KR20130124320A - Copolymer and cosmetic material composition - Google Patents

Abstract

(일반식 (1) 중, R¹ 은 수소 원자 또는 메틸기를 나타내고, R² 는 탄소수 2 ∼ 4 의 알킬렌기를 나타내고, R³ 은 수소 원자 또는 탄소수 1 ∼ 3 의 알킬기를 나타낸다. m 은 15 ∼ 50 을 만족시키는 정수를 나타낸다.
일반식 (2) 중, R⁴ 는 수소 원자 또는 메틸기를 나타내고, R⁵ 는 탄소수 2 ∼ 10 의 알킬기를 나타낸다. p 및 q 는 각각 0 또는 1 의 정수를 나타내고, p ＋ q = 1 이다.)An object of the present invention is to provide a copolymer having a high degree of setability and resetting property, having a degree of freedom of a wide range of preparations such as spray, mist, and wax, and a composition containing the copolymer and a cosmetic. This invention contains the structural unit corresponded to the vinyl monomer (A) represented by following General formula (1), and the structural unit corresponded to the vinyl monomer (B) represented by following General formula (2), and is in water below 30 degreeC It is related with the copolymer which does not melt and has an endothermic starting point between -25 degreeC-40 degreeC, and the cosmetic composition containing this copolymer.

(In general formula (1), R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C2-C4 alkylene group and R <^3> represents a hydrogen atom or a C1-C3 alkyl group. M is 15- The integer which satisfy | fills 50 is shown.
In general formula (2), R ⁴ Represents a hydrogen atom or a methyl group, R ⁵ Represents an alkyl group having 2 to 10 carbon atoms. p and q represent an integer of 0 or 1, respectively, and p + q = 1.)

Description

Copolymer and Cosmetic Composition {COPOLYMER AND COSMETIC MATERIAL COMPOSITION}

The present invention relates to a copolymer of a specific structure, and a cosmetic composition containing the copolymer.

In recent years, waxy hairdressing materials (hair wax) have been widely accepted, mainly on the younger layers. Whereas hair mousse, gel, spray, and the like, which are conventional hair-sets, resins form a film on the hair to express setability, hair wax is mainly based on carnauba wax, cantella wax, and microcrystalline wax. By the solid fraction, the hair-setting effect which arranges and arranges hair is implement | achieved (for example, patent document 1 and 2).

Hair wax has also been developed so far requiring higher hairdressing properties (set force, oil retaining properties, non-hairing properties) and good feeling of use. For example, the hairdressing compound (patent document 3) which mix | blended high polymerization degree polyethyleneglycol, wax, and nonionic surfactant (patent document 4), the hair wax which mix | blended 12-hydroxystearic acid and an alkali chemical agent (patent document 4), etc. are disclosed.

On the other hand, the copolymer which has a structural unit derived from the vinylic monomer which has a specific alkylene oxide group as a hydrophilic group, and the vinylic monomer which has a specific alkyl group as a hydrophobic group, melt | dissolves in water, and has a cloud point in 30 degreeC-70 degreeC is known. (Patent Document 5). In this copolymer, a hydrophobic film can be formed on the hair using a hair dryer, and it is said that the cosmetics useful for hairdressing etc. can be provided.

Japanese Patent Laid-Open No. 10-45546 JP 2001-316228 A Japanese Unexamined Patent Publication No. 2002-241243 Japanese Unexamined Patent Publication No. 2000-86450 Japanese Laid-Open Patent Publication 2001-316422

However, when high hair-setting property is requested | required like patent documents 3-4, and a solid component and resin are mix | blended in large quantity, the problem which becomes difficult to formulate and cannot be formulated, and spreading to hair is bad even if it can be formulated, There is a problem that the texture is deteriorated. In addition, waxes, which are solid fractions derived from natural products, have problems in terms of providing odor and stable quality over time, and a material for replacing them is required.

In addition, the copolymer as described in Patent Document 5 has treatment properties by forming a hydrophobic film on the hair when a hair dryer or the like is used, but the setability as a hair dressing agent is not sufficient at all.

In particular, in the use of hair wax etc., in addition to high set-up force, what is excellent in the hair repellency which can change the texture of a flexible hair and the style which was set once is calculated | required.

The present invention has been made in view of solving the above problems, a copolymer having a high degree of setability and resetting property, having a degree of freedom of a wide range of preparations such as spray, mist, and wax, and a cosmetic composition containing the copolymer. The purpose is to provide.

MEANS TO SOLVE THE PROBLEM In view of the said subject, as a result of earnestly examining, it is a copolymer which consists of a structural unit derived from the vinyl monomer of a specific structure, and does not melt | dissolve in water below 30 degreeC, and it raises from -25 degreeC when it raises from low temperature. A copolymer having an endothermic initiation point between -40 ° C has a high setability and resetting property when applied to hair, and is widely used as a cosmetic composition by dispersing the copolymer in water or ethanol, for example. It has been found that the formulation form can be realized and the present invention has been completed.

That is, the summary of this invention exists in the following [1]-[16].

[1] A copolymer comprising a structural unit corresponding to a vinyl monomer (A) represented by the following General Formula (1) and a structural unit corresponding to a vinyl monomer (B) represented by the following General Formula (2), which is less than 30 ° C. The copolymer which does not melt | dissolve in water and has an endothermic starting point between -25 degreeC-40 degreeC.

[Formula 1]

(In general formula (1), R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C2-C4 alkylene group and R <^3> represents a hydrogen atom or a C1-C3 alkyl group. M is 15- An integer satisfying 50 is represented.)

(2)

(In formula (2), R ⁴ Represents a hydrogen atom or a methyl group, R ⁵ Represents an alkyl group having 2 to 10 carbon atoms. p and q represent an integer of 0 or 1, respectively, and p + q = 1.)

[2] The copolymer according to the above [1], further comprising a structural unit corresponding to a crosslinkable vinyl monomer (vinyl monomer (C)).

[3] The copolymer according to the above [2], which includes a structural unit corresponding to each of the vinyl monomers (A) to (C) in the following ratio with respect to the entire copolymer.

Vinyl monomer (A): 30-80 weight%

Vinyl monomer (B): 20 to 70% by weight

Vinyl monomer (C): 0.1-10 weight%

[4] The copolymer according to any one of the above [1] to [3], wherein p is 1 in the general formula (2) representing the vinyl monomer (B).

[5] The copolymer according to any one of the above [2] to [4], wherein the vinyl monomer (C) is represented by the following General Formula (3) or the following General Formula (4).

(3)

(In formula (3), R ⁶ Represents a hydrogen atom or a methyl group. Q ¹ represents a linking group represented by -CH ₂ -or the following General Formula (5), and Q ¹ Is -CH ₂ - if, s represents an integer which satisfies the range of 0 to 50. Moreover, when Q <^1> is a coupling group represented by following General formula (5), s represents the integer of 0 or 1. Q ² Represents an alkylene group having 1 to 6 carbon atoms, and t represents an integer that satisfies 0 to 50. However, s and t shall be either 0.)

[Formula 4]

(In formula (5), R ⁷ Represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, u represents an integer of 0 or 1, and v represents an integer satisfying 1 to 100.)

[Chemical Formula 5]

(In formula (4), R ⁸ Represents an alkylene group having 2 to 4 carbon atoms, R ⁹ Represents a hydrogen atom or a methyl group, w represents an integer that satisfies 0 to 100, R ¹⁰ and R ¹¹ Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or a substituent represented by the following general formula (6), respectively.)

[Chemical Formula 6]

(In formula (6), R ¹² Represents an alkylene group having 2 to 4 carbon atoms, R ¹³ Represents a hydrogen atom or a methyl group, x represents an integer of 0 or 1, and y represents an integer satisfying 0 to 100.)

[6] The copolymer according to any one of the above [1] to [5], further comprising a structural unit corresponding to a vinyl monomer (D) having an alkyl group having 12 to 22 carbon atoms.

[7] The copolymer according to any one of the above [2] to [6], wherein the crosslinking rate by the vinyl monomer (C) is 0.05 to 20%.

[8] Furthermore, the structure as described in said [1] containing the structural unit corresponded to the vinyl monomer (E) which consists of at least one of the monomer represented by following General formula (7) and the monomer represented by following General formula (8). Copolymer.

[Formula 7]

(In formula (7), R ¹⁴ Represents a hydrogen atom or a methyl group, R ¹⁵ and R ¹⁶ Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

[Formula 8]

(In formula (8), R ¹⁷ Represents a hydrogen atom or a methyl group. r is 0 or 1, and z is an integer which satisfy | fills 1-4. X represents either of the following General Formulas (9) to (11).)

[Chemical Formula 9]

(In General Formulas (9) to (11), R ¹⁸ and R ^19. Each independently represents an alkyl group having 1 to 4 carbon atoms, and R ²⁰ in General Formula (10) Represents an alkyl group having 1 to 4 carbon atoms or-(CH ₂ ) _k -COO- (k is an integer of 1 to 4) and its salt.)

[9] The copolymer according to the above [8], which comprises a structural unit corresponding to each of the vinyl monomers (A), (B), and (E) in the following ratio with respect to the entire copolymer.

Vinyl monomer (A): 30-80 weight%

Vinyl monomer (B): 20 to 70% by weight

Vinyl monomer (E): 0.1-50 weight%

[10] The copolymer according to any one of the above [1], [8] and [9], wherein the weight average molecular weight is 5,000 or more and 2,000,000 or less.

[11] An aqueous dispersion in which the fine particles of the copolymer according to any one of [1] to [10] are dispersed in a continuous phase containing water.

[12] An aqueous dispersion in which the fine particles of the copolymer according to any one of [1] to [10] are dispersed in a volume average particle diameter of 10 to 500 nm.

[13] A copolymer including a structural unit corresponding to the vinyl monomer (A) represented by the following General Formula (1) and a structural unit corresponding to the vinyl monomer (B) represented by the following General Formula (2), contains water. After disperse | distributing in the continuous phase to add, the process of adding and copolymerizing a vinyl monomer (C) represented by following General formula (3) or following General formula (4), or

In the copolymer including the structural unit corresponding to the vinyl monomer (A) represented by the following General Formula (1) and the structural unit corresponding to the vinyl monomer (B) represented by the following General Formula (2), the following General Formula (3) Or after adding the vinyl monomer (C) represented by following General formula (4), the manufacturing method of the copolymer including the process of disperse | distributing and copolymerizing in a continuous phase containing water.

[Formula 10]

(In General Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² Represents an alkylene group having 2 to 4 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents the integer satisfying 15-50.)

[Formula 11]

(In formula (2), R ⁴ Represents a hydrogen atom or a methyl group, R ⁵ Represents an alkyl group having 2 to 10 carbon atoms. p and q represent an integer of 0 or 1, respectively, and p + q = 1.)

[Chemical Formula 12]

(In formula (3), R ⁶ Represents a hydrogen atom or a methyl group. Q ¹ Represents -CH ₂ -or a linking group represented by the following General Formula (5), and when Q ¹ is -CH _2- , s represents an integer satisfying 0 to 50. Moreover, when Q <^1> is a coupling group represented by following General formula (5), s represents the integer of 0 or 1. Q ² Represents an alkylene group having 1 to 6 carbon atoms, and t represents an integer that satisfies 0 to 50. However, s and t shall be either 0.)

[Chemical Formula 13]

(In formula (5), R ⁷ Represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, u represents an integer of 0 or 1, and v represents an integer satisfying 1 to 100.)

[Formula 14]

(In formula (4), R ⁸ Represents an alkylene group having 2 to 4 carbon atoms, R ⁹ Represents a hydrogen atom or a methyl group, w represents an integer that satisfies 0 to 100, R ¹⁰ and R ¹¹ Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or a substituent represented by the following general formula (6), respectively.)

