JP6209010B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a polymer composition containing an organopolysiloxane graft polymer, and more particularly to a polymer composition useful as a hair cosmetic.

Since organopolysiloxane has many excellent features, various forms of organopolysiloxane are used as a touch improver for shampoos and hair conditioners.
For example, Patent Document 1 has no stickiness, can impart excellent luster, luster and smooth feel to the hair, and has hair shape retention ability and can accumulate even after repeated use over a long period of time. In addition, a polyacryl-modified organopolysiloxane having no compounding problems is disclosed.
In Patent Document 2, a hair cosmetic containing a poly (N-acylalkylenimine) -modified organopolysiloxane is applied to hair, and after shaping the hair at a hair temperature of 50 ° C. or higher, the hair temperature is 50. A hair styling method is disclosed in which the shaped hairstyle is fixed by cooling to less than 0C.
Patent Document 3 discloses a cosmetic composition containing an organopolysiloxane graft polymer obtained by solution polymerization of mercapto-modified silicone and a radical polymerizable vinyl monomer.
Patent Document 4 discloses a hair cosmetic containing an organopolysiloxane graft polymer.
Patent Document 5 discloses a personal care product including an anionic polyorganosiloxane graft polymer-treated powder and a cosmetic using the same.

Japanese Patent No. 3600623 International Publication No. 2011/062210 Japanese National Patent Publication No. 10-512233 JP-A-6-92825 JP 2009-161598 A

The polyacryl-modified organopolysiloxane described in Patent Document 1 has a problem that the film has a low elastic modulus at room temperature, and the hair setting force and the hair shape retention force are insufficient. There is also a problem that stickiness is felt when the blending amount in the hair cosmetic is increased.
The poly (N-acylalkylenimine) -modified organopolysiloxane described in Patent Document 2 cannot be said to have sufficient set retention under high humidity.
Patent Documents 3 to 5 disclose organopolysiloxane graft polymers having a cationic group or an anionic group, but after shaping the hair at a hair temperature of 50 ° C or higher, the temperature of the hair is cooled to less than 50 ° C. Therefore, it cannot be used for a hair styling method (for example, a hair setting method using a hair iron or a dryer) for fixing the shaped hairstyle.

  An object of the present invention is to shape a hair at a hair temperature of 50 ° C. or higher and then cool the hair temperature to less than 50 ° C. so that the shaped hair can be fixed and has excellent set retention. The object is to provide a polymer composition and a hair cosmetic containing the polymer composition.

The present invention provides the following polymer composition and hair cosmetic.
[1] A polymer composition containing the following polymer A and polymer B, wherein the content of the organopolysiloxane segment with respect to the total of the polymer A and the polymer B is 30% by mass or more and 70% by mass or less.
Polymer A: an organopolysiloxane graft polymer having an organopolysiloxane segment as a main chain and a polymer segment derived from an unsaturated monomer as a side chain, wherein the organopolysiloxane segment in the organopolysiloxane graft polymer An organopolysiloxane graft polymer having a content of more than 70% by mass and 90% by mass or less.
Polymer B: A polymer containing 90% by mass or more of a repeating unit derived from the same unsaturated monomer as the unsaturated monomer constituting the side chain of the polymer A.
[2] A hair cosmetic containing the polymer composition.

  According to the present invention, after shaping hair at a hair temperature of 50 ° C. or higher, the shaped hairstyle can be fixed by cooling the hair temperature to less than 50 ° C., and has a high set holding power. A composition and a hair cosmetic containing the composition can be provided.

[Polymer composition]
The polymer composition of the present invention is a polymer composition containing the following polymer A and polymer B, wherein the content of the organopolysiloxane segment with respect to the total of polymer A and polymer B is 30% by mass or more and 70% by mass or less.
Polymer A: an organopolysiloxane graft polymer having an organopolysiloxane segment as a main chain and a polymer segment derived from an unsaturated monomer as a side chain, wherein the organopolysiloxane segment in the organopolysiloxane graft polymer An organopolysiloxane graft polymer having a content of more than 70% by mass and 90% by mass or less.
Polymer B: A polymer containing 90% by mass or more of a repeating unit derived from the same unsaturated monomer as the unsaturated monomer constituting the side chain of the polymer A.

<Polymer A>
The polymer A is an organopolysiloxane graft polymer having an organopolysiloxane segment as a main chain and a polymer segment derived from an unsaturated monomer as a side chain, the organopolysiloxane in the organopolysiloxane graft polymer It is an organopolysiloxane graft polymer (hereinafter also referred to as “graft polymer”) having a segment content of more than 70% by mass and 90% by mass or less.
In the graft polymer of the present invention, it is preferable that two or more side chains are bonded to any silicon atom of the organopolysiloxane segment constituting the main chain via an alkylene group containing a hetero atom. It is more preferable that it is bonded to one or more silicon atoms except for through the alkylene group, and it is further preferable to bond to two or more silicon atoms other than both ends via the alkylene group.

[Organopolysiloxane segment]
The graft polymer has an organopolysiloxane segment as the main chain.
The chemical structure of the organopolysiloxane segment is not particularly limited, but a preferred specific example is a modified organopolysiloxane segment represented by the following general formula (1) or (2).

In the general formulas (1) and (2), R ¹ independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ² contains a hetero atom. Represents an optionally substituted alkylene group. p represents a number of 2 to 4000, and q represents a number of 2 to 250. In the formula, the coupling mode of p repeating units and q repeating units may be such that each repeating unit is connected in a block shape or in a random shape.

In the general formulas (1) and (2), examples of the alkyl group represented by R ¹ include a linear, branched, or cyclic alkyl group. The carbon number of the alkyl group represented by R ¹ is From the viewpoint of dispersibility of the graft polymer in ethanol, it is preferably 1 or more and 10 or less, more preferably 6 or less. Specific examples of the alkyl group represented by R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl. Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group, nonadecyl group, eicosyl group, docosyl group and the like. The dispersibility of the graft polymer in ethanol is a property that allows the graft polymer to be stably dispersed in a composition containing ethanol as a main component. If this property is good, the solvent is ethanol. It is preferable because it can be blended in the hair cosmetic composition containing the main component and the hair washability is improved.
The number of carbon atoms of the aryl group represented by R ¹ is preferably 6 or more and 12 or less, more preferably 9 or less, from the viewpoint of dispersibility of the graft polymer in ethanol. Specific examples of the aryl group represented by R ¹ include phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group and the like.
Among these, as R ¹ , a linear or branched alkyl group having 1 to 6 carbon atoms is preferable from the viewpoint of dispersibility of the graft polymer in ethanol, and linear or branched having 1 to 3 carbon atoms. A chain alkyl group is more preferred, and a methyl group is still more preferred.

In the general formulas (1) and (2), p represents a number of 2 to 4000, and q represents a number of 2 to 250.
p is preferably 50 or more from the viewpoint of hair feel after setting hair with a hair cosmetic using an organopolysiloxane graft polymer (hereinafter also referred to as “hair cosmetic of the present invention”), that is, stickiness reduction. More preferably, the number is 80 or more, more preferably 100 or more, and from the viewpoint of dispersibility of the graft polymer in ethanol, the number is preferably 2000 or less, more preferably 1300 or less, and still more preferably 700 or less. It is.
From the viewpoint of dispersibility of the graft polymer in ethanol, q is preferably a number of 3 or more, more preferably 5 or more, and the setting power of the hair cosmetic of the present invention, the sustainability of the hair shape after setting, From the viewpoint, the number is preferably 50 or less, more preferably 30 or less.

In the general formulas (1) and (2), part or all of the alkylene group (R ² ) which may contain a hetero atom is bonded to the polymer chain derived from the main chain and the unsaturated monomer, It functions as a linking group for a polymer segment derived from an unsaturated monomer as a main chain and a side chain. When there is an alkylene group that may contain a hetero atom that is not bonded to the polymer segment derived from the unsaturated monomer, the alkylene group that may contain the hetero atom includes the main chain and a hydrogen atom. Are connected.
In the present invention, the number of carbon atoms of the alkylene group which may contain a hetero atom is preferably 2 or more, more preferably 3 or more, from the viewpoint of availability of raw materials during the production of the graft polymer. From the viewpoint of dispersibility in ethanol, it is preferably 20 or less, more preferably 10 or less, and still more preferably 8 or less.

In the present invention, the alkylene group which may contain a hetero atom is one or more atoms or functional groups selected from an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and —NR ³ CO—. It may be divided by a group. That is, the alkylene group which may contain a hetero atom may have a structure of “— (alkylene group moiety 1) — (the above atom or functional group) — (alkylene group moiety 2) —”. The carbon number of the alkylene group means the sum of the carbon number of the alkylene group part 1 and the carbon number of the alkylene group part 2. Here, R ³ is an alkyl group having 1 to 3 carbon atoms. When the alkylene group which may contain a hetero atom is interrupted by the above atom or functional group, it is preferably interrupted by —NHCO— from the viewpoint of ease of production of the graft polymer.

  In the present invention, the alkylene group which may contain a hetero atom includes a hydroxyl group, an amino group, an alkylamino group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, an amino group and 2 or more carbon atoms. One or more monovalent groups selected from an amide group obtained by dehydration condensation of 4 or less fatty acid, a carboxy group, and an alkyl ester group having 1 to 3 carbon atoms may be substituted. In this case, the carbon number of the alkylene group which may contain a hetero atom does not include the carbon number of the substituent. From the viewpoint of availability of raw materials at the time of producing the graft polymer, the alkylene group which may contain a hetero atom is at least one monovalent selected from an acetamido group, an alkylamino group having 1 to 3 carbon atoms, and an amino group. These groups are preferably substituted.

In the present invention, an alkylene group which may contain a hetero atom, -O -, - S -, - NH -, - NR 30 -, - NHCO- and selected from -COO-, 2-valent hetero atom, Alternatively, a divalent group containing a hetero atom may be substituted. Here, R ³⁰ is an alkyl group having 1 to 3 carbon atoms which may be substituted by a dimethylamino group. In the case where the heteroatom or a divalent group containing a heteroatom serves as a linking group with a polymer segment derived from an unsaturated monomer, the alkylene group that may contain a heteroatom is an unsaturated monomer. It is bound to the polymer segment derived from the body. In other cases, it is bonded to a hydrogen atom.
From the viewpoint of ease of production of the graft polymer, the alkylene group which may contain a hetero atom is preferably substituted with -S-.
The alkylene group (R ² ) which may contain a hetero atom is a polymer segment derived from an unsaturated monomer via the hetero atom, preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a sulfur atom. It is preferable that it is couple | bonded with.
Therefore, the “alkylene group optionally containing a hetero atom” represented by R ² includes (i) an unsubstituted alkylene group, (ii) an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO. An alkylene group interrupted by one or more atoms or functional groups selected from — and —NR ³ CO—, (iii) a hydroxyl group, an amino group, an alkyl (having 1 to 3 carbon atoms) amino group, a dialkyl (having a carbon number) 1 or more and 3 or less) one or more selected from an amino group, an amide group obtained by dehydration condensation of an amino group and a fatty acid having 2 to 4 carbon atoms, a carboxy group, and an alkyl (1 to 3 carbon atoms) ester group monovalent alkylene radical group is substituted, (iv) -O -, - S -, - NH -, - NR 30 - and divalent heteroatoms selected from -COO- 2 or containing a hetero atom, Alkyl substituted with a valent group Other emissions group, the (ii), (iii), the appropriate alkylene group comprising a combination of (iv).

  Specific examples of the alkylene group that may contain a hetero atom in the present invention include the following formulas (i) to (xii). Of these, the following formulas (xi) and (xii) are preferred from the viewpoint of ease of production of the graft polymer.

