阅读说明：本技术 具有碳硅氧烷树枝状大分子结构的共聚物、以及含有该共聚物的组合物、化妆料原料、成膜剂及化妆料 (Copolymer having carbosiloxane dendrimer structure, and composition, cosmetic raw material, film-forming agent and cosmetic containing the copolymer ) 是由 早田達央 杉浦常仁 枳梖正圭 松叶将史 于 2020-03-12 设计创作，主要内容包括：提供一种具有碳硅氧烷树枝状大分子结构的共聚物、含有该共聚物的组合物、化妆料原料、成膜剂及化妆料、该共聚物等的制备方法,该共聚物的特征在于,显著降低具有碳硅氧烷树枝状大分子结构的单体含量。一种共聚物及其用途,该共聚物为具有含有能够自由基聚合的有机基团的碳硅氧烷树枝状大分子结构的不饱和单体(a1)和具有自由基聚合性乙烯基的与成分(a1)不同的不饱和单体(a2)的共聚物,相对于共聚物,未反应不饱和单体(a1)及衍生自该未反应不饱和单体(a1)的饱和单体的含量为2500ppm以下。(Provided are a copolymer having a carbosiloxane dendrimer structure, a composition containing the copolymer, a cosmetic raw material, a film-forming agent, a cosmetic, a method for producing the copolymer, and the like, wherein the copolymer is characterized in that the content of a monomer having a carbosiloxane dendrimer structure is significantly reduced. A copolymer of an unsaturated monomer (a1) having a carbosiloxane dendrimer structure containing an organic group capable of radical polymerization and an unsaturated monomer (a2) having a radical polymerizable vinyl group, which is different from the component (a1), wherein the content of an unreacted unsaturated monomer (a1) and a saturated monomer derived from the unreacted unsaturated monomer (a1) is 2500ppm or less relative to the copolymer, and use thereof.)

1. A copolymer which is an unsaturated monomer (a1) having a carbosiloxane dendrimer structure containing an organic group capable of radical polymerization and

a copolymer of an unsaturated monomer (a2) having a radically polymerizable vinyl group, which is different from the component (a1),

the content of the unreacted unsaturated monomer (a1) and the saturated monomer derived from the unreacted unsaturated monomer (a1) is 2500ppm or less with respect to the copolymer.

2. The copolymer according to claim 1, wherein the mass% of the component (a1) is 20 mass% or more with respect to the total mass of the component (a1) and the component (a2) constituting the copolymer.

3. The copolymer according to claim 1 or 2, wherein the component (a1) is an unsaturated monomer having a carbosiloxane dendrimer structure represented by formula (1),

formula (1):

[ chemical formula 1]

{ in the formula (I) { in the formula (II),

z is a 2-valent organic group,

p is 0 or 1, and p is,

R¹and R²Each independently an alkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms,

when i is 1, L1 is a silylalkyl group represented by the following formula (2),

[ chemical formula 2]

(in the formula (I) shown below,

z and p are as defined above,

R¹and R²In the same manner as defined above, the first and second substrates,

i is an integer of 1 to 10 representing the total number of layers of the silylalkyl group,

Lⁱ⁺¹is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group and the silylalkyl group, and when i ═ c (c is an integer of 1 to 10 representing the layer of the silylalkyl group), L isⁱ⁺¹Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and when i < c, Lⁱ⁺¹Is said silylalkyl group, aⁱAn integer of 0 to 3).

4. A copolymer composition characterized by containing, as a main component,

the copolymer composition comprising the copolymer according to any one of claims 1 to 3,

And one or more alcohols (C) and/or oils (D).

5. A cosmetic raw material characterized in that it comprises the copolymer according to any one of claims 1 to 3.

6. A film forming agent, characterized in that it comprises a copolymer according to any one of claims 1 to 3.

7. A cosmetic material, characterized in that it comprises a copolymer according to any one of claims 1 to 3.

8. A cosmetic characterized in that it comprises the copolymer composition according to claim 4.

9. A cosmetic material, characterized in that it comprises a copolymer according to any one of claims 1 to 3 and

comprises at least one selected from the group consisting of water (B), alcohols (C), an oil (D), a powder or a colorant (E), a surfactant (F), an oil-soluble gelling agent (G), an organically modified clay mineral (H), a silicone resin (I), a silicone rubber (J), a silicone elastomer (K), an organically modified silicone (L), an ultraviolet-shielding component (M), and a water-soluble polymer (N).

10. The cosmetic according to any one of claims 7 to 9, wherein the cosmetic is one or more cosmetic selected from the group consisting of a skin care product, a hair product, an antiperspirant product, a deodorant product, a cosmetic product, and an ultraviolet protection product.

11. A method for producing a copolymer according to any one of claims 1 to 3, characterized by comprising adding an unsaturated monomer (a1) having a carbosiloxane dendrimer structure containing an organic group capable of radical polymerization and a monomer having a carbosiloxane dendrimer structure

A step of adding a polymerization initiator to an unsaturated monomer (a2) having a radically polymerizable vinyl group, which is different from the component (a1), to perform a radical polymerization reaction,

and comprises a step (I): after at least two hours following the first addition of the polymerization initiator in the free-radical polymerization,

and (Ia) adding a polymerization initiator which is the same as or different from the polymerization initiator added for the first time.

12. The method of producing a copolymer according to claim 11, wherein the step (I) further comprises a step (Ib) of adding a monomer (a 2') having a radically polymerizable vinyl group having a boiling point of less than 160 ℃ under normal pressure (1atm) to promote a radical polymerization reaction of the unreacted component (a 1).

13. The method for producing a copolymer according to claim 11 or 12, further comprising a step (II): and (ii) distilling off the unreacted unsaturated monomer or saturated monomer remaining in the system under normal pressure or reduced pressure after the step (I).

14. The method for producing a copolymer according to any one of claims 11 to 13, further comprising a step (III): a step of subjecting the unreacted unsaturated monomer remaining in the system to a hydrogenation reaction to convert the unsaturated monomer into a saturated monomer.

15. The method for producing a copolymer according to any one of claims 11 to 14, further comprising a step (IV): adding one or more alcohols (C) and/or oils (D) to the system to remove the reaction solvent in the radical polymerization reaction.

Technical Field

The present invention relates to a copolymer having a carbosiloxane dendrimer structure characterized by significantly reducing the content of a monomer having a carbosiloxane dendrimer structure, a composition containing the copolymer, a cosmetic raw material, a film-forming agent, and a cosmetic, and further relates to a method for producing the copolymer having the carbosiloxane dendrimer structure and a method for producing the copolymer composition.

Background

It is known that a copolymer having a carbosiloxane dendrimer structure, which has excellent film-forming properties, is used in a cosmetic to improve the makeup retention effect of the cosmetic, and to improve water resistance, sebum resistance, and the like (for example, patent document 1 and the like). The copolymer having a carbosiloxane dendrimer structure is formed by radical copolymerization of an unsaturated monomer having a carbosiloxane dendrimer structure with other unsaturated monomers.

On the other hand, in recent years, in addition to the improvement of durability of the above-mentioned cosmetic materials, there has been a demand for cosmetic materials having low irritation to skin and hair, but since radical polymerizable unsaturated monomers have such a problem of irritation, copolymers and copolymer compositions having a small amount of unreacted monomers are required. However, unsaturated monomers having a carbosiloxane dendrimer structure or saturated monomers derived therefrom are so-called macromonomers having a relatively large molecular weight, and have a problem that they are generally difficult to remove from the copolymer or composition thereof by distillation.

For example, in patent document 1, a purification method of reprecipitating the obtained copolymer with methanol and drying the obtained solid is proposed, but a large amount of methanol is required, and it is difficult to redisperse or dissolve the obtained solid in a cosmetic oil agent, and it is not suitable for the actual production of a liquid composition. Also, methanol used for purification itself has irritation and toxicity, and such residue is worried about. In addition to this, when a polar functional group such as a carboxylic acid-modifying group is introduced into a copolymer having a carbosiloxane dendrimer structure, it becomes a polar molecule, methanol becomes a poor solvent, and thus it is necessary to change to another solvent, but, for example, a copolymer obtained in ethanol or the like and an unsaturated monomer having a carbosiloxane dendrimer structure are both dissolved, and thus there is a technical problem that reprecipitation cannot be performed.

In addition, in order to reduce the odor of the unsaturated monomer having a carbosiloxane dendrimer structure and other unsaturated monomers remaining in the system, patent document 2 proposes to reduce the odor by converting the remaining saturated monomers into corresponding esters (saturated monomers) through a hydrogenation reaction. However, there is a problem that an equal amount of the hydrogenated unreacted monomer (saturated monomer) derived from the unsaturated monomer having a carbosiloxane dendrimer structure remains in the copolymer, and it is difficult to achieve the purpose of reducing the monomer having a carbosiloxane dendrimer structure. In addition, there is a problem that the hydrogenation reaction itself requires a special apparatus, and particularly, mass production cannot be easily carried out.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2000-63225

Patent document 2: japanese patent laid-open No. 2014-40512

Disclosure of Invention

Problems to be solved by the invention

In view of the above-mentioned problems and technical circumstances, an object of the present invention is to provide a copolymer having a carbosiloxane dendrimer structure, which has low irritation and excellent safety performance, and has high purity, by significantly reducing the content of a monomer having a carbosiloxane dendrimer structure, a composition containing the copolymer, a cosmetic raw material, a film-forming agent, and a cosmetic. It is another object of the present invention to provide a copolymer having a carbosiloxane dendrimer structure and a method for producing the copolymer composition, which can be easily carried out on an industrial production scale.

Means for solving the problems

As a result of intensive studies by the present inventors, it was found that in radical copolymerization of an unsaturated monomer having a carbosiloxane dendrimer structure and other unsaturated monomers, a polymerization initiator is added in two steps with a time difference set for the addition, additional other unsaturated monomers are optionally added to react the unreacted unsaturated monomer having a carbosiloxane dendrimer structure, and after this process, the content of the monomer having a carbosiloxane dendrimer structure can be significantly reduced by distilling the unreacted unsaturated monomer or saturated monomer remaining in the system under normal pressure or reduced pressure, thereby completing the present invention. The copolymer having a carbosiloxane dendrimer structure of the present invention is characterized in that the content of monomers having a carbosiloxane dendrimer structure (unsaturated monomers and saturated monomers) which are generally difficult to remove is very low.

That is, the first aspect of the present invention is a copolymer of an unsaturated monomer (a1) having a carbosiloxane dendrimer structure containing a radical-polymerizable organic group and an unsaturated monomer (a2) having a radical-polymerizable vinyl group, which is different from the component (a1), wherein the content of the unreacted unsaturated monomer (a1) and the saturated monomer derived from the unreacted unsaturated monomer (a1) is 2500ppm or less relative to the copolymer. Among them, the mass% of the component (a1) is preferably 20 mass% or more with respect to the total mass of the component (a1) and the component (a2) constituting the copolymer.

The second aspect of the present invention is a copolymer composition containing the above-mentioned copolymer and one or more alcohols (C) and/or oils (D).

The third aspect of the present invention is a cosmetic raw material, a film-forming agent and a cosmetic containing the above copolymer or the composition thereof.

The fourth aspect of the present invention is a method for producing the above-mentioned copolymer, which comprises adding an unsaturated monomer (a1) having a carbosiloxane dendrimer structure containing an organic group capable of radical polymerization and

a step of adding a polymerization initiator to an unsaturated monomer (a2) having a radically polymerizable vinyl group, which is different from the component (a1), to perform a radical polymerization reaction, the method comprising the step (I):

and (Ia) a step of adding a polymerization initiator which is the same as or different from the polymerization initiator added for the first time, after at least two hours have elapsed after the first addition of the polymerization initiator in the radical polymerization reaction.

The production method optionally comprises, in the step (I), a step (Ib) of adding a radically polymerizable vinyl group-containing monomer (a 2') having a boiling point of less than 160 ℃ under normal pressure (1atm) to accelerate the radical polymerization of the unreacted component (a1), and further,

the method may further comprise a step (II): and (ii) distilling off the unreacted unsaturated monomer or saturated monomer remaining in the system under normal pressure or reduced pressure after the step (I).

The preparation method can also comprise a working procedure (III): the step of hydrogenating the unreacted unsaturated monomer remaining in the system to convert the unsaturated monomer into a saturated monomer may further comprise the step (IV): adding one or more alcohols (C) and/or oils (D) to the system to remove the reaction solvent in the radical polymerization reaction.

Advantageous effects

According to the present invention, a copolymer having a carbosiloxane dendrimer structure, a composition containing the copolymer, a cosmetic material, a film-forming agent, and a cosmetic can be provided which are low in irritation, excellent in safety, and high in purity. Further, the present invention provides a copolymer having such a carbosiloxane dendrimer structure and a method for producing the copolymer composition, which can be easily carried out on an industrial production scale.

Detailed Description

Herein, "(meth) acrylic acid" means to include both acrylic acid and methacrylic acid. Similarly, "(meth) acrylate", "(meth) acryloyloxy", "(meth) acrylamide" also indicate two types including acrylate and methacrylate, acryloyloxy and methacryloyloxy, acrylamide and methacrylamide, respectively. Herein, "cosmetic" and "makeup" are used interchangeably.

The copolymer having a carbosiloxane dendrimer structure of the present invention is obtained by copolymerizing a component (a1) of an unsaturated monomer having a carbosiloxane dendrimer structure and a component (a2) of an unsaturated monomer different from the component (a 1). Preferably, the component (a1) is an unsaturated monomer having a carbosiloxane dendrimer structure represented by formula (1).

Formula (1):

[ chemical formula 1]

{ in the formula (I) { in the formula (II),

z is a 2-valent organic group,

p is 0 or 1, and p is,

R¹and R²Each independently an alkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms,

when i is 1, L1 is a silylalkyl group represented by the following formula (2),

[ chemical formula 2]

(in the formula (I) shown below,

z and p are as defined above,

R¹and R²In the same manner as defined above, the first and second substrates,

i is an integer of 1 to 10 representing the total number of layers of the silylalkyl group,

Lⁱ⁺¹is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group and the silylalkyl group, and when i ═ c (c is an integer of 1 to 10 representing the layer of the silylalkyl group), L isⁱ⁺¹Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and when i < c, Lⁱ⁺¹Is said silylalkyl group, aⁱAn integer of 0 to 3).

Further, the carbosiloxane dendrimer structure is a chemical structure highly branched radially from one silicon atom, and i, which represents the total number of layers of the silylalkyl group, represents the degree of branching. For example, the total number of layers i is 1 and Lⁱ⁺¹The carbosiloxane dendrimer structure means the following structure when such as methyl.

[ chemical formula 3]

(in the formula, Z, p, R¹And R²As defined above, a¹Is an integer of 0 to 3)

Similarly, when layer i is 2 and L isⁱ⁺¹Such as methyl, the carbosiloxane dendrimer structure means the following structure (but with the setting p ═ 1).

[ chemical formula 4]

(in the formula, Z, R¹And R²As defined above, a¹And a²Is an integer of 0 to 3)

Preferably, a and a are¹And a²Is 0, the following structure is particularly preferable as the carbosiloxane dendrimer structure.

