JP2010168310A - Hair cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair cosmetic that exhibits effects of ameliorating or repairing damages of a damaged hair and imparts gloss and smoothness to the hair. <P>SOLUTION: The hair cosmetic comprises (1) 0.01-2 mass% of hydroxyethylurea, (2) 0.001-0.5 mass% of a copolymer comprising a constituting unit corresponding to a cationic vinyl monomer (A) of a specific structure and a constituting unit corresponding to a nonionic vinyl monomer (B) of a specific structure, where the ratio of the constituting unit corresponding to the cationic vinyl monomer (A) is 25-45 mol% and the ratio of the constituting unit corresponding to the nonionic vinyl monomer (B) is 75-55 mol%, each based on all constituting units constituting the copolymer, and (3) 0.001-2 mass% of a vegetable oil. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hair cosmetic. More specifically, the present invention relates to a hair cosmetic that is excellent in improving and repairing damaged hair, and that is excellent in hair gloss and smoothness.

  In recent years, hair damage due to fashion such as hair color and permanent wave has become serious, and consumer needs for such hair damage improvement are increasing. Conventionally, methods such as using various hydrolyzed proteins or combining amino acids such as arginine and glutamic acid have been known as ingredients for improving and repairing damaged hair. Recently, a technique using hydroxyethylurea has been proposed (see, for example, Patent Document 1).

  On the other hand, silicone oil and cationic polymers have been used as a method for imparting smoothness and gloss to hair. Recently, cationic vinyl has been used as a component that has a smooth feel and is excellent in smoothness, smoothness and the like. A detergent composition and a hair cosmetic composition in which a copolymer composed of a monomer and a nonionic vinyl monomer is blended have been proposed (see, for example, Patent Documents 2 to 3).

  However, there has never been a hair cosmetic that has an excellent effect of improving and repairing damaged hair, and also has an effect that can sufficiently satisfy the gloss and smoothness of the hair.

JP 2007-91615 A JP 2007-63543 A JP 2008-189854 A

  The present invention has been made in view of the above-described conventional circumstances, and an object of the present invention is to provide a hair cosmetic that exhibits damage improvement / repair effects on damaged hair and has gloss and smoothness of the hair.

  In order to solve the above-mentioned problems, the present invention provides (1) 0.01-2% by mass of hydroxyethylurea represented by the following formula (I) and (2) a cationic vinyl represented by the following formula (II). A copolymer comprising a structural unit corresponding to the monomer (A) and a structural unit corresponding to the nonionic vinyl monomer (B) represented by the following formula (III): The ratio of the structural unit corresponding to the cationic vinyl monomer (A) in all the structural units constituting is 25 to 45 mol%, and the structure corresponding to the nonionic vinyl monomer (B) Provided is a hair cosmetic containing 0.001 to 0.5 mass% of a copolymer having a unit ratio of 75 to 55 mol% and (3) 0.001 to 2 mass% of a vegetable oil.

[Formula (I)]:

［式中、Ｒ₁は水素原子またはメチル基を表し；Ｒ₂、Ｒ₃はそれぞれ独立に炭素原子数１〜２４のアルキル基、アリール基またはアラルキル基を表し；Ｒ₄は水素原子、炭素原子数１〜２４のアルキル基、アリール基、アラルキル基または−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−Ｎ⁺Ｒ₅Ｒ₆Ｒ₇・Ｙ^-を表し（ここで、Ｒ₅、Ｒ₆、Ｒ₇はそれぞれ独立に炭素原子数１〜２４のアルキル基、アリール基またはアラルキル基を表し、Ｙ−は陰イオンを表す）；Ｘ^-は陰イオンを表し；ｎは１〜１０の整数を表す。］ [Formula (II)]:

