JP5262376B2 - Silicone-containing block polymer and cosmetic composition containing the silicone-containing block polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a block polymer which is industrially advantageously produced in a simple process at low cost, and to provide a cosmetic composition which contains the block polymer and is excellent in curl retention, flexibility, non tackiness, non flaking, and silicone oil dispersion stability as, for example, hair set agent compositions. <P>SOLUTION: A silicone block polymer is provided which includes a polysiloxane block and two or more blocks composed of a monomer having a vinyl-based functional group. The two or more blocks composed of the monomer having the vinyl-based functional group are linked via a linkage monomer having a radical-polymerizable vinyl-based functional group and a non-radical-polymerizable functional group. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a silicone-containing block polymer suitable for industrial production, and a cosmetic composition such as a hair set composition containing the silicone-containing block polymer.

  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. 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.

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 having extremely low reactivity is used, it may not react even in the second stage polymerization. Furthermore, there is a problem that a block polymer cannot always be obtained easily because there are restrictions on reaction conditions such as temperature, time, and monomer species to be copolymerized.

An object of the present invention is to provide a silicone-containing block polymer that can solve the above-mentioned conventional problems and can be produced industrially advantageously.
Another object of the present invention is to provide a cosmetic composition such as a hair setting composition comprising such a silicone-containing 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.
Furthermore, it has been found that by introducing a polysiloxane block into the block polymer using a silicone macromer, it is possible to impart excellent silicone-specific feel and silicone oil dispersion stability.

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

[1] A silicone- containing block polymer having a polysiloxane block and two or more blocks composed of a monomer having a vinyl functional group, wherein the two or more blocks are composed of a monomer having the vinyl functional group Is a silicone-containing block polymer bonded via a linking monomer 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 an optional divalent linking group or a direct bond.)
[2] Two or more blocks composed of a monomer having a vinyl functional group include at least a first block and a second block having monomer compositions different from each other.
] The silicone containing block polymer as described in any one of.
[3] Reactivity in which the radical polymerizable vinyl functional group of the linking monomer is bonded to the constituent monomer of the first block by radical polymerization, and the oxazoline functional group of the linking monomer is derived from the constituent monomer of the second block. As described in [2], the amount of the linking monomer is 0.1 to 20 wt% with respect to the total amount of monomers constituting the first block, when the linking monomer is included in the first block. Silicone-containing block polymer.
[4 ] The silicone according to [2] or [ 3], wherein the monomer having a vinyl functional group constituting the second block includes a monomer having a carboxylic acid group and / or an epoxy group and a vinyl functional group. Contains block polymer.
[ 5 ] The bond between the oxazoline functional group and the reactive group derived from the constituent monomer of the second block is a structure in which the oxazoline functional group and the carboxylic acid group are reacted, and / or the oxazoline functional group and the epoxy. The silicone-containing block polymer according to [ 4 ], which has a structure in which a group has reacted.
[ 6 ] The silicone-containing block polymer according to any one of [2] to [ 5 ], wherein either one of the first block and the second block is water-insoluble and the other is water-soluble or water-dispersible. .
[ 7 ] The silicone-containing block polymer according to any one of [1] to [ 6 ], which is soluble or dispersible in water and / or ethanol.
[ 8 ] The first block and the second block are each composed of the following monomer composition, and at least one of the first block and the second block contains a silicone macromer in a proportion of 0.1 wt% or more. [2] to [ 7 ], the silicone-containing block polymer.
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 0-99.9wt%
Hydrophobic vinyl monomer 0-99.9wt%
Silicone macromer 0-50 wt%
(The total of the first block is 100wt%)
(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%
Silicone macromer 0-50 wt%
(The total of the second block is 100wt%)
[9] or 20 wt% of the previous SL vinyl monomer containing carboxylic acid groups and / or epoxy groups of the second block is a vinyl monomer containing carboxylic acid groups, silicone-containing block according to [8] polymer.
[10] The vinyl monomer containing carboxylic acid groups is represented by (meth) acrylic acid, or lower following general formula (6), silicone block polymer according to [9].
_{^{CH 2 = C (R 20)}} -COO- (CH 2) e-OCO-Y-COOH ··· (6)
[ 11 ] The silicone-containing block polymer according to [ 10 ], wherein at least a part of the vinyl monomer containing a carboxylic acid group is neutralized.
[ 12 ] The silicone-containing block polymer according to any one of [ 8 ] to [ 11 ], wherein the hydrophilic vinyl monomer is 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. ~
3 linear or branched alkyl groups are represented. )
_{^{CH 2 = C (R 14)}} -CO (O) - (CH 2) a- (CHOH) b-O-R 15
(3) (wherein 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, and a is an integer of 1 to 4) And b represents 0 or 1.)
[ 13 ] The silicone-containing block polymer according to any one of [ 8 ] to [ 12 ], wherein the hydrophobic vinyl-based monomer is 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.)
[ 14 ] The silicone-containing block polymer according to any one of [ 8 ] to [ 13 ], wherein the silicone macromer is represented by the following general formula (8).
_{^{CH 2 = C (R 23)}} -Z- (SiR 24 R 25 -O) n-R 26 ··· (8)
(In the formula, R ²³ represents a hydrogen atom or a methyl group, R ²⁴ and R ²⁵ each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ²⁶ represents an alkyl having 1 to 8 carbon atoms. Represents a group, Z represents a divalent linking group or a direct bond, and n represents an integer of 2 to 300.)
[ 15 ] A cosmetic composition comprising 0.01 to 50 wt% of the silicone-containing block polymer according to any one of [1] to [ 14 ].
[16] The cosmetic composition further comprises 0.1-10% silicone oils as additives, cosmetic composition according to [15].

