to 8, wherein the mass ratio [(A) / (C)] of the component (A) to the component (C) is 0.1 or more and 15 or less. The cosmetic according to any one of claims 1 to 9, wherein the mass ratio [(A) / (B)] of the component (A) to the component (B) is 0.1 or more and 20 or less.