[ chemical formula 5]

(in the formula, Z and R²Same as defined above)

[ chemical formula 6]

(in the formula, Z and R²Same as defined above)

The unsaturation-containing group of the component (a1) is not limited as long as it has unsaturation capable of radical polymerization, and examples thereof include vinyl group, allyl group, (meth) acryloyl group, and the like. In particular, the component (a1) is preferably the acrylate-based monomer or methacrylate-based monomer having a carbosiloxane dendrimer structure described above, and among them, particularly preferred unsaturated monomers are those in which an unsaturated group represented by the following structure is bonded to a silicon atom (Si) through- (Z) p-or-Z-in the carbosiloxane dendrimer structure described above, or those in which a silicon atom (Si) is directly bonded thereto.

[ chemical formula 7]

(in the formula, R⁴Is a hydrogen atom or a methyl group, R⁵Is an alkylene group having 1 to 10 carbon atoms. ) Or

[ chemical formula 8]

(in the formula, R⁴And R⁵As defined above. ) The acryloyl or methacryloyl group represented contains an organic group.

More specifically, the present component includes an unsaturated monomer having a carbosiloxane dendrimer structure represented by the following average composition formula.

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

[ chemical formula 21]

[ chemical formula 22]

The polymerization of the unsaturated monomer having a carbosiloxane dendrimer structure can be carried out by the production methods described in Japanese patent application laid-open No. 11-1530, Japanese patent application laid-open No. 2000-63225, Japanese patent application laid-open No. 2001-192424, and Japanese patent application laid-open No. 2014-40512.

The component (a2) constituting the copolymer having a carbosiloxane dendrimer structure of the present invention is an unsaturated monomer different from the component (a1), and is preferably a monomer having a radical polymerizable vinyl group, and the kind thereof is not particularly limited. More specifically, it is a vinyl monomer having no carbosiloxane dendrimer structure in the molecule.

As such a vinyl monomer, there are generally monomers as starting materials of organic resins called vinyl resins, and specific examples thereof include: lower alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate; glycidyl (meth) acrylate; higher (meth) acrylates such as n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate; higher fatty acid esters such as vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, and vinyl stearate; aromatic vinyl monomers such as styrene, vinyltoluene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and vinylpyrrolidone; amide group-containing vinyl monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, isobutoxymethoxy (meth) acrylamide, and N, N-dimethyl (meth) acrylamide; hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate: fluorine-containing vinyl monomers such as trifluoropropyl (meth) acrylate, perfluorobutylethyl (meth) acrylate, and perfluorooctylethyl (meth) acrylate; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate and 3, 4-epoxycyclohexylmethyl (meth) acrylate; carboxylic acid-containing vinyl monomers such as (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiglycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether; unsaturated group-containing organosilicon compounds such as (meth) acryloyloxypropyltrimethoxysilane, a (branched or linear) polydimethylsiloxane having a (meth) acryloyl group at one end, and a polydimethylsiloxane having a styryl group at one end; butadiene; vinyl chloride; vinylidene chloride; (meth) acrylonitrile; dibutyl fumarate; maleic anhydride; dodecyl succinic anhydride; glycidyl (meth) acrylate: alkali metal salts, ammonium salts, and organic amine salts of radical polymerizable unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid; radical polymerizable unsaturated monomers having a sulfonic acid group such as styrenesulfonic acid, and alkali metal salts, ammonium salts, and organic amine salts thereof; quaternary ammonium salts derived from (meth) acrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, methacrylic acid esters of alcohols having a tertiary amine group such as diethylamine methacrylate, and quaternary ammonium salts thereof.

Furthermore, a polyfunctional vinyl monomer may be used, and examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, a diol di (meth) acrylate which is an adduct of ethylene oxide or propylene oxide of bisphenol A, a diol di (meth) acrylate which is an adduct of ethylene oxide or propylene oxide of hydrogenated bisphenol A, and the like, And (meth) acryloyl group-containing monomers such as triethylene glycol divinyl ether, polydimethylsiloxanes end-capped with styrene groups at both ends, and unsaturated group-containing organosilicon compounds such as polydimethylsiloxanes end-capped with methacryloxypropyl groups at both ends.

Further, an organosilicon compound having a vinyl radical polymerizable unsaturated group and a hydrolyzable group can also be used. In this case, the film strength is hardened and the water-proof durability is improved, so that it is preferable. Examples of the radical polymerizable group include a (meth) acryloyloxy group-containing organic group, a (meth) acrylamide group-containing organic group, a styryl group-containing organic group, an alkenyl group having 2 to 10 carbon atoms, a vinyloxy group, an allyloxy group, and the like.

Similarly, an unsaturated monomer having at least one acidic group or a salt thereof in the molecule can also be used. The unsaturated monomer having at least one acid group or a salt thereof in a molecule is a compound having a radically polymerizable vinyl group and at least one acid group or a salt thereof in a molecule. Examples of acidic groups include carboxylic acids, sulfonic acids, and phosphonic acids. Examples of such salts include alkali metal salts, alkaline earth metal salts, basic amino acid salts, ammonium salts, alkylammonium salts, alkylamine salts, alkanolamine salts, specifically, sodium salts, potassium salts, magnesium salts, calcium salts, L-arginine salts, L-histidine salts, L-lysine salts, ammonium salts, triethanolamine salts, aminomethylpropanediol salts and complex salts thereof. Compounds having such acidic groups dissociate in aqueous solution from protons (H) at a specific pH value⁺) Or combine with cationic components in the solution to form salts, thereby changing the hydrophilicity-hydrophobicity of the compound. Class ISimilarly, compounds having salts of acidic groups also undergo salt dissociation at a particular pH and exhibit hydrophilic-hydrophobic changes in the compound. Therefore, by appropriately blending a compound having such an acidic group or a salt thereof in a cosmetic composition, the cosmetic composition exhibits an effect of being easily washed off during washing even if the cosmetic composition has excellent makeup-holding performance.

Similarly, in order to improve the water repellency and the like of the copolymer containing a carbosiloxane dendrimer structure in the present invention, an unsaturated monomer having a fluorine-containing organic group such as a perfluoroalkyl group can be used. For example, a vinyl monomer such as an acrylic monomer or a methacrylic monomer having a fluorine-containing organic group such as a perfluoroalkyl group.

The copolymer having a carbosiloxane dendrimer structure of the present invention is obtained by copolymerizing the above-mentioned component (a1) and component (a2), and the mass ratio of (a1) to (a2) is preferably 10: 90 to 90: 10, more preferably 20: 80 to 85: 15, and still more preferably 30: 70 to 60: 40. In particular, the mass% of the component (a1) is preferably 20 mass% or more and 30 mass% or more based on the total mass of the component (a1) and the component (a2), and particularly preferably 20 mass% to 60 mass% based on the total monomer unit of the component (a 1).

The copolymer containing a carbosiloxane dendrimer structure in the present invention includes a step of adding a polymerization initiator to a raw material composition containing the monomer to perform a polymerization reaction. Next, the method may optionally further comprise a step of contacting the obtained polymerization reactant with a nickel catalyst or a palladium catalyst to perform a hydrogenation reaction.

As a polymerization method used in the polymerization reaction, a radical polymerization method or an ionic polymerization method is used, but the radical polymerization method is preferable. Among the radical polymerization methods, the solution polymerization method is preferably used. The solution polymerization is carried out by reacting the monomer composition comprising the component (a1) and the component (a2) in a solvent at a temperature of 50 to 150 ℃ for 3 to 20 hours in the presence of a radical initiator. As the solvent used in the polymerization reaction, examples thereof include: aliphatic hydrocarbons such as hexane, octane, decane, cyclohexane and the like; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like; esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, etc.; alcohols such as methanol, ethanol, isopropanol, butanol, etc.; and organosiloxane oligomers such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, and the like. Such a solvent may be used alone or in combination of two or more.

As the radical initiator, conventionally known compounds generally used in the radical polymerization method are used, and specific examples thereof include: azobis compounds such as 2, 2 ' -azobis (isobutyronitrile), 2 ' -azobis (2-methylbutyronitrile), and 2, 2 ' -azobis (2, 4-dimethylvaleronitrile); and organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, and the like. The radical initiator may be used alone or in combination of two or more. Preferably, the amount of the radical initiator used is in the range of 0.1 to 5 parts by weight relative to 100 parts by weight of the total of the monomer compositions.

Also, a chain transfer agent may be added at the time of polymerization. Specifically, as the chain transfer agent, examples thereof include: mercapto compounds such as 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, polydimethylsiloxane having mercaptopropyl group, and the like; and halides such as dichloromethane, chloroform, carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysilane, and the like.

The polymerization reactants may be contacted with a nickel catalyst or a palladium catalyst as a hydrogenation catalyst. By contacting with such a catalyst, vinyl groups of the unreacted monomer remaining in the polymerization reaction product are saturated, and thus irritation or odor upon addition to the cosmetic can be reduced. Examples of the nickel catalyst include a nickel/diatomaceous earth catalyst and a raney nickel catalyst, but are not necessarily limited thereto. Examples of the palladium catalyst include palladium compounds such as tetrakis (triphenylphosphine) palladium (0) and dichlorobis (triphenylphosphine) palladium (II), palladium on carbon, palladium hydroxide on carbon, platinum oxide, and the like, but are not necessarily limited thereto.

The temperature of the polymerization reactant in contact with the nickel catalyst or the palladium catalyst is 50 to 200 ℃, preferably 70 to 130 ℃. The pressure is 1 to 1000kg/cm²(absolute pressure), preferably 2 to 100kg/cm². The contact time is 1 to 15 hours, preferably 3 to 10 hours. The reaction may be carried out in a solvent, and the solvent used in the polymerization may be used as it is or may be replaced with a solvent. The solvent which can be used is the same as that described for the polymerization reaction.

[ content of monomer having carbosiloxane dendrimer Structure and significance thereof ]

The copolymer having a carbosiloxane dendrimer structure of the present invention is characterized in that the content of the unreacted unsaturated monomer (a1) of the present invention and a saturated monomer derived from the unreacted unsaturated monomer (a1) is 2500ppm or less relative to the copolymer. Preferably, such a monomer having a carbosiloxane dendrimer structure has a content of 2400ppm or less, and a copolymer having a reduced content of 2000ppm or less and 1500ppm or less can be also prepared as necessary by using the preparation method described hereinafter, and as a cosmetic raw material, a copolymer having an extremely low content of the monomer having a carbosiloxane dendrimer structure with a risk of causing irritation can be obtained.

The present invention has an object to provide a copolymer having a reduced content of carbosiloxane dendrimer structure-containing monomers (unsaturated monomers and saturated monomers as hydrogenated products thereof) which have a risk of causing irritation and have properties of being difficult to separate or remove from the copolymer by a conventional distillation method, as a cosmetic raw material or film-forming agent when the content of unreacted unsaturated monomer (a1) and saturated monomers derived from the unreacted unsaturated monomer (a1) is reduced to less than the reduced amount, the present copolymer is used in an amount of about 4 mass% of the total amount of cosmetic materials in a general composition, and when incorporated into cosmetic materials (including external preparations or quasi drugs), the monomer content in the final composition or preparation is 100ppm or less, the influence of which is substantially negligible. Further, the monomer can be reduced in content in the copolymer by the method described below, and even if the content is reduced, the function as a cosmetic raw material or film-forming agent of the copolymer containing a carbosiloxane dendrimer structure is not impaired.

The content of the unreacted unsaturated monomer (a1) and the saturated monomer derived from the unreacted unsaturated monomer (a1) in the above-mentioned copolymer can be determined by a method such as High Performance Liquid Chromatography (HPLC), and can be calculated based on the peak intensity thereof. Further, even in the copolymer composition, cosmetic raw material or film-forming agent in which the copolymer is dispersed in the organic solvent (D) or the like, the monomer content of the copolymer portion alone or excluding the dispersion medium thereof can be easily calculated. In addition, the content of the unreacted unsaturated monomer (a1) and the saturated monomer derived from the unreacted unsaturated monomer (a1) in the final cosmetic composition can be specified relatively accurately by the same method, and the cosmetic composition of the present invention contains the copolymer of the present invention and the monomer content is 100ppm or less with respect to the total amount of the cosmetic composition.

For example, when a copolymer in which the above-mentioned specific unreacted monomer is reduced is blended in a cosmetic, the blending amount is not particularly limited, but the copolymer of the present invention containing no solvent, solvent or the like may be blended in an amount of 0.1 to 4% by mass, preferably 1 to 4% by weight, based on the total amount of the cosmetic, as the single mass. In particular, when the amount is in this range, a cosmetic can be provided in which the amount of the carbosiloxane dendrimer structure-containing monomer that imparts a function such as film-forming property to the cosmetic and has a risk of causing irritation and a property of being difficult to separate or remove from the copolymer by a conventional distillation method is 100ppm or less, and the monomer is not substantially contained.

Similarly, in the case of dispersing a copolymer reduced in the above-mentioned specific unreacted monomer in the organic solvent (D) or the like described below and the content of the copolymer is 40 mass%, a copolymer composition, a cosmetic raw material or a film-forming agent can be provided in which the content of a monomer containing a carbosiloxane dendrimer structure, which has a risk of generating irritation and has a property of being difficult to separate or remove from the copolymer by a conventional distillation method, is 1000ppm or less and, in addition, the monomer is not substantially contained.

The copolymer of the present invention can be incorporated into a cosmetic or the like as it is or as a composition dissolved in a solvent or dispersed in a dispersion medium. Such a solvent and a dispersion medium are not particularly limited, but examples thereof include an alcohol (C) and an oil (D), and particularly, in practical use as a cosmetic raw material or a film-forming agent, a mode of a copolymer composition containing one or more dispersion media selected from the alcohol (C) and the oil (D) is particularly preferable.

[ copolymer composition ]

That is, the copolymer composition of the present invention contains a copolymer in which the above-mentioned specific unreacted monomer is reduced and at least one selected from the group consisting of the alcohol (C) and the oil (D). When the copolymer of the first invention is blended into a cosmetic, a solution dissolved in a solvent, a dispersion dispersed in a dispersion medium, or a solid form such as a powder, a granule, or a block can be used. In particular, it is preferable that the copolymer according to the present invention is incorporated into a cosmetic by dissolving or dispersing in one or more alcohols (C) and/or oils (D) to prepare a copolymer composition containing the copolymer and such a dispersion medium.

The copolymer of the present invention is particularly excellent in compatibility and dispersibility with various oils, and a uniform polymer composition can be obtained over a long period of time. Such a composition can be incorporated directly into a cosmetic, and is extremely useful as a cosmetic raw material or a film-forming agent from the viewpoint of handling properties and storage stability. Specifically, the copolymer composition of the present invention may preferably contain 5 to 1000 parts by mass of at least one oil agent per 100 parts by mass of the copolymer, more preferably 50 to 500 parts by mass of the copolymer composition, and still more preferably 100 to 400 parts by mass of the copolymer composition. Further, when a copolymer composition comprising a copolymer and an oil agent is obtained, it is particularly preferable that the copolymer from which the solvent and the unreacted monomer are removed after the polymerization reaction is uniformly dispersed in the oil agent by using mechanical force, and the volatile solvent in the polymerization reaction is replaced by the oil agent as described above. Further, as described above, in the case of the copolymer composition containing the alcohol (C) and/or the oil (D) as the dispersion medium and having a copolymer content of 40 mass%, it is possible to provide or design a composition having a content of the carbosiloxane dendrimer structure-containing monomer of 1000ppm or less.