[Formula 15]

(In formula (6), R ¹² Represents an alkylene group having 2 to 4 carbon atoms, R ¹³ Represents a hydrogen atom or a methyl group, x represents an integer of 0 or 1, and y represents an integer satisfying 0 to 100.)

[14] A copolymer obtained by the production method described in [13].

[15] A cosmetic composition containing the copolymer according to any one of the above [1] to [10].

[16] A cosmetic composition containing the aqueous dispersion according to the above [11] or [12].

According to the present invention, there is provided a copolymer having a high setability and resetting property, having a degree of freedom of a wide range of preparations such as a spray, mist, and wax, and a composition containing the copolymer and a cosmetic composition.

EMBODIMENT OF THE INVENTION Although embodiment of this invention is described in detail below, description of the element | module described below is a typical example of embodiment of this invention, and this invention is not limited to these content.

In addition, in this specification, "(meth) acryl" is a generic term of "acryl" and "methacryl". The same applies to "(meth) acrylate" and "(meth) acryloyl". In addition, in this specification, a vinyl monomer is a generic name of the compound which has a structure which substituted hydrogen of ethylene, such as a vinyl group, a vinylene group, and a vinylidene group. In addition, in this specification, "-" shall be used by the meaning containing the numerical value or physical value described before and after.

1. Copolymer

The copolymer of the present invention is a copolymer comprising a structural unit corresponding to a vinyl monomer (A) represented by the following general formula (1) and a structural unit corresponding to a vinyl monomer (B) represented by the following general formula (2) ( Hereinafter, simply referred to as "copolymer". In addition, the copolymer is characterized in that it does not dissolve in water of less than 30 ° C and has an endothermic initiation point between -25 ° C and 40 ° C when the temperature is raised from low temperature.

[Chemical Formula 16]

(In General Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² Represents an alkylene group having 2 to 4 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents the integer satisfying 15-50.)

[Chemical Formula 17]

(In formula (2), R ⁴ Represents a hydrogen atom or a methyl group, R ⁵ Represents an alkyl group having 2 to 10 carbon atoms. p and q represent an integer of 0 or 1, respectively, and p + q = 1.)

<Non-water soluble>

The copolymer of this invention does not melt | dissolve in water below 30 degreeC of water temperature.

Here, "dissolving in water" is a heating and stirrer stirring process, when adding the dried copolymer to solid water below 30 degreeC, for example, about 10-30 degreeC water as solid content, so that it may become 1 weight%. Even if it is carried out, it shows that the sample is in a non-uniform state at the temperature below 30 degreeC, and the insoluble matter of 100 micrometers or more which can be confirmed visually specifically exists, or the volume average particle diameter of an insoluble matter is 50 micrometers. As mentioned above, Preferably it means the state used as 100 micrometers or more.

As a copolymer which melt | dissolves in water below 30 degreeC, the ratio of the structural unit corresponded to the vinyl monomer (A) in a copolymer is too large, the molecular weight of a copolymer is too small, or arbitrary hydrophilic vinyl in a copolymer It is considered that the ratio of the structural unit corresponding to the monomer is too large.

When there are too many ratios of the structural unit corresponded to the vinyl monomer (A) in a copolymer, since there are few hydrophobic parts and the film strength of a copolymer is small, there exists a tendency for regrowth to be impaired. Moreover, even when the molecular weight of a copolymer is too small, since the fluidity | liquidity of a copolymer is high, there exists a tendency for inferior removability to be inferior. In addition, when there are too many ratios of the structural unit corresponded to arbitrary hydrophilic vinyl monomers, the adhesiveness falls by the inhibition of the crystallinity of a polyoxyalkylene group, and the film strength which arises because there are few hydrophobic parts, Both vocalizations are inferior. Moreover, in either case, the hair dressing property and hair-setting retention under high humidity tend to fall remarkably.

In order to make a copolymer insoluble in water below 30 degreeC, the ratio of the structural unit corresponded to the vinyl monomer (A) in a copolymer is reduced, for example; Increasing the degree of polymerization or adding a crosslinking agent to increase the molecular weight of the copolymer; The proportion of the structural units corresponding to any hydrophilic vinyl monomer in the copolymer is reduced; Or the structural unit corresponding to the vinyl monomer which has a high hydrophobic side chain, such as a long chain alkyl group, is introduce | transduced into a copolymer; And other means. In addition, it is possible to control the water solubility by appropriately combining the above methods.

<Endothermic starting point>

The copolymer of the present invention has an endothermic initiation point between -25 deg. C and 40 deg.

The endothermic initiation point of the copolymer is, for example, using a differential scanning calorimeter (DSC), using an aluminum sealed cell, and raising the copolymer in the cell at a rate of 10 ° C./min from the low temperature side with reference to air. When doing so, it indicates the heat flow increase start temperature when the increase in the heat flow from the base line was confirmed, and the endothermic start point at -25 to 40 ° C means that there was a phase transition point in the vicinity of room temperature (20 ° C). The endothermic starting point of the copolymer can be specifically evaluated by the method described in Examples described later.

In the copolymer of the present invention, the structural part derived from the hydrophilic monomer (A) may be microphase separated from the structural part derived from the hydrophobic monomer (B). The endothermic behavior described in the present invention is considered to be derived from the crystallinity of the polyoxyalkylene group of the structural unit corresponding to the vinyl monomer (A) separated in the copolymer. In the vicinity of the endothermic onset temperature, the crystallinity of the polyoxyalkylene chain is weakened to form a paste, and when applied onto the hair, it is considered to exhibit adhesiveness and increase hair dressing.

On the other hand, the phase which mainly comprises the structural unit corresponded to a hydrophobic vinyl monomer (B) connects hydrophobic parts of a copolymer chain with each other by van der Waals force or a hydrophobic bond, and suppresses the fluidity of a copolymer. As a result, the strength of the copolymer is improved, and adhesion between the hairs adhered by the adhesion of the polyoxyalkylene group can be maintained. In view of the above, in addition to high setability, resetting is realized.

In addition, by the minority part, when the light contact is performed by hand, the stickiness derived from the polyoxyalkylene chain is less, and the hairs can be strongly adhered to each other when the pressure is strongly applied to the hair by an action such as trimming by hand. .

When the endothermic initiation point is -25 ° C or more and 40 ° C or less, adhesiveness is exhibited when the copolymer is applied on the hair at room temperature (20 ° C), and high setability is exhibited when the hair cosmetic composition containing it is obtained.

Preferably the copolymer of this invention is 35 degrees C or less, More preferably, it is 30 degrees C or less, Especially preferably, it is 20 degrees C or less, More preferably, it is 18 degrees C or less, On the other hand, Preferably it is -25 degreeC or more, Preferably it has an endothermic starting point between -10 degreeC or more, More preferably, it is 0 degreeC or more.

<Heat absorption amount>

In the copolymer of the present invention, the endothermic amount of 0.5 to 90 mJ / mg measured in the measurement of the endothermic initiation point increases the adhesiveness of the structure of the part of the polyoxyalkylene group in the copolymer, thereby improving hair dressing properties. It is preferable because of that. The endothermic amount is more preferably 1.0 mJ / mg or more, still more preferably 1.5 mJ / mg or more, on the other hand, more preferably 70 mJ / mg or less, still more preferably 50 mJ / mg or less, particularly preferably Is 35 mJ / mg or less. The endothermic amount of a copolymer can be adjusted by selecting suitably the hydrophobic vinyl monomer as a monomer which forms a copolymer, and introducing a structure with high hydrophobicity in a copolymer.

<Molecular weight>

The weight average molecular weight of the copolymer of this invention becomes like this. Preferably it is 5,000 or more, More preferably, it is 10,000 or more, Preferably it is 1,000,000 or less, More preferably, it is 500,000 or less, More preferably, it is 300,000 or less. It is preferable from the viewpoint of the dispersibility with respect to the water of the copolymer when it is set as the cosmetic composition because the weight average molecular weight of a copolymer is below the said upper limit, and it is preferable from the viewpoint of making a copolymer insoluble in water more than the said lower limit. However, when using a monomer (C), since a weight average molecular weight becomes high by forming a crosslinked structure normally, 10,000 or more are preferable, 20,000 or more are more preferable, 50,000 or more are more preferable, and 10,000,000 or less Preferably, 5,000,000 or less are more preferable.

Moreover, when using the monomer (E) mentioned later, Preferably it is 5,000 or more, More preferably, it is 10,000 or more, Preferably it is 2,000,000 or less, More preferably, it is 1,000,000 or less, More preferably, it is 500,000 or less, Especially preferable Preferably 300,000 or less.

The weight average molecular weight of a copolymer can be measured by various conventionally well-known methods, such as gel permeation chromatography (for example, using tetrahydrofuran as a developing solvent) and the light scattering method.

The molecular weight distribution [Mw / Mn] represented by the weight average molecular weight / number average molecular weight of the copolymer of the present invention is usually 1.0 or more, preferably 1.5 or more, preferably 5.0 or less, more preferably 3.0 or less, further Preferably it is 2.5 or less.

<Structural unit which comprises a copolymer>

Hereinafter, the structural unit which comprises the copolymer of this invention is explained in full detail.

The copolymer of this invention is represented by the vinyl monomer (vinyl monomer represented by General formula (1)), the alkyl (meth) acrylate monomer, and / or (meth) acrylamide (General formula (2)) which have a polyoxyalkylene group It has a structure corresponding to the copolymer of the monomer mixture containing a vinyl monomer). That is, it is a copolymer containing the structural unit corresponded to the vinyl monomer (A) represented by the said General formula (1), and the structural unit corresponded to the vinyl monomer (B) represented by the said General formula (2).

Here, the copolymer of this invention is not limited to the copolymer obtained by copolymerizing the monomer mixture containing the vinyl monomer (A) represented by General formula (1), and the vinyl monomer (B) represented by General formula (2). If it has a structural unit equivalent to this, the raw material and a manufacturing method are not restrict | limited.

<Structural Unit Corresponding to Vinyl Monomer (A)>

It will not specifically limit, if it is a monomer represented by following General formula (1) as a vinyl monomer (A) (Hereinafter, it may be called "monomer (A).") Represented by General formula (1).

[Chemical Formula 18]

(In General Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² Represents an alkylene group having 2 to 4 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents the integer satisfying 15-50.)

R ¹ in General Formula (1) is a hydrogen atom or a methyl group.

R ² in General Formula (1) Is a C2-C4 alkylene group, Preferably it is an ethylene group and a propylene group. In addition, there are a plurality of R ^{2 in} one molecule May be the same or different, preferably the same.

R <^3> in General formula (1) is a hydrogen atom or a C1-C3 alkyl group, Preferably it is a hydrogen atom or a methyl group.

M in General formula (1) is an integer of 15-50. M is 15 or more, Preferably it is 20 or more from the point which ensures the hydrophilicity of a copolymer and obtains sufficient crystallinity. On the other hand, since the monomer residual amount after a polymerization reaction is small and it is easy to acquire in industrial grade, m is 50 or less, Preferably it is 40 or less, More preferably, it is 30 or less.

Specifically as a monomer (A), a methoxy polyoxyethylene (meth) acrylate, a polyoxyethylene (meth) acrylate, a methoxy polyoxyethylene / polyoxypropylene (meth) acrylate is mentioned, for example. have. Among these, for reasons of hydrophilic strength and crystallinity, methoxypolyoxyethylene (23 mol) (meth) acrylate, methoxypolyoxyethylene (40 mol) (meth) acrylate, polyoxyethylene (23 mol) (meth Acrylate and polyoxyethylene (40 mol) (meth) acrylate are preferable (the number of moles in parentheses represents the value of m in the general formula (1).).

