JP2008189907A - Block polymer, method for producing it and cosmetic composition containing this block polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a block polymer suitable for industrial production and a cosmetic composition such as hair-setting agent composition including the block polymer or the like. <P>SOLUTION: The block polymer is obtained by connecting two or more blocks that comprises monomers bearing vinyl functional groups through connecting monomers having radical polymerizable vinyl functional groups and non-radical polymerizable functional group. The two or more blocks include at least a first block and a second block, different from each other, and the radically polymerizable vinyl functional groups of the connecting monomer connects with the first block monomer and the non-radical polymerizable functional group connects with the second block monomer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a block polymer suitable for industrial production, a method for producing the same, and a hair set agent composition, an aqueous composition for hair cosmetics, and a cosmetic composition such as a cosmetic detergent composition containing the block polymer. It relates to a composition.

  Structure-controlled polymers, such as block polymers, may exhibit specific performance that cannot be obtained with random-structure polymers. For example, AB type block polymers and ABA type block polymers in which two blocks having different properties are connected in series are applied to polymer emulsifiers, thickeners, and the like. Further, in the sense of having a block site, it can be said that a graft polymer is a kind of block polymer, and a graft polymer obtained by using a macromonomer having a reactive functional group has also been proposed. Since each block site has a different property from other sites, it is possible to mix those that cannot be mixed normally or to have a strong aggregating action, so that specific performance can be achieved. It is expressed.

  These block polymers having specific performance have begun to be used in various fields, and are expected as means for simultaneously solving various requirements.

  Conventionally, as a method for producing an AB type block polymer or an ABA type block polymer, there are a living radical polymerization method and a method using a special polymer type initiator, but in the case of living radical polymerization, a catalyst is used. After the reaction, it is necessary to remove the used catalyst, and there is a problem of cost increase in industrial production. In addition, the method using a special polymer-type initiator has problems that the initiator is limited and the cost of the initiator is high.

  In the case of a graft polymer, since it can be easily synthesized by using a macromonomer, there are relatively few restrictions on production, but there is a problem of increased cost because the method for producing the macromonomer is special.

Patent Document 1 discloses a block polymer using a monomer having two vinyl functional groups having different reactivities. This is because one highly reactive vinyl functional group is polymerized with a certain monomer in the first stage polymerization, and then the low reactive vinyl functional group is polymerized with another monomer in the second stage polymerization. It is a method to make it.
JP 2002-534540 A

  However, in the method described in Patent Document 1, since any functional group is radically polymerizable, there is a problem that a vinyl functional group having low reactivity reacts in the first-stage polymerization. In addition, when a functional group that is too low in reactivity is used, it may not react even in the second stage polymerization. Furthermore, there are limitations on reaction conditions such as temperature, time, monomer species to be copolymerized and the like, and there is a problem that a block polymer cannot always be obtained easily.

An object of the present invention is to solve the above-mentioned conventional problems and to provide a block polymer that can be produced industrially advantageously and a method for producing the same.
Another object of the present invention is to provide a cosmetic composition such as a hair set composition, a hair cosmetic aqueous composition, and a cosmetic detergent composition comprising such a block polymer.

  As a result of intensive studies to solve the above problems, the present inventor is a simple process as long as it is a block polymer bonded via a linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group. It has been found that it can be produced at low cost, and that an excellent cosmetic composition can be prepared using such a block polymer.

  The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.

[1] A block comprising two or more blocks composed of a monomer having a vinyl functional group bonded via a linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group. polymer.

[2] The block polymer according to [1], wherein the two or more blocks include at least a first block and a second block having different monomer compositions.

[3] A radical polymerizable vinyl functional group of the linking monomer is bonded to the monomer of the first block, and a non-radical polymerizable functional group of the linking monomer is bonded to the monomer of the second block. The block polymer according to [2], wherein the amount of connected monomer with respect to the total amount of monomers constituting the first block is 0.1 to 20 wt% when the monomer is included in the first block.

[4] The block polymer according to any one of [1] to [3], wherein the non-radically polymerizable functional group is an oxazoline-based functional group.

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２〜Ｒ^５はそれぞれ独立して水素原子、アルキル基、アルコキシアルキル基、アリール基、アルキルアリール基、又はアルコキシアリール基を表し、Ａは任意の２価の連結基又は直接結合を表す。） [5] The block polymer according to any one of [1] to [4], wherein the linking monomer is represented by the following general formula (1).

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ^{2 to} R ⁵ each independently represents a hydrogen atom, an alkyl group, an alkoxyalkyl group, an aryl group, an alkylaryl group, or an alkoxyaryl group; Represents any divalent linking group or direct bond.)

[6] The block polymer according to [4] or [5], wherein the second block includes a monomer having a carboxylic acid group and / or an epoxy group and a vinyl functional group.

[7] The bond between the non-radically polymerizable functional group and the monomer of the second block is a structure in which an oxazoline functional group and a carboxylic acid group react, and / or an oxazoline functional group and an epoxy group react. [6] The block polymer according to [6].

[8] The block polymer according to any one of [2] to [7], wherein either one of the first block and the second block is water-insoluble and the other is water-soluble or water-dispersible.

[9] The block polymer according to any one of [1] to [8], which is soluble or dispersible in water and / or ethanol.

[10] The block polymer according to any one of [2] to [9], wherein the first block and the second block each have the following monomer composition.
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 0-79.9 wt%
Hydrophobic vinyl monomer 20-99.9 wt%
(II) Second block Vinyl monomer containing a carboxylic acid group and / or an epoxy group
0.1 to 100 wt%
Hydrophilic vinyl monomer 0-99.9wt%
(However, hydrophilic vinyl monomers that do not contain carboxylic acid groups and / or epoxy groups)
Hydrophobic vinyl monomer 0-90 wt%

[11] The block polymer according to [9], which is soluble or dispersible in water.

[12] The block polymer according to [11], wherein each of the first block and the second block has the following monomer composition.
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 10-89.9wt%
Hydrophobic vinyl monomer 10-89.9 wt%
(II) Second block Vinyl monomer containing a carboxylic acid group and / or an epoxy group
10-90 wt%
Hydrophilic vinyl monomer 0-90 wt%
(However, hydrophilic vinyl monomers that do not contain carboxylic acid groups and / or epoxy groups)
Hydrophobic vinyl monomer 0-50 wt%

[13] The block polymer according to [9], which is soluble in water.

[14] The block polymer according to [13], wherein each of the first block and the second block has the following monomer composition.
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 60-99.9 wt%
Hydrophobic vinyl monomer 0-30 wt%
(II) Second block Vinyl monomer containing a carboxylic acid group and / or an epoxy group
0.1-20 wt%
Hydrophilic vinyl monomer 60-99.9 wt%
(However, hydrophilic vinyl monomers that do not contain carboxylic acid groups and / or epoxy groups)
Hydrophobic vinyl monomer 0-30 wt%

[15] The block polymer according to [10], [12] or [14], wherein the hydrophilic vinyl monomer includes a monomer represented by the following general formula (2) or (3).
_{^{CH 2 = C (R 11)}} -CO-NR 12 R 13 ··· (2)
(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a carbon number 1 having a hydroxyl group. Represents a linear or branched alkyl group of ˜3.)
_{^{CH 2 = C (R 14)}} -CO (O) - (CH 2) a- (CHOH) b-O-R 15
... (3)
(In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, R ¹⁵ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, a represents an integer of 1 to 4, and b represents 0. Or 1)

[16] The hydrophilic vinyl monomer of the first block includes a monomer represented by the following general formula (2) or (3), and the hydrophilic vinyl monomer of the second block is represented by the following general formula (10). The block polymer according to [14], comprising a monomer represented by:
_{^{CH 2 = C (R 11)}} -CO-NR 12 R 13 ··· (2)
(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a carbon number 1 having a hydroxyl group. Represents a linear or branched alkyl group of ˜3.)
_{^{CH 2 = C (R 14)}} -CO (O) - (CH 2) a- (CHOH) b-O-R 15
... (3)
(In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, R ¹⁵ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, a represents an integer of 1 to 4, and b represents 0. Or 1)
_{^{CH 2 = C (R 25)}} -CO- (O) c - (NH) 1-c - (CH 2) d -N + R 26 R 27 R 28 · X - ··· (10)
(In the formula, R ²⁵ represents a hydrogen atom or a methyl group, R ²⁶ and R ²⁷ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and R ²⁸ represents a hydrogen atom or carbon number. Represents an alkyl group of 1 to 24, an aryl group, an aralkyl group, or —CH ₂ —CH (OH) —CH ₂ —N ⁺ R ²⁹ R ³⁰ R ³¹ • Z ^— , wherein R ^{29 to} R ³¹ are each independently carbon; the number 1 to 24 alkyl group, an aryl group or an aralkyl group, X ^- and Z ^- is any negative ions independently, c is 0 or 1, d represents an integer of 1 to 10).

[17] The [10], [12], [14], [15] or [16], wherein the hydrophobic vinyl-based monomer includes a monomer represented by the following general formula (4) or (5) Block polymer.
CH ₂ = C (R ¹⁶ ) —CO—O—R ¹⁷ (4)
(Wherein R ¹⁶ represents a hydrogen atom or a methyl group, and R ¹⁷ represents a linear, branched or cyclic alkyl group having 2 to 30 carbon atoms.)
^{_{CH 2 = C (R 18)}} -CO-NH-R 19 ··· (5)
(Wherein R ¹⁸ represents a hydrogen atom or a methyl group, and R ¹⁹ represents a linear, branched or cyclic alkyl group having 6 to 30 carbon atoms.)

[18] A cosmetic composition comprising 0.01 to 50 wt% of the block polymer according to any one of [1] to [17].

[19] A hair setting agent composition having the following composition.
The block polymer according to any one of [1] to [17], 0.1 to 20 wt%
0 ~ 99wt% of water
Ethanol 0-99wt%
LPG or / and DME 0-70 wt%
(However, the total amount of water, ethanol, LPG and / or DME is 49.9 to 99.9 wt%)
Additive 0-50wt%

[20] The hair setting agent composition according to [19], wherein the hair setting agent composition contains 0.1 to 10 wt% of silicones as an additive.

[21] An aqueous composition for hair cosmetics having the following composition.
The block polymer according to any one of [1] to [17], 0.1 to 20 wt%
Water 40-99wt%
Ethanol 0-40wt%
Additive 0-50wt%

[22] The aqueous composition for hair cosmetics according to [21], wherein the aqueous cosmetic composition for hair cosmetics contains 0.1 to 10 wt% of silicones as an additive.

[23] A cosmetic cleaning composition having the following composition.
The block polymer according to any one of [1] to [17], 0.1 to 20 wt%
Water 40-99wt%
Surfactant 1-40wt%
Additive 0-50wt%

[24] The cosmetic cleaning composition according to [23], wherein the cosmetic cleaning composition contains 0.1 to 10 wt% of silicones as an additive.

[25] The first block and the second block, which are composed of monomers having a vinyl functional group and have different monomer compositions, are bonded via a linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group. A method for producing a block polymer, wherein the first block-constituting vinyl monomer containing the linking monomer is radically polymerized to obtain a first block, and then the non-radically polymerizable functional group of the linking monomer is obtained. A block polymer is obtained by performing a step of adding a vinyl monomer having a functional group capable of reacting with the non-radically polymerizable functional group and a step of radically polymerizing the second block constituent vinyl monomer to obtain a second block. A process for producing a block polymer.

[26] The first block and the second block, which are composed of monomers having a vinyl functional group and have different monomer compositions, are bonded via a linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group. A method for producing a block polymer comprising the steps of radical polymerization of a vinyl monomer having a second block containing a vinyl monomer having a functional group capable of reacting with the non-radically polymerizable functional group to obtain a second block Thereafter, a block polymer is obtained by performing a step of adding the linking monomer to a functional group capable of reacting with the non-radically polymerizable functional group and a step of obtaining a first block by radical polymerization of the first block constituent vinyl monomer. A method for producing a block polymer.

[27] The method for producing a block polymer according to [25] or [26], wherein the non-radically polymerizable functional group is an oxazoline-based functional group.

[28] The method for producing a block polymer according to [27], wherein the functional group capable of reacting with the non-radically polymerizable functional group is a carboxylic acid group and / or an epoxy group.

  The block polymer of the present invention can be produced at a low cost by a simple process without requiring a special initiator and without using a macromonomer, and is suitable for industrial production.

  Such a cosmetic composition containing the block polymer of the present invention provides, for example, an excellent cosmetic composition having no gas compatibility, curl retention, flexibility, non-stickiness and flaking as a hair set composition. can do. Furthermore, the aqueous composition for hair cosmetics which suppressed the compounding quantity of the volatile organic solvent (VOC) can be provided by using the block polymer excellent also in water solubility and moisture resistance. Further, by using the cationic block polymer of the present application having an excellent conditioning effect, it is possible to provide a cosmetic detergent composition having excellent smoothness during rinsing, no stickiness after drying, smoothness and the like.

  Hereinafter, embodiments of the present invention will be described in detail.

[Block polymer of the present invention]
In the block polymer of the present invention, the linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group has at least one radical polymerizable vinyl functional group, and is a normal radical polymerization condition. However, it has a functional group (hereinafter referred to as a non-radically polymerizable functional group) capable of reacting and forming a covalent bond under other conditions.

  In the present invention, by using such a linking monomer, the radical polymerizable vinyl functional group radically polymerizes with another monomer having a vinyl functional group to form one block, while the non-radical A polymerizable functional group reacts with a monomer that forms another block to form a covalent bond, and a block polymer can be obtained very efficiently.

  The radical polymerizable vinyl functional group and the non-radical polymerizable functional group have completely different reaction mechanisms, so that the non-radical polymerizable functional group does not react during the reaction of the radical polymerizable vinyl functional group. Easy to control. Also, there are few restrictions on reaction conditions such as temperature, time, and monomer species to be copolymerized.

  The linking monomer only needs to have at least one of each group, and may have a plurality, but from the viewpoint of easy control of the molecular weight of the polymer, the linking monomer has a radical polymerizable vinyl functional group and a non-radical polymerizable property. Most preferred are those each having one functional group. The radical polymerizable vinyl functional group and the non-radical polymerizable functional group in the linking monomer may be linked by a covalent bond.

  At this time, the radical polymerizable vinyl functional group is copolymerized with a part of at least one block structure, and the non-radical polymerizable functional group reacts with a part of the functional group of at least one block structure and is covalently bonded. ing.

  Non-radical polymerizable functional groups include isocyanate groups, epoxy groups, hydroxyl groups, amine groups, carboxylic acid groups, acid anhydrides, thiosulfide groups, oxazoline groups, and the like. Oxazoline-based functional groups are particularly preferable because of their high reactivity, ease of handling, and limited reaction conditions.

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２〜Ｒ^５はそれぞれ独立して水素原子、アルキル基、アルコキシアルキル基、アリール基、アルキルアリール基、又はアルコキシアリール基を表し、Ａは任意の２価の連結基又は直接結合を表す。） The radical polymerizable vinyl functional group and the oxazoline functional group in the linking monomer may be connected by a covalent bond, and each of the radical polymerizable vinyl functional group and the oxazoline functional group has at least one. It may be sufficient and it may have more than one.
The oxazoline-based functional group here is a general term for those having an oxazoline ring structure including an oxazoline group having a substituent such as an alkyl group or an aryl group. In view of easy control of the molecular weight of the polymer, the linking monomer preferably has one of each group. Among these, from the viewpoint of high reactivity and ease of production or availability of raw materials, the connecting monomer is preferably represented by the following general formula (1).

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ^{2 to} R ⁵ each independently represents a hydrogen atom, an alkyl group, an alkoxyalkyl group, an aryl group, an alkylaryl group, or an alkoxyaryl group; Represents any divalent linking group or direct bond.)

Here, R ¹ is preferably a hydrogen atom in order to increase the reactivity of the oxazoline-based functional group.

R ^{2 to} R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, an aryl group, an alkylaryl group, or an alkoxyaryl group, and the alkyl group portion and the alkoxy group in these groups are linear. But it may be branched. The aryl group in these groups is preferably a phenyl group.

More preferably, R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms having an alkoxy group having 1 to 6 carbon atoms, or 1 to carbon atoms. 6 is a phenyl group optionally substituted by an alkyl group having 6 or an alkoxy group having 1 to 6 carbon atoms. More preferred are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms having an alkoxy group having 1 to 6 carbon atoms. Among them, a hydrogen atom or a methyl group is preferred, and most preferred Is a hydrogen atom. This is to increase the reactivity of the oxazoline functional group.