[Wherein, R ₁ represents a hydrogen atom or a methyl group; R ₂ and R ₃ each independently represents an alkyl group, an aryl group or an aralkyl group having 1 to 24 carbon atoms; R ₄ represents a hydrogen atom or a carbon atom; Represents an alkyl group, an aryl group, an aralkyl group or —CH ₂ —CH (OH) —CH ₂ —N ⁺ R ₅ R ₆ R ₇ • Y ⁻ (wherein R ₅ , R ₆ , R − ₇ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, Y— represents an anion); X ⁻ represents an anion; and n represents an integer of 1-10. ]

［式中、Ｒ₅は水素原子またはメチル基を表し；Ｒ₆、Ｒ₇はそれぞれ独立に水素原子または炭素原子数１〜３のアルキル基を表し、Ｒ₆とＲ₇の炭素原子数の和は１〜４である。］ [Formula (III)]:

[Wherein R ₅ represents a hydrogen atom or a methyl group; R ₆ and R ₇ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the sum of the number of carbon atoms of R ₆ and R ₇ ; Is 1-4. ]

  Moreover, this invention provides the said hair cosmetics whose mass mean molecular weights of the said copolymer are 10,000-2,000,000.

  According to the present invention, there is provided a hair cosmetic which is excellent in the effect of improving / repairing damaged hair and having excellent gloss and smoothness imparting effect.

  Hereinafter, the present invention will be described in detail.

  In the present specification, “(meth) acryl” means acryl or methacryl, and “(meth) acryloyl” means acryloyl or methacryloyl.

(1) Hydroxyethylurea The hydroxyurea used in the present invention is represented by the following formula (I).

  The compounding quantity of hydroxyethyl urea is 0.01-2 mass% in the hair cosmetics whole quantity of this invention. If the amount is less than 0.01% by mass, no hair damage improving effect or repair effect hair can be obtained. On the other hand, if it exceeds 2% by mass, stickiness is felt during use.

(2) Copolymer The copolymer used in the present invention includes a structural unit corresponding to the cationic vinyl monomer (A) and a structural unit corresponding to the nonionic vinyl monomer (B). It is a copolymer.

As the cationic vinyl monomer (A), one represented by the following formula (II) is used.

In the above formula (II), each substituent has the following meaning.
R ₁ represents a hydrogen atom or a methyl group. In the present invention, a methyl group is preferred.
R ₂ and R ₃ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group. In the present invention, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
R ₄ is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an aryl group, an aralkyl group or _{-CH 2 -CH (OH) -CH 2} -N + R 5 R 6 R 7 · Y - are expressed (here , R ₅ , R ₆ and R ₇ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and Y − represents an anion). In the present invention, R ⁴ is preferably a methyl group or an ethyl group, and more preferably a methyl group. R ₅ , R ₆ and R ₇ are each independently preferably a methyl group or an ethyl group, more preferably a methyl group. Y ^- is a chlorine ion, an iodine ion or a bromine ion.
X ⁻ represents an anion. In the present invention, chlorine ion, iodine ion or bromine ion is preferred.
n represents an integer of 1 to 10, an integer of 1 to 5 is preferable, and 3 is more preferable.

  Examples of the cationic vinyl monomer (A) represented by the above formula (II) include N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride, N- (meth) acryloylamino. Propyl-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'- diethylammonium} -2-hydroxypropyl] -N, N, N- trimethyl ammonium chloride having a cationic group of the ride, etc. (meth) acrylamides, and the like. However, it is not limited to these examples. Of these, N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride is preferred. One or more cationic vinyl monomers (A) can be used.

  The cationic vinyl monomer (A) represented by the above formula (II) has an amide bond in its structure, but if the copolymer has an amide bond, it has the advantage that adsorption to hair is promoted. is there. 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 is peeled off is increased.

The nonionic vinyl monomer (B) is represented by the following formula (III).

In the above formula (III), each substituent has the following meaning.
R ₅ represents a hydrogen atom or a methyl group. In the present invention, a hydrogen atom is preferable.
R ₆ and R ₇ each independently represents 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 atoms of R ₆ and R ₇ is 1 to 4, preferably 2 to 4, and most preferably 2.

