JP5042652B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic, and more particularly to a hair cosmetic using a copolymer.

In recent years, hair damage due to trends such as hair coloring and permanent waves has become serious. In such damaged hair, since the hair is hydrophilized by peeling of the cuticle, there is a tendency for the hair style to be unsettled because the hair has a smooth and smooth feel.
In general, hair treatment agents used to repair and protect hair containing damaged hair as described above, such as hydrophobizing hair to prevent electrification and smoothing hair that is stiff For the purpose, a cationic surfactant is blended. However, the above-mentioned heavy damaged hair from which the cuticle has been peeled off cannot be provided with sufficient smoothness only by adding a cationic surfactant.
As a solution to such a problem, it has been studied to blend a polymer having a cuticle effect.

As the above-mentioned polymer, for example, it has been proposed to combine a cationic polymer having a cationic group having a high affinity with hair into a cosmetic composition in combination with amphoteric starch to overcome hair stiffness (Patent Document 1). . Further, a hair cosmetic containing a copolymer of a dialkyl diallylammonium salt and a cationized dextran derivative is known as a component that gives an excellent conditioning effect to the hair when finished (Patent Document 2).
Furthermore, hair cosmetics that are excellent in the coating feeling and finger feeling, are not sticky in the drying process, and have a smooth feeling are disclosed by blending a copolymer having a cationic group and a crosslinked structure in the molecule (patent) References 3, 4).
JP 2001-226217 A JP 2001-220323 A Japanese Patent Application Laid-Open No. 11-71435 JP 2000-143462 A

However, the cationic polymer as described above has a problem of usability peculiar to the polymer, such as being sticky at the time of application, as well as being sticky at the time of finishing.
Further, the copolymer having a cationic group and a crosslinked structure in the molecule is inferior in smoothness on the hair surface due to the crosslinked structure, and does not supplement the peeled cuticle function.
In this situation, smooth and supple health can be achieved by combining a cationic surfactant with a polymer that can coat the surface of damaged hair to hydrophilize the hair that has been hydrophilized and supplement the cuticle function. There has been a strong demand for hair cosmetics that can restore the hair feel and protect the hair from damage caused by heat and physical irritation such as a dryer and brushing.

  The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a hair cosmetic that is not sticky during use and has excellent smoothness, suppleness, and elasticity when finished.

  As a result of intensive studies in view of the above problems, the present inventors have found that a structural unit corresponding to a cationic vinyl monomer and a structural unit corresponding to a nonionic vinyl monomer having a specific structure are included in a specific ratio. The present invention is completed by finding that a hair cosmetic containing a polymer and a cationic surfactant is not sticky during use, and gives a smooth and supple feel to the hair even when dried or finished. It came to.

That is, the present invention comprises (1) a structural unit corresponding to the cationic vinyl monomer (A) represented by the general formula (I) and a nonionic vinyl monomer represented by the general formula (II). And a proportion of the structural unit corresponding to the cationic vinyl monomer (A) in all the structural units constituting the copolymer. A copolymer in which the proportion of the structural unit corresponding to the nonionic vinyl monomer (B) is 75 to 55 mol%,
(2) a cationic surfactant;
The present invention relates to a hair cosmetic containing

^{_{CH 2 = C (R 1)}} -CO-NH- (CH 2) n -N + R 2 R 3 R 4 · X - (I)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and R ⁴ represents a hydrogen atom or carbon number. 1-24 alkyl group, an aryl group, an aralkyl group or ^{_{-CH 2 -CH (OH) -CH 2}} -N + R 5 R 6 R 7 · Y - ^represents, R 5 to R ⁷ each independently carbon It represents the number 1 to 24 alkyl group, aryl group or aralkyl group, X ^- and Y ^- is any negative ions independently, n is an integer of 1 to 10).

^{_{CH 2 = C (R 8)}} -CO-NR 9 R 10 (II)

(In the formula, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the sum of the carbon numbers of R ⁹ and R ^10. Is 1 or more and 4 or less.)

Moreover, this invention relates to the hair cosmetics whose compounding quantity of the said copolymer is 0.01-1 mass%.
Moreover, this invention relates to the hair cosmetics whose weight average molecular weights of the said copolymer are 10,000-2,000,000.

Moreover, this invention relates to the hair cosmetics in which the said copolymer does not contain a crosslinking agent as a structural component.
Moreover, this invention relates to the hair cosmetics in which the said hair cosmetics contain a silicone oil and / or a higher alcohol further.

The hair cosmetic composition of the present invention improves the slippage of the hair surface, and after drying, can protect the surface of the object to be cleaned, so it has excellent conditioning effect, smoothness when rinsing, smoothness after drying, suppleness, flexibility Excellent.
A particularly suitable feeling of use can be obtained depending on the usage forms such as a hair conditioner after shampooing, an out bath hair treatment after washing, a hair color, and a permanent agent.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The concentration and viscosity of the present invention are those at 25 ° C. unless otherwise specified.

