JP6167635B2 - Copolymer, cosmetic composition and conditioning agent - Google Patents

Description

  The present invention relates to a copolymer that is very excellent in the effect of enhancing the conditioning effect of hair, a cosmetic composition containing the copolymer, and a conditioning agent comprising the cosmetic composition.

  In recent years, consumers' awareness of damage to hair has been increasing, as shown in the booming market for damage care products such as luxury shampoos, rinses and out bath treatments. In order to reduce the feeling of hair damage (improved feel), a rinse (conditioner) is used after washing the hair with shampoo. If there is still a feeling of damage, treatments used in the bathroom or treatments that are not washed away and used outside the bathroom are used.

  The feeling of hair damage is mainly expressed by sensory evaluation such as a feeling of dryness due to friction between hairs or between hair and hands, lack of moisture, and hardness. In order to suppress this feeling of damage, a cationic surfactant such as stearyltrimethylammonium chloride is blended in the rinse and treatment as a component that reduces friction and softens the hair (softener component).

  On the other hand, in order to reduce the feeling of hair damage, attempts have been made so far to devise a surfactant structure, a silicone oil component, or a resin component. In the case of blending a resin, for example, a copolymer containing a unit having an anionic group and a unit having a silicon atom or a cosmetic containing a resin compound having an anionic group and a silicon atom in one molecule is applied to the hair. It has been shown that excellent conditioning effects such as flexibility and smoothness can be imparted (for example, Patent Document 1). Furthermore, it has also been shown that cosmetics containing a resin compound containing an anionic vinyl monomer and a nonionic vinyl monomer containing a hydroxyl group enhance conditioning performance (for example, Patent Documents 2 and 3).

JP 2004-018414 A JP 2007-161986 JP 2007-137830 A

  In recent years, higher conditioning effects than those described in Patent Documents 1 to 3 have been required. In particular, there is a growing demand for further improvement of a highly damaged portion such as a hair tip, and the absence of unevenness after drying and the goodness of fingering. Also, if a high treatment effect can be obtained by treatment of shampoo and rinse instead of using a number of treatments, the burden on consumers can be reduced. There is a growing demand for improvements.

  On the other hand, agents that require rinsing, such as rinsing and treatment, need to be rinsed after being applied to the hair, but according to the study by the present inventors, many of the blended softener components are present during rinsing. The problem was found that the feeling of damage was not sufficiently reduced.

  The present invention solves the above-mentioned problems, and does not impair the feeling of smoothness during use, and a copolymer excellent in conditioning effects such as lack of dryness and good fingering after drying, and this copolymer An object of the present invention is to provide a cosmetic composition and a conditioning agent containing a coalescence.

  As described above, the rinse needs to be rinsed with water after being applied to the hair, and a problem has been found in that much of the softener component flows away during rinsing. If the present inventors can leave a lot of softening agent components such as cationic surfactants and conditioning components such as silicone oil even after rinsing, an improvement in conditioning properties can be expected. As a result of intensive studies from the viewpoint, the copolymer having a specific proportion of structural units derived from a specific monomer and having a specific mass-average molecular weight can be used after drying without impairing the feeling of smoothness during use. The present inventors have found that a high conditioning effect can be obtained in the absence of the squeak and the goodness of the finger, and the present invention has been completed.

That is, the gist of the present invention resides in the following [1] to [ 8 ].

[1] A copolymer having a structural unit derived from the following monomer (a) and at least one of structural units derived from the following monomers (b) to ( c ), wherein the total mass of the copolymer In contrast, the structural unit derived from the following monomer (a) is included in an amount of 1 to 99% by mass, the structural unit derived from a vinyl monomer having a carboxyl group (A) is included in an amount of 50 to 100% by mass, A copolymer having a viscosity at 25 ° C. of 5 mPa · s or more and 20000 mPa · s or less and a mass average molecular weight of 3,000 to 400,000.
Monomer (a): Acrylic acid and / or methacrylic acid Monomer (b): One or more vinyl monomers represented by the following formula (1), (2) or (3) CH ₂ = C (R ¹ _{) -CO- (O- (CH 2)} m -CO) n -OH ... (1)
(In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 4, and n represents an integer of 1 to 4.)
^{_{CH 2 = C (R 2)}} -COO- (CH 2) p -OCO- (CH 2) q -COOH
... (2)
(In the above formula (2), ^{R 2} represents a hydrogen atom or a methyl group, p, q represent each independently an integer of from 2 to 6.)
^{_{CH 2 = C (R 3)}} -COO- (CH 2) e -OCO-X-COOH ... (3)
(In the above formula (3), R ³ represents a hydrogen atom or a methyl group, e represents an integer of 1 to 4, X is not a good cyclohexylene group or a substituted group which may have a substituent Represents an optional phenylene group.)
Monomer (c): Vinyl monomer represented by the following formula (4) CH ₂ ═C (R ⁴ ) —CO—Y— (Z—O) _r —R ⁵ (4)
(In the above formula (4), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Y represents an oxygen atom or NH, and Z represents a substituent. Represents an optionally substituted alkylene group having 2 to 4 carbon atoms, and r represents an integer of 1 to 15. )

[2] The copolymer according to [1], comprising 10 to 95% by mass of a structural unit derived from the monomer (a) based on the total mass of the copolymer.

[3] The copolymer according to [1] or [2], comprising 1 to 99% by mass of a structural unit derived from the monomer (b) based on the total mass of the copolymer.

[4] The copolymer according to any one of [1] to [3], which contains 1 to 50% by mass of a structural unit derived from the monomer (c) based on the total mass of the copolymer.

[ 5 ] 0.05 to 5% by mass of the copolymer according to any one of [1] to [ 4 ], 0.1 to 20% by mass of a cationic surfactant, and 0.1 to 20% by mass of a higher alcohol. A cosmetic composition comprising.

[ 6 ] The cosmetic composition according to [ 5 ], further comprising 0.1 to 10% by mass of a silicone oil.

[ 7 ] The cosmetic composition according to [ 5 ], wherein the silicone oil content is less than 0.1% by mass.

[ 8 ] A conditioning agent comprising the cosmetic composition according to any one of [ 5 ] to [ 7 ].

  The cosmetic composition using the copolymer of the present invention is excellent in conditioning effects such as smoothness at the time of application, no wrinkle after drying, and good fingering. Moreover, when silicone oil is used in combination, the adsorption of silicone oil can be enhanced, and a higher conditioning effect can be imparted. By using the copolymer of the present invention, it is possible to obtain a hair cosmetic having an excellent conditioning effect. Therefore, the cosmetic composition of the present invention is particularly useful as a conditioning agent.

  Embodiments of the present invention will be described in detail below, but the following descriptions are representative examples of embodiments of the present invention, and the present invention is not limited to these contents. In this specification, when an expression such as “(meth) acrylic acid” is used, it is used as an expression including both “acrylic acid” and “methacrylic acid”. In addition, when the expression “to” is used in the present specification, it is used in a sense including numerical values or physical values described before and after the expression. Further, in the present specification, “smoothness at the time of application” refers to the evaluation shown in the examples described later, and the dryness and smoothness after drying, the viscosity of the cosmetic composition is Even if it is excellent, if the smoothness at the time of application is worse than the “comparative standard product”, the effect is considered to be inferior.

[Copolymer]
The copolymer of the present invention is a copolymer having a structural unit derived from the following monomer (a) and at least one of structural units derived from the following monomers (b) to (d). 1 to 99% by mass of structural units derived from the following monomer (a) with respect to the total mass of the polymer, 50 to 100% by mass of structural units derived from the vinyl monomer (A) having a carboxyl group, and The mass average molecular weight is 3,000 to 400,000.

Monomer (a): Acrylic acid and / or methacrylic acid Monomer (b): One or more vinyl monomers represented by the following formula (1), (2) or (3) CH ₂ = C (R ¹ _{) -CO- (O- (CH 2)} m -CO) n -OH ... (1)
(In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 4, and n represents an integer of 1 to 4.)
^{_{CH 2 = C (R 2)}} -COO- (CH 2) p -OCO- (CH 2) q -COOH
... (2)
(In the above formula (2), ^{R 2} represents a hydrogen atom or a methyl group, p, q represent each independently an integer of from 2 to 6.)
^{_{CH 2 = C (R 3)}} -COO- (CH 2) e -OCO-X-COOH ... (3)
(In the above formula (3), R ³ represents a hydrogen atom or a methyl group, e represents an integer of 1 to 4, X is not a good cyclohexylene group or a substituted group which may have a substituent Represents an optional phenylene group.)
Monomer (c): Vinyl monomer represented by the following formula (4) CH ₂ ═C (R ⁴ ) —CO—Y— (Z—O) _r —R ⁵ (4)
(In the above formula (4), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Y represents an oxygen atom or NH, and Z represents a substituent. Represents an optionally substituted alkylene group having 2 to 4 carbon atoms, and r represents an integer of 1 to 15.)
Monomer (d): Vinyl monomer represented by the following formula (5) CH ₂ ═C (R ⁶ ) —COO—R ⁷ (5)
(In the above formula (5), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ is a linear or branched alkyl group having 12 to 22 carbon atoms, a cyclohexyl group or a substituent optionally having a substituent. Represents a phenyl group which may have

<Constitutional unit derived from vinyl monomer (A)>
The copolymer of the present invention has a structural unit derived from the vinyl monomer (A) having a carboxyl group, and the proportion of the structural unit derived from the vinyl monomer (A) is based on the total mass of the copolymer. It is 50-100 mass%.