The block polymer of the present invention can be produced at a low cost by a simple process without requiring a special initiator, and is suitable for industrial production.
In addition, by having a polysiloxane block, it gives the block polymer an excellent feel peculiar to silicone and dispersion stability of silicone oil without impairing the properties of the block polymer composed of monomers having vinyl functional groups. I can do it.

  Such a cosmetic composition containing the block polymer of the present invention is, for example, as a hair setting agent composition, a makeup excellent in curl retention, polymer flexibility, no stickiness, no flaking, and silicone oil dispersion stability. The composition can be provided.

Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present specification, “(meth) acrylic acid” represents acrylic acid and / or methacrylic acid, and “(meth) acrylate” represents acrylate and / or methacrylate.

[Silicone-containing block polymer]
In the silicone-containing 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. It has a functional group (hereinafter referred to as a non-radically polymerizable functional group) that does not react under the above conditions but can react to form 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. It is easy to control the molecular weight of the block polymer. 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.

  Examples of non-radically polymerizable functional groups include isocyanate groups, epoxy groups, hydroxyl groups, amino groups, carboxylic acid groups, acid anhydrides, thiosulfide groups, and oxazoline groups. Oxazoline-based functional groups are particularly preferable because of their high reactivity, ease of handling, and limited reaction conditions.

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.

(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 silicone-containing block polymer of the present invention will be described.
The silicone-containing block polymer of the present invention is a silicone-containing block polymer having two or more blocks composed of a polysiloxane block and a monomer having a vinyl functional group, and is composed of a monomer having the vinyl functional group. 2 or more blocks are bonded via a linking monomer having a radical polymerizable vinyl functional group and a non-radical polymerizable functional group, and preferably comprises a monomer having the vinyl functional group. The two or more blocks to be included include at least a first block and a second block having different monomer compositions.

  The polysiloxane block included in the silicone-containing block polymer of the present invention is not particularly limited as long as it includes a polysiloxane structure having a structure in which two or more of the following repeating structural units are connected.

^{- (SiR 27 R 28 -O)} -
(In the formula, R ²⁷ and R ²⁸ each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.)