Alcohols (C)

The copolymer of the present invention can be dispersed or dissolved in an alcohol for use, and also can coexist as a formulation for a cosmetic material because the copolymer of the present invention has a predetermined affinity with an alcohol which is a general-purpose component of a cosmetic material. As the alcohol, one or two or more kinds of polyhydric alcohols and/or lower monohydric alcohols can be used. As the lower alcohol, examples thereof include ethanol, isopropanol, n-propanol, tert-butanol, sec-butanol and the like, with ethanol being preferred. Examples of the polyhydric alcohol include: dihydric alcohols such as 1, 3-propanediol, 1, 3-butanediol, 1, 2-butanediol, propanediol, trimethylene glycol, tetramethylene glycol, 2, 3-butanediol, pentamethylene glycol, 2-butene-1, 4-diol, dibutylene glycol, pentanediol, hexanediol, octanediol, etc.; trihydric alcohols such as glycerin, trimethylolpropane, 1, 2, 6-hexanetriol, and the like; four or more polyhydric alcohols such as pentaerythritol and xylitol; and sugar alcohols such as sorbitol, mannitol, maltitol, maltotriose, sucrose, erythritol, glucose, fructose, starch degradation products, maltose, xylitol, starch degradation sugar-reducing alcohols, and the like. Examples of the low molecular weight polyol include polyol polymers such as diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerol, and polyglycerol. Among them, ethanol, 1, 3-propanediol, 1, 3-butanediol, sorbitol, dipropylene glycol, glycerin, and polyethylene glycol are particularly preferable. Among such alcohols, isopropyl alcohol and the like can also be used as the above-mentioned reaction solvent, and therefore a polymerization reaction composition containing such alcohols can be directly used as a copolymer composition.

Oiling agent (D)

The copolymer of the present invention can be dispersed or dissolved in an oil agent for use, and examples thereof include animal oils, vegetable oils, synthetic oils, and the like which are commonly used in cosmetics. The oil agent can be solid, semi-solid or liquid, and can also be non-volatile, semi-volatile or volatile oil agent. The oil agent is used for imparting lubricity to the skin or hair, softening the skin, and imparting a moist feeling. Further, an oil agent may be used for the purpose of diluting the copolymer of the present invention to obtain a copolymer composition, and in particular, the copolymer is liquid at 5 to 100 ℃, and preferably, at least one selected from the group consisting of a silicone oil agent (D1) and an organic oil agent (D2), and the type, viscosity, and the like of such an oil agent can be appropriately selected depending on the type and use of the cosmetic. Such an oil agent is blended in the cosmetic of the present invention together with the above-mentioned copolymer composition.

Silicone oils (D1)

The silicone oil is generally hydrophobic, and the molecular structure thereof may be linear, cyclic or branched. The viscosity of the silicone oil at 25 ℃ is usually 0.65-100000 mm²In the range of 0.65 to 10000mm, preferably²In the range of/s. The silicone oil may be volatile, and preferably is volatile.

Specific examples of the silicone oils include cyclic organopolysiloxanes, linear organopolysiloxanes, and branched organopolysiloxanes. Among them, linear organopolysiloxanes, branched organopolysiloxanes, and cyclic organopolysiloxanes having volatility are preferable.

As the silicone oil, for example, an organopolysiloxane represented by the following general formula (3), (4), or (5) can be used.

[ chemical formula 23]

(in the formula, R⁹Is selected from the group consisting of a monovalent unsubstituted or fluorine-or amino-substituted alkyl group having 1 to 30 hydrogen atoms, hydroxyl group or carbon atoms, aryl group, alkoxy group and a group represented by (CH3)3SiO { (CH3)2SiO } lSi (CH3)2CH2CH2- (1 is an integer of 0 to 1000), a' is an integer of 0 to 3, b is an integer of 0 to 1000, c is an integer of 0 to 1000, provided that 1. ltoreq. b + c. ltoreq.2000)

[ chemical formula 24]

(in the formula, R⁹D is an integer of 0 to 8, e is an integer of 0 to 8, but 3. ltoreq. d + e. ltoreq.8)

[ chemical formula 25]

(in the formula, R⁹F is an integer of 1 to 4, g is an integer of 0 to 500, the same as defined above

Examples of the monovalent alkyl group, aryl group and alkoxy group having 1 to 30 carbon atoms which may be unsubstituted or substituted with fluorine or amino include linear or branched alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl and dodecyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl and cyclohexyl; aryl groups having 6 to 30 carbon atoms such as phenyl, tolyl, xylyl, naphthyl, and the like; alkoxy groups having 1 to 30 carbon atoms such as methoxy, ethoxy, and propoxy; and groups in which hydrogen atoms bonded to carbon atoms of such groups are at least partially substituted with fluorine or amino groups. Preferably, the alkyl group or the aryl group is unsubstituted, more preferably, the alkyl group or the aryl group has 1-6 carbon atoms and is unsubstituted, and particularly preferably, the alkyl group or the aryl group is methyl, ethyl or phenyl.

Specific examples of the silicone oil having such a structure include, more specifically, as the cyclic organopolysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1-diphenylhexamethylcyclotetrasiloxane, 1, 3, 5, 7-tetravinyltetramethylcyclotetrasiloxane, 1, 3, 5, 7-tetramethylcyclotetrasiloxane, tris (3, 3, 3-trifluoropropyl) trimethylcyclotrisiloxane, 1, 3, 5, 7-tetrakis (3-methacryloxypropyl) tetramethylcyclotetrasiloxane, 1, 3, 5, 7-tetrakis (3-acryloyloxypropyl) tetramethylcyclotetrasiloxane, 1, 3, 5, 7-tetrakis (3-carboxypropyl) tetramethylcyclotetrasiloxane, 1, 3, 5, 7-tetrakis (3-vinyloxypropyl) tetramethylcyclotetrasiloxane, 1, 3, 5, 7-tetrakis (p-vinylphenyl) tetramethylcyclotetrasiloxane, 1, 3, 5, 7-tetrakis [3- (p-vinylphenyl) propyl ] tetramethylcyclotetrasiloxane, 1, 3, 5, 7-tetrakis (N-acryloyl-N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1, 3, 5, 7-tetrakis (N, N-bis (lauroyl) -3-aminopropyl) tetramethylcyclotetrasiloxane and the like.

Examples of the linear organopolysiloxane include: dimethylpolysiloxane blocked at both ends of the molecular chain by trimethylsiloxy groups (high-viscosity dimethylsilicone having a viscosity of 2 mPa. s or 6 mPa. s, etc., low viscosity to 100 ten thousand mPa. s, etc.), organohydrogenpolysiloxane, methylphenylpolysiloxane blocked at both ends of the molecular chain by trimethylsiloxy groups, dimethylsiloxane/methylphenylsiloxane copolymer blocked at both ends of the molecular chain by trimethylsiloxy groups, diphenylpolysiloxane/diphenylsiloxane copolymer blocked at both ends of the molecular chain by trimethylsiloxy groups, trimethylpentaphenyltrisiloxane, phenyl (trimethylsiloxy) siloxane, methylalkylpolysiloxane blocked at both ends of the molecular chain by trimethylsiloxy groups, dimethylpolysiloxane/methylalkylsiloxane copolymer blocked at both ends of the molecular chain by trimethylsiloxy groups, organopolysiloxane/methylalkylsiloxane copolymer, and the like, Dimethylsiloxane/methyl (3, 3, 3-trifluoropropyl) siloxane copolymer end-capped at both ends of the molecular chain with trimethylsiloxy groups, α, ω -dihydroxypolydimethylsiloxane, α, ω -diethoxypolydimethylsiloxane, 1, 1, 1, 3, 5, 5, 5-heptamethyl-3-octyltrisiloxane, 1, 1, 1, 3, 5, 5, 5-heptamethyl-3-dodecyltrisiloxane, 1, 1, 1, 3, 5, 5, 5-heptamethyl-3-hexadecyltrisiloxane, tri-trimethylsiloxymethylsilane, tri-trimethylsiloxyalkylsilane, tetra-trimethylsiloxysilane, tetramethyl-1, 3-dihydroxydisiloxane, octamethyl-1, 7-dihydroxytetrasiloxane, hexamethyl-1, 5-diethoxytrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, higher alkoxy-modified silicone, higher fatty acid-modified silicone, and the like.

Examples of the branched organopolysiloxane include methyltri-trimethylsiloxysilane, ethyltri-trimethylsiloxysilane, propyltri-trimethylsiloxysilane, tetra-trimethylsiloxysilane, phenyltri-trimethylsiloxysilane, and the like.

When the cosmetic of the present invention or the present composition is used as a cosmetic raw material, if at least one of such silicone oils is contained, the stability with time can be improved and the refreshing feeling peculiar to silicone oil can be realized. Among the silicone oils, decamethylcyclopentasiloxane having a viscosity in the low viscosity range of 2 to 6mPa · s, linear organopolysiloxane, 1, 1, 1, 3, 5, 5, 5-heptamethyl-3-octyltrisiloxane (also referred to as "octylmethicone"), and tris-trimethylsiloxymethylsilane (also referred to as "M3T") are particularly preferably used.

Organic oil (D2)

Typical organic oils include hydrocarbon oils (D2-1), fatty acid ester oils (D2-2), higher alcohols, higher fatty acids, oils and fats, and fluorine oils, but the present invention is not limited thereto, and the organic oils are preferably liquid at 5 to 100 ℃. Also, hydrocarbon oils and/or fatty acid ester oils are preferred. These may be used alone or in combination, and may be used in combination with the silicone oil agent. By combining an appropriate oil agent, the composition and/or the cosmetic can be provided with a desired touch while the stability with time of the composition and/or the cosmetic is improved. By blending the silicone oil agent, a refreshing feeling peculiar to silicone oil can be imparted, by using a high-volatility oil agent, a refreshing feeling can be imparted to the skin, and by using a hydrocarbon oil and/or a fatty acid ester oil in combination with the silicone oil agent, a moisturizing and moisturizing feeling (also referred to as a "moist feeling") and a smooth feeling can be imparted to the skin or hair.

As the hydrocarbon oil (D2-1), examples thereof include liquid paraffin, light liquid isoparaffin, heavy liquid isoparaffin, vaseline, n-paraffin, isoparaffin, isododecane, isohexadecane, polyisobutylene, hydrogenated polyisobutylene, polybutene, ozokerite (ozokerite), ceresin (ceresin), microcrystalline wax, paraffin wax, polyethylene/polypropylene wax, squalane, squalene, pristane, polyisoprene, and the like. In particular, isododecane is preferably used in the composition of the present invention because it has excellent volatility, is excellent in compatibility with other cosmetic raw materials and affinity (compounding stability), and imparts a refreshing feeling to the skin.

As the fatty acid ester oil (D2-2), examples thereof include hexyldecyl octanoate, hexadecyl octanoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, hexyldecyl dimethyl octanoate, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol dioleate, glyceryl monostearate, glyceryl monooleate, glyceryl tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, ditrimethylolpropane triethylhexanoate, ditrimethylolpropane (isostearic acid/sebacic acid) ester, trimethylolpropane tricaprylate, caprylic acid ester, isopropyl myristate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, decyl myristate, octyl myristate, hexyl caprylate, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol dioleate, glyceryl monostearate, glyceryl monooleate, glyceryl tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, ditrimethylolpropane triethylhexanoate, ditrimethylolpropane (isostearic acid/sebacic acid) ester, trimethylolpropane tricaprylate, and the like, Trimethylolpropane triisostearate, diisopropyl adipate, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, diisostearyl malate, hydrogenated castor oil monoisostearate, N-alkyldiol monoisostearate, octyldodecyl isostearate, isopropyl isostearate, isocetyl isostearate, ethylene glycol di-2-ethylhexanoate, hexadecyl 2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, octyldodecyl acetate, ethyl oleate, octyldodecyl oleate, neopentyl glycol didecanoate, triethyl citrate, 2-ethylhexyl succinate, dioctyl succinate, isocetyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, isopropyl stearate, N-butyl stearate, ethyl oleate, N-octyl stearate, octyl dodecyl stearate, isopropyl stearate, ethyl hexyl stearate, isopropyl stearate, ethyl hexyl stearate, ethyl, Diethyl sebacate, dioctyl sebacate, dibutyl octyl sebacate, cetyl palmitate, octyl dodecyl palmitate, octyl palmitate, 2-ethylhexyl palmitate, 2-hexyl palmitate, 2-heptyl undecyl palmitate, cholesterol 12-hydroxystearate, dipentaerythritol fatty acid ester, 2-hexyl decyl myristate, ethyl laurate, 2-octyl dodecyl N-lauroyl-L-glutamate, di (cholesterol/behenyl/octyl dodecyl) N-lauroyl-L-glutamate, di (phytosterol/behenyl/octyl dodecyl) N-lauroyl-L-glutamate, N-lauroyl-L-glutamic acid di (phytosterol/octyldodecyl) ester, isopropyl N-lauroyl sarcosinate, diisostearyl malate, neopentyl glycol dicaprylate, isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, isotridecyl isononanoate, diethylpentanediol dineopentanoate, methylpentanediol dineopentanoate, octyldodecyl neodecanoate, 2-butyl-2-ethyl-1, 3-propanediol dioctanoate, pentaerythritol tetracaprylate, hydrogenated pentaerythritol pentaerythrite, pentaerythritol triethylhexanoate, dipentaerythritol (hydroxystearic acid/stearic acid/abietic acid) ester, polyglycerol tetraisostearate, glycerol tetraisostearate, Polyglyceryl-10 nonaisostearate, polyglyceryl-8 deca (erucic/isostearic/ricinoleic), diglyceryl (hexyldecanoic/sebacic) oligoester, glycol distearate (ethylene glycol distearate), diisopropyl dimerate, diisostearyl dimerate, distearyl dimerate, behenyl dimerate, dioleyl dioleate, diisoisostearyl dimerate, hydrogenated rosin dilinoleate condensate, hardened castor oil dilinoleate, hydroxyalkyl dilinoleyl ether, triisocaprylic glyceride, triisostearic glyceride, Glyceryl trimyristate, glyceryl triisopalmitate, glyceryl trioctoate, glyceryl trioleate, glyceryl diisostearate, glyceryl tri (caprylate/caprate), glyceryl tri (caprylate/caprate/myristate/stearate), hydrogenated rosin triglyceride (hydrogenated ester gum), rosin triglyceride (ester gum), glyceryl behenate, glyceryl di-2-heptyl undecanoate, diglyceryl isostearate myristate, cholesterol acetate, cholesterol pelargonate, cholesterol stearate, cholesterol isostearate, cholesterol oleate, cholesterol 12-hydroxystearate, cholesterol macadamia nut oil fatty acid ester, the phytosterol macadamia nut oil fatty acid, the phytosterol isostearate, cholesterol soft lanolin fatty acid ester, cholesterol hard lanolin fatty acid ester, glycerol fatty acid ester, glyceryl diisostearate, glyceryl monostearate, glyceryl stearate, Cholesterol long chain branched chain fatty acid ester, cholesterol long chain alpha-hydroxy fatty acid, octyl dodecyl ricinoleate, octyl dodecyl lanolin fatty acid, octyl dodecyl erucic acid, hardened castor oil isostearate, avocado oil fatty acid ethyl ester, lanolin fatty acid isopropyl ester and the like. Lanolin and lanolin derivatives are also useful as fatty acid ester oils.

