阅读说明：本技术 化妆料用聚氨酯以及化妆料用聚氨酯的制造方法 (Polyurethane for cosmetic and method for producing polyurethane for cosmetic ) 是由 宫园圭大郎 松仓范佳 津岛康宏 白井博明 于 2020-02-17 设计创作，主要内容包括：本发明提供一种化妆料用聚氨酯、制造方法、包含该化妆料用聚氨酯的化妆料,所述化妆料用聚氨酯是使如下物质进行反应而得到的重均分子量为50000～300000的化妆料用聚氨酯：(A)每一个分子具有两个以上的羟基的聚酯多元醇；(B)由碳原子数3～8的脂肪族烃基和两个羟基构成的脂肪族二醇；(C)分子内具有羧基和两个羟基且分子量为100～300的含羧基的二醇；(D)包含选自由异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯以及二环己基甲烷－4,4’－二异氰酸酯构成的组中的至少一种的二异氰酸酯；以及(E)包含选自由水、亚乙基二胺以及亚丙基二胺构成的组中的至少一种的扩链剂。(The invention provides a polyurethane for cosmetics, a preparation method and a cosmetic containing the polyurethane for cosmetics, wherein the polyurethane for cosmetics is a polyurethane for cosmetics with the weight-average molecular weight of 50000-300000 obtained by reacting the following substances: (A) a polyester polyol having two or more hydroxyl groups per molecule; (B) an aliphatic diol composed of an aliphatic hydrocarbon group having 3 to 8 carbon atoms and two hydroxyl groups; (C) a carboxyl group-containing diol having a carboxyl group and two hydroxyl groups in a molecule and having a molecular weight of 100 to 300; (D) a diisocyanate comprising at least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4, 4' -diisocyanate; and (E) a chain extender containing at least one selected from the group consisting of water, ethylenediamine, and propylenediamine.)

1. A polyurethane for cosmetics, which is obtained by reacting the following substances and has a weight-average molecular weight of 50000-300000:

(A) a polyester polyol having two or more hydroxyl groups per molecule;

(B) an aliphatic diol composed of an aliphatic hydrocarbon group having 3 to 8 carbon atoms and two hydroxyl groups;

(C) a carboxyl group-containing diol having a carboxyl group and two hydroxyl groups in a molecule and having a molecular weight of 100 to 300;

(D) a diisocyanate comprising at least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4, 4' -diisocyanate; and

(E) a chain extender containing at least one selected from the group consisting of water, ethylenediamine, and propylenediamine.

2. The cosmetic polyurethane according to claim 1,

(A) the polyester polyol is obtained by reacting a polycarboxylic acid selected from one or more of the group consisting of phthalic acid, isophthalic acid, terephthalic acid and adipic acid with an aliphatic polyol selected from one or more of the group consisting of ethylene glycol, diethylene glycol, butane diol, neopentyl glycol, hexane diol and hexane diol.

3. The polyurethane for cosmetics according to claim 1 or 2, wherein,

the cosmetic polyurethane is obtained by reacting a material comprising the polyester polyol (A), the aliphatic diol (B), the carboxyl group-containing diol (C), the diisocyanate (D) and the chain extender (E),

the (D) diisocyanate is composed of at least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4, 4' -diisocyanate, and the (E) chain extender is composed of at least one selected from the group consisting of water, ethylene diamine, and propylene diamine.

4. The polyurethane for cosmetics according to any one of claims 1 to 3, wherein,

the carboxyl group in the cosmetic polyurethane is neutralized.

5. A cosmetic material comprising the polyurethane for cosmetic material according to any one of claims 1 to 4.

6. The cosmetic according to claim 5,

the cosmetic is used for treating hair.

7. A method for producing a polyurethane for cosmetic materials, comprising the steps of:

a step for producing a polyurethane prepolymer by reacting (A) a polyester polyol having two or more hydroxyl groups per molecule, (B) an aliphatic diol composed of an aliphatic hydrocarbon group having 3 to 8 carbon atoms and two hydroxyl groups, (C) a carboxyl group-containing diol having a carboxyl group in the molecule and a molecular weight of 100 to 300, and (D) a diisocyanate containing at least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4, 4' -diisocyanate; and

and (E) a step of reacting the polyurethane prepolymer with (E) a chain extender containing at least one member selected from the group consisting of water, ethylenediamine, and propylenediamine.