In the silicone-containing block polymer of the present invention, the polysiloxane block may be connected to the main chain by a graft structure, and conversely, the polysiloxane structure is the main chain and other structures are connected by the graft structure. Furthermore, the polysiloxane structure and another structure may be linked in a straight chain. Among these, from the viewpoint of easy availability of raw materials for introducing a polysiloxane block and structural control, those in which a polysiloxane structure is connected to the main chain by a graft structure are preferable.
The method for introducing the polysiloxane block is not particularly limited, but a method using a silicone macromer is preferable. The silicone macromer here is a compound having a polysiloxane structure and a structure capable of being covalently linked to a polymer.

The structure that can be covalently linked to the polymer is, for example, a structure that has a vinyl structure such as (meth) acrylic ester or (meth) acrylamide and can be copolymerized with other monomers, or has a functional group such as thiol. And a structure that can be linked to a polymer by chain transfer during polymerization, or a structure that has an isocyanate group, a carboxylic acid, a hydroxyl group, an amino group, etc. and can be linked by reacting with a functional group of the polymer. It is not limited.
Among these reactive functional groups, those having a vinyl structure are preferable from the viewpoint of reactivity and ease of handling.
One silicone macromer may have a plurality of these connectable structures. However, from the viewpoint of controlling the molecular weight of the resulting silicone-containing block polymer, it is preferable that there is one connectable structure.

  The method for linking the silicone macromer is not particularly limited. For example, the above-mentioned silicone macromer is polymerized together with a constituent monomer of a block composed of a monomer having a vinyl functional group, and a polysiloxane structure is introduced into the block. And a method of adding a silicone macromer after polymerization of the constituent monomers constituting the block. Among these, from the viewpoint of the ease of the reaction process and the high reaction rate, a method of polymerizing together with the constituent monomer of the block composed of the monomer having a vinyl functional group is preferable.

  When the silicone-containing block polymer of the present invention contains a first block and a second block, the radical polymerizable vinyl functional group of the linking monomer is bonded to the constituent monomer of the first block by radical polymerization, and the non-radical of the linking monomer When the polymerizable functional group is bonded to the reactive group derived from the constituent monomer of the second block and the connected monomer is included in the first block, the amount of connected monomer relative to the total amount of monomers constituting the first block (hereinafter referred to as “the connected monomer”) , “Sometimes referred to as“ linking monomer ratio in the first block ””) 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 contains a monomer having a carboxylic acid group and / or an epoxy group and a vinyl functional group as constituent monomers. 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.

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- (CH2) 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 carboxylic acid such as (meth) acrylic acid as a monomer component constituting the block may be used in the form of a salt, and the salt may be formed before polymerization. It may be later. 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.
A suitable neutralizing agent can be used depending on the use, but it is preferable to use amines when gas compatibility is required when making a cosmetic composition, or when there is a concern about can corrosion, Particularly preferred are monoethanolamine, diethanolamine, triethanolamine and aminomethylpropanol, and most preferred is aminomethylpropanol.
Further, when it is desired to increase curl retention when the obtained silicone-containing block polymer is used as a hair cosmetic, or to eliminate stickiness, a metal hydroxide is preferable, and sodium hydroxide or potassium hydroxide is particularly 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.

(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.

  The monomer having an epoxy group and a vinyl functional group is not particularly limited as long as it is included in the above formula (7). For example, glycidyl (meth) acrylate, glycidyl (ethyleneoxy) 2 (meth) acrylate, glycidyl (Propyleneoxy) 2 (meth) acrylate, glycidyl (ethyleneoxy) 2 (propyleneoxy) 2 (meth) acrylate, glycidyl (ethyleneoxy) 5 (propyleneoxy) 2 (meth) acrylate and the like.

  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.

  Therefore, the bond between the non-radically polymerizable functional group and the reactive group derived from the constituent monomer of the second block is a structure in which an oxazoline functional group and a carboxylic acid group are reacted, and / or an oxazoline functional group. A structure in which an epoxy group and an epoxy group are reacted is particularly preferable.

  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 silicone-containing block polymer of the present invention may be water-soluble, water-dispersible or water-insoluble.