  A is preferably a direct bond in order to increase the reactivity of the oxazoline functional group.

The linking monomer having the vinyl functional group and the oxazoline functional group represented by the general formula (1) is not particularly limited.
2-vinyl-2-oxazoline,
2-vinyl-4-methyl-2-oxazoline,
2-vinyl-4-dimethyl-2-oxazoline,
2-vinyl-4-diethyl-2-oxazoline,
2-vinyl-4-methoxy-2-oxazoline,
2-vinyl-4-ethoxy-2-oxazoline,
2-vinyl-4-methoxymethyl-2-oxazoline,
2-vinyl-4-phenyl-2-oxazoline,
2-vinyl-5-methyl-2-oxazoline,
2-vinyl-5-ethyl-2-oxazoline,
2-vinyl-5-dimethyl-2-oxazoline,
2-vinyl-5-methoxy-2-oxazoline,
2-vinyl-5-ethoxy-2-oxazoline,
2-vinyl-5-methoxymethyl-2-oxazoline,
2-vinyl-5-phenyl-2-oxazoline,
2-vinyl-4-methoxymethyl-5-phenyl-2-oxazoline 2-isopropenyl-2-oxazoline,
2-isopropenyl-4-methyl-2-oxazoline,
2-isopropenyl-4-dimethyl-2-oxazoline,
2-isopropenyl-4-diethyl-2-oxazoline,
2-isopropenyl-4-methoxy-2-oxazoline,
2-isopropenyl-4-ethoxy-2-oxazoline,
2-isopropenyl-4-methoxymethyl-2-oxazoline,
2-isopropenyl-4-phenyl-2-oxazoline,
2-isopropenyl-5-methyl-2-oxazoline,
2-isopropenyl-5-ethyl-2-oxazoline,
2-isopropenyl-5-dimethyl-2-oxazoline,
2-isopropenyl-5-methoxy-2-oxazoline,
2-isopropenyl-5-ethoxy-2-oxazoline,
2-isopropenyl-5-methoxymethyl-2-oxazoline,
2-isopropenyl-5-phenyl-2-oxazoline,
And 2-isopropenyl-4-methoxymethyl-5-phenyl-2-oxazoline.

  Of these, 2-vinyl-2-oxazoline, 2-vinyl-4-dimethyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline are preferred because of their high reactivity and availability of raw materials. 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-dimethyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-vinyl-4-methoxymethyl-5-phenyl-2 -Oxazoline, more preferably 2-vinyl-2-oxazoline, 2-vinyl-4-dimethyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, most preferably 2-vinyl- 2-oxazoline.

  In forming the block structure, the covalent bond formed using the oxazoline-based functional group is not particularly limited, but is preferably one that has reacted with a carboxylic acid group or one that has reacted with an epoxy group. . The structure after the reaction is as shown below.

（式中、Ｂ及びＣはそれぞれブロックポリマーの一部であり、Ｒ^６は前記一般式（１）におけるＲ^１と同義であり、Ｒ^７〜Ｒ^１０はそれぞれ独立して前記一般式（１）におけるＲ^２〜Ｒ^５と同義である。）

(Wherein, B and C are part of a block polymer, respectively, ^{R 6} has the same meaning as ^{R 1} in the general formula ^(1), the general formula R 7 ^{to R 10} are each independently (1) And is synonymous with R ^{2 to} R ⁵ in FIG.

Hereinafter, the block polymer of the present invention will be described.
The block polymer of the present invention is formed by bonding two or more blocks composed of monomers having a vinyl functional group via a linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group. Preferably, the two or more blocks include at least a first block and a second block having different monomer compositions.

  When the block polymer of the present invention includes a first block and a second block, the radically polymerizable vinyl functional group of the linking monomer is bonded to the monomer of the first block, and the non-radically polymerizable functional group of the linking monomer is the first. Assuming that a linking monomer is included in the first block by combining with two block monomers, the amount of linking monomer relative to the total amount of monomers constituting the first block (hereinafter referred to as “linking monomer ratio in the first block”). In some cases) is preferably 0.1 to 20 wt%.

  When the proportion of the linked monomer in the first block is 0.1 wt% or more, the first block and the second block are easily linked with each other, which is efficient. The proportion of linked monomers in the first block is more preferably 0.2 wt% or more, and even more preferably 0.5 wt% or more. Further, when the proportion of the linked monomer in the first block is 20 wt% or less, the molecular weight is easily controlled, and gelation during polymerization tends to be difficult to handle. The proportion of linked monomers in the first block is more preferably 10 wt% or less, still more preferably 5 wt% or less, and particularly preferably 3 wt% or less.

  The second block preferably includes a monomer having a carboxylic acid group and / or an epoxy group and a vinyl functional group. By having a carboxylic acid group and / or an epoxy group in the second block, it is possible to form a covalent bond with an oxazoline functional group that is a non-radically polymerizable functional group, and by having a vinyl functional group It becomes possible to use for radical polymerization as a part of 2nd block.

  The monomer having a carboxylic acid group and / or an epoxy group and a vinyl functional group may have at least one of either a carboxylic acid group or an epoxy group, and may have a plurality. As long as it has at least one vinyl functional group, it may have a plurality. From the viewpoint of easy control of the molecular weight of the polymer, one vinyl functional group is preferable. Moreover, it is preferable to have only one kind of carboxylic acid group or epoxy group, and it is preferable to have only one carboxylic acid group or epoxy group.

  Although it does not specifically limit as a monomer which has the carboxylic acid group which comprises a 2nd block, and a vinyl type functional group, For example, unsaturated carboxylic acids, such as (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, crotonic acid Monomer. Here, “(meth) acrylic acid” represents acrylic acid and / or methacrylic acid.

As the monomer having a carboxylic acid group and a vinyl functional group, (meth) acrylic acid or a monomer represented by the following formula (6) is particularly preferable.
^{_{CH 2 = C (R 20)}} -COO- (CH 2) e-OCO-Y-COOH ··· (6)
(In the formula, R ²⁰ represents a hydrogen atom or a methyl group, e represents an integer of 1 to 4, and Y represents an optionally substituted phenyl group.)

  In the general formula (6), the substituent that the phenyl group of Y may have is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably 1 to 1 carbon atoms. 3 linear or branched alkyl groups. Most preferably Y is a phenyl group having no substituent. A phenyl group having no substituent is preferable from the viewpoint of easy reaction.

  In the general formula (6), e is preferably an integer of 1 to 3, and most preferably 2. If it is e = 2, it is preferable at the point of the ease of reaction.

What is represented by General formula (6) will not be specifically limited if it is contained in this formula, For example, (meth) acrylic-acid ethyl terephthalate, (meth) acrylic-acid propyl terephthalate etc. are mentioned.
As the monomer having a carboxylic acid group and a vinyl functional group, (meth) acrylic acid is preferable because of its high reactivity and easy availability of raw materials.

In the present invention, a part or all of the carboxylic acid such as (meth) acrylic acid as the monomer component may be used in the form of a salt, and the salt may be formed before or after polymerization. Preferably after polymerization.
In the case of the salt form, hydrogen of the carboxylic acid is substituted with a part of the neutralizing agent, and examples thereof include a metal ion or an ammonium ion which may have a substituent. Examples of monovalent metal ions include alkali metal ions, such as sodium ions, potassium ions, and lithium ions.

Although an ammonium ion may have a substituent, Preferably it is a C1-C30 linear or branched alkyl group which may have a hydroxyl group as a substituent. For example, in addition to ammonium ions, quaternized products of primary to tertiary amines can be mentioned. Specifically, quaternized products of tertiary amines such as lauryldimethylamine, tetradecyldimethylamine, octadecyldimethylamine, and triethanolamine, and primary amines such as laurylamine, tetradecylamine, octadecylamine, and aminomethylpropanol. There are quaternized compounds.
Of these, quaternary ammonium ions are preferred.

The neutralizing agent used for obtaining the salt as described above is not particularly limited. For example, metal hydroxide such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, laurylamine, trimethylamine, Preferable examples include amines such as lauryldimethylamine, monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanol, aminomethylpropanediol, aminoethylpropanediol, N-methylglucamine, arginine, and lysine. These may be used alone or in combination of two or more. The neutralizing agent is more preferably sodium hydroxide or potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, or aminomethylpropanol.
Of these, amines are preferable from the viewpoint of excellent gas compatibility, and monoethanolamine, diethanolamine, triethanolamine, and aminomethylpropanol are particularly preferable, and aminomethylpropanol is most preferable.

  As the monomer having an epoxy group and a vinyl functional group constituting the second block, those represented by the following general formula (7) are preferable.

（式中、Ｒ^２１は水素原子又はメチル基を表し、Ｒ^２２はそれぞれ独立して水素原子又はメチル基を表し、ｎは０〜２０の整数を表す。）
ここで、Ｒ^２１はメチル基が好ましく、Ｒ^２２は水素原子が好ましい。また、ｎは０が好ましい。

(Wherein R ²¹ represents a hydrogen atom or a methyl group, R ²² each independently represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 20).
Here, R ²¹ is preferably a methyl group, and R ²² is preferably a hydrogen atom. N is preferably 0.

Although the monomer which has an epoxy group and a vinyl type functional group will not be specifically limited if it is contained in the said Formula (7), For example, glycidyl (meth) acrylate, glycidyl (ethyleneoxy) ₂ (meth) acrylate, glycidyl _{(propyleneoxy) 2} (meth) acrylate, glycidyl _{(ethyleneoxy) 2 (propyleneoxy) 2} (meth) acrylate, and glycidyl _{(ethyleneoxy) 5 (propyleneoxy) 2} (meth) acrylate. Here, “(meth) acrylate” represents acrylate and / or methacrylate.

  As the monomer having an epoxy group and a vinyl functional group, glycidyl (meth) acrylate is preferable, and glycidyl methacrylate is most preferable in view of easiness of reaction and availability of raw materials.

In addition, the monomer which has the carboxylic acid group and / or epoxy group of a 2nd block, and a vinyl type functional group may be used individually by 1 type, or may use 2 or more types together.
As the monomer having a carboxylic acid group and / or an epoxy group and a vinyl functional group constituting the second block, a monomer having a carboxylic acid group and a vinyl functional group is preferable from the viewpoint that hydrophilicity can be imparted.

  When a linking monomer having a functional group other than the oxazoline functional group is used, it is preferable to have a vinyl monomer having a functional group highly reactive with it in the second block. Examples of the combination include an isocyanate group and a hydroxyl group and / or an amine group, an epoxy group and / or a thiosulfide group and a carboxylic acid group, and an acid anhydride and an amine group.

  The monomer composition of the first block and the second block may be the same, but are preferably different. More specific performance can be expressed by using blocks with different properties.

The first block and the second block may be water-soluble, water-dispersible, or water-insoluble when evaluated independently.
The block polymer of the present invention may be water-soluble, water-dispersible or water-insoluble.

When blending the block polymer of the present invention in a cosmetic composition, for example, a water-insoluble block polymer can be used by dissolving or dispersing in an oil component. If present, it can be used by dissolving and dispersing in water or lower alcohol.
Among them, the block polymer of the present invention is preferably soluble or dispersible in water and / or ethanol because it can be easily incorporated into a cosmetic composition.

In order to express specific performance, it is preferable that the first block and the second block constituting the block polymer of the present invention have significantly different properties, and in particular, either the first block or the second block. It is preferable that one is water-insoluble and the other is water-soluble or water-dispersible.
When the water solubility of the polymer changes depending on the pH, for example, when the block polymer of the present invention has a carboxylic acid group or an amino group, a part or all of it is neutralized with an alkaline substance or an acidic substance. When it is evaluated in the state, the solubility in water is judged. The degree of neutralization is determined by the degree of neutralization in a state as close as possible to the state in which the block polymer is used.

  Water-soluble or water-dispersible here (soluble or dispersible in water) means an effort to homogenize by heating or stirring when the polymer is dissolved in water at a concentration of 1% by weight. When the solution is allowed to stand at 25 ° C. for 24 hours, the polymer does not precipitate and the solution is homogeneous without phase separation. In particular, water-soluble means that the solution in which the polymer is dissolved is transparent, and the transmittance of a 1 cm cell with an optical path length of light having a wavelength of 655 nm is 80% or more. The other state, that is, the state where the polymer precipitates or phase separates or the solution is non-uniform is called water insoluble.

  If either the first block or the second block is water-insoluble and the other is water-soluble or water-dispersible, the first block is water-insoluble and the second block is water-soluble for ease of production. Or it is preferable to set it as water dispersibility.

  Moreover, as for the 1st block and 2nd block which comprise the block polymer of this invention, it is preferable in the physical property that either one is a soft segment and the other is a hard segment. Thereby, for example, when the block polymer of the present invention is used as a hair setting agent, it is possible to obtain a flexible and high setting power.

  Here, the soft segment and the hard segment are indices determined by the softness of the polymer at room temperature, which is a normal use temperature, and are generally determined by the glass transition temperature (Tg). In the present invention, the Tg of each block calculated from the Tg of the homopolymer of each monomer is determined, and those having a Tg of −20 ° C. or lower are defined as soft segments, and those having higher Tg are defined as hard segments. If not, the block with a high value was set as a hard segment, and the block with a low value was set as a soft segment.

  When one of the physical properties of the first block and the second block is a soft segment and the other is a hard segment, the first block is a soft segment and the second block is a hard segment for ease of manufacturing. It is preferable to do.

  In this case, the Tg of the first block is preferably −100 to −20 ° C. More preferably, it is −50 to −20 ° C. Moreover, Tg of a 2nd block becomes like this. Preferably it is -20-150 degreeC, More preferably, it is -10-50 degreeC, Most preferably, it is -5-30 degreeC.

  In the block polymer of the present invention, it is particularly preferable that the first block is a water-insoluble and soft segment and the second block is a water-soluble or water-dispersible and hard segment because of ease of production.

  The water solubility and Tg of each block can be adjusted by appropriately selecting the type and amount of the vinyl monomer constituting each block. The preferred first block and second block configurations are obtained by polymerizing the following monomer compositions, respectively (the preferred monomer composition shown below may be referred to as “preferred monomer composition (1)”). .

<< Preferred monomer composition (1) >>
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 0-79.9 wt%
Hydrophobic vinyl monomer 20-99.9 wt%
(II) Second block Vinyl monomer containing a carboxylic acid group and / or an epoxy group
0.1 to 100 wt%
Hydrophilic vinyl monomer 0-99.9wt%
(However, hydrophilic vinyl monomers that do not contain carboxylic acid groups and / or epoxy groups)
Hydrophobic vinyl monomer 0-90wt%

  The hydrophilic vinyl monomer here is usually a monomer having a solubility in distilled water at 20 ° C. (g / 100 g water) of greater than 1. The solubility is preferably 2 or more, more preferably 5 or more. The hydrophilic vinyl monomer is not particularly limited, and can be arbitrarily selected from, for example, an ionic monomer, a nonionic monomer, or a semipolar monomer.

  On the other hand, the hydrophobic vinyl monomer is a monomer having a solubility in distilled water at 20 ° C. (g / 100 g-water) of 1 or less. The solubility is preferably 0.1 or less, more preferably 0.01 or less. The hydrophobic vinyl monomer is not particularly limited, but is preferably a nonionic monomer.

The amount of linked monomers in the total amount of monomers constituting the first block is preferably 0.1 to 20 wt%.
As described above, when the proportion of the linking monomer in the first block is 0.1 wt% or more, the first block and the second block are easily and reliably connected, which is efficient. This ratio is more preferably 0.2 wt% or more, and still more preferably 0.5 wt% or more. Further, when the proportion of the linked monomer in the first block is 20 wt% or less, the molecular weight is easily controlled, and gelation during polymerization tends to be difficult to handle. This ratio is more preferably 10 wt% or less, further preferably 5 wt% or less, and particularly preferably 3 wt% or less.