(1) Copolymer The copolymer that can be blended in the hair cosmetic composition of the present invention comprises a structural unit corresponding to the cationic vinyl monomer (A) and a nonionic vinyl monomer (B) having a specific structure. ). At this time, the ratio of the structural unit corresponding to the cationic vinyl monomer (A) in all the structural units constituting the copolymer is 25 to 45 mol%.

Since this copolymer exhibits an excellent conditioning effect when incorporated into hair cosmetics, hair cosmetics containing it are particularly suitable for damaged hair that has been subjected to hair color / bleaching treatment or from which cuticles have been peeled off. It has excellent effects such as smoothness, smoothness and flexibility.
In the copolymer, the structural unit corresponding to the cationic vinyl monomer (A) is adsorbed on the part of the damaged hair where the cuticle is particularly damaged, so that the function of the peeled cuticle is supplemented. It is done. This is considered to give the hair smoothness, smoothness and flexibility.

  On the other hand, in the copolymer, the structural unit corresponding to the nonionic vinyl monomer (B) represented by the general formula (II) has an amide bond, and the copolymer is derived from the hydrophilicity derived therefrom. Has the effect of imparting hydrophilicity. Those that have an amide bond have a high affinity with the skin and hair surface, and as a result, the polymer is uniformly covered over the entire hair, giving the skin and hair a smooth, smooth, suppleness and elasticity. Conceivable.

  The ratio of the structural unit corresponding to the cationic vinyl monomer (A) in all the structural units constituting the copolymer is 25 mol% or more. As a result, the copolymer contains a sufficient amount of cationic groups, so that the amount of adsorption to the hair is increased, and for example, good fingering and smoothness during rinsing, smoothness after drying, and flexibility are increased. More preferably, it is 26 mol% or more, More preferably, it is 27 mol% or more.

However, the ratio of the structural unit corresponding to the cationic vinyl monomer (A) in all the structural units constituting the copolymer is 45 mol% or less. More preferably, it is 42 mol% or less, More preferably, it is 38 mol% or less, Most preferably, it is 35 mol% or less.
When the proportion of the cationic vinyl monomer (A) exceeds 45 mol%, the adsorptivity of the copolymer to the damaged part where the cuticle is peeled off becomes too high, resulting in a non-uniform adsorption state for the entire hair. This is not preferable because it may impair smoothness, flexibility, and elasticity.

The proportion of the structural unit corresponding to the nonionic vinyl monomer (B) in all the structural units constituting the copolymer is preferably 55 mol% or more. It becomes easy to keep the adsorptive power to hair etc. sufficiently, and it becomes easy to keep smoothness and smoothness after drying more effectively. More preferably, it is 56 mol% or more, More preferably, it is 57 mol% or more.
However, the proportion of the structural unit corresponding to the nonionic vinyl monomer (B) in all the structural units constituting the copolymer is preferably 75 mol% or less. This is because if it is higher than 75 mol%, the proportion of the cationic group in the copolymer becomes low, and the adsorptivity to a particularly damaged part where the cuticle is peeled off is lowered. The ratio is more preferably 70 mol%.

The copolymer of the present invention usually polymerizes a cationic vinyl monomer (A) and a nonionic vinyl monomer (B) having a structure corresponding to each structural unit at a corresponding mole fraction. Is obtained.
The vinyl monomer is a monomer capable of vinyl polymerization. The cationic vinyl monomer is a vinyl monomer having one or more cationic groups and having no anionic group or having an anionic group smaller than the number of cationic groups.

As the nonionic vinyl monomer (B), one represented by the general formula (II) is used.

^{_{CH 2 = C (R 8)}} -CO-NR 9 R 10 (II)

(In the formula, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the sum of the carbon numbers of R ⁹ and R ^10. Is 1 or more and 4 or less.)
Here, R ⁸ is preferably a hydrogen atom. R ⁹ and R ¹⁰ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The sum of the carbon numbers of R ⁹ and R ¹⁰ is preferably 2 or more and 4 or less, and most preferably 2.

  The nonionic vinyl monomer (B) represented by the general formula (II) is not particularly limited as long as it is included in this formula. For example, N-methyl (meth) acrylamide, N-ethyl ( Alkyl acrylamides such as meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and dialkyl acrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide (Where “(meth) acryl” represents acrylic and methacrylic).

  Among these, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meta) are preferred because the solubility of the monomer in water and the hydrophilicity of the obtained copolymer are high. ) Acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N, N-diethyl (meth) acrylamide.

The nonionic vinyl monomer (B) represented by the general formula (II) has an amide bond and is preferable because adsorption to hair or the like is promoted. More preferably, the sum of the carbon numbers of R ⁹ and R ^{10 in} the formula (II) is 2 or more and 4 or less because the hair has a smooth feeling after washing and no tingling feeling. For example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, or N-isopropyl (meth) acrylamide. Most preferred is N, N-dimethyl (meth) acrylamide.

In addition, a nonionic vinyl-type monomer (B) may be used individually by 1 type, or may use 2 or more types together.
As the cationic vinyl monomer (A), those represented by the general formula (I) are used.