In addition to the above, oils and fats, higher alcohols, higher fatty acids, fluorine-based oils and the like may be used as the oil agent, or two or more kinds may be used in combination. For example, two or more of the following oils may be combined. Hereinafter, other oils that can be used in the present invention are more specifically exemplified. Specifically, the use of one or more oils selected from the group consisting of fats and oils, higher alcohols, higher fatty acids, and fluorine-containing oils is exemplified.

Examples of the oils and fats include natural animal and vegetable oils and fats and semisynthetic oils and fats, such as avocado oil, linseed oil, almond oil, white wax, perilla oil, olive oil, cacao butter, kapok wax, torreya oil, carnauba wax, liver oil, candelilla wax, beef tallow, beef shank fat, beef bone fat, hardened beef tallow, almond oil, spermaceti, hardened oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, camellia oil, safflower oil, shea butter, paulownia oil, cinnamon oil, jojoba wax, olive squalane, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, japanese tung oil, rice bran wax, germ oil, horse fat, peach kernel oil, palm kernel oil, castor oil, hardened castor oil, methyl ricinoleate, sunflower oil, grape seed oil, laurel fruit wax, bay wax, palm oil, palm kernel oil, sesame oil, palm kernel oil, sunflower oil, palm kernel oil, sesame oil, palm kernel oil, sesame oil, palm kernel oil, sesame oil, palm kernel oil, and palm kernel oil, sesame oil, olive oil, sesame oil, olive oil, sesame oil, olive oil, sesame oil, olive oil, sesame oil, olive oil, sesame oil, jojoba oil, hydrogenated jojoba esters, macadamia nut oil, beeswax, mink oil, cottonseed oil, cotton wax, wood wax kernel oil, montan wax, coconut oil, hardened coconut oil, tricocouma fatty acid glyceride, lanolin, groundnut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, isopropyl lanolate, POE lanolin alcohol ether, POE lanolin alcohol acetate, polyethylene glycol lanolin fatty acid esters, POE hydrogenated lanolin alcohol ether, egg yolk oil, and the like. However, POE means polyoxyethylene.

Examples of the higher alcohol include higher alcohols having 10 to 30 carbon atoms. The higher alcohol is a saturated or unsaturated monohydric aliphatic alcohol, and the hydrocarbon group of the higher alcohol may be linear or branched, but linear is more preferable. Examples of the higher alcohol having 10 to 30 carbon atoms include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, cetyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecanol, cholesterol, sitosterol, phytosterol, lanosterol, hydrogenated lanosterol, POE cholesterol ether, monostearyl glyceryl ether (batyl alcohol), monooleyl glyceryl ether (batyl alcohol), and the like. In the present invention, it is preferable to use a higher alcohol having a melting point of 40 to 80 ℃ alone, or to combine a plurality of higher alcohols so that the melting point is 40 to 70 ℃. These higher alcohols are particularly useful as bases for cosmetics in the form of emulsions because they form aggregates called α -gels together with surfactants and increase the viscosity of the preparation to stabilize the emulsion.

As the higher fatty acid, examples thereof include: lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid, and the like.

Examples of the fluorine-based oil include perfluoropolyether, perfluorodecalin, perfluorooctane, and the like.

[ cosmetics and optional ingredients thereof ]

The present invention relates to a cosmetic composition containing the copolymer. Among these, in the case where the copolymer in which the above-mentioned specific unreacted monomer is reduced is blended in the cosmetic composition, the preferable range of the blending amount is as described above in the foregoing, and the cosmetic composition having the above-mentioned specific unreacted monomer content of 100ppm or less can be designed or provided.

The cosmetic of the present invention may contain various cosmetic raw materials in addition to the above-mentioned copolymer. The cosmetic may include both a case where the copolymer composition according to the third aspect of the present invention is incorporated into a cosmetic and a case where the copolymer and other cosmetic raw materials are separately incorporated into a cosmetic. Such an arbitrary component is not particularly limited, and preferable examples thereof include a cosmetic material containing at least one selected from the group consisting of water (B), an alcohol (C), an oil agent (D), a powder or a colorant (E), a surfactant (F), an oil-soluble gelling agent (G), an organically modified clay mineral (H), a silicone resin (I), a silicone rubber (J), a silicone elastomer (K), an organically modified silicone (L), an ultraviolet shielding component (M), and a water-soluble polymer (N).

The water (B) used in the cosmetic of the present invention is a medium for the cosmetic, does not contain components harmful to the human body, and may be clean, and examples thereof include tap water, purified water such as distilled water or ion-exchanged water, mineral water, deep sea water, and the like. Further, the buffer solution may be in the form of physiological saline, a phosphoric acid buffered aqueous solution, or the like, as necessary.

Examples of the alcohols (C) include the same compounds.

Examples of the oil agent (D) include the same compounds.

Powder or colorant (E)

The cosmetic preparation containing the copolymer or copolymer composition of the present invention may further contain a powder or a colorant, particularly any powder used in cosmetics (including powder/pigment used as a colorant). When the powder or the colorant is used in a common cosmetic, it can be used regardless of the shape (spherical, rod-like, needle-like, plate-like, flake-like, irregular, spindle-like, bowl-like, raspberry-like, etc.) or particle size (aerosol-like, fine particle, pigment-like, etc.), particle structure (porous, non-porous, secondary aggregation, etc.), but when such a powder and/or colorant is blended as a pigment, it is preferable to blend one or two or more kinds selected from inorganic pigment powder, organic pigment powder, and resin powder having an average particle size in the range of 1nm to 20 μm.

Specific examples of the powder or the colorant include inorganic powder, organic powder, surfactant metal salt powder (metal soap), colored pigment, pearl pigment, metal powder pigment, silicone elastomer powder, and the like, and further, a composite thereof may be used. Further, such powder or colorant contains an ingredient that functions as an ultraviolet-screening ingredient.

Specifically, examples of the inorganic powder include: titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, lepidolite, biotite, lepidolite (lepidolite), silicic acid, silicic anhydride, aluminum silicate, sodium magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite (vermicite), Higilite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, aluminum oxide, aluminum hydroxide, boron nitride, and the like; as the organic powder, there can be exemplified: polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk powder (silk powder), nylon powder, 12 nylon, 6 nylon, silicone powder, silicone rubber powder, silicone elastomer spherical powder coated with polymethylsilsesquioxane on the surface, polymethylsilsesquioxane spherical powder, styrene/acrylic acid copolymer, divinylbenzene/styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder, starch powder, lauroyl lysine, and the like; as the surfactant metal salt powder, there are illustrated, for example: zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc palmitate, zinc laurate, zinc cetyl phosphate, calcium cetyl phosphate, sodium zinc cetyl phosphate, and the like; as the colored pigment, there are exemplified: inorganic red pigments of iron oxide red, iron oxide, iron hydroxide, iron titanate, inorganic brown pigments such as gamma-iron oxide, inorganic yellow pigments such as yellow iron oxide, yellow ocher, inorganic black pigments such as black iron oxide, carbon black, inorganic violet pigments such as manganese violet, cobalt violet, chromium hydroxide, chromium oxide, cobalt titanate, inorganic green pigments such as iron blue, ultramarine, inorganic blue pigments such as red No. 3, red No. 104, red No. 106, red No. 201, red No. 202, red No. 204, red No. 205, red No. 220, red No. 226, red No. 227, red No. 228, red No. 230, red No. 401, red No. 505, yellow No. 4, yellow No. 5, yellow No. 202, yellow No. 203, yellow No. 204, yellow No. 401, blue No. 1, blue No. 2, blue No. 404, green No. 3, green No. 201, green No. 204, yellow No. 5, yellow No. 202, yellow No. 1, blue No. 2, blue No. 404, blue No. 3, blue No. 201, blue No. 5, blue No. 1, blue No. 5, blue No. 3, blue No. 5, blue No. 1, blue No. 5, blue No. 1, blue No. 5, blue No. 1, blue No. 5, blue No. 201 No. 5, blue No. 201 No. 5, blue No. 201 No. 5, blue No. 201 No. 5, blue No, Examples of the colorant include a colorant obtained by laking a tar-based colorant such as green 205, orange 201, orange 203, orange 204, orange 206, orange 207, and the like, and a colorant obtained by laking a natural colorant such as carminic acid, laccaic acid, carthamin (carthamin), Brazilin (Brazilin), crocin (crocin), and the like; as the pearl pigment, there are illustrated, for example: titanium oxide-coated mica, mica titanium, iron oxide-treated mica titanium, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated talc, fish scale foil, titanium oxide-coated colored mica, and the like; examples of the metal powder pigment include metal powders of aluminum, gold, silver, copper, platinum, and stainless steel.

The silicone elastomer powder is a powdery component among the silicone elastomers (K) described below. These are crosslinked products of a linear diorganopolysiloxane composed mainly of diorganosiloxy units (D units), and an organohydrogenpolysiloxane having a silicon-bonded hydrogen atom in a side chain or a terminal and a diorganopolysiloxane having an unsaturated hydrocarbon group such as an alkenyl group in a side chain or a terminal can be preferably obtained by a crosslinking reaction under a hydrosilylation reaction catalyst. The silicone elastomer powder is softer and more elastic than a silicone resin powder containing T units and Q units, and further, has excellent oil absorption, and therefore can absorb oil on the skin and prevent removal of makeup.

The silicone elastomer powder may be in various shapes such as spherical, flat, irregular, and the like. The silicone elastomer powder may be in the form of an oil dispersion. In the cosmetic of the present invention, it is preferable to blend a silicone elastomer powder having a particle shape, an average primary particle diameter measured by a laser diffraction/scattering method and/or a primary particle diameter observed by an electron microscope in the range of 0.1 to 50 μm, and a spherical shape. The hardness of the silicone elastomer forming the silicone elastomer powder is preferably 80 or less, more preferably 65 or less, as measured by a type a durometer in accordance with JIS K6253 "hardness test methods for vulcanized rubber and thermoplastic rubbers".

Furthermore, silicone elastomer powders can also be used in the form of aqueous dispersions in the cosmetic compositions of the invention. As commercially available products of such aqueous dispersions, examples thereof include BY29-129, PF-2001 PIF Emulsion and the like, which are available from Toray Dow Corning.

The silicone elastomer powder may be optionally subjected to surface treatment with silicone resin, silica, or the like. As the surface treatment, examples thereof include treatment methods described in Japanese patent laid-open No. Hei 2-243612, Japanese patent laid-open No. Hei 8-12545, Japanese patent laid-open No. Hei 8-12546, Japanese patent laid-open No. Hei 8-12524, Japanese patent laid-open No. Hei 9-241511, Japanese patent laid-open No. Hei 10-36219, Japanese patent laid-open No. Hei 11-193331, Japanese patent laid-open No. 2000-281523 and the like. Further, the silicone elastomer powder corresponds to the crosslinked silicone powder listed in "cosmetic-type compounding ingredient standard". As commercially available products of the silicone elastomer Powder, examples thereof include Trefil E-506S, Trefil E-508, 9701 Cosmetic Powder, 9702Powder and the like, which are available from Toray Dow Corning.

In addition, it is particularly preferable that a part or the whole of such powder or colorant is subjected to a water repellent treatment. This allows the oil to be stably blended in the oil phase. Further, such powders or colorants may be used as a composite with each other or after surface-treated with a common oil agent, an organic silicon compound other than the organopolysiloxane copolymer of the present invention, a fluorine compound, a surfactant, or the like.

Examples of the other water repellent treatment include a treatment of the powder or the colorant with various water repellent surface treatment agents, and examples thereof include a methylhydrogenpolysiloxane treatment, a silicone resin treatment, an organosiloxane treatment such as a silicone rubber treatment, an acrylic silicone treatment, a fluorinated silicone treatment, a metal soap treatment such as a zinc stearate treatment, a silane coupling agent treatment, a silane treatment such as an alkylsilane treatment, a fluorine compound treatment such as a perfluoroalkylsilane, a perfluoroalkyl phosphate salt, and a perfluoropolyether treatment, an amino acid treatment such as an N-lauroyl-L-lysine treatment, an oil treatment such as a squalane treatment, and an acrylic acid treatment such as an alkyl acrylate treatment, and one or more of them can be used in combination.

The powder or the colorant is preferably treated with another powder dispersant or a surface treatment agent, and in particular, the powder or the colorant can be treated into a slurry by a novel powder treatment agent and a treatment method proposed by the inventors of the present application in international publication No. WO2009/022621, japanese patent application laid-open No. 2011-148784, japanese patent laid-open No. 2011-149017, japanese patent laid-open No. 2011-246704, japanese patent laid-open No. 2011-246705, japanese patent laid-open No. 2011-246706, international publication No. WO2009/022621, international publication No. WO2011/049246, international publication No. WO2011/049248, japanese patent application laid-open No. 2011-286973, and the like. Since the novel treatment agent is more excellent in the inherent touch improvement effect, dispersion stability and other properties, the effect of further improving the function, touch, storage stability and the like of a cosmetic can be expected by using the novel cosmetic raw material of the present invention in combination.

In addition, a part or the whole of such powder or colorant may be subjected to hydrophilization treatment. In this way, a powder or a colorant for the aqueous phase can be blended.

In addition, a part or the whole of the powder or the colorant may be subjected to hydrophobization and hydrophilization treatment. Thereby, the powder itself can be given emulsification properties. As a commercially available product, MZY-500SHE manufactured by the company TAYCA, Japan, and the like are exemplified.

The powder or colorant (E) in the copolymer composition or cosmetic of the present invention may be used in one or more kinds as needed, and the amount thereof is not particularly limited, but may be in the range of 0.1 to 99.5% by mass, preferably 1 to 99% by weight, based on the total amount of the composition or cosmetic. In particular, the amount of the powdery solid cosmetic is preferably in the range of 80 to 99 mass% of the total amount of the cosmetic.

The cosmetic preparation containing the copolymer composition or copolymer of the present invention may contain a surfactant (F) as an optional component. Depending on the purpose, the surfactant (F) may be used in combination with one or more surfactants selected from the group consisting of silicone surfactants (F1), anionic surfactants (F2), cationic surfactants (F3), nonionic surfactants (F4), amphoteric surfactants (F5), and semipolar surfactants (F6).

Examples of the silicone surfactant (F1) include polyglyceryl-modified silicones, diglyceryl-modified silicones, glyceryl-modified silicones, sugar-modified silicones, fluoropolyether-modified silicones, polyether-modified silicones, carboxylic acid-modified silicones, linear silicone-polyether block copolymers (such as polysiloxane-13), long-chain alkyl/polyether co-modified silicones, polyglyceryl-modified silicone elastomers, diglyceryl-modified elastomers, glycerin-based modified elastomers, polyether-modified elastomers, and the like. Further, a surfactant obtained by simultaneously applying an alkyl branch, a linear silicone branch, a siloxane dendrimer branch, or the like and a hydrophilic group to the silicone-based or elastomer-based compounds as required can be preferably used. As commercially available products, examples thereof include SH3771M, SH3772M, SH3773M, SH3775M, BY22-008M, BY11-030, ES-5373 FORMULATOID, ES-5612 FORMULAID, ES-5300 FORMULAID, ES-5600SILICONE GLYCEROL EMULSIIR (all available from Toray Dow Corning Co., Ltd.).