The structural unit equivalent to a monomer (A) acts as a part which has hydrophilicity in a copolymer, When a copolymer is disperse | distributed to an aqueous solvent, it forms microparticles | fine-particles, exists in the outer side of the microparticles | fine-particles containing a copolymer, and is used for cosmetics It is thought to have the function of improving the stability of the composition. In addition, the detail of a "fine particle" is mentioned later.

Moreover, it is inferred that adhesiveness is expressed after hair application in the composition for cosmetics containing the copolymer of this invention by the crystallinity of the polyoxyalkylene group which the structural unit corresponded to a monomer (A) has.

The copolymer of the present invention may include a structural unit corresponding to one type of monomer (A), or may include a structural unit corresponding to two or more types of monomers (A).

In the copolymer of the present invention, the content of the structural unit corresponding to the monomer (A) is preferably 30% by weight or more, more preferably 35% by weight or more, and preferably 80% by weight or less. It is more preferable that it is 70 weight% or less. If the content of the structural unit corresponding to the monomer (A) is equal to or greater than the lower limit, since the copolymer has suitable hydrophilicity, it is easy to disperse it in an aqueous solvent. It is preferable because of that.

<Structural Unit Corresponding to Vinyl Monomer (B)>

It will not specifically limit, if it is a monomer represented by following General formula (2) as a vinyl monomer (B) represented by General formula (2) (Hereinafter, it may be called "monomer (B).").

[Chemical Formula 19]

(In formula (2), R ⁴ Represents a hydrogen atom or a methyl group, R ⁵ Represents an alkyl group having 2 to 10 carbon atoms. p and q represent an integer of 0 or 1, respectively, and p + q = 1.)

R ⁴ in General Formula (2) Is a hydrogen atom or a methyl group.

R ⁵ in General Formula (2) Is a C2-C10 linear, branched or cyclic alkyl group, Preferably it is a C4-C8 linear or branched alkyl group, More preferably, it is a C4-C4 linear or branched alkyl group.

P and q in General formula (2) represent the integer of 0 or 1, respectively, and p + q = 1. Preferably p = 1 and q = 0.

Specifically as a monomer (B), For example, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acryl Rate, pentyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, ethyl (meth) acrylamide, propyl (meth) acrylamide, n-butyl (meth) acrylamide, isobutyl (Meth) acrylamide, t-butyl (meth) acrylamide, pentyl (meth) acrylamide, cyclohexyl (meth) acrylamide, ethylhexyl (meth) acrylamide, etc. are mentioned. Among these, it is preferable that monomer (B) contains n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate in the balance of the overall texture.

The copolymer of the present invention may include a structural unit corresponding to one type of monomer (B), or may include a structural unit corresponding to two or more types of monomers (B).

The structural unit corresponding to the monomer (B) has an effect of imparting hydrophobicity to the copolymer corresponding to an alkyl group having 2 to 10 carbon atoms for R ⁵ , and when the copolymer is dispersed in a continuous phase containing water, the copolymer Has the effect of promoting the formation of fine particles.

In the case where the structural unit corresponding to the monomer (B) is low in compatibility with the structural unit corresponding to the monomer (A) having high hydrophilicity in the residue obtained by drying a copolymer such as a coating, etc., phase separation occurs. There is. In this invention, a film strength becomes high by the phase of the structural unit corresponded to this phase-separated monomer (B), maintains the hairstyling power derived from the adhesive which generate | occur | produces with the structural unit corresponded to monomer (A), and has high setability and the It seems to be a factor of holding power. In this mechanism, it is inferred that the surface contaminated with sebum or the like can be renewed by applying pressure, thereby enabling it to function repeatedly and exerting recurrence.

In the copolymer of the present invention, the content of the structural unit corresponding to the monomer (B) is preferably 20% by weight or more, more preferably 22% by weight or more, and preferably 70% by weight or less of the entire copolymer. It is more preferable that it is 65 weight% or less. When content of the structural unit corresponding to a monomer (B) is more than the said lower limit and below an upper limit, since a copolymer has moderate hydrophilicity, maintaining water resistance, since it becomes easy to disperse | distribute to an aqueous solvent, it is preferable.

In the copolymer of the present invention, the monomer (A) in the copolymer is obtained from the viewpoint of obtaining a water-insoluble copolymer by containing a structural unit corresponding to the monomer (A) and a structural unit corresponding to the monomer (B). 22 to 60 parts by weight of the structural unit corresponding to the monomer (A) and the structural unit corresponding to the monomer (B) are contained in 100 parts by weight of the total of the structural unit corresponding to the monomer and the monomer (B). It is preferable to include 65 parts by weight.

<Structural unit equivalent to a crosslinkable vinyl monomer (C)>

The copolymer of this invention corresponds to a crosslinkable vinyl monomer (C) (henceforth a "monomer (C)") in addition to the structural unit corresponded to the said monomer (A) and (B). It is preferable to include a structural unit.

The monomer (C) is not particularly limited as long as it can introduce a crosslinked structure into the copolymer of the present invention, but is preferably represented by the following General Formula (3) or the following General Formula (4).

The crosslinkable monomer (C) forms a crosslinked structure with the hydrophobic portion of the copolymer of the present invention. Therefore, the cohesiveness of a hydrophobic group part becomes high, the fluidity | liquidity of a copolymer is suppressed and the intensity | strength of a copolymer improves. As a result, especially among the evaluation items in the Example mentioned later, "a feeling of grooming maintenance of a head" can be improved.

[Chemical Formula 20]

(In formula (3), R ⁶ Represents a hydrogen atom or a methyl group. Q ¹ represents a linking group represented by -CH ₂ -or the following General Formula (5), and Q ¹ Is -CH ₂ - if, s represents an integer which satisfies the range of 0 to 50. In addition, Q ¹ In the case of the linking group shown by following General formula (5), s represents the integer of 0 or 1. Q ² Represents an alkylene group having 1 to 6 carbon atoms, and t represents an integer that satisfies 0 to 50. However, s and t shall be either 0.)

[Chemical Formula 21]

(In formula (5), R ⁷ Represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, u represents an integer of 0 or 1, and v represents an integer satisfying 1 to 100.)

[Chemical Formula 22]

(In formula (4), R ⁸ Represents an alkylene group having 2 to 4 carbon atoms, R ⁹ Represents a hydrogen atom or a methyl group, w represents an integer that satisfies 0 to 100, R ¹⁰ and R ¹¹ Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or a substituent represented by the following general formula (6), respectively.)

(23)

(In formula (6), R ¹² Represents an alkylene group having 2 to 4 carbon atoms, R ¹³ Represents a hydrogen atom or a methyl group, x represents an integer of 0 or 1, and y represents an integer satisfying 0 to 100.)

R ⁶ in General Formula (3) Is a hydrogen atom or a methyl group.

Q ¹ Represents -CH ₂ -or a linking group represented by the general formula (5), but Q ¹ It is -CH ₂ - if, s is an integer which satisfies the range of 0 to 50, preferably an integer that satisfies 0 to 30. Q ¹ In the case of the coupling group represented by the said General formula (5), s represents 0 or 1.

Q ² Is a C1-C6 alkylene group, Preferably it is a C2-C4 alkylene group, More preferably, it is a C2-C3 alkylene group.

t is an integer which satisfies 0-50. However, one of s and t shall be 0.

In General Formula (5), R ⁷ Silver represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, preferably an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and u represents 0 or 1. v represents the integer satisfying 1-100, Preferably v represents the integer satisfying 1-50.

In formula (4), R ⁸ Represents a C2-C4 alkylene group, Preferably it is a C2-C3 alkylene group. R ⁹ Represents a hydrogen atom or a methyl group. w represents the integer which satisfy | fills 0-100, Preferably it is an integer which satisfy | fills 0-50.

In formula (4), R ¹⁰ and R ¹¹ Are each a substituent represented by the group, or the formula (6) of 1 to 6 carbon atoms which may have a hydrogen atom, a hydroxyl group, a hydroxyl group, preferably R ¹⁰ and R ¹¹ Either is a substituent represented by General formula (6), and represents the C1-C6 alkyl group or hydroxyl group which the other may have a hydroxyl group. In the formula (6), R ¹² Is a C2-C4 alkylene group, Preferably it is a C2-C3 alkylene group. R ¹³ Represents a hydrogen atom or a methyl group, and x represents an integer of 0 or 1. y represents the integer which satisfy | fills 0-100, Preferably it is an integer which satisfy | fills 0-50.

As a monomer (C), bifunctional vinylic monomers and polyfunctional vinylic monomers are mentioned, for example.

Specific examples of the difunctional vinyl monomers include di (meth) acrylate of polyoxyalkylene glycol, di (meth) acrylate of alkanediol, dimethacryloyloxyalkyldimethyl silicone, and the like. .

Examples of the polyfunctional vinyl monomers include di, tri or tetra (meth) acrylates of trimethylolpropane and glycerin derivatives, di, tri, tetra, penta, hexa (meth) acrylates of pentaerythritol derivatives, and the like. Or di, tri (meth) acrylate of an isocyanuric acid derivative. Examples of the trimethylolpropane and glycerin derivatives include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and polyoxyethylene-added glycerin tri (meth) acrylate. Moreover, as a pentaerythritol derivative, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate, etc. are mentioned. Moreover, as an isocyanuric acid derivative, an ethoxylated isocyanuric acid triacrylate etc. are mentioned.

Among these, more hydrophobic is preferable. Moreover, ethylene glycol di (meth) acrylate, polyethylene glycol (2-3 mol) di (meth) acrylate, dimethacryloyloxypropyl dimethyl silicone (functional group equivalent 100-5000), trimethylol propane tri (meth) Acrylate, pentaerythritol triacrylate, etc. are especially preferable.

The copolymer of the present invention may include a structural unit corresponding to one type of monomer (C) or may include a structural unit corresponding to two or more types of monomers (C).

In the copolymer of the present invention, the content of the structural unit corresponding to the monomer (C) is preferably from 0.1 to 10% by weight of the whole, more preferably from 0.2 to 5% by weight. If the content of the structural unit corresponding to the monomer (C) is equal to or greater than the lower limit, a good feeling of grooming holding of the hair is obtained, and if it is equal to or less than the upper limit, the "initial hairstyling property" evaluated in Examples described later becomes good.

<Structural Unit Corresponding to Vinyl Monomer (D)>

In addition to the structural units corresponded to the said monomers (A) and (B), the copolymer of this invention may have a vinyl monomer (D) which has a C12-C22 alkyl group (henceforth "monomer (D)". It is preferable to include the structural unit equivalent to.). By including the structural unit equivalent to a monomer (D), hydrophobicity of a hydrophobic group part becomes high, the phase separation of a polyoxyalkylene part is promoted, and as a result, an endothermic amount becomes large. As carbon number of the alkyl group which a monomer (D) has, it is especially preferable that it is 16-20.

As a vinyl monomer (D) which has a C12-C22 alkyl group, stearyl (meth) acrylate, behenyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, etc. are mentioned, for example. Can be mentioned.

The copolymer of the present invention may include a structural unit corresponding to one type of monomer (D) or may include a structural unit corresponding to two or more types of monomers (D).

In the copolymer of the present invention, the content of the structural unit corresponding to the monomer (D) is preferably 0 to 40% by weight of the whole, more preferably 5 to 35% by weight, particularly preferably 10 to 30% by weight. to be. When content of the structural unit corresponded to a monomer (D) is more than the said lower limit, it is preferable from a viewpoint of the compoundability with respect to water when a copolymer is used as a composition for cosmetics, and if it is below the said upper limit, a copolymer is hydrophobic structure. Since the adhesiveness at the time of setting it as a cosmetic composition improves by setting it as it is, it is preferable.