^{_{CH 2 = C (R 1)}} -CO-NH- (CH 2) n -N + R 2 R 3 R 4 · X - (I)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and R ⁴ represents a hydrogen atom or carbon number. 1-24 alkyl group, an aryl group, an aralkyl group or ^{_{-CH 2 -CH (OH) -CH 2}} -N + R 5 R 6 R 7 · Y - ^represents, R 5 to R ⁷ each independently carbon It represents the number 1 to 24 alkyl group, aryl group or aralkyl group, X ^- and Y ^- is any negative ions independently, n is an integer of 1 to 10).

R ¹ is preferably a methyl group. R ² and R ³ are each independently preferably a methyl group or an ethyl group, and more preferably a methyl group. R ⁴ is preferably a methyl group or an ethyl group, and more preferably a methyl group. R ^{5 to} R ⁷ are each independently preferably a methyl group or an ethyl group, and more preferably a methyl group. X ^- and Y ^- as an anion represented by the halogen ion is preferable independently, a chlorine ion, an iodine ion or a bromine ion is more preferable. n is preferably an integer of 1 to 5, and more preferably 3.

  Examples of the cationic vinyl monomer represented by the formula (I) include N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride, N- (meth) acryloylaminopropyl- N-ethyl-N, N-dimethylammonium = monoethyl sulfate, N- (meth) acryloylaminopropyl-N, N-diethyl-N-methylammonium chloride, N- (meth) acryloylaminopropyl-N, N-diethyl -N-methylammonium monomethyl sulfate, N- [3- {N '-(meth) acryloylaminopropyl-N', N'-dimethylammonium} -2-hydroxypropyl] -N, N, N-trimethylammonium Chloride, N- [3- {N '-(meth) acryloylaminopropyl-N', N And (meth) acrylamides having a cationic group such as' -diethylammonium} -2-hydroxypropyl] -N, N, N-trimethylammonium chloride.

  Of these, N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride is preferable.

  The cationic vinyl monomer (A) preferably has an amide bond. When the copolymer has an amide bond, there is an advantage that adsorption to hair is promoted. That is, by having an amide bond, the cationic strength of the cationic functional group is increased, and the adsorptive power to the particularly damaged hair portion from which the cuticle has been peeled is increased.

  The role of the conditioning polymer blended in the hair cosmetic is to give the finished hair smoothness and smoothness without stickiness during use. For cleaning applications, the smoothness during rinsing is also important, but the most important is the suppleness and elasticity of the finished hair. This is because the cuticle on the surface is peeled off in particularly damaged hair that has been repeatedly subjected to hair coloring and bleaching treatment, and the suppleness and elasticity are significantly impaired. If a smoothness or conditioning effect is imparted, hair cosmetics containing a cationic activator or various oils can be used, but it is difficult to reproduce the cuticle-derived feel inherent in hair, such as suppleness and elasticity.

The structure corresponding to the cationic vinyl monomer (A) is obtained by polymerizing a precursor of the cationic vinyl monomer with the vinyl monomer (B) to form a copolymer, Can also be obtained by converting to a structure having a corresponding cationic group.
Examples of the cationic vinyl monomer precursor include tertiary amines such as N- (meth) acryloylaminopropyl-N, N-dimethylamine and N- (meth) acryloylaminopropyl-N, N-diethylamine. Examples include (meth) acrylamides.

Examples of the cationizing agent include alkyl halides such as methyl chloride and cation group-containing cationizing agents such as 3-chloro-2-hydroxypropyl-N, N, N-trimethylammonium chloride. The cationization reaction can be carried out, for example, by adding a cationizing agent to a polymer solution under the conditions of 20 to 100 ° C. and 1 to 20 hours.
The cationic vinyl monomer (A) or its precursor may be used alone or in combination of two or more.

Derived from the structural unit corresponding to the cationic vinyl monomer (A) in the copolymer, the structural unit corresponding to the nonionic vinyl monomer (B) having an amide bond, and other vinyl monomers The content of the structural unit to be measured can be measured by IR absorption at the amide bond site, ¹ H-NMR of the methyl group adjacent to the amide bond site or the cation group, or ¹³ C-NMR thereof.

The copolymer blended in the hair cosmetic composition of the present invention can form an aqueous solution having a concentration of 5% by mass or more at room temperature, that is, 25 ° C., that is, the transmittance (550 nm) of an aqueous solution having a concentration of 5% by mass or more. ) Is 80% or more, and the aqueous solution is preferably uniform and stable. More preferably, an aqueous solution having a concentration of 20% by mass or more can be formed.
The copolymer according to the present invention is, for example, mixed with a monomer that gives each constituent unit or a precursor thereof, and copolymerized by a method such as solution polymerization, suspension polymerization, emulsion polymerization, etc. And can be produced by performing a cationization reaction.

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

  As polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), 2,2 ′ -Azo compounds such as azobis (2-methyl-N- (2-hydroxyethyl) -propionamide), 2,2'-azobis (2-amidinopropane) dihydrochloride, benzoyl peroxide, dicumyl peroxide, di It can be used without particular limitation, such as peroxides such as -t-butyl peroxide and lauroyl peroxide, persulfates, or redox systems thereof. The polymerization initiator is preferably used in the range of 0.01 to 5% by mass, more preferably in the range of 0.1 to 3% by mass with respect to the total monomers.