In formulas (i) to (xii), * represents a site bonded to a silicon atom in the general formula (1) or (2), and ** is bonded to a polymer segment derived from an unsaturated monomer. Represents a site.
In the formula (xii), X ¹ is one or more selected from —O—, —OCO—, —COO—, —CONH—, —NHCO—, and —CONH— from the viewpoint of ease of production of the graft polymer. -NHCO- is preferable, and -NHCO- is more preferable.

In the formula (xii), R ⁴ represents a hydroxyl group, an amino group, an alkyl (C 1 or more and 3 or less) amino group, a dialkyl (C 1 or more and 3 or less) amino group, an amino group and 2 or more and 4 or less carbon atoms. Is an alkylene group which may be substituted with one or more monovalent groups selected from an amide group, a carboxy group, and an alkyl (having 1 to 3 carbon atoms) ester group obtained by dehydration condensation. The substituent is preferably an acetamido group, an alkyl (having 1 to 3 carbon atoms) amino group, and an amino group from the viewpoint of availability of raw materials during production. The number of carbon atoms of the alkylene group represented by R ⁴ is preferably 2 or more, more preferably 3 or more from the viewpoint of ease of production of the graft polymer, and from the viewpoint of dispersibility of the graft polymer in ethanol. , Preferably 10 or less, more preferably 6 or less.
Specific examples of R ⁴ include the following formulas (xiii) to (xv).

In the formula (xiv), X ⁻ represents an anion such as a halide ion such as a chloride ion or a bromide ion, an acetate ion, or an alkyl (having 1 to 3 carbon atoms) sulfate ion.

[Polymer segment derived from unsaturated monomer]
There are no particular limitations on the unsaturated monomer that can be used in the polymer segment derived from the unsaturated monomer, such as a nonionic unsaturated monomer, a cationic unsaturated monomer, and an anion. Unsaturated monomers can be used.
In the present invention, in particular, when (1) N, N-dimethylacrylamide (hereinafter also referred to as “DMAAm”) is used as the nonionic unsaturated monomer, (2) a cationic unsaturated monomer is used. In this case, it is preferable to use (3) an unsaturated monomer having a carboxylic acid or a salt thereof as the anionic unsaturated monomer. Hereinafter, preferred embodiments in each case will be described in detail.

(When DMAAm is used as a nonionic unsaturated monomer)
When DMAAm is used as the nonionic unsaturated monomer, the polymer segment derived from the unsaturated monomer of the polymer A contains 50% by mass to 100% by mass of the repeating unit derived from DMAAm, and is ionic. The content of the repeating unit derived from the unsaturated monomer is preferably 1% by mass or less.
The glass transition temperature of the polymer segment derived from the unsaturated monomer is more preferably 60 ° C. or higher and 150 ° C. or lower.
Further, a repeating unit derived from a nonionic unsaturated monomer having a glass transition temperature of 60 ° C. or higher and 150 ° C. or lower (hereinafter also referred to as “Tg _60-150 ° C. nonionic unsaturated monomer”) of the homopolymer. It is preferable to contain 90 mass% or more.

The content of the repeating unit derived from DMAAm in the polymer segment derived from the unsaturated monomer of the polymer A is determined in view of the setting power of the hair cosmetic, the sustainability of the hair shape after setting, and the hair cosmetic. From the viewpoint of hair washability and the dispersibility of the graft polymer in ethanol, it is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 75% by mass. From the viewpoint of the feel of the hair after setting the hair, it is preferably 100% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, and still more preferably 85% by mass. It is as follows.
In the graft polymer, the content of the repeating unit derived from DMAAm in the polymer segment derived from the unsaturated monomer can be measured by NMR method.

  The glass transition temperature of the polymer segment derived from the unsaturated monomer is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting. Further, from the viewpoint of easy shaping of hair at a hair temperature of 50 ° C. or higher, it is preferably 150 ° C. or lower, more preferably 140 ° C. or lower.

The content of the repeating unit derived from the Tg _60-150 ° C. nonionic unsaturated monomer in the polymer segment derived from the unsaturated monomer of the polymer A is the hair cosmetic setting power, the hair after setting. From the viewpoint of shape sustainability, it is preferably 90% by mass or more, more preferably 95% by mass, still more preferably substantially 100% by mass, and still more preferably 100% by mass.

The glass transition temperature of the Tg _60-150 ° C. nonionic unsaturated monomer is preferably 60 ° C. or more, more preferably 70 ° C., from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting. From the viewpoint of easy shaping of hair at a hair temperature of 50 ° C. or higher, the temperature is preferably 150 ° C. or lower, more preferably 140 ° C. or lower.

In the present invention, Tg _60-150 ° C. may be used DMAAm only as a non-ionic unsaturated monomer, or may be used Tg _60-150 ° C. nonionic unsaturated monomer other than DMAAm.
The glass transition temperature of the Tg _60-150 ° C. nonionic unsaturated monomer other than the DMAAm is preferably 80 ° C. or more, more preferably from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting. Is 100 ° C. or higher, more preferably 120 ° C. or higher, and is preferably 135 ° C. or lower, more preferably 130 ° C. or lower, from the viewpoint of ease of hair shaping at a hair temperature of 50 ° C. or higher.

The content of Tg _60-150 ° C. nonionic unsaturated monomer other than the above DMAAm depends on the setting power of the hair cosmetics, the viewpoint of durability of the hair shape after setting, and the feel of the hair after setting the hair. From the viewpoint, it is preferably 0% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. Also, the setting power of the hair cosmetic, the viewpoint of the sustainability of the hair shape after setting, and the graft From the viewpoint of dispersibility of the polymer in ethanol, it is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

  Examples of nonionic unsaturated monomers other than DMAAm are unsaturated monomers copolymerizable with DMAAm, such as olefins, halogenated olefins, vinyl esters, (meth) acrylates, or (meta ) Repeating units derived from unsaturated monomers such as acrylamides (excluding DMAAm). In the polymer segment derived from the unsaturated monomer, the portion other than the repeating unit derived from DMAAm may consist of a repeating unit derived from a single type of unsaturated monomer copolymerizable with DMAAm, or two types. You may consist of the above repeating unit derived from an unsaturated monomer.

  Specific examples of olefins include ethylene, propylene, and isobutylene. Specific examples of the halogenated olefin include vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride. Specific examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate and the like.

  Specific examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Tert-butyl acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate (Meth) acrylate having an alkyl group having 1 to 16 carbon atoms such as (meth) acrylate having a hydroxyl group substituted with a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; ) Polyethylene glycol acrylate and the like.

  Specific examples of (meth) acrylamides excluding DMAAm include (meth) acrylamides such as acrylamide and methacrylamide; N, N-dialkyl (meth) acrylamides such as N, N-diethyl (meth) acrylamide (however, DMAAm is Except); N-alkyl (meth) acrylamides such as N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-tert-octyl (meth) acrylamide; diacetone N-monosubstituted (meth) acrylamides having a carbonyl group as a substituent on the nitrogen atom such as (meth) acrylamide; substitution on the nitrogen atom such as N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide Hydroxyl group To N- monosubstituted (meth) acrylamides and the like.

  Among these, acrylamide, methacrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl are used from the viewpoint of hair setting ability and retention of the hair shape after setting. (Meth) acrylamide, diacetone (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ( More preferred are isobutyl acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-tert-butyl (meth) acrylamide, N-hydroxy Ethyl (meth) acrylamide More preferred are diacetone (meth) acrylamide, methyl (meth) acrylate, and tert-butyl (meth) acrylate, N-tert-butyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, diacetone (meth) acrylamide, More preferred are methyl (meth) acrylate and tert-butyl (meth) acrylate.

  When N, N-dimethylacrylamide is used as the nonionic unsaturated monomer, the repeating unit derived from the ionic unsaturated monomer in the polymer segment derived from the unsaturated monomer of the polymer A is: From the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting, it is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less. More preferably still substantially 0% by mass, still more preferably 0% by mass.

(When using a cationic unsaturated monomer)
When a cationic unsaturated monomer is used as the unsaturated monomer, the polymer segment derived from the unsaturated monomer of the polymer A is a repeating unit derived from a nonionic unsaturated monomer (provided that 40 mass% to 90 mass%) (excluding repeating units derived from unsaturated monomers having an amino group) and 10 mass% to 60 mass% repeating units derived from cationic unsaturated monomers And it is preferable that content of the repeating unit derived from an anionic unsaturated monomer is 1 mass% or less.
The glass transition temperature of the polymer segment derived from the unsaturated monomer is more preferably 60 ° C. or higher and 150 ° C. or lower.
Furthermore, as the nonionic unsaturated monomer, it is preferable to use a nonionic unsaturated monomer having a glass transition temperature of 60 ° C. or higher and 150 ° C. or lower.

  The content of the repeating unit derived from the cationic unsaturated monomer in the polymer segment derived from the unsaturated monomer of the polymer A is determined from the viewpoint of the set power of the hair cosmetic, the hair to which the hair cosmetic is attached. From the viewpoint of hair washability and from the viewpoint of dispersibility of the graft polymer in ethanol, it is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. From the viewpoint of setting force (when the content is large, the film becomes soft), it is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

Examples of the cationic unsaturated monomer include one or more selected from an unsaturated monomer having an amino group and an unsaturated monomer having a quaternary ammonium base.
Specific examples of the unsaturated monomer having an amino group include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Examples include diethylaminopropyl (meth) acrylamide, 2-vinylpyridine, 4-vinylpyridine, and structures obtained by neutralizing these with an acid represented by H ⁺ X ⁻ .
X ⁻ represents a halide ion such as a chloride ion or a bromide ion; an alkyl sulfate ion having 1 to 3 carbon atoms, an acetate ion, a lactate ion, a benzoate ion, an adipate ion, a formate ion, a malate ion, Anion such as organic acid ion such as glycolate ion; From the viewpoint of the feel of the hair after setting when the hair is set with the hair cosmetic composition of the present invention, and the set retention property under high humidity, alkyl sulfate ion, lactate ion, formate ion, malate ion, glycolate ion It is preferable that it is a lactate ion.
Specific examples of the unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium, (meth) acryloyloxypropyltrimethylammonium, (meth) acrylo having X ⁻ as a counter ion. Ilaminoethyltrimethylammonium, (meth) acryloylaminopropyltrimethylammonium, diallyldimethylammonium, 1-ethyl-4-vinylpyridinium, 1,2-dimethyl-5-vinylpyridinium and the like can be mentioned.

  Content of repeating unit derived from nonionic unsaturated monomer in polymer segment derived from unsaturated monomer of polymer A (excluding repeating unit derived from unsaturated monomer having amino group) Is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of the setting power of the hair cosmetic, the sustainability of the hair shape after setting, and the feel of the hair after setting the hair. The amount is preferably 60% by mass or more, and from the viewpoint of dispersibility of the graft polymer in ethanol, it is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less.

  The glass transition temperature of the polymer segment derived from the unsaturated monomer is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting. Further, from the viewpoint of easy shaping of hair at a hair temperature of 50 ° C. or higher, it is preferably 150 ° C. or lower, more preferably 140 ° C. or lower.

The nonionic unsaturated monomer is more preferably a nonionic unsaturated monomer whose homopolymer has a glass transition temperature of 60 ° C. or higher and 150 ° C. or lower.
The glass transition temperature of the Tg _60-150 ° C. nonionic unsaturated monomer is preferably 60 ° C. or higher, more preferably 70 ° C., from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting. More preferably, it is 80 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 120 ° C. or higher, and preferably 150 from the viewpoint of ease of hair shaping at a hair temperature of 50 ° C. or higher. ° C or lower, more preferably 140 ° C or lower, still more preferably 130 ° C or lower.