  The hydrophilic vinyl monomer amount in the total monomer amount constituting the first block is preferably 0 to 79.9 wt%. This ratio is preferably 79.9 wt% or less because gas compatibility and flexibility are maintained. The amount of the hydrophilic vinyl monomer in the first block is more preferably 70 wt% or less, still more preferably 60 wt% or less, and most preferably 50 wt% or less. Further, the hydrophilic vinyl monomer may not be contained at all, but since the solubility in water or ethanol can be maintained by having an appropriate hydrophilic property, the hydrophilic vinyl monomer is more preferably 10 wt% or more, More preferably, it is 20 wt% or more, and most preferably 30 wt% or more.

  The amount of the hydrophobic vinyl monomer in the total amount of monomers constituting the first block is preferably 20 to 99.9 wt%. By setting this ratio to 20 wt% or more, gas compatibility, flexibility, lack of flaking, and the like are improved. The amount of the hydrophobic vinyl monomer in the first block is more preferably 30 wt% or more, and further preferably 40 wt% or more. In addition, when the amount of the hydrophobic vinyl monomer is 99.9 wt% or less, the connection with the second block by the connection monomer is easily performed. The amount of the hydrophobic vinyl monomer in the first block is more preferably 90 wt% or less, still more preferably 70 wt% or less, and most preferably 60 wt% or less.

  The amount of the vinyl monomer containing a carboxylic acid group and / or an epoxy group in the total monomer amount constituting the second block is preferably 0.1 to 100 wt%. By setting this ratio to 0.1 wt% or more, the connection with the first block by the connecting monomer is easily performed. The amount of the vinyl monomer containing a carboxylic acid group and / or an epoxy group in the second block is more preferably 5 wt% or more, further preferably 10 wt% or more, and most preferably 20 wt% or more. Further, the total monomer of the second block may be a vinyl monomer containing a carboxylic acid group and / or an epoxy group, but more preferably 90 wt% from the viewpoint of affinity to hair and lack of flaking. Or less, more preferably 80 wt% or less, particularly preferably 50 wt% or less, and most preferably 40 wt% or less.

  The amount of the hydrophilic vinyl monomer not containing a carboxylic acid group and / or an epoxy group in the total monomer amount constituting the second block is preferably 0 to 99.9 wt%. By setting this ratio to 99.9 wt% or less, the hydrophilic block monomer containing no carboxylic acid group and / or epoxy group reacts with the linking monomer, so that the first block is sufficiently linked. . The amount of the hydrophilic vinyl monomer that does not contain a carboxylic acid group and / or an epoxy group in the second block is more preferably 80 wt% or less, further preferably 50 wt%, from the viewpoint of gas compatibility and flexibility. Or less, and most preferably 30 wt% or less.

  The amount of the hydrophobic vinyl monomer in the total amount of monomers constituting the second block is preferably 0 to 90 wt%. By setting this ratio to 90 wt% or less, moderate hydrophilicity can be imparted and the affinity for hair tends to increase. The amount of the hydrophobic vinyl monomer in the second block is more preferably 80 wt% or less. The second block may not contain any hydrophobic vinyl monomer, but from the viewpoint of gas compatibility and flexibility, the amount of the hydrophobic vinyl monomer is more preferably 10 wt% or more, and still more preferably. It is 30 wt% or more, and most preferably 50 wt% or more.

  What is suitable as a hydrophilic vinyl-type monomer contained in a 1st block and a 2nd block has a structure of following General formula (2) and / or (3).

_{^{CH 2 = C (R 11)}} -CO-NR 12 R 13 ··· (2)
(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a carbon number 1 having a hydroxyl group. Represents a linear or branched alkyl group of ˜3.)

^{_{CH 2 = C (R 14)}} -CO (O) - (CH 2) a- (CHOH) b-O-R 15
... (3)
(In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, R ¹⁵ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, a represents an integer of 1 to 4, and b represents 0. Or 1)

In General Formula (2), R ¹¹ is preferably a hydrogen atom, and R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group that may have a hydroxyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms of R ¹² and R ¹³ include a methyl group, an ethyl group, a propyl group, and an isopropyl group. As a C1-C3 alkyl group which has a hydroxyl group, a hydroxymethyl group, 2-hydroxyethyl group, etc. are mentioned, for example. The sum of the carbon numbers of R ¹² and R ¹³ is preferably 2 or more and 4 or less, and most preferably 2.

In the general formula (3), R ¹⁴ is preferably a methyl group, R ¹⁵ is preferably an ethyl group, a is preferably an integer of 1 to 3, and most preferably 2. b is preferably 0.

  The vinyl monomer represented by the general formula (2) is not particularly limited as long as it is included in this formula. For example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl Alkyl acrylamides such as (meth) acrylamide and N-isopropyl (meth) acrylamide; Dialkyl acrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide; N-hydroxymethyl (meth) Hydroxyalkyl (meta) such as acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide ) Acrylamides; In "(meth) acrylic" means acrylic and methacrylic). Among these, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N are preferable. -Diethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide.

  The vinyl monomer represented by the general formula (3) is not particularly limited as long as it is included in this formula. For example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxy Hydroxyalkyl (meth) acrylates such as propyl (meth) acrylate, 1,2-dihydroxypropyl (meth) acrylate, methoxymethyl (meth) acrylate, ethoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl ( Examples include alkoxyalkyl (meth) acrylates such as (meth) acrylate and butoxyethyl (meth) acrylate. Of these, 2-hydroxyethyl (meth) acrylate, 1,2-dihydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, and ethoxyethyl (meth) acrylate are preferable.

  In addition, as hydrophilic vinyl monomers other than the monomers represented by the general formulas (2) and (3), short-chain alkyl acrylates such as methyl (meth) acrylate; methyl (meth) acrylamide, ethyl (meth) acrylamide, Short chain alkylamides such as propyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, trimethylammonioethyl ( (Meth) acrylate = chloride, trimethylammoniopropyl (meth) acrylate = chloride, trimethylammonioethyl (meth) acrylamide = chloride, trimethylammonioethyl (meth) acrylamide = Cationic acrylics such as Ride; Nonionic acrylics having a cyclic structure such as N-acryloylmorpholine and tetrahydrofurfuryl (meth) acrylate; ethyl carboxybetaine (meth) acrylate, (meth) acrylamidopropyl carboxybetaine, Acrylic compounds having a betaine structure such as (meth) acrylic acid ethylsulfobetaine and (meth) acrylamidopropylsulfobetaine; amine oxide structures such as (meth) acrylic acid ethyldimethylamine oxide and (meth) acrylamidopropyldimethylamine oxide Acrylics having the following can also be used.

  Moreover, what was illustrated as a monomer containing the carboxylic acid group and / or epoxy group which are contained in a 2nd block as a hydrophilic vinyl-type monomer of a 1st block can also be used.

  When used as a hair setting agent, it is included in the first block and the second block from the viewpoints of affinity for hair, solubility in water and / or ethanol, and compatibility with a propellant. The hydrophilic vinyl monomer is preferably a hydrophilic vinyl monomer represented by the general formula (3), preferably hydroxyalkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, more preferably 2-hydroxy. Ethyl (meth) acrylate, methoxyethyl (meth) acrylate, and ethoxymethyl (meth) acrylate.

  In addition, a hydrophilic vinyl monomer may be used individually by 1 type, may use 2 or more types together, and may use what is represented by General formula (2) or (3) together.

  A thing suitable as a hydrophobic vinyl-type monomer contained in a 1st block and a 2nd block has a structure of following General formula (4) and / or (5).

CH ₂ = C (R ¹⁶ ) —CO—O—R ¹⁷ (4)
(Wherein R ¹⁶ represents a hydrogen atom or a methyl group, and R ¹⁷ represents a linear, branched or cyclic alkyl group having 2 to 30 carbon atoms.)

^{_{CH 2 = C (R 18)}} -CO-NH-R 19 ··· (5)
(Wherein R ¹⁸ represents a hydrogen atom or a methyl group, and R ¹⁹ represents a linear, branched or cyclic alkyl group having 6 to 30 carbon atoms.)

In the general formulas (4) and (5), R ¹⁶ and R ¹⁸ are preferably methyl groups, and R ¹⁷ is preferably an alkyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 4 to 18 carbon atoms. R ¹⁹ is preferably an alkyl group having 6 to 18 carbon atoms.

  The vinyl monomer represented by the general formula (4) is not particularly limited as long as it is included in this formula. For example, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like. Of these, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate are preferable.

  The vinyl monomer represented by the general formula (5) is not particularly limited as long as it is included in this formula. For example, hexyl (meth) acrylamide, octyl (meth) acrylamide, 2-ethylhexyl (meth) acrylamide , Lauryl (meth) acrylamide, stearyl (meth) acrylamide and the like. Of these, octyl (meth) acrylamide, lauryl (meth) acrylamide, and stearyl (meth) acrylamide are preferable.

  Examples of the hydrophobic vinyl monomer other than the monomers represented by the general formulas (4) and (5) include benzyl (meth) acrylate, p-bromophenyl (meth) acrylate, and pt-butylphenyl (meth). Acrylic group-containing acrylics such as acrylate; Fluorine-containing acrylics such as trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate; Silicone macromonomers such as polydimethylsiloxane alkyl (meth) acrylate; Can be used.

  When the block polymer is used for a hair setting agent, it has the following characteristics in terms of affinity for hair and solubility in water and / or ethanol, compatibility with a propellant, and flexibility during use. The hydrophobic vinyl monomer contained in the first block and the second block is preferably a hydrophobic vinyl monomer represented by the general formula (4).

  In addition, a hydrophobic vinyl type monomer may be used individually by 1 type, may use 2 or more types together, and may use what is represented by General formula (4) or (5) together.

  As for the weight average molecular weight of each block which comprises the block polymer of this invention, 1,000-500,000 are respectively preferable. By setting the weight average molecular weight of each block to 1,000 or more, the properties of each block are easily reflected in the entire block polymer, and the setting power and flexibility are improved in the use as a hair setting agent composition. More preferably, the weight average molecular weight is 3,000 or more, and more preferably 5,000 or more. By setting the weight average molecular weight to 500,000 or less, the handleability during production becomes easy. More preferably, the weight average molecular weight is 100,000 or less, more preferably 50,000, and most preferably 20,000 or less.

  The weight average molecular weight of the block polymer of the present invention is preferably 3,000 to 1,000,000. By setting the weight average molecular weight to 3,000 or more, the setting power is increased in the use as a hair setting agent composition. More preferably, it is 5,000 or more, More preferably, it is 10,000 or more. When the weight average molecular weight is 1,000,000 or less, the handleability during production becomes easy. More preferably, it is 500,000 or less, More preferably, it is 100,000, Most preferably, it is 50,000 or less.

  The weight ratio of the first block and the second block constituting the block polymer of the present invention is preferably in the range of 1/99 to 99/1. Thereby, the property of each block is easily reflected in the entire block polymer, and the setting power and flexibility are improved in the use as a hair setting agent composition. More preferably, the weight ratio is 1/50 to 50/1, more preferably 1/9 to 9/1, still more preferably 1/3 to 3/1, and most preferably 1/2 to 2. / 1.

The weight average molecular weight of the polymer can be measured by gel permeation chromatography (for example, using tetrahydrofuran as a developing solvent).
In the block polymer, when each block has extremely different properties, the solubility of the block is different, so that it may be difficult to accurately measure the molecular weight under a single condition.
Since it is known that the magnitude of the molecular weight is relatively correlated with the solution viscosity, in such a case, the solution viscosity may be evaluated instead of the molecular weight.

  The block polymer of the present invention preferably has a viscosity capable of preparing a 30 wt% ethanol solution at 25 ° C., more preferably the viscosity of the 30 wt% ethanol solution at 25 ° C. is 10,000 mPa · s or less, Preferably, it is 5,000 mPa · s or less. However, this viscosity is usually 10 mPa · s or more.

  The molecular weight and viscosity of the polymer can be adjusted, for example, by controlling the degree of polymerization of the polymer in the method for producing a block polymer of the present invention described later. The molecular weight and viscosity can also be controlled by increasing or decreasing the addition amount of a crosslinking agent such as a polyfunctional acrylate. However, if the crosslinking agent is added too much, the molecular weight and the viscosity are rapidly increased. For industrial production, it is difficult to control the addition amount. For this reason, it is most preferable not to use a crosslinking agent.

<Block polymer for hair set composition>
When the block polymer of the present invention is used in a hair setting agent composition, preferably, in the above-mentioned preferred monomer composition (1), the water solubility and Tg of each block are adjusted to make it suitable as a hair setting agent. .

Below, the block polymer suitable when using for a hair set agent composition is demonstrated.
In this case, the first block may be water-soluble, water-dispersible, or water-insoluble, but is preferably water-dispersible or water-insoluble, and most preferably water-insoluble. The second block is preferably water-soluble and water-dispersible, and most preferably water-soluble.

  The water solubility and Tg of the block polymer are adjusted by appropriately selecting the type and amount of vinyl monomers constituting each block. Especially when used as a hair set agent, affinity for hair and gas From the viewpoint of compatibility, the hydrophilic vinyl monomer contained in the first block is preferably the hydrophilic vinyl monomer represented by the general formula (3), preferably hydroxyalkyl (meth) acrylates, alkoxy Alkyl (meth) acrylates, more preferably 2-hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, and ethoxymethyl (meth) acrylate. The hydrophilic vinyl monomer contained in the second block includes the hydrophilic vinyl monomer represented by the general formula (3), short chain alkyl acrylates such as methyl (meth) acrylate, and methyl (meth) acrylamide. , Short chain alkylamides such as ethyl (meth) acrylamide and propyl (meth) acrylamide are preferred, and preferably short chains such as hydroxyalkyl (meth) acrylates, alkoxyalkyl (meth) acrylates and methyl (meth) acrylate Alkyl acrylates, more preferably 2-hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and methyl (meth) acrylate.

In addition, the hydrophobic vinyl monomer contained in the first block is a hydrophobic vinyl monomer represented by the general formula (4) in terms of curl retention, flexibility, non-stickiness, and gas compatibility. Are more preferable, and 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate are more preferable. The hydrophobic vinyl monomer contained in the second block is preferably a hydrophobic vinyl monomer represented by the general formula (4), more preferably ethyl (meth) acrylate, propyl (meth) acrylate, butyl. (Meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, most preferably ethyl Hydrophobic vinyl monomers having a short alkyl chain length such as (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, - ethylhexyl (meth) acrylate, is that the combination lauryl (meth) acrylate, stearyl (meth) alkyl chain length such as acrylates and long hydrophobic vinyl-based monomer by at least one, respectively.
In addition, a hydrophobic vinyl type monomer may be used individually by 1 type, may use 2 or more types together, and may use what is represented by General formula (4) or (5) together.

<Block polymer for aqueous composition for hair cosmetics>
When the block polymer of the present invention is used in an aqueous composition for hair cosmetics, among the block polymers of the present invention, if it is soluble or dispersible in water, there is a formulation that suppresses the amount of volatile organic solvent blended. It is easy to perform and is preferable.

  The aqueous composition for hair cosmetics using the block polymer of the present invention can be suitably used as a hair setting agent because of its good setting power, and also suitable for use as a treatment agent because of its conditioning effect. be able to.

Below, the block polymer of this invention suitable when using for the aqueous composition for hair cosmetics is demonstrated.
In this case, the first block may be water-soluble, water-dispersible, or water-insoluble, but is preferably water-dispersible or water-insoluble, and most preferably water-insoluble. The second block is preferably water soluble or water dispersible, most preferably water soluble.

  The Tg of the first block is preferably -100 to 20 ° C. More preferably, it is −50 to 0 ° C. Moreover, Tg of a 2nd block becomes like this. Preferably it is 20-150 degreeC, More preferably, it is 20-100 degreeC, Most preferably, it is 30-90 degreeC.

  The water solubility and Tg of each block can be adjusted by appropriately selecting the type and amount of the vinyl monomer constituting each block. The preferred first block and second block configurations are obtained by polymerizing the following monomer compositions, respectively (the preferred monomer composition shown below may be referred to as “preferred monomer composition (2)”).

<< Preferred monomer composition (2) >>
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 10-89.9wt%
Hydrophobic vinyl monomer 10-89.9 wt%
(II) Second block Vinyl monomer containing a carboxylic acid group and / or an epoxy group
10-90 wt%
Hydrophilic vinyl monomer 0-90 wt%
(However, hydrophilic vinyl monomers that do not contain carboxylic acid groups and / or epoxy groups)
Hydrophobic vinyl monomer 0-50 wt%

  The hydrophilic vinyl monomer amount in the total monomer amount constituting the first block is preferably 10 to 89.9 wt%. By making this ratio 10 wt% or more, it is possible to have affinity for water and maintain solubility or dispersibility in water, which is preferable. The amount of the hydrophilic vinyl monomer in the first block is more preferably 20 wt% or more, and further preferably 30 wt% or more. In addition, it is preferable that the amount of the hydrophilic vinyl monomer is 89.9 wt% or less because moisture resistance and flexibility are maintained. This ratio is more preferably 70 wt% or less, and still more preferably 60 wt% or less.