8. The method for producing a polyurethane for cosmetics according to claim 7, wherein,

the molar number of isocyanate groups contained in the diisocyanate (D) is 1.05 to 2.00, when the total molar number of hydroxyl groups contained in the polyester polyol (A), the aliphatic diol (B), and the carboxyl group-containing diol (C) is 1 mole.

9. The method for producing a polyurethane for cosmetics according to claim 7 or 8, wherein,

the ratio of the number of moles of the hydroxyl groups of the polyester polyol (A) to the number of moles of the hydroxyl groups of the aliphatic diol (B) to the number of moles of the hydroxyl groups of the carboxyl group-containing diol (C) is 1: 0.5 to 2.0: 0.5 to 6.0, where the number of moles of the hydroxyl groups of the polyester polyol (A) is 1 mole.

10. The method for producing a polyurethane for cosmetics according to any one of claims 7 to 9, wherein,

the method for producing the polyurethane for cosmetics comprises the following steps: and a step of adding a neutralizing agent after the production of the polyurethane prepolymer.

11. The method for producing a polyurethane for cosmetics according to any one of claims 7 to 9, wherein,

the method for producing the polyurethane for the cosmetic comprises the following steps:

a step for producing a polyurethane prepolymer by reacting (A) a polyester polyol having two or more hydroxyl groups per molecule, (B) an aliphatic diol composed of an aliphatic hydrocarbon group having 3 to 8 carbon atoms and two hydroxyl groups, (C) a carboxyl group-containing diol having a carboxyl group in the molecule and a molecular weight of 100 to 300, and (D) a diisocyanate containing at least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4, 4' -diisocyanate; and

and (E) a step of reacting the polyurethane prepolymer with (E) a chain extender containing at least one member selected from the group consisting of water, ethylenediamine, and propylenediamine.

12. The method for producing a polyurethane for cosmetics according to any one of claims 7 to 9, wherein,

the method for producing the polyurethane for the cosmetic comprises the following steps:

a step for producing a polyurethane prepolymer by reacting (A) a polyester polyol having two or more hydroxyl groups per molecule, (B) an aliphatic diol composed of an aliphatic hydrocarbon group having 3 to 8 carbon atoms and two hydroxyl groups, (C) a carboxyl group-containing diol having a carboxyl group in the molecule and a molecular weight of 100 to 300, and (D) a diisocyanate containing at least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4, 4' -diisocyanate;

reacting the polyurethane prepolymer with (E) a chain extender containing at least one member selected from the group consisting of water, ethylenediamine, and propylenediamine; and

and adding a neutralizing agent.

13. A use of a polyurethane for cosmetics in the manufacture of cosmetics, wherein,

the cosmetic polyurethane according to any one of claims 1 to 4.

14. A method of styling hair comprising applying the cosmetic of claim 6 to hair.

Technical Field

The present invention relates to a cosmetic polyurethane which can be preferably used in a cosmetic, and a method for producing a cosmetic polyurethane which can be preferably used in a cosmetic.

Background

Polyurethanes of various structures have been developed and used in cosmetics, taking advantage of the flexibility, elasticity, strength, stability, safety, and the like of particles and films thereof. For example, patent document 1 proposes a cosmetic composition containing an organic fine spherical powder containing a specific spherical polyurethane fine powder, which is excellent in smoothness and touch to the skin. Further, patent document 2 proposes an aerosol composition which is composed of an aqueous stock solution containing a urethane resin and a liquefied gas and is used as an aerosol exfoliating (gommage) cosmetic. Patent document 3 proposes that a salt of polyurethane comprising a polylactic acid polyol, a diol and a diisocyanate is used as an auxiliary agent for the preparation of cosmetics and pharmaceuticals.