The nonionic unsaturated monomer is an unsaturated monomer copolymerizable with a cationic unsaturated monomer (excluding a repeating unit derived from an unsaturated monomer having an amino group). Examples thereof include unsaturated monomers such as olefins, halogenated olefins, vinyl esters, (meth) acrylates, and (meth) acrylamides. Specific examples of these unsaturated monomers include those described above.
In the polymer segment derived from the unsaturated monomer, the portion other than the repeating unit derived from the cationic unsaturated monomer is a single type of unsaturated monomer copolymerizable with the cationic unsaturated monomer. It may consist of a repeating unit derived from, or may consist of a repeating unit derived from two or more unsaturated monomers.
Among these, Nt-butylacrylamide is still more preferable from the viewpoint of hair setting ability and hair shape retention after setting.

  When a cationic unsaturated monomer is used as the unsaturated monomer, the repeating unit derived from the anionic unsaturated monomer in the polymer segment derived from the unsaturated monomer of the polymer A is polymer production. From the viewpoint of solubility in the solvent at the time, it is preferably 1% by mass or less, more preferably substantially 0% by mass, and still more preferably 0% by mass.

(When using an anionic unsaturated monomer)
When an anionic unsaturated monomer is used as the unsaturated monomer, the polymer segment derived from the unsaturated monomer of the polymer A is a repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof. 15% to 80% by weight of a repeating unit derived from a nonionic unsaturated monomer (excluding a repeating unit derived from an unsaturated monomer having an amino group). The content of repeating units derived from a cationic unsaturated monomer is preferably 1% by mass or less.
The glass transition temperature of the polymer segment derived from the unsaturated monomer is more preferably 60 ° C. or higher and 150 ° C. or lower.
Furthermore, as the nonionic unsaturated monomer, it is preferable to use a nonionic unsaturated monomer whose homopolymer has a glass transition temperature of 60 ° C. or higher and 150 ° C. or lower.

  The content of the unsaturated monomer having a carboxylic acid or a salt thereof in the polymer segment derived from the unsaturated monomer of the polymer A is determined from the viewpoint of the hair washability of the hair to which the hair cosmetic is attached, and the graft polymer. From the viewpoint of dispersibility in ethanol, it is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, and from the viewpoint of the feel of the hair after setting the hair, Preferably it is 85 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less, More preferably, it is 70 mass% or less.

Specific examples of the unsaturated monomer having the carboxylic acid or a salt thereof include, for example, an unsaturated carboxylic acid monomer such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, and crotonic acid. Examples include the body. Among these, (meth) acrylic acid and maleic acid are preferable from the viewpoint of availability, and (meth) acrylic acid is more preferable.
The repeating unit derived from the unsaturated monomer having a carboxylic acid may be an acid or may be partially or wholly neutralized. Specific examples of the base compound used for neutralization include, for example, alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide; ammonia; mono-, di-, or triethanolamine, triethylamine, morpholine And amine compounds such as aminomethylpropanol and aminoethylpropanediol. Among these, from the viewpoint of dispersibility of the graft polymer in ethanol, a part or all of the graft polymer is preferably neutralized.

  The glass transition temperature of the polymer segment derived from the unsaturated monomer is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting. Further, from the viewpoint of easy shaping of hair at a hair temperature of 50 ° C. or higher, it is preferably 150 ° C. or lower, more preferably 140 ° C. or lower.

The nonionic unsaturated monomer is more preferably a nonionic unsaturated monomer whose homopolymer has a glass transition temperature of 60 ° C. or higher and 150 ° C. or lower.
The glass transition temperature of the Tg _60-150 ° C. nonionic unsaturated monomer is preferably 60 ° C. or more, more preferably 70 ° C., from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting. More preferably, it is 80 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 120 ° C. or higher, and from the viewpoint of easy shaping of hair at a hair temperature of 50 ° C. or higher, preferably 150 ° C. C. or lower, more preferably 140.degree. C. or lower, still more preferably 130.degree.

The content of the repeating unit derived from the nonionic unsaturated monomer is set from the viewpoint of the hair cosmetic setting power, the sustainability of the hair shape after setting, and the hair feel after setting the hair. , Preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and still more preferably 30% by mass or more, and from the viewpoint of dispersibility of the graft polymer in ethanol, Preferably it is 80 mass% or less, More preferably, it is 75 mass% or less, More preferably, it is 70 mass% or less.
Specific examples of the nonionic unsaturated monomer include those described above.
Among these, Nt-butylacrylamide is still more preferable from the viewpoint of hair setting ability and hair shape retention after setting.

  When an anionic unsaturated monomer is used as the unsaturated monomer, the repeating unit derived from the cationic unsaturated monomer in the polymer segment derived from the unsaturated monomer of the polymer A is a polymer production. From the viewpoint of solubility in the solvent at the time, it is preferably 1% by mass or less, more preferably substantially 0% by mass, and still more preferably 0% by mass.

[Configuration of polymer A (organopolysiloxane graft polymer)]
The content of the organopolysiloxane segment in the organopolysiloxane graft polymer is more than 70% by mass, preferably 72% by mass or more, more preferably from the viewpoint of hair feel after setting the hair with the hair cosmetic composition of the present invention. Is 74% by mass or more, and from the viewpoint of dispersibility of the graft polymer in ethanol, it is 90% by mass or less, preferably 86% by mass or less, and more preferably 80% by mass or less.
The content of the organopolysiloxane segment in the graft polymer can be determined by the method described in the examples.

In addition, the number average molecular weight (MNg) of the organopolysiloxane segment between adjacent polymer segments derived from unsaturated monomers (hereinafter sometimes referred to as “molecular weight between graft points”) includes the organopolysiloxane graft polymer. From the viewpoint of improving the setting power when the hair is set with the hair cosmetic to be performed and the holding power of the hair shape after setting, preferably 500 or more, more preferably 1,000 or more, still more preferably 1,500 or more, more Preferably, it is 2,000 or more, and from the viewpoint of dispersibility of the graft polymer in ethanol, it is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 4,100 or less, and even more preferably 3 2,000 or less, more preferably 2,500 or less.
Here, “an organopolysiloxane segment between polymer segments derived from adjacent unsaturated monomers” means an organopolysiloxane of a polymer segment derived from an unsaturated monomer as shown in the following formula (3). A portion surrounded by a broken line between two points from the bond point (bond point A) to the segment to the bond point (bond point B) of the polymer segment derived from the unsaturated monomer adjacent thereto, A segment composed of one R ¹ SiO unit, one R ² , and y + 1 R ¹ ₂ SiO units.

In the formula, each R ¹ independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, R ² represents an alkylene group which may contain a hetero atom, and —W -R ⁵ represents a polymer segment derived from an unsaturated monomer, R ⁵ represents a residue or a hydrogen atom of the polymerization initiator, y represents a positive number.

  The molecular weight between graft points is the average value of the molecular weight of the portion surrounded by the broken line in the above formula (3), and the mass of the organopolysiloxane segment per mole of the polymer segment derived from the unsaturated monomer (g / mol). The molecular weight between graft points is the case where the graft polymer is produced from the radical reactive organopolysiloxane described later, and all radical reactive functional groups and the polymer derived from the unsaturated monomer are bonded. In this case, the value is considered to be the same as the reciprocal value of the number of moles of radical reactive functional groups (mol / g) present per unit mass of the radical reactive organopolysiloxane.

In addition, the weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is determined by the setting power when the hair is set with a hair cosmetic containing an organopolysiloxane graft polymer and the holding power of the hair shape after setting. From the viewpoint, it is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and still more preferably 20,000 or more. MWsi is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less, and still more preferably 40,000 or less, from the viewpoint of dispersibility of the graft polymer in ethanol.
When the organopolysiloxane graft polymer is produced from the radical reactive organopolysiloxane described below, the MWsi is the radical reactive organopolysiloxane because the organopolysiloxane segment has a common skeleton with the radical reactive organopolysiloxane. Is substantially the same as the weight average molecular weight (MWra), and is regarded as the same in the present invention. In addition, MWra is measured by gel permeation chromatography (GPC) under the measurement conditions described in the Examples, and converted to polystyrene.

The weight average molecular weight (MWt) of the graft polymer (Polymer A) is preferably from the viewpoint of the setting power when the hair is set with a hair cosmetic containing an organopolysiloxane graft polymer and the holding power of the hair shape after setting. 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more, still more preferably 40,000 or more, and preferably 200,000 or less from the viewpoint of dispersibility of the graft polymer in ethanol. More preferably, it is 150,000 or less, More preferably, it is 100,000 or less, More preferably, it is 80,000 or less, More preferably, it is 60,000 or less. Within this range, sufficient film strength can be ensured, in addition, dispersibility in ethanol will be excellent, and it will not be sticky, and the setting power and the holding power of the hair shape after setting will be further improved. Can be.
In this specification, MWt is measured by GPC under the measurement conditions described in the examples and converted to polystyrene.

[Method for producing organopolysiloxane graft polymer]
Next, a method for producing an organopolysiloxane graft polymer (Polymer A) will be described. In addition, according to the manufacturing method of the organopolysiloxane graft polymer demonstrated below, the polymer BI mentioned later can also be obtained as a by-product. In the present invention, a mixture of polymer A and polymer BI obtained by the method described below may be referred to as “polymer mixture C”.
The method for producing the graft polymer is not particularly limited. For example, it is derived from (i) an organopolysiloxane having a reactive functional group and an unsaturated monomer having a functional group capable of reacting with the reactive functional group at the terminal. Examples thereof include a graft-onto method (polymer reaction method) in which a polymer segment is reacted, (ii) a graft-from method in which an unsaturated monomer is radically polymerized in the presence of a radical-reactive organopolysiloxane described later. Among these, from the viewpoint of reducing the load during production, (ii) the graft-from method in which an unsaturated monomer is radically polymerized in the presence of a radical-reactive organopolysiloxane is preferable.
Hereinafter, a method for producing a graft polymer by the graft-from method will be described.

(Radical reactive organopolysiloxane)
The graft polymer can be produced by radical polymerization of an unsaturated monomer in the presence of a radical reactive organopolysiloxane represented by the following general formula (4) or (5).

In the formula, each R ¹¹ independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ¹² represents an alkyl group having a radical reactive functional group (hereinafter referred to as “radical reaction”). Also referred to as a functional group-containing alkyl group).
In the general formulas (4) and (5), a preferred embodiment of R ^{11 is the same as} the preferred embodiment of R ^{1 in} the general formulas (1) and (2).
In the general formulas (4) and (5), p and q have the same meanings as p and q in the general formulas (1) and (2), respectively, and preferable modes are the general formulas (1) and (2), respectively. ) In the preferred embodiments of p and q.

  In the present invention, the radical reactive functional group means a functional group capable of generating a radical, and examples thereof include an ethylenically unsaturated group, a halogeno group such as a chloro group and a bromo group, and a sulfanyl group (mercapto group). It is done. Among these, a sulfanyl group is preferable from the viewpoint of reactivity with an unsaturated monomer and molecular weight control.

In general formulas (4) and (5), the number of carbon atoms of the radical-reactive group-containing alkyl group represented by R ¹² is preferably 2 or more, more preferably from the viewpoint of easy availability of the radical-reactive organopolysiloxane. Is 3 or more, and from the viewpoint of dispersibility of the graft polymer in ethanol, it is preferably 20 or less, more preferably 10 or less, and still more preferably 8 or less.
In the present invention, the number of carbon atoms of the radical reactive functional group-containing alkyl group does not include the number of carbon atoms of the radical reactive functional group even when the radical reactive functional group has carbon. Also when the containing alkyl group is the above-described monovalent group substituted, the carbon number of the monovalent group is not included.

In general formulas (4) and (5), the radical-reactive group-containing alkyl group represented by R ¹² is a hydroxyl group, an amino group, an alkylamino group having 1 to 3 carbon atoms, or a dialkylamino group having 1 to 3 carbon atoms. One or more monovalent groups selected from an amide group obtained by dehydration condensation of a group, an amino group and a fatty acid having 2 to 4 carbon atoms, a carboxy group, and an alkyl ester group having 1 to 3 carbon atoms are substituted. It may be. Among these substituents, an acetamido group, an alkylamino group having 1 to 3 carbon atoms, or an amino group is preferable from the viewpoint of easy availability of raw materials when producing radical-reactive organopolysiloxane.