  The reason why the copolymer of the present invention needs to contain the structural unit derived from the vinyl monomer (A) having a carboxyl group in a specific ratio is as follows.

One of the problems in the present invention is to enhance the conditioning effect by increasing the amount of conditioning components adsorbed on damaged hair. The copolymer of the present invention has been designed to enhance the interaction with the cationic surfactant, and the following two points can be cited as the main points of the estimation mechanism.
1) Interaction between the copolymer and the cationic surfactant: The interaction between the copolymer and the cationic surfactant is enhanced by the polarization of -OH oxygen of the carboxyl group in the copolymer.
2) Interaction between the complex of the copolymer and the cationic surfactant and the hair: The interaction between the polarized hydrogen atom of the cationic group of the cationic surfactant and the carboxyl group of the copolymer and the hair surface (anion) Enhanced.

  According to the study by the present inventors, when the proportion of the structural unit derived from the vinyl monomer (A) is 50 to 100% by mass with respect to the total mass of the copolymer, the above 1) and 2) It has been found that the effect of the estimation mechanism is enhanced, and the conditioning effects such as smoothness at the time of application, roughness after drying, fingering after drying, and unity after drying are improved. From the viewpoint of enhancing these conditioning effects in a well-balanced manner, the proportion of the structural unit derived from the vinyl monomer (A) to the total mass of the copolymer is preferably 55% by mass or more, more preferably more than 60% by mass, and more Preferably it is 65 mass% or more, Most preferably, it is 70 mass% or more, On the other hand, Preferably it is 99 mass% or less, More preferably, it is 90 mass% or less.

  As described above, in the copolymer of the present invention, the technical significance of the structural unit derived from the vinyl monomer (A) is that the structural unit derived from the vinyl monomer (A) includes the cationic surfactant and the hair surface. It has a carboxyl group for interaction. Accordingly, the structural unit derived from the vinyl monomer (A) other than the monomer (a) is not particularly limited as long as it has a carboxyl group, but specific examples include crotonic acid and maleic acid. , Fumaric acid, itaconic acid, angelic acid, tiglic acid, 2- (meth) acryloyloxyethyl succinate, 2-carboxyethyl (meth) acrylate, 2 (2-carboxyethoxy) ethyl (meth) acrylate, hexahydrophthalic acid Examples thereof include 2- (meth) acryloyloxyethyl and (meth) acrylic acid terephthalate. Among these, (meth) acrylic acid and unsaturated carboxylic acid monomers represented by compounds represented by the following formula (1), formula (2), or formula (3) are preferable. The unsaturated carboxylic acid monomer preferably has 3 to 22 carbon atoms, more preferably 4 or more carbon atoms, more preferably 20 or less carbon atoms, more preferably 18 or less carbon atoms, Those having several tens or less are more preferable, and those having six or less carbons are particularly preferable. The number of carboxyl groups in the structural unit derived from the vinyl monomer (A) is preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and 1. Is most preferred.

<Constitutional unit derived from monomer (a)>
In the copolymer of the present invention, the vinyl monomer (A) contains the following monomer (a) in order to enhance the interaction with the cationic surfactant.
Monomer (a): acrylic acid and / or methacrylic acid

  The monomer (a) has a high amount of carboxyl groups per mass, and therefore, the copolymer of the present invention contains a structural unit derived from the monomer (a), thereby obtaining a good conditioning effect as a base as a conditioning polymer. be able to. In addition, the conditioning effect can be obtained by increasing the amount of the carboxyl group in the copolymer including the monomer (a) by a certain amount or more. Further, the monomer (a) is also preferable because it is generally easily available.

  As the monomer (a), acrylic acid is preferable from the viewpoint that the complex with the cationic surfactant is uniformly dissolved or dispersed in the composition. On the other hand, methacrylic acid is preferable because it can impart hydrophobicity to the copolymer and can improve the absence of roughness after drying. The copolymer of the present invention may contain only acrylic acid as monomer (a), may contain only methacrylic acid, or contains acrylic acid and methacrylic acid. Also good. Especially, what contains acrylic acid and methacrylic acid is preferable. At this time, it is more preferable that acrylic acid is 50-99 mass% with respect to the total mass of a monomer (a).

  The copolymer of this invention contains 1-99 mass% of structural units derived from a monomer (a) with respect to the total mass of a copolymer. The content of the structural unit derived from the monomer (a) in the copolymer is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably based on the total mass of the copolymer. 50 mass% or more, particularly preferably more than 60 mass%, most preferably 65 mass% or more. It is preferable that the content of the structural unit derived from the monomer (a) in the copolymer is not less than the above lower limit value in order to enhance the effect of including the acrylic acid and / or methacrylic acid. On the other hand, the content of the structural unit derived from the monomer (a) in the copolymer is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably with respect to the total mass of the copolymer. 80% by mass or less. When the content of the structural unit derived from the monomer (a) in the copolymer is not more than the above upper limit value, the hydrophilic hair and / or the hydrophobic monomer other than the monomer (a) is copolymerized to damage hair. It is preferable because it can increase the affinity for and improve the feel after drying.

<Constitutional unit derived from monomer (b)>
The copolymer of the present invention has a viewpoint that the affinity to damaged hair can be increased by imparting hydrophilicity to the copolymer, and a feeling after drying can be improved by imparting hydrophobicity. From a viewpoint, it is preferable to contain the structural unit derived from the following monomers (b) with the monomer (a) as a structural unit derived from the said vinyl monomer (A).

Monomer (b): One or more vinyl monomers represented by the following formula (1), (2) or (3) CH ₂ ═C (R ¹ ) —CO— (O— (CH ₂ ) _m -CO) _n- OH (1)
(In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 4, and n represents an integer of 1 to 4.)
^{_{CH 2 = C (R 2)}} -COO- (CH 2) p -OCO- (CH 2) q -COOH
... (2)
(In the above formula (2), ^{R 2} represents a hydrogen atom or a methyl group, p, q represent each independently an integer of from 2 to 6.)
^{_{CH 2 = C (R 3)}} -COO- (CH 2) e -OCO-X-COOH ... (3)
(In the above formula (3), R ³ represents a hydrogen atom or a methyl group, e represents an integer of 1 to 4, X is not a good cyclohexylene group or a substituted group which may have a substituent Represents an optional phenylene group.)

In the above formula (1), R ¹ is preferably a hydrogen atom. m is preferably 2 or 3. n is preferably 1 to 2, and most preferably 1.
Specific examples of the vinyl monomer represented by the above formula (1) include 2-carboxyethyl (meth) acrylate, 2 (2-carboxyethoxy) ethyl (meth) acrylate, and the like.

In the above formula (2), R ² is preferably a hydrogen atom. p is preferably 2 or 3, and q is preferably 2 or 3.
Specific examples of the vinyl monomer represented by the above formula (2) include 2- (meth) acryloyloxyethyl succinate.

In the above formula (3), R ³ is preferably a methyl group. e is preferably an integer of 1 to 3, and most preferably 2. As the substituent of the cyclohexylene group which may have a substituent of X or the phenylene group which may have a substituent, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. And more preferably a linear or branched alkyl group having 1 to 3 carbon atoms. Preferably, X is a phenylene group having no substituent or a cyclohexylene group, and most preferably a cyclohexylene group.
Specific examples of the vinyl monomer represented by the above formula (3) include (meth) acrylic acid ethyl terephthalate, (meth) acrylic acid propyl terephthalate, hexahydrophthalic acid 2- (meth) acryloyloxyethyl and the like.