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

As a copolymer mix | blended with the hair cosmetics of this invention, the thing of arbitrary structures, such as a random copolymer, a block copolymer, and a graft copolymer, can be utilized, and it does not specifically limit.
Random copolymers can be synthesized by a method in which an initiator is added to a state in which all monomers used for polymerization are mixed and reacted at once, a method in which some or all of the monomers are gradually reacted while dropping, and the like. it can. It can also be dropped and polymerized while changing the monomer composition. The block copolymer can be synthesized using a known radical initiator or a catalyst. The graft copolymer can be synthesized by a method using a macromer having a vinyl functional group, a method of reacting polymers having a reactive functional group, or the like.

Among them, those that can be synthesized from inexpensive raw materials without requiring a special process are desirable because they have high industrial utility value, and random copolymers that can be most easily produced using ordinary raw materials are most preferable.
In addition, when mix | blending a copolymer with the hair cosmetics of this invention, multiple types of copolymers can also be used together. In that case, the copolymers may be synthesized separately and then mixed and blended. Alternatively, a mixture of two types of copolymers can be obtained by first producing one type of copolymer and adding the monomer components constituting the other type of copolymer to the reaction solution for polymerization. Can do. Similarly, if the addition of the monomer component and the polymerization are repeated, a mixture of various types of copolymers can be obtained. In the present invention, the latter method, which can be easily produced, is preferred.

  As for the weight average molecular weight of the copolymer mix | blended with the hair cosmetics of this invention, 10,000-2,000,000 are preferable. When the weight average molecular weight is 10,000 or more, the conditioning effect due to the complex with the anionic surfactant adhering to the hair or skin is further enhanced. More preferably, it is 100,000 or more, More preferably, it is 200,000 or more. By setting it to 2,000,000 or less, the viscosity can be kept moderately, the compoundability is enhanced, and the handling in production becomes easier. The weight average molecular weight of the copolymer can be measured by gel permeation chromatography (for example, using water / methanol / acetic acid / sodium acetate as a developing solvent). More preferably, it is 1,000,000 or less, and more preferably 700,000 or less.

  In other words, the solution viscosity is preferably in an appropriate range, for example, preferably such that a 20% by mass aqueous solution of the copolymer can be prepared. More preferably, the viscosity of a 20% by mass aqueous solution at 25 ° C. is 100,000 mPa · s or less, more preferably 50,000 mPa · s or less, still more preferably 20,000 mPa · s or less, and most preferably 5 1,000 mPa · s or less. However, it is usually 10 mPa · s or more. This is because transportation at a higher concentration is easier.

  The viscosity can be adjusted, for example, by controlling the degree of polymerization of the copolymer. The molecular weight and viscosity can also be controlled by increasing or decreasing the amount of a crosslinking agent such as a polyfunctional acrylate. However, if a cross-linking agent is added too much, the molecular weight and the viscosity are rapidly increased, which makes it difficult to control industrially. When the molecular weight and the viscosity are too large, the compoundability may deteriorate as described above, which is not preferable. For this reason, the addition amount of the cross-linking agent is preferably set in such a range that the molecular weight does not increase during the polymerization. For example, it is 0.1% or less, more preferably 0.01% or less with respect to the amount of the copolymer. Most preferably, no crosslinking agent is used in the polymerization of the copolymer, and no crosslinking agent is contained as a component of the copolymer.

  As a method for controlling the molecular weight of the copolymer, there is also a method using a chain transfer agent. When a chain transfer agent is added, the molecular weight can be reduced. However, if the amount added is too large, the molecular weight becomes too small, and thus there are aspects that are difficult to control in industrial production. In addition, thiols generally used as chain transfer agents, such as thioglycol, alkylthiol, and thioglycolic acid, have a demerit that causes odor deterioration. Therefore, it is preferable not to contain a chain transfer agent.

  Moreover, 0.01-2 mass% is preferable and the compounding quantity of the said copolymer with respect to the hair cosmetics of this invention has more preferable 0.05-1 mass%. When the blending amount is less than 0.01% by mass, the effect may not be sufficiently exhibited, and when the copolymer is blended excessively, stickiness may be felt during use.

(2) Cationic surfactant The hair cosmetic composition of the present invention contains a cationic surfactant in addition to the copolymer. By blending the substance together with the above-mentioned copolymer, a smoother feel can be realized in rinsing hair cosmetics and in dry hair after finishing.
The cationic surfactant is not particularly limited, and examples thereof include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, behenyltrimethylammonium chloride, etc.); alkylpyridinium salts (eg, cetylpyridinium chloride, etc.); Distearyldimethylammonium dialkyldimethylammonium salt; poly (N, N′-dimethyl-3,5-methylenepiperidinium) chloride; quaternary ammonium salt (alkylammonium salt etc.); alkyldimethylbenzylammonium salt; Norinium salt; Dialkyl morpholinium salt; POE-alkylamine; Amine salt (alkylamine salt etc.); Polyamine fatty acid derivative; Amyl alcohol fatty acid derivative; Fatty acid amide pro Le derivatives; benzalkonium chloride; benzethonium chloride, etc. can be mentioned. In the present invention, use of stearyltrimethylammonium chloride and stearoxyhydroxypropylamine is particularly preferred.