When the silicone-containing block polymer of the present invention is blended in a cosmetic composition, for example, a water-insoluble silicone-containing block polymer can be used by dissolving or dispersing in an oil component. Any silicone-containing block polymer can be used by dissolving and dispersing in water or lower alcohol.
In particular, the silicone-containing 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 silicone-containing block polymer of the present invention are of very different properties, and in particular, the first block and the second block. Either one is water-insoluble and the other is preferably water-soluble or water-dispersible.
When the water solubility of the polymer changes depending on the pH, for example, when the silicone-containing block polymer of the present invention has a carboxylic acid group or an amino group, at least a part 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 silicone-containing block polymer is used.

  The term “water-soluble or water-dispersible” as used herein means that when an attempt is made to dissolve the polymer in water at a concentration of 1 wt. When the solution is left for a period of time, the polymer does not precipitate, and the solution is homogeneous without phase separation. 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 silicone-containing block polymer of the present invention is used as a hair setting agent, a polymer having flexibility and high setting power can be obtained.

  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 a 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.

  The Tg of each block is calculated according to a conventional method from Tg (catalog value) when each constituent monomer of the block composed of a monomer having a vinyl functional group is a homopolymer and the weight ratio of each constituent monomer. However, when a block composed of a monomer having a vinyl functional group contains a silicone macromer as the constituent monomer, Tg in each monomer excluding the silicone macromer was calculated and regarded as the Tg of the block. This is because the polysiloxane block in the silicone macromer has an independent Tg when it becomes a silicone-containing block polymer, and therefore the Tg of a block composed of a monomer having a vinyl-based functional group has little influence on the Tg. Due to considerations.

  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 -50-10 degreeC. Moreover, Tg of a 2nd block becomes like this. Preferably it is 21-150 degreeC, More preferably, it is 30-100 degreeC, Most preferably, it is 50-90 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. A preferable configuration of the first block and the second block is a configuration obtained by polymerizing the following monomer compositions, respectively, and at least one of the first block and the second block has a silicone macromer of 0.1 wt% or more. It is contained in proportions.

(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 0-99.9wt%
Hydrophobic vinyl monomer 0-99.9wt%
Silicone macromer 0-50 wt%
(The total of the first block is 100 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%
Silicone macromer 0-50 wt%
(The total of the second block is 100 wt%.)

  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 99.9 wt%. This ratio is preferably 99.9 wt% or less because the gas compatibility and the flexibility of the polymer are maintained when the cosmetic composition is prepared. The amount of the hydrophilic vinyl monomer in the constituent monomer of the first block is more preferably 70 wt% or less, further 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 0 to 99.9 wt%. When it has a hydrophobic vinyl monomer, the curl retention, the flexibility of the polymer, the lack of flaking, and the like of the cosmetic composition are improved. The amount of the hydrophobic vinyl monomer in the first block is more preferably 10 wt% or more, and further preferably 20 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 constituent monomer of the first block is more preferably 90 wt% or less, further 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 constituent monomer of the second block is more preferably 5 wt% or more, further preferably 10 wt% or more, and most preferably 20 wt% or more. is there. 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 70 wt% or less, and most preferably 60 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 constituent monomer of the second block is more preferably 80 wt% or less from the viewpoint of monomer compatibility and polymer flexibility. More preferably, it is 50 wt% 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 constituent monomer of the second block is more preferably 70 wt% or less, and most preferably 50 wt% or less. The second block may not contain any hydrophobic vinyl monomer, but from the viewpoint of moisture resistance and flexibility, the amount of the hydrophobic vinyl monomer is more preferably 10 wt% or more, and further preferably 20 wt%. % Or more, and most preferably 30 wt% or more.

  What is suitable as a hydrophilic vinyl-type monomer contained in the constituent monomer of 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, the hydrophilic vinyl monomer contained in the first block and the second block is represented by the general formula from the viewpoints of affinity to hair and solubility in water and / or ethanol. The hydrophilic vinyl monomer represented by (3) is preferred, preferably hydroxyalkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, more preferably 2-hydroxyethyl (meth) acrylate, methoxyethyl ( It is 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 suitable hydrophobic vinyl-based monomer contained in the constituent monomers of the first block and the second block has a structure represented by the 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 Examples include (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 acrylates; fluorine-containing acrylics such as trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate; and the like can also be used.