<Structural unit equivalent to a vinyl monomer (E)>

The copolymer of this invention is further a structural unit corresponded to the vinyl monomer (E) (henceforth a "monomer (E)") represented by at least one of following General formula (7) and General formula (8). It is preferable to have.

The monomer (E) is a vinyl monomer having a highly polar functional group containing a nitrogen atom, and includes a structural unit corresponding to the monomer (E), so that the copolymer of the present invention and the hair containing a lot of amide groups and the like. It is inferred that interfacial interaction can be improved, and this interaction can realize a high sense of organization even in a place where there is much movement among hairs such as the hair.

&Lt; EMI ID =

(In formula (7), R ¹⁴ Represents a hydrogen atom or a methyl group, R ¹⁵ and R ¹⁶ Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

(25)

(In formula (8), R ¹⁷ Represents a hydrogen atom or a methyl group. r is 0 or 1, and z is an integer which satisfy | fills 1-4. X represents either of the following General Formulas (9) to (11).)

(26)

(In General Formulas (9) to (11), R ¹⁸ and R ^19. Each independently represents an alkyl group having 1 to 4 carbon atoms, and R ²⁰ in General Formula (10) Represents an alkyl group having 1 to 4 carbon atoms or-(CH ₂ ) _k -COO- (k is an integer of 1 to 4) and its salt. On the manufacturing side, k is preferably 1).

In formula (7), R ¹⁵ and R ¹⁶ Each independently is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, R ¹⁵ With R ¹⁶ It is preferable that it is especially the same alkyl group.

In General formula (8), it is preferable that r is 1, and it is preferable that z is 1-6. R ¹⁸ And R ¹⁹ Is preferably the same alkyl group.

Specifically as a vinyl monomer represented by General formula (7) in a monomer (E), it is N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N, for example. -Diisopropyl (meth) acrylamide, (meth) acrylamide, and the like, and preferred examples thereof include N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide. As a more preferable example, N, N-dimethyl (meth) acrylamide is mentioned.

In addition, specifically, as a vinyl monomer represented by General formula (8) in a monomer (E), it is N, N- dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acryl, for example. 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-diethylaminopropyl (meth) acrylamide, these amphoterics, or these amine oxides, etc. are mentioned. have.

Among these monomers (E), the monomer (E) is N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, in the balance of the overall texture when used as a hair cosmetic. N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, or amphoterics thereof, or amine oxides thereof, N, N-dimethylacrylamide, N, N- It is preferable to contain diethylacrylamide and methacrylamide.

The copolymer of this invention may include the structural unit corresponded to one type of monomer (E), and may include the structural unit corresponded to two or more types of monomers (E).

In the copolymer of the present invention, the content of the structural unit corresponding to the monomer (E) is preferably from 0 to 30% by weight, more preferably from 0.1 to 30% by weight, still more preferably from 1 to 25% by weight. % to be. When content of the structural unit corresponded to a monomer (E) is more than the said lower limit and below an upper limit, since the removability of the copolymer of this invention can be maintained, it is preferable.

<Structural unit equivalent to other monomers>

In the copolymer of this invention, in the range which does not impair the effect of this invention, the structure corresponded to vinyl monomers (Hereinafter, it may be called "monomer (F).") Other than the above-mentioned monomer. You may contain a unit.

As a monomer (F), For example, Monoester with ethylene glycol, 1, 3- propylene glycol, etc. (meth) acrylic acid; Furthermore, ester in which the hydroxyl group of this monoester was etherified with methanol, ethanol, etc .; Nonionic monomers such as (meth) acryloyl morpholine, hydroxymethyl acrylamide and hydroxyethyl acrylamide; Anionic monomers such as acrylic acid and methacrylic acid; N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride, N- [3- ｛N '-(meth) acryloyloxyethyl-N', N'-diethylammonium｝- (Meth) acrylic acid esters having cationic groups such as 2-hydroxypropyl] -N, N, N-triethylammonium chloride; N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride, N- [3- ｛N '-(meth) acryloylaminopropyl-N', N'-diethylammonium｝- (Meth) acrylamides having cationic groups such as 2-hydroxypropyl] -N, N, N-trimethylammonium chloride; Diallyl quaternary ammonium salts such as N, N-dimethyl-N, N-diallyl ammonium chloride; Amino acid-based cationic monomers such as a reaction product of L-arginine and glycidyl methacrylate; Alkyl ethers of vinyl acetate, vinyl alcohol and vinyl alcohol; Styrene, alpha-alkylstyrene, butadiene, isoprene, propene, vinyl chloride, acrylonitrile, polyfunctional (meth) acrylate, and the like.

The copolymer of the present invention may include a structural unit corresponding to one type of monomer (F), or may include a structural unit corresponding to two or more types of monomers (F).

In the copolymer of the present invention, the content of the structural unit corresponding to the monomer (F) is preferably 0 to 30% by weight of the whole, more preferably 0 to 25% by weight.

<Bridging rate>

The copolymer of this invention contains the structural unit corresponded to the monomer (C) mentioned above, and it is preferable that the crosslinking rate by this monomer (C) is 0.05 to 20%.

The crosslinking rate here refers to the ratio of the amount (mole) of the polymerizable double bond in the monomer (C) which is a crosslinking agent with respect to the total amount (mol) of injected monomers, and can be calculated | required by calculation from an injected amount.

When the crosslinking ratio of the copolymer is 0.05% or more, the film strength is increased, the feeling of organization of the hair is increased, and the stiffness at the time of setting can be suppressed by being 20% or less. It is preferable that especially the crosslinking rate of a copolymer is 0.1 to 10%, and it is especially preferable that it is 0.2 to 7.5%.

<Method for Producing Copolymer>

Although the manufacturing method of the copolymer of this invention is not restrict | limited, For example, it can manufacture by mixing the monomer which gives each structural unit or its precursor, and copolymerizing by methods, such as solution polymerization, suspension polymerization, and emulsion polymerization. Can be.

It is preferable to perform a polymerization reaction in the solvent containing at least one of water and a hydrophilic solvent. As a hydrophilic solvent, For example, 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, etc. are mentioned. These water and hydrophilic solvents may be used independently or may use 2 or more types together. Especially, it is preferable to use alcohol solvent, water, or a mixture thereof.

A polymerization initiator may be used for the polymerization reaction, and as the polymerization initiator, 2,2'-azobisisobutyronitrile and 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) -propionamide ), Dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy -2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutylate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (1- Cyclohexanecarbonitrile), 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) -propionamide), 2,2'-azobis (2-amidinopropane) dihydrochloride, etc. It can be used without particular limitation, such as peroxides, persulfates, or the redox system, such as an azo compound, a benzoyl peroxide, a dicumyl peroxide, di-t-butyl peroxide, a lauroyl peroxide.

It is preferable to use a polymerization initiator in 0.01-5 weight% with respect to all the monomers, and it is more preferable to use it in 0.1-3 weight%.

For example, polymerization reaction can be performed in inert gas atmosphere, such as nitrogen and argon, Preferably it is 30-120 degreeC, More preferably, it is 40 to 100 degreeC normally for 1 to 30 hours. After completion of the polymerization, the produced copolymer may be isolated from the reaction solution by appropriate means such as solvent distillation removal and addition of a poor solvent. The obtained copolymer can be used as it is or after further purification to produce a cosmetic composition of the present invention. Purification can be performed by selecting suitably well-known means, such as reprecipitation, solvent washing, membrane separation, etc. as needed and combining them.

As a copolymer of this invention, it can be set as arbitrary structures, such as a random copolymer, a block copolymer, and a graft copolymer, and it is not specifically limited.

A random copolymer can be synthesize | combined by the method of making it react by adding an initiator in the state which mixed all the monomers used for superposition | polymerization at once, or making it react slowly, dropping a part or whole quantity of monomer. It can also superpose | polymerize by dripped, changing a monomer composition. A block copolymer can be synthesize | combined using a well-known radical initiator, a catalyst, etc. The graft copolymer can be synthesized by a method using a macromer having a vinyl-based functional group, a method of reacting polymers having a reactive functional group with each other, and the like.

Among them, it is preferable to be able to synthesize a low cost raw material without requiring a special process because of the high industrial utilization value, and a random copolymer which can be most easily produced using a conventional raw material is most preferred.

In particular, the copolymer of the present invention comprising a structural unit corresponding to the monomer (C) is firstly air containing the structural unit corresponding to the monomer (A) and the structural unit corresponding to the monomer (B) by the above-described method. The copolymer is prepared from a solvent in which the resin is soluble, and the copolymer (hereinafter, referred to as "copolymer (A) / (B)") is dispersed in a continuous phase containing water, followed by monomer (C ) By adding and copolymerizing to obtain an aqueous dispersion containing fine particles, or after the monomer (C) is sufficiently dissolved in a solution of the copolymer (A) / (B), water is added and dispersed to contain fine particles. It is preferable to obtain an aqueous dispersion. In addition, when using what is represented by General formula (3) as monomer (C), and represented by General formula (5) as Q <^1> in General formula (3), it melt | dissolves in the copolymer (A) / (B) solution. Since it can manufacture more easily by using the method by adding and disperse | distributing after making it carry out, it is preferable. By this method, it is preferable to obtain the aqueous dispersion in which the microparticles | fine-particles containing the copolymer of this invention are disperse | distributed to volume average particle diameters 10-500 nm preferably in a continuous phase containing water.

Here, as a medium other than water of the dispersion medium containing 30 weight% or more of water, 1 type, or 2 or more types of what was illustrated as a hydrophilic solvent used for manufacture of a copolymer are mentioned, The water content of this dispersion medium is More preferably, it is 40-100 weight% or more.

In addition, the suitable range of the water content and volume average particle diameter in the aqueous dispersion obtained in this way is as mentioned later.

2. Cosmetic composition

Since the copolymer of the present invention has high setability and resetting property, and has a wide degree of freedom of a wide range of formulations, it can be used as a cosmetic composition containing this in a wide continuous phase from aqueous to oil-based. Especially, it is especially preferable to set it as the composition for cosmetics in which the microparticles | fine-particles containing the copolymer of this invention are disperse | distributed to the continuous phase containing 30 weight% or more of water.

The microparticles | fine-particles here are microparticles formed by the cohesion force of the hydrophobic group part in a copolymer by 1 or more molecules of copolymer molecules with respect to the continuous phase containing 30 weight% or more of water, Especially about the shape, such as spherical shape and block shape, Regardless. The microparticles | fine-particles should just mainly contain the copolymer of this invention, 1 type of copolymers may be sufficient, or may use 2 or more types of copolymers together.

Moreover, the microparticles | fine-particles containing the copolymer of this invention may contain 1 type, or 2 or more types of polymers other than the copolymer of this invention in the range which does not impair the effect of this invention. As such a polymer, for example, polyacrylic acid, partially hydrophobized polyacrylic acid (copolymer of acrylic acid and vinyl monomer and / or (alkoxy) polyalkylene glycol methacrylate, etc.), acrylic acid and / or vinyl monomer Resin for sets, such as a copolymer of these, etc. are mentioned. As these content in microparticles | fine-particles, it is preferable that it is 0-10 weight% with respect to the whole.

It does not specifically limit about the manufacturing method of microparticles | fine-particles, For example, the method which melt | dissolves in a good solvent and adds to a poor solvent, precipitates, avoiding aggregation, the method by self-emulsification with a solvent, the method using a dispersing machine, etc. Etc. can be mentioned.