  Moreover, it is preferable that the compounding quantity of the cationic surfactant in the hair cosmetics of this invention is 0.1-10 mass%. If the blending amount is less than 0.1% by mass, the effect may not be sufficiently exhibited. Even if the blending amount exceeds 10% by mass, a remarkable effect cannot be obtained.

In addition to the above essential components, the hair cosmetic of the present invention can optionally contain components that can be usually blended in cosmetics.
In particular, in order to further improve the conditioning effect of the hair cosmetic, it is preferable to blend silicone oil and / or higher alcohol as the oil. In particular, higher alcohols are known to form lamellar structures with cationic surfactants. Such gels are used for hair rinses and conditioners because of their good stretch and good hair fit.

Examples of silicone oils include linear polysiloxanes (dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxanes (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.). Examples thereof include silicone resin, silicone rubber, various modified silicones (alkyl-modified silicone, phenyl-modified silicone, amino-modified silicone, polyether-modified silicone, fluorine-modified silicone, etc.) that form a three-dimensional network structure.
Moreover, although there is no restriction | limiting in the viscosity of the silicone oil which can be mix | blended, From the point of the high conditioning effect, a highly viscous silicone oil is especially preferable.

Examples of higher alcohols include linear alcohols (lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.), branched chain alcohols (monostearyl glycerin ether (batyl alcohol), 2-decyl). Tetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, etc.).
The higher alcohol usually refers to an alcohol having 8 or more carbon atoms, but in the present invention, an alcohol having 8 to 22 carbon atoms is preferably used, and cetyl alcohol (cetanol), stearyl alcohol or behenyl alcohol is more preferably used. .
The blending amount of the oil is preferably 0.1 to 3% by mass with respect to the hair cosmetic.

  Other components contained in the hair cosmetic are not particularly limited, and can be blended within a range that does not impair the object and effect of the present invention. Specifically, water-soluble polymers other than the copolymer of the present invention, cationic polymers, anionic polymers, nonionic polymers, amphoteric polymers, various active agents, oils, and the like.

Other optional components that can be blended in the hair cosmetic are exemplified below.
Examples of the water-soluble polymer include methyl cellulose and hydroxymethyl cellulose. Examples of the cationic polymer include a cation-modified cellulose ether derivative, polydimethyldiallylammonium halide, a copolymer of dimethyldiallylammonium halide and acrylamide. As anionic polymers, acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid / acrylamide / ethyl acrylate copolymers and salts thereof), methacrylic acid derivatives, crotonic acid derivatives, and the like have high nonionic properties. As molecules, acrylic acid derivatives (hydroxyethyl acrylate / methoxyethyl acrylate copolymer, polyacrylamide, etc.), vinylpyrrolidone derivatives (polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, etc.), and amphoteric polymers And dimethyldiallylammonium chloride derivatives (acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, acrylic acid / dimethyldiallylammonium chloride copolymer, etc.). These are preferably contained in an amount of 0.1 to 1% by mass.

Examples of the oil component include olive oil, jojoba oil, liquid paraffin, fatty acid alkyl ester oil and the like in addition to the above-described silicone oil and higher alcohol. The oil content is preferably 0.1 to 3% by mass.
Other ingredients include natural extracts of animals and plants and derivatives thereof, organic acids such as citric acid and lactic acid, inorganic salts such as sodium chloride, amino acids (glutamic acid or salts thereof, arginine or salts thereof, glycine, etc.), solubilizers ( Ethanol, isopropanol, butanol, etc.), polyhydric alcohols (ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, isoprene glycol, etc.), sugars (sorbitol, Maltitol, xylitol, glucose, fructose, mannitol, inositol, etc.), polymers such as hyaluronic acid, antioxidants, UV absorbers, bactericides, preservatives, chelating agents, fragrances, colorants, higher fatty acids, increased Agents, sequestering agents (edetic acid salts, etc.), pH adjusting agent, may be appropriately blended foam boosters such as within a range not to impair the effects of the present invention.

  The hair cosmetic of the present invention means any cosmetic used for hair, for example, rinse, conditioner, treatment, hair dye, permanent, out bath treatment, hair pack, hair spray, hair foam, styling. It includes a wide range of so-called hair treatment agents such as hair preparations. Moreover, the usage form may include any of those that are applied to the skin, hair, and the like and rinsed after thoroughly blending, and those that are not washed away.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
(Manufacture of copolymer)
A reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device was charged with 200 parts by weight of distilled water, and N-methacryloylaminopropyl-N, N, N-trimethylammonium chloride ( DMAPAAC) was charged with a monomer mixture consisting of 47 parts by mass (59 parts by mass as an 80% by mass aqueous solution), 53 parts by mass of N, N-dimethylacrylamide (DMAA), and 80 parts by mass of distilled water, and the reactor was purged with nitrogen. After that, it was heated to 90 ° C. After adding 0.5 part by mass of 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) -propionamide) to the reactor, the monomer mixture was added dropwise over 4 hours. After the completion of the dropwise addition, the mixture was reacted for 20 hours and then cooled to obtain a copolymer (1).