  When the silicone-containing graft block polymer is used for cosmetics, the first block and the polymer are used in view of the affinity for hair and the solubility in water and / or ethanol, and the flexibility of the polymer in use. The hydrophobic vinyl monomer contained in 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.

The ratio of the polysiloxane block in the silicone-containing graft block polymer of the present invention is preferably 0.1 to 50 wt% in terms of the weight ratio of the polysiloxane structure. By setting it to 0.1 wt% or more, it is possible to impart dispersion stability of a silicone oil generally used in cosmetics. More preferably, it is 1 wt% or more, More preferably, it is 2 wt%, Most preferably, it is 5 wt% or more. Moreover, the stickiness by a silicone macromer can be suppressed by setting it as 50 wt% or less. Furthermore, an increase in cost due to the silicone macromer can be suppressed. More preferably, it is 30 wt% or less, More preferably, it is 20 wt% or less, Most preferably, it is 15% or less.
The amount of silicone macromer is 0-50 wt% in the first and second blocks.

  The silicone macromer may be contained in one or both of the constituents of the first block and the second block, but may be contained in both, but at least one of the blocks contains 0.1% by weight of the silicone macromer. It is preferable to contain in the above ratio. From the viewpoint of feel and silicone oil dispersion stability, it is preferable that a silicone macromer is contained in the constituent components of both the first block and the second block.

  What is suitable as a silicone macromer has a structure of the following general formula (8).

_{^{CH 2 = C (R 23)}} -Z- (SiR 24 R 25 -O) n-R 26 ··· (8)
(In the formula, R ²³ represents a hydrogen atom or a methyl group, R ²⁴ and R ²⁵ each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ²⁶ represents an alkyl having 1 to 8 carbon atoms. Represents a group, Z represents a divalent linking group or a direct bond, and n represents an integer of 2 to 300.)
More preferably, n is 3 or more, and still more preferably n is 5 or more. The larger n is, the more the affinity with silicone oil is improved. Further, n is more preferably 200 or less, still more preferably 100 or less, and most preferably 50 or less. The smaller the value, the better the copolymerizability with other monomers.
Z represents a divalent linking group or a direct bond, and among them, a structure composed of one or a combination of two or more of the structures listed below is preferable. The number of combinations is not particularly limited, but is usually 5 or less. Further, the orientation of the following structure (which end is on the polysiloxane group side) is arbitrary. R represents an alkylene group having 1 to 6 carbon atoms or a phenylene group.

-COO-R-
-CONH-R-
-O-R-
-R-

The silicone macromer represented by the general formula (8) is not particularly limited as long as it is included in this formula, and examples thereof include α- (vinylphenyl) polydimethylsiloxane and α- (vinylbenzyloxypropyl) polydimethyl. Examples include siloxane, α- (vinylbenzyl) polymethylphenylsiloxane, α- (methacryloyloxypropyl) polydimethylsiloxane, α- (methacryloyloxypropyl) polymethylphenylsiloxane, α- (methacryloylaminopropyl) polydimethylsiloxane, and the like. . Commercially available products can also be used. For example, as α- (methacryloyloxypropyl) polydimethylsiloxane, Silaplane (Chisso Corporation) is available, and Silaplane FM0711 (molecular weight 1000), Silaplane FM0721 (molecular weight). 5000) and Silaplane FM0722 (molecular weight 10,000).
In addition, a silicone macromer may be used individually by 1 type, or may use 2 or more types together.

  As for the weight average molecular weight of each block which comprises the silicone containing 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 the flexibility of the polymer 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.

  Moreover, the weight average molecular weight of the silicone-containing 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 silicone-containing block polymer of the present invention is preferably in the range of 1/99 to 99/1. 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 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 silicone-containing 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. More 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.

[Method for producing silicone-containing block polymer]
The silicone-containing 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 obtained by bonding will be described by illustrating <Method 1> and <Method 2>.

<Method 1>
After the step of radical polymerization of the vinyl monomer constituting the first block containing the linking monomer to obtain the first block, the non-radically polymerizable functional group of the linking monomer has a function capable of reacting with the non-radical polymerizable functional group. A block polymer is obtained by performing a step of adding a vinyl monomer having a group (addition step) and a step of radical polymerization of the vinyl monomer constituting the second block to obtain a second block (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 comprising a second block 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 a step of adding (addition step) and a step of obtaining a first block by radical polymerization of a vinyl monomer constituting the first block (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 silicone-containing block polymer and cosmetic composition]
The silicone-containing 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.

  The cosmetic composition preferably contains 0.01 to 50 wt% of the silicone-containing block polymer of the present invention. In order to make the effect of blending the polymer in the cosmetic composition sufficient, the content of the silicone-containing block polymer of the present invention is preferably 0.01 wt% or more. A more preferable silicone-containing block polymer content is 0.1 wt% or more, and further preferably 0.3 wt% or more. Also, from the viewpoint of moderate viscosity and easy handling and cost, the silicone-containing 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 Is 5 wt% or less.

Especially, the silicone containing block polymer of this invention can be used conveniently for a hair setting agent composition, The preferable compounding composition in this case is as follows.
Silicone-containing block polymer of the present invention 0.1-20 wt%
Water 0-99.9wt%
Ethanol 0-99.9wt%
Additive 0-50wt%
(The total of water and ethanol is 30wt% or more)

  In the hair setting agent composition using the silicone-containing block polymer of the present invention, the silicone-containing block polymer of the present invention is preferably contained in an amount of 0.1 to 20 wt%. That is, in order to make the setting force sufficient, the content of the silicone-containing block polymer is preferably 0.1 wt% or more, more preferably 1 wt% or more, and further preferably 2 wt% or more. In addition, the silicone-containing block polymer content is preferably 20 wt% or less, more preferably 10 wt% or less, and even more preferably 5 wt% or less from the viewpoint of moderate viscosity and easy handling and cost.

In general, the amount of water and ethanol effective to dissolve the polymer is preferably in the range of 30 to 99.9 wt% in total. In order to make the setting force sufficient, the content of these solvents is preferably 99.9 wt% or less, and is preferably 30 wt% or more from the viewpoint of easy viscosity and easy handling and cost.
Preferably, the ethanol content is in the range of 0 to 99.9 wt% and the water content is in the range of 0 to 99.9 wt%. These ratios can be appropriately selected depending on the product form.

When the silicone-containing block polymer of the present invention is used as a hair setting agent, a desired additive 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, the content of other additives is preferably 0.1 wt% or more, more preferably 1 wt% or more, and most preferably 5 wt% or more.
In order not to inhibit the performance, the content of other additives is preferably 30 wt% or less, more preferably 10 wt% or less, and most preferably 5 wt% or less.

  Preferably, the hair set composition includes a composition containing 0.1 to 10 wt% of silicone oil as one of the additives. In order to give gloss to hair and improve combing, the hair setting agent composition preferably contains 0.1 wt% or more of silicone oil, more preferably 0.2 wt% or more, and still more preferably 0 0.3 wt% or more, and most preferably 0.5 wt% or more. In addition, the content of the silicone oil is preferably 10 wt% or less, more preferably 5 wt% or less, and further preferably 2 wt% or less from the viewpoint of moderate viscosity and easy handling and cost.

  Here, the silicone oil refers to a polymer 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 silicone oils include, but are not limited to, polydimethylsiloxane, polydimethylsiloxane alkylene oxide copolymer, amino-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, methylphenylpolysiloxane, epoxy-modified polydimethylsiloxane, Examples include fluorine-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-mentioned siloxane having an aminoalkyl group, or by modifying polydimethylsiloxane later with the above-mentioned compound having an aminoalkyl group. It is obtained by introducing an aminoalkyl group into

  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.