It is preferable that the volume average particle diameter measured by the dynamic light scattering method of the microparticles | fine-particles disperse | distributed in a continuous phase is 10-500 nm. As for a volume average particle diameter, it is more preferable that it is 15 nm or more. Moreover, it is more preferable that it is 200 nm or less, It is further more preferable that it is 150 nm or less, It is especially preferable that it is 100 nm or less. If a volume average particle diameter is more than the said lower limit, the effect of setability etc. is excellent, and if it is below the said upper limit, it is preferable because it is excellent in the effects, such as resetting property. This volume average particle diameter can be adjusted by changing the length and quantity of the polyoxyalkylene group in a vinyl monomer (A), and the height and quantity of hydrophobicity of the structural unit (vinyl monomer) which comprises a copolymer.

The amount of water in the continuous phase of the cosmetic composition is preferably 30% by weight or more, more preferably 40% by weight or more. If the amount of water is more than this, the fine particles are likely to be formed without dissolving the copolymer, and therefore, there is a tendency for excellent hair-setting effects such as setability and resetting property. The amount of water in the continuous phase may be 100% by weight. As components other than water in a continuous phase, 1 type, or 2 or more types of what was illustrated as a hydrophilic solvent used for manufacture of a copolymer is mentioned.

Although there is no restriction | limiting in particular in the quantity of the copolymer of this invention contained in the cosmetic composition of this invention, It is preferable that it is 0.1-20 weight%, especially 0.5-15 weight%. Hairstyling property is expressed when content of the copolymer of this invention in a composition for cosmetics is more than the said lower limit, and excess stickiness is reduced by being below the said upper limit.

In addition to the copolymer of this invention, the component which can be normally mix | blended with the cosmetic composition can be arbitrarily added to the composition for cosmetics of this invention, unless the effect is impaired.

The other component contained in a cosmetic composition is not specifically limited, It is possible to mix | blend in the range which does not impair the objective and effect of this invention. As such a component, the following can be mentioned, The composition for cosmetics can be manufactured by mix | blending the following component suitably.

Other arbitrary components which can be mix | blended in a cosmetic composition are explained in full detail below. However, each component described below is "1. The copolymer of this invention described in "copolymer" shall not be included.

<Polymer>

As a water-soluble polymer, methyl cellulose, hydroxymethyl cellulose, etc. are mentioned, for example.

Examples of the cationic polymer include a cation-modified cellulose ether derivative, a cation-modified galactomannan polysaccharide, a polydimethyldiallylammonium halide, a copolymer of dimethyldiallylammonium halide and acrylamide, and the like.

Examples of the anionic polymer include acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid acrylamide and ethyl acrylate copolymers and salts thereof, acrylic acid / alkyl acrylate esters / steares 20 methacrylate copolymers and salts thereof, and the like) Acid derivatives, crotonic acid derivatives, and the like.

Examples of the nonionic polymer include acrylic acid derivatives (hydroxyethyl acrylate, methoxyethyl acrylate, polyacrylamide, and the like), vinylpyrrolidone derivatives (polyvinylpyrrolidone, vinylpyrrolidone, vinyl acetate copolymer, and the like). Can be mentioned.

Examples of the amphoteric polymer include dimethyl diallyl ammonium chloride derivatives (acrylamide acrylic acid dimethyl diallyl ammonium copolymer and acrylic acid dimethyl diallyl ammonium copolymer).

It is preferable to contain these 1 type, or 2 or more types of these polymers in 0.1 to 10 weight% in a cosmetic composition, and it is further more preferable to contain 0.5 to 5 weight%. Moreover, among these polymers, when using the cosmetic composition of this invention as a hair cosmetic, using together "the resin for hair sets" used for hairdressing is especially preferable from a viewpoint of the improvement of initial stage hairstyling property.

As resin for hair | bristle sets, the following resin is preferable.

As a cationic polymer, vinylpyrrolidone methacrylate dimethylaminoethyl copolymer diethyl sulfate, vinylpyrrolidone dimethylaminopropyl methacrylamide, lauryl dimethylaminopropyl methacrylamide copolymer, and vinylpyrrolidone Methacrylic acid N, N-dimethylaminoethyl alkyl acrylate, diacrylate tripropylene glycol copolymer, dimethyl methylene piperidinium chloride, dimethyl diallyl ammonium acrylamide copolymer, trimethylaminopropyl acrylamide dimethylacryl chloride Amide copolymer etc. are mentioned.

Examples of the anionic polymer include alkyl acrylate diacetone acrylamide copolymers, alkyl acrylate octyl acrylamide copolymers, polyethylene glycol polypropylene glycol-25 dimethicone acrylate copolymers, acrylic acid amide acrylate and ethyl acrylate copolymers. And alkyl acrylate copolymers.

As a nonionic polymer, For example, polyvinylpyrrolidone, a vinylpyrrolidone vinyl acetate copolymer, a vinyl methyl ether, maleic acid copolymer, a vinylpyrrolidone methacrylamide vinylimidazole air Copolymer, silicone / polyether-based polyurethane resin, and the like.

As the amphoteric polymer, octylic acid acrylate, hydroxypropylpropyl acrylate, butyl aminoethyl methacrylate, methacryloyloxyethylcarboxybetaine, alkyl methacrylate copolymer, dimethyldiallylammonium ammonium acrylate copolymer And dimethyl diallyl ammonium chloride acrylamide acrylic acid copolymer.

<Surfactant>

As the amphoteric surfactant, for example, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide Imidazoline-based amphoteric surfactants such as -1-carboxyethyloxysodium salt; 1 such as betaine-based surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amide betaine and sulfobetaine Or 2 or more types can be mentioned.

As an anionic surfactant, (alpha)-olefin sulfonate, a higher alcohol sulfate ester salt, a polyoxyethylene alkyl ether sulfate ester salt, a paraffin sulfonate salt, a polyoxyethylene alkyl ether carboxylic acid ester salt, an alkyl sulfosuccinate salt, N-acyl What is commonly used for cosmetic compositions, such as-(beta)-alanine salt, N-acyl glutamate, and acyl methyl taurine salt, is mentioned. As counter ion of these anionic surfactant, 1 type (s) or 2 or more types, such as sodium, potassium, ammonium, triethanolamine, and diethanolamine, are mentioned.

As the hydrophilic nonionic surfactant, for example, polyoxyethylene (hereinafter sometimes abbreviated as POE) sorbitan fatty acid esters (for example, POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan) Monooleate, POE sorbitan tetraoleate, etc.); POE sorbitol fatty acid esters (for example, POE sorbitol monolaurate, POE sorbitol monooleate, POE sorbitol pentaoleate, POE sorbitol monostearate, etc.); POE glycerin fatty acid esters (for example, POE glycerol monostearate, POE glycerol monoisostearate, POE glycerol triisostearate, etc.); POE fatty acid esters (for example, POE distearate, POE monodioleate, ethylene glycol distearate, etc.); POE alkyl ethers (for example, POE lauryl ether, POE oleyl ether, POE stearyl ether, POE- behenyl ether, POE-2-octyldodecyl ether, POE cholestanol ether, etc.); Pluronic molds (e. G., Pluronic and the like); POE polyoxypropylene (hereinafter abbreviated as POP) Alkyl ethers (for example, POE PPO cetyl ether, POE PPO 2-decyl tetradecyl ether, POE PPO monobutyl ether, POE PPO hydrogen Added lanolin, POE-POP glycerin ether, etc.); Tetra POE-tetra POP ethylenediamine condensation products (for example, tetronic etc.); POE castor oil-cured castor oil derivatives (e.g., POE castor oil, POE-cured castor oil, POE-cured castor oil monoisostearate, POE-cured castor oil triisostearate, POE-cured castor oil monopyroglutamic acid monoisostearic acid Ester, POE hardened castor oil maleic acid, etc.); POE beeswax lanolin derivatives (for example, POE sorbet beeswax etc.); Alkanolamides (for example, palm oil fatty acid diethanolamide, lauric monoethanolamide, fatty acid isopropanolamide, etc.); POE propylene glycol fatty acid ester; POE alkylamine; POE fatty acid amides; Sucrose fatty acid ester; Alkyl ethoxy dimethylamine oxide; 1 type, or 2 or more types, such as a trioleyl phosphate, are mentioned.

Examples of cationic surfactants include alkyltrimethylammonium salts (e.g., stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, and the like), alkylpyridinium salts (e.g., cetylpyridinium chloride and the like), and distearyldimethylammonium chloride. Dialkyl dimethyl ammonium salts, poly (N, N'-dimethyl-3,5-methylene piperidinium), alkyl quaternary ammonium salts, alkyl dimethylbenzyl ammonium salts, alkyl isoquinolinium salts, dialkyl mol morpholinium salts, and the like, 1 type (s) or 2 or more types, such as a POE alkylamine, an alkylamine salt, a polyamine fatty acid derivative, an amyl alcohol fatty acid derivative, benzalkonium chloride, and benzetonium chloride, is mentioned.

As lipophilic nonionic surfactant, for example, sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan mono) Stearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexyl diglycerol sorbitan, tetra-2-ethylhexyl diglycerol sorbitan and the like); Glycerin polyglycerol fatty acids (for example, monosilicone oil fatty acid glycerin, monoercaic acid glycerin, sesquioleic acid glycerin, glycerin monostearate, glycerin α, α'-oleic acid pyroglutamic acid, glycerin monostearate, etc.); Propylene glycol fatty acid esters (for example, propylene glycol monostearate, etc.); Cured castor oil derivatives; 1 type, or 2 or more types, such as glycerin alkyl ether, is mentioned.

These surfactant can contain 1 type, or 2 or more types in the ratio of 5.0 weight% or less in a cosmetic composition.

<Oil>

As the oil, a chain polysiloxane (dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxane (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.), and a three-dimensional network structure are formed. Silicone resin, silicone rubber, various modified silicone (alkyl modified silicone, phenyl modified silicone, amino modified silicone, polyether modified silicone, fluorine modified silicone, etc.), linear alcohol (lauryl alcohol, cetyl alcohol, stearyl alcohol, Heyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.), branched chain alcohol (monostearyl glycerin ether (batyl alcohol), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol , Isostearyl alcohol, octyldodecanol, etc., hydrocarbon-based (fluid paraffin, squaw Alan, petrolatum, microcrystalline wax), ester oil (jojoba oil, carnauba wax, octyldodecyl oleate), triglyceride oil (olive oil, tallow oil, palm oil), fatty acids (stearic acid, oleic acid, ricinolic acid) 1 type, or 2 or more types, such as these, can be mentioned.

It is preferable that oil component contains 0.1-20 weight% of the 1 type, or 2 or more types in the cosmetic composition.

<Polyhydric alcohols, sugars>

Examples of the polyhydric alcohols include ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, glycerin, diglycerine, and isoprene glycol. Examples of the saccharide include sorbitol, multitol, xylitol, glucose, fructose, mannitol, inositol and the like.

It is preferable to contain 0.1-20 weight% of polyhydric alcohols and / or saccharides in 1 type, or 2 or more types in a cosmetic composition. Moreover, it is especially preferable from a viewpoint of hair dressing to use polyhydric alcohol and / or sugar together with the copolymer of this invention.

&Lt; Other components &gt;

Other components include natural extracts and derivatives of animals and plants, organic acids such as citric acid and lactic acid, inorganic salts such as sodium chloride, amino acids (glutamic acid or salts thereof, arginine or salts thereof, glycine, etc.), solubilizers (ethanol, isopropanol, butanol) Polyhydric alcohols (ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, isoprene glycol, etc.), sugars (sorbitol, multitol, xylitol, etc.) , Glucose, fructose, mannitol, inositol, etc.), polymers such as hyaluronic acid, antioxidants, ultraviolet absorbers, fungicides, preservatives, chelating agents, flavoring agents, colorants, higher fatty acids, thickeners, metal sequestrants (edetates, etc.) ), a pH adjuster, a bubble enhancer, etc. can be suitably blended in the range which does not impair the effect of this invention.