The ratio of the structural unit corresponding to each monomer in all the structural units of the obtained copolymer is DMAPAAC / DMAA = 30/70 (mole percentage), and the weight average molecular weight is 430,000. The viscosity of the 20% by mass aqueous solution was 1490 mPa · s.
The weight average molecular weight was measured as follows. Gel permeation chromatography (apparatus: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wako Pure Chemical Industries, Ltd. Wakopak (Wakobeads G-50), developing solvent: water / methanol / acetic acid / sodium acetate = 6/4 / 0.3 / 0.41), the weight average molecular weight was determined using polyethylene glycol as the standard substance.

  Viscosity was measured using a B-type viscometer. 2 was performed at 30 rpm and 25 ° C.

＊１ 表における数値は全て固形分としての質量である。
＊２ ｋは１０００を表す。 (Table 1)

* 1 All values in the table are mass as solid content.
* 2 k represents 1000.

DMAPAAC: N-acryloylaminopropyl-N, N, N-trimethylammonium chloride DMAA: N, N-dimethylacrylamide DEAA: N, N-diethylacrylamide

(Preparation of hair cosmetics)
Using the copolymers (1), (3) and (4) having the monomer composition shown in Table 1, hair cosmetics (hair conditioners) having the composition shown in Table 2 were prepared by a conventional method. The sensory test shown below was implemented about each prepared sample, and it evaluated according to each evaluation item. The results are shown in Table 2. In addition, all the numerical values in Table 2 indicate mass% of the active ingredient.
The copolymers (3) and (4) were produced in the same manner as the copolymer (1) except that the monomer composition shown in Table 1 was used. Table 1 shows the mole percentage, weight average molecular weight, and 20% aqueous solution viscosity of the structural unit corresponding to each monomer in the total structural unit of the obtained copolymer.

<Sensory test>
A use test was conducted by six specialist panels, and the following five levels were evaluated for each item, and an average value was calculated. 1. When the average value is 4.5 or more, it is very good (◎), when it is 3.5-4.4, good (◯), when 2.5-3.5 is normal (Δ), 2. The case of 4 or less was determined to be defective (x).

Smoothness at the time of rinsing 5: I feel that the smoothness at the time of rinsing is good.
4: I feel that the smoothness during rinsing is slightly better.
3: Smoothness during rinsing is normal.
4: Feels that the smoothness during rinsing is slightly bad.
1: I feel that the smoothness at the time of rinsing is bad.

Smoothness after towel drying 5: Feels smooth after towel drying.
4: I feel the smoothness after towel drying is a little better.
3: Smoothness after towel drying is normal.
4: I feel the smoothness after towel drying is a little bad.
1: Feels smooth after towel drying.

Smoothness of the finish 5: I feel that the smoothness of the finish is good.
4: I feel that the smoothness of the finish is slightly good.
3: The smoothness of the finish is normal.
4: I feel that the smoothness of the finish is a little bad.
1: I feel that the finish is not smooth.

Finished suppleness and elasticity 5: I feel that the finished suppleness and elasticity are good.
4: I feel that the finish is supple and elastic.
3: The finish is supple and elastic.
4: Feels that the finish is supple and elastic.
1: I feel that the finish is supple and elastic.

(Table 2)

As shown in Table 2, the hair cosmetics of Examples 1 and 2 in which the copolymer (1) and the cationic surfactant are blended give a smooth feel upon rinsing and give a suppleness and elasticity after finishing. It was a thing. In addition, even after towel drying, the hair had a smooth feel and was excellent as a finger.
On the other hand, in Comparative Example 1 in which the copolymer (3) having a molar composition ratio of DMAPAAC of 20 mol% was blended, the feel was inferior to that of the Example, and the copolymer (4 In the comparative example 2 which mix | blended), uniform hair cosmetics were not able to be obtained.
Further, Comparative Example 3 containing no copolymer was inferior in smoothness after rinsing or after towel drying, and lacked the flexibility and elasticity of the finished hair. In Comparative Examples 4 and 5 in which a cationized cellulose or dimethylammonium chloride copolymer, which is a conventional conditioning agent, is blended in place of the specific copolymer, it is smoother, more supple and elastic than the hair cosmetics of the examples. The result was inferior in feeling, and in Comparative Example 6 in which no cationic surfactant was blended, the smoothness was inferior to the hair cosmetics of the examples, and in particular, the inflexibility and the antistatic effect were inferior.