  Examples of the nonionic vinyl monomer (B) represented by the above formula (II) include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- Examples include alkyl acrylamides such as isopropyl (meth) acrylamide, and dialkyl acrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide. Among them, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) are preferable because the solubility of the monomer in water and the hydrophilicity of the copolymer obtained 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 above formula (III) has an amide bond and promotes adsorption to hair or the like. More preferably, the sum of the number of carbon atoms of R ₆ and R _{7 in} the above formula (III) is 2 to 4 because the hair feels smooth after washing and does not feel rough. Specific examples include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide and the like. However, it is not limited to these examples. Most preferred is N, N-dimethyl (meth) acrylamide. The nonionic vinyl monomer (B) can be used alone or in combination of two or more.

  In the present invention, a copolymer comprising a structural unit corresponding to the cationic vinyl monomer (A) and a structural unit corresponding to the nonionic vinyl monomer (B) constitutes a copolymer. The proportion of the structural unit corresponding to the cationic vinyl monomer (A) in all the structural units is 25 to 45 mol%. A suitable lower limit is 26 mol% or more, More preferably, it is 27 mol% or more. A suitable upper limit is 42 mol% or less, More preferably, it is 38 mol% or less, Most preferably, it is 35 mol% or less. By setting the ratio to 25 mol% or more, the copolymer contains a sufficient amount of cationic groups, so that the amount of adsorption to the hair is increased. For example, the ease of fingering during rinsing, smoothness, and after drying Increased smoothness and flexibility. On the other hand, when the above ratio exceeds 45 mol%, the adsorptivity of the copolymer to the particularly damaged part where the cuticle is peeled becomes too high, resulting in a non-uniform adsorption state as a whole hair, and is smooth and supple. This is not preferable because the elasticity may be lost.

  Moreover, in this invention, the ratio of the structural unit corresponded to the said nonionic vinyl-type monomer (B) in all the structural units which comprise a copolymer shall be 75-55 mol%. A suitable lower limit is 56 mol% or more, More preferably, it is 57 mol% or more. A suitable upper limit is 70 mol% or less. By making the above ratio 55 mol% or more, it becomes easy to keep the adsorptive power to the hair etc. sufficiently, and it becomes easier to keep the smoothness and smoothness after drying more effectively. On the other hand, when the ratio exceeds 75 mol%, the ratio of the cationic group in the copolymer is lowered, and the adsorptivity to a particularly damaged portion where the cuticle is peeled is lowered.

  The copolymer is usually obtained by polymerizing the cationic vinyl monomer (A) having a structure corresponding to each structural unit and the nonionic vinyl monomer (B) at a corresponding mole percentage. can get.

  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 no anionic group or having an anionic group smaller than the number of cationic groups.

  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. In addition, 1 type, or 2 or more types can be used for the cationic vinyl-type monomer (A) or its precursor.

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

  The copolymer used in the present invention can form an aqueous solution having a concentration of 5% by mass or more at room temperature (25 ° C.), that is, the transmittance (550 nm) of an aqueous solution having a concentration of 5% by mass or more is 80%. As described above, 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 above-mentioned copolymer is, for example, mixed with a monomer that gives each constituent unit or a precursor thereof, copolymerized by a method such as solution polymerization, suspension polymerization, emulsion polymerization, and then cationized as necessary. It can manufacture by performing 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. An alcohol solvent or water is preferably used. The hydrophilic solvent can use 1 type (s) or 2 or more types.

  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 to produce the hair cosmetic composition of the present invention. Purification can be performed by combining appropriate means such as reprecipitation, solvent washing, and membrane separation as required.

  The copolymer in the present invention may be of any structure such as a random copolymer, a block copolymer, or a graft copolymer, and is not particularly limited. Random copolymers can be synthesized by adding initiators to a mixture of all monomers used for polymerization and reacting at once, or by gradually reacting while dropping a part or all of the monomers. 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 kinds of copolymers is obtained by first producing one kind of copolymer and adding the monomer component constituting the other kind 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 mass average molecular weight of the said 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, for example, when a surfactant or the like is blended, the conditioning effect due to the complex with the 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.