  As the monomer (b) for imparting hydrophilicity, those represented by the above formula (1) or (2) are preferable. When the monomer (b) having these hydrophilic groups is used, The coalescence is easily adsorbed, and the fingering is good. The monomer (b) for imparting hydrophobicity is preferably the one represented by the above formula (3). When the monomer (b) having such a hydrophobic group is used, the copolymer is adsorbed. The feel of the cut hair itself is improved, and the effect of reducing the roughness of the hair can be obtained.

  In the copolymer of the present invention, as the structural unit derived from the monomer (b), one type may be used alone, or two or more types may be used in combination, and the general formulas (1), (2) and ( You may use together what is represented by 3).

  It is preferable that 1-99 mass% of structural units derived from the monomer (b) are contained with respect to the total mass of the copolymer of the present invention. The structural unit derived from the monomer (b) in the copolymer is more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass with respect to the total mass of the copolymer. % Or more, most preferably 40% by mass or more. The content of the structural unit derived from the monomer (b) in the copolymer is preferably not less than the above lower limit value in order to enhance the effect described above. On the other hand, the content of the structural unit derived from the monomer (b) in the copolymer is more preferably 90% by mass or less, still more preferably 80% by mass or less, particularly preferably relative to the total mass of the copolymer. Is 60% by mass or less. When the content of the structural unit derived from the monomer (b) in the copolymer is not more than the above upper limit, the content of the monomer (a) is ensured and the effect of the structural unit derived from the monomer (a) From the viewpoint of increasing

<Constitutional unit derived from monomer (c)>
When the copolymer of the present invention contains a structural unit derived from the monomer (c) represented by the following formula (4), it is preferable because appropriate hydrophilicity can be imparted to the copolymer. By having an appropriate hydrophilicity, the affinity for damaged hair can be increased without impairing the feel of smoothness during use, and it becomes easy to adsorb to damaged hair. For this reason, a finger passage can be made favorable.

^{_{CH 2 = C (R 4)}} -CO-Y- (Z-O) r -R 5 ... (4)
(In the above formula (4), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Y represents an oxygen atom or NH, and Z represents a substituent. Represents an optionally substituted alkylene group having 2 to 4 carbon atoms, and r represents an integer of 1 to 15.)

In the above formula (4), R ⁴ is preferably a hydrogen atom. In addition, since the monomer (c) preferably has moderate hydrophilicity, R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. It is more preferable that Y is preferably an oxygen atom. r is preferably 2 or more, on the other hand, preferably 10 or less, more preferably 6 or less, and even more preferably 3 or less.

In addition, in the above formula (4), when the alkylene group of Z has a substituent, the substituent refers to one that does not react with other parts in the copolymer of the present invention, and the volume occupied by the substituent. Is too large, the volume occupied by the substituents with respect to the Y— (ZO) _r —R ⁵ structural portion of the monomer (c) increases, thereby causing the carboxyl group and the cationic surface activity of the vinyl monomer (A). Since the interaction of the agent is weakened and the adsorptivity of the conditioning component may be lowered, this substituent is preferably a molecular weight of 50 or less. Specific examples include a hydroxyl group, a methoxy group Ethoxy group, alkyl group, hydroxyalkyl group, methoxyalkyl group, ethoxyalkyl group and the like. Further, the substituent of the alkylene group of Z is preferably one having a molecular weight smaller than that of the structural portion of — (Z—O) _r —. However, it is more preferable that Z has no substituent. Z is preferably an alkylene group having 2 to 3 carbon atoms, and most preferably an ethylene group having 2 carbon atoms.

  Examples of the monomer (c) represented by the above formula (4) include methoxypolyethylene glycol (meth) acrylate (repeating number of polyethylene glycol (r in formula (4) is 2 to 15), polyethylene glycol (meth) acrylate. (Repeated number of polyethylene glycol (r in formula (4) is 2 to 15), methoxy polyethylene glycol / polypropylene glycol (meth) acrylate (repeated number of polyethylene glycol / polypropylene glycol (r in formula (4) is 2). 15), polyethylene glycol / polypropylene glycol (meth) acrylate (repeating number of polyethylene glycol / polypropylene glycol (r in formula (4) is 2 to 15), methoxypolyethylene glycol / polybutylene glycol (meth) acrylate Relate (polyethylene glycol / polybutylene glycol repeat number (r in formula (4) is 2 to 15), polyethylene glycol / polybutylene glycol (meth) acrylate (polyethylene glycol / polybutylene glycol repeat number (formula (4) R) is 2 to 15), methoxypolyethylene glycol (meth) acrylamide (polyethylene glycol repeat number (r in formula (4) is 2 to 15), polyethylene glycol (meth) acrylamide (polyethylene glycol repeat number (formula (4) r) is 2 to 15), 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylamide. All Preferably, methoxy polyethylene glycol (meth) acrylate (repeating number of polyethylene glycol (r in formula (4) is 2 to 10), polyethylene glycol (meth) acrylate (repeating number of polyethylene glycol (of formula (4) r) is 2-10), methoxypolyethylene glycol / polypropylene glycol (meth) acrylate (polyethylene glycol / polypropylene glycol repeat number (r in formula (4) is 2-10), polyethylene glycol / polypropylene glycol (meth) acrylate (Repeated number of polyethylene glycol / polypropylene glycol (r in formula (4) is 2 to 10), methoxy polyethylene glycol / polybutylene glycol (meth) acrylate (polyethylene glycol) Of polyethylene / polybutylene glycol (r in formula (4) is 2 to 10), polyethylene glycol / polybutylene glycol (meth) acrylate (polyethylene glycol / polybutylene glycol is repeated (r in formula (4)) 2-10), 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylamide, more preferably methoxy polyethylene glycol (meth) acrylate (repeating number of polyethylene glycol (r in formula (4) is 2 to 10)), polyethylene glycol (meth) acrylate (repeating number of polyethylene glycol (formula (4) ) r) is 2 to 10), it is.

  In the copolymer of the present invention, as the structural unit derived from the monomer (c), one type may be used alone, or two or more types may be used in combination.

  In the copolymer of the present invention, the proportion of the structural unit derived from the monomer (c) is preferably 1 to 50% by mass with respect to the total mass of the copolymer. When the proportion of the structural unit derived from the monomer (c) is 1% by mass or more, the adsorptivity of the conditioning component can be sufficiently obtained by increasing the affinity for damaged hair, and is 50% by mass or less. By being, it can ensure the ratio of the structural unit derived from the said vinyl monomer (A) in a copolymer, and can improve the adsorptivity of a conditioning component. From the viewpoint of enhancing such an effect, the proportion of the structural unit derived from the monomer (c) in the copolymer is more preferably 3% by mass or more, and further preferably 5% by mass with respect to the total mass of the copolymer. As mentioned above, it is 10 mass% or more especially preferably, On the other hand, More preferably, it is 40 mass% or less, Most preferably, it is 30 mass% or less.

<Constitutional unit derived from monomer (d)>
The copolymer of the present invention includes the monomer (d) represented by the following formula (5) as a structural unit, thereby increasing the hydrophobicity of the copolymer. In particular, when a material having a chain alkyl group as a hydrophobic group (in which R ⁷ in formula (5) is “a linear or branched alkyl group having 12 to 22 carbon atoms”), the rinse viscosity is in an appropriate range. An effect can be obtained. In addition, those having a cyclic structure as a hydrophobic group (R ⁷ in the formula (5) is “a cyclohexyl group which may have a substituent or a phenyl group which may have a substituent”) When used, it is possible to obtain an effect of improving the feel when the copolymer is adsorbed on the hair.

^{_{CH 2 = C (R 6)}} -COO-R 7 ... (5)
(In the formula (5), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a linear or branched alkyl group, which may have a substituent cyclohexyl group or a substituent having 12 to 22 carbon atoms Represents a phenyl group which may have

In the above formula (5), R ⁶ is preferably a methyl group. R ⁷ is preferably a linear or branched alkyl group having 12 to 20 carbon atoms, more preferably 16 to 18 carbon atoms, an optionally substituted cyclohexyl group or an optionally substituted phenyl. It is a group. When the cyclohexyl group or phenyl group of R ⁷ has a substituent, the substituent is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a linear chain having 1 to 3 carbon atoms. Or it is a branched alkyl group. Preferred is a cyclohexyl group having no substituent or a phenyl group, and most preferred is a cyclohexyl group.

  In the copolymer of the present invention, as the structural unit derived from the monomer (d), one type may be used alone, or two or more types may be used in combination.