In the general formulas (4) and (5), the radical-reactive group-containing alkyl group represented by R ¹² is an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and —NR ¹³ CO—. It may be interrupted by one or more selected atoms or functional groups. Here, R ¹³ is an alkyl group having 1 to 3 carbon atoms. When the radical-reactive group-containing alkyl group is interrupted by the above atoms or functional groups, it is preferable that the radical-reactive group-containing alkyl group is interrupted by —NHCO— from the viewpoint of availability of radical-reactive organopolysiloxane or production. .

Specific examples of the radical-reactive group-containing alkyl group in the present invention include the following formulas (xvii) to (xx). Above all, from the viewpoint of the production of a radical-reactive organopolysiloxane or availability, (Xix) or (xx) is preferred. X ¹¹ and R ^{14 in} formula (xx) and preferred embodiments thereof are the same as X ¹ and R ^{4 in} formula (xii) and preferred embodiments thereof, respectively.

The weight-average molecular weight (MWra) of the radical-reactive organopolysiloxane is considered to be the same as the MWsi in the present invention, and therefore its preferred mode is the same as the preferred mode of the MWsi.
In the present invention, MWra is measured by GPC under the measurement conditions described in the Examples and converted to polystyrene.

  The number of moles of radical-reactive functional groups present per unit mass of the radical-reactive organopolysiloxane depends on the setting force when the hair is set with a hair cosmetic containing an organopolysiloxane graft polymer and the hair shape after setting. From the viewpoint of improving the holding power, it is preferably 1/500 mol / g or less, more preferably 1/700 mol / g or less, and still more preferably 1/1000 mol / g or less. From the viewpoint of dispersibility of the graft polymer in ethanol. Therefore, it is preferably 1 / 10,000 mol / g or more, more preferably 1/5000 mol / g or more, and still more preferably 1/3000 mol / g or more.

  The radical reactive organopolysiloxane whose radical reactive group is a sulfanyl group can be obtained as a commercial product, for example, “KF-2001” (manufactured by Shin-Etsu Chemical Co., Ltd.).

(Organopolysiloxane having a reactive functional group)
The radical reactive organopolysiloxane can also be obtained by reacting an organopolysiloxane having a reactive functional group represented by the following general formula (6) or (7) with a radical reactivity imparting agent. Organopolysiloxanes having reactive functional groups represented by the general formulas (6) and (7) are commercially available in various structures and are easily available.

In the formula, each R ²¹ independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ²² represents an alkyl group having a reactive functional group (hereinafter referred to as “reactive group-containing”). Also referred to as an “alkyl group”. p and q are respectively synonymous with p and q of the general formulas (4) and (5), and preferable modes are the same as the preferable modes of p and q in the general formulas (4) and (5), respectively. is there.
In the general formulas (6) and (7), a preferred embodiment of R ^{21 is the same as} the preferred embodiment of R ^{11 in} the general formulas (4) and (5).

In the present invention, the reactive functional group means a hydroxyl group, an amino group, a carboxy group, or an epoxy group.
The organopolysiloxane having a reactive functional group has one or more substituents selected from a hydroxyl group, an amino group, a carboxy group, and an epoxy group.
As the reactive functional group, a hydroxyl group, an amino group, or an epoxy group is preferable from the viewpoint of availability, and an amino group is preferable from the viewpoint of reactivity and handleability.

In the general formulas (6) and (7), the number of carbon atoms of the reactive group-containing alkyl group represented by R ²² is preferably 2 or more from the viewpoint of easy availability of the organopolysiloxane having a reactive functional group. More preferably, it is 3 or more, and from the viewpoint of dispersibility of the graft polymer in ethanol, it is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less.

  Specific examples of the reactive group-containing alkyl group in the present invention include the following formulas (xxi) to (xxviii), and from the viewpoint of availability, one or more selected from (xxi) to (xxiv) are preferable, and the reactivity In view of the above, (xxiv) is more preferable.

The weight average molecular weight (MWsim) of the organopolysiloxane having a reactive functional group is determined from the viewpoint of the setting power when the hair is set with a hair cosmetic containing an organopolysiloxane graft polymer and the holding power of the hair shape after setting. , Preferably 3,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, still more preferably 20,000 or more, and from the viewpoint of dispersibility of the graft polymer in ethanol, Preferably it is 200,000 or less, More preferably, it is 100,000 or less, More preferably, it is 50,000 or less, More preferably, it is 40,000 or less.
In the present invention, MWsim is measured by GPC under the measurement conditions described in the Examples and converted to polystyrene.

  The number of moles of the reactive functional group present per unit mass of the organopolysiloxane having a reactive functional group is the setting force when the hair is set with a hair cosmetic containing an organopolysiloxane graft polymer and the hair after setting. From the viewpoint of improving the holding power of the shape, it is preferably 1/500 mol / g or less, more preferably 1/700 mol / g or less, still more preferably 1/1000 mol / g or less, and the graft polymer in ethanol. From the viewpoint of dispersibility, it is preferably 1 / 10,000 mol / g or more, more preferably 1 / 5,000 mol / g or more, and still more preferably 1 / 3,000 mol / g or more.

(Radical reactivity imparting agent)
In the present invention, the radical reactivity imparting agent is an agent that reacts with a reactive functional group of an organopolysiloxane having a reactive functional group to add a radical reactive functional group to the organopolysiloxane having a reactive functional group. Say.

As the radical reactivity imparting agent, a radical reactive functional group in the molecule, a carboxy group capable of reacting with the reactive functional group of the organopolysiloxane having the reactive functional group, an ester group, an epoxy group, a hydroxyl group, and In the case where a compound having one or more functional groups selected from lactones can be used, and the reactive functional group of the organopolysiloxane having the reactive functional group is a hydroxyl group, an amino group, or an epoxy group , Thiolactones which may have a substituent can be used.
The radical-reactive functional group of the radical reactivity-imparting agent and its preferred mode are the same as the radical-reactive functional group of the radical-reactive organopolysiloxane and its preferred mode. Among these, from the viewpoint of reactivity during polymerization, the radical reactivity imparting agent preferably has a sulfanyl group (mercapto group) as a radical reactive functional group, for example, a sulfanyl group such as 3-mercaptopropionic acid. And a compound having a carboxy group in the molecule, and lactones having a sulfanyl group such as γ-butyrolactone thiol. Examples of the thiolactone which may have a substituent include γ-thiobutyrolactone, N-acetyl-DL-homocysteine thiolactone, DL-homocysteine thiolactone hydrochloride and the like. Among these, as the radical reactivity imparting agent, N-acetyl-DL-homocysteine thiolactone is more preferable from the viewpoint of reactivity with the reactive organopolysiloxane and reactivity during polymerization.

  The amount of radical reactivity imparting agent used is preferably 0.8 equivalents or more, more preferably 0.9 equivalents or more from the viewpoint of reactivity with respect to the total amount of reactive functional groups of the organopolysiloxane having a reactive functional group. Preferably, from the viewpoint of reducing the unreacted radical reactivity imparting agent after the reaction, 1.2 equivalents or less is preferable, and 1.1 equivalents or less is more preferable.

(Production of radical-reactive organopolysiloxane)
In the reaction between the radical reactivity imparting agent and the organopolysiloxane having a reactive functional group, a solvent may be used.
Solvents include water, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as hexane and cyclohexane, ethers such as diethyl ether and tetrahydrofuran. , Aromatic compounds such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane and chloroform.
From the viewpoint of reducing environmental burden, it is preferable not to use a solvent.

The reaction temperature is preferably 70 ° C. or higher from the viewpoint of reactivity, more preferably 90 ° C. or higher, and preferably 200 ° C. or lower, more preferably 150 ° C. or lower, from the viewpoint of chemical stability of the resulting radical reactive polysiloxane. .
The reaction time is preferably 1 hour or longer, more preferably 2 hours or longer, from the viewpoint of sufficiently allowing the reaction to proceed, preferably 10 hours or shorter, more preferably 5 hours or shorter, from the viewpoint of productivity.
From the viewpoint of the reactivity of the resulting radical reactive organopolysiloxane, the conversion rate of at least one of the reactive functional group of the organopolysiloxane having a reactive functional group and the radical reactivity imparting agent is 80% or more. It is preferable to carry out until it becomes, and it is more preferable to carry out until it becomes 90% or more.
The method for measuring the conversion rate varies depending on the reactive functional group of the organopolysiloxane having a reactive functional group used for the reaction and the radical reactivity imparting agent, and any of them can be measured by a known method. For example, when the reactive functional group of the organopolysiloxane having a reactive functional group is an amino group and the radical reactivity-imparting agent is a thiolactone, the conversion rate of the amino group is “a total base number test method for petroleum products ( Perchloric acid method) ”(JIS K2501), and the conversion rate of thiolactones can be determined using a liquid chromatographic method.

(Production of organopolysiloxane graft polymer)
The method for polymerizing the unsaturated monomer in the presence of the radical-reactive organopolysiloxane is not particularly limited, and a bulk polymerization method, a solution polymerization method, a suspension polymerization method, etc. can be adopted, but an organo with a more uniform composition. Solution polymerization methods are preferred for producing polysiloxane graft polymers.
From the viewpoint of the dispersibility of the graft polymer in ethanol, the amount of the unsaturated monomer used as the raw material is based on the total amount of the radical reactive organopolysiloxane used as the raw material and the unsaturated monomer used as the raw material. Preferably it is 10 mass% or more, More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more, and the viewpoint of the touch of the hair after setting hair with the hair cosmetics containing an organopolysiloxane graft polymer Therefore, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

When the polymerization of the unsaturated monomer is carried out by a solution polymerization method, the solvent used is such that the radical reactive organopolysiloxane, the unsaturated monomer, and the resulting graft polymer are all dissolved or homogeneous. If dispersed, there is no particular limitation.
Specific examples of the solvent include water, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as hexane and cyclohexane, diethyl ether and tetrahydrofuran. And ethers such as benzene, toluene and the like, and halogenated hydrocarbons such as dichloromethane and chloroform. These may be used alone or in combination of two or more.
Among these, from the viewpoint of obtaining a graft polymer having a more uniform side chain molecular weight distribution, alcohols having 1 to 8 carbon atoms such as water, ethanol and isopropanol, and having 2 to 8 carbon atoms such as ethyl acetate and butyl acetate. It is preferable to use one or more solvents selected from ethers having 2 to 8 carbon atoms, such as esters, diethyl ether, and tetrahydrofuran. From the viewpoint of bringing a solvent into the hair cosmetic composition, water, It is more preferable to use one or more selected from alcohols having 1 to 3 carbon atoms such as ethanol.

  The amount of the solvent used is not particularly limited as long as all of the raw material radical-reactive organopolysiloxane, unsaturated monomer and the resulting organopolysiloxane graft polymer are dissolved or uniformly dispersed. From the viewpoint of ease of production and productivity, it is preferably 20% by mass or more, more preferably 40% by mass or more, and more preferably 40% by mass or more, based on the total mass of the radical-reactive organopolysiloxane and unsaturated monomer added at the time of production. Preferably, it is 60% by mass or more, more preferably 100% by mass or more, and from the viewpoint of reactivity, it is preferably 1000% by mass or less, more preferably 900% by mass or less, still more preferably 400% by mass or less, more More preferably, it is 300 mass% or less.