As the anionic surfactant (F2), examples thereof include saturated or unsaturated fatty acid salts (sodium laurate, sodium stearate, sodium oleate, sodium linolenate, etc.), alkyl sulfates, alkylbenzene sulfonic acids (hexylbenzene sulfonic acid, octylbenzene sulfonic acid, dodecylbenzene sulfonic acid, etc.) and salts thereof, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyethylene alkyl sulfate ester salts, sulfosuccinic acid alkyl ester salts, polyoxyalkylene alkylphenyl ether sulfates, alkane sulfonates, octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, alkyl sulfonates, polyoxyethylene alkylphenyl ether sulfates, polyoxyalkylene alkyl ether acetates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, acyl glutamates, α -acyl sulfonates, alkyl sulfates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, acyl glutamates, alkyl sulfonates, alkyl sulfates, etc., and the salts of salts, Alkylallyl sulfonate, alpha-olefin sulfonate, alkylnaphthalene sulfonate, alkane sulfonate, alkyl or alkenyl sulfate, alkylamide sulfate, alkyl or alkenyl phosphate, alkylamide phosphate, alkanoylalkyltaurate, N-acylamino acid salt, sulfosuccinate, alkyl ether carboxylate, amide ether carboxylate, alpha-sulfo fatty acid ester salt, alanine derivative, glycine derivative, arginine derivative. Examples of the salt include alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts, alkanolamine salts such as triethanolamine salts, and ammonium salts are also included.

As the cationic surfactant (F3), examples thereof include alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, tallowalkyltrimethylammonium chloride, behenyltrimethylammonium chloride, stearyltrimethylammonium bromide, behenyltrimethylammonium bromide, distearyldimethylammonium chloride, dicocoyldimethylammonium chloride, dioctyldimethylammonium chloride, di (POE) oleylmethylammonium chloride (2EO), benzalkonium chloride, alkylbenzalkonium chloride, alkyldimethylammonium chloride, benzethonium chloride, stearyldimethylbenzylammonium chloride, lanolin-derived quaternary ammonium salts, diethylaminoethylamide stearate, dimethylaminopropylamide stearate, behenamidopropyldimethylhydroxypropylammonium chloride, stearoylcholinesteramylmethylpyridinium chloride, cetyltrimethylammonium chloride, and the like, Cetyl pyridinium chloride, tall oil alkylbenzyl hydroxyethyl imidazolinium chloride, benzyl ammonium salt.

As the nonionic surfactant (F4), examples thereof include polyglycerin diisostearate or diglycerin polyhydroxystearate, isostearyl glyceryl ether, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene fatty acid diester, polyoxyalkylene resin acid ester, polyoxyalkylene (hardened) castor oil, polyoxyalkylene alkylphenols, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene phenyl ethers, polyoxyalkylene alkyl esters, sorbitol fatty acid ester, polyoxyalkylene sorbitol alkyl esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyglycerol alkyl ethers, polyglycerol fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkyl glycoside fatty acid esters, and the like, Polyoxyalkylene fatty acid bisphenyl ethers, polypropylene glycol, diethylene glycol, polyoxyethylene/polyoxypropylene block polymers, alkylpolyoxyethylene/polyoxypropylene block polymer ethers, fluorine-based surfactants, and the like.

As the amphoteric surfactant (F5), examples thereof include imidazoline type, amide betaine type, alkyl betaine type, alkylamide betaine type, alkylsulfobetaine type, amidosulfobetaine type, hydroxysulfobetaine type, carbonylbetaine type, phosphobetaine type, aminocarboxylic acid type, amidoamino acid type amphoteric surfactants. Specifically, examples thereof include: imidazoline type amphoteric surfactants such as 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazolinium sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethoxy disodium salt, and the like; alkyl betaine-type amphoteric surfactants such as lauryl dimethylamino acetic acid betaine and myristyl betaine; amidobetaine-type amphoteric surfactants such as coconut oil fatty acid amide propyldimethylamino acetic acid betaine, palm kernel oil fatty acid amide propyldimethylamino acetic acid betaine, tallow fatty acid amide propyldimethylamino acetic acid betaine, hardened tallow fatty acid amide propyldimethylamino acetic acid betaine, lauramidopropyldimethylamino acetic acid betaine, myristamidopropyldimethylamino acetic acid betaine, palmitamidopropyldimethylamino acetic acid betaine, stearamidopropyldimethylamino acetic acid betaine, oleamidopropyldimethylamino acetic acid betaine, and the like; alkyl sulfobetaine-type amphoteric surfactants such as coconut oil fatty acid dimethyl sulfopropyl betaine; alkyl hydroxy sulfobetaine-type amphoteric surfactants such as lauryl dimethylamino hydroxysulfobetaine; a betaine phosphate type amphoteric surfactant such as lauryl hydroxy betaine phosphate; sodium N-lauroyl-N '-hydroxyethyl-N' -carboxymethylglyoxalamine, sodium N-oleoyl-N '-hydroxyethyl-N' -carboxymethylglyoxalamine, sodium N-cocoyl-N '-hydroxyethyl-N' -carboxymethylglyoxalamine, potassium N-lauroyl-N '-hydroxyethyl-N' -carboxymethylglyoxalamine, potassium N-oleoyl-N '-hydroxyethyl-N' -carboxymethylglyoxalamine, sodium N-lauroyl-N-hydroxyethyl-N '-carboxymethylglyoxalamine, sodium N-oleoyl-N-hydroxyethyl-N' -carboxymethylglyoxalamine, sodium N-cocoyl-N-hydroxyethyl-N '-carboxymethylglyoxalamine, sodium N-oleoyl-N' -carboxymethylglyoxalamine, sodium N-cocoyl-N '-hydroxyethyl-N' -carboxymethylglyoxalamine, sodium, Amide amino acid type amphoteric surfactants such as N-lauroyl-N-hydroxyethyl-N ', N' -dicarboxymethylethylenediamine monosodium salt, N-oleoyl-N-hydroxyethyl-N ', N' -dicarboxymethylethylenediamine monosodium salt, N-cocoyl-N-hydroxyethyl-N ', N' -dicarboxymethylethylenediamine monosodium salt, N-lauroyl-N-hydroxyethyl-N ', N' -dicarboxymethylethylenediamine disodium salt, N-oleoyl-N-hydroxyethyl-N ', N' -dicarboxymethylethylenediamine disodium salt, and N-cocoyl-N-hydroxyethyl-N ', N' -dicarboxymethylethylenediamine disodium salt.

The semipolar surfactant (F6) may, for example, be an alkylamine oxide surfactant, alkylamine oxide, alkylamide amine oxide or alkylhydroxylamine oxide, and preferably an alkyldimethylamine oxide having 10 to 18 carbon atoms or an alkoxyethyl-dihydroxyethylamine oxide having 8 to 18 carbon atoms is used. Specific examples include dodecyldimethylamine oxide, dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyldimethylamine oxide, hexadecyldimethylamine oxide, stearyldimethylamine oxide, tallow dimethylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, isostearyl dimethylamine oxide, palmitic fatty acid alkyldimethylamine oxide, caprylic amidopropyldimethylamine oxide, capric amidopropyldimethylamine oxide, lauric amidopropyldimethylamine oxide, myristic amidopropyldimethylamine oxide, palmitic acid amidopropyldimethylamine oxide, stearic acid amidopropyl dimethyl amine oxide, isostearic acid amidopropyl dimethyl amine oxide, oleic acid amidopropyl dimethyl amine oxide, ricinoleic acid amidopropyl dimethyl amine oxide, 12-hydroxystearic acid amidopropyl dimethyl amine oxide, palm fatty acid amidopropyl dimethyl amine oxide, palm kernel oil fatty acid amidopropyl dimethyl amine oxide, castor oil fatty acid amidopropyl dimethyl amine oxide, lauric acid amidoethyl dimethyl amine oxide, myristic acid amide ethyl dimethyl amine oxide, palmitic acid amide ethyl dimethyl amine oxide, lauric acid amide ethyl diethyl amine oxide, myristic acid amide ethyl diethyl amine oxide, palmitic acid amide ethyl diethyl amine oxide, lauric acid amide ethyl dihydroxy ethyl amine oxide, myristic acid amide ethyl dihydroxy ethyl amine oxide, and palmitic acid amide ethyl dihydroxy ethyl amine oxide.

The amount of the surfactant (F) to be incorporated in the emulsion composition of the present invention is not particularly limited, but may be, for example, in the range of 0.05 to 90% by weight in the emulsion composition or in the dispersion composition in order to stabilize the emulsion or dispersion, and the amount of the surfactant (F) to be incorporated is preferably 0.1 to 50% by weight, more preferably 0.5 to 25% by weight, per one composition.

Oil soluble gel (G)

As the gelling agent, an oil-soluble gelling agent is preferable, having a gelling or thickening effect. Specific examples thereof include metal soaps of aluminum stearate, magnesium stearate, zinc myristate and the like, amino acid derivatives of N-lauroyl-L-glutamic acid, α, γ -di-N-butylamine and the like, dextrin palmitate, dextrin stearate, dextrin fatty acid esters of dextrin 2-ethylhexanoate palmitate and the like, sucrose palmitate, sucrose fatty acid esters of sucrose stearate and the like, benzylidene derivatives of sorbitol such as monobenzylidene sorbitol, dibenzylidene sorbitol and the like, and the like. These may be used singly or in combination as necessary.

Organically modified clay mineral (H)

Examples of the organically modified clay mineral include dimethyl benzyl dodecyl ammonium montmorillonite clay, dimethyl dioctadecyl ammonium montmorillonite clay, dimethyl alkyl ammonium hectorite, benzyl dimethyl stearyl ammonium hectorite, distearyl dimethyl ammonium chloride-treated magnesium aluminum silicate, and the like. Examples of such commercially available products include Bentone27 (hectorite treated with benzyldimethylstearylammonium chloride, available from National Lead), Bentone38 (hectorite treated with distearyldimethylammonium chloride, available from National Lead).

Silicone resin (I)

The silicone resin is an organopolysiloxane having a highly branched structure, a network structure, or a cage structure, and is liquid or solid at ordinary temperature, provided that it is a silicone resin generally used in cosmetics unless it is contrary to the object of the present invention. As the solid silicone resin, there may be exemplified MQ resins, MDQ resins, MTQ resins, MDTQ resins, TD resins, TQ resins, TDQ resins including any combination of trisilicoalkoxy units (M units) (organic groups are only methyl, methyl and vinyl groups or phenyl groups), disalicoalkoxy units (D units) (organic groups are only methyl, methyl and vinyl groups or phenyl groups), monosilicoalkoxy units (T units) (organic groups are methyl, vinyl, or phenyl groups), and siloxy units (Q units). Examples thereof may include trimethylsiloxysilicacid, polyalkylsilanoxysilicacid, trimethylsiloxysilicacid containing dimethylsiloxy units, and alkyl (perfluoroalkyl) silanoxysilicacid. These silicone resins are oil-soluble, and are particularly preferably soluble in D4 or D5.

Silicone resins form a uniform film when applied to skin, hair, etc. to impart a protective effect against dryness and low temperatures. Further, the silicone resin having such a branched unit is closely attached to the skin or hair to impart gloss and transparency to the skin or hair.

Organic silicon rubber (J)

In the present invention, 1000000mm which will be referred to as silicone rubber may also be mentioned²An organopolysiloxane having an ultra-high viscosity of at least s is used as the silicone oil. The silicone rubber is a straight-chain diorganopolysiloxane with an ultrahigh polymerization degree, and is also called silicone raw rubber or organopolysiloxane rubber. Silicone rubber differs from the oily silicone in that it has a measurable plasticity due to its high degree of polymerization. Examples of the silicone raw gum include substituted or unsubstituted organopolysiloxanes having a dialkylsiloxy unit (D unit) such as dimethylpolysiloxane, methylphenylpolysiloxane, aminopolysiloxane, and methylfluoroalkylpolysiloxane, and organopolysiloxanes having a micro-crosslinked structure thereof, and typical examples thereof include those represented by the general formula: r¹⁰(CH₃)₂SiO{(CH₃)₂SiO}_s{(CH₃)R¹¹SiO}_tSi(CH₃)₂R¹⁰(in the formula, R¹¹Is selected from vinyl, phenyl, C6-20 alkyl, C3-15 aminoalkyl, C3-15 perfluoroalkyl, and C3-15 quaternary ammonium saltOf alkyl groups of (a) terminal group R¹⁰Is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, a phenyl group, a vinyl group, an aminoalkyl group having 3 to 15 carbon atoms, a hydroxyl group and an alkoxy group having 1 to 8 carbon atoms. And s is 2000 to 6000, t is 0 to 1000, and s + t is 2000 to 6000). Among them, dimethylpolysiloxane raw rubber having a polymerization degree of 3000 to 20000 is preferable. The silicone rubber may be incorporated directly into the cosmetic of the present invention or may be incorporated into a liquid rubber dispersion (oil dispersion of silicone rubber) dispersed in an oily silicone.

Examples of such a raw silicone rubber include substituted or unsubstituted organopolysiloxanes having a dialkysiloxane alkoxy unit (D unit) such as dimethylpolysiloxane, methylphenylpolysiloxane, aminopolysiloxane, and methylfluoroalkyl polysiloxane, and organopolysiloxanes having a micro-crosslinked structure thereof, and typical examples thereof include those represented by the general formula: r¹⁰(CH₃)₂SiO{(CH₃)₂SiO}_s{(CH₃)R¹²SiO}_tSi(CH₃)₂R¹⁰(in the formula, R¹²A terminal group R selected from the group consisting of a vinyl group, a phenyl group, an alkyl group having 6 to 20 carbon atoms, an aminoalkyl group having 3 to 15 carbon atoms, a perfluoroalkyl group having 3 to 15 carbon atoms, and an alkyl group having 3 to 15 carbon atoms and containing a quaternary ammonium salt group¹⁰Is a group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, a phenyl group, a vinyl group, an aminoalkyl group having 3 to 15 carbon atoms, a hydroxyl group and an alkoxy group having 1 to 8 carbon atoms. And s is 2000 to 6000, t is 0 to 1000, and s + t is 2000 to 6000). Among them, dimethylpolysiloxane raw rubber having a polymerization degree of 3000 to 20000 is preferable. Also, amino-modified methylpolysiloxane raw rubber having 3-aminopropyl group, N- (2-aminoethyl) 3-aminopropyl group or the like in a side chain or a terminal of the molecule is preferable. In the present invention, the silicone rubber may be used singly or in combination of two or more kinds as required.

The silicone rubber has an ultrahigh polymerization degree, and therefore, has excellent durability to skin and hair, and forms a protective film having excellent air permeability. Thus, silicone rubber is especially an ingredient that imparts moisturization and luster to skin and hair, and imparts a tensile and tight texture to the entire skin and hair during and after use.