When the monomer (d) represented by the above formula (5) is exemplified, as the (meth) acrylate monomer having an alkyl group having 12 to 22 carbon atoms as R ⁷ , for example, myristyl (meth) acrylate, isostearyl (meth) Acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, synthetic lauryl (meth) acrylate (however, "synthetic lauryl (meth) acrylate" is an alkyl having 12 carbon atoms) And an alkyl (meth) acrylate in which a group and an alkyl group having 13 carbon atoms are mixed). (Meth) acrylate monomer having an alkyl group having a carbon number of 12 to 20 are preferred as R ⁷ Among them, more preferably (meth) acrylate monomer having an alkyl group having 16 to 18 carbon atoms. Examples of the (meth) acrylate monomer having a cyclohexyl group which may have a substituent as R ⁷ or a phenyl group which may have a substituent include cyclohexyl (meth) acrylate and phenyl (meth). An acrylate etc. are mentioned.

  In the copolymer of the present invention, the proportion of the structural unit derived from the monomer (d) is preferably 1 to 50% by mass with respect to the total mass of the copolymer. When the proportion of the structural unit derived from the monomer (d) is 1% by mass or more, an effect that the rinse viscosity is in an appropriate range, and an effect that the feel when the copolymer is adsorbed on the hair is improved. By being 50 mass% or less, the ratio of the structural unit derived from the said vinyl monomer (A) in a copolymer can be ensured, and the adsorptivity of a conditioning component can be improved. From the viewpoint of enhancing such an effect, the proportion of the structural unit derived from the monomer (d) in the copolymer is more preferably 3% by mass or more, and further preferably 5% by mass with respect to the total mass of the copolymer. As mentioned above, it is 10 mass% or more especially preferably, On the other hand, More preferably, it is 40 mass% or less, Most preferably, it is 30 mass% or less.

<Constitutional unit derived from monomer (e)>
The copolymer of this invention can also contain the monomer (e) represented by following formula (6) as a structural unit. By containing the structural unit derived from the monomer (e), the hydrophilicity / hydrophobicity of the copolymer can be adjusted, and the fingering after drying can be improved.

^{_{CH 2 = C (R 8)}} -CO-N (R 9) R 10 ... (6)
(In the above formula (6), R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.)

In the above formula (6), R ⁸ is preferably a hydrogen atom. Moreover, in which the sum of the carbon atoms of ^{R 9} and ^{R 10} is 2 or more and 4 or less is preferable. Examples of such a monomer (e) include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide. Especially, it is preferable that the sum of carbon number of R < ⁹ > and R < ¹⁰ > is 2. As such a monomer (e), N, N- dimethyl (meth) acrylamide is mentioned, for example.

  In the copolymer of the present invention, as the structural unit derived from the monomer (e), one type may be used alone, or two or more types may be used in combination.

  In the copolymer of the present invention, the content ratio of the structural unit derived from the monomer (e) is preferably 1% by mass or more based on the total mass of the copolymer, from the viewpoint of enhancing the effect described above. It is more preferably 3% by mass or more, and further preferably 5% by mass or more. On the other hand, in order to secure the proportion of the structural unit derived from the vinyl monomer (A) in the copolymer and enhance the adsorptivity of the conditioning component, the content of the structural unit derived from the monomer (e) Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 15 mass% or less, Especially preferably, it is 10 mass% or less.

<Constituent units derived from other monomers>
In addition to the above-mentioned monomers (a), (b), (c), (d) and (e), the copolymer of the present invention includes other vinyl-based compounds as long as the effects of the present invention are not impaired. A structural unit derived from a monomer may be contained. Examples of other vinyl monomers include nonionic monomers, amphoteric monomers, semipolar monomers, cationic monomers, and the like, as well as polysiloxane group-containing monomers. However, these other monomers do not include the vinyl monomers (a), (b), (c), (d) and (e).

  In the copolymer of the present invention, the content of structural units derived from other monomers can be determined as appropriate without departing from the spirit of the present invention. For example, the affinity of the copolymer to the skin and hair, and when used for hair cosmetics, it can be appropriately determined within a range that does not impair the conditioning effect and the like, and is usually 40 mass relative to the total mass of the copolymer. % Or less, preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.

  However, the presence of a cationic functional group in the copolymer of the present invention may hinder the formation of a complex with the above-mentioned cationic surfactant, so the cationic functional group in the copolymer of the present invention is For example, the amount of the cationic functional group is preferably 10 mol% or less of the total functional group in the copolymer, and more preferably substantially free of this.

  Examples of other monomers that can be included in the copolymer of the present invention are shown below, but the copolymer of the present invention may include structural units derived from monomers other than those listed below. Moreover, only one type of structural unit derived from another monomer may be contained in the copolymer of the present invention, or two or more types may be contained.

Nonionic monomers include, for example, esters of alcohols having 1 to 11 carbon atoms and (meth) acrylic acid, amides of alkylamines having 1 to 22 carbon atoms and (meth) acrylic acid, and (meth) acrylic. Ilmorpholine and the like can be mentioned.
Examples of the amphoteric monomers include betaine group-containing (meth) acrylic esters, betaine group-containing (meth) acrylamides, and the like.
Examples of the semipolar monomer include amine oxide group-containing (meth) acrylic acid esters and amine oxide group-containing (meth) acrylamides.
Examples of the cationic monomer include quaternary ammonium group-containing (meth) acrylic acid ester, quaternary ammonium group-containing (meth) acrylamide, and the like.

  The polysiloxane group-containing monomer is a compound having a polysiloxane structure and a structure capable of being covalently linked to a copolymer. Such a structural unit has a high affinity with the silicone oil that is usually used in cosmetic compositions, and in the copolymer, serves to bind other structural units to the silicone oil, particularly on skin and hair, It is considered that there is a function to increase the adsorption power of silicone oil to damaged hair and the like. However, in order not to impair the effect of the copolymer of the present invention, when a polysiloxane group-containing monomer is used as a copolymerization component, the content of structural units derived from the polysiloxane group-containing monomer in the copolymer is 40. The mass is not more than mass%, preferably not more than 30 mass%, more preferably not more than 20 mass%.

The polysiloxane structure is a structure in which two or more repeating structural units represented by the following formula (7) are connected.
— (SiR ¹¹ R ¹² —O) — (7)
(In the above formula (7), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.)

  The structure that can be covalently linked to the copolymer is, for example, a structure that has a vinyl structure such as (meth) acrylic ester or (meth) acrylamide and can be copolymerized with other monomers, or a functional group such as thiol. And a structure that can be linked to the copolymer by chain transfer during polymerization, or a structure that has an isocyanate group, a carboxylic acid group, a hydroxyl group, an amino group, etc. and can be linked by reacting with a functional group of the copolymer. However, it is not limited to these.

  One polysiloxane group-containing monomer may have a plurality of these connectable structures. In the copolymer, the polysiloxane structure may be connected to the main chain by a graft structure, and conversely, the polysiloxane structure may be the main chain and other structures may be connected by a graft structure. A siloxane structure and another structure may be connected in a straight chain with a block structure.

As the polysiloxane group-containing monomer, those represented by the following formula (8) are particularly preferable.
_{^{CH 2 = C (R 13)}} -Q- (SiR 14 R 15 -O) s -R 16 ... (8)
(In the formula ^{(8), R 13} represents a hydrogen atom or a methyl ^{group, R 14} and ^{R 15} each independently represent an alkyl group, or a phenyl group having 1 to 3 carbon ^{atoms, R 16} is C 1 -C Represents an alkyl group of ˜8, Q represents a divalent linking group or a direct bond, and s represents an integer of 2 to 200.
)

  More preferably, s is 3 or more, and further preferably s is 5 or more. The larger s is, the better the affinity with silicone oil is. Further, s is more preferably 50 or less. The smaller s, the better the copolymerizability with other monomers.

  Q represents a divalent linking group or a direct bond, and among them, a linking group composed of one or a combination of two or more of the structures listed below is preferable. The number of combinations is not particularly limited, but is usually 5 or less. Further, the orientation of the following structure (which end is on the polysiloxane group side) is arbitrary. In the following, R represents an alkylene group having 1 to 6 carbon atoms or a phenylene group.

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

  The polysiloxane group-containing monomer represented by the formula (8) is not particularly limited as long as it is included in this formula. For example, α- (vinylphenyl) polydimethylsiloxane, α- (vinylbenzyloxypropyl) ) Polydimethylsiloxane, α- (vinylbenzyl) polymethylphenylsiloxane, α- (methacryloyloxypropyl) polydimethylsiloxane, α- (methacryloyloxypropyl) polymethylphenylsiloxane, α- (methacryloylaminopropyl) polydimethylsiloxane, etc. Is mentioned. The polysiloxane group-containing monomer may be used alone or in combination of two or more.