  Examples of the polymerization initiator include azo-based initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), and peroxides such as lauroyl peroxide and benzoyl peroxide. Examples thereof include oxide initiators and persulfate initiators such as ammonium persulfate. Further, polymerization may be initiated by generating radicals by light irradiation or the like. As the polymerization initiator, 2,2'-azobis (2,4-dimethylvaleronitrile) is preferable from the viewpoint of reactivity. Although there is no restriction | limiting in particular in the usage-amount of a polymerization initiator, From a viewpoint of the weight average molecular weight of the graft polymer obtained, Preferably it is 10 mass% or less with respect to the total mass of the unsaturated monomer thrown in, More preferably, it is 1 From the viewpoint of reactivity, it is preferably 0.001% by mass or more, and more preferably 0.01% by mass or more.

  The temperature during the polymerization reaction can be appropriately selected depending on the polymerization initiator used, the type of the solvent, and the like, but is preferably 50 ° C. or higher, more preferably 60 ° C. or higher from the viewpoint of the polymerization reaction rate. Moreover, it is preferable to make it react at normal pressure for the equipment load reduction used for polymerization reaction, and from the viewpoint of making it react below the boiling point of a solvent, the temperature at the time of polymerization reaction becomes like this. Preferably it is 100 degrees C or less, More preferably, it is 90 degrees C or less. is there.

The polymerization reaction is preferably performed until the conversion rate of the unsaturated monomer is 80% or more, and more preferably 90% or more. The upper limit of conversion is 100%.
The conversion rate of the unsaturated monomer can be determined by gas chromatography analysis. Specific operations are described in the examples.
The polymerization reaction time is usually from 0.1 hours to 60 hours, and from the viewpoint of operability, it is preferably 0.5 hours or more, more preferably 1 hour or more, still more preferably 2 hours or more, and even more preferably 4 hours. From the viewpoint of productivity, it is preferably 30 hours or less, more preferably 20 hours or less, and even more preferably 10 hours or less. In the case where the polymerization reaction is added over time, such as dropwise addition or divided addition of raw materials, the polymerization reaction time includes the time required for addition of the raw materials. The polymerization reaction time can be shortened, for example, by raising the polymerization reaction temperature, and can be changed according to the polymerization temperature.

The radical-reactive organopolysiloxane and unsaturated monomer, solvent, polymerization initiator, etc. that are the raw materials may be added all at once, and the polymerization reaction may be carried out. A reaction may be performed. For example, (1) A method in which a radical-reactive organopolysiloxane, an unsaturated monomer, and a solvent are mixed and heated, and a solution in which an initiator is dissolved is added all at once or dropwise; (2) the solvent is heated Then, a method in which a radical-reactive organopolysiloxane, an unsaturated monomer, and an initiator are separately or mixed, and a solution dissolved in a solvent is dropped; (3) radical-reactive organopolysiloxane, unsaturated There is a method in which a part of the monomer and a solvent are mixed and heated, and a solution in which the initiator and the remainder of the unsaturated monomer are dissolved is added all at once or dropwise.
Further, after completion of the polymerization reaction, purification or reduction of unreacted unsaturated monomers may be performed by a known method as necessary. For example, unreacted unsaturated monomers and other impurities may be reduced by adding a polymerization initiator and heating, membrane purification, adsorbent treatment, or the like.

<Polymer B>
The polymer B in the present invention is a polymer containing 90% by mass or more of a repeating unit derived from the same unsaturated monomer as the unsaturated monomer constituting the side chain of the polymer A.
A part of the polymer B is produced as a by-product during the production of the organopolysiloxane graft polymer (polymer A). In the present invention, a polymer that satisfies the conditions of the polymer B is separated from the polymer A. Preferably, it is manufactured and used as polymer B.
In the present invention, polymer B produced as a by-product during production of polymer A is referred to as “polymer BI”, and polymer B produced separately from polymer A is referred to as “polymer BII”.

[Polymer BI]
As described above, the polymer BI is a polymer produced as a by-product when the polymer A is produced.
In the polymer BI, the content of the unsaturated monomer constituting the side chain of the polymer A is preferably 90% by mass or more, more preferably 95% by mass or more, from the viewpoint of improving the compatibility with the polymer A. Preferably it is 100 mass% substantially, More preferably, it is 100 mass%.
In addition, the preferable aspect of polymer BI is the same as that of the unsaturated monomer which comprises the side chain of the polymer A.

<Polymer mixture C>
As described above, the polymer mixture C includes the polymer A and the polymer BI obtained in the production process of the polymer A. The polymer composition of the present invention may be a mixture of the polymer mixture C and a solvent as necessary. The polymer mixture C is a polymer BII described later and further mixed with a solvent as necessary. It may be.
The content of the polymer A in the polymer mixture C is preferably 70% by mass or more, more preferably 72% by mass or more, and still more preferably from the viewpoint of easy determination of the mixing ratio at the time of production of the polymer composition. It is 80% by mass or more, more preferably 90% by mass or more, and from the viewpoint of easy reaction control, it is preferably 99.5% by mass or less, more preferably 99.0% by mass or less.

The mass ratio of the polymer A to the polymer BI in the polymer mixture C [Polymer A / Polymer BI] is preferably 2.3 or more from the viewpoint of easy determination of the mixing ratio at the time of producing the polymer composition. Preferably it is 3.0 or more, more preferably 9.0 or more, still more preferably 20, or more, still more preferably 40 or more, still more preferably 60 or more, and from the viewpoint of ease of reaction control, preferably Is 200 or less, more preferably 100 or less, still more preferably 80 or less, and still more preferably 70 or less.
In addition, content of the polymer BI in the polymer mixture C can be adjusted by changing the radical chargeable organopolysiloxane and the pre-charge ratio of the unsaturated monomer, and the dropping speed.

[Polymer BII]
The polymer BII is a polymer produced separately from the production of the polymer A as described above.
In the polymer BII, the content of the unsaturated monomer constituting the side chain of the polymer A is preferably 90% by mass or more, more preferably 95% by mass or more, from the viewpoint of improving the compatibility with the polymer A. Preferably it is 100 mass% substantially, More preferably, it is 100 mass%.
Since the polymer BII is a polymer containing 90% by mass or more of the same unsaturated monomer as the unsaturated monomer constituting the side chain of the polymer A as described above, the preferred mode of the polymer BII is the side of the polymer A This is the same as the unsaturated monomer constituting the chain.

[Method for producing polymer BII]
The production method of the polymer BII is not particularly limited, and a bulk polymerization method, a solution polymerization method, a suspension polymerization method and the like can be adopted, but a solution polymerization method is particularly preferable.
When the polymerization of the unsaturated monomer as a raw material is carried out by a solution polymerization method, the solvent used is not particularly limited as long as both the unsaturated monomer and the resulting polymer BII are dissolved or uniformly dispersed. .
Specific examples of the solvent include the same solvents as those used in the production of the organopolysiloxane graft polymer.
Among these, from the viewpoint of obtaining a polymer BII having a more uniform composition, alcohols having 1 to 8 carbon atoms such as water, ethanol and isopropanol, esters having 2 to 8 carbon atoms such as ethyl acetate and butyl acetate, It is preferable to use one or more solvents selected from diethyl ether and ethers having 2 to 8 carbon atoms, such as tetrahydrofuran, and when the polymer composition is used for hair cosmetics, etc. From the viewpoint of bringing in the solvent, it is more preferable to use at least one selected from alcohols having 1 to 3 carbon atoms such as water and ethanol.

  The amount of the solvent used is not particularly limited as long as both the unsaturated monomer and the resulting polymer BII are dissolved or uniformly dispersed, but from the viewpoint of ease of operation during production and productivity, Preferably it is 50 mass% or more with respect to the total mass of a monomer, More preferably, it is 100 mass% or more, More preferably, it is 150 mass% or more, More preferably, it is 200 mass% or more, and a reactive viewpoint Therefore, it is preferably 1,500% by mass or less, more preferably 1,000% by mass or less, still more preferably 500% by mass or less, and still more preferably 300% by mass or less.

The preferred embodiment of the kind and amount of the polymerization initiator is the same as the preferred embodiment of the polymerization initiator at the time of producing the organopolysiloxane graft polymer.
Preferred embodiments of the temperature and reaction time during the polymerization reaction are the same as the preferred embodiments during the production of the organopolysiloxane graft polymer.

The polymerization reaction is preferably performed until the conversion rate of the unsaturated monomer is 80% or more, and more preferably 90% or more. The upper limit of conversion is 100%.
The conversion rate of the unsaturated monomer can be determined by gas chromatography analysis. Specific operations are described in the examples.

Unsaturated monomers, solvents, polymerization initiators, and the like as raw materials may be added all at once to carry out the polymerization reaction, but in order to control the composition, the polymerization reaction may be carried out by adding in portions or dropwise. For example, (1) a method in which an unsaturated monomer and a solvent are mixed and heated, and a solution having an initiator dissolved therein is added all at once or dropwise; (2) when the solvent is heated, A method in which a solution in which a monomer and an initiator are separately or mixed and dissolved in a solvent is dropped; (3) A part of the unsaturated monomer and the solvent are mixed and heated, and the initiator and the initiator are mixed therewith. There is a method of adding a solution in which the remainder of the saturated monomer is dissolved all at once or dropwise.
Further, after completion of the polymerization reaction, purification or reduction of unreacted unsaturated monomers may be performed by a known method as necessary. For example, unreacted unsaturated monomers and other impurities may be reduced by adding a polymerization initiator and heating, membrane purification, adsorbent treatment, or the like.

The polymer BII is preferably a solution from the viewpoint of handleability. As a solvent, 1 or more types chosen from water and a C1-C3 linear or branched saturated or unsaturated alcohol as a solvent can be contained. Among these, from the viewpoint of bringing the solvent into the hair cosmetic into the polymer BII, the solvent is preferably one or more selected from water, ethanol, and isopropanol, and more preferably one or more selected from water and ethanol. .
The content of the polymer BII in the solution is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and still more preferably, from the viewpoint of operability when preparing a hair cosmetic. Is 25% by mass or more, and is preferably 50% by mass or less, more preferably 45% by mass or less, from the viewpoint of solubility of the polymer BII.

The weight average molecular weight of the polymer B is preferably 2,000 or more, more preferably from the viewpoint of the setting power when the hair is set with a hair cosmetic containing an organopolysiloxane graft polymer and the holding power of the hair shape after setting. Is 5,000 or more, more preferably 10,000 or more, still more preferably 15,000 or more, preferably 100,000 or less, more preferably 50,000 or less, still more preferably 40,000 or less, More preferably, it is 35,000 or less.
In addition, the weight average molecular weight of the polymer B can be measured by a method described in Examples described later.

<Composition of polymer composition>
The polymer composition of the present invention contains the aforementioned polymer A and polymer B.
The content of polymer A and polymer B in the polymer composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 2 from the viewpoint of operability when preparing a hair cosmetic. % By mass, more preferably 3% by mass or more, still more preferably 4% by mass or more, and from the viewpoint of the solubility of the polymer A, preferably 50% by mass or less, more preferably 40% by mass or less, More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less.

  In the polymer composition of the present invention, the content of the organopolysiloxane segment based on the total of the polymer A and the polymer B is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, from the feel of the hair. More preferably, it is 50% by mass or more, and from the viewpoint of improving the dispersibility of the graft polymer in ethanol, it is less than 70% by mass, preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably. It is 55 mass% or less.

  The mass ratio of the polymer A to the polymer B in the polymer composition [Polymer A / Polymer B] is preferably 0.6 or more, more preferably from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting. Is 1.0 or more, more preferably 1.5 or more, still more preferably 2.0 or more, and from the viewpoint of the feel of the hair after setting the hair, it is preferably 30 or less, more preferably 10 or less. Further, it is preferably 6 or less, more preferably 4.5 or less, still more preferably 4.0 or less, and still more preferably 3.5 or less.