  The amount of the hydrophobic vinyl monomer in the total amount of monomers constituting the first block is preferably 10 to 89.9 wt%. By setting this ratio to 10 wt% or more, flexibility, lack of flaking, and the like are improved. The amount of the hydrophobic vinyl monomer in the first block is more preferably 20 wt% or more, and further preferably 30 wt% or more. In addition, when the amount of the hydrophobic vinyl monomer is 89.9 wt% or less, the connection with the second block by the connection monomer is easily performed. The amount of the hydrophobic vinyl monomer in the first block is more preferably 70 wt% or less, and still more preferably 60 wt% or less.

  The amount of vinyl monomers containing carboxylic acid groups and / or epoxy groups in the total amount of monomers constituting the second block is preferably 10 to 90 wt%. By making this ratio 10 wt% or more, the connection with the first block by the connecting monomer is sufficiently performed. This ratio is more preferably 20 wt% or more, and further preferably 30 wt% or more. Moreover, since the moisture resistance can be improved by setting the amount of the vinyl monomer containing a carboxylic acid group and / or an epoxy group to 90 wt% or less, it is preferable. From the viewpoint of affinity to hair and lack of flaking, this ratio is more preferably 80 wt% or less, still more preferably 70 wt% or less, and most preferably 60 wt% or less.

  Moreover, it is preferable that there are more vinyl-type monomers containing the carboxylic acid group and / or epoxy group which comprise a 2nd block than the connection monomer which comprises a 1st block. At this time, some of the vinyl monomers containing a carboxylic acid group and / or an epoxy group constituting the second block contribute to the reaction with the linking monomer, but the surplus part functions as a hydrophilic monomer. Furthermore, since the vinyl monomer containing a carboxylic acid group contributes more to the solubility and dispersibility in water than the vinyl monomer containing an epoxy group, it is preferable to use a vinyl monomer containing a carboxylic acid group. . Preferably, the proportion of the amount of vinyl monomer containing a carboxylic acid group in the amount of vinyl monomer containing a carboxylic acid group and / or an epoxy group constituting the second block is 50 wt% or more, more preferably It is 70 wt% or more, more preferably 90 wt%, and most preferably 100 wt%.

  The amount of the hydrophilic vinyl monomer not containing a carboxylic acid group and / or an epoxy group in the total monomer amount constituting the second block is preferably 0 to 90 wt%. When the amount of the vinyl monomer containing a carboxylic acid group and / or an epoxy group is small, water-solubility is imparted by using a hydrophilic vinyl monomer that does not contain a carboxylic acid group and / or an epoxy group. preferable. This ratio is more preferably 10 wt% or more, still more preferably 20 wt% or more, particularly preferably 30 wt% or more, and most preferably 40 wt% or more. In addition, the amount of the hydrophilic vinyl monomer that does not contain a carboxylic acid group and / or an epoxy group in the second block is 90 wt% or less, so that a hydrophilic vinyl monomer that contains a carboxylic acid group and / or an epoxy group By the reaction with the linking monomer, the linking with the first block is sufficiently performed. The amount of the hydrophilic vinyl monomer that does not contain a carboxylic acid group and / or an epoxy group in the second block is more preferably 80 wt% or less, still more preferably 70 wt% or less, from the viewpoint of flexibility and the like. Preferably it is 60 wt% or less.

  The hydrophobic vinyl monomer amount in the total monomer amount constituting the second block is preferably 0 to 50 wt%. By setting this ratio to 50 wt% or less, moderate hydrophilicity can be imparted, and the affinity for hair tends to increase. The amount of the hydrophobic vinyl monomer in the second block is more preferably 40 wt% or less, further preferably 30 wt% or less, and most preferably 20 wt% or less. The second block may not contain any hydrophobic vinyl monomer, but from the viewpoint of flexibility, the amount of the hydrophobic vinyl monomer is more preferably 1 wt% or more, and further preferably 3 wt% or more. Yes, most preferably 5 wt% or more.

  When the block polymer of the present invention is used as an aqueous composition for hair cosmetics, the hydrophilic vinyl monomer contained in the first block is the above-mentioned from the viewpoints of affinity for hair and solubility in water. The hydrophilic vinyl monomer represented by the general formula (3) is preferable, preferably hydroxyalkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, more preferably 2-hydroxyethyl (meth) acrylate, methoxy. They are ethyl (meth) acrylate and ethoxymethyl (meth) acrylate. These may be used alone or in combination of two or more.

  The hydrophilic vinyl monomer contained in the second block includes the hydrophilic vinyl monomer represented by the general formula (3), short chain alkyl acrylates such as methyl (meth) acrylate, and methyl (meth) acrylamide. , Short chain alkylamides such as ethyl (meth) acrylamide and propyl (meth) acrylamide are preferred, and preferably short chains such as hydroxyalkyl (meth) acrylates, alkoxyalkyl (meth) acrylates and methyl (meth) acrylate Alkyl acrylates, more preferably 2-hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and methyl (meth) acrylate. These may be used alone or in combination of two or more.

  When the block polymer of the present invention is used as an aqueous composition for hair cosmetics, the first block and the second block are used from the viewpoints of affinity for hair, solubility in water, and flexibility during use. The hydrophobic vinyl monomer contained in the block is preferably a hydrophobic vinyl monomer represented by the general formula (4). In addition, a hydrophobic vinyl monomer may be used individually by 1 type, may use 2 or more types together, and may use what is represented by the said General formula (4) or (5) together.

  When the block polymer of the present invention is used as an aqueous composition for hair cosmetics, the weight average molecular weight of each block constituting the block polymer of the present invention is preferably 1,000 to 500,000, respectively. By setting the weight average molecular weight of each block to 1,000 or more, the properties of each block are easily reflected in the entire block polymer, and the setting power and flexibility are improved in applications as an aqueous composition for hair cosmetics. . More preferably, the weight average molecular weight is 3,000 or more, and more preferably 5,000 or more. Moreover, the handleability at the time of manufacture becomes easy by making a weight average molecular weight into 500,000 or less. More preferably, the weight average molecular weight is 100,000 or less, more preferably 50,000, and most preferably 20,000 or less.

  When the block polymer of the present invention is used as an aqueous composition for hair cosmetics, the weight average molecular weight of the block polymer of the present invention is preferably 3,000 to 1,000,000. By setting the weight average molecular weight to 3,000 or more, the setting power is increased in applications as an aqueous composition for hair cosmetics. More preferably, the weight average molecular weight of the block polymer is 5,000 or more, and more preferably 10,000 or more. Moreover, the handleability at the time of manufacture becomes easy by making the weight average molecular weight of a block polymer into 1,000,000 or less. The weight average molecular weight of the block polymer is more preferably 500,000 or less, still more preferably 100,000, and most preferably 50,000 or less.

  When the block polymer of the present invention is used as an aqueous composition for hair cosmetics, the weight ratio of the first block and the second block constituting the block polymer of the present invention is in the range of 1/99 to 99/1. It is preferable that Thereby, the properties of each block are easily reflected in the entire block polymer, and the setting power and flexibility are improved in the use as an aqueous composition for hair cosmetics. A more preferable weight ratio is 1/50 to 50/1, further preferably 1/9 to 9/1, still more preferably 1/3 to 3/1, and most preferably 1/2 to 2 /. 1.

  When the block polymer of the present invention is used as an aqueous composition for hair cosmetics, the block polymer of the present invention preferably has a viscosity capable of preparing a 5% by weight aqueous solution having fluidity at 25 ° C., more preferably The viscosity of a 10 wt% aqueous solution at 25 ° C. is 10,000 mPa · s or less, more preferably 5,000 mPa · s or less. However, this viscosity is usually 10 mPa · s or more.

<Block polymer for detergent composition for cosmetics>
When the block polymer of the present invention is used in a detergent composition for cosmetics, among the block polymers of the present invention, those soluble in water are preferable. It is preferable because it can be easily blended into products.
Since the cosmetic cleaning composition using the block polymer of the present invention has a high conditioning effect, it can be used as a skin cleaning composition or a hair cleaning composition. In particular, shampoos, conditioners, and treatments can be mentioned as hair cleaning compositions. The cosmetic detergent composition using the block polymer of the present invention is particularly suitable for shampooing.
Below, the block polymer of this invention suitable when using it for the cleaning composition for cosmetics is demonstrated.

  The first block and the second block are preferably water-soluble or water-dispersible, and most preferably water-soluble.

  The water solubility of each block can be adjusted by appropriately selecting the type and amount of the vinyl monomer constituting each block. The preferred first block and second block configurations are obtained by polymerizing the following monomer compositions, respectively (the preferred monomer composition shown below may be referred to as “preferred monomer composition (3)”). .

<< Preferred monomer composition (3) >>
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 60-99.9 wt%
Hydrophobic vinyl monomer 0-30 wt%
(II) Second block Vinyl monomer containing a carboxylic acid group and / or an epoxy group
0.1-20 wt%
Hydrophilic vinyl monomer 60-99.9 wt%
(However, hydrophilic vinyl monomers that do not contain carboxylic acid groups and / or epoxy groups)
Hydrophobic vinyl monomer 0-30 wt%

  The amount of the hydrophilic vinyl monomer in the total amount of monomers constituting the first block is preferably 60 to 99.9 wt%. It is preferable to set this ratio to 60 wt% or more because solubility or dispersibility in water can be improved. The amount of the hydrophilic vinyl monomer in the first block is more preferably 70 wt% or more, and further preferably 80 wt% or more. Further, by setting the amount of the hydrophilic vinyl monomer to 99.9 wt% or less, the connection with the second block is sufficiently performed, so that the smoothness at the time of rinsing is improved, which is preferable. This ratio is more preferably 99.8 wt% or less, and still more preferably 99.5 wt% or less.

  The amount of the hydrophobic vinyl monomer in the total amount of monomers constituting the first block is preferably 0 to 30 wt%. By making this ratio 30 wt% or less, water solubility can be maintained. The amount of the hydrophobic vinyl monomer in the first block is more preferably 20 wt% or less, and further preferably 10 wt% or less.

  The amount of the vinyl monomer containing a carboxylic acid group and / or an epoxy group in the total monomer amount constituting the second block is preferably 0.1 to 20 wt%. By setting this ratio to 0.1 wt% or more, the connection with the first block by the connection monomer is sufficiently facilitated. This ratio is more preferably 1 wt% or more, and further preferably 3 wt% or more. In addition, when the amount of the vinyl monomer containing a carboxylic acid group and / or an epoxy group is 20 wt% or less, the interaction with the surfactant can be maintained, and the smoothness during rinsing is maintained. Therefore, it is preferable. From the viewpoint of smoothness at the time of rinsing, it is more preferably 15 wt% or less, further preferably 10 wt% or less, and most preferably 5 wt% or less.

  The amount of the hydrophilic vinyl monomer not containing a carboxylic acid group and / or an epoxy group in the total amount of monomers constituting the second block is preferably 60 to 99.9 wt%. This ratio is preferably 60 wt% or more because water solubility is imparted. This ratio is more preferably 70 wt% or more, further preferably 80 wt% or more, particularly preferably 90 wt% or more, and most preferably 95 wt% or more. Moreover, the hydrophilic vinyl type monomer containing a carboxylic acid group and / or an epoxy group is set to 99.9% by weight or less of the amount of the hydrophilic vinyl monomer containing no carboxylic acid group and / or epoxy group in the second block. The monomer and the linking monomer react with each other, so that the linking with the first block is sufficiently performed. The amount of the hydrophilic vinyl monomer that does not contain a carboxylic acid group and / or an epoxy group in the second block is more preferably 99.5 wt% or less from the viewpoint of water solubility and smoothness at the time of rinsing. 99 wt% or less, and most preferably 98 wt% or less.

  The amount of the hydrophobic vinyl monomer in the total amount of monomers constituting the second block is preferably 0 to 30 wt%. By setting this ratio to 30 wt% or less, moderate hydrophilicity can be imparted and the affinity for hair tends to increase. The amount of the hydrophobic vinyl monomer in the second block is more preferably 20 wt% or less, further preferably 10 wt% or less, and most preferably 5 wt% or less.

  When the block polymer is used as a cosmetic cleaning composition, the hydrophilic vinyl monomer contained in the first block is represented by the above general formula (from the viewpoints of affinity for hair and solubility in water). It is preferable that the monomer represented by 2) or (3) is included. Among these, the hydrophilic vinyl monomer represented by the general formula (2) is preferable, and dialkyl acrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide; -Hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide Hydroxyalkyl (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxy) Ethyl) (meth) acrylamide and most preferred Ku is a N, N-dimethyl (meth) acrylamide, N- (2- hydroxyethyl) (meth) acrylamide. These may be used alone or in combination of two or more.

  The hydrophilic vinyl monomer contained in the second block is preferably a hydrophilic vinyl monomer (cationic group-containing vinyl monomer) represented by the general formula (2) or the following general formula (10).

^{_{CH 2 = C (R 25)}} -CO- (O) c - (NH) 1-c - (CH 2) d -N + R 26 R 27 R 28 · X - ··· (10)
(In the formula, R ²⁵ represents a hydrogen atom or a methyl group, R ²⁶ and R ²⁷ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and R ²⁸ represents a hydrogen atom or carbon number. Represents an alkyl group of 1 to 24, an aryl group, an aralkyl group, or —CH ₂ —CH (OH) —CH ₂ —N ⁺ R ²⁹ R ³⁰ R ³¹ • Z ^— , wherein R ^{29 to} R ³¹ are each independently carbon; It represents the number 1 to 24 alkyl group, aryl group or aralkyl group, X ^- and Y ^- is any negative ions independently, c is 0 or 1, d represents an integer of 1 to 10).

  More preferable examples of the hydrophilic vinyl monomer represented by the general formula (2) include dialkylacrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide; N-hydroxymethyl Hydroxy such as (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide Alkyl (meth) acrylamides, and more preferably N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) ( Meth) acrylamide, most preferably N, - dimethyl (meth) acrylamide, N- (2- hydroxyethyl) (meth) acrylamide. These may be used alone or in combination of two or more.

In the hydrophilic vinyl monomer represented by the general formula (10), R ²⁵ is preferably a methyl group. R ²⁶ and R ²⁷ are each independently preferably a methyl group or an ethyl group, and more preferably a methyl group. R ²⁸ is preferably a methyl group or an ethyl group, and more preferably a methyl group. R ^{29 to} R ³¹ are each independently preferably a methyl group or an ethyl group, and more preferably a methyl group.
X ^- and Z ^- as the anion represented by a halogen ion is preferable independently, a chlorine ion, an iodine ion or a bromine ion is more preferred.
c is preferably 0, d is preferably an integer of 1 to 5, and more preferably 3.

  Examples of the hydrophilic vinyl monomer represented by the general formula (10) include N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride, N- (meth) acryloyloxyethyl-N -Ethyl-N, N-dimethylammonium monoethyl sulfate, N- (meth) acryloyloxyethyl-N, N, N-triethylammonium monoethyl sulfate, N- [3- {N '-(meth) acryloyloxy Ethyl-N ′, N′-dimethylammonium} -2-hydroxypropyl] -N, N, N-trimethylammonium chloride, N- [3- {N ′-(meth) acryloyloxyethyl-N ′, N′- Diethylammonium} -2-hydroxypropyl] -N, N, N-triethylammonium chloride, etc. (Meth) acrylic acid esters having a thione group; N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride, N- (meth) acryloylaminopropyl-N-ethyl-N, N-dimethyl Ammonium = monoethyl sulfate, N- (meth) acryloylaminopropyl-N, N-diethyl-N-methylammonium chloride, N- (meth) acryloylaminopropyl-N, N-diethyl-N-methylammonium = monomethyl sulfate N- [3- {N ′-(meth) acryloylaminopropyl-N ′, N′-dimethylammonium} -2-hydroxypropyl] -N, N, N-trimethylammonium chloride, N- [3- {N '-(Meth) acryloylaminopropyl-N', N'-diethyla Moniumu} -2-hydroxypropyl] -N, N, N- trimethyl ammonium chloride having a cationic group of the ride, etc. (meth) acrylamides, and the like. These hydrophilic vinyl monomers may be used alone or in combination of two or more.