  A commercial item can also be used as such a polysiloxane group containing monomer. For example, as α- (methacryloyloxypropyl) polydimethylsiloxane, Silaplane (Chisso Corporation) is available, Silaplane FM0711 (molecular weight 1000), Silaplane FM0721 (molecular weight 5000), Silaplane FM0722 (molecular weight 10,000). ) Etc.

  In order to adjust the molecular weight and viscosity of the copolymer, a cross-linking agent such as a polyfunctional acrylate can be introduced into the copolymer of the present invention, but it is preferable that no cross-linking agent is contained as described later.

<Structural analysis>
In the copolymer of the present invention, the content of each structural unit derived from the monomers (a), (b), (c), (d), (e) and other monomers includes a carbonyl group, an amide bond, IR absorption and Raman scattering of polysiloxane structure, various functional groups, carbon skeleton, etc., ¹ H-NMR of methyl group or amide bond site of polydimethylsiloxane and adjacent methyl group, methylene group, etc., or ¹³ C thereof It can be measured by various NMR typified by -NMR and the like.

<Mass average molecular weight>
The weight average molecular weight of the copolymer of the present invention is 3,000 to 400,000. By setting the weight average molecular weight of the copolymer of the present invention to 3,000 or more, the conditioning effect due to the complex with the cationic surfactant adhering to the hair or skin is further enhanced. From the viewpoint of further enhancing this effect, the weight average molecular weight of the copolymer of the present invention is preferably 5,000 or more, more preferably 10,000 or more. On the other hand, when the weight average molecular weight of the copolymer of the present invention is 400,000 or less, the feel after drying can be further enhanced. From the viewpoint of further enhancing this effect, the weight average molecular weight of the copolymer of the present invention is preferably 200,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, and most preferably 30. , 000 or less.

  The molecular weight of the copolymer can be adjusted, for example, by controlling the degree of polymerization of the copolymer. The molecular weight can also be controlled by increasing or decreasing the addition amount of a crosslinking agent such as a polyfunctional acrylate. However, if a crosslinking agent is added as much as possible, the molecular weight and the viscosity are rapidly increased, and thus there are aspects that are difficult to control in industrial production. For this reason, it is most preferable not to contain a crosslinking agent.

  The weight average molecular weight of the copolymer can be measured by gel permeation chromatography (GPC). The developing solvent used in the gel permeation chromatography is not particularly limited as long as it is usually used. For example, a water / methanol / acetic acid / sodium acetate mixed solvent shown in the Examples section below will be used. The value using polyethylene glycol or polystyrene as a standard substance can be used.

<Viscosity>
The copolymer of the present invention preferably has a 20 mass% ethanol solution having a viscosity at 25 ° C. of 5 mPa · s or more and 20000 mPa · s or less. This viscosity is more preferably 10 mPa · s or more, further preferably 15 mPa · s or more, and more preferably 10000 mPa · s or less, and still more preferably 5000 mPa · s or less. It is preferable in terms of handling that the viscosity of the ethanol solution of the copolymer is within the above range. This viscosity can be measured using a B-type viscometer or the like.

  Furthermore, the copolymer of the present invention is preferably water-soluble, and the viscosity of a 30% by mass aqueous solution at 25 ° C. is preferably 5 mPa · s or more and 20000 mPa · s or less. This viscosity is more preferably 10 mPa · s or more, further preferably 15 mPa · s or more, and more preferably 10000 mPa · s or less, and still more preferably 5000 mPa · s or less. The viscosity of the aqueous solution of the copolymer is preferably in the above range from the viewpoint of handling. This viscosity can be measured using a B-type viscometer or the like.

  Similar to the mass average molecular weight, the viscosity of the copolymer can be controlled, for example, by controlling the degree of polymerization of the copolymer or by increasing or decreasing the amount of a crosslinking agent such as a polyfunctional acrylate.

<Method for producing copolymer>
For example, the copolymer of the present invention is prepared by mixing monomers that give respective structural units or precursors thereof, copolymerizing them by a method such as solution polymerization, suspension polymerization, emulsion polymerization, and the like, and then polysiloxane as necessary. It can be produced by carrying out structure addition, condensation reaction and the like.

  Further, the counter ion of the vinyl monomer (A) having a carboxyl group can be subjected to polymerization by substituting a part or all of it for other than hydrogen ion by polymerization before polymerization, A part other than hydrogen ions can be replaced by a neutralization reaction after the reaction. These can be appropriately selected depending on the ease of synthesis.

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

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

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

<Neutralization of carboxyl group>
A part of the total carboxyl groups of the copolymer of the present invention may be neutralized. By neutralization, the ionicity of the carboxyl group is increased and the interaction with the cationic surfactant is strengthened. On the other hand, if the ionicity is high, the structure of the lamellar gel formed from water, a cationic surfactant, and a higher alcohol may be destroyed. Therefore, it is preferable that the number of neutralized carboxyl groups is small.

  For the above reasons, it is preferable that 50 to 100 mol% of the total carboxyl groups of the copolymer of the present invention is blended in an unneutralized state. This ratio is more preferably 60 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Most preferably, it is mix | blended in the state in which all the carboxyl groups are not neutralized.

  In addition, in the cosmetic composition of the present invention containing the copolymer of the present invention, any component of the cosmetic composition of the present invention can be used as long as the copolymer before the blending is not intentionally neutralized. As long as the pH after blending is 6.9 or less, and even 6.5 or less, it is considered that the carboxyl group in the copolymer is not neutralized. be able to.

  Examples of the neutralizing agent that can be used for the copolymer include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; Amines such as ammonia, ditylamine, triethylamine, diethanolamine and 2-amino-2-methylpropanol can be mentioned.

[Cosmetic composition]
The cosmetic composition of the present invention comprises 0.05 to 5% by mass of the above-described copolymer of the present invention, 0.1 to 20% by mass of a cationic surfactant, and 0.1 to 20% by mass of a higher alcohol. It is preferably contained by further blending water, silicone oil and the like.

  The cationic surfactant and higher alcohol contained in the cosmetic composition of the present invention, and water blended as necessary, form a gel structure called lamella by heating and mixing, and have a smooth, moist feeling. By adding the copolymer of the present invention to this, an excellent conditioning effect can be obtained. Furthermore, smoothness can be imparted by blending silicone oil into the cosmetic composition of the present invention.

  The cosmetic composition to which the present invention is applied means any cosmetic composition used for hair and skin, for example, shampoo, rinse, conditioner, treatment, hair dye, permanent agent, out bath. Treatment, Hair Pack, Hair Spray, Hair Foam, Styling, Body Shampoo, Makeup Cleansing, Hand Soap, Emulsion, Lotion, Lotion, Cream, Essence, Sunscreen, Foundation, Lipstick, Mascara, Eye Shadow, Hair Removal And so-called cosmetic compositions. Moreover, the usage form may include any of those that are applied to the skin, hair, and the like and rinsed after thoroughly blending, and those that are not washed away.

<Copolymer>
The cosmetic composition of the present invention contains 0.05% by mass or more of the copolymer of the present invention with respect to the entire cosmetic composition, thereby increasing the adsorptive power to the skin and hair, and smoothness during rinsing. Conditioning effects such as smoothness after drying can be provided.

  From the viewpoint of enhancing such effects, the cosmetic composition of the present invention preferably contains the copolymer of the present invention in an amount of 0.1% by mass or more, more preferably 0.2% by mass or more. However, the content of the copolymer of the present invention in the cosmetic composition of the present invention is 5% by mass or less in order to eliminate the feeling of dryness after drying and to increase the moist feeling, and preferably the content is 3% by mass. % Or less.

  In the cosmetic composition of the present invention, the copolymer of the present invention may be used alone or in combination of two or more.

<Solvent or dispersion medium>
The copolymer of the present invention is used after being dissolved or dispersed in a solvent or dispersion medium that can be used in a cosmetic composition. Examples of these solvents or dispersion media include water and lower alcohols such as ethanol, isopropanol, and butanol. The cosmetic composition of the present invention preferably contains water.

In the cosmetic composition of the present invention, the water content is preferably 55% by mass or more with respect to the entire cosmetic composition of the present invention. By containing 55% by mass or more of water, it is possible to suppress the viscosity from becoming too high, to maintain a viscosity that is easy to handle, and to improve the usability during application. A more preferable water content is 60% by mass or more. However, the water content is preferably 99.6% by mass or less.
By containing water within the above range, the cosmetic composition of the present invention can have an appropriate viscosity, and the smoothness at the time of application and the adsorptivity to skin and hair are improved.