The polymer composition of the present invention is preferably a solution from the viewpoint of handleability. As a solvent, 1 or more types chosen from water and a C1-C3 linear or branched saturated or unsaturated alcohol can be contained. Among these, from the viewpoint of bringing the solvent into the hair cosmetic, the solvent is preferably one or more selected from water, ethanol, and isopropanol, and more preferably one or more selected from water and ethanol.
The content of the solvent in the polymer composition is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 58% by mass or less from the viewpoint of solubility of the polymer composition. From the viewpoint of operability when preparing the material, it is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 90% by mass or less, still more preferably 80% by mass or less, and still more preferably. 70% by mass or less.

[Hair cosmetic]
<Polymer composition (component (A))>
The hair cosmetic composition of the present invention contains the polymer composition of the present invention (hereinafter also referred to as “component (A)”). As a result, a soft feel, a set characteristic in which the hairstyle does not collapse even when a finger is passed through the hair, and a more natural finish are obtained.

  The content of the component (A) is based on the total mass of the hair cosmetic from the viewpoint of the setting power of the hair cosmetic of the present invention, the holding power of the hair shape after setting, and the dispersibility of the graft polymer in ethanol. (However, when the hair cosmetic is a spray type and contains a propellant, the total mass does not include the mass of the propellant. The same applies hereinafter.), Preferably 0.01% by mass Or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass. Hereinafter, it is further preferably 20% by mass or less, and still more preferably 10% by mass or less.

  The content of the polymer A is preferably 0.5% by mass or more, more preferably 1% by mass, based on the total mass of the hair cosmetic, from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting. Above, more preferably 2% by mass or more, and still more preferably 3% by mass or more, and from the viewpoint of hair feel after setting the hair, from the viewpoint of solubility of the polymer A and from the viewpoint of economy, Is 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less, and still more preferably 5% by mass or less.

  The content of the polymer B is preferably 0.1% by mass or more, more preferably 0.3% from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting, based on the total mass of the hair cosmetic. It is preferably 8% by mass or more, more preferably 0.5% by mass or more, and even more preferably 0.7% by mass or more, and preferably 8 from the viewpoint of hair feel and economy after setting the hair. It is at most 5% by mass, more preferably at most 5% by mass, even more preferably at most 3% by mass, even more preferably at most 2% by mass.

  The content of the polymer A and the polymer B is based on the total mass of the hair cosmetic, and from the viewpoint of the setting power of the hair cosmetic and the sustainability of the hair shape after setting, the setting power of the hair cosmetic, the hair shape after setting From the viewpoint of sustainability, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, still more preferably 3% by mass or more, and still more preferably 4% by mass or more. In addition, from the viewpoint of the feel of the hair after setting the hair and from the viewpoint of economy, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and still more preferably 7%. It is at most 6% by mass, more preferably at most 6% by mass.

<Solvent>
In addition, in the hair cosmetic composition of the present invention, from the viewpoint of hair setting power, good usability, and operability when preparing the hair cosmetic composition, water, a straight chain or branched chain having 1 to 3 carbon atoms is used as a solvent. One or more selected from saturated or unsaturated alcohols of the chain can be contained. Especially, as a solvent, 1 or more types chosen from water, ethanol, and isopropanol are preferable, and 1 or more types chosen from water and ethanol are especially preferable.

  The hair cosmetic composition of the present invention comprises butanol, isobutanol, N-methylpyrrolidone, γ-butyrolactone, γ-caprolactone, cyclopentanone, cyclohexanone and other organic solvents; conditioning components; surfactants; polyhydric alcohols; Antidandruff agents such as topirox; vitamins; bactericides such as triclosan and trichlorocarban; anti-inflammatory agents such as dipotassium glycyrrhizinate and tocopherol acetate; antiseptics such as methylparaben and butylparaben; chelating agents; moisturizers such as panthenol Colorants such as dyes and pigments; viscosity modifiers such as hydroxyethylcellulose, methylcellulose, polyethylene glycol and clay minerals; pH adjusters such as organic acids, sodium hydroxide and potassium hydroxide; plant extracts; pearlizing agents; Dye; ultraviolet Wire absorber; You may contain components, such as antioxidant.

The hair cosmetic composition of the present invention can be obtained by mixing the polymer composition of the present invention, a solvent, and other components as required. Instead of mixing the polymer composition, the polymer mixture C and the polymer BII may be mixed.
Moreover, you may use the polymer composition of this invention as hair cosmetics as it is.

<Form of hair cosmetic>
The hair cosmetic used in the present invention can be prepared in various dosage forms according to a conventional method, for example, not only liquid compositions such as mist, lotion, tonic, but also gel, paste, cream, wax, etc. The semi-solid composition of

Moreover, the hair cosmetic composition of the present invention may be an aerosol type hair cosmetic composition containing a propellant. The propellant is not particularly limited as long as it is usually used in aerosol-type cosmetics. For example, lower saturated hydrocarbons such as propane, butane or a mixture thereof (including liquefied petroleum gas), Ethers such as dimethyl ether, nitrogen gas, carbon dioxide gas, nitrous oxide gas and the like can be used. These can be used alone or in combination of two or more.
The content of the propellant in the hair cosmetic composition of the present invention is preferably 0.01% by mass or more, more preferably 10% by mass or more, and preferably 100% by mass or less, more preferably 40% by mass or less. It is.

  Furthermore, the hair cosmetic composition of the present invention can be made into a non-aerosol hair cosmetic composition by filling a foam discharge container with a composition containing the organopolysiloxane of component (A). The foam discharge container is not particularly limited as long as the composition is mixed with air and discharged as a foam state. For example, a squeeze foamer used by pressing the body of a soft container with fingers. Examples include a pump former and a trigger type that are used by pressing the head of a cap equipped with a pump mechanism with fingers.

  Such a hair cosmetic is preferably used as a hair styling agent, hair conditioning agent, etc., and as its dosage form, pump spray, aerosol spray, pump foam, aerosol foam, gel, lotion, mist, cream, etc. are preferable. . Among these, pump spray, pump foam, and aerosol foam are more preferable.

<GPC measurement conditions for weight average molecular weight (MWsim, MWra) of organopolysiloxane having reactive functional group and radical reactive organopolysiloxane>
Column: Two K-804Ls (manufactured by Tosoh Corporation) are connected in series. Eluent: 1 mM dimethyldodecylamine / chloroform solution Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI
Sample concentration and sample volume: 5 mg / mL, 500 μL
Using the above conditions, the weight average molecular weight of each of the organopolysiloxane having a reactive functional group or the radical reactive organopolysiloxane was measured in terms of polystyrene.

<GPC measurement conditions for weight average molecular weight (MW _A , MW _BII ) of organopolysiloxane graft polymer (Polymer A) and polymer derived from unsaturated monomer (Polymer BII-1 to 3)>
Column: Two α-Ms (manufactured by Tosoh Corporation) are connected in series. Eluent: 50 mM LiBr / 1 mass% acetic acid / ethanol / water (8/2) mixed solution Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI
Sample concentration and sample volume: 5 mg / mL, 500 μL
Using the above conditions, the weight average molecular weight of each of the polymer A or the polymers BII-1 to B-3 was measured in terms of polyethylene oxide.

<GPC measurement conditions for weight average molecular weight (MW _BII ) of polymer derived from unsaturated monomer of Production Example 10 (Polymer BII-4)>
Column: Two α-Ms (manufactured by Tosoh Corporation) are connected in series. Eluent: 50 mM LiBr / 60 mM phosphoric acid / DMF solution Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI
Sample concentration and sample volume: 5 mg / mL, 500 μL
Using the above conditions, the weight average molecular weight of the polymer BII-4 was measured in terms of polyethylene oxide.

<Calculation of moles of sulfanyl groups per unit mass of sulfanyl group-modified organopolysiloxane (radical reactive organopolysiloxane) synthesized from side chain primary aminopropyl-modified organopolysiloxane (organopolysiloxane having a reactive functional group) >
Side-chain primary aminopropyl-modified organopolysiloxane (organopolysiloxane having a reactive functional group), side-chain primary aminopropyl-modified organopolysiloxane and N-acetyl-DL-homocysteine thiolactone (radical reactivity-imparting agent) The amount of amino groups consumed by the reaction was measured by measuring the amount of amino groups in the mixture containing the sulfanyl group-modified organopolysiloxane (radical reactive organopolysiloxane) obtained by the above reaction. The amount of amino groups was measured by a method based on ASTM D 2073. Specifically, about 10 g of a sample (radical reactive organopolysiloxane) was weighed into a flask, 50 mL of ethanol was added and stirred, and titrated with a 0.2 mol / L ethanolic hydrochloric acid solution using a potentiometric titrator. At the same time, a blank test was performed and corrected.
From the measurement result of the amount of amino groups, first, the conversion rate of amino groups; α (%) was determined by the following formula (IV).

α (%) = [1− [a ₁ × (f + g) / (a ₀ × f)]] × 100 (IV)
In the above formula, a ₀ and a ₁ are the number of moles of amino groups per unit mass of the side chain primary aminopropyl-modified organopolysiloxane, and the unit mass in the reaction mixture after reaction with the radical reactivity-imparting agent. Represents the total number of charged primary masses of the side chain primary aminopropylorganopolysiloxane, and g represents the total charged mass of the radical reactivity imparting agent.
Assuming that the same number of sulfanyl groups as the amino groups consumed by the reaction were formed on the radical-reactive organopolysiloxane after the reaction, from the following calculation formula (V), per unit mass of the sulfanyl group-modified organopolysiloxane The number of moles (S) of the sulfanyl group was calculated.

S (mol / g) = (a ₀ × f × α / 100) / [f + (a ₀ × f × α / 100) × h] (V)
In the above formula, _{a 0, a 1, f,} g each represent the same meaning as _{a 0, a 1, f,} g in the formula (IV), h represents the molecular weight of the radical reactive imparting agent.

<Measurement method of residual ratio of sulfanyl group (mercapto group)>
In a 10 mL screw tube, 0.6 g of a 40 wt% ethanol solution of an organopolysiloxane graft polymer, 0.15 g of a 10 wt% ethanol solution of N-methylmaleimide (manufactured by Sigma Aldrich), and 0.55 g of ethanol are placed at room temperature. For 2 hours. After stirring, 1 g of ethanol was added, the solution was analyzed by gas chromatography, and the amount of N-methylmaleimide was quantified. The residual amount of sulfanyl groups was calculated from the consumption rate of N-methylmaleimide, and the residual rate of sulfanyl groups was calculated from this value and the number of moles of sulfanyl groups per unit mass of the sulfanyl group-modified organopolysiloxane.

<Calculation of molecular weight between graft points of polymer A>
The molecular weight between graft points was calculated from the number of moles of sulfanyl group per unit mass of the sulfanyl group-modified organopolysiloxane used as a raw material and the residual ratio of the sulfanyl group obtained in the above <Method for measuring residual ratio of sulfanyl group>. .

<Measurement method of content of polymer (polymer BI) derived from unsaturated monomer not bonded to organopolysiloxane graft polymer in polymer mixture C>
When the graft-from method for radical polymerization of unsaturated monomers in the presence of radical-reactive organopolysiloxane is used, in addition to polymer A, derived from unsaturated monomers not bonded to the organopolysiloxane graft polymer The polymer (polymer BI) is produced. After completion of the polymerization reaction, the content (% by mass) of the polymer derived from the unsaturated monomer in the polymer mixture C after removing the solvent was measured by liquid chromatography. The measurement conditions are shown below. The peak where the peak top position is 28.5 to 29.0 minutes is polymer BI, and a calibration curve was created using a polymer of the same composition separately synthesized in advance as a standard, and the content of polymer BI in the sample was calculated. .