From the above results, it is recognized that the hair cosmetic composition of the present invention containing a specific copolymer and a cationic surfactant gives an excellent feel to the hair after rinsing, after towel drying and after drying. It was.
Moreover, in this invention, the ratio of the structural unit corresponding to the cationic vinyl monomer (A) in all the structural units which comprise a copolymer is 25-45 mol%, and a nonionic vinyl monomer ( The proportion of the structural unit corresponding to B) is preferably 75 to 55 mol%.

(Blending amount of copolymer)
In order to study the blending amount of the specific copolymer blended in the present invention, hair cosmetics having the composition shown in Table 3 below were prepared and evaluated for usability. In addition, preparation of hair cosmetics and the evaluation method of each sample were performed according to the said Example 1. FIG. The evaluation results are shown in Table 3.

(Table 3)

As shown in Table 3, in Comparative Example 7 in which the blending amount of the copolymer was 0.005% by mass, the sufficient conditioning effect of the copolymer could not be exhibited, and the finished product lacked flexibility and elasticity. there were. Moreover, in Comparative Example 8 in which the blending amount of the copolymer was 2.0% by mass, stickiness was felt during use, and the feel after rinsing or after towel drying was poor.
From the above results, it was recognized that 0.01 to 1% by mass of the specific copolymer in the hair cosmetic composition of the present invention was suitable.

Hereinafter, although the formulation example of the hair cosmetics of this invention is given, this invention is not limited to these. In addition, all compounding quantities are shown by mass%, and all the manufacturing methods are a conventional method.
Moreover, the copolymer in a formulation example applies to the monomer composition of the said Table 1.

<Prescription Example 1 Hair Conditioner>
Dilaurylethylhydroxyethylmonium methosulfate 1.0
Behenyltrimethylammonium chloride 2.0
Stearyl alcohol 3.0
Behenyl alcohol 3.0
Cetyl alcohol 1.0
Mineral oil 1.0
Glycerin 3.0
Silicone emulsion 5.0
Example Copolymer (2) 0.5
Purified water residue

<Prescription Example 2 Hair Conditioner>
Stearic acid dimethylaminopropylamide 2.0
Behenyltrimethylammonium chloride 0.5
Stearyl alcohol 4.0
Behenyl alcohol 1.0
Cetyl alcohol 1.0
Cetyl octanoate 1.0
Polyoxyethylene (20) cetyl ether 1.0
Silicone emulsion 5.0
Example copolymer (2) 1.0
Purified water residue

<Prescription Example 3 Hair Color>
(1 agent)
Liquid paraffin 3.0
Cetanol 2.0
Behenyl alcohol 2.0
Propylene glycol 0.1
Stearyltrimethylammonium chloride 3.0
Example Copolymer (1) 0.3
Ethanolamine 5.0
Hydrosulfite sodium 0.4
Ascorbic acid 0.005
Cationized silk protein 0.1
Hydroxyethane diphosphonic acid (60%) 0.002
Resorcinol 0.05
Fragrance 0.1
Purified water residue (2 agents)
Liquid paraffin 2.0
Vaseline 1.0
Stearyl alcohol 6.0
Decyltetradecanol 2.0
Self-emulsifying glyceryl monostearate 1.0
Behenyltrimethylammonium chloride 2.0
Example Copolymer (2) 0.5
Hydrogen peroxide solution (30%) 18.0
Phosphoric acid 0.8
Anhydrous sodium monohydrogen phosphate 0.3
Sodium stannate 0.2
Paraben 0.1
Purified water residue

<Prescription Example 4 Hair Color>
(1 agent)
1,3-butylene glycol 5.0
Oleic acid 4.0
Sodium polyoxyethylene lauryl ether sulfate 8.0
Polyoxyethylene lauryl ether sulfate triethanolamine 4.0
2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine 0.5
Lauryldimethylaminoacetic acid betaine 2.0
Stearic acid diethylaminoethylamide 2.0
Copolymer of Example (2) 0.3
Cationized cellulose 0.5
Strong ammonia water 15.0
Ethanolamine 2.0
Ascorbic acid 0.6
DL-pyrrolidonecarboxylate sodium solution 0.1
Hydroxyethanediphosphonic acid tetrasodium 0.3
Resorcin 0.15
Fragrance Appropriate amount of purified water Residue (2 agents)
Liquid paraffin 0.6
Amino-modified silicone 2.0
Cetostearyl alcohol 2.0
Polyoxyethylene cetyl ether 0.6
Stearoxypropyldimethylamine 2.0
Copolymer of Example (1) 0.5
Hydrogen peroxide solution (30%) 18.0
Phosphoric acid 0.1
Anhydrous sodium monohydrogen phosphate 0.1
Sodium stannate 0.02
P-Hydroxybenzoic acid ester