<Cationic surfactant>
The cosmetic composition of the present invention contains a cationic surfactant.
The cationic surfactant contained in the cosmetic composition of the present invention is not particularly limited, but alkyltrimethylammonium salts such as stearyltrimethylammonium chloride and lauryltrimethylammonium chloride, alkylpyridinium salts such as cetylpyridinium chloride, distearyl chloride Dimethylammonium dialkyldimethylammonium salt, poly (N, N′-dimethyl-3,5-methylenepiperidinium), alkyl quaternary ammonium salt, alkyldimethylbenzylammonium salt, alkylisoquinolinium salt, dialkyl morpholinium Examples thereof include salts, polyoxyethylene alkylamines, alkylamine salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, and benzethonium chloride.
The cationic surfactant can be used alone or in combination of two or more.

  The content of these cationic surfactants is 20% by mass or less, preferably 10% by mass or less, with respect to the entire cosmetic composition of the present invention. On the other hand, in order to sufficiently provide the function of the cationic surfactant, the content of the cationic surfactant is 0.1% by mass or more, more preferably 1% by mass or more, based on the entire cosmetic composition. .

<Higher alcohol>
The cosmetic composition of the present invention contains a higher alcohol. In the present specification, “higher alcohol” means an alcohol having 12 to 24 carbon atoms, and a monovalent alcohol is preferred. Specific examples of higher alcohols include cetyl alcohol and stearyl alcohol.

  By using a higher alcohol together with water and a cationic surfactant, a gel called a lamellar structure can be formed, and the cosmetic composition can be given a smooth and moist function. For this reason, the higher alcohol is preferably used together with water and a cationic surfactant. The higher alcohol may be used alone or in combination of two or more. However, in order to improve the smoothness at the time of application by appropriately suppressing the viscosity of the cosmetic composition, the total content of the higher alcohol is: It is 20 mass% or less with respect to the whole cosmetics composition, Preferably it is 10 mass% or less. On the other hand, in order to sufficiently provide the function of the higher alcohol, the total content of the higher alcohol is 0.1% by mass or more, preferably 1% by mass or more with respect to the entire cosmetic composition.

<Silicone oil>
The cosmetic composition of the present invention preferably contains silicone oil. The type of silicone oil used in the cosmetic composition of the present invention is not particularly limited. For example, polydimethylsiloxane, polydimethylsiloxane alkylene oxide copolymer, amino-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, methylphenyl poly Examples include siloxane, epoxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane, alcohol-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane, alkoxy-modified polydimethylsiloxane, and cyclic silicone. These are described in JP-A-2000-336018.

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

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

  Examples of the amino-modified polydimethylsiloxane include those having an aminoalkyl group such as aminoethyl group and aminopropyl group, and amino groups to which propylene glycol has been added (aminoglycol-modified), and substitution of alkyl groups and hydroxyl groups. It may have a group. As the alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable.

  These amino-modified polydimethylsiloxanes are obtained by copolymerizing dimethylsiloxane and the above siloxane having an aminoalkyl group, or by post-modifying polydimethylsiloxane with a compound having an aminoalkyl group as described above to form a polydimethylsiloxane skeleton. It is obtained by introducing an aminoalkyl group. Examples of commercially available products include “US AR SILICONE ALE56” (Union Carbide), “ABIL 9905” (The Goldschmidt AG), “KF857”, “KF867”, “KF865” (all Shinetsu) Chemical Industry Co., Ltd.), “SM8702C”, “JP8500” (Toray Dow Corning Silicone Co., Ltd.), “FZ-3707” (Nihon Unicar Co., Ltd.), and the like.

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

The method for producing such a modified polydimethylsiloxane having an oxyalkylene group is, for example, a method of copolymerizing dimethylsiloxane and a siloxane having an oxyalkylene group, or a compound having a polyoxysiloxane having the oxyalkylene group. There is a method of post-modifying and introducing an oxyalkylene group into the polydimethylsiloxane skeleton.
Most preferably, the polyether-modified polydimethylsiloxane is obtained by copolymerizing dimethylsiloxane and siloxane having an oxyalkylene group of the copolymer skeleton.

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

  As methylphenylpolysiloxane, "KF56" (Shin-Etsu Chemical Co., Ltd.), "SH5 Koshi Chemical Industry Co., Ltd.", "PS922" (Chisso Corporation), "L-930" (Nihon Unicar Co., Ltd.), etc. are commercially available. Has been.

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

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

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

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

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

  One type of silicone oil may be used alone, or two or more types may be used in combination. If the amount of the silicone oil is excessive, it is applied to the hair and dried to give a heavy feel. Therefore, the silicone oil is preferably contained in a total amount of 10% by mass or less, more preferably based on the total cosmetic composition. Is 8 mass% or less. On the other hand, in order to sufficiently provide the function of silicone oil, it is preferably contained in an amount of 0.1% by mass or more, more preferably 1% by mass or more, based on the entire cosmetic composition.

  On the other hand, in the cosmetic composition of the present invention, it is also preferable that the silicone oil content is less than 0.1% by mass. When the content of the silicone oil is less than 0.1% by mass, a cosmetic composition having excellent finger-feel after drying can be obtained. In this respect, it is more preferable not to include silicone oil.

<Other ingredients>
As long as the effect of the cosmetic composition of the present invention is not impaired, in addition to the copolymer of the present invention, water, a cationic surfactant, a higher alcohol, and a silicone oil, a hydrocarbon oil component, a humectant (water-soluble polymer) ), Polymers such as cationic polymers, anionic polymers, nonionic polymers, amphoteric polymers, various surfactants other than cationic surfactants, pH adjusters, preservatives, thickeners, etc. Can be used.

  Examples of the hydrocarbon oil include liquid paraffin such as isoparaffin, solid paraffin, petrolatum, ceresin, and microcrystalline wax. These hydrocarbon oils may be used alone or in combination of two or more, but are preferably contained in a total amount of 5% by mass or less with respect to the entire cosmetic composition. These hydrocarbon oils may be used alone or in combination of a plurality of types in any combination and blending ratio.

  Examples of the humectant include polyhydric alcohols such as glycerin, dipropylene glycol, 1,3-butanediol, and erythritol, and water-soluble polymers such as methylcellulose and hyaluronic acid. Examples of the cationic polymer include a cation-modified cellulose ether derivative, a cation-modified galactomannan polysaccharide, polydimethyl diallyl ammonium halide, and a copolymer of dimethyl diallyl ammonium halide and acrylamide. Examples of anionic polymers and nonionic polymers include acrylic acid derivatives (hydroxyethyl acrylate / methoxyethyl acrylate copolymer, polyacrylamide, etc.), vinylpyrrolidone derivatives (polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer). Examples of the amphoteric polymer include dimethyldiallylammonium chloride derivatives (acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, acrylic acid / dimethyldiallylammonium chloride copolymer, etc.) and the like. The cationic polymer, anionic polymer, nonionic polymer and amphoteric polymer mentioned above do not include the copolymer of the present invention. In the case of using these humectants, it is possible to use only one kind or a plurality of kinds in any combination and blending ratio, but the total amount of the polymer is 5% by mass with respect to the entire cosmetic composition. It is preferable to make it contain below.

  Examples of the surfactant other than the cationic surfactant include an anionic surfactant, a hydrophilic nonionic surfactant, an amphoteric surfactant, and a semipolar surfactant. Specific examples of surfactants other than the cationic surfactant are listed below. When these are used, it is preferable to contain them in a total amount of 5% by mass or less with respect to the entire cosmetic composition.

  As an anionic surfactant, α-olefin sulfonate, higher alcohol sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, paraffin sulfonate, polyoxyethylene alkyl ether carboxylate ester salt, alkyl sulfosuccinate, N -What is necessary is just to use what is normally used for normal cosmetics compositions, such as acyl- (beta) -alanine salt, N-acyl glutamate, and acylmethyl taurate. Examples of counterions of these anionic surfactants include sodium, potassium, ammonium, triethanolamine, diethanolamine and the like. These anionic surfactants can be used alone or in combination of a plurality of kinds in any combination and blending ratio.