[Combination Example] Below, a blending example of a cosmetic composition using the copolymer of the present invention is shown.

<Formulation Example 1: Hair Lotion>

4 wt% of the copolymer of the present invention

Glycerin 5 wt%

(Acrylate / stearyl acrylate /

Ethyl methacrylate copolymer) ^{* 1} 1% by weight

Ethanol 4 wt%

Fragrance

Other regulators

Water balance

(* 1: For example, Mitsubishi Chemical Corporation "Diaformer Z632")

<Formulation Example 2: Hair Mist>

4 wt% of the copolymer of the present invention

Glycerin 5 wt%

(Acrylate / stearyl acrylate /

Ethyl methacrylate copolymer) ^{* 2} 1 wt%

Polyquaternium-73 ^{* 3} 0.5 wt%

Ethanol 4 wt%

Fragrance

Other regulators

water

(* 2: For example, Mitsubishi Chemical Corporation "Diaformer Z772")

(* 3: Mitsubishi Chemical Corporation "Dia's Leak C802", for example)

3. Hair cosmetic

The composition for cosmetics of this invention is used for arbitrary cosmetics used for hair and skin. Such cosmetics include, for example, shampoos, rinses, conditioners, treatments, hair dyes, perms, outverse treatments, hair packs, hair waxes, hair sprays, hair foams, styling agents and the like, and hair shampoos. , Make cleansing, hand soap, latex, lotion, lotion, cream, essence, sunscreen, foundation, lipstick, mascara, eye shadow, hair loss and the like. Moreover, the use form can also include both the thing which wash | cleans (rinse) after applying to skin, hair, etc. and soaking well in the whole, and the thing which does not wash away.

The composition for cosmetics of this invention is especially suitable as a hair cosmetics containing this. As a hair cosmetic, it can take various forms, such as a lotion, mist, spray, emulsion, cream, and wax form, The hair cosmetics which mix | blended the cosmetic composition of this invention are excellent in initial setability, If it is distracted, free reorganization is possible.

The composition for cosmetics of this invention is especially preferable as a hair cosmetic which has a repositionable rehair property, suppressing stickiness of a hair, and it is especially preferable to use it as a hair wax among hair cosmetics.

Example

Although an aspect and a specific example are given to the specific aspect of this invention below, this invention is not limited to these Examples, unless the summary is exceeded.

`` Examples 1 to 10 and Comparative Examples 1 to 3 ''

[Production of Copolymer]

<Production of Copolymer (1-1)>

100 parts by weight of ethanol in a reactor equipped with a reflux cooler, a dropping funnel, a thermometer, a nitrogen gas introduction tube and a stirring device, and monomers other than the monomer (C) (ethylene glycol dimethacrylate) in the monomers shown in Table 1 49.5 parts by weight of oxypolyoxyethylene (23 mol) methacrylate, 25 parts by weight of t-butyl methacrylate and 25 parts by weight of stearyl methacrylate) were injected, and the reactor was nitrogen-substituted and heated to 84 ° C. 0.2 weight part of dimethyl-2,2'- azobis (2-methylpropionate) was thrown in to a reactor, and it stirred at 84 degreeC under heating for 3 hours. Thereafter, 300 parts by weight of water were added, and the reactor was stirred for 1 hour while maintaining the reactor at 84 ° C. Thereafter, 0.5 parts by weight of ethylene glycol dimethacrylate was dissolved in 4 parts by weight of ethanol and introduced into the reactor, followed by 0.3 parts by weight of dimethyl-2,2'-azobis (2-methylpropionate) into the reactor, It stirred for 3 hours. Further, 0.3 part by weight of dimethyl-2,2'-azobis (2-methylpropionate) was added to the reactor, followed by stirring for 3 hours to obtain a copolymer (1-1).

<Production of Copolymer (1-2) to Copolymer (1-5), Copolymer (1-8) to Copolymer (1-10)>

Except having used the monomer of Table 1 and Table 2, monomer (C) was post-added similarly to manufacture of copolymer (1-1), and copolymer (1-2)-copolymer (1-5) and a copolymer (1-8)-the copolymer (1-10) were prepared.

<Production of Copolymer (1-6)>

In a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introduction tube, and a stirring device, 100 parts by weight of ethanol and monomer (C) (dimethacryloyloxypropyldimethylsilicone (functional group) 39.5 parts by weight of monomers (methoxypolyoxyethylene (23 mol) methacrylate, 25 parts by weight of t-butyl methacrylate, 25 parts by weight of stearyl methacrylate, other than N, N-dimethylacrylamide) 10 parts by weight) was injected, and the reactor was nitrogen-substituted and heated to 84 ° C. 0.2 weight part of dimethyl-2,2'- azobis (2-methylpropionate) was thrown in to a reactor, and it stirred at 84 degreeC under heating for 3 hours. Thereafter, 0.5 parts by weight of dimethacryloyloxypropyldimethylsilicone (functional group equivalent 190) was dissolved in 4 parts by weight of ethanol, added to the reactor to be uniformly dissolved, and then 300 parts by weight of water was added to maintain the reactor at 84 ° C. While stirring for 1 hour. Thereafter, 0.3 part by weight of dimethyl-2,2'-azobis (2-methylpropionate) was added to the reactor, followed by stirring for 3 hours. Further, 0.3 part by weight of dimethyl-2,2'-azobis (2-methylpropionate) was added to the reactor and stirred for 3 hours to obtain a copolymer (1-6).

<Production of Copolymer (1-7)>

Except having used the monomer of Table 1, the monomer (C) was added before adding water similarly to manufacture of the copolymer (1-6), and the copolymer (1-7) was manufactured.

<Production of Copolymer (1-11)>

100 weight part of ethanol and the monomer shown in Table-2 were injected into the reactor equipped with the reflux cooler, the dropping funnel, the thermometer, the nitrogen gas introduction tube, and the stirring apparatus, and it heated to 84 degreeC after nitrogen-substituting the reactor. 0.2 weight part of dimethyl-2,2'- azobis (2-methylpropionate) was thrown in to a reactor, and it stirred at 84 degreeC under heating for 4 hours. Thereafter, 0.3 part by weight of dimethyl-2,2'-azobis (2-methylpropionate) was added to the reactor, and the operation of stirring for 4 hours was further performed twice to obtain a copolymer (1-11). .

<Production of Copolymer (1-12) and Copolymer (1-13)>

Except having used the monomer of Table 2, all the monomers were thrown in the same way as manufacture of copolymer (1-11), and the copolymer (1-12) was manufactured. Preparation of the copolymer (1-11) was carried out except that the monomers shown in Table 2 were used and the injection amount of dimethyl-2,2'-azobis (2-methylpropionate) as a polymerization initiator was 1.2 parts by weight. In the same manner as in the above, copolymer (1-13) was produced.

[Measurement of Copolymer Properties]

The following physical properties were measured about the copolymers (1-1) (1-13) obtained above, and the result was shown to Table 1 and Table 2.

<Endothermic starting point, endothermic amount>

Calorie measurement was performed using the Seiko Instruments company "DSC-7". 10 mg of sufficiently dried copolymer samples were placed in a sample cell and sealed, and in the following temperature cycle, the thermal behavior from the low temperature was measured and recorded at the second temperature rise, and the start temperature and endothermic amount of the endothermic peak were measured. .

Temperature cycle: room temperature → -100 ° C. (temperature drop at 50 ° C./min) → hold for 10 minutes at -100 ° C. → 100 ° C. (heat up at 10 ° C./min) → hold at 100 ° C. for 5 min → 100 ° C. (10 ° C. / Temperature lowering in minutes) → holding at -100 ° C for 5 minutes → 100 ° C (heating at 10 ° C / min)

<Water solubility>

9.9g of water was added with respect to 0.1g of copolymer samples fully dried, and it fully stirred with the stirrer. When the copolymer sample did not dissolve, heating (70 ° C. and 90 ° C.) and stirring, cooling, and stirring were repeated twice, and when dissolving further, ultrasonic treatment (ultrasound washer, 5 minutes) and stirring were performed. . After performing these operations, it cooled to less than 30 degreeC, and confirmed the insoluble matter which can be confirmed visually. In the absence of visible insoluble matters, the particle size distribution was measured by dynamic light scattering measurement using a nanotrack 150 manufactured by Microtrack, or by particle size distribution measurement using an ASVR manufactured by Microtrack. It measured and evaluated according to the following evaluation criteria.

○ (Soluble in water below 30 ° C): There is no insoluble matter visible to the sample.

× (insoluble in water below 30 ° C): Insoluble matter that can be visually observed in the sample

<Weight average molecular weight>

Gel permeation chromatography (apparatus: Tosoh Corporation make, SC8010, SD8022, RI8020, CO8011, PS8010, column: Tosoh Corporation TSK GEL G6600H, developing solvent: tetrahydrofuran, using polyethylene glycol as a reference material, weight average molecular weight Saved.

[Preparation of Cosmetic Composition]

About the copolymers (1-1) to (1-10), the copolymers (1-11) to (1-13) were further diluted by diluting the sample dispersed in water / ethanol shown in the preparation example of the copolymer with water. The composition for cosmetics of the composition shown in Table 3 was prepared by diluting to 20 weight% of solid content with ethanol, and then dripping slowly to stirring water in order to prevent aggregation.

[Evaluation of Cosmetic Composition]

The following evaluation was performed about the composition for cosmetics obtained above, and the result was shown in Table 4. In Table 4, the volume average particle diameter of the microparticles | fine-particles of the copolymer in each composition for cosmetics measured by the dynamic light scattering method using the nanotrack 150 by a microtrack company was written together.

<Initial hair dressing>

Five evaluation panelists test the use of the composition for cosmetics obtained by each Example and the comparative example, and evaluate the setability (initial hairdressing property) at the time of sample application to hair based on the following evaluation point criteria. did. Subsequently, the average score of the individual evaluation points was computed and evaluated based on the following evaluation criteria.

(Based on score)

5 points: very easy to set

4 points: easy to set

3 points: Normal

2 points: hard to set

1 point: very difficult to set

(Evaluation standard)

4: the average score is 4 or more points

3: Average score is 3 or more and less than 4 points

2: average score is 2 or more and less than 3 points

1: Average point is 1 or more and less than 2 points

<Financial recurrence>

Setability at the time of carrying out the test of the use of the cosmetic composition obtained by each evaluation panelist and the comparative example by the evaluation panelist of five, and hair-washing after 3 hours from sample application to hair, and setting again (refinability ) Was evaluated based on the following evaluation point criteria. Subsequently, the average score of the evaluation points which each ranked was computed and it evaluated based on the following evaluation criteria.

(Based on score)

5 points: very easy to set

4 points: easy to set

3 points: Normal

2 points: hard to set

1 point: very difficult to set

(Evaluation standard)

4: the average score is 4 or more points

3: Average score is 3 or more and less than 4 points

2: average score is 2 or more and less than 3 points

1: Average point is 1 or more and less than 2 points

<a feeling of arrangement of the head>

After applying 0.3g of the composition for cosmetics obtained by each Example and the comparative example to 15 mm in length, 3 cm in width, and 3 g of weight (made by Beaux), and drying at 50 degreeC for 1 hour, 23 degreeC, It left to stand in the constant temperature and humidity chamber of 60% of humidity for 1 hour or more, and prepared the hair sample. After the comb was passed through the hair 60 times to the hair tips, the feeling of arrangement (arrangement state) of the hair tips when the shape of the hair tips was trimmed by hand was evaluated based on the following evaluation criteria.