For example, the amount of the silicone rubber is in the range of 0.05 to 30% by weight (mass), preferably 1 to 15% by weight (mass) of the total amount of the cosmetic. Further, when the silicone rubber is used as an emulsion composition prepared in advance through an emulsification step (including emulsion polymerization), the incorporation thereof is easier, and the cosmetic of the present invention can be stably incorporated. If the amount of the silicone rubber blended is less than the lower limit, there is a risk that the skin and hair glossing effect will be insufficient.

Silicone elastomer (K)

The silicone elastomer may be blended in any form depending on the purpose, but in particular, it is preferably blended as a crosslinkable organopolysiloxane in addition to the silicone elastomer powder described in the above [ powder (E) ]. The silicone elastomer powder can also be used in the form of an aqueous dispersion in the cosmetic of the invention. As commercially available products of such an aqueous dispersion, BY29-129 and PF-2001 PIF Emulsion, which are available from Toray Dow Corning, Inc., can be mentioned. The incorporation of such an aqueous dispersion (suspension) of the silicone elastomer powder is extremely useful in that the feeling of use of the cosmetic of the present invention can be further improved.

As the crosslinkable organopolysiloxane, a non-emulsifying organopolysiloxane in which an organopolysiloxane chain forms a three-dimensionally crosslinked structure by a reaction with a crosslinkable component or the like and which does not have a hydrophilic portion such as a polyoxyalkylene unit or the like is preferable. Any such crosslinkable organopolysiloxane can be used without limitation on the physical form, the production method, and the like of dilution, properties, and the like, and particularly preferred examples thereof include α, ω -diene crosslinked Silicone elastomers described in U.S. Pat. No. 5654362 (as commercially available products, DC 9040Silicone Elastomer Blend, DC 9041Silicone Elastomer Blend, DC 9045 Silicone Elastomer Blend, DC 9046Silicone Elastomer Blend, available from dow corning). Furthermore, it is also preferable to use a crosslinkable organopolysiloxane having fluidity at room temperature, and examples thereof include 3901 LIQUID SATIN BLEND (available from Dow Corning Co., Ltd.).

Organically modified silicones (L)

Preferably, the organically modified silicone has lipophilicity. Specifically, examples thereof may include amino-modified silicones, aminopolyether-modified silicones, epoxy-modified silicones, carboxyl-modified silicones, amino-acid-modified silicones, methanol-modified silicones, acrylic-modified silicones, phenol-modified silicones, amidoalkyl-modified silicones, aminodiol-modified silicones, alkoxy-modified silicones, in addition to the above. The organically modified silicone may have an alkylene chain, an aminoalkylene chain, or a polyether chain to the extent that the compound does not have hydrophilicity, in addition to the polysiloxane bond as a main chain, and the organically modified group may be contained at one or both ends of a side chain or a terminal of the polysiloxane chain. In the case of using the cosmetic of the present invention as a hair cosmetic, an amino-modified silicone, a methanol-modified silicone, an aminopolyether-modified silicone or an aminodiol-modified silicone may be preferably used, and an amino-modified silicone having a 3-aminopropyl group, an N- (2-aminoethyl) 3-aminopropyl group or the like may be used as a general example.

The higher alkyl-modified silicone, alkyl-modified silicone resin, and polyamide-modified silicone resin which are particularly preferable as the organic-modified silicone will be described below. The higher alkyl-modified silicone is waxy at room temperature and is a useful raw material component for cosmetics. Therefore, the cosmetic of the present invention can be preferably used. Examples of such a higher alkyl-modified silicone wax include methyl long-chain alkyl polysiloxane blocked at both ends of the molecular chain with trimethylsiloxy groups, dimethylpolysiloxane/methyl long-chain alkyl siloxane copolymer blocked at both ends of the molecular chain with trimethylsiloxy groups, long-chain alkyl-modified dimethylpolysiloxane at both ends of the molecular chain, and the like. As such commercially available products, AMS-C30Cosmetic Wax, 2503Cosmetic Wax, etc. (products of Dow Corning, USA) may be mentioned.

In the cosmetic of the present invention, the melting point of the higher alkyl-modified silicone wax is preferably 60 ℃ or higher from the viewpoint of long-lasting cosmetic effect and high-temperature stability.

The alkyl-modified silicone resin is a component that imparts sebum durability, moisture retention, and a fine texture to the cosmetic, and a wax-like resin can be preferably used at room temperature. Preferably, a silsesquioxane resin wax described in Japanese patent laid-open No. 2007-532754 is preferably exemplified. Examples of such commercially available products include SW-8005C30 RESIN WAX (available from Dow Corning, USA).

As the polyamide-modified silicone, there may be mentioned a silicone-based polyamide compound described in U.S. Pat. No. 5981680 (Japanese patent laid-open No. 2000-038450) and Japanese patent laid-open No. 2001-512164, and commercially available products may be mentioned 2-8178Gellant, 2-8179Gellant and the like (products of Dow Corning Co., Ltd.). Polyamide-modified silicones are also used as oily raw materials, in particular as thickening/gelling agents for silicone oils.

Ultraviolet ray preventing component (M)

The ultraviolet screening component contains an inorganic ultraviolet screening component and an organic ultraviolet screening component. Preferably, if the cosmetic of the present invention is a sunscreen cosmetic, it contains at least one inorganic or organic, especially organic, ultraviolet screening component. The copolymer of the present invention has excellent compatibility with an organic uv screening component which is usually hardly soluble, for example, diethylamino hydroxybenzoyl hexyl benzoate known as "Uvinul a", bisethylhexyloxyphenol methoxyphenyl triazine known as "Tinosorb S", 2-cyano-3, 3-diphenylprop-2-enoic acid 2-ethylhexyl ester known as "Octocrylene", other lauric acid type uv absorbers, and the like, and can improve the compounding stability with the copolymer of the present invention.

The inorganic ultraviolet screening component may be prepared by blending the inorganic pigment powder and the metal powder pigment as the ultraviolet screening agent, and examples thereof include titanium oxide, zinc oxide, cerium oxide, low-order titanium oxide, metal oxides such as iron-doped titanium oxide, metal hydroxides such as iron hydroxide, plate-like iron oxide, metal flakes such as aluminum flakes, and ceramics such as silicon carbide. Among them, at least one selected from the group consisting of particulate, plate-like, needle-like or fibrous fine-particle metal oxides and fine-particle metal hydroxides having an average particle diameter in the range of 1 to 100nm is particularly preferable. It is preferable to subject such powder to conventionally known surface treatment such as fluorine compound treatment (perfluoroalkyl phosphate treatment or perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment are preferable), silicone treatment (methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, vapor-phase tetramethyltetrahydrocyclotetrasiloxane treatment are preferable), silicone resin treatment (trimethylsiloxysilicates treatment is preferable), side chain treatment (method of adding an alkyl chain after vapor-phase silicone treatment or the like), silane coupling agent treatment, titanium coupling agent treatment, silane treatment (alkylsilane or alkylsilazane treatment is preferable), oil treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment (stearic acid or myristate is preferable), acrylic resin treatment, acrylic acid resin treatment, and the like, Metal oxide treatment, etc., and preferably, such treatment is performed a plurality of times. Examples thereof include coating the surface of fine particulate titanium oxide with a metal oxide such as silicon oxide or aluminum oxide, followed by surface treatment with an alkylsilane, and the like. Preferably, the total amount of surface treatment is in the range of 0.1 to 50 mass% relative to the powder.

The organic ultraviolet screening component is a lipophilic ultraviolet screening component, and examples thereof include: benzoic acid-based ultraviolet absorbers such as p-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglyceride, N-dipropoxypolyPABA ethyl ester, N-diethoxypolyPABA ethyl ester, N-dimethyl PABA butyl ester, diethylamino hydroxybenzoylbenzoic acid hexyl ester, and the like; anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetyl anthranilate; salicylic acid-based ultraviolet absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropyl phenyl salicylate; octyl cinnamate, ethyl 4-isopropyl cinnamate, methyl 2, 5-diisopropyl cinnamate, ethyl 2, 4-diisopropyl cinnamate, methyl 2, 4-diisopropyl cinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl- α -cyano- β -phenylcinnamate, 2-ethylhexyl- α -cyano- β -phenylcinnamate, mono-2-ethylhexanoyl-di-p-methoxycinnamate, 3, 4, 5-trimethoxycinnamate 3-methyl-4- [ methyl bis (trimethylsiloxy) cinnamate A phenyl) silyl ] butyl ester, etc.; 2, 4-dihydroxybenzophenone, 2 '-dihydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxybenzophenone, 2', benzophenone-based ultraviolet absorbers such as 4, 4 ' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4 ' -methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4 ' -phenyl-benzophenone-2-carboxylate, hydroxy-4-n-octyloxybenzophenone, and 4-hydroxy-3-carboxybenzophenone; 3- (4 ' -methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid, ethyl urocanite, 2-phenyl-5-methylbenzoxazole, 2 ' -hydroxy-5-methylphenylbenzotriazole, 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, dibenzylazine, dianisil formylmethane, 4-methoxy-4 ' -tert-butyldibenzoylmethane, 5- (3, 3-dimethyl-2-norbornylidene)) -3-pentan-2-one, and the like.

Further, a powder containing the above-mentioned organic ultraviolet screening component in a hydrophobic polymer powder may also be used. The polymer powder may be hollow or not, as long as the average primary particle diameter is in the range of 0.1 to 50 μm, and the particle size distribution may be broad or sharp. As the polymer species, examples thereof include acrylic resins, methacrylic resins, styrene resins, polyurethane resins, polyethylene, polypropylene, polyethylene terephthalate, silicone resins, nylon, acrylamide resins, silylated polypeptide resins. The polymer powder containing an organic ultraviolet screening component in an amount of 0.1 to 30% by mass is preferable, and the polymer powder containing 4-tert-butyl-4' -methoxydibenzoylmethane as a UV-A absorber is particularly preferable.

Further, the organic ultraviolet screening component dispersed in water may be used. Examples of commercially available products include Tinosorb A2B (available from BASF, Germany).

In the cosmetic of the present invention, the ultraviolet screening component which can be preferably used is at least one selected from the group consisting of fine-particle titanium oxide, fine-particle zinc oxide, 2-ethylhexyl p-methoxycinnamate, 4-tert-butyl-4' -methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, bisethylhexyloxyphenol methoxyphenyl triazine, 2-cyano-3, 3-diphenylprop-2-enoic acid 2-ethylhexyl ester, and other benzophenone-based ultraviolet absorbers. Such an ultraviolet-screening component is a general-purpose component, is easily available, and has a high ultraviolet-screening effect, and therefore can be preferably used. In particular, it is preferable to use inorganic-based and organic-based ultraviolet-blocking components in combination, and more preferable to use an ultraviolet-blocking component corresponding to UV-a and an ultraviolet-blocking component corresponding to UV-B in combination.

Water-soluble Polymer (N)

On the other hand, the cosmetic of the present invention may be an aqueous or emulsion type cosmetic containing a large amount of water-soluble ingredients, and the water-soluble polymer (N) may be compounded depending on the formulation thereof, and is preferable. As the water-soluble polymer, one or two or more water-soluble polymers may be used. Examples of the natural water-soluble polymer include gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince seed), algin (brown algae extract), starch (rice, corn, potato, wheat), vegetable polymers such as glycyrrhizic acid, microbial polymers such as xanthan gum, dextran, succinoglycan, and pullulan, and animal polymers such as collagen, casein, albumin, and gelatin. Examples of the semisynthetic water-soluble polymer include starch polymers such as carboxymethyl starch and methylhydroxypropyl starch, cellulose polymers such as methyl cellulose, nitrocellulose, ethyl cellulose, methylhydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, sodium carboxymethylcellulose (CMC), crystalline cellulose and cellulose powder, and alginic acid polymers such as sodium alginate and propylene glycol alginate. Examples of the synthetic water-soluble polymer include polyvinyl alcohol, polyvinyl methyl ether polymers, polyvinyl pyrrolidone, vinyl polymers such as carboxyvinyl polymers (CARBOPOL940, 941: BF Goodrich) and the like, polyoxyethylene polymers such as polyethylene glycol 20000, polyethylene glycol 6000, polyethylene glycol 4000 and the like, polyoxyethylene/polyoxypropylene copolymers, copolymer polymers such as PEG/PPG methyl ether and the like, acrylic polymers such as sodium polyacrylate, polyethyl acrylate, polyacrylamide and the like, polyethyleneimine, cationic polymers and the like. Examples of the other cationic water-soluble polymer, particularly as an ingredient which can be preferably blended in a hair cosmetic, include quaternary nitrogen-modified polysaccharides (e.g., cationic-modified cellulose, cationic-modified hydroxyethyl cellulose, cationic-modified guar gum, cationic-modified locust bean gum, cationic-modified starch, etc.), dimethyldiallylammonium chloride derivatives (e.g., dimethyldiallylammonium chloride/acrylamide copolymer, dimethylmethylenepiperidinium chloride, etc.), vinylpyrrolidone derivatives (e.g., vinylpyrrolidone/dimethylaminoethylmethacrylate copolymer salt, vinylpyrrolidone/acrylamidopropyltrimethylammonium chloride copolymer, vinylpyrrolidone/methylvinylimidazolium chloride copolymer, etc.).

Other ingredients used in conventional cosmetics may be added to the cosmetic of the present invention within a range not interfering with the effects of the present invention: organic resin, humectant, antiseptic, antibacterial agent, perfume, salt, antioxidant, pH regulator, chelating agent, refreshing agent, antiinflammatory agent, skin caring component (whitening agent, cell activator, pachylosis improving agent, blood circulation promoter, skin astringent, anti-seborrheic agent, etc.), vitamins, amino acids, nucleic acid, hormone, clathrate, etc. These specific examples are the same as those specifically disclosed in paragraphs 0100 to 0113 of japanese patent application laid-open No. 2011-149017, but are not limited thereto.

The cosmetic of the present invention may be blended with natural plant extract components, seaweed extract components, and crude drug components depending on the purpose. Two or more of such components may be blended. These specific examples are the same as those specifically disclosed in paragraph 0115 of japanese patent laid-open publication No. 2011-149017, but are not limited thereto.

The cosmetic of the present invention may further contain a solvent such as light isoparaffin, ether, LPG (liquefied petroleum gas), N-methylpyrrolidone, next-generation chlorofluorocarbon, or the like, depending on the purpose.

In addition, an alkyl-modified silicone resin wax may be used in the cosmetic of the present invention in addition to the copolymer of the present invention. These are the same molding components as the copolymer of the present invention.

As the alkyl-modified silicone resin wax, a silsesquioxane resin wax described in Japanese patent laid-open No. 2007-532754 is preferably exemplified.

[ kinds and preparations of cosmetic materials ]

Also, the kind of cosmetic and the formulation form thereof are not particularly limited, and may be skin cosmetics such as skin care products, antiperspirant products, deodorant products, make-up products, ultraviolet ray protection products, and the like; cosmetics for Hair such as eyelash cosmetics products, Hair cleanser products, Hair finishing products, Hair coloring products, Hair tonic products, Hair care products (Hair rinse products), Hair conditioner products (Hair conditioner products), Hair care products (Hair treatment products), and the like; hair cosmetic products such as bath cosmetics. The form is not particularly limited, but may be any of a solution-like, emulsion-like, paste-like, solid-like, semisolid-like, paste-like, gel-like, powder-like, multi-layer-like, mousse-like, water-in-oil, or oil-in-water type emulsion composition (emulsion composition).