(Measurement conditions for liquid chromatography)
Detector: UV absorption photometer (measurement wavelength: 230 nm)
Column: ODS column (manufactured by Chemicals Evaluation and Research Organization, trade name: L-c
(olumn ODS, size: 4.6 × 150 mm, 5 μm)
Column temperature: constant temperature around 30 ° C. Mobile phase A: 2% phosphoric acid aqueous solution, mobile phase B: 2% phosphoric acid ethanol solution Gradient conditions:
Less than 7 minutes from the start, the concentration of mobile phase B was 15% by mass.
From 7 minutes to less than 20 minutes, the concentration of mobile phase B was 30% by mass.
From 20 minutes to 35 minutes, the concentration of mobile phase B was 100% by mass.
Flow rate: 0.5 mL / min
Sample concentration and sample volume: 1-2 mg / mL 10.0 μL

<Content of organopolysiloxane segment in polymer A>
The content of the organopolysiloxane segment in the polymer A is “the total mass of the radical-reactive organopolysiloxane (a) introduced during the production of the polymer mixture C” and {(a) and “at the production of the polymer mixture C”. From the sum of the “total mass (b1) of unsaturated monomers to be charged” ”, the total of polymers derived from unsaturated monomers not bonded to the organopolysiloxane (polymer BI) produced during the production of the polymer mixture C (polymer BI) It is considered to be the same as the ratio to the value obtained by subtracting “mass (c)”, and is obtained from a / (a + b1−c).

<Content of organopolysiloxane segment in total content of polymer A and polymer B>
The content of the organopolysiloxane segment in the total content of the polymer A and the polymer B is the above-mentioned a, a, b1, and “the total mass (b2) of unsaturated monomers charged during the production of the polymer BII”. It calculates | requires from ratio (a / (a + b1 + b2)) with the sum total mass.

<Method for Measuring Conversion of Unsaturated Monomer in Polymer A and Polymer BII Production>
The conversion rate of the unsaturated monomer during the polymerization reaction was determined by measuring the unreacted unsaturated monomer under the following conditions using gas chromatography and calculating the conversion rate.
(Measurement conditions for gas chromatography)
Column: SUPELCO PTA-5
(Manufactured by Sigma-Aldrich, 30 m × 250 μm × 0.5 μm)
Mode: Splitless mode Inlet temperature: 250 ° C
Oven: 40-280 ° C
Detector: FID
Detector temperature: 300 ° C
Sample: 50 mg / g ethanol solution, 1.0 μL

<Glass transition temperature of unsaturated monomer homopolymer used in Examples and Comparative Examples>
N, N-dimethylacrylamide: 80 ° C
Nt-butylacrylamide: 125 ° C
N, N-dimethylaminopropylacrylamide: 134 ° C
Methacrylic acid: 228 ° C

Production Example 1
<Production of radical reactive organopolysiloxane R1>
Side chain primary aminopropyl modified organopolysiloxane (weight average molecular weight 25,000, unit mass) as an organopolysiloxane having a reactive functional group in a separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirring device The number of moles of amino groups per unit; 1/2078 mol / g, manufactured by Toray Dow Corning) was charged 100 g, and 8 g of N-acetyl-DL-homocysteine thiolactone was charged. Under a nitrogen atmosphere, the temperature was raised to 100 ° C. and stirred for 3 hours to synthesize a radical-reactive organopolysiloxane R1 having a sulfanyl group. When the residual amount of amino groups was measured by potentiometric titration measurement, 98.4% of the amino groups of the side chain primary aminopropyl-modified organopolysiloxane used as a raw material reacted with N-acetyl-DL-homocysteine thiolactone. (Amino group conversion 98.4%). Therefore, the number of moles of the sulfanyl group per unit mass of the radical reactive organopolysiloxane R1 is 1/2271 mol / g. The weight average molecular weight of the radical-reactive organopolysiloxane R1 determined by GPC measurement was 25,000.

Production Example 2
<Production of radical reactive organopolysiloxane R2>
As an organopolysiloxane having a reactive functional group in a separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer, a side chain primary aminopropyl-modified organopolysiloxane (weight average molecular weight 31,000, unit mass) 200 g of N-acetyl-DL-homocysteine thiolactone (8.34 g) was charged. Under a nitrogen atmosphere, the temperature was raised to 100 ° C. and stirred for 3 hours to synthesize a radical-reactive organopolysiloxane R2 having a sulfanyl group. When the residual amount of amino groups was measured by potentiometric titration measurement, 99.3% of the amino groups of the side chain primary aminoisopropyl-modified organopolysiloxane used as a raw material reacted with N-acetyl-DL-homocysteine thiolactone. (Amino group conversion 99.3%). Therefore, the number of moles of sulfanyl group per unit mass of the radical reactive organopolysiloxane R2 is 1/4066 mol / g. The weight average molecular weight of the radical-reactive organopolysiloxane R2 determined by GPC measurement was 31,000.

Production Example 3
<Production of polymer mixture C1 containing polymer A1 and polymer BI-1>
A separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device was charged with 16.45 g of ethanol, 2.49 g of dimethylacrylamide, and 0.62 g of t-butylacrylamide. While stirring the above mixed solution under reflux at 80 ° C. in a nitrogen atmosphere, the following solution (a) and solution (b) were respectively added to separate dropping funnels and simultaneously dropped over about 1 hour.
Solution (a): A solution in which 9.96 g of dimethylacrylamide, 2.50 g of t-butylacrylamide, and 30.5 g of ethanol are mixed.
Solution (b): 43.19 g of radical-reactive organopolysiloxane R1 synthesized in Production Example 1 above, 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., azo type) Polymerization initiator “V-65B”) 0.0038 g and ethanol 30.2 g mixed.

After completion of the dropwise addition, a mixed solution of 0.0114 g of V-65B and 11.1 g of ethanol was added dropwise over 1 hour, and the mixture was further stirred for 1 hour and then cooled. The reaction time is 3 hours in total. The obtained solution was an ethanol solution containing 40% by mass of polymer mixture C1 containing polymer A1 which is an organopolysiloxane graft polymer as a solid content. When the residual ratio of the sulfanyl group was measured, it was 0%. Moreover, the conversion rate calculated | required by GC measurement was 99.5% and 99.6%, respectively for dimethyl acrylamide and t-butyl acrylamide.
It was 1.5 mass% when content of the polymer (polymer BI-1) derived from the unsaturated monomer which is not couple | bonded with the organopolysiloxane graft polymer in the obtained polymer mixture C1 was measured. . That is, the obtained polymer solution D1 contains 39.4% by mass of polymer A1 and 0.6% by mass of polymer BI-1.
The content of the organopolysiloxane segment in the polymer A1 was 76% by mass. Moreover, the weight average molecular weight (MWt) of the polymer A1 was 50,000.

Production Example 4
<Production of polymer mixture C2 containing polymer A2 and polymer BI-2>
7.26 g of ethanol was charged into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring device. While stirring ethanol under reflux at 80 ° C. in a nitrogen atmosphere, the following solution (a) and solution (b) were placed in separate dropping funnels, respectively, with solution (a) taking 80 minutes and solution (b) being 60 It was added dropwise over a period of minutes. The solution (c) was added dropwise over 30 minutes immediately after the completion of the addition of the solution (b).
Solution (a): A solution in which 18.68 g of dimethylacrylamide, 4.67 g of t-butylacrylamide, and 35.23 g of ethanol are mixed.
Solution (b): A solution obtained by mixing 27.00 g of the radical-reactive organopolysiloxane RI synthesized in Production Example 1 above, 0.0099 g of V-65B, and 9.83 g of ethanol.
Solution (c): A solution obtained by mixing 0.0049 g of V-65B and 4.92 g of ethanol.

After completion of the dropwise addition of all the solutions, the reaction mixture was stirred at 80 ° C. under reflux for 1 hour and then cooled. The obtained solution was an ethanol solution containing 40% by mass of polymer mixture C2 containing polymer A2 as an organopolysiloxane graft polymer as a solid content. When the residual ratio of the sulfanyl group was measured by the above method, it was 0%. Moreover, the conversion rate calculated | required by GC measurement was 98.7% and 99.2%, respectively for dimethyl acrylamide and t-butyl acrylamide.
It was 25.2 mass% when content of the polymer (polymer BI-2) derived from the unsaturated monomer which is not couple | bonded with the organopolysiloxane graft polymer in the obtained polymer mixture C2 was measured. . That is, the obtained polymer solution D2 contains 30.0% by mass of polymer A2 and 10.0% by mass of polymer BI-2.
The content of the organopolysiloxane segment in the polymer A2 was 72% by mass. Moreover, the weight average molecular weight (MWt) of the polymer A2 was 53,000.

Production Example 5
<Production of polymer mixture C3 containing polymer A3 and polymer BI-3>
A separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device was charged with ethanol 13.17 g, dimethylaminopropyl acrylamide 0.94 g, and t-butyl acrylamide 2.19 g. While stirring the above mixture under reflux at 80 ° C. in a nitrogen atmosphere, the following solution (a) and solution (b) are put in separate dropping funnels, and at the same time, the solution (a) is added for about 40 minutes. Was dropped over about 1 hour.
Solution (a): A solution in which 1.87 g of dimethylaminopropylacrylamide, 4.37 g of t-butylacrylamide, and 9.51 g of ethanol are mixed.
Solution (b): A solution obtained by mixing 46.7 g of radical reactive organopolysiloxane R2 synthesized in Production Example 2 above, 0.0077 g of V-65B, and 50.4 g of ethanol.

After the completion of dropping, a mixed solution of 0.023 g of V-65B and 11.1 g of ethanol was dropped over about 1 hour, and the mixture was further stirred for 1 hour and then cooled. The reaction time is 3 hours in total. The obtained solution was an ethanol solution containing 40% by mass of polymer mixture C3 containing polymer A3, which is an organopolysiloxane graft polymer, as a solid content. When the residual ratio of the sulfanyl group was measured, it was 4.2%. Moreover, the conversion rate calculated | required by GC measurement was 99.4% and 98.2%, respectively for dimethylaminopropyl acrylamide and t-butyl acrylamide.
The content of the polymer (polymer BI-3) derived from an unsaturated monomer not bonded to the organopolysiloxane graft polymer in the obtained polymer mixture C3 cannot be directly measured by the liquid chromatography method. . Since the production method of the polymer mixture C3 of Production Example 5 is the same as that of the polymer mixture C1 of Production Example 3, the content of the polymer BI-3 in the polymer mixture C3 is the content of the polymer BI-1 in the polymer mixture C1. Assuming that the amount is the same, it was 1.5% by mass. That is, the obtained polymer solution D3 contains 39.4% by mass of polymer A3 and 0.6% by mass of polymer BI-3.

Production Example 6
<Production of polymer mixture C4 containing polymer A4 and polymer BI-4>
12.6 g of ethanol, 0.93 g of methacrylic acid, and 1.87 g of t-butylacrylamide were charged in a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring device. While stirring the above mixed solution under reflux at 80 ° C. under a nitrogen atmosphere, the following solution (a) and solution (b) are put in separate dropping funnels, and at the same time, the solution (a) is added for about 45 minutes. Was dropped over about 1 hour.
Solution (a): A solution in which 1.87 g of methacrylic acid, 3.74 g of t-butylacrylamide, and 8.65 g of ethanol are mixed.
Solution (b): A solution obtained by mixing 46.7 g of radical reactive organopolysiloxane R2 synthesized in Production Example 2 above, 0.0060 g of V-65B, and 3.69 g of ethanol.

After completion of the dropwise addition, a mixed solution of 0.0181 g of V-65B and 11.1 g of ethanol was dropped over about 1 hour, and the mixture was further stirred for 1 hour and then cooled. The reaction time is 3 hours in total. The obtained solution was an ethanol solution containing 40% by mass of polymer mixture C4 containing polymer A4 which is an organopolysiloxane graft polymer as a solid content. When the residual ratio of the sulfanyl group was measured, it was 4.4%. Moreover, the conversion rate calculated | required by GC measurement was 98.6% and 93.7%, respectively for methacrylic acid and t-butylacrylamide.
The content of the polymer (polymer BI-4) derived from an unsaturated monomer not bonded to the organopolysiloxane graft polymer in the obtained polymer mixture C4 cannot be directly measured by the liquid chromatography method. . Since the polymer mixture C4 of Production Example 6 has the same production method as the polymer mixture C1 of Production Example 3, the content of the polymer BI-4 in the polymer mixture C4 is the content of the polymer BI-1 in the polymer mixture C1. Assuming that the amount is the same, it was 1.5% by mass. That is, the obtained polymer solution D4 contains 39.4% by mass of polymer A4 and 0.6% by mass of polymer BI-4.