  Commercially available products of polyether-modified polydimethylsiloxane include, for example, “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 silicone oils may be used alone or in combination of two or more.

  Other additives that can be incorporated into the hair setting composition using the silicone-containing block polymer of the present invention include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, semipolar surfactants. Surfactants, higher alcohols, water-soluble polymers, cationic polymers, anionic polymers, nonionic polymers, amphoteric polymers, oils, pearlizing agents, suspending agents and the like can be mentioned.

  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, a cation-modified guar gum 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.), propellant (LPG, dimethyl ether, carbon dioxide, etc.), antioxidant, ultraviolet absorber, bactericidal agent, preservative, chelating agent, fragrance, One or more of colorants, higher fatty acids, thickeners, sequestering agents (such as edetate), pH adjusters, and foam enhancers can be appropriately blended within a range that does not impair the effects of the present invention.

  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 stirrer was charged with 200 parts by weight of ethanol, monomers of composition A in Table 1 and a connected monomer, 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 stirrer 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 as 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 carried out in the same manner as in Production Example 1 except that 2 parts by weight of bifunctional allyl methacrylate was added as a crosslinking agent 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 calculated from the glass transition temperature (Tg) of the homopolymer of each constituent monomer is shown in Tables 1 to 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. However, the linking monomer, the silicone macromer, and the cross-linking agent are treated as those having little influence on the Tg of the first and second blocks, and are not considered in the calculation.

  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 containing acrylic acid (AA) and methacrylic acid (MAA) which are acidic substances as a constituent monomer was evaluated by neutralizing the polymer with aminomethylpropanol (AMP).

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 the same amount of monomers and linked monomers as the composition A in Table 1 in the polymer (1). The inside of the reactor was purged 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.

Production Example 16 <Production of Comparative Polymer (16)>
The polymer (1) was synthesized in the same manner as the polymer (1) except that a composition obtained by removing SiMM from the composition A of the polymer (1) in Table 1 was used.

Production Example 17 <Production of Comparative Polymer (17)>
The polymer (2) in Table 1 was synthesized in the same manner as the polymer (2) except that the composition obtained by removing SiMM from each of the compositions A and B was used.

Examples 1-10, Comparative Examples 1-3
The appearance of the polymers (1) to (13) obtained in Production Examples 1 to 13 in a 30 wt% 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 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 and 12, Comparative Examples 4 and 5
Using the polymers (1), (2), (16), and (17) obtained in Production Examples 1 and 2, 16, and 17, the hair setting agent composition solution having the composition shown in Table 5 was prepared. . The silicone oil dispersion stability, curl retention, flexibility, non-stickiness, and non-flaking of the solution were evaluated. The results are shown in Tables 7 and 8.

Examples 13 to 19, Comparative Examples 6 and 7
Using the polymers (1), (2), (3), (4), (7), (14), and (15) obtained in Production Examples 1 to 4, 7, 14, and 15, Table 6 A hair set composition having the composition described was prepared. The solution was evaluated for curl retention, flexibility, no stickiness, and no flaking. The results are shown in Table 8.

<Silicon oil dispersion stability>
The appearance of the solution after each adjusted hair setting agent composition solution was placed at 40 ° C. for 1 week was visually observed to evaluate the silicone oil dispersion stability.
Further, each hair setting agent composition solution was applied to a glass plate with a 100 μm applicator, dried for 1 hour in a dryer at 50 ° C., and then left in a 23 ° C./60% humidity atmosphere for 1 day. The appearance was visually observed and evaluated.

  As is clear from Table 7, the polymers (1) and (2) were able to exist stably in a state containing silicone oil, and the film was also uniform, but the polymer (16), (17) caused phase separation in the solution and the film was non-uniform.

<Curl retention>
1.0 g of each composition was applied to 23 cm, 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>
1.0 g of each composition was applied to 23 cm and 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

<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 silicone oil dispersion stability, curl retention, and a softness | flexibility, and the outstanding hair setting agent composition without stickiness and flaking is obtained.

Claims (16)

A polysiloxane block, a silicone-containing block polymer having a two or more blocks composed of monomers having a vinyl functional group, two or more blocks is composed of a monomer having the vinyl-based functional group, the following A silicone-containing block polymer, which is bonded via a linking monomer represented by the 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 silicone-containing block polymer according to claim 1, wherein the two or more blocks composed of the monomer having a vinyl functional group include at least a first block and a second block having monomer compositions different from each other.   The radical polymerizable vinyl functional group of the linking monomer is bonded to the constituent monomer of the first block by radical polymerization, and the oxazoline functional group of the linking monomer is bonded to the reactive group derived from the constituent monomer of the second block. The silicone-containing block according to claim 2, wherein when the linking monomer is included in the first block, the amount of the linking monomer with respect to the total amount of monomers constituting the first block is 0.1 to 20 wt%. polymer. The silicone-containing block polymer according to claim 2 or 3, wherein the monomer having a vinyl functional group constituting 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 oxazoline functional group and the reactive group derived from the constituent monomer of the second block is a structure in which the oxazoline functional group and the carboxylic acid group react, and / or the oxazoline functional group and the epoxy group. The silicone-containing block polymer according to claim 4 , which has a reacted structure. The silicone-containing block polymer according to any one of claims 2 to 5 , wherein one of the first block and the second block is water-insoluble and the other is water-soluble or water-dispersible. The silicone-containing block polymer according to any one of claims 1 to 6 , which is soluble or dispersible in water and / or ethanol. The first block and the second block are each composed of the following monomer composition, and the silicone macromer is contained in a ratio of 0.1 wt% or more in at least one of the first block and the second block. 8. The silicone-containing block polymer according to any one of 2 to 7 .
(I) 1st block Linking monomer 0.1-20 wt%
Hydrophilic vinyl monomer 0-99.9wt%
Hydrophobic vinyl monomer 0-99.9wt%
Silicone macromer 0-50 wt%
(The total of the first block is 100wt%)
(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%
Silicone macromer 0-50 wt%
(The total of the second block is 100wt%) The silicone-containing block polymer according to claim 8 , wherein 20% by weight or more of the vinyl monomer containing a carboxylic acid group and / or an epoxy group of the second block is a vinyl monomer containing a carboxylic acid group. The silicone-containing block polymer according to claim 9 , wherein the vinyl monomer containing the carboxylic acid group is represented by (meth) acrylic acid or the following general formula (6).
_{^{CH 2 = C (R 20)}} -COO- (CH 2) e-OCO-Y-COOH ··· (6) ( ^{wherein, R 20} represents a hydrogen atom or a methyl group, e is an integer from 1 to 4 Y represents a phenyl group which may have a substituent. The silicone-containing block polymer according to claim 10 , wherein at least a part of the vinyl monomer containing the carboxylic acid group is neutralized. The silicone-containing block polymer according to any one of claims 8 to 11 , wherein the hydrophilic vinyl monomer is 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) (wherein 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, and a is an integer of 1 to 4) And b represents 0 or 1.) The silicone-containing block polymer according to any one of claims 8 to 12 , wherein the hydrophobic vinyl-based monomer is 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.) The silicone-containing block polymer according to any one of claims 8 to 13 , wherein the silicone macromer is represented by the following general formula (8).
_{^{CH 2 = C (R 23)}} -Z- (SiR 24 R 25 -O) n-R 26 ··· (8
)
(In the formula, R ²³ represents a hydrogen atom or a methyl group, R ²⁴ and R ²⁵ each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ²⁶ represents an alkyl having 1 to 8 carbon atoms. Represents a group, Z represents a divalent linking group or a direct bond, and n represents an integer of 2 to 300.) A cosmetic composition comprising 0.01 to 50 wt% of the silicone-containing block polymer according to any one of claims 1 to 14 .   The cosmetic composition according to claim 15, wherein the cosmetic composition further contains 0.1 to 10 wt% of silicone oil as an additive.