Among them, the external preparations are those suitable for the skin, nails, hair, etc. of the human body, and can be used for the treatment of various diseases in combination with, for example, pharmaceutically active ingredients. Cosmetics are also substances applied to the skin, nails, hair, etc. of the human body, but are also substances used for cosmetic purposes. Even when used as an "external preparation", it may be used in the same dosage and amount as the cosmetic. Therefore, in the cosmetic of the present invention, these external preparations are also described as substances contained as cosmetics. Examples thereof include antiperspirants, skin cleansers, skin external preparations, hair cleansers, hair external preparations, and the like. Examples of the application of the external preparation agent include, but are not limited to, hair growth agents, hair tonics, analgesics, bactericides, anti-inflammatory agents, refreshing agents, and anti-aging agents for the skin.

(film Forming Property/touch Effect of Hair)

The cosmetic of the present invention comprises the above copolymer, and thus can form a film having excellent water-repellent properties and excellent persistence and sebum durability on skin or hair. In particular, in the copolymer of the present invention, the content of the carbosiloxane dendrimer structure-containing monomer, which has a risk of causing irritation and has a property of being difficult to separate or remove from the copolymer by a conventional distillation method, is extremely small, and a film having excellent water resistance and sebum resistance can be formed on skin or hair, so that a cosmetic material which is free from irritation problems and imparts such a functional film can be designed.

The skin cosmetic can be applied to scalp, face (including lip, eyebrow, cheek), finger, nail, and whole body. Specific examples thereof include: skin cleanser products such as cleansing gel, cleansing cream, cleansing foam, cleansing milk, eye makeup remover, cleansing milk, liquid soap (bath lotion), hand sanitizer, gel soap, shaving cream, nail cleanser, acne removal cosmetic, etc.; skin care products such as skin cream, scalp conditioner, skin cream, milk lotion, milky lotion, pack, toilet powder, essence, shaving lotion, massage lotion, etc.; makeup products such as foundation, foundation solution, oil foundation, makeup base solution, white powder, honey powder, blush, lipstick, rouge, lip gloss, eye cream, mascara, eyebrow brush, eyebrow makeup, and the like; antiperspirants such as deodorants; and ultraviolet screening products such as sunscreen agents, tanning agents (tanning agents), and the like.

Examples of the hair cosmetic include a hair cleanser such as a shampoo and a rinse and care product; hair care products such as pomade, hair curl retention agent, setting agent, hair cream, hair gel, and hair liquid; hair dyeing products such as hair dye, hair dyeing spray, hair dye, hair dyeing stick, etc.; hair nourishing products such as hair conditioner, hair essence, and hair mask; hair care oil, hair rinse, conditioner, and the like. The cosmetic for bathing may, for example, be a foam bath.

[ design and guidance of the inventive cosmetic formulations comprising the copolymer ]

In the copolymer of the present invention, the content of the carbosiloxane dendrimer structure-containing monomer, which has a risk of causing irritation and has properties that are difficult to separate or remove from the copolymer by a conventional distillation method, is extremely small, and in addition, has the same characteristics of water resistance, detergency, film-forming properties, and the like as those of known acrylic silicone dendrimers. Therefore, for example, in a known formulation in a vinyl polymer having a carbosiloxane dendrimer structure in a side chain as described in Japanese patent publication No. 4009382 (Japanese patent laid-open No. 2000-063225) or the like, a part or all of the components may be used instead. That is, in a cosmetic formulation comprising a known vinyl-based polymer having a carbosiloxane dendrimer structure in a side chain, the corresponding vinyl-based polymer is substituted by the copolymer of the present invention to design or prepare a cosmetic formulation, which is specifically taught herein by the present applicant.

Similarly, in a known formulation of a commercially available product in which a vinyl-based polymer having a carbosiloxane dendrimer structure in a side chain is proposed, the copolymer of the present invention may be used in place of a part or all thereof. For example, as commercially available products, examples thereof include FA 4001 CM Silicone Acrylate, FA 4002 ID Silicone Acrylate, dowsil (tm) FA 4003 DM Silicone Acrylate and the like available from Dow Corning Toray Co Ltd, and cosmetic formulations using these are known in most products, patents, formulation samples provided by Dow sil CORPORATION, published information in ip.com and the like, but the copolymer of the present invention can be used by substituting a part or all of a vinyl-based polymer having a carbosiloxane dendrimer structure in the side chain without limitation, and is preferable.

When the copolymer according to the invention is used in place of the vinyl-based polymer having a carbosiloxane dendrimer structure in the side chain in known cosmetic formulations, it is possible, according to the customary formulation of the person skilled in the art, to replace the corresponding materials in cosmetic formulations simply by this copolymer, not only that the known formulations are used without impairing the properties/characteristics of the cosmetics thereof, there being the practical advantage that it is possible to provide cosmetics which contain only a reduced or substantially no content of monomers having a carbosiloxane dendrimer structure which have the risk of causing irritation and which have properties which are difficult to separate or remove from the copolymer by customary distillation methods.

The copolymer of the present invention can be used for other applications, and can be incorporated into products other than cosmetics, for example, various external preparations, paints, coating agents, antifoaming agents, deodorants, and the like.

< film Forming agent >

The copolymer film-forming agent of the present invention can be used for applications other than cosmetics. That is, the film can be used in any field as long as it is required to have water repellency, oil repellency, integrity (integrity), strength and abrasion resistance. In particular, it is also useful as a water-repellent effect imparting agent for coating compositions and fibers, a treating agent for inorganic materials/organic materials, and the like. Also, the film-forming agent of the present invention can be used in an aqueous environment as needed, and thus is easy to handle.

Specifically, the film-forming agent of the present invention has excellent compounding stability and does not impair film-forming properties and feeling upon use, and therefore, can be preferably used as a film-forming agent for industrial use as a fiber-treating agent or a cotton/fabric-treating agent.

[ Process for producing copolymer of the present invention ]

As described above, the carbosiloxane dendrimer structure-containing monomer, which is a raw material of the copolymer of the present invention, has a property of being difficult to separate or remove from the copolymer by a conventional distillation method. However, the monomer can be reduced to 2500ppm or less relative to the copolymer by the method for producing the copolymer of the present invention. In addition, by the production method comprising the following step (I), the reaction time required for radical polymerization can be shortened and the industrial production efficiency can be improved.

The method for producing the copolymer of the present invention is characterized in that,

to unsaturated monomer (a1) having a carbosiloxane dendrimer structure containing an organic group capable of radical polymerization and

a step of adding a polymerization initiator to an unsaturated monomer (a2) having a radically polymerizable vinyl group, which is different from the component (a1), to perform a radical polymerization reaction, and which comprises

A step (I): and (Ia) a step of adding a polymerization initiator which is the same as or different from the polymerization initiator added for the first time, after at least two hours have elapsed after the first addition of the polymerization initiator in the radical polymerization reaction. The step (I) of the production method may optionally include a step of adding (Ib) a monomer (a 2') having a radically polymerizable vinyl group having a boiling point of less than 160 ℃ under normal pressure (1atm) to promote a radical polymerization reaction of the unreacted component (a1), and may further include a step (II): the step of distilling off the unreacted unsaturated monomer or saturated monomer remaining in the system under normal pressure or reduced pressure after the step (I) is preferable.

The component (a1), the component (a2) and the polymerization initiator are as described above. The radically polymerizable vinyl group-containing monomer (a 2') having a boiling point of less than 160 ℃ under normal pressure (1atm) is not particularly limited as long as it has such properties, but the component (a2) is preferably methyl (meth) acrylate or ethyl (meth) acrylate, which has a low boiling point and is easily distilled under reduced pressure. Also, the radical polymerization reaction may be carried out in the above-mentioned reaction solvent, which may be solvent-substituted by the step (IV) described later, and is preferable.

The step (I) is a step (Ia) required for increasing the reaction efficiency of the unsaturated monomer having a carbosiloxane dendrimer structure containing a radical polymerizable organic group (a1) to be reduced and suppressing the residual amount thereof, and is a step (Ia) of adding a polymerization initiator that is the same as or different from the polymerization initiator that was added first after at least two hours from the first addition of the polymerization initiator in the radical polymerization reaction. A time difference is set from the first addition of the polymerization initiator, specifically, at least two hours, preferably, two and a half hours or more, and additional polymerization initiator is added to the reaction system, so that the radical polymerization of the component (a1) not consumed in the initial radical polymerization proceeds and the residual amount in the system is remarkably reduced. The amount of the polymerization initiator to be added is not particularly limited, but may be in the range of 0.5 to 5.0 equivalent, and particularly preferably in the range of 0.6 to 4.5 equivalent, to the amount of the polymerization initiator to be added first. In addition, by providing a time difference from the first addition of the polymerization initiator and additionally adding the polymerization initiator, the reaction time required for the radical polymerization reaction can be shortened, and the industrial production efficiency of the copolymer of the present invention can be improved.

The step (I) may optionally include a step (Ib) of adding a radically polymerizable vinyl group-containing monomer (a 2') having a boiling point of less than 160 ℃ under normal pressure (1atm) to promote a radical polymerization reaction of the unreacted component (a 1). A time difference was set from the first addition of the polymerization initiator, and an additional polymerization initiator and other reactive unsaturated monomers were added to the reaction system, so that the component (a1) not consumed in the initial radical polymerization reaction was subjected to radical polymerization together with the additional component (a 2'), and the residual amount in the system was remarkably reduced. Since the component (a 2') has a low boiling point, it can be easily distilled under reduced pressure after the component (a1) is reacted.

By the above step (I), the component (a1) having a property that it is difficult to separate/remove from the copolymer by a method such as distillation under reduced pressure or the like, or the saturated monomer as a hydrogenated product thereof can be efficiently reacted in advance to be consumed, so that the residual amount in the system is remarkably reduced.

The production process of the present invention may further comprise, after the step (I), a step (II) of distilling off the unreacted unsaturated monomer or saturated monomer remaining in the system under normal pressure or reduced pressure. Further, this step is intended to distill low boiling point components in the unreacted monomers to perform purification, and the content of the component (a1) has been reduced by the step (I) of the previous step. The distillation of the unreacted unsaturated monomer or saturated monomer under normal pressure or reduced pressure in the step (II) can be carried out by a known method such as steam stripping without any particular limitation.

After the step (I), in the step of the subsequent step, a step of refluxing, reprecipitation, filtration, or the like may be performed at any time before or after.

In the production method of the present invention, the above-mentioned step (III) of subjecting the unreacted unsaturated monomer remaining in the system to hydrogenation reaction to convert the unsaturated monomer into a saturated monomer may be further included after the step (I), before the step (II) or simultaneously with the step (II). This step is carried out by bringing the hydrogenation catalyst (nickel catalyst or palladium catalyst) into contact with the polymerization reaction product of the step (I) to form a saturated monomer as a hydrogenation reaction product of the unreacted component (a1) or the like, and to reduce the odor of the copolymer. Since the step (III) is a step of converting the unreacted component (a1) into a saturated monomer, the amount of the monomer derived from the unreacted component (a1) does not decrease in the step (III).

The production method of the present invention preferably includes, at any time, a step (IV) of adding one or more alcohols (C) and/or oils (D) as a dispersion medium to the system and removing the reaction solvent in the radical polymerization reaction, before or simultaneously with the step (II). By this step, a copolymer composition containing the alcohol (C) and/or the oil (D) excellent in blending stability and handling processability in cosmetics and the like can be obtained. Similarly to the step (II), the reaction solvent in the radical polymerization reaction can be removed by a known method such as steam stripping under normal pressure or reduced pressure without any particular limitation, and can be replaced with one or more of the alcohols (C) and/or the oil (D). In addition, in the case where the reaction solvent in the radical polymerization reaction is the alcohol (C), the radical polymerization reaction solution itself forms a copolymer composition containing the alcohol (C), and thus, can be used as it is as a cosmetic raw material or a film-forming agent, if necessary.

Examples

The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples.

The respective characteristics in examples and the like were measured by the following methods.

[ GPC Peak molecular weight ]

GPC analysis was performed using toluene in the elution solvent and TSKgel Multipore HXL-M on the column, and the molecular weight was determined using a calibration curve for standard polystyrene.

[ quantification of residual carbosiloxane dendrimer monomer (A-1) ]

The amount was determined by high performance liquid chromatography (calibration-i LC-2030C3D manufactured by Shimadzu, Japan, column: Atlantis T3-3 μm (3.0X 100mm), UV-visible absorption detector, gradient pattern of eluting solvent: water/methanol/THF).

[ kinematic viscosity ]

The viscosity of the composition at 25 ℃ was measured using a Ubbelohde viscosity tube.

[ non-volatile component ]

1g of a sample was weighed on an aluminum pan having a diameter of 6cm and determined from the sample remaining after heating at 150 ℃ for 1 hour.

[ film tackiness ]

When the film formed on the aluminum tray was touched with a finger in the same manner as described above, and it was judged whether or not the aluminum tray integrated with the film was swollen.

[ contact Angle (Water) ]

After coating an IPA solution of a vinyl copolymer on a glass plate, the solvent was dried and removed at room temperature to obtain a film of the vinyl polymer. On the surface of the coating film, 5 μ L of a water droplet was placed, and the contact angle with water was measured. The measurement apparatus used a Drop shape analysis system (KRUSS DSA10 Mk-2), and found an average value of n equal to or greater than 5.

[ contact Angle (Artificial sebum) ]

After coating an IPA solution of a vinyl copolymer on a glass plate, the solvent was dried and removed at room temperature to obtain a film of the vinyl polymer. On the surface of the coating film, 5 μ L of a droplet of artificial sebum (triolein: a mixture of oleic acid and squalane: 3: 1) was placed, and a contact angle with respect to the artificial sebum was measured. The measurement apparatus used a Drop shape analysis system (KRUSS DSA10 Mk-2), and found an average value of n equal to or greater than 5.