(Evaluation standard)

4: well organized

3: to be cleaned up

2: not much organized

1: not cleaned up at all

<a feeling of rearranging maintenance of the head>

0.3 g of the sample samples obtained in each Example and Comparative Example were applied to a human hair (manufactured by Beaux) having a length of 15 cm, a width of 3 cm, and a weight of 3 g, and dried at 50 ° C for 1 hour, and then at 23 ° C and humidity. It left to stand in 60% of constant temperature and humidity chamber for 1 hour or more, and prepared the hair sample. After the comb passes through the hair 60 times, trim the shape of the hair by hand, continue to hold the root of the hair, and shake the hair 3 times strongly. Based on the evaluation.

(Evaluation standard)

4: well-organized

3: keep the arrangement

2: not very much organized

1: does not maintain cleanup at all

[Evaluation of results]

(1) The compositions for cosmetics of Examples 1 to 10 had a good initial hair dressing, a hairstyling property, a feeling of arrangement of hair, and a feeling of arrangement of hair. Moreover, the composition maintenance of the cosmetics of Examples 2-10 which used the monomer (E) was especially favorable for the feeling of organ grooming of a hair | tip.

(2) The composition for cosmetics of the comparative example 1 used the copolymer which does not have an endothermic peak, and was inferior in rehair property, and inferior in the sense of arrangement | finish of a hair | tip and the arrangement | finish of holding | maintenance of a hair | tip.

(3) The composition for cosmetics of the comparative example 2 used the copolymer which did not mix | blend the monomer corresponding to a monomer (A), and is inferior to initial stage hairstyling property and a hairstyling property, and also has a feeling of arrangement | finish of a hair tip and a hair tip It was inferior in feeling of organizing.

(4) The composition for cosmetics of the comparative example 3 used the copolymer with high solubility in water, was inferior in hairstyling property, and inferior in the sense of arrangement | finish of a hair | tip and the feeling of arrangement | finish of a hair | tip.

`` Examples 11 to 17 and Comparative Examples 4 to 6 ''

[Production of Copolymer]

<Production of Copolymer (2-1)>

100 parts by weight of ethanol and the monomers shown in Table 5 were injected into a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introduction tube, and a stirring device, and the reactor was nitrogen-substituted, and then heated to 84 ° C. 0.2 weight part of dimethyl-2,2'- azobis (2-methylpropionate) was thrown in to a reactor, and it stirred at 84 degreeC under heating for 4 hours. Thereafter, 0.3 part by weight of dimethyl-2,2'-azobis (2-methylpropionate) was added to the reactor, and the operation of stirring for 4 hours was performed twice to obtain a copolymer (2-1).

<Production of Copolymers (2-2) to (2-5) and Copolymers (2-8) to (2-10)>

Except having used the monomer of Table 5, it carried out similarly to manufacture of copolymer (2-1), and copolymers (2-2)-(2-5) and copolymers (2-8)-(2-10) Manufactured.

<Production of Copolymer (2-6)>

87.2 parts by weight of ethanol and the monomers shown in Table 5 were injected into a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube, and a stirring device, and the reactor was nitrogen-substituted and heated to 84 ° C. 0.2 weight part of dimethyl-2,2'- azobis (2-methylpropionate) was thrown in to a reactor, and it stirred at 84 degreeC under heating for 3 hours. Thereafter, 0.3 parts by weight of dimethyl-2,2'-azobis (2-methylpropionate) was added to the reactor, and the operation of stirring for 3 hours was further performed twice. Then, the reactor was made into 75 degreeC, 6.2 g of hydrogen peroxides were thrown in, and it stirred for 3 hours, The temperature of the reactor was set to 80 degreeC, and also it stirred for 10 hours, and the copolymer (2-6) was obtained.

<Production of Copolymer (2-7)>

Except having used the monomer of Table 5, it carried out similarly to manufacture of copolymer (2-6), and manufactured the copolymer (2-7).

[Measurement of Copolymer Properties]

The following physical properties were measured about the copolymers (2-1)-(2-10) obtained above, and the result was shown in Table 5.

<Endothermic starting point, endothermic amount>

Calorie measurement was performed using "DSC-7" by Seiko Instruments. 10 mg of sufficiently dried copolymer samples were placed in a sample cell and sealed, and in the following temperature cycle, the thermal behavior from the low temperature was measured and recorded at the second temperature rise, and the start temperature and endothermic amount of the endothermic peak were measured. .

Temperature cycle: room temperature → -100 ° C. (temperature drop at 50 ° C./min) → hold for 10 minutes at -100 ° C. → 100 ° C. (heat up at 10 ° C./min) → hold at 100 ° C. for 5 min → 100 ° C. (10 ° C. / Temperature lowering in minutes) → holding at -100 ° C for 5 minutes → 100 ° C (heating at 10 ° C / min)

<Water solubility>

9.9g of water was added with respect to 0.1g of copolymer samples fully dried, and it fully stirred with the stirrer. When a copolymer sample did not melt | dissolve, heating (90 degreeC) and stirring, cooling, and stirring were repeated twice, and when dissolving further, sonication (ultrasound washer, 5 minutes) and stirring were performed. After performing these operations, it cooled to less than 30 degreeC, and confirmed the insoluble matter which can be confirmed visually. In the absence of visible insoluble matters, the particle size distribution was measured by dynamic light scattering measurement using a nanotrack 150 manufactured by Microtrack, or by particle size distribution measurement using an ASVR manufactured by Microtrack. It measured and evaluated according to the following evaluation criteria.

○ (soluble in water below 30 ° C): No visible insoluble matter is present in the sample, or the volume average particle diameter of the insoluble matter is less than 50 µm.

× (insoluble in water below 30 ° C): Insoluble matter visible to the naked eye exists in the sample, or the volume average particle diameter of the insoluble matter is 50 μm or more

<Weight average molecular weight>

Using polyethylene permeation chromatography (apparatus: Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: TOS GEL G6600H manufactured by Tosoh Corporation), developing solvent: tetrahydrofuran) The weight average molecular weight was calculated | required.

[Preparation of Cosmetic Composition]

The copolymers (2-1) to (2-10) are diluted with ethanol up to 20% by weight of solids, then slowly added dropwise to the stirred predetermined amount of water to prevent aggregation, and then adjusted to a predetermined concentration with ethanol again. The composition for cosmetics of the composition shown in Table 6 was prepared.

[Evaluation of Cosmetic Composition]

The following evaluation was performed about the composition for cosmetics obtained above, and the result was shown in Table 7. In Table 7, the volume average particle diameter of the microparticles | fine-particles of the copolymer in each cosmetic composition measured by the dynamic light scattering method using the nanotrack 150 by a microtrack company was written together.

<Initial hair dressing>

Five evaluation panelists test the use of the composition for cosmetics obtained by each Example and the comparative example, and evaluate the setability (initial hairdressing property) at the time of sample application to hair based on the following evaluation point criteria. did. Subsequently, the average score of the evaluation points which each ranked was computed and it evaluated based on the following evaluation criteria.

(Based on score)

5 points: very easy to set

4 points: easy to set

3 points: Normal

2 points: hard to set

1 point: very difficult to set

(Evaluation standard)

4: the average score is 4 or more points

3: Average score is 3 or more and less than 4 points

2: average score is 2 or more and less than 3 points

1: Average point is 1 or more and less than 2 points

<Financial recurrence>

Setability at the time of carrying out the test of the use of the cosmetic composition obtained by each evaluation panelist and the comparative example by the evaluation panelist of five, and hair-washing after 3 hours from sample application to hair, and setting again (refinability ) Was evaluated based on the following evaluation point criteria. Subsequently, the average score of the evaluation points which each ranked was computed and it evaluated based on the following evaluation criteria.

(Based on score)

5 points: very easy to set

4 points: easy to set

3 points: Normal

2 points: hard to set

1 point: very difficult to set

(Evaluation standard)

4: the average score is 4 or more points

3: Average score is 3 or more and less than 4 points

2: average score is 2 or more and less than 3 points

1: Average point is 1 or more and less than 2 points

<a feeling of arrangement of the head>

After applying 0.3g of the composition for cosmetics obtained by each Example and the comparative example to 15 mm in length, 3 cm in width, and 3 g of weight (made by Beaux), and drying at 50 degreeC for 1 hour, 23 degreeC, It left to stand in the constant temperature and humidity chamber of 60% of humidity for 1 hour or more, and prepared the hair sample. After the comb was passed through the hair 60 times to the hair tips, the feeling of arrangement (arrangement state) of the hair tips when the shape of the hair tips was trimmed by hand was evaluated based on the following evaluation criteria.

(Evaluation standard)

4: well organized

3: to be cleaned up

2: not much organized

1: not cleaned up at all

<a feeling of rearranging maintenance of the head>

0.3 g of the sample samples obtained in each Example and Comparative Example were applied to a human hair (manufactured by Beaux) having a length of 15 cm, a width of 3 cm, and a weight of 3 g, and dried at 50 ° C for 1 hour, and then at 23 ° C and humidity. It left to stand in 60% of constant temperature and humidity chamber for 1 hour or more, and prepared the hair sample. After passing the comb 60 times to the end of the hair, the shape of the end of the hair is trimmed by hand, followed by grasping the source of the hair and shaking the hair 3 times strongly. Based on evaluation.

(Evaluation standard)

4: well-organized

3: keep the arrangement

2: not very much organized

1: does not maintain cleanup at all

[Evaluation of results]

(1) As for the composition for cosmetics of Examples 11-17, the initial stage hair dressing agent, the hair dressing agent, the feeling of arrangement | finish of a hair | tip, and the feeling of grooming maintenance of a hair | tip were favorable. Moreover, Examples 14-17 containing the copolymer which mix | blended the monomer (C) had especially the sense of arrangement | finish of a hair | tip.

(2) The composition for cosmetics of the comparative example 4 used the copolymer which does not have an endothermic peak, and was inferior in rehair property, and inferior in the sense of arrangement | finish of a hair | tip and the arrangement | finish of a hair | bristle maintenance of a hair | tip.

(3) The composition for cosmetics of the comparative example 5 used the copolymer which did not mix | blend the monomer corresponding to monomer (A), and it is inferior to initial stage hairstyling property and a hairstyling property, and also has a feeling of organarity of a hair | tip and a hair tip It was inferior in feeling of organizing.

(4) The composition for cosmetics of the comparative example 6 used the copolymer with high solubility in water, was inferior in hairstyling property, and inferior in the sense of arrangement | finish of a hair | tip and the arrangement | finish of holding | maintenance of a hair | tip.

`` Examples 18 to 19 and Comparative Examples 7 to 9 ''

<Production of Copolymer (3-1)>

Copolymer (1--1) except that 49.5 parts by weight of methoxypolyoxyethylene (15 mole) methacrylate was used instead of 49.5 parts by weight of methoxypolyoxyethylene (23 mole) methacrylate of the copolymer (1-1). In the same manner as in 1), the copolymer (3-1) was produced.

<Production of Copolymer (3-2)>

Copolymer (1--1) except that 49.5 parts by weight of methoxypolyoxyethylene (40 mole) methacrylate was used instead of 49.5 parts by weight of methoxypolyoxyethylene (23 mole) methacrylate of the copolymer (1-1). In the same manner as in 1), the copolymer (3-2) was produced.

<Production of Copolymers (3-3) and (3-4)> (corresponds to Production Example 1 and Production Example 2 of JP-A-2006-160725)

Using a 200 ml three-necked flask equipped with a reflux tube and a nitrogen introduction tube, methoxypolyoxyethylene (90 moles) methacrylate (50 mol) of water-ethanol mixed solvent (water: ethanol = 40: 60 volume ratio) Nichiyu Co., Ltd. product Brenma PME-4000. Hereinafter, "PME-4000"), methyl methacrylate (MMA) or butyl methacrylate (nBMA), and ethylene glycol dimethacrylate (EGDMA) were dissolved. After sufficiently dissolving, 2,2 'azobis (2 methylpropionamidine dihydrochloride) was added at a rate of 1 mol% based on the total monomer amount and dissolved again. The completely homogeneous polymerization solution was nitrogen-substituted for 20 minutes to remove dissolved oxygen, followed by polymerization at an oil bath at 65 to 70 ° C. for 8 hours while stirring with a magnetic stirrer. The blending ratio of the copolymer (3-3) and the copolymer (3-4) is as follows.