In addition, as a cosmetic material utilizing the touch feeling of polyurethane and the characteristics of a coating film in particular, patent document 4 proposes a hair cosmetic material which, by containing a chitosan and a polyurethane resin, imparts toughness and elasticity to damaged thin and soft hair, has good finger-passing ability, is a hair which is not coarse and soft, suppresses stickiness and hardness, is easy to finish, and can impart a good hair touch feeling. Patent document 5 proposes a hair cosmetic composition containing a cationic surfactant, an aliphatic alcohol, a polyurethane resin, a nonionic surfactant, and the like, which is excellent in natural voluminous feeling of hair at the top of the head, softness of hair, and hairless hardness of hair, is easy to stretch along the hair during application, and is easy to finish the hair, for hair whose hair quality changes with age. However, conventional polyurethane coatings have an insufficient balance among flexibility, strength, stability, and the like, and there is a demand for polyurethanes that satisfy various properties required for use in cosmetics.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 5-262622

Patent document 2: japanese patent laid-open publication No. 2003-137730

Patent document 3: japanese Kohyo publication Hei 7-509741

Patent document 4: japanese Kohyo publication No. WO2008/035563

Patent document 5: japanese patent laid-open publication No. 2016-117715

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide a cosmetic polyurethane which is excellent in various properties such as flexibility, strength and stability when used in a cosmetic, and a method for producing a cosmetic polyurethane which can be preferably used in a cosmetic.

Means for solving the problems

Accordingly, the present inventors have conducted extensive studies and found a polyurethane for cosmetics which is excellent in various properties when used in cosmetics, and have completed the present invention. Namely, the present invention is a polyurethane for cosmetics having a weight average molecular weight of 50000 to 300000, which is obtained by reacting: (A) a polyester polyol having two or more hydroxyl groups per molecule; (B) an aliphatic diol composed of an aliphatic hydrocarbon group having 3 to 8 carbon atoms and two hydroxyl groups; (C) a carboxyl group-containing diol having a carboxyl group and two hydroxyl groups in a molecule and having a molecular weight of 100 to 300; (D) a diisocyanate comprising at least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4, 4' -diisocyanate; and (E) a chain extender containing at least one selected from the group consisting of water, ethylenediamine, and propylenediamine.

Effects of the invention

The polyurethane for cosmetics of the present invention is excellent in various properties such as flexibility, strength and stability when used in cosmetics.

Detailed Description

As the polyester polyol (a) having two or more hydroxyl groups per molecule used in the present invention, a known polyester polyol can be used, and for example, a compound obtained by esterification reaction of a polycarboxylic acid with a low-molecular-weight polyol; and compounds obtained by ring-opening polymerization of cyclic ester compounds such as e-caprolactone and y-valerolactone. The weight average molecular weight of the polyester polyol (a) is not particularly limited, but is, for example, preferably 200 to 10000, more preferably 400 to 5000, and still more preferably 600 to 3000, from the viewpoint of the balance of various properties of the resulting cosmetic polyurethane. In the present invention, the weight average molecular weight can be determined in terms of styrene by Gel Permeation Chromatography (GPC) measurement.

(A) The upper limit of the number of hydroxyl groups per molecule of the polyester polyol is not particularly limited, and is preferably four, more preferably three, and most preferably two. In particular, it is preferable that one hydroxyl group is present at each of both ends of the molecule of the (a) polyester polyol.

As the polycarboxylic acid, for example, one or two or more of the following may be used in combination: aliphatic polycarboxylic acids such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, and dimer acid; alicyclic polycarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid and cyclohexanetricarboxylic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, trimellitic acid (trimestic acid), pyromellitic acid (pyromelitic acid); and anhydride or ester derivatives thereof.

Examples of the low molecular weight polyol include aliphatic polyols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propane diol, dipropylene glycol, tripropylene glycol, butane diol, pentane diol, hexane diol (hexane diol), heptane diol, octane diol, nonane diol, decane diol, undecane diol, dodecane diol, 2-methyl-1, 3-propane diol, neopentyl glycol, hexane diol (hexylene diol), 2-butyl-2-ethyl-1, 3-propane diol, 3-methyl-1, 5-pentane diol, 2-ethyl-1, 3-hexane diol, 2-methyl-1, 8-octane diol, glycerin, trimethylolpropane, ditrimethylolpropane, trimethylolpropane and pentaerythritol; and polyols containing an aliphatic ring structure such as 1, 4-cyclohexanedimethanol and hydrogenated bisphenol A.