[ example 1]

[ preparation of copolymer and liquid composition thereof ]

A1L four-necked flask equipped with a stirrer, a thermometer and a reflux tube was charged with 163g of isopropyl alcohol (IPA), bubbled with nitrogen gas, sufficiently degassed, and heated to 70 ℃. To the dropping funnel were added 110g of methyl methacrylate (55% by weight), 10g of n-butyl acrylate (5% by weight), and 80g of a compound represented by the following formula (A-1):

[ chemical formula 26]

The carbosiloxane dendrimer monomer (40% by weight) shown, 4.4g of methyl 2, 2' -azobis-2-isobutyrate (V-601, manufactured by Fuji film and Wako pure chemical industries) (2.2% by weight), 107g of IPA, and dissolution were carried out. The monomer mixture was added dropwise from the dropping funnel under a nitrogen atmosphere while maintaining a temperature of 70 ℃ for 1 hour. After completion of the dropwise addition, the mixture was stirred under heating for 3 hours under a nitrogen atmosphere, and a solution prepared by dissolving 4.4g of V-601(2.2 wt%) in 30g of IPA was added. Also, after stirring for 9 hours, a reaction product of 40.8% of non-volatile components was obtained. GPC analysis showed that the polymer had a peak molecular weight of 15900. Further, as a result of analysis by high performance liquid chromatography, 1330ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

[ reference example 1]

163g of IPA was put into a 1L four-necked flask equipped with a stirrer, a thermometer and a reflux tube, and then, nitrogen gas was bubbled into the flask, followed by sufficient deaeration and heating to 70 ℃. To the dropping funnel were added 110g of methyl methacrylate (55% by weight), 10g of n-butyl acrylate (5% by weight), 80g of carbosiloxane dendrimer monomer (A-1) (40% by weight), 2g of V-601 (1% by weight), and 107g of IPA, and dissolved. The monomer mixture was added dropwise from the dropping funnel under a nitrogen atmosphere while maintaining a temperature of 70 ℃ for 1 hour. After the completion of the dropwise addition, the mixture was stirred under heating under a nitrogen atmosphere for 8 hours to obtain a reaction product containing 40.6% of nonvolatile components. GPC analysis showed that the polymer had a peak molecular weight of 23600. Further, as a result of analysis by high performance liquid chromatography, 30750ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

[ reference example 2]

The same operation was carried out except that the amount of V-601 in reference example 1 was set to 4.4g (2.2% by weight), thereby obtaining a reaction product. GPC analysis showed that the polymer had a peak molecular weight of 16000. As a result of analysis by high performance liquid chromatography, 11000ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

[ reference example 3]

The same operation was carried out except that the amount of V-601 in reference example 1 was set to 8.8g (4.4% by weight), thereby obtaining a reaction product. GPC analysis showed that the polymer had a peak molecular weight of 12600. Further, as a result of analysis by high performance liquid chromatography, 2250ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

[ conclusion 1]

The above results are summarized in table 1. From the comparison between example 1 and reference example 2 and the comparison between reference examples l to 3, it can be seen that the polymer molecular weight is determined in accordance with the amount of V-601 as the first-added polymerization initiator. Further, by additionally adding the polymerization initiator V-601 with a time difference, the residual amount of the carbosiloxane dendrimer monomer (A-1) having poor reactivity can be significantly reduced.

[ Table 1]

[ example 2]

163g of IPA was put into a 1L four-necked flask equipped with a stirrer, a thermometer and a reflux tube, and then, nitrogen gas was bubbled into the flask, followed by sufficient deaeration and heating to 70 ℃. To the dropping funnel were added 110g of methyl methacrylate (55% by weight), 10g of n-butyl acrylate (5% by weight), 80g of carbosiloxane dendrimer monomer (A-1) (40% by weight), 4.4g of V-601 (2.2% by weight), and 107g of IPA, and dissolved. The monomer mixture was added dropwise from the dropping funnel under a nitrogen atmosphere while maintaining a temperature of 70 ℃ for 1 hour. After completion of the dropwise addition, the mixture was stirred under heating for 6 hours under a nitrogen atmosphere, and a solution prepared by dissolving 0.6g of V-601(0.3 wt%) in 30g of IPA was added. Also, after stirring for 6 hours, a reaction product of 40.0% of non-volatile components was obtained. GPC analysis showed that the polymer had a peak molecular weight of 17200. Further, as a result of analysis by high performance liquid chromatography, 2350ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

Comparative example 1

The same operations were carried out except that the amount of V-601 of reference example 1 was set to 4.4g (2.2% by weight) and the time for heating and stirring was set to 12 hours, thereby obtaining a reaction product. GPC analysis showed that the polymer had a peak molecular weight of 17000. Further, as a result of analysis by high performance liquid chromatography, 5200ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

Comparative example 2

The same operations were carried out except that the amount of V-601 of reference example 1 was set to 4.4g (2.2% by weight) and the time for heating and stirring was set to 24 hours, thereby obtaining a reaction product. GPC analysis showed that the polymer had a peak molecular weight of 18000. Further, as a result of analysis by high performance liquid chromatography, 2740ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

[ conclusion 2]

The above results are summarized in table 2. From this, it was found that the addition of the initiator not only reduced the residual amount of the carbosiloxane dendrimer monomer (A-1) having poor reactivity, but also significantly shortened the reaction time.

[ Table 2]

[ example 3]

163g of IPA was put into a 1L four-necked flask equipped with a stirrer, a thermometer and a reflux tube, and then, nitrogen gas was bubbled into the flask, followed by sufficient deaeration and heating to 70 ℃. To the dropping funnel were added 110g of methyl methacrylate (55 wt%), 10g of n-butyl acrylate (5 wt%), 80g of carbosiloxane dendrimer monomer (A-1) (40 wt%), 4.4g of 1, 1, 3, 3-tetramethylbutylperoxy-2-ethylhexanoate (PEROCTA O, produced by Nissan oil Co., Ltd.) (2.2 wt%), and 107g of IPA, and dissolved. The monomer mixture was added dropwise from the dropping funnel under a nitrogen atmosphere while maintaining a temperature of 70 ℃ for 1 hour. After completion of the dropwise addition, the mixture was stirred under heating under a nitrogen atmosphere for 4 hours, and a solution prepared by dissolving 4.4g of PEROCTA (registered trademark) O (1, 1, 3, 3-tetramethylbutylperoxy-2-ethylhexanoate) (2.2% by weight) in 30g of IPA was added. After further stirring for 4 hours, a reaction product was obtained. GPC analysis showed that the polymer had a peak molecular weight of 19400. As a result of analysis by high performance liquid chromatography, 1350ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

[ example 4]

163g of IPA was put into a 1L four-necked flask equipped with a stirrer, a thermometer and a reflux tube, and then, nitrogen gas was bubbled into the flask, followed by sufficient deaeration and heating to 70 ℃. 110g of methyl methacrylate (55% by weight), 10g of n-butyl acrylate (5% by weight), 80g of carbosiloxane dendrimer monomer (A-1) (40% by weight), 4.4g of PEROCTA O (2.2% by weight), 107g of IPA were counted and dissolved in a dropping funnel. The monomer mixture was added dropwise from the dropping funnel under a nitrogen atmosphere while maintaining a temperature of 70 ℃ for 1 hour. After completion of the dropwise addition, the mixture was stirred under heating under a nitrogen atmosphere for 6 hours, and then 0.6g of PEROCTA (registered trademark) O (1, 1, 3, 3-tetramethylbutylperoxy-2-ethylhexanoate) (0.3 wt%) was dissolved in 30g of IPA to prepare a solution. After further stirring for 6 hours, a reaction product was obtained. GPC analysis showed that the polymer had a peak molecular weight of 18700. Further, as a result of analysis by high performance liquid chromatography, it was found that 1320ppm of carbosiloxane dendrimer monomer (A-1) remained.

Comparative example 3

163g of IPA was put into a 1L four-necked flask equipped with a stirrer, a thermometer and a reflux tube, and then, nitrogen gas was bubbled into the flask, followed by sufficient deaeration and heating to 70 ℃. To the dropping funnel were added 110g of methyl methacrylate (55% by weight), 10g of n-butyl acrylate (5% by weight), 80g of carbosiloxane dendrimer monomer (A-1) (40% by weight), 4.4g of PEROCTA O (2.2% by weight), and 107g of IPA, and dissolved. The monomer mixture was added dropwise from the dropping funnel under a nitrogen atmosphere while maintaining a temperature of 70 ℃ for 1 hour. After the end of the dropwise addition, stirring was performed under heating under a nitrogen atmosphere for 12 hours to obtain a reaction product. GPC analysis indicated that the polymer had a peak molecular weight of 17000. As a result of analysis by high performance liquid chromatography, 9.580ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

[ conclusion 3]

The above results are summarized in table 3. Similar trends and results were obtained even when a peroxide-based initiator was used as the polymerization initiator.

[ Table 3]

In examples 5 and 6, comparative examples 4 and 5, polymers having different monomer compositions were examined.

[ example 5]

In a1 liter four-necked flask equipped with a stirrer, a thermometer and a reflux tube, 163g of IPA was charged, nitrogen gas was bubbled, sufficient deaeration was performed, and the flask was heated to 75 ℃. To the dropping funnel, 76g of methyl methacrylate (38% by weight), 24g of n-butyl acrylate (12% by weight), 100g of carbosiloxane dendrimer monomer (A-1) (50% by weight), 2g of V-601 (1% by weight), and 107g of IPA were added and dissolved. The monomer mixture was added dropwise from the dropping funnel under a nitrogen atmosphere while maintaining a temperature of 75 ℃ for 3 hours. After completion of the dropwise addition, the mixture was stirred under heating for 4 hours under a nitrogen atmosphere, and a solution prepared by dissolving 8g of V-601(4 wt%) in 30g of IPA and 0.6g of n-butyl acrylate (0.3 wt%) were added. After further stirring for 6 hours, a reaction product having a nonvolatile content of 40.0% was obtained. GPC analysis showed that the polymer had a peak molecular weight of 23100. Further, as a result of analysis by high performance liquid chromatography, 1380ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

[ example 6]

163g of IPA was put into a 1L four-necked flask equipped with a stirrer, a thermometer and a reflux tube, and then, nitrogen gas was bubbled into the flask, followed by sufficient deaeration and heating to 70 ℃. To the dropping funnel, 76g of methyl methacrylate (38% by weight), 24g of n-butyl acrylate (12% by weight), 100g of carbosiloxane dendrimer monomer (A-1) (50% by weight), 2g of V-601 (1% by weight), and 107g of IPA were added and dissolved. The monomer mixture was added dropwise from the dropping funnel under a nitrogen atmosphere while maintaining a temperature of 70 ℃ for 3 hours. After completion of the dropwise addition, the mixture was stirred under heating for 4 hours under a nitrogen atmosphere, and a solution prepared by dissolving 8g of V-601(4 wt%) in 30g of IPA and 0.6g of n-butyl acrylate (0.3 wt%) were added. After further stirring for two hours, a reaction product having a nonvolatile content of 39.8% was obtained. GPC analysis showed that the polymer had a peak molecular weight of 28900. Further, as a result of analysis by high performance liquid chromatography, it was found that 2240ppm of carbosiloxane dendrimer monomer (A-1) remained.

Comparative example 4

163g of IPA was put into a 1L four-necked flask equipped with a stirrer, a thermometer and a reflux tube, and then, nitrogen gas was bubbled into the flask, followed by sufficient deaeration and heating to 70 ℃. To the dropping funnel, 76g of methyl methacrylate (38% by weight), 24g of n-butyl acrylate (12% by weight), 100g of carbosiloxane dendrimer monomer (A-1) (50% by weight), 2g of V-601 (1% by weight), and 107g of IPA were added and dissolved. The monomer mixture was added dropwise from the dropping funnel under a nitrogen atmosphere while maintaining a temperature of 70 ℃ for 3 hours. After completion of the dropwise addition, the mixture was stirred under heating for 1 hour under a nitrogen atmosphere, and a solution prepared by dissolving 2g of V-601(1 wt%) in 30g of IPA was added. After further stirring for two hours, a reaction product having a nonvolatile content of 40.7 mass% was obtained. GPC analysis showed that the polymer had a peak molecular weight of 28400. Further, as a result of analysis by high performance liquid chromatography, 4320ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

Comparative example 5

163g of IPA was put into a 1L four-necked flask equipped with a stirrer, a thermometer and a reflux tube, and then, nitrogen gas was bubbled into the flask, followed by sufficient deaeration and heating to 70 ℃. To the dropping funnel, 76g of methyl methacrylate (38% by weight), 24g of n-butyl acrylate (12% by weight), 100g of carbosiloxane dendrimer monomer (A-1) (50% by weight), 2g of V-601 (1% by weight), and 107g of IPA were added and dissolved. The monomer mixture was added dropwise from the dropping funnel under a nitrogen atmosphere while maintaining a temperature of 70 ℃ for 3 hours. After the end of the dropwise addition, the mixture was stirred under heating under a nitrogen atmosphere for 7 hours to obtain a reaction product having a nonvolatile content of 40.9 mass%. GPC analysis showed that the polymer had a peak molecular weight of 29300. As a result of analysis by high performance liquid chromatography, 14750ppm of carbosiloxane dendrimer monomer (A-1) was found to remain.

[ conclusion 4]

The above results are summarized in table 4. In the polymerization of monomers having different compositions, a low-molecular monomer is added together with a polymerization initiator, whereby the residual amount of the carbosiloxane dendrimer monomer (A-1) having poor reactivity can be reduced.

[ Table 4]

[ examples 7 to 11]

Hereinafter, the polymer obtained in the above example was passed through an oil agent (isododecane or the like) in place of the reaction solvent to obtain a liquid copolymer composition. The details and attributes thereof are summarized in table 5. Further, the nonvolatile component was a vinyl copolymer having a carbosiloxane dendrimer structure in each example, and the content of the component (A-1) in this liquid copolymer composition

The concentration is reduced to below 1000 ppm.

[ example 7]

120g of isododecane (Mercazole R, available from Nippon Bow oil Co., Ltd.) was added to 200g of the isopropanol solution of the vinyl polymer of example 1, and then IPA was distilled at 120 ℃. Under reduced pressure, the unreacted monomers were distilled to obtain a liquid composition. The nonvolatile content was 37.0% by mass, and the kinematic viscosity was 27mm 2/s. The contact angle (water) was 105 DEG, the contact angle (artificial sebum) was 52 DEG, and the film was non-tacky and useful as a film agent for cosmetics.

[ example 8]

After 120g of Mercazole R was added to 200g of the vinyl polymer isopropanol solution of example 2, IPA was distilled at 120 ℃. Under reduced pressure, the unreacted monomers were distilled to obtain a liquid composition. The nonvolatile content was 40.5% by mass, and the kinematic viscosity was 66mm 2/s.

[ example 9]

After 120g of Mercazole R was added to 200g of the vinyl polymer isopropanol solution of example 3, IPA was distilled at 120 ℃. Under reduced pressure, the unreacted monomers were distilled to obtain a liquid composition. The nonvolatile content was 41.6% by mass, and the kinematic viscosity was 172mm 2/s.

[ example 10]

120g of dodecane (PARAFOL 12-97, a product of Sasol, Germany) was added to 200g of the isopropanol solution of the vinyl polymer of example 5, and then IPA was distilled at 120 ℃. Under reduced pressure, the unreacted monomers were distilled to obtain a liquid composition. The nonvolatile content was 39.4% by mass, and the kinematic viscosity was 76mm 2/s. The contact angle (water) is 113 DEG, the contact angle (artificial sebum) is 59 DEG, and the film is non-tacky and useful as a film agent for cosmetics.

[ example 11]

To 200g of the isopropyl alcohol solution of the vinyl polymer of example 5, 120g of a mixture of undecane and tridecane (CETIOL ULTIMATE, manufactured by BASF corporation, Germany) was added, and then IPA was distilled at 120 ℃. Under reduced pressure, the unreacted monomers were distilled to obtain a liquid composition. The nonvolatile content was 37.6% by mass, and the kinematic viscosity was 49mm 2/s. The contact angle (water) was 109 DEG, the contact angle (artificial sebum) was 51 DEG, and the film was non-tacky and useful as a film agent for cosmetics.

[ Table 5]