  Of these, N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride and N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride are preferably used. ) Acryloylaminopropyl-N, N, N-trimethylammonium chloride is preferred. Most preferred is the combined use of N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride and N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride.

  In particular, the hydrophilic vinyl monomer of the second block preferably includes a cationic group-containing vinyl monomer represented by the general formula (10). In particular, it is preferable to use, as the cationic group-containing vinyl monomer, one having an amide bond, that is, a vinyl monomer having c = 0 in the general formula (10). By using such a cationic group-containing vinyl monomer, when the block polymer has an amide bond, there is an advantage that the adsorption to the hair is promoted. That is, by having an amide bond, the cationic strength of the cationic functional group is increased, the binding force with the anionic surfactant is increased, and the adsorptive power to the hair is increased. Thereby, when using the detergent composition for cosmetics which mix | blended the block polymer of this invention, the smoothness at the time of a rinse can be heightened especially.

  The amount of the cationic group-containing vinyl monomer represented by the general formula (10) in the total amount of monomers constituting the second block is preferably 10 to 90 wt%. By making this ratio 10 wt% or more, smoothness during rinsing is imparted, which is preferable. This ratio is more preferably 20 wt% or more, still more preferably 30 wt% or more, and most preferably 40 wt% or more. Further, by setting the amount of the cationic group-containing vinyl monomer represented by the general formula (10) in the second block to 90 wt% or less, other than the cationic group-containing vinyl monomer represented by the general formula (10) These hydrophilic vinyl monomers are preferred because they maintain water solubility. The amount of the cationic group-containing vinyl monomer represented by the general formula (10) in the second block is more preferably 80 wt% or less, further preferably 70 wt%, from the viewpoint of water solubility and smoothness during rinsing. Or less, and most preferably 60 wt% or less.

  The role of the conditioning polymer blended in the hair cleaning composition is to impart smoothness when rinsing, smoothness after drying, no wrinkle after drying, etc. But most important is the smoothness of the rinse. Because after treatment with a detergent composition, treatment with a rinse, conditioner or non-wash-out type of out bath treatment agent can increase the feel after drying, but the smoothness of rinsing is otherwise This is because it cannot be compensated by this method. Accordingly, the conditioning polymer is most preferably a polymer excellent in smoothness during rinsing.

  The structure corresponding to the general formula (10) is converted to a structure having a corresponding cationic group by a cationizing agent after polymerizing a precursor of a cationic group-containing vinyl monomer with another monomer to form a copolymer. By doing so, it can also be introduced into the block polymer.

  In this case, as the cationic group-containing vinyl monomer precursor, for example, N- (meth) acryloyloxyethyl-N, N-dimethylamine, N- (meth) acryloyloxyethyl-N, N-diethylamine, etc. (Meth) acrylic acid esters having a secondary amine; tertiary amines such as N- (meth) acryloylaminopropyl-N, N-dimethylamine, N- (meth) acryloylaminopropyl-N, N-diethylamine ( And (meth) acrylamides.

Examples of the cationizing agent include alkyl halides such as methyl chloride and cation group-containing cationizing agents such as 3-chloro-2-hydroxypropyl-N, N, N-trimethylammonium chloride.
The cationization reaction can be carried out, for example, by adding a cationizing agent to a polymer solution under the conditions of 20 to 100 ° C. and 1 to 20 hours.
In addition, as for said hydrophilic vinyl type monomer, its precursor, and a cationizing agent, all may be used individually by 1 type, or may use 2 or more types together.

  In the case where the block polymer of the present invention is used as a cosmetic detergent composition, from the viewpoints of affinity to hair and solubility in water, smoothness during rinsing, and feel after drying. The hydrophobic vinyl monomer contained in the first block and the second block is preferably a hydrophobic vinyl monomer represented by the general formula (4). In addition, a hydrophobic vinyl monomer may be used individually by 1 type, may use 2 or more types together, and may use what is represented by the said General formula (4) or (5) together.

  When the block polymer of the present invention is used as a cosmetic detergent composition, the weight average molecular weight of each block constituting the block polymer of the present invention is preferably 5,000 to 1,000,000. By setting the weight average molecular weight of each block to 5,000 or more, the properties of each block are easily reflected in the entire block polymer, and in use as a cosmetic detergent composition, smoothness during rinsing and after drying The touch is improved. More preferably, the weight average molecular weight is 10,000 or more, and further preferably 50,000 or more. Moreover, the handleability at the time of manufacture becomes easy by making a weight average molecular weight into 1,000,000 or less. More preferably, the weight average molecular weight is 500,000 or less, more preferably 20,000 or less, and most preferably 10,000 or less.

  When the block polymer of the present invention is used as a cosmetic detergent composition, the weight average molecular weight of the block polymer of the present invention is preferably 10,000 to 2,000,000. By setting the weight average molecular weight to 10,000 or more, the smoothness at the time of rinsing and the feeling after drying are improved in the use as a cleaning composition for cosmetics. The weight average molecular weight of the block polymer is more preferably 50,000 or more, and still more preferably 100,000 or more. Moreover, the handleability at the time of manufacture becomes easy by making the weight average molecular weight of a block polymer into 2,000,000 or less. The weight average molecular weight of the block polymer is more preferably 1,000,000 or less, still more preferably 500,000 or less, and most preferably 300,000 or less.

  Moreover, when using the block polymer of this invention as a detergent composition for cosmetics, the weight ratio of the 1st block which comprises the block polymer of this invention, and a 2nd block is the range of 1 / 99-99 / 1. It is preferable that By setting such a weight ratio, the properties of each block are easily reflected in the entire block polymer, and the smoothness at the time of rinsing and the feeling after drying are improved in the use as a detergent composition for cosmetics. A more preferred weight ratio is 1/50 to 50/1, still more preferably 1/9 to 9/1, still more preferably 1/3 to 3/1, and most preferably 1/2 to 2. / 1.

  When the block polymer of the present invention is used as a cosmetic detergent composition, the block polymer of the present invention preferably has a viscosity capable of preparing a 5 wt% aqueous solution at 25 ° C, more preferably 10 at 25 ° C. The viscosity of the weight% aqueous solution is 10,000 mPa · s or less, more preferably 5,000 mPa · s or less. However, this viscosity is usually 10 mPa · s or more.

[Method for producing block polymer of the present invention]
The block polymer of the present invention can be produced, for example, by mixing monomers that give respective structural units or precursors thereof, and performing solution polymerization, suspension polymerization, emulsion polymerization, or the like.
Moreover, about a raw material monomer, when superposing | polymerizing, a precursor can be used and can also be changed into a desired form by neutralization reaction, addition reaction, etc. after superposition | polymerization. These can be appropriately selected depending on the ease of synthesis.

The polymerization reaction is preferably performed in a hydrophilic solvent.
Examples of the hydrophilic solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and sec-butanol, water, and the like. Is mentioned. These may be used alone or in combination of two or more. Among these, it is preferable to use an alcohol solvent.

As polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), 2,2 ′ -Azo compounds such as azobis (2-methyl-N- (2-hydroxyethyl) -propionamide), 2,2'-azobis (2-amidinopropane) dihydrochloride, benzoyl peroxide, dicumyl peroxide, di It can be used without particular limitation, such as peroxides such as -t-butyl peroxide and lauroyl peroxide, persulfates, or redox systems thereof. These may be used alone or in combination of two or more.
The polymerization initiator is preferably used in the range of 0.01 to 5% by mass with respect to all monomers.

  The polymerization reaction can be performed, for example, under an inert gas atmosphere such as nitrogen or argon, preferably at 30 to 120 ° C., more preferably at 40 to 100 ° C., usually for 1 to 30 hours. After completion of the polymerization, the produced polymer may be isolated from the reaction solution by an appropriate means such as solvent distillation or addition of a poor solvent. This polymer can be used as it is or after further purification, for example, in the production of cosmetics. Purification can be performed by combining appropriate means such as reprecipitation, solvent washing, and membrane separation as required.

  Below, the first block and the second block, which are composed of monomers having a vinyl functional group and have different monomer compositions, are connected via a linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group. A preferred method for producing the block polymer of the present invention which is bonded will be described by illustrating the following <Method 1> and <Method 2>.

<Method 1>
After the step of obtaining a first block by radical polymerization of the first block constituting vinyl monomer containing a linking monomer, a functional group capable of reacting with the non-radical polymerizable functional group is added to the non-radically polymerizable functional group of the linking monomer. A block polymer is obtained by performing a step (addition step) of adding the vinyl-based monomer possessed and a step of obtaining a second block by radical polymerization of the second block-constituting vinyl-based monomer (second block polymerization step). At that time, either the addition step or the second block polymerization step may be performed first or simultaneously.

For example, first, a linking monomer having a radical polymerizable vinyl functional group and an oxazoline functional group is used to form a first block containing the linking monomer. Next, a monomer having a carboxylic acid group and a vinyl functional group is added to react the oxazoline functional group with the carboxylic acid group. Furthermore, a block polymer can be obtained by adding and polymerizing another monomer constituting the second block.
Alternatively, the second block is separately formed by polymerizing other monomers constituting the second block including the monomer having a carboxylic acid group and a vinyl functional group, and the first block oxazoline functional group and the second block are formed. These carboxylic acid groups may be reacted to form a block polymer.
Furthermore, after the first block is formed, a block polymer can be obtained by adding another monomer constituting the second block including a monomer having a carboxylic acid group and a vinyl-based functional group, and simultaneously polymerizing and reacting. . According to this method, the block polymer can be obtained most simply.

<Method 2>
After the step of obtaining a second block by radical polymerization of a vinyl monomer containing a vinyl monomer having a functional group capable of reacting with a non-radically polymerizable functional group, the linking monomer is added to the functional group. A block polymer is obtained by performing the step (addition step) and the step of obtaining a first block by radical polymerization of the first block constituent vinyl monomer (first block polymerization step). At that time, either the addition step or the first block polymerization step may be performed first or simultaneously.

For example, first, the other block constituting the second block including the monomer having a vinyl functional group having a carboxylic acid group is polymerized in advance to form the second block. Next, a linking monomer having an oxazoline functional group and a radical polymerizable vinyl functional group is added to react the oxazoline functional group with a carboxylic acid group. Furthermore, a block polymer can be obtained by adding and polymerizing another monomer constituting the first block.
Alternatively, the first block is separately formed by polymerizing other monomers constituting the first block including the linking monomer, and the carboxylic acid group of the second block and the oxazoline-based functional group of the first block are reacted, It may be a block polymer.
Furthermore, a block polymer can be obtained by adding a first block constituent monomer including a linking monomer after the second block is formed and simultaneously polymerizing and reacting. According to this method, the block polymer can be obtained most simply.

  When the method 1 and the method 2 are compared, the method 1 is preferable because of high reactivity and easy reaction.

[Use of block polymer of the present invention and cosmetic composition]
The block polymer of the present invention is useful as a surface treatment agent such as an antistatic agent and a hard coat agent, and as a thickener or dispersant for paints, cosmetics, agricultural chemicals, pharmaceuticals, and the like.

<Cosmetic composition>
In a cosmetic composition, it is preferable to contain 0.01-50 wt% of block polymers of this invention. In order to make the effect of blending the polymer in the cosmetic composition sufficient, the content of the block polymer of the present invention is preferably 0.01 wt% or more. The block polymer content is more preferably 0.1 wt% or more, and still more preferably 0.3 wt% or more. From the viewpoint of moderate viscosity and easy handling and cost, the block polymer content is preferably 50 wt% or less, more preferably 20 wt% or less, still more preferably 10 wt% or less, and most preferably 5 wt%. % Or less.

<Hair hair set composition>
The block polymer of the present invention can be suitably used for a hair set composition among cosmetic compositions, and preferred blending compositions in this case are as follows.
0.1-20 wt% of block polymer of the present invention
0 ~ 99wt% of water
Ethanol 0-99wt%
LPG or / and DME 0-70 wt%
(However, the total amount of water, ethanol, LPG and / or DME is 49.9 to 99.9 wt%)
Additive 0-50wt%

  In the hair setting agent composition of the present invention, the block polymer of the present invention preferably contains 0.1 to 20 wt%. That is, in order to make the setting force sufficient, the block polymer content is preferably 0.1 wt% or more, more preferably 1 wt% or more, and further preferably 2 wt% or more. Further, the block polymer content is preferably 20 wt% or less, more preferably 10 wt% or less, and further preferably 5 wt% or less from the viewpoint of moderate viscosity and easy handling and cost.

The amount of water and ethanol, LPG (liquefied petroleum gas) or / and DME (dimethyl ether) effective to dissolve the polymer is generally preferably in the range of 49.9 to 99.9 wt%. . In order to make the set force sufficient, the content of these solvents is preferably 99.9 wt% or less, and is preferably 49.9 wt% or more from the viewpoint of moderate viscosity and easy handling and cost.
Preferably, the ethanol content ranges from 0 to 99 wt%, the water content ranges from 0 to 99 wt%, and the LPG or / and DME content ranges from 0 to 70 wt%. These ratios are appropriately selected depending on the product form. Can do.

  For so-called sprays using a volatile gas as a propellant, the water content is preferably 5 wt% or less, more preferably 3% or less, and most preferably 1% or less. In that case, the content of ethanol is preferably 20 to 80 wt%, more preferably 30 to 70 wt%, and most preferably 40 to 60 wt%. In that case, since the content of LPG or / and DME works as a propellant in addition to dissolving the polymer, it is preferably 10 to 70 wt%, more preferably 30 to 60 wt%, most preferably 40 to 60 wt%. is there.

  In addition, LPG here is liquefied petroleum gas which has butane, propane, etc. as a main component. The composition of LPG is not particularly limited, but propane and butane are preferably 80 wt% or more, more preferably 90 wt% or more of the whole. The weight ratio of propane and butane is preferably 9: 1 to 1: 9, more preferably 9: 1 to 5: 5, and still more preferably 8: 2 to 6: 4. As butane, n-butane or iso-butane can be used.

  Carbon dioxide or the like can also be used as another propellant not included in the above composition.

  When used as a hair setting agent, additives can be blended within a range that does not significantly impair the performance, and the content is preferably 0 to 50 wt%. In order to impart the performance of the active ingredient and not hinder the performance, the content of other additives is preferably 0.1 to 30 wt%, more preferably 0.5 to 10 wt%, most preferably 0. 0.5 to 5 wt%.

  Preferably, the hair set agent composition includes a composition containing 0.1 to 10 wt% of silicones as one of the additives. In order to give gloss to hair and improve combing, the hair set composition preferably contains 0.1 wt% or more of silicones, more preferably 0.2 wt% or more, and still more preferably 0.8%. It is 3 wt% or more, and most preferably 0.5 wt% or more. Further, from the viewpoint of moderate viscosity and easy handling and cost, the silicone content is preferably 10 wt% or less, more preferably 5 wt% or less, and further preferably 2 wt% or less.

  Here, the silicones refer to polymers having a structure in which silicon (organosilicon) to which organic groups are bonded and oxygen are alternately linked by chemical bonds. These may further have a substituent.

  Examples of silicones include, but are not limited to, polydimethylsiloxane, polydimethylsiloxane alkylene oxide copolymer, amino-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, methylphenylpolysiloxane, epoxy-modified polydimethylsiloxane, fluorine Examples include modified polydimethylsiloxane, alcohol-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane, alkoxy-modified polydimethylsiloxane, and cyclic silicone. These are described in JP-A-2000-336018.

  Examples of polydimethylsiloxane include “KF96H-1 million” (Shin-Etsu Chemical Co., Ltd.), “SH200”, “BY11-007”, “BY22-029” (all are Toray Dow Corning Silicone Co., Ltd.), “TSF451. "(Toshiba Silicone Co., Ltd.)" and "L-45" (Nihon Unicar Co., Ltd.).

  As a polydimethylsiloxane alkylene oxide copolymer, what is marketed as "F-178-21" (Nihon Unicar Co., Ltd.) is mentioned.