<Copolymer (3-3)>

PME-4000 26.7 parts by weight

MMA 60.3 parts by weight

EGDMA 0.2 parts by weight

<Copolymer (3-4)>

PME4000 26.7 parts by weight

nBMA 85.7 parts by weight

EGDMA 0.2 parts by weight

<Production of Copolymer (3-5)> (corresponds to Production Example 1 of JP-A 2010-241730)

A mixture of 100 parts by weight of monomers having the following composition was prepared in advance, and a 1 L five-necked flask equipped with a dropping funnel, a reflux condenser, a thermometer, a nitrogen replacement tube, and a stirrer containing the mixture was prepared. 1 part by weight of a polymerization initiator (2,2'-azobisisobutyronitrile) was added to the ethanol at the time when the parts were injected, and the temperature was raised under a stream of nitrogen to reflux (about 80 ° C). Was dripped for 2 hours in a row. Thereafter, the mixture was left at reflux for 8 hours to proceed with the polymerization reaction.

<Monomer composition>

40 parts by weight of butyl acrylate

Brenma AE-400 (manufactured by Nichiyu Co., Ltd., polyoxyethylene (10 mol) acrylate)

55 parts by weight

NK ester A-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd., polyoxyethylene (23 moles) dimethacrylate) 5 parts by weight

<Production of Copolymer (3-6)>

49.5 parts by weight of AE-400 (manufactured by Nichi Oil Co., Ltd., polyoxyethylene (10 moles) acrylate) instead of 49.5 parts by weight of methoxypolyoxyethylene (23 mol) methacrylate of the copolymer (1-1) Except what was used, it carried out similarly to copolymer (1-1), and manufactured copolymer (3-6).

Table 8 shows the physical properties of the prepared copolymer.

[Preparation of Cosmetic Composition]

Copolymers (3-1), (3-2), (3-3), (3-4) and (3-6) were diluted with ethanol to 20% by weight of solids, and then aggregated into stirred water. In order to prevent this, it was dripped slowly, ie, the cosmetic composition of the composition of Table 9 was prepared like copolymer (1-11)-(1-13). Copolymer (3-5) could not prepare a solution of the composition of Table 9.

EVALUATION OF THE COMPOSITION FOR COSMETICS The evaluation similar to Example 1 was performed about the cosmetic composition obtained above, and the result was shown in Table 10. FIG.

[Evaluation of results]

(1) The composition for cosmetics of Examples 18-19 had the initial stage hair dressing agent, the hair refining agent, the feeling of arrangement | finish of a hair | tip, and the feeling of grooming maintenance of a hair | tip.

(2) The cosmetic composition of Comparative Example 7 used a copolymer in which monomers corresponding to monomer (A) and monomer (B) were not blended. Was inferior in the sense of organizing at the end of the head.

(3) The composition for cosmetics of the comparative example 8 used the copolymer which did not mix | blend the monomer corresponding to monomer (A), and it is inferior to initial stage hairstyling property and non-refining property, and also has a feeling of arrangement | finish of a hair tip and a hair tip It was inferior in feeling of organizing.

(4) The cosmetic composition of Comparative Example 9 used a copolymer having high solubility in water.

(5) The cosmetic compositions of Comparative Examples 7 and 8 used a copolymer using a monomer having m of General Formula (1) in place of the monomer corresponding to the monomer (A). It was inferior in the sense of organizing at the end of the head and the feeling of organizing at the end of the head.

(6) The cosmetic composition of Comparative Example 9 used a copolymer using a monomer whose m is 10 in General Formula (1) instead of the monomer corresponding to the monomer (A). It was inferior in the sense of organizing and the feeling of organizing at the tip of the head.

Although this invention was demonstrated in detail and with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention. This application is a Japanese patent application (patent application 2010-244381) filed October 29, 2010, a Japanese patent application (patent application 2010-244382) filed October 29, 2010, and a filed December 16, 2010. It is based on Japanese patent application (patent application 2010-280565), The content is taken in here as a reference.

Industrial availability

The copolymer of the present invention is useful as a composition for cosmetics such as hair dressing, because it has high settability and resetting property and has a degree of freedom of a wide range of preparations such as spray, mist, and wax.

Claims (16)

A copolymer containing a structural unit corresponding to a vinyl monomer (A) represented by the following General Formula (1) and a structural unit corresponding to a vinyl monomer (B) represented by the following General Formula (2), in water of less than 30 ° C. The copolymer which does not melt but has an endothermic starting point between -25 degreeC-40 degreeC.
[Formula 1]

(In general formula (1), R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C2-C4 alkylene group and R <^3> represents a hydrogen atom or a C1-C3 alkyl group. M is 15- An integer satisfying 50 is represented.)
(2)

(In formula (2), R ⁴ Represents a hydrogen atom or a methyl group, R ⁵ Represents an alkyl group having 2 to 10 carbon atoms. p and q represent an integer of 0 or 1, respectively, and p + q = 1.) The method of claim 1,
Furthermore, the copolymer containing the structural unit corresponded to a crosslinkable vinyl monomer (vinyl monomer (C)). 3. The method of claim 2,
The copolymer which contains the structural unit corresponding to each of the said vinyl monomers (A)-(C) with respect to the whole copolymer in the following ratios.
Vinyl monomer (A): 30-80 weight%
Vinyl monomer (B): 20 to 70% by weight
Vinyl monomer (C): 0.1-10 weight% The method according to any one of claims 1 to 3,
The copolymer which is p = 1 in the said General formula (2) which shows a vinyl monomer (B). 5. The method according to any one of claims 2 to 4,
The copolymer in which the said vinyl monomer (C) is represented by following General formula (3) or following General formula (4).
(3)

(In formula (3), R ⁶ Represents a hydrogen atom or a methyl group. Q ¹ represents a linking group represented by -CH ₂ -or the following General Formula (5), and Q ¹ Is -CH ₂ - if, s represents an integer which satisfies the range of 0 to 50. Moreover, when Q <^1> is a coupling group represented by following General formula (5), s represents the integer of 0 or 1. Q ² Represents an alkylene group having 1 to 6 carbon atoms, and t represents an integer that satisfies 0 to 50. However, s and t shall be either 0.)
[Chemical Formula 4]

(In formula (5), R ⁷ Represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, u represents an integer of 0 or 1, and v represents an integer satisfying 1 to 100.)
[Chemical Formula 5]

(In formula (4), R ⁸ Represents an alkylene group having 2 to 4 carbon atoms, R ⁹ Represents a hydrogen atom or a methyl group, w represents an integer that satisfies 0 to 100, R ¹⁰ and R ¹¹ Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or a substituent represented by the following general formula (6), respectively.)
[Chemical Formula 6]

(In formula (6), R ¹² Represents an alkylene group having 2 to 4 carbon atoms, R ¹³ Represents a hydrogen atom or a methyl group, x represents an integer of 0 or 1, and y represents an integer satisfying 0 to 100.) 6. The method according to any one of claims 1 to 5,
Furthermore, the copolymer containing the structural unit corresponded to the vinyl monomer (D) which has a C12-C22 alkyl group. 7. The method according to any one of claims 2 to 6,
The copolymer whose crosslinking rate by a vinyl monomer (C) is 0.05 to 20%. The method of claim 1,
Furthermore, the copolymer containing the structural unit corresponded to the vinyl monomer (E) which consists of at least one of the monomer represented by following General formula (7) and the monomer represented by following General formula (8).
(7)

(In formula (7), R ¹⁴ Represents a hydrogen atom or a methyl group, R ¹⁵ and R ¹⁶ Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
[Chemical Formula 8]

(In formula (8), R ¹⁷ Represents a hydrogen atom or a methyl group. r is 0 or 1, and z is an integer which satisfy | fills 1-4. X represents either of the following General Formulas (9) to (11).)
[Chemical Formula 9]

(In General Formulas (9) to (11), R ¹⁸ and R ^19. Each independently represents an alkyl group having 1 to 4 carbon atoms, and R ²⁰ in General Formula (10) Represents an alkyl group having 1 to 4 carbon atoms or-(CH ₂ ) _k -COO- (k is an integer of 1 to 4) and its salt.) The method of claim 8,
The copolymer containing the structural unit corresponding to each of the vinyl monomers (A), (B), and (E) in the following ratio with respect to the whole copolymer.
Vinyl monomer (A): 30-80 weight%
Vinyl monomer (B): 20 to 70% by weight
Vinyl monomer (E): 0.1-50 weight% 10. A method according to any one of claims 1, 8 and 9,
The copolymer whose weight average molecular weight is 5,000 or more and 2,000,000 or less. An aqueous dispersion in which the fine particles of the copolymer according to any one of claims 1 to 10 are dispersed in a continuous phase containing water. The aqueous dispersion in which the microparticles | fine-particles of the copolymer as described in any one of Claims 1-10 are disperse | distributed to 10-500 nm of volume average particle diameters. Continuous phase containing water the copolymer containing the structural unit corresponded to the vinyl monomer (A) shown by following General formula (1), and the structural unit corresponded to the vinyl monomer (B) represented by following General formula (2). After disperse | distributing to, the process of adding and copolymerizing a vinyl monomer (C) represented by following General formula (3) or following General formula (4), or
In the copolymer including the structural unit corresponding to the vinyl monomer (A) represented by the following General Formula (1) and the structural unit corresponding to the vinyl monomer (B) represented by the following General Formula (2), the following General Formula (3) Or after adding the vinyl monomer (C) represented by following General formula (4), the manufacturing method of the copolymer including the process of disperse | distributing and copolymerizing in a continuous phase containing water.
[Formula 10]

(In General Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² Represents an alkylene group having 2 to 4 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents the integer satisfying 15-50.)
(11)

(In formula (2), R ⁴ Represents a hydrogen atom or a methyl group, R ⁵ Represents an alkyl group having 2 to 10 carbon atoms. p and q represent an integer of 0 or 1, respectively, and p + q = 1.)
[Chemical Formula 12]

(In formula (3), R ⁶ Represents a hydrogen atom or a methyl group. Q ¹ Represents a coupling group represented by -CH ₂ -or the following general formula (5), and when Q ¹ is -CH _2- , s represents an integer satisfying 0 to 50. Moreover, when Q <^1> is a coupling group represented by following General formula (5), s represents the integer of 0 or 1. Q ² Represents an alkylene group having 1 to 6 carbon atoms, and t represents an integer that satisfies 0 to 50. However, s and t shall be either 0.)
[Chemical Formula 13]

(In formula (5), R ⁷ Represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, u represents an integer of 0 or 1, and v represents an integer satisfying 1 to 100.)
[Chemical Formula 14]

(In formula (4), R ⁸ Represents an alkylene group having 2 to 4 carbon atoms, R ⁹ Represents a hydrogen atom or a methyl group, w represents an integer that satisfies 0 to 100, R ¹⁰ and R ¹¹ Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or a substituent represented by the following general formula (6), respectively.)
[Chemical Formula 15]

(In formula (6), R ¹² Represents an alkylene group having 2 to 4 carbon atoms, and R ¹³ Represents a hydrogen atom or a methyl group, x represents an integer of 0 or 1, and y represents an integer satisfying 0 to 100.) The copolymer obtained by the manufacturing method of Claim 13. The cosmetic composition containing the copolymer as described in any one of Claims 1-10. The cosmetic composition containing the aqueous dispersion of Claim 11 or 12.