  The copolymer is preferably a solution having an appropriate viscosity. For example, the viscosity of a 20% by mass aqueous solution at 25 ° C. is preferably 100,000 mPa · s or less, more preferably 50,000 mPa · s. Hereinafter, it is more preferably 20,000 mPa · s or less, and most preferably 5,000 mPa · s or less. However, it is usually 10 mPa · s or more. Higher concentrations are easier to transport.

  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 industrial production. When the molecular weight and the viscosity are too large, the compoundability may be lowered, 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 mass% or less with respect to the quantity of a copolymer, More preferably, it is 0.01 mass% or less. 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.

  The blending amount (actual portion) of the copolymer in the hair cosmetic composition is 0.001 to 0.5 mass% in the total amount of the hair cosmetic composition of the present invention. If it is less than 0.001% by mass, it is not smooth. On the other hand, if it exceeds 0.5% by mass, it feels stiff after use.

(3) Vegetable oil The vegetable oil used for this invention will not be specifically limited if it can be normally used for cosmetics, For example, avocado oil, camellia oil, evening primrose oil, turtle oil, macadamia nut oil, corn oil , Mink oil, olive oil, rapeseed oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, flaxseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran And natural vegetable oils such as oil, cinnagar oil, Japanese drill oil, jojoba oil, and germ oil. One or more vegetable oils can be used.

  The blending amount of the vegetable oil in the hair cosmetic composition is 0.001 to 2 mass%, preferably 0.01 to 1 mass%, based on the total amount of the hair cosmetic composition of the present invention. If it is less than 0.001% by mass, the effect of hair gloss cannot be obtained, while if it exceeds 2% by mass, the stability of the composition is impaired.

  A surfactant can be further blended in the hair cosmetic composition of the present invention. Examples of the surfactant include an anionic surfactant, an amphoteric surfactant, a lipophilic nonionic surfactant, a hydrophilic nonionic surfactant, and a cationic surfactant.

  Anionic surfactants include fatty acid soaps (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (eg, polysulfate) Oxyethylene (hereinafter referred to as POE) lauryl sulfate triethanolamine, POE sodium lauryl sulfate, etc .; N-acyl sarcosine acid (eg, sodium lauroyl sarcosine, etc.); higher fatty acid amide sulfonate (eg, N-myristoyl-N) -Methyl taurine sodium, cocoyl methyl taurine sodium, lauryl methyl taurine sodium, etc .; hydroxy ether carboxylates (for example, dodecane-1,2-diol acetate ether salt (sodium, potassium) Magnesium, ammonium, monoethanolamine, triethanolamine, etc.)); phosphoric acid ester salts (POE oleyl ether sodium phosphate, POE stearyl ether phosphoric acid, etc.); sulfosuccinate (eg, di-2-ethylhexyl) Sodium sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); alkylbenzene sulfonates (eg, sodium linear dodecyl benzene sulfonate, triethanolamine linear dodecyl benzene sulfonate, linear dodecyl) Benzene sulfonic acid etc.); higher fatty acid ester sulfate ester salt (for example, hydrogenated coconut oil fatty acid sodium glycerin sulfate, etc.); N-ashi Glutamate (eg monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate); sulfated oil (eg funnel oil); POE alkyl ether carboxylic acid; POE alkyl Allyl ether carboxylates; α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfates; higher fatty acid alkylolamide sulfates; lauroyl monoethanolamide sodium succinate; N-palmitoyl aspartate ditri Ethanolamine; sodium caseinate and the like.

  Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (eg, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide). Side-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine) , Sulfobetaine, etc.).

  Examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate). Sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate); glycerin fatty acid esters (for example, mono cottonseed oil fatty acid glycerin, monoerucic acid glycerin, sesquioleate glycerin, monostearin) Glycerin acid, α, α'-oleic acid pyroglutamate glycerin, monostearate glycerin malate, etc.); propylene glycol fatty acid esters (eg mono And propylene glycol stearate); hardened castor oil derivatives; glycerin alkyl ethers and the like.

  Examples of the hydrophilic nonionic surfactant include POE sorbitan fatty acid esters (for example, POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monooleate, POE sorbitan tetraoleate, etc.); POE sorbite fatty acid Esters (eg, POE sorbite monolaurate, POE sorbite monooleate, POE sorbite pentaoleate, POE sorbite monostearate, etc.); POE glycerin fatty acid esters (eg, POE glycerin monostearate, POE glycerin monoisostearate) POE monooleate such as POE glycerin triisostearate); POE fatty acid esters (eg POE distearate, POE monodiolate, distea) 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 type ( POE / POP alkyl ethers (for example, POE / POP cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP monobutyl ether, POE / POP hydrogenated lanolin, POE / POP glycerin ether) Tetra POE / tetra POP ethylenediamine condensates (eg, Tetronic, etc.); POE castor oil hardened castor oil derivatives (eg, POE castor oil, POE hardened castor oil, POE hardened) Castor oil monoisostearate, POE hydrogenated castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, POE hydrogenated castor oil maleic acid, etc.); Alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, lauric acid diethanolamide, fatty acid isopropanolamide, etc.); POE propylene glycol fatty acid ester; POE alkylamine; POE fatty acid amide; sucrose fatty acid ester; Examples include dimethylamine oxide; trioleyl phosphate.

  Examples of the cationic surfactant include alkyltrimethylammonium salts (for example, stearyltrimethylammonium chloride and lauryltrimethylammonium chloride); alkylpyridinium salts (for example, cetylpyridinium chloride); distearyldimethylammonium dialkyldimethylammonium chloride Poly (N, N′-dimethyl-3,5-methylenepiperidinium) chloride; alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkyl morpholinium salt; POE alkylamine; Examples include alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

  As the surfactant, any type of surfactant can be used as appropriate according to the type and use of the hair cosmetic. For example, anionic surfactants, amphoteric surfactants, and nonionic surfactants are suitably applied to shampoos and the like as detersive components, and cationic surfactants can be applied to rinses, etc. Needless to say, the application of each surfactant is not limited.

  When the surfactant is blended, the blending amount is preferably 0.1 to 30% by mass, more preferably 1 to 15% by mass in the total amount of the hair cosmetic. If it is less than 0.1% by mass, it is difficult to obtain the effect of blending the surfactant. On the other hand, if it exceeds 30% by mass, for example, an anionic surfactant tends to feel squeezed or slime after use.

  The hair cosmetic composition of the present invention may further contain a silicone oil or a higher alcohol as an oil from the viewpoint of further improving the conditioning effect. In particular, higher alcohols are known to form lamellar structures with cationic surfactants. Such gels have good stretch and good hair fit, and are suitable for hair rinses, conditioners and the like.

  Examples of the silicone oil include chain polysiloxane (dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxane (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.) And silicone resins, silicone rubbers, various modified silicones (alkyl-modified silicones, phenyl-modified silicones, amino-modified silicones, polyether-modified silicones, fluorine-modified silicones, 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 the higher alcohol include linear alcohols (lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.), branched chain alcohols (monostearyl glycerol ether (batyl alcohol), 2- Decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, etc.). Higher alcohols usually refer to alcohols having 8 or more carbon atoms, but in the present invention, alcohols having 8 to 22 carbon atoms are preferably used, and cetyl alcohol (cetanol), stearyl alcohol, and behenyl alcohol may be used. More preferred.

  When mix | blending the above-mentioned silicone oil and other oil components of a higher alcohol, the compounding quantity has preferable 0.1-3 mass% with respect to hair cosmetics.

  As the oil component, liquid paraffin, fatty acid alkyl ester oil and the like may be blended in addition to the above silicone oil and higher alcohol.

  Furthermore, a solid or semi-solid oil component can be blended at room temperature, and it is preferably blended particularly for improving hair styling. Examples of oils that are solid or semi-solid at room temperature include, for example, paraffin wax, microcrystalline wax, ceresin, polyethylene wax, carnauba wax, candelilla wax, beeswax, cotton wax, bayberry wax, montan wax, lanolin, moclaw, ozokerite, lanolin acetate, reduced Examples include lanolin, hard lanolin, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, fatty acid glyceride, hydrogenated castor oil, coconut oil, palm oil, petrolatum, shellac wax, and bees wax. It is not limited to the examples. When blending a solid or semi-solid oil at room temperature, the blending amount is preferably about 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the total amount of the hair cosmetic as a dry solid.

  In the present invention, a water-soluble polymer other than the copolymer used in the present invention, a cationic polymer, an anionic polymer, a nonionic polymer, an amphoteric polymer, etc. may be further blended as a film-forming component. Good.

  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.

  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, Nebazai, 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, a hair cleaning type such as shampoo, hair rinse, hair conditioner, in-bass hair treatment, out bath hair styling agent, out bath hair. It broadly includes so-called hair treatment agents such as hair styling types for hair such as treatment, out bath hair spray, out bath hair foam, out bath styling and the like. The dosage form can take a wide variety of forms such as an aqueous solution system, an emulsion system, and a gel system.

  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.

  Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

1. Production of copolymer 200 parts by mass of distilled water was charged into a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirring device, and N-acryloylaminopropyl-N, N, N was added to the dropping funnel. -A monomer mixed solution consisting of 47 parts by mass of trimethylammonium chloride (DMAPAAC) (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, The reactor was purged with nitrogen and then 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 reacting for 20 hours after the completion of the dropwise addition, the mixture was 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 1 is DMAPAAC / DMAA = 30/70 (mol%), and the mass average molecular weight is 430,000. The viscosity of the 20% by mass aqueous solution was 1490 mPa · s.

  The mass 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 mass 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.

  Further, copolymer 2 was obtained in the same manner as described above using DMAPAAC and N, N-diethylacrylamide (DEAA) as monomers. Table 1 shows the mol%, the weight average molecular weight, and the 20% aqueous solution viscosity of the structural unit corresponding to each monomer in all the structural units of the copolymer 2 together with the copolymer 1. In addition, all the numerical values of the monomer composition in Table 1 are masses as solid content (actual content). In the column of mass average molecular weight, k represents 1000.

In Table 1, each symbol represents the following compound.
DMAPAAC: N-acryloylaminopropyl-N, N, N-trimethylammonium chloride,
DMAA: N, N-dimethylacrylamide,
DEAA: N, N-diethylacrylamide.

2. Preparation of hair cosmetics Using cosmetics 1 and 2 having the monomer compositions shown in Table 1 above, hair cosmetics (hair conditioners) having the compositions shown in Table 2 below were prepared by conventional methods. Each prepared sample was subjected to the following evaluation test and 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 blending amount (actual portion).

[Hair pull strength improvement effect]
Forty healthy black hairs that had been labeled were subjected to a tensile strength test in a state in which they were conditioned in water for 3 minutes using a high-sensitivity hair tensile tester (“KES-G1-SH”; manufactured by Kato Tech Co., Ltd.). In the measurement, the tensile strength load value was 20% INDEX under the condition that the hair length developed 20%, specifically, 5 cm of hair was extended to 6 cm.

  On the other hand, the tensile strength was measured in the same manner as described above for hair that had undergone perm treatment (perm 1 part soak for 15 minutes, perm 2 soak for 15 minutes, then washed and dried).

  Then, the perm-treated hair was divided into 10 pieces, and after treatment with the sample (solution) shown in Table 2 (60 minutes immersion and drying in the solution), the tensile strength was measured again by the above method.

  The evaluation of hair tensile strength is based on the formula shown in the following formula 1, from 20% INDEX of each healthy hair, perm-treated hair, and hair after treatment with the sample (solution) shown in Table 2. The average value of N = 10 was rounded down.

(Hair pull strength improvement)
(Equation 1)
Hair pull strength improvement (%) = [(CB) / (AB)] × 100
However, in the above formula, A, B, and C represent the following values.
A: Healthy hair 20% INDEX
B: Perm-treated hair 20% INDEX
C: 20% INDEX processed in Examples and Comparative Examples

From the above-mentioned degree of improvement in hair pull strength (%), the effect of improving hair pull strength was evaluated according to the following criteria.
(Evaluation criteria)
◎: Hair pull strength improvement degree is 20% or more ○: Hair pull strength improvement degree is 10% or more and less than 20% △: Hair pull strength improvement degree is 5% or more and less than 10% ×: Hair pull strength improvement degree is less than 5% .

[Hair shine effect]
1 g of a sample is applied to a damaged hair bundle consisting of 500 to 600 pieces of 15 cm in length, and after shaking and rinsing (100 cycles) twice in warm water (300 ml) at 40 ° C., the hair bundle is dried. It was. From this hair bundle, 10 hairs are arbitrarily selected, and the reflected light distribution of the light with respect to the incident light is measured with a goniophotometer GP-IR [Murakami Color Research Laboratory Co., Ltd.], and the glossiness of the hair is measured. (Glossy) was determined by the mathematical formula shown in the following formula 2.
(Equation 2)
G = s / d (G: glossiness, s: regular reflection light amount, d: diffuse reflection light amount)
Based on the glossiness G obtained by the above method, the gloss imparting effect on the hair was evaluated as follows.
(Evaluation criteria)
A: Glossiness (G) is 15 or more B: Glossiness (G) is 10 or more and less than 15 Δ: Glossiness (G) is 5 or more and less than 10 ×: Glossiness (G) is less than 5.

[Smoothness]
Using a special panel (10 persons), 2 g of the sample was applied to the bleached hair strand and tested, and the smoothness after drying was subjected to sensory evaluation. The evaluation criteria are as follows.
(Evaluation criteria)
◎: 8 or more responded that they were smooth ○: 6-7 responded that they were smooth △: 3 to 5 responded that they were smooth ×: 2 or less responded that they were smooth .

As is apparent from the results in Table 2, the hair cosmetics of Examples 1 to 6 are superior to Comparative Examples 1 to 3 in combination with the constituents of the present invention to improve hair damage, and are smooth and smooth. It was confirmed that the effect of granting was significantly improved.
Further formulation examples are shown below.

(Example 7: Shampoo)
(Mixed component) (mass%)
Hydroxyethylurea 1.0
Copolymer 1 0.2
Camellia oil 0.01
Cationized guar gum 0.2
Sodium polyoxyethylene lauryl sulfate 10.0
Coconut oil fatty acid amidopropyl betaine 1.0
Sodium cocoamphoacetate 1.0
Palm oil fatty acid monoethanolamide 1.0
Ethylene glycol distearate 1.5
Citric acid 0.2
Glutamic acid 0.1
Dipropylene glycol 1.5
Hydrolyzed conchiolin 0.01
Dilauroyl glutamate lysine Na 0.01
Hydrolyzed wheat protein 0.1
Hydrolyzed wheat starch 0.01
Lauroyl glutamate di (phytosteryl / octyldodecyl) 0.1
Sodium benzoate 0.3
Perfume Appropriate amount Ion-exchanged water Residual

(Example 8: Shampoo)
(Mixed component) (mass%)
Hydroxyethylurea 0.1
Copolymer 2 0.4
Soybean oil 0.5
Sodium polyoxyethylene lauryl sulfate 14.0
Palm oil fatty acid amidopropyl betaine 6.0
Acylmethyl taurine sodium 4.0
Palm oil fatty acid monoethanolamide 2.0
Ethylene glycol distearate 1.5
Cationized locust bean gum 0.4
Cationized cellulose 0.1
Citric acid 0.2
Dimethicone 1.0
Dipropylene glycol 2.0
Sodium benzoate 0.3
Perfume Appropriate amount Ion-exchanged water Residual

(Example 9: Hair conditioner)
(Mixed component) (mass%)
Hydroxyethylurea 2.0
Copolymer 1 0.002
Camellia oil 0.01
Liquid paraffin 1.0
Dimethylpolysiloxane 5.0
Polysilicone-13 0.2
("FZ-2250"; manufactured by Toray Dow Corning)
Cetanol 4.0
Stearyl alcohol 1.0
Stearyl PG dimethylamine 1.0
Behenyltrimethylammonium chloride 1.0
Glutamic acid 0.05
Dipropylene glycol 5.0
Polyethylene glycol (average molecular weight 4 million) 0.1
Phenoxyethanol 0.3
Hydroxyethyl cellulose 0.2
Perfume Appropriate amount Ion-exchanged water Residual

(Example 10: Hair conditioner)
(Mixed component) (mass%)
Hydroxyethylurea 2.0
Copolymer 1 0.002
Jojoba oil 0.01
Octyl palmitate 1.0
Dimethylpolysiloxane 3.0
Behenyl alcohol 2.0
Stearyl alcohol 2.0
Stearyltrimethylammonium chloride 1.5
Citric acid 0.01
Isoprene glycol 2.0
Phenoxyethanol 0.3
Perfume Appropriate amount Ion-exchanged water Residual

(Example 11: Hair treatment)
(Mixed component) (mass%)
Hydroxyethylurea 0.5
Copolymer 1 0.2
Olive oil 2.0
Vaseline 1.0
Dimethylpolysiloxane 3.0
Aminopropyl dimethicone 3.0
(Bisisobutyl PEG-14 / amodimethicone) copolymer 0.1
("Silstyle 104"; manufactured by Toray Dow Corning)
Cetanol 3.0
Stearyl alcohol 4.0
Stearyl PG dimethylamine 2.0
Behenyltrimethylammonium chloride 1.5
Glutamic acid 0.05
Dipropylene glycol 5.0
Dilauryl glutamic acid ricin Na 0.01
Phenoxyethanol 0.3
Perfume Appropriate amount Ion-exchanged water Residual

  The hair cosmetic composition of the present invention exhibits a damage improving / repairing effect on damaged hair and is excellent in hair gloss and smoothness.

Claims (2)

(1) 0.01-2% by mass of hydroxyethylurea represented by the following formula (I):
(2) A structural unit corresponding to the cationic vinyl monomer (A) represented by the following formula (II) and a nonionic vinyl monomer (B) represented by the following formula (III) 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 0.001 to 0.5% by mass of a copolymer having a proportion of structural units corresponding to the nonionic vinyl monomer (B) of 75 to 55 mol%,
(3) A hair cosmetic containing 0.001 to 2% by mass of vegetable oil.
[Formula (I)]:

[Formula (II)]:

[Wherein, R ₁ represents a hydrogen atom or a methyl group; R ₂ and R ₃ each independently represents an alkyl group, an aryl group or an aralkyl group having 1 to 24 carbon atoms; R ₄ represents a hydrogen atom or a carbon atom; Represents an alkyl group, an aryl group, an aralkyl group or —CH ₂ —CH (OH) —CH ₂ —N ⁺ R ₅ R ₆ R ₇ • Y ⁻ (wherein R ₅ , R ₆ , R − ₇ each independently represents an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, Y— represents an anion); X ⁻ represents an anion; and n represents an integer of 1-10. ]
[Formula (III)]:

[Wherein R ₅ represents a hydrogen atom or a methyl group; R ₆ and R ₇ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the sum of the number of carbon atoms of R ₆ and R ₇ ; Is 1-4. ]   The hair cosmetic according to claim 1, wherein the copolymer has a mass average molecular weight of 10,000 to 2,000,000.