  Examples of the hydrophilic nonionic surfactant include polyoxyethylene (hereinafter sometimes abbreviated as POE) sorbitan fatty acid esters (for example, POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monooleate). POE sorbite fatty acid esters (eg, POE sorbite monolaurate, POE sorbite monooleate, POE sorbite pentaoleate, POE sorbite monostearate, etc.); POE glycerin fatty acid esters (eg, POE glycerol monostearate, POE glycerol monoisostearate, POE monooleate such as POE glycerol triisostearate, etc.); POE fatty acid esters (for example, POE dies) Aleate, POE monodiolate, ethylene glycol distearate, etc.); POE alkyl ethers (for example, POE lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE2-octyldodecyl ether, POE cholestanol ether, etc.); Pluronic type (For example, Pluronic); POE / polyoxypropylene (hereinafter sometimes abbreviated as POP) alkyl ethers (for example, POE / POP cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP) Monobutyl ether, POE / POP hydrogenated lanolin, POE / POP glycerin ether, etc.); tetra-POE / tetra-POP ethylenediamine condensates (eg, Tetronic, etc.); OE castor oil hydrogenated castor oil derivatives (for example, POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, POE hydrogenated castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, POE Hardened castor oil maleic acid etc.); POE beeswax lanolin derivatives (eg POE sorbite beeswax etc.); alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide etc.); POE propylene glycol fatty acid ester POE alkylamine; POE fatty acid amide; sucrose fatty acid ester; alkyl ethoxydimethylamine oxide; trioleyl phosphate and the like. These hydrophilic nonionic surfactants can be used alone or in a combination of a plurality of kinds in any combination and blending ratio.

  Examples of amphoteric surfactants include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium. Imidazoline-based amphoteric surfactants such as salts; betaine-based surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaines, amide betaines, sulfobetaines, etc. Is mentioned. These amphoteric surfactants can be used alone or in combination of a plurality of types in any combination and blending ratio.

  Examples of the semipolar surfactant include lauramine oxide (lauryl dimethylamine oxide), which can be suitably used. Only one type of semipolar surfactant can be used, or a plurality of types of semipolar surfactants can be used in any combination and combination ratio.

  Such surfactants are generally commercially available and can be used as they are.

  Examples of the pH adjuster include citric acid and tartaric acid. When using a pH adjuster, it is preferable to make it contain at 0.1 mass% or less with respect to the cosmetic composition whole. These pH adjusters can be used alone or in combination of a plurality of kinds in any combination and blending ratio.

  Examples of the preservative include sodium benzoate. When using an antiseptic, it is preferable to make it contain at 0.1 mass% or less with respect to the whole cosmetic composition. One preservative can be used alone, or a plurality of preservatives can be used in any combination and combination ratio.

  Examples of the thickener include hydroxymethyl cellulose and hydroxyethyl cellulose. When using a thickener, it is preferable to make it contain at 5 mass% or less with respect to the whole cosmetics composition. These thickeners can be used alone or in combination of multiple kinds in any combination and blending ratio.

  Other than those listed above, natural extracts of animals and plants and derivatives thereof, organic acids such as lactic acid, inorganic salts such as sodium chloride, amino acids (glutamic acid or salts thereof, arginine or salts thereof, glycine, etc.), antioxidants, An ultraviolet absorber, a bactericidal agent, a chelating agent, a fragrance, a colorant, a metal sequestering agent (such as edetate), a foaming enhancer and the like can be appropriately blended within a range not impairing the effects of the present invention. When using these components, it is preferable to contain 20 mass% or less in total with respect to the whole cosmetic composition.

  In addition, the cosmetic composition of this invention does not prevent using other than the component mentioned above.

  The viscosity of the cosmetic composition of the present invention varies depending on its use. For example, when the cosmetic composition of the present invention is used as a hair cosmetic, the viscosity at 25 ° C. is 300 mPa · s or more and 100,000 mPa · s or less. Preferably there is. This viscosity is more preferably 1,000 mPa · s or more, still more preferably 2,000 mPa · s or more, particularly preferably 5,000 mPa · s or more, most preferably 10,000 mPa · s or more, more preferably Is 90,000 mPa · s or less, more preferably 80,000 mPa · s or less. It is preferable in terms of handling that the viscosity of the cosmetic composition is within the above range. The viscosity of the cosmetic composition can be measured using a B-type viscometer or a B8H-type viscometer as shown in the examples of the present specification.

[Hair cosmetic]
The cosmetic composition of the present invention is particularly useful as a hair cosmetic. In this specification, the hair cosmetic is not particularly limited, and examples thereof include shampoos, rinses, conditioners, treatments, treatments for out baths, hair dyes, permanents, hair packs, hair sprays, hair foams, styling agents, and the like. Can be mentioned. Among these, the hair cosmetic composition of the present invention is particularly useful as a conditioning agent such as a shampoo, a rinse, a conditioner, a treatment, or an out bath treatment, which requires a conditioning effect.

  The cosmetic composition of the present invention is particularly useful as a hair treatment cosmetic among hair cosmetics. Hair treatment cosmetics are mainly intended to give a conditioning effect after washing with shampoo, etc. What is said to be a rinse-off conditioner, such as a rinse, conditioner, treatment, etc., and what is not washed away include what is called an out-bath treatment or leave-on conditioner. Among these, the cosmetic composition of the present invention is particularly useful as a rinse-off conditioner.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely using an Example, this invention is not limited to a following example, unless the summary is exceeded. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[Production of copolymer]
<Production of copolymer (1)>
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introduction tube and a stirring device was charged with 100 parts by mass of ethanol, and 40 parts by mass of methoxypolyethylene glycol (2 mol) methacrylate and 60 parts by mass of acrylic acid were added to the dropping funnel. And a monomer mixed solution consisting of 100 parts by mass of ethanol was charged, the reactor was purged with nitrogen, and then heated to 80 ° C. Into the reactor, 0.5 part by mass of dimethyl-2,2′-azobisisobutyrate (V-601; manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the copolymer mixture was dropped over 2 hours. did. After reacting for 8 hours after completion of the dropwise addition, distilled water was added while distilling off the ethanol solvent to obtain an aqueous solution of the copolymer (1).

<Production of Copolymer (2) to Copolymer (12)>
A copolymer (2) to a copolymer (12) are produced in the same manner as the production of the copolymer (1) except that the monomers listed in Table 1 are used in the proportions described in Table 1. (“Copolymer (9)” is not a “copolymer” but a “polymer” using a single monomer, but is referred to as “copolymer (9)” for convenience).

[Measurement of physical properties of copolymer]
<Measurement of mass average molecular weight>
Gel permeation chromatography (apparatus: “SC8010, SD8022, RI8020, CO8011, PS8010” manufactured by Tosoh Corporation, column: “Wakopak (Wakobeads G-50)”, developing solvent: water / methanol / acetic acid / Sodium acetate = 6/4 / 0.3 / 0.41), and using polyethylene glycol as a standard substance, the mass average of copolymers (1) to (8), (10), (11) and (12) The molecular weight was determined.
The copolymer (9) is gel permeation chromatography (apparatus: “SC8020, SD8022, CCPM-II, RI8020, CO8020” manufactured by Tosoh Corporation, column: “G6000Hxl, G4000Hxl, G2500Hxl”, developed by Tosoh Corporation. Solvent: Tetrahydrofuran) was used to determine the mass average molecular weight using polystyrene as a standard substance.
The obtained results are shown in Table-1.

[Measurement and evaluation of physical properties of cosmetic composition]
The physical property measurement methods and evaluation methods of cosmetic compositions in the following examples and comparative examples are as follows.

<Damaged hair>
As hair bundles for evaluation, human hair black hair (100%) root alignment (untreated hair, 10 g × 30 cm, Beaulux Co., Ltd.) was used as a “damaged hair” after bleaching. That is, 12 g of “Promatis Brave Oxytan 6.0 (hydrogen peroxide 6% cream)” manufactured by Milbon Co., Ltd. and “Powder Bleach MR2” manufactured by Melos Chemical Co., Ltd. are used as a bleaching agent for each hair bundle. 6 g of the mixture was applied, allowed to stand for 30 minutes, washed with water, washed with sodium lauroyl (EO) trisulfate (polyoxyethylene (3) sodium lauryl ether sulfate) to prepare damaged hair. A bundle of 5 g of damaged hair was used as a damaged hair sample hair bundle.

<Evaluation of smoothness during application>
The above-mentioned damaged hair sample hair bundle was washed and rinsed using 25% by mass polyoxyethylene (3) sodium lauryl ether sulfate as a shampoo, and then each cosmetic prepared in Examples and Comparative Examples After applying the composition, the smoothness of the finger when the hair bundle was rinsed in running water at 40 ° C. was evaluated in the following four steps. The comparative standard product refers to a cosmetic composition prepared using the copolymer (11).
+2: Excellent compared to the comparative standard product +1: Slightly superior to the comparative standard product 0: Same as the comparative standard product -1: Inferior to the comparative standard product

<Evaluation of absence of dryness after drying>
The above-mentioned damaged hair sample hair bundle was washed and rinsed using 25% by mass polyoxyethylene (3) sodium lauryl ether sulfate as a shampoo, and then each cosmetic prepared in Examples and Comparative Examples After applying the composition, the hair bundles were rinsed in running water at 40 ° C., and then naturally dried at 23 ° C. and 60% RH for one day. did. The evaluation of the absence of unevenness here is an evaluation of how much the unevenness of damaged hair has been reduced, and is an evaluation that combines the uniformity of the hair surface and the softness of the hair bundle. The comparative standard product refers to a cosmetic composition prepared using the copolymer (11).
+2: Excellent compared to the comparative standard product +1: Slightly superior to the comparative standard product 0: Same as the comparative standard product -1: Inferior to the comparative standard product

<Evaluation of the goodness of fingers after drying>
The above-mentioned damaged hair sample hair bundle was washed and rinsed using 25% by mass polyoxyethylene (3) sodium lauryl ether sulfate as a shampoo, and then each cosmetic prepared in Examples and Comparative Examples After applying the composition, after rinsing the hair bundle in running water at 40 ° C., the hair bundle is lightly pressed with a towel to remove moisture, and then the condition of passing the finger through the finger in the following four steps evaluated. The comparative standard product refers to a cosmetic composition prepared using the copolymer (11).
+2: Excellent compared to the comparative standard product +1: Slightly superior to the comparative standard product 0: Same as the comparative standard product -1: Inferior to the comparative standard product

<Evaluation of unity after drying>
The above-mentioned damaged hair sample hair bundle was washed and rinsed using 25% by mass polyoxyethylene (3) sodium lauryl ether sulfate as a shampoo, and then each cosmetic prepared in Examples and Comparative Examples After applying the composition, after rinsing the hair bundle in flowing water at 40 ° C., the hair bundle is lightly pressed with a towel to remove moisture, and then the bundle of hair bundles is good when the hair tip is lifted and dropped. (Non-expanded hair tip) was evaluated in the following four stages. The comparative standard product refers to a cosmetic composition prepared using the copolymer (11).
+2: Excellent compared to the comparative standard product +1: Slightly superior to the comparative standard product 0: Same as the comparative standard product -1: Inferior to the comparative standard product

<Measurement of viscosity>
About each cosmetics composition prepared by the Example and the comparative example, the viscosity was measured using the B-type viscometer at 25 degreeC, the rotor number 4, and rotation speed 12rpm.

[Preparation and evaluation of cosmetic composition]
<Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-3>
Using the copolymers (1) to (11), a cosmetic composition having the composition shown in Table 2 was prepared according to a conventional method. In addition, all the components are the mass as an active ingredient, and the entrained water was adjusted with the quantity of the water to add. The obtained cosmetic composition was evaluated and measured for the above-mentioned “smoothness at the time of application”, “no wrinkle after drying”, “goodness of finger after drying”, and “viscosity”. The results are shown in Table-3.

<Evaluation result (1)>
(1-1) In the cosmetic composition of Comparative Example 1-3, the content of the structural unit derived from the vinyl monomer (A) of the copolymer used was 30% by mass, which is less than the scope of the present invention. On the other hand, the copolymer used in the cosmetic composition of Examples 1-1 to 1-8 has a content ratio of the structural unit derived from the vinyl monomer (A) including the monomer (a) of 50% by mass or more. The smoothness at the time of application was not impaired, there was no roughness after drying, and the fingering after drying was also good.
(1-2) In the cosmetic composition of Example 1-5, the copolymer used is a structural unit derived from the vinyl monomer represented by formula (3) having high hydrophobicity as the monomer (b). The cosmetic composition of Example 1-8 has a structural unit derived from cyclohexyl methacrylate having high hydrophobicity as a structural unit derived from the monomer (d). It was good without dryness after drying.
(1-3) In the cosmetic compositions of Example 1-1 and Example 1-3, the copolymer used was a highly hydrophobic monomer (c) with a short polyethylene glycol chain (meth) Since it has a structural unit derived from an acrylic ester monomer, there was no roughness after drying, and the fingering after drying was also good.
(1-4) In the cosmetic composition of Comparative Example 1-1, the copolymer used was a polymer composed only of the monomer (a), whereas Examples 1-1 to 1-8 were used. In the cosmetic composition, since the copolymer used was a copolymer with other monomers, the dryness after drying was good.
(1-5) The cosmetic composition of Comparative Example 1-2 is a copolymer in which the copolymer used does not contain any of the constituent units derived from the monomer (b), the monomer (c), and the monomer (d). In contrast, the copolymers used in the cosmetic compositions of Examples 1 to 1-8 are copolymers containing any of the structural units derived from the monomers (b) to (d). For this reason, the smoothness at the time of coating and the absence of roughness after drying were good.

<Examples 2-1 to 2-8 and Comparative Example 2-1>
Using the polymers (1) to (6), (8), (11) and (12), a cosmetic composition having the composition shown in Table 4 was prepared according to a conventional method. In addition, all the components are the mass as an active ingredient, and the entrained water was adjusted with the quantity of the water to add. The obtained cosmetic composition was evaluated for the “smoothness at the time of application”, “goodness of fingers after drying”, and “goodness of unity after drying”. The results are shown in Table-5.

<Evaluation result (2)>
(2-1) In the cosmetic composition of Comparative Example 2-1, the content ratio of the structural unit derived from the vinyl monomer (A) of the copolymer used was 30% by mass, which is less than the scope of the present invention. On the other hand, the copolymer used in the cosmetic composition of Examples 2-1 to 2-8 has a content ratio of the structural unit derived from the vinyl monomer (A) including the monomer (a) of 50% by mass or more. The smoothness at the time of application was not impaired, there was no roughness after drying, and the fingering after drying was also good.
(2-2) In the cosmetic compositions of Example 2-2 and Example 2-8, the copolymer used had a higher content of monomer (a) than other examples and comparative examples. The fingering after drying was particularly good.

  The cosmetic composition of the present invention can be obtained as an excellent conditioning effect when used as a special hair cosmetic. For this reason, it is particularly suitable as a conditioning agent.

Claims (8)

A copolymer having a structural unit derived from the following monomer (a) and at least one of structural units derived from the following monomers (b) to ( c ), and based on the total mass of the copolymer 1 to 99% by mass of a structural unit derived from the following monomer (a), 50 to 100% by mass of a structural unit derived from a vinyl monomer (A) having a carboxyl group, and a 20% by mass ethanol solution at 25 ° C. Is a copolymer having a viscosity of 5 mPa · s or more and 20000 mPa · s or less and a mass average molecular weight of 3,000 to 400,000.
Monomer (a): Acrylic acid and / or methacrylic acid Monomer (b): One or more vinyl monomers represented by the following formula (1), (2) or (3) CH ₂ = C (R ¹ _{) -CO- (O- (CH 2)} m -CO) n -OH ... (1)
(In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 4, and n represents an integer of 1 to 4.)
^{_{CH 2 = C (R 2)}} -COO- (CH 2) p -OCO- (CH 2) q -COOH
... (2)
(In the above formula (2), ^{R 2} represents a hydrogen atom or a methyl group, p, q represent each independently an integer of from 2 to 6.)
^{_{CH 2 = C (R 3)}} -COO- (CH 2) e -OCO-X-COOH ... (3)
(In the above formula (3), R ³ represents a hydrogen atom or a methyl group, e represents an integer of 1 to 4, X is not a good cyclohexylene group or a substituted group which may have a substituent Represents an optional phenylene group.)
Monomer (c): Vinyl monomer represented by the following formula (4) CH ₂ ═C (R ⁴ ) —CO—Y— (Z—O) _r —R ⁵ (4)
(In the above formula (4), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Y represents an oxygen atom or NH, and Z represents a substituent. Represents an optionally substituted alkylene group having 2 to 4 carbon atoms, and r represents an integer of 1 to 15. )   The copolymer of Claim 1 which contains 10-95 mass% of structural units derived from the said monomer (a) with respect to the total mass of a copolymer.   The copolymer of Claim 1 or 2 which contains 1-99 mass% of structural units derived from the said monomer (b) with respect to the total mass of a copolymer.   The copolymer of any one of Claims 1 thru | or 3 which contains 1-50 mass% of structural units derived from the said monomer (c) with respect to the total mass of a copolymer. Cosmetics comprising 0.05 to 5% by mass of the copolymer according to any one of claims 1 to 4 , 0.1 to 20% by mass of a cationic surfactant, and 0.1 to 20% by mass of a higher alcohol. Composition. Furthermore, the cosmetic composition of Claim 5 containing 0.1-10 mass% of silicone oils. The cosmetic composition according to claim 5 , wherein the silicone oil content is less than 0.1% by mass. A conditioning agent comprising the cosmetic composition according to any one of claims 5 to 7 .