From the viewpoint of balancing the various properties of the cosmetic polyurethane of the present invention, the (a) polyester polyol is preferably a polyester polyol obtained by reacting an aliphatic polycarboxylic acid selected from one or more of the group consisting of phthalic acid, isophthalic acid, terephthalic acid, and adipic acid with an aliphatic polyol selected from one or more of the group consisting of ethylene glycol, diethylene glycol, butane diol, neopentyl glycol, hexane diol, and particularly preferably a polyester polyol obtained by reacting at least one selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid with adipic acid and hexane diol.

The aliphatic diol (B) used in the present invention, which is composed of an aliphatic hydrocarbon group having 3 to 8 carbon atoms and two hydroxyl groups, includes, for example: propane diol, butane diol, pentane diol, hexane diol, heptane diol, octane diol, 2-methyl-1, 3-propane diol, neopentyl glycol, 3-methyl-1, 5-pentane diol, 2-ethyl-1, 3-hexane diol, and the like. Among such compounds, from the viewpoint of balancing various properties of the polyurethane for cosmetics of the present invention, the aliphatic diol (B) is preferably an aliphatic diol composed of an aliphatic hydrocarbon group having 4 to 6 carbon atoms and two hydroxyl groups, specifically, at least one selected from butane diol, pentane diol, hexane diol, 2-methyl-1, 3-propane diol, neopentyl glycol and 3-methyl-1, 5-pentane diol, more preferably at least one selected from hexane diol, 2-methyl-1, 3-propane diol and neopentyl glycol, and still more preferably neopentyl glycol.

The carboxyl group-containing diol (C) having a carboxyl group and two hydroxyl groups in the molecule and having a molecular weight of 100 to 300 used in the present invention is not particularly limited, and examples thereof include: dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid, and the like. Among these, dimethylolpropionic acid is preferred as the (C) carboxyl group-containing diol from the viewpoint of the balance of various properties of the cosmetic polyurethane of the present invention.

The diisocyanate (D) used in the present invention includes at least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4, 4' -diisocyanate. By using at least such a compound as a diisocyanate, the cosmetic polyurethane of the present invention can exhibit excellent flexibility, strength, and stability of the coating film. From the viewpoint of balancing various properties of the cosmetic polyurethane of the present invention, the diisocyanate (D) preferably contains isophorone diisocyanate.

In the present invention, other diisocyanate compounds may be used within a range not impairing the effects of the present invention, and for example, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2, 4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, dodecamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, dicyclohexylmethane-2, 2 '-diisocyanate, dicyclohexylmethane-2, 4' -diisocyanate, toluene diisocyanate (toluene diisocyanate), M-phenylene diisocyanate, p-phenylene diisocyanate, dimethylphenylene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, m-phenylene dimethyldiisocyanate, p-phenylene dimethyldiisocyanate, 1, 4-naphthalene diisocyanate, 1, 5-naphthalene diisocyanate, 2, 6-naphthalene diisocyanate, 2, 7-naphthalene diisocyanate, and the like.

From the viewpoint of balancing the various properties of the polyurethane for cosmetics of the present invention, the ratio of the total amount of (D) diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4, 4' -diisocyanate, to the amount of the other diisocyanate compound is preferably 1 to 0.5: 0 to 0.5 in terms of a molar ratio (the total of the molar ratios is 1), more preferably 1 to 0.8: 0 to 0.2 in terms of a molar ratio (the total of the molar ratios is 1), and further preferably no other diisocyanate compound is used.

The (E) chain extender used in the present invention contains at least one selected from the group consisting of water, ethylenediamine and propylenediamine, and the (E) chain extender is preferably composed of at least one selected from the group consisting of water, ethylenediamine and propylenediamine. By using at least such a compound as a chain extender, the cosmetic polyurethane of the present invention can exhibit excellent flexibility, strength, and stability of the coating film. In the present invention, the chain extender functions as a chain extender by adding/reacting to another material in the presence of an isocyanate group capable of reacting with the chain extender.

The weight-average molecular weight of the polyurethane for cosmetics is 50000-300000. When the weight average molecular weight is within this range, the cosmetic polyurethane of the present invention can exhibit excellent flexibility, strength and stability of the coating film. From the viewpoint of balancing the properties of the cosmetic polyurethane, the weight average molecular weight is preferably 60000 to 250000, more preferably 80000 to 200000, and still more preferably 100000 to 160000. In the present invention, the weight average molecular weight can be determined in terms of styrene by Gel Permeation Chromatography (GPC) measurement.