Production Example 7
<Production of polymer BII-1>
17.2 g of ethanol was charged in advance into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Subsequently, a mixed solution of 15.00 g of dimethylacrylamide, 15.00 g of t-butylacrylamide and 41.8 g of ethanol, and a mixed solution of V6B650.66 g and 12.6 g of ethanol are simultaneously added dropwise at 80 ° C. for 1 hour. did. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour to obtain a 30% by mass ethanol solution of polymer BII-1. The conversion rates determined by gas chromatography (GC) measurement were 99.7% and 98.8% for dimethylacrylamide and t-butylacrylamide, respectively. The weight average molecular weight of the polymer BII-1 determined by GPC measurement was 21,000.

Production Example 8
<Production of polymer BII-2>
17.2 g of ethanol was charged in advance into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Next, a mixed solution of 24.00 g of dimethylacrylamide, 6.00 g of t-butylacrylamide, and 50.0 g of ethanol, and a mixed solution of 0.71 g of V-65B and 13.5 g of ethanol are simultaneously added dropwise at 80 ° C. for 1 hour. did. After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 1 hour to obtain a 30 mass% ethanol solution of polymer BII-2. Conversion determined by GC measurement was 99.5% and 99.6% for dimethylacrylamide and t-butylacrylamide, respectively. The weight average molecular weight of the polymer BII-2 determined by GPC measurement was 19,000.

Production Example 9
<Production of polymer BII-3>
A separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged in advance with 7.37 g of ethanol, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Next, a mixed solution of 9.00 g of dimethylaminopropylacrylamide, 21.00 g of t-butylacrylamide, and 46.4 g of ethanol, and a mixed solution of 1.58 g of V-65B and 19.9 g of ethanol were simultaneously added under a reflux of 80 ° C. Dropped for hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour to obtain a 30% by mass ethanol solution of polymer BII-3. Conversion determined by GC measurement was 99.4% and 98.2% for dimethylaminopropylacrylamide and t-butylacrylamide, respectively. The weight average molecular weight of the polymer BII-3 determined by GPC measurement was 8,000.

Production Example 10
<Production of polymer BII-4>
A separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer was charged in advance with 7.37 g of ethanol, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Next, a mixed solution of 20.00 g of methacrylic acid, 10.00 g of t-butylacrylamide and 46.4 g of ethanol, and a mixed solution of 1.58 g of V-65B and 19.9 g of ethanol are simultaneously added dropwise at 80 ° C. for 1 hour. did. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour to obtain a 30% by mass ethanol solution of polymer BII-4. Conversion determined by GC measurement was 98.7% and 94.3% for methacrylic acid and t-butylacrylamide, respectively. The weight average molecular weight of the polymer BII-4 determined by GPC measurement was 13,000.

Examples 1-7, Comparative Examples 1-2
According to the formulation shown in Table 4, the solution D of the polymer mixture C obtained in Production Examples 3 to 6, the solution of the polymer BII obtained in Production Examples 7 to 10 and ethanol were mixed to obtain a polymer composition.
The polymer compositions of Examples 1 to 7 and Comparative Examples 1 and 2 thus obtained were evaluated as follows.

[Evaluation]
<Evaluation of hair setting>
(Evaluation conditions)
The polymer compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were used as hair cosmetics as they were. A hair bundle of caucasian hair having a length of 30 cm and a weight of 10 g was used for evaluation. The whole hair bundle was moistened with water so that 1.2 g of the polymer compositions of Examples 1 to 7 and Comparative Examples 1 to 2 were applied, and passed through the front and back 5 times. Next, after the hair bundle was completely dried with a dryer, it was stretched three times with a comb with a straight iron set at a temperature of 150 ° C. After this series of treatments was completed, sensory evaluation was performed according to the following criteria. Each evaluation showed the average value of five evaluations by three expert panelists.

(Evaluation criteria)
(1) Hairstyle finish (visual)
Under the above-described hair bundle treatment conditions, the state of the hair bundle after removing the iron was visually evaluated according to the following criteria. If the average evaluation value is 3.5 or more, it can be said that the finish of the hairstyle is good.
5: The habit of the hair is straight and the whole hair bundle is bundled like a single plate.
4: The hair's habit is straight and almost all of the hair bundle is gathered.
3: Although the hair is stretched, the bundle of hair bundles is weak.
2: Although the hair's habit is stretched, there is no bundle of hair bundles.
1: The hair habit does not grow at all.

(2) Hair style finish (spreading hair bundle)
Under the above-described hair bundle treatment conditions, the hair bundle after the iron was removed was suspended with the hair tip down, and the width of the hair bundle 5 cm above the hair tip was measured. If the average evaluation value is 6.0 cm or less, it can be said that the finish of the hairstyle is good.

(3) Feel (no swell)
Under the hair treatment conditions described above, the feel of the hair bundle after the iron was removed (no undulation when passing through the finger) was sensory evaluated according to the following criteria. If the average evaluation value is 4.0 or more, it can be said that the touch is good.
5: Even if it passes through a finger, it does not catch at all, and passes through.
4: A slight swell is felt, but the finger passes without being caught.
3: The finger passes through without being caught, but feels swell.
2: A finger passes while getting caught.
1: A finger is caught and cannot pass.

(4) Shape retention after hairstyle set (visual)
The hair bundle after a series of treatments was completed under the above-mentioned hair treatment conditions was left hanging with the hair tips down in an environment of a temperature of 25 ° C. and a relative humidity of 40 to 60%. The condition of the hair bundle when left for 18 hours was visually evaluated. If the average evaluation value is 3.0 or more, it can be said that the holding power is good.
5: The whole hair bundle is gathered, and the habit remains stretched.
4: The whole hair bundle is gathered, but the tip of the hair bundle is wavy.
3: Almost all of the hair bundles are gathered, but there is overall swell.
2: The bundle of hair bundles is weak and the undulation appears remarkably.
1: The entire hair bundle is separated.

(5) Shape retention after hairstyle set (expansion of hair bundle)
The hair ends after a series of treatments have been completed under the above-mentioned hair treatment conditions, the hair ends after being hung in the environment of a temperature of 25 ° C. and a relative humidity of 40 to 60% with the hair tips down and left standing for 18 hours. The width of the hair bundle 5 cm above was measured. If the average evaluation value is 7.0 cm or less, it can be said that the finish of the hairstyle is good.

  As is apparent from the results in Table 4, the polymer composition of the present invention containing an organopolysiloxane graft polymer and a polymer derived from an unsaturated monomer is swelled after setting the hair when used in hair cosmetics. There are few good feelings, and it is excellent in the hair setting ability and the holding power of the hair shape after setting.

  The polymer composition containing the organopolysiloxane graft polymer has a good feel, is useful as a hair cosmetic that can firmly fix the hairstyle and maintain it for a long time.

Claims (9)

A hair cosmetic containing a polymer composition,
The polymer composition contains a polymer A and polymer B, Ri der content of less than 30 wt% to 70 wt% of the organopolysiloxane segment to the total of polymer A and polymer B,
The mass ratio of polymer A to polymer B (polymer A / polymer B) is 0.6 or more and 30 or less,
Polymer A: an organopolysiloxane graft polymer having an organopolysiloxane segment as a main chain and a polymer segment derived from an unsaturated monomer as a side chain, wherein the organopolysiloxane segment in the organopolysiloxane graft polymer An organopolysiloxane graft polymer having a content of more than 70% by mass and 90% by mass or less.
Polymer B: A polymer containing 90% by mass or more of a repeating unit derived from the same unsaturated monomer as the unsaturated monomer constituting the side chain of the polymer A.
The polymer segment derived from the unsaturated monomer of polymer A and polymer B are (1) a repeating unit derived from N, N-dimethylacrylamide, and (2) the glass transition temperature of the homopolymer is 60 ° C. or higher and 150 ° C. or lower. Repeating units derived from nonionic unsaturated monomers (excluding repeating units derived from unsaturated monomers having an amino group) and repeating units derived from cationic unsaturated monomers, or (3 ) Repeating units derived from nonionic unsaturated monomers whose homopolymer has a glass transition temperature of 60 ° C. or more and 150 ° C. or less (excluding repeating units derived from unsaturated monomers having an amino group) and anions A polymer segment derived from an unsaturated monomer of the polymer A of (1) above, which contains a repeating unit derived from an unsaturated monomer having a carboxylic acid or a salt thereof as a functional unsaturated monomer And non-ionic, wherein the content of repeating units derived from N, N-dimethylacrylamide in the polymer and the polymer B is 50% by mass or more and 100% by mass or less, and the glass transition temperature of the homopolymer is 60 ° C. or more and 150 ° C. or less. Hair cosmetics in which the content of repeating units derived from unsaturated monomers is 90% by mass or more. Polymer segment and a polymer B derived from an unsaturated monomer of the polymer A, wherein (1) of the have-containing repeating unit derived from an unsaturated monomer, repeating units derived from ionic unsaturated monomer The hair cosmetic composition according to claim 1, wherein the content of is 1% by mass or more and 0% by mass or less. The polymer segment derived from the unsaturated monomer of the polymer A and the polymer B contain a repeating unit derived from the unsaturated monomer of the above (2) , and the polymer derived from the unsaturated monomer of the polymer A Repeating unit derived from a nonionic unsaturated monomer having a glass transition temperature of 60 ° C. or higher and 150 ° C. or lower in the segment and polymer B (however, a repeating unit derived from an unsaturated monomer having an amino group) the content of excluding unit) is 90 wt% or less than 40% by weight, the content of the repeating unit derived from a cationic unsaturated monomer than 10 wt% to 60 wt%, of anionic non The hair cosmetic according to claim 1, wherein the content of the repeating unit derived from the saturated monomer is 0% by mass or more and 1% by mass or less. The polymer segment derived from the unsaturated monomer of the polymer A and the polymer B contain a repeating unit derived from the unsaturated monomer of (3) , and the polymer derived from the unsaturated monomer of the polymer A The content of the repeating unit derived from the unsaturated monomer having a carboxylic acid or a salt thereof in the segment and the polymer B is 20% by mass to 85% by mass , and the glass transition temperature of the homopolymer is 60 ° C. or higher and 150 ° C. repeating units derived from one non-ionic unsaturated monomer below (excluding the repeating unit derived from an unsaturated monomer having an amino group) or less 80 mass% content of more than 15 mass% of, The hair cosmetic according to claim 1, wherein the content of the repeating unit derived from the cationic unsaturated monomer is 0% by mass or more and 1% by mass or less. Hair cosmetics in any one of Claims 1-4 whose content of the polymer A and the polymer B in the said polymer composition is 0.5 mass% or more and 50 mass% or less. The hair cosmetic according to any one of claims 1 to 5 , wherein the organopolysiloxane segment of the polymer A has a weight average molecular weight of 3,000 or more and 200,000 or less. The polymer a number average molecular weight of the organopolysiloxane segments between polymer segments from adjacent unsaturated monomers in the organopolysiloxane segment of A (mng) of 500 to 10,000, according to claim 1 to 6 Hair cosmetics according to any one of the above. The hair cosmetic according to any one of claims 1 to 7 , wherein the polymer A is obtained by polymerizing an unsaturated monomer in the presence of a radical-reactive organopolysiloxane. The hair cosmetic composition according to claim 8 , wherein the radical-reactive organopolysiloxane is obtained by reacting an organopolysiloxane having a reactive functional group with a radical reactivity-imparting agent.