  Examples of the amino-modified polydimethylsiloxane include those having an aminoalkyl group such as an aminoethyl group and an aminopropyl group, and may have a substituent such as an alkyl group or a hydroxyl group. The alkyl group for the substituent is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.

  These amino-modified polydimethylsiloxanes are obtained by copolymerizing dimethylsiloxane and the above siloxane having an aminoalkyl group, or by post-modifying polydimethylsiloxane with a compound having an aminoalkyl group as described above to form a polydimethylsiloxane skeleton. It is obtained by introducing an aminoalkyl group.

  Commercially available products of amino-modified polydimethylsiloxane include, for example, “USAR SILICONE ALE56” (Union Carbide), “ABIL9905” (The Goldschmidt AG), “KF857”, “KF867”, “KF865” (all And Shin-Etsu Chemical Co., Ltd.), “SM8702C” (Toray Dow Corning Silicone Co., Ltd.), “FZ-3707” (Nihon Unicar Co., Ltd.), and the like.

  Examples of the polyether-modified polydimethylsiloxane include those having a monomer skeleton such as oxyethylene, oxypropylene, oxybutylene, oxypentamethylene, oxyhexamethylene, oxy (2,2-dimethyl) propylene, and polyoxyethylene And those having an oxyalkylene group of a homopolymer skeleton such as polyoxypropylene, polyoxybutylene, polyoxypentamethylene, polyoxyhexamethylene, or a copolymer skeleton such as a poly (oxyethyleneoxypropylene) copolymer. It is done. These may have a substituent such as a hydroxyl group or an alkyl group. The alkyl group for the substituent is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. Particularly preferred are those having an oxyalkylene group of the polymer skeleton.

  Examples of a method for producing such a modified polydimethylsiloxane having an oxyalkylene group include a method of copolymerizing dimethylsiloxane and a siloxane having an oxyalkylene group, and polydimethylsiloxane by a compound having an oxyalkylene group. There is a method of post-modifying and introducing an oxyalkylene group into the polydimethylsiloxane skeleton.

  Most preferably, the polyether-modified polydimethylsiloxane is obtained by copolymerizing dimethylsiloxane and siloxane having an oxyalkylene group in the polymer skeleton.

  Examples of commercially available polyether-modified polydimethylsiloxane include “KF945A”, “KF351A”, “KF354A” (Shin-Etsu Chemical Co., Ltd.), “SH3771C”, “SH3749” (Toray Dow Corning Silicone Co., Ltd.) , “L-7602C”, “L-720” (Nihon Unicar Co., Ltd.), “SF1066” (General Electric Company), and the like.

  As methylphenylpolysiloxane, “KF56” (Shin-Etsu Chemical Co., Ltd.), “SH556” (Toray Dow Corning Silicone Co., Ltd.), “FZ-209” (Nihon Unicar Co., Ltd.) and the like are commercially available.

  As the epoxy-modified polydimethylsiloxane, “X-60-164” (Shin-Etsu Chemical Co., Ltd.), “PS922” (Chisso Corporation), “L-9300” (Nihon Unicar Corporation) and the like are commercially available.

  As the fluorine-modified polydimethylsiloxane, “X-22-820” (Shin-Etsu Chemical Co., Ltd.), “PS182” (Chisso Corporation) and the like are commercially available.

  As alcohol-modified polydimethylsiloxane, “KF851” (Shin-Etsu Chemical Co., Ltd.), “FM4411” (Chisso Corporation), “FZ-3722”, “F-235-21” (Nihon Unicar Corporation), etc. are commercially available. Has been.

  As the alkyl-modified polydimethylsiloxane, “KF410”, “KF-413” (Shin-Etsu Chemical Co., Ltd.), “PS130”, “PS137” (Chisso Corporation) and the like are commercially available.

  As the alkoxy-modified polydimethylsiloxane, “PS912” (Chisso Corporation), “FZ-3701” (Nihon Unicar Corporation) and the like are commercially available.

  As the cyclic silicone, “SH244”, “SH245”, “SH246” (Toray Dow Corning Silicone) are commercially available.

  These silicones may be used alone or in combination of two or more.

  Other additives that can be incorporated into the hair set composition of the present invention include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, semipolar surfactants, higher alcohols, water-soluble Include a cationic polymer, a cationic polymer, an anionic polymer, a nonionic polymer, an amphoteric polymer, an oil component, a pearling agent, and a suspending agent.

  Although the component which may be mix | blended is illustrated below, it is not limited to these.

  Examples of the anionic surfactant include α-olefin sulfonate, higher alcohol sulfate, polyoxyethylene alkyl ether sulfate, paraffin sulfonate, polyoxyethylene alkyl ether carboxylate, alkyl sulfosuccinate. , N-acyl-β-alanine salts, N-acyl glutamate salts, acylmethyl taurine salts, and the like commonly used in detergent compositions can be used. Examples of counter ions of these anionic surfactants include sodium, potassium, ammonium, triethanolamine, diethanolamine and the like. An anionic surfactant may be used individually by 1 type, and may use 2 or more types together.

  As the cationic surfactant, for example, a long-chain alkyl group-containing quaternary ammonium salt is preferable. The long chain alkyl group is preferably one having 6 to 24 carbon atoms. Long chain alkyl group-containing quaternary ammonium salts include, for example, long chains such as cetyl trimethyl ammonium salt, stearyl trimethyl ammonium salt, behenyl trimethyl ammonium salt, cetyl dimethyl benzyl ammonium salt, stearyl dimethyl benzyl ammonium salt, and behenyl dimethyl benzyl ammonium salt. Two long chains such as one, dicetyldimethylammonium salt, distearyltrimethylammonium salt, dibehenyltrimethylammonium salt, dicetylmethylbenzylammonium salt, distearylmethylbenzylammonium salt, dibehenylmethylbenzylammonium salt And three long chains such as tricetylmethylammonium salt, tristearylmethylammonium salt, and tribehenylmethylammonium salt. And the like of it. Among them, one having one or two long chains is preferable, and one having one long chain is more preferable. These may be used alone or in combination of two or more.

  Examples of amphoteric surfactants include those containing a betaine group and a long-chain alkyl group such as aminoacetic acid betaine, imidazolium betaine, sulfobetaine, and amidopropyl betaine. These may be used alone or in combination of two or more.

  Examples of nonionic surfactants include polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, fatty acid monoethanolamide, and fatty acid diethanolamide. These may be used alone or in combination of two or more.

  Examples of the semipolar surfactant include lauramine oxide (lauryl dimethylamine oxide). Such surfactants are generally commercially available and can be used as they are. These may be used alone or in combination of two or more.

  Examples of the water-soluble polymer include methyl cellulose and hydroxymethyl cellulose. These may be used alone or in combination of two or more.

  The higher alcohol is not particularly limited as long as it is a compound having a long-chain alkyl group and a hydroxyl group, but an alkyl group having 6 to 24 carbon atoms and a linear or branched alkyl group is preferable. The higher alcohol may have two or more hydroxyl groups, but preferably has only one hydroxyl group, and examples thereof include octyl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol. Of these, cetyl alcohol, stearyl alcohol, and behenyl alcohol are preferable. These may be used alone or in combination of two or more.

  Examples of the cationic polymer include a cation-modified cellulose ether derivative, polydimethyldiallylammonium halide, a copolymer of dimethyldiallylammonium halide and acrylamide, and the like. These may be used alone or in combination of two or more.

  Examples of the anionic polymer include acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid-acrylamide-ethyl acrylate copolymer and salts thereof), methacrylic acid derivatives, crotonic acid derivatives, and the like. These may be used alone or in combination of two or more.

  Examples of nonionic polymers include acrylic acid derivatives (hydroxyethyl acrylate-methoxyethyl acrylate copolymer, polyacrylamide, etc.) and vinylpyrrolidone derivatives (polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, etc.). It is done. These may be used alone or in combination of two or more.

  Examples of the amphoteric polymer include dimethyldiallylammonium chloride derivatives (acrylamide-acrylic acid-dimethyldiallylammonium chloride copolymer, acrylic acid-dimethyldiallylammonium chloride copolymer, etc.) and the like. These may be used alone or in combination of two or more.

  Examples of the oil include olive oil, jojoba oil, liquid paraffin, and fatty acid alkyl ester oil. These may be used alone or in combination of two or more.

  Examples of the pearling agent include fatty acid ethylene glycol such as ethylene glycol distearate. These may be used alone or in combination of two or more.

  Examples of the suspending agent include polystyrene emulsions. These may be used alone or in combination of two or more.

  Other ingredients include natural extracts of animals and plants and derivatives thereof, organic acids such as citric acid and lactic acid, inorganic salts such as sodium chloride, solubilizers (ethanol, ethylene glycol, propylene glycol, etc.), moisturizers (glycerin, sorbitol, Maltitol, dipropylene glycol, 1,3-butylene glycol, hyaluronic acid, etc.), antioxidants, UV absorbers, bactericides, preservatives, chelating agents, fragrances, colorants, higher fatty acids, thickeners, metal sequestering 1 type (s) or 2 or more types, such as an agent (edetate etc.), a pH adjuster, a foaming enhancer, etc. can be mix | blended suitably in the range which does not impair the effect of this invention.

<Aqueous composition for hair cosmetics>
The block polymer of the present invention can also be suitably used for an aqueous composition for hair cosmetics. In this case, the preferred composition is as follows.
0.1-20 wt% of block polymer of the present invention
Water 40-99wt%
Ethanol 0-40wt%
Additive 0-50wt%

  In the aqueous composition for hair cosmetics of the present invention, the block polymer of the present invention preferably contains 0.1 to 20 wt%. That is, in order to make the setting force sufficient, the block polymer content is preferably 0.1 wt% or more, more preferably 1 wt% or more, and further preferably 2 wt% or more. Further, the block polymer content is preferably 20 wt% or less, more preferably 10 wt% or less, and further preferably 5 wt% or less from the viewpoint of moderate viscosity and easy handling and cost.

  The amount of water effective to dissolve the polymer is usually preferably in the range of 40 to 99 wt%. In order to make the setting force sufficient, the water content is preferably 99 wt% or less, and 40 wt% or more is preferable from the viewpoint of easy viscosity and easy handling and cost.

  Moreover, when a thing with high hydrophobicity is included, solubility can be improved by using ethanol. The content of ethanol is usually preferably 40 wt% or less. For the purpose of reducing the volatile organic solvent, it is preferable that the ethanol content is low, more preferably 30 wt% or less, still more preferably 20 wt% or less, particularly preferably 10 wt% or less, and most preferably 5 wt%. % Or less.

  When used as an aqueous composition for hair cosmetics, additives can be blended within a range that does not significantly impair the performance, and the content is preferably 0 to 50 wt%. In order to impart the performance of the active ingredient and not hinder the performance, the content of other additives is preferably 0.1 to 30 wt%, more preferably 0.5 to 10 wt%, most preferably 0. 0.5 to 5 wt%.

  Preferably, the composition for hair cosmetics containing 0.1 to 10 wt% of silicones as one of the additives is mentioned. In order to give gloss to the hair and improve the combing, the hair cosmetic aqueous composition preferably contains 0.1 wt% or more of silicones, more preferably 0.2 wt% or more, and still more preferably. It is 0.3 wt% or more, and most preferably 0.5 wt% or more. Further, from the viewpoint of moderate viscosity and easy handling and cost, the silicone content is preferably 10 wt% or less, more preferably 5 wt% or less, and further preferably 2 wt% or less.

Here, the silicones refer to polymers having a structure in which silicon (organosilicon) to which organic groups are bonded and oxygen are alternately linked by chemical bonds. These may further have a substituent.
In addition, as an additive that can be blended in the aqueous composition for hair cosmetics of the present invention, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, a semipolar surfactant, Examples include higher alcohols, water-soluble polymers, cationic polymers, anionic polymers, nonionic polymers, amphoteric polymers, oil components, pearling agents, suspending agents, and the like.
Specific examples of the silicones and other additives are the same as those given as examples that can be used for the hair set composition described above.

<Cosmetic detergent composition>
The block polymer of the present invention can also be suitably used in a cosmetic detergent composition. In this case, the preferred composition is as follows.
0.1-20 wt% of block polymer of the present invention
Water 40-99wt%
Surfactant 1-40wt%
Additive 0-50wt%

  In the cosmetic detergent composition of the present invention, the block polymer of the present invention preferably contains 0.1 to 20 wt%. That is, the block polymer content is preferably 0.1 wt% or more, more preferably 0.2 wt% or more, and still more preferably 0.3 wt%, in order to ensure smoothness during rinsing and a feeling after drying. % Or more. In view of moderate viscosity and easy handling and cost, the block polymer content is preferably 20 wt% or less, more preferably 5 wt% or less, and even more preferably 1 wt% or less.

  The amount of water effective to dissolve the polymer is usually preferably in the range of 40 to 99 wt%. The water content is preferably 99 wt% or less, more preferably 90 wt% or less, and still more preferably 80 wt% or less, in order to ensure smoothness during rinsing and a feeling after washing and cleanability. Most preferably, it is 70 wt% or less. From the viewpoint of moderate viscosity and easy handling and cost, it is preferably 40 wt% or more, more preferably 50 wt% or more, and further preferably 60 wt% or more.

  The surfactant amount for imparting detergency is usually preferably in the range of 1 to 40 wt%. In order to obtain sufficient cleaning properties, the surfactant content is preferably 1 wt% or more, more preferably 5 wt% or more, still more preferably 10 wt% or more, and most preferably 15 wt% or more. is there. From the viewpoint of moderate viscosity and easy handling and cost, it is preferably 40 wt% or less, more preferably 30 wt% or less, and still more preferably 20 wt% or less.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a semipolar surfactant. Especially, it is preferable to contain the anionic surfactant excellent in the detergency as a main component of a cleaning agent.

  The content of the anionic surfactant in the cosmetic detergent composition is preferably 5 to 20 wt%, more preferably 5 to 15 wt%, and still more preferably 7 to 13 wt%.

  Examples of the anionic surfactant include α-olefin sulfonate, higher alcohol sulfate, polyoxyethylene alkyl ether sulfate, paraffin sulfonate, polyoxyethylene alkyl ether carboxylate, alkyl sulfosuccinate. , N-acyl-β-alanine salts, N-acyl glutamate salts, acylmethyl taurine salts, and the like commonly used in detergent compositions can be used. Examples of counter ions of these anionic surfactants include sodium, potassium, ammonium, triethanolamine, diethanolamine and the like. Of these, polyoxyethylene alkyl ether sulfates are preferably used. An anionic surfactant may be used individually by 1 type, and may use 2 or more types together.

  Since the amphoteric surfactant has an effect of helping foaming, it is preferable to use it together with an anionic surfactant. The content of the amphoteric surfactant in the cosmetic detergent composition is preferably 1 to 10 wt%, more preferably 3 to 10 wt%, and even more preferably 3 to 8 wt%.

  Examples of amphoteric surfactants include those containing a betaine group and a long-chain alkyl group such as aminoacetic acid betaine, imidazolium betaine, sulfobetaine, and amidopropyl betaine. Of these, alkylamidopropylbetaine and the like are preferably used. These may be used alone or in combination of two or more.

  Since the semipolar surfactant has an effect of improving the smoothness at the time of rinsing, it is preferably used in combination with the anionic surfactant and the amphoteric surfactant. At this time, the content of the semipolar surfactant in the cosmetic cleaning composition is preferably 0.1 to 5 wt%, more preferably 0.5 to 5 wt%, and still more preferably 0.8. It is 5 to 3 wt%, and most preferably 0.5 to 2 wt%.

  Examples of the semipolar surfactant include lauramine oxide (lauryl dimethylamine oxide), which can be suitably used. Such surfactants are generally commercially available and can be used as they are. These may be used alone or in combination of two or more.

The cationic surfactant has an effect of improving the feeling after drying, and can be suitably used. The content of the cationic surfactant in the cosmetic detergent composition is preferably 0 to 3 wt%, more preferably 0.1 to 2 wt%, and still more preferably 0.2 to 1 wt%. .
As the cationic surfactant, for example, a long-chain alkyl group-containing quaternary ammonium salt is preferable. The long chain alkyl group is preferably one having 6 to 24 carbon atoms. Examples of the long-chain alkyl group-containing quaternary ammonium salt include long chains such as cetyltrimethylammonium salt, stearyltrimethylammonium salt, behenyltrimethylammonium salt, cetyldimethylbenzylammonium salt, stearyldimethylbenzylammonium salt, and behenyldimethylbenzylammonium salt. Two long chains such as one, dicetyldimethylammonium salt, distearyltrimethylammonium salt, dibehenyltrimethylammonium salt, dicetylmethylbenzylammonium salt, distearylmethylbenzylammonium salt, dibehenylmethylbenzylammonium salt And three long chains such as tricetylmethylammonium salt, tristearylmethylammonium salt, and tribehenylmethylammonium salt. And the like of it. Among them, one having one or two long chains is preferable, and one having one long chain is more preferable. These may be used alone or in combination of two or more.

Nonionic surfactants can be suitably used because they have a thickening effect. The content of the nonionic surfactant in the cosmetic cleaning composition is preferably 0 to 5 wt%, more preferably 0.1 to 3 wt%, and still more preferably 0.2 to 1 wt%. .
Examples of nonionic surfactants include polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, fatty acid monoethanolamide, and fatty acid diethanolamide. These may be used alone or in combination of two or more.

  When used as a cosmetic cleaning composition, additives can be blended within a range that does not significantly impair the performance, and the content is preferably 0 to 50 wt%. In order to impart the performance of the active ingredient and not hinder the performance, the content of other additives is preferably 0.1 to 30 wt%, more preferably 0.5 to 10 wt%, most preferably 0. 0.5 to 5 wt%.

  Preferably, the cosmetic cleaning composition includes a composition containing 0.1 to 10 wt% of silicones as one of the additives. In order to give gloss to hair and improve combing, the cosmetic cleaning composition preferably contains 0.1 wt% or more of silicones, more preferably 0.2 wt% or more, and still more preferably It is 0.3 wt% or more, and most preferably 0.5 wt% or more. Further, from the viewpoint of moderate viscosity and easy handling and cost, the silicone content is preferably 10 wt% or less, more preferably 5 wt% or less, and further preferably 2 wt% or less.

Here, the silicones refer to polymers having a structure in which silicon (organosilicon) to which organic groups are bonded and oxygen are alternately linked by chemical bonds. These may further have a substituent.
In addition, other additives that can be blended in the cosmetic cleaning composition of the present invention include higher alcohols, water-soluble polymers, cationic polymers, anionic polymers, nonionic polymers, and amphoteric polymers. , Oil, pearling agent, suspending agent and the like.
Specific examples of silicones and other additives are the same as the examples given for the hair set agent composition described above.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples unless it exceeds the gist.

Production Examples 1 to 6 <Production of Polymers (1) to (6) of the Present Invention>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 200 parts by weight of ethanol and monomers of composition A shown in Table 1, and the inside of the reactor was purged with nitrogen. After adding 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate to this reactor, the reactor was heated from 35 ° C. to 80 ° C. over 1 hour and aged at 80 ° C. for 3 hours. Then, it was cooled to 40 ° C.
Subsequently, the monomers having the composition B shown in Table 1 and 100 parts by weight of ethanol were charged into the reactor and stirred at 40 ° C. for 1 hour. Thereafter, the inside of the reactor was again purged with nitrogen, 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate was charged into the reactor, and then the reactor was heated from 40 ° C. to 80 ° C. over 1 hour. The mixture was aged at 80 ° C. for 5 hours and then cooled.

Production Examples 7 to 10 <Production of Polymers (7) to (10) of the Present Invention>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 200 parts by weight of ethanol and monomers of composition A shown in Table 2, and the inside of the reactor was purged with nitrogen. After adding 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate to this reactor, the reactor was heated from 35 ° C. to 80 ° C. over 1 hour and aged at 80 ° C. for 3 hours. Then, it was cooled to 40 ° C.

Subsequently, the linked monomers shown in Table 2 were charged into the reactor and stirred at 40 ° C. for 1 hour.
Subsequently, monomers of composition B in Table 2 and 100 parts by weight of ethanol were charged into this reactor, the inside of the reactor was purged with nitrogen, and 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate was reacted. After charging the reactor, the reactor was heated from 40 ° C. to 80 ° C. over 1 hour, aged at 80 ° C. for 5 hours, and then cooled.

Production Example 11 <Production of Comparative Polymer (11)>
The synthesis was performed in the same manner as in Production Example 1 except that no linking monomer was used. The monomer composition is shown in Table 3.

Production Example 12 <Production of Comparative Polymer (12)>
It synthesize | combined like the manufacture example 1 except having added 2 weight part of polyoxyethylene (3) diacrylate which is a crosslinking agent instead of the connection monomer. The monomer composition is shown in Table 3.

Production Example 13 <Production of Comparative Polymer (13)>
The synthesis was conducted in the same manner as in Production Example 1 except that 2 parts by weight of bifunctional allyl methacrylate was added instead of the linking monomer. The monomer composition is shown in Table 3.

About the polymer (1)-(13) synthesize | combined in the above manufacture examples 1-13, the viscosity was measured in the ethanol solution of polymer solid content 30weight%.
Viscosity was measured using a B-type viscometer. 2 was performed at 30 rpm and 25 ° C. The measurement results are shown in Tables 1-3.

  Moreover, the value of Tg of each block computed from Tg of the homopolymer of each constituent monomer was described in Tables 1-3. Tg was calculated according to a conventional method from Tg (catalog value) when each constituent monomer was a homopolymer and the weight ratio of each constituent monomer.

  Furthermore, the water-soluble evaluation result of each block was described in Tables 1-3. The water solubility was evaluated by synthesizing only each block (composition A, composition B) alone. Moreover, the block of MAA (methacrylic acid) which is an acidic substance was evaluated in a state neutralized with AMP (aminomethylpropanol).

Production Example 14 <Production of Comparative Polymer (14)>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 200 parts by weight of ethanol and monomers in the same amount as the composition A in Table 1 in the polymer (1). The inside was replaced with nitrogen. After adding 0.5 part by weight of dimethyl-2,2′-azobisisobutyrate to this reactor, the reactor was heated from 35 ° C. to 80 ° C. over 1 hour and aged at 80 ° C. for 3 hours. After cooling to 40 ° C.

Production Example 15 <Production of Comparative Polymer (15)>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introduction pipe and a stirring device was charged with 200 parts by weight of ethanol and monomers in the same amount as the composition B of Table 1 in the polymer (1). The inside was replaced with nitrogen. After adding 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate to this reactor, the reactor was heated from 35 ° C. to 80 ° C. over 1 hour and aged at 80 ° C. for 5 hours. And then cooled.

Examples 1-10, Comparative Examples 1-3
The state of the polymers (1) to (13) obtained in Production Examples 1 to 13 in a 30% by weight ethanol solution was visually observed and evaluated.
In addition, each solution was applied to a glass plate with a 100 μm applicator, dried for 1 hour in a dryer at 50 ° C., and then visually observed for 1 day in a 23 ° C./60% humidity atmosphere. And evaluated.
The results are shown in Table 4.

  As is clear from Table 4, the polymers (1) to (10) were uniform and transparent in both the solution and the film, but the polymers (11) and (13) caused phase separation in the solution, and the film Was non-uniform and opaque. The solution of polymer (12) was gelled and a film could not be prepared.

Examples 11 to 17, Comparative Examples 4 and 5
Using the polymers (1), (2), (3), (4), (7), (14), and (15), a hair set composition having the composition shown in Table 5 was prepared. Was evaluated.
The results are shown in Table 5.

<Gas compatibility>
Each composition was evaluated according to the following criteria based on the transparency of the solution when placed at −15 ° C. for 24 hours.
3 Uniform transparent 2 Uniform but slightly fluorescent mist 1 Uniform but mist 0 Non-uniform

<Curl retention>
A fixed amount of the spray of each composition was applied to 23 cm and 2 g of a bristles, and immediately wound around a curler having a diameter of 2 cm. Next, the hair bundle was removed from the curler, and the apparent length (L0) of the hair bundle was measured. Next, this hair bundle was hung in a constant temperature and humidity chamber at 30 ° C. and a humidity of 90%, taken out after 3 hours, and the apparent length (L1) of the hair bundle was measured again. The set force was calculated from the obtained measurement value based on the following equation.
Setting force (%) = 100 × (23−L0) / (23−L1)
Evaluation was performed according to the following criteria based on the calculated set force.
3 Setting force is 80% or more and 100% or less 2 Setting force is 70% or more and less than 80% 1 Setting force is 50% or more and less than 70% 0 Setting force is 0% or more and less than 50%

<Flexibility>
A fixed amount of spray of each composition was applied to 23 cm and 2 g of a bristles with no hair, and dried. The softness was evaluated according to the following criteria from the hardness when the hair bundle was bent.
3 Maintains hardness no matter how many times it is bent.
2 The hardness is reduced by bending, but the shape is maintained.
1 Although it breaks, the shape is maintained slightly.
0 It broke and did not retain any hardness after that. brittle.

<No stickiness>
The hair bundles evaluated for flexibility were used as they were, and the non-stickiness was evaluated according to the following criteria from the degree of stickiness when touched by hand.
3 I do not feel any stickiness.
2 There is a slight stickiness.
1 I feel sticky.
0 Sticky

<No flaking>
The hair bundles evaluated for non-stickiness were used as they were, and the flaking state when the hair bundles were rubbed together by hand was visually observed and evaluated according to the following criteria.
3 Flaking is not seen at all.
2 Slight flaking is observed.
1 There is a lot of flaking.
0 Vigorous flaking is observed.

From the above results, the following can be understood.
The block polymer of the present invention connected by a linking monomer having a radically polymerizable vinyl functional group and an oxazoline functional group does not require a purification step and is advantageously produced industrially using readily available raw materials. It is possible and is superior to existing methods.
Moreover, according to the composition which mix | blended the block polymer of this invention, it is excellent in gas compatibility, curl retention, and a softness | flexibility, and the outstanding hair set agent composition without stickiness and flaking is obtained.

Production Example 16 <Production of Polymer (16) of the Present Invention>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 200 parts by weight of ethanol and monomers of composition A shown in Table 6, and the inside of the reactor was purged with nitrogen. After adding 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate to this reactor, the reactor was heated from 35 ° C. to 80 ° C. over 1 hour and aged at 80 ° C. for 3 hours. Then, it was cooled to 40 ° C.

  Subsequently, monomers of composition B in Table 6 and 100 parts by weight of ethanol were charged into this reactor, and stirred at 40 ° C. for 1 hour. Thereafter, the inside of the reactor was again purged with nitrogen, 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate was charged into the reactor, and then the reactor was heated from 40 ° C. to 80 ° C. over 1 hour. The mixture was aged at 80 ° C. for 5 hours and then cooled.

  After the polymerization reaction, the reactor was neutralized by adding the used MAA (methacrylic acid) and equimolar amount of AMP (aminomethylpropanol). Thereafter, 200 g of distilled water was added, and the reactor was heated to distill off ethanol. In the middle, 200 g of distilled water was further added, and ethanol was further distilled off.

Production Example 17 <Production of Polymer (17) of the Present Invention>
Polymerization was carried out in the same manner as in the polymer (16) except that the reaction was carried out with the composition shown in Table 6.
After the polymerization reaction, the reactor was neutralized by adding AA (acrylic acid) and equimolar AMP (aminomethylpropanol) to the reactor. Thereafter, 200 g of distilled water was added, and the reactor was heated to distill off ethanol. In the middle, 200 g of distilled water was further added, and ethanol was further distilled off.

Production Example 18 <Production of Comparative Polymer (18)>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 200 parts by weight of ethanol and monomers of composition A shown in Table 6, and the inside of the reactor was purged with nitrogen. After adding 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate to this reactor, the reactor was heated from 35 ° C. to 80 ° C. over 1 hour and aged at 80 ° C. for 3 hours. Then, it was cooled to 40 ° C.

  Subsequently, monomers of composition B in Table 6 and 100 parts by weight of ethanol were charged into this reactor, and stirred at 40 ° C. for 1 hour. Thereafter, the inside of the reactor was again purged with nitrogen, 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate was charged into the reactor, and then the reactor was heated from 40 ° C. to 80 ° C. over 1 hour. The mixture was aged at 80 ° C. for 5 hours and then cooled.

  After the polymerization reaction, the reactor was neutralized by adding the used MAA (methacrylic acid) and equimolar amount of AMP (aminomethylpropanol). Thereafter, 200 g of distilled water was added, and the reactor was heated to distill off ethanol. In the middle, 200 g of distilled water was further added, and ethanol was further distilled off.

Production Example 19 <Production of Comparative Polymer (19)>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 200 parts by weight of ethanol and monomers having composition A and composition B shown in Table 6, and the inside of the reactor was purged with nitrogen. . After adding 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate to this reactor, the reactor was heated from 35 ° C. to 80 ° C. over 1 hour and aged at 80 ° C. for 3 hours. Then, it was cooled to 40 ° C.

  After the polymerization reaction, the reactor was neutralized by adding the used MAA (methacrylic acid) and equimolar amount of AMP (aminomethylpropanol). Thereafter, 200 g of distilled water was added, and the reactor was heated to distill off ethanol. In the middle, 200 g of distilled water was further added, and ethanol was further distilled off.

About the polymer (16)-(19) synthesize | combined by said manufacture examples 16-19, the viscosity was measured in aqueous solution with a polymer solid content of 20 weight%.
Viscosity was measured using a B-type viscometer. 2 was performed at 30 rpm and 25 ° C. The measurement results are shown in Table 6.

  Table 6 shows the Tg value of each block calculated from the Tg of the homopolymer of each constituent monomer. Tg was calculated according to a conventional method from Tg (catalog value) when each constituent monomer was a homopolymer and the weight ratio of each constituent monomer.

  Furthermore, the water solubility evaluation results of each block are shown in Table 6. The water solubility was evaluated by synthesizing only each block (composition A, composition B) alone. Moreover, the block containing MAA (methacrylic acid) which is an acidic substance, or AA (acrylic acid) was evaluated in a state neutralized with AMP (aminomethylpropanol).

Examples 18 and 19, Comparative Examples 6 and 7
The state of the polymers (16) to (19) obtained in Production Examples 16 to 19 in a 20% by weight aqueous solution was visually observed and evaluated.
In addition, each solution was applied to a glass plate with a 100 μm applicator, dried for 1 hour in a dryer at 50 ° C., and then visually observed for 1 day in a 23 ° C./60% humidity atmosphere. And evaluated.
The results are shown in Table 7.

  As is clear from Table 7, the solutions of polymers (16) and (17) were uniform and the film was uniform and transparent, but the solution of polymer (18) was uniform, but the film was It was uneven and opaque. Moreover, the polymer (19) became a gel form, and the film was nonuniform and opaque.

Examples 20 to 22, Comparative Examples 8 and 9
Using the polymers (16) to (19), aqueous compositions for hair cosmetics listed in Table 8 were prepared and evaluated as follows.
The results are shown in Table 8.

<Curl retention>
1 g of each composition was applied to 23 cm, 2 g of a bunch of hair, and immediately wound around a curler having a diameter of 2 cm. Next, the hair bundle was removed from the curler, and the apparent length (L0) of the hair bundle was measured. Next, this hair bundle was hung in a constant temperature and humidity chamber at 30 ° C. and a humidity of 90%, taken out after 3 hours, and the apparent length (L1) of the hair bundle was measured again. The set force was calculated from the obtained measurement value based on the following equation.
Setting force (%) = 100 × (23−L0) / (23−L1)
Judgment was made based on the calculated set force.
3 Setting force is 80% or more and 100% or less 2 Setting force is 70% or more and less than 80% 1 Setting force is 50% or more and less than 70% 0 Setting force is 0% or more and less than 50%

<Flexibility>
1 g of each composition was applied to 23 cm, 2 g of a hair bundle having no habit, and dried. The softness was evaluated according to the following criteria from the hardness when the hair bundle was bent.
3 Maintains hardness no matter how many times it is bent.
2 The hardness is reduced by bending, but the shape is maintained.
1 Although it breaks, the shape is maintained slightly.
0 It broke and did not retain any hardness after that. brittle.

<No stickiness>
The hair bundles evaluated for flexibility were used as they were, and the non-stickiness was evaluated according to the following criteria from the degree of stickiness when touched by hand.
3 I do not feel any stickiness.
2 There is a slight stickiness.
1 I feel sticky.
0 Sticky

<Smoothness of hair ends>
The hair bundle evaluated for non-stickiness was used as it was, and the non-stickiness and smoothness when the hair tips were touched by hand were evaluated according to the following criteria.
3 I don't feel any wrinkles. Smooth.
2 I feel a little bit rough.
1 I feel a crawl.
0 Gowaki is intense.

<No flaking>
The hair bundles evaluated for the smoothness of the bristles were used as they were, and the flaking state when the hair bundles were rubbed together by hand was visually observed and evaluated according to the following criteria.
3 Flaking is not seen at all.
2 Slight flaking is observed.
1 There is a lot of flaking.
0 Vigorous flaking is observed.

  From the above results, it can be seen that according to the composition containing the block polymer of the present invention, an aqueous composition for hair cosmetics which is excellent in curl retention and flexibility and has no stickiness or flaking is obtained.

Production Examples 20 to 22 <Production of Polymers (20) to (22) of the Present Invention>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 200 parts by weight of ethanol and monomers of composition A shown in Table 9, and the inside of the reactor was purged with nitrogen. After adding 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate to this reactor, the reactor was heated from 35 ° C. to 80 ° C. over 1 hour and aged at 80 ° C. for 3 hours. Then, it was cooled to 40 ° C.

Subsequently, AA (acrylic acid) or MAA (methacrylic acid) and GMA (glycidyl methacrylate) of composition B in Table 9 were charged, stirred at 60 ° C. for 2 hours, and cooled to 40 ° C. Thereafter, the remaining monomers having the composition B shown in Table 9 and 100 parts by weight of ethanol were charged into the reactor and stirred for 1 hour. Thereafter, the inside of the reactor was again purged with nitrogen, 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate was charged into the reactor, and then the reactor was heated from 40 ° C. to 80 ° C. over 1 hour. And aged at 80 ° C. for 5 hours.
Thereafter, 200 g of distilled water was added, and the reactor was heated to distill off ethanol. In the middle, 200 g of distilled water was further added, and ethanol was further distilled off.

Production Example 23 <Production of Comparative Polymer (23)>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 200 parts by weight of ethanol and monomers of composition A shown in Table 9, and the inside of the reactor was purged with nitrogen. After adding 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate to this reactor, the reactor was heated from 35 ° C. to 80 ° C. over 1 hour and aged at 80 ° C. for 3 hours. Then, it was cooled to 40 ° C.

Subsequently, the monomers having the composition B shown in Table 9 and 100 parts by weight of ethanol were added to the reactor and stirred for 1 hour. Thereafter, the inside of the reactor was again purged with nitrogen, 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate was charged into the reactor, and then the reactor was heated from 40 ° C. to 80 ° C. over 1 hour. And aged at 80 ° C. for 5 hours.
Thereafter, 200 g of distilled water was added, and the reactor was heated to distill off ethanol. In the middle, 200 g of distilled water was further added, and ethanol was further distilled off.

Production Example 24 <Production of Comparative Polymer (24)>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 200 parts by weight of ethanol and monomers of compositions A and B shown in Table 9, and the inside of the reactor was purged with nitrogen. After adding 0.5 parts by weight of dimethyl-2,2′-azobisisobutyrate to this reactor, the reactor was heated from 35 ° C. to 80 ° C. over 1 hour and aged at 80 ° C. for 3 hours. Then, it was cooled to 40 ° C.
Thereafter, 200 g of distilled water was added, and the reactor was heated to distill off ethanol. In the middle, 200 g of distilled water was further added, and ethanol was further distilled off.

For the polymers (20) to (24) synthesized in the above Production Examples 20 to 24, the viscosity was measured in an aqueous solution having a polymer solid content of 10% by weight.
Viscosity was measured using a B-type viscometer. 2 was performed at 30 rpm and 25 ° C. The measurement results are shown in Table 9.

When the water solubility of the polymers (20) to (24) was evaluated, all of them were water soluble. The transmittance of each 1 wt% aqueous solution (optical path length 1 cm cell, wavelength 655 nm) was 100%.
Furthermore, Table 9 shows the water solubility evaluation results of each block. The water solubility was evaluated by synthesizing only each block (composition A, composition B) alone.

Examples 23-26, Comparative Examples 10-12
Using the polymers (20) to (24) and commercially available cationized cellulose, cosmetic cleaning compositions described in Table 10 were prepared and evaluated as follows.
The results are shown in Table 10.

[Evaluation methods]
Each cleaning composition was applied to the prepared hair bundle, and the following items were evaluated. The hair bundle used was “human hair black hair (100%) rooted (untreated hair 10 g × 30 cm)” purchased from Beaulux Co., Ltd. as “untreated hair”. A product obtained by bleaching “hair” was used as “damaged hair”. For producing damaged hair, Promatis Brave Oxytan 6.0 (hydrogen peroxide 6% cream) manufactured by Milbon Co., Ltd. and Powder Bleach MR2 manufactured by Melos Chemical Co., Ltd. were used as bleaching agents, and 12 g and 6 g were mixed, respectively. The product was applied to one hair bundle, left for 30 minutes after coating, and then washed with water and coated with sodium lauroyl (EO) trisulfate (polyoxyethylene (3) sodium lauryl ether sulfate) and washed.
In addition, each evaluation was performed by relative evaluation by using Comparative Example 12 as a comparative standard product.

<Compoundability>
The transmittance of each cleaning composition (transmittance of a 1 cm cell with an optical path length of light having a wavelength of 655 nm) was evaluated in the following three stages. However, Example 24 evaluated the transparency of the shampoo before adding silicone oil.
0: A shampoo that is as transparent as a comparative standard product can be obtained. -1: Although a transparency is lower than that of a comparative standard product, a uniform shampoo can be obtained. -2: White turbidity cannot be obtained.

<Smoothness when rinsing>
After treating the hair bundles with each composition, the smoothness of the fingers when the hair bundles were rinsed in running water at 40 ° C. and the duration of the smoothness were evaluated in the following four stages.
+2: Excellent smoothness and sustainability compared to comparative standard products +1: Superior smoothness and sustainability compared to comparative standard products 0: Same as comparative standard products -1: Compared to comparative standard products Inferior

<Feeling smooth after drying>
After the hair bundle after the smoothness evaluation at the time of rinsing was dried overnight in a thermostatic chamber at 23 ° C. and 60% RH, the smoothness of the hair bundle was evaluated in the following four stages.
+2: The smoothness is remarkably superior to the comparison standard product. +1: The smoothness is superior to the comparison standard product. 0: Same as the comparison standard product. -1: Inferior to the comparison standard product.

<No dryness after drying>
With the hair bundles that were evaluated for smoothness, the following four levels were evaluated for the absence of roughness.
+2: Little sensation compared to the comparison standard product +1: No sensation compared to the comparison standard product, but slightly felt 0: Same as the comparison standard product -1: Inferior to the comparison standard product

<Smoothness after rinsing>
After treating the hair bundle with each composition, rinsing the hair bundle in flowing water at 40 ° C., and then rinsing with a model rinse (stearyltrimethylammonium chloride / cetyl alcohol / distilled water = 2/3/95). The smoothness and the sustainability of the smoothness were evaluated according to the following four grades.
+2: Excellent smoothness and sustainability compared to comparative standard products +1: Superior smoothness and sustainability compared to comparative standard products 0: Same as comparative standard products -1: Compared to comparative standard products Inferior

<Moist feeling after rinsing>
The hair bundle after the rinse treatment after the smoothness evaluation was dried overnight in a thermostatic chamber at 23 ° C. and 60% RH, and then the moist feeling of the hair bundle was evaluated in the following four stages.
+2: The moist feeling is remarkably superior to the comparative standard product. +1: The moist feeling is superior to the comparative standard product. 0: Same as the comparative standard product. -1: Inferior to the comparative standard product.

  From the above results, according to the composition containing the block polymer of the present invention, it is possible to obtain a cosmetic detergent composition excellent in smoothness during rinsing, feel after drying, and compatibility with rinsing. I understand.

Claims (28)

  2. A block polymer comprising two or more blocks composed of a monomer having a vinyl functional group bonded via a linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group.   The block polymer according to claim 1, wherein the two or more blocks include at least a first block and a second block having different monomer compositions. A radical polymerizable vinyl functional group of the linking monomer is bonded to the monomer of the first block, and a non-radical polymerizable functional group of the linking monomer is bonded to the monomer of the second block;
3. The block polymer according to claim 2, wherein when the linking monomer is included in the first block, the amount of the linking monomer relative to the total amount of monomers constituting the first block is 0.1 to 20 wt%.   The block polymer according to any one of claims 1 to 3, wherein the non-radically polymerizable functional group is an oxazoline-based functional group. The block polymer according to any one of claims 1 to 4, wherein the linking monomer is represented by the following general formula (1).

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ^{2 to} R ⁵ each independently represents a hydrogen atom, an alkyl group, an alkoxyalkyl group, an aryl group, an alkylaryl group, or an alkoxyaryl group; Represents any divalent linking group or direct bond.)   The block polymer according to claim 4 or 5, wherein the second block includes a monomer having a carboxylic acid group and / or an epoxy group, and a vinyl functional group.   The bond between the non-radically polymerizable functional group and the monomer of the second block is a structure in which an oxazoline functional group and a carboxylic acid group react and / or a structure in which an oxazoline functional group and an epoxy group react. The block polymer according to claim 6.   The block polymer according to any one of claims 2 to 7, wherein one of the first block and the second block is water-insoluble and the other is water-soluble or water-dispersible.   The block polymer according to any one of claims 1 to 8, which is soluble or dispersible in water and / or ethanol. The block polymer according to any one of claims 2 to 9, wherein each of the first block and the second block has the following monomer composition.
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 0-79.9 wt%
Hydrophobic vinyl monomer 20-99.9 wt%
(II) Second block Vinyl monomer containing a carboxylic acid group and / or an epoxy group
0.1 to 100 wt%
Hydrophilic vinyl monomer 0-99.9wt%
(However, hydrophilic vinyl monomers that do not contain carboxylic acid groups and / or epoxy groups)
Hydrophobic vinyl monomer 0-90 wt%   The block polymer according to claim 9, which is soluble or dispersible in water. The block polymer according to claim 11, wherein the first block and the second block each have the following monomer composition.
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 10-89.9wt%
Hydrophobic vinyl monomer 10-89.9 wt%
(II) Second block Vinyl monomer containing a carboxylic acid group and / or an epoxy group
10-90 wt%
Hydrophilic vinyl monomer 0-90 wt%
(However, hydrophilic vinyl monomers that do not contain carboxylic acid groups and / or epoxy groups)
Hydrophobic vinyl monomer 0-50 wt%   The block polymer according to claim 9, which is soluble in water. The block polymer according to claim 13, wherein the first block and the second block each have the following monomer composition.
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 60-99.9 wt%
Hydrophobic vinyl monomer 0-30 wt%
(II) Second block Vinyl monomer containing a carboxylic acid group and / or an epoxy group
0.1-20 wt%
Hydrophilic vinyl monomer 60-99.9 wt%
(However, hydrophilic vinyl monomers that do not contain carboxylic acid groups and / or epoxy groups)
Hydrophobic vinyl monomer 0-30 wt% The block polymer according to claim 10, 12 or 14, wherein the hydrophilic vinyl monomer includes a monomer represented by the following general formula (2) or (3).
_{^{CH 2 = C (R 11)}} -CO-NR 12 R 13 ··· (2)
(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a carbon number 1 having a hydroxyl group. Represents a linear or branched alkyl group of ˜3.)
_{^{CH 2 = C (R 14)}} -CO (O) - (CH 2) a- (CHOH) b-O-R 15
... (3)
(In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, R ¹⁵ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, a represents an integer of 1 to 4, and b represents 0. Or 1) The hydrophilic vinyl monomer of the first block includes a monomer represented by the following general formula (2) or (3), and the hydrophilic vinyl monomer of the second block is represented by the following general formula (10). The block polymer according to claim 14, wherein the block polymer comprises a monomer.
_{^{CH 2 = C (R 11)}} -CO-NR 12 R 13 ··· (2)
(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a carbon number 1 having a hydroxyl group. Represents a linear or branched alkyl group of ˜3.)
_{^{CH 2 = C (R 14)}} -CO (O) - (CH 2) a- (CHOH) b-O-R 15
... (3)
(In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, R ¹⁵ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, a represents an integer of 1 to 4, and b represents 0. Or 1)
_{^{CH 2 = C (R 25)}} -CO- (O) c - (NH) 1-c - (CH 2) d -N + R 26 R 27 R 28 · X - ··· (10)
(In the formula, R ²⁵ represents a hydrogen atom or a methyl group, R ²⁶ and R ²⁷ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and R ²⁸ represents a hydrogen atom or carbon number. Represents an alkyl group of 1 to 24, an aryl group, an aralkyl group, or —CH ₂ —CH (OH) —CH ₂ —N ⁺ R ²⁹ R ³⁰ R ³¹ • Z ^— , wherein R ^{29 to} R ³¹ are each independently carbon; the number 1 to 24 alkyl group, an aryl group or an aralkyl group, X ^- and Z ^- is any negative ions independently, c is 0 or 1, d represents an integer of 1 to 10). The block polymer according to claim 10, 12, 14, 15 or 16, wherein the hydrophobic vinyl monomer includes a monomer represented by the following general formula (4) or (5).
CH ₂ = C (R ¹⁶ ) —CO—O—R ¹⁷ (4)
(Wherein R ¹⁶ represents a hydrogen atom or a methyl group, and R ¹⁷ represents a linear, branched or cyclic alkyl group having 2 to 30 carbon atoms.)
^{_{CH 2 = C (R 18)}} -CO-NH-R 19 ··· (5)
(Wherein R ¹⁸ represents a hydrogen atom or a methyl group, and R ¹⁹ represents a linear, branched or cyclic alkyl group having 6 to 30 carbon atoms.)   A cosmetic composition comprising 0.01 to 50 wt% of the block polymer according to any one of claims 1 to 17. The hair set agent composition characterized by having the following composition.
The block polymer according to any one of claims 1 to 17, 0.1 to 20 wt%
0 ~ 99wt% of water
Ethanol 0-99wt%
LPG or / and DME 0-70 wt%
(However, the total amount of water, ethanol, LPG and / or DME is 49.9 to 99.9 wt%)
Additive 0-50wt%   The hair set agent composition according to claim 19, wherein the hair set agent composition contains 0.1 to 10 wt% of silicones as an additive. An aqueous composition for hair cosmetics characterized by having the following composition.
The block polymer according to any one of claims 1 to 17, 0.1 to 20 wt%
Water 40-99wt%
Ethanol 0-40wt%
Additive 0-50wt%   The aqueous composition for hair cosmetics according to claim 21, wherein the aqueous composition for hair cosmetics contains 0.1 to 10 wt% of silicones as an additive. A cosmetic detergent composition having the following composition:
The block polymer according to any one of claims 1 to 17, 0.1 to 20 wt%
Water 40-99wt%
Surfactant 1-40wt%
Additive 0-50wt%   The cosmetic cleaning composition according to claim 23, wherein the cosmetic cleaning composition contains 0.1 to 10 wt% of silicones as an additive. A first block and a second block, which are composed of monomers having a vinyl functional group and have different monomer compositions, are bonded via a linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group. A method for producing a block polymer comprising:
After the step of obtaining a first block by radical polymerization of the first block constituent vinyl monomer containing the linking monomer,
Adding a vinyl monomer having a functional group capable of reacting with the non-radical polymerizable functional group to the non-radically polymerizable functional group of the linking monomer, radically polymerizing the second block constituent vinyl monomer, And a step of obtaining the block polymer to obtain a block polymer. A first block and a second block, which are composed of monomers having a vinyl functional group and have different monomer compositions, are bonded via a linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group. A method for producing a block polymer comprising:
After the step of obtaining a second block by radical polymerization of a vinyl monomer having a second block containing a vinyl monomer having a functional group capable of reacting with the non-radically polymerizable functional group,
A block polymer is obtained by performing a step of adding the linking monomer to a functional group capable of reacting with the non-radically polymerizable functional group and a step of radically polymerizing the first block constituent vinyl monomer to obtain a first block. A method for producing a block polymer.   The method for producing a block polymer according to claim 25 or 26, wherein the non-radically polymerizable functional group is an oxazoline-based functional group.   The method for producing a block polymer according to claim 27, wherein the functional group capable of reacting with the non-radically polymerizable functional group is a carboxylic acid group and / or an epoxy group.