<Prescription Example 5 Permanent>
(1 agent)
Liquid paraffin 3.0
Cetanol 16.0
Propylene glycol 3.0
Cetyltrimethylammonium chloride 2.0
Copolymer of Example (1) 0.5
Oleic acid 1.0
Polyoxyethylene (20) oleyl ether 1.5
Monoethanolamine 4.0
Ammonium thioglycolate 20.0
Diammonium dithioglycolate 3.0
Cationized silk protein 0.1
Hydroxyethanediphosphonic acid 0.3
Carboxyvinyl polymer 0.5
Legal dye Appropriate amount of perfume Appropriate amount of purified water Residue (2 agents)
Polyether-modified silicone 1.0
Decyltetradecanol 0.5
Polyoxyethylene (5) stearyl ether 1.5
Behenyltrimethylammonium chloride 1.0
Example copolymer (1) 1.0
Sodium monohydrogen phosphate 0.3
Sodium bromate 10.0
Potassium dihydrogen phosphate 0.2
Sodium benzoate Appropriate amount Purified water Residual amount

<Prescription Example 6 Permanent>
Cetostearyl alcohol 0.2
Polyoxyethylene cetyl (20) ether 0.2
Polyoxyethylene (10) stearyl ether 1.5
Stearyltrimethylammonium chloride 0.2
Copolymer of Example (2) 0.1
Strong ammonia water 2.0
Monoethanolamine 3.5
Ammonium thioglycolate 2.0
DL-cysteine hydrochloride 6.5
Cationized silk protein 0.1
Hydroxyethanediphosphonic acid 0.6
Lecithin 0.1
Fragrance Appropriate amount of purified water Residue (2 agents)
Dimethylpolysiloxane 3.0
Cetanol 8.0
Cetyl 2-ethylhexanoate 1.0
Polyoxyethylene (20) cetyl ether 0.3
Self-emulsifying glyceryl monostearate 0.3
Stearoxyhydroxypropyltrimethylammonium chloride 2.0
Example Copolymer (2) 0.05
Hydrogen peroxide solution (30%) 7.0
Phosphoric acid 0.4
Sodium monohydrogen phosphate 1.0
Sodium stannate 0.2
Diethylenetriaminepentaacetic acid 5sodium 0.1
P-Hydroxybenzoic acid ester

<Prescription example 7 out bath treatment agent>
Stearyltrimethylammonium chloride 1.0
Copolymer of Example (2) 0.1
Polyoxyethylene (10) Polyoxypropylene (20) Decyl tetradecyl ether
1.0
Propylene glycol 5.0
Silicone emulsion 1.0
Polyether-modified silicone 1.0
Phenoxyethanol 0.3
Alcohol 10.0
Ion exchange water

<Prescription example 8 out bath treatment agent>
Stearyltrimethylammonium chloride 0.5
Example copolymer (1) 1.0
Polyoxyethylene (40) hydrogenated castor oil 2.0
Polyoxyethylene (15) Polyoxypropylene (10) Dimethyl ether
2.0
1,3-butylene glycol 10.0
Methylphenylpolysiloxane 5.0
Phenoxyethanol 0.1
Alcohol 10.0
Ion exchange water

<Prescription example 9 out bath treatment agent>
Dilaurylethylhydroxyethylmonium methosulfate 0.3
Example Copolymer (2) 0.5
2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine
1.0
Stearic acid 1.0
Polyoxyethylene (40) hydrogenated castor oil 1.0
Amino-modified silicone 4.0
Glycerin 4.0
Phenoxyethanol 1.0
Alcohol 10.0
Residual ion exchange water
An aerosol mousse was prepared by blending 10% of LPG as a propellant to 90% of the above formulation.

  All of the hair cosmetics of Formulation Examples 1 to 9 were not sticky at the time of use, had a smooth feel at the time of rinsing and finishing, and had excellent conditioning effects.

Claims (4)

(1) A structural unit corresponding to the cationic vinyl monomer (A) represented by the general formula (I) and a nonionic vinyl monomer (B) represented by the general formula (II) The proportion of the structural unit corresponding to the cationic vinyl monomer (A) in all the structural units constituting the copolymer is 25 to 45 mol%, And 0.01-1 mass% of the copolymer whose ratio of the structural unit corresponding to the said nonionic vinyl-type monomer (B) is 75-55 mol%,
(2) a cationic surfactant;
A hair cosmetic, characterized by comprising

^{_{CH 2 = C (R 1)}} -CO-NH- (CH 2) n -N + R 2 R 3 R 4 · X - (I)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and R ⁴ represents a hydrogen atom or carbon number. 1-24 alkyl group, an aryl group, an aralkyl group or ^{_{-CH 2 -CH (OH) -CH 2}} -N + R 5 R 6 R 7 · Y - ^represents, R 5 to R ⁷ each independently carbon It represents the number 1 to 24 alkyl group, aryl group or aralkyl group, X ^- and Y ^- is any negative ions independently, n is an integer of 1 to 10).

^{_{CH 2 = C (R 8)}} -CO-NR 9 R 10 (II)

(In the formula, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the sum of the carbon numbers of R ⁹ and R ^10. Is 1 or more and 4 or less.)   The hair cosmetic according to claim 1, wherein the copolymer has a weight average molecular weight of 10,000 to 2,000,000. The hair cosmetic according to claim 1 or 2 , wherein the copolymer does not contain a crosslinking agent as a constituent component. The hair cosmetic according to any one of claims 1 to 3 , wherein the hair cosmetic further contains silicone oil and / or higher alcohol.