The polyurethane for cosmetics of the present invention can be obtained by reacting the above-mentioned components (a) to (E). Preferably, the reaction product can be obtained by reacting only the above components (a) to (E), that is, materials composed of the above components (a) to (E). In addition, as another embodiment, the polyurethane for a cosmetic material of the present invention can be obtained by reacting the materials composed of the above-mentioned components (a) to (E) and a neutralizing agent described later. First, a urethane bond is formed by the reaction of each hydroxyl group contained in the above-mentioned components (a) to (C) with an isocyanate group contained in the component (D), thereby forming a prepolymer. On the other hand, since the diisocyanate (D) and the component having a hydroxyl group are arbitrarily reacted, it is impossible to uniquely describe the structure of the prepolymer by the general formula, and as a result, it is impossible to uniquely describe the structure of the cosmetic polyurethane of the present invention by the general formula. Further, the reaction rate of the hydroxyl group and the isocyanate group is high, and there is no need to consider the ester reaction between the hydroxyl group and the carboxyl group in the (C) carboxyl group-containing diol having a molecular weight of 100 to 300, and such an ester reaction does not affect the structure of the cosmetic polyurethane of the present invention.

The polyurethane for cosmetics of the present invention can be used for widely known cosmetics, and examples of the cosmetics include: lotions, creams (cream), cleansing foams, cleansing milks (cleansing milk), cleansing lotion (cleansing deposition), hair restorer (hair tonic), hair liquid (hair liquid), styling liquid (set deposition), hair bleach (hair lotion), hair dye (color), permanent wave (permanent wave), lipstick, face mask, foundation, cologne (eaux de color), shampoo, hair conditioner, treatment (hair), sunscreen, deodorant, perfume, cleansing oil, and make-up oil, among others.

The amount of the polyurethane for a cosmetic of the present invention to be blended in the cosmetic is not particularly limited, and may be adjusted according to the state of the cosmetic to be blended, for example, may be 0.01 to 50% by mass based on the total amount of the cosmetic.

The method for adding the cosmetic polyurethane of the present invention to a cosmetic is not particularly limited, and a known method can be used, and examples thereof include the following: the compound obtained by mixing a part or all of the other components of the cosmetic is added at normal temperature or under temperature control, and stirred as necessary. Since the cosmetic polyurethane of the present invention has the above-described structure, various properties can be improved simultaneously when it is added to a cosmetic.

The present invention also encompasses a cosmetic composition comprising the above-mentioned polyurethane for cosmetic compositions. Examples of the cosmetic include: lotions, creams, cleansing foams, makeup removing milks, makeup removing lotions, skin sprays (skin mists), hair tonics, hair lotions, styling lotions, hair bleaches, hair dyes, permanent wave lotions, lipsticks, masks, foundations, colognes, shampoos, conditioners, sun screens, deodorants, perfumes, makeup removing oils, and make-up oils. The properties of the cosmetic of the present invention may be appropriately adjusted depending on the purpose and application, and may be, for example, liquid, emulsion, jelly, paste, solid powder, foam, mist, or the like.

The content of the aforementioned cosmetic polyurethane in the cosmetic of the present invention is not particularly limited, and may be adjusted according to the purpose and use, and may be, for example, 0.01 to 50% by mass based on the total amount of the cosmetic.

The cosmetic of the present invention may be modified in various properties (solubility, dispersibility, stability, feeling in use, coatability, permeability, moisture retention, safety, design property, optical property, fragrance, whitening property, etc.) during storage, during use, and after use, depending on the purpose and use, in addition to the above-mentioned polyurethane for cosmetic, and may be used as a component generally used in a cosmetic composition. Examples of such components include: powder components, liquid oil, solid oil, wax, higher alcohol, higher fatty acid, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, humectant, high molecular compound, metal ion capping agent, lower alcohol, polyhydric alcohol, sugar, amino acid and its derivatives, organic amine, pH regulator, antioxidant, antiseptic, blood circulation promoter, antiphlogistic, activator, whitening agent, anti-overflow agent, antiphlogistic, various extracts, plant seaweed extract, etc., and one or more than two of them can be optionally blended.

The cosmetic containing the polyurethane for a cosmetic of the present invention is preferably a cosmetic for hair treatment from the viewpoint of flexibility, strength and stability of the coating film. The cosmetic for hair treatment is not particularly limited, and examples thereof include cosmetic for hair care, eyebrow, and eyelash, and specifically include: hair dyes, permanent wave, shampoos, conditioners, hair conditioners (hair conditioners), hair conditioners, hair creams, hair gels, hair creams, hair mousses, hair oils, setting agents, curling agents, hair straightening agents (hair straightening agents), hair gels, hair tonics, eyebrow pencils, eyebrow creams, eyebrow powders, mascara, eyeliners, and the like. The cosmetic of the present invention may be a hair cosmetic for hair styling. The properties of the cosmetic for hair treatment may be appropriately selected depending on the kind of the cosmetic, and examples thereof include liquid, emulsion, gel, paste, solid powder, foam, mist, and the like.

The content of the aforementioned cosmetic polyurethane in the cosmetic for hair treatment containing the cosmetic polyurethane of the present invention is not particularly limited, and is, for example, preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, and most preferably 0.5 to 15% by mass, relative to the total amount of the cosmetic for hair treatment, from the viewpoint of balance of various characteristics.

The hair treatment cosmetic containing the cosmetic polyurethane of the present invention may contain other components generally used in hair treatment cosmetics. Examples of the other components include: one or more of cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants, hydrocarbon oils, silicone oils (silicone oils), ester oils, higher alcohols, polyhydric alcohols, saccharides and derivatives thereof, pH adjusters, dyes and pigments, perfumes, ultraviolet absorbers, solvents, and the above-mentioned components generally used in cosmetic compositions can be used.

Examples of the cationic surfactant include: lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, chloro stearyl trimethyl ammonium chloride, alkyltrimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyl trimethyl ammonium saccharinate, cetyl trimethyl ammonium saccharinate, behenyl trimethyl ammonium methylsulfate, behenyl dimethyl amine, behenyl diethyl amino ethyl amine, behenyl dimethyl amino propyl amine, behenyl dimethyl amino ethyl amine, stearyl dimethyl amine, palmitylpropyl dimethyl amine (palmitylpropylmethyl amine), and stearyloxypropyldimethyl amine. The concentration of the cationic surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the anionic surfactant include: examples of the counter ion include alkyl ether sulfates, alkyl ether sulfate salts, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α -sulfofatty acid salts, N-acylamino acid type surfactants, phosphoric acid mono-or diester type surfactants, sulfosuccinic acid esters, N-alkanoylmethylaminoethanesulfonates, derivatives thereof, and the like, and specific examples of the counter ion as an anionic group include: sodium ion, potassium ion, triethanolamine, etc., and one or more of them may be used. The concentration of the anionic surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the amphoteric surfactant include betaine-type amphoteric surfactants such as coconut oil fatty acid aminopropyl dimethyl acetate betaine, lauryl dimethyl amino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethyl imidazolinium betaine, lauryl hydroxysulfobetaine, lauramidoethyl hydroxyethyl carboxymethyl betaine, and metal salts of hydroxypropyl phosphoric acid; amino acid type amphoteric surfactants such as metal salts of beta-lauryl amino propionic acid; and a sulfate type amphoteric surfactant and a sulfonic acid type amphoteric surfactant, and one kind or two or more kinds thereof may be used. The concentration of the amphoteric surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the nonionic surfactant include: POE cetyl ether (ceteth), POE stearyl ether (steareth), POE behenyl ether, POE oleyl ether (oleyl polyether), POE lauryl ether (lauryl polyether), POE octyldodecyl ether, POE hexyldecyl ether, POE isostearyl ether, POE nonylphenyl ether, POE octylphenyl ether, POE polyoxypropylene cetyl ether, POE polyoxypropylene decyltetradecyl ether, POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monopalmitate, POE sorbitan monolaurate, POE sorbitan trioleate, POE glycerol monostearate, POE glycerol monomyristate, POE sorbitol tetraoleate, POE sorbitol hexastearate, POE sorbitol monolaurate, POE sorbitol beeswax, polyethylene glycol monooleate, polyethylene glycol monostearate, polyethylene glycol monolaurate, lauric acid, stearic acid, or the like, Oleophilic glyceryl monooleate, oleophilic glyceryl monostearate, self-emulsifying glyceryl monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, sucrose fatty acid ester, monolaurate, decaglycerol monostearate, decaglycerol monooleate, decaglycerol monomyristate, alkyl glucoside, POE methyl glucoside, POE dioleate methyl glucoside and the like, and one or more of these may be used. The concentration of the nonionic surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the hydrocarbon oil include: one or more kinds of liquid paraffin, squalane, pristane, ceresin, paraffin, ceresin, vaseline, polyisobutylene, polyisoprene, isodecane, isododecane, isohexadecane, n-pentane, isopentane, n-hexane, isohexane, kerosene, decalin, tetrahydronaphthalene, and microcrystalline wax may be used. The concentration of the hydrocarbon oil is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the silicone oil include: chain silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, diphenylsiloxyphenyltrimethicone, octamethyltrisiloxane and the like; cyclic silicone oils such as decamethylcyclotetrasiloxane, dodecamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, cyclopentasiloxane, dodecamethylcyclopentasiloxane, octamethylcyclopentasiloxane, decamethylcyclohexasiloxane, dodecamethylcyclohexasiloxane, and octamethylcyclohexasiloxane; one or more kinds of modified silicone oils such as alkyl-modified dimethylpolysiloxane, polyether-modified dimethylpolysiloxane, fatty acid-modified polysiloxane, higher alcohol-modified polysiloxane, amino-modified polysiloxane, and fluorine-modified polysiloxane can be used. The concentration of the silicone oil is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the ester oil include: ethyl acetate, butyl acetate, hexyl acetate, decyl acetate, butyl propionate, cetyl octanoate, hexyldecyl dimethyl octanoate, isononyl isononanoate, isotridecyl isononanoate, ethyl laurate, hexyl laurate, myristyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, decyl oleate, oleyl oleate, octyldodecyl oleate, isocetyl stearate, glycerol stearate, butyl stearate, ethylhexyl hydroxystearate, ethylene glycol stearate, octyl oxystearate, diethyl phthalate, triethyl citrate, 2-ethylhexyl succinate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, Synthetic ester oils such as diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, cetyl ethylhexanoate, triethylhexanoate, polyglycerin-2 triisostearate, neopentylglycol dicaprylate, neopentylglycol dicaprate, pentaerythritol tetraisostearate, etc.; lanolin, mink oil, cacao butter, coconut oil, palm kernel oil, camellia oil (camellia oil), sesame oil, castor oil, and animal and vegetable ester oil such as olive oil, and one or more of them may be used. The concentration of the ester oil is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the higher alcohol include: cetyl alcohol, isostearyl alcohol, lauryl alcohol, cetyl alcohol, octyl dodecyl alcohol, and the like, and one or two or more of these may be used. The concentration of the higher alcohol is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the polyol include: one or more of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, high polymer polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, isoprene glycol, 1, 3-butylene glycol, glycerin, diglycerin, and polyglycerin may be used. The concentration of the polyhydric alcohol is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the saccharides and derivatives thereof include: xylose, D-glucose, sucrose, trehalose, fructose, maltose, mannose, cyclodextrin, β -glucan (glucan), chitin, chitosan, pectin, arabinogalactan, dextrin, dextran (dextran), a glucosylethyl methacrylate polymer or copolymer, and the like, and one or more of these may be used. The concentration of the saccharide and the derivative thereof is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the pH adjuster include: citric acid, glycolic acid, succinic acid, tartaric acid, lactic acid, malic acid, levulinic acid, acetic acid, butyric acid, valeric acid, oxalic acid, maleic acid, fumaric acid, mandelic acid, phosphoric acid, pyrophosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, and the like, and one or two or more of them may be used. The pH adjuster is preferably added so that the pH of the hair treatment cosmetic of the present invention is 3.0 to 13.0.

Examples of the dye/pigment include: one or more of various legal pigments, acid dyes, alkali dyes, oxidation dye intermediates, couplers (coupler), auto-oxidation dyes, nitro dyes, disperse dyes, inorganic pigments, metal powder pigments, and surface-treated products thereof can be used. The concentration of the dye/pigment is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the perfume include: cedryl methyl (allyl cetyl), allyl amyl glycolate, beta-ionone, isobutyl quinoline, iris oil (iris oil), irone (irone), indole, undecanal, undecenal (undecenal), gamma undecalactone, estragole (estragole), eugenol (erubenol), oak moss, red myrrh extract (opoona resinoid), orange oil, eugenol, nerol, galaxolide (galaxolide), carvacrol, camphor, carrot seed oil, clove oil (clovir oil), methyl cinnamate, geraniol (geraniol), geranonitrile (geranyl triene), isobornyl acetate, geranyl acetate, dimethylbenzyl acetate, styryl acetate (styryl acetate), cedryl acetate (cetyl acetate), pinyl acetate (acetyllinalyl acetate), linalyl acetate (linalyl acetate), isovaleryl acetate (isovaleryl acetate), linalyl acetate (isovaleryl acetate), eugenyl acetate (isovaleryl acetate, linalyl acetate (isovaleryl acetate), eugenyl acetate (linalyl acetate), eugenyl acetate, linalyl acetate, eugenyl acetate, jasmonate, eugenyl acetate, jasmonate, eugenyl acetate, jasmonate, eugenyl acetate, jasmonate, eugenyl acetate, cinnamyl propionate, cinnamyl acetate, eugenyl acetate, cinnamyl acetate, eugenyl acetate, eugen, Benzyl salicylate, sandalwood oil (santalol oil), santalol (santalol), cyclamen aldehyde (cyclamen aldehyde), cyclopentadecanolide, methyl dihydrojasmonate (methyl dihydrojasmonate), dihydromyrcenol (dihydromyrenol), jasmonate, citral, citronellol (citronellol), citronellal (citronellal), cassia oil (cinmamon bark oil), styrax extract (styrresoinoid), cedarwood oil (cedar wood oil), cedarrene (cedrene), cedarwood brain (cedrol), celery seed oil, thyme oil, dihydrodamascenone, damascenone, thymol (thymol), cedarwood absolute (turmerosol), terpineol, gamma-terpinene, privet aldehyde (triphyllal), vanillin (vanillin), vanillol (vanillic acid), citronellol (piperonal alcohol), patchouli oil (patchouli oil), patchouli oil (patchouli oil), patchouli oil (patchouli oil), patchouli oil (patchouli oil), patchouli oil (patchouli oil), patchouli oil (patchouli oil), patchouli oil (patchouli oil), patchouli oil (patchouli oil), patchouli oil (patchouli oil), patchouli oil (patchouli oil), patchouli oil (patchouli oil, Peppermint oil, pepper oil (pepper oil), piperonal (heliotropene), bergamot oil, benzyl benzoate, borneol (borneel), myrrh extract (myrrh resinoid), muscone (musk ketone), methyl nonyl acetaldehyde, gamma-methyl ionone (methylionone), menthol (menthol), L-menthol, L-menthone, eucalyptus oil (eucalyptus oil), beta-ionone, lime oil, lavender oil, D-limonene, linalool, lyral (lyral), lilial (lilial), lemon oil, rose absolute, rose ether (rose oxide), rose oil, rosemary oil (rosemary oil), and the like, and one or two or more of them may be used. The concentration of the perfume is preferably 0.001 to 5% by mass, and more preferably 0.01 to 3% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the ultraviolet absorber include: 2, 4-dihydroxybenzophenone, 5 '-methylenebis (2-hydroxy-4-methoxybenzophenone), 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3, 5-dicumylphenyl) benzotriazole, 2' -methylenebis (4-tert-octyl-6-benzotriazolyl phenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [ 2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl ] benzotriazole, 2- [ 2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl ] benzotriazole 2- [ 2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl ] benzotriazole, 2- [ 2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl ] -5-chlorobenzotriazole, 2- [ 2-hydroxy-5- (2-methacryloyloxyethyl) phenyl ] benzotriazole, 2- [ 2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl ] benzotriazole, 2- [ 2-hydroxy-3-tert-pentyl-5- (2-methacryloyloxyethyl) phenyl ] benzotriazole, 2- [ 2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl ] -5-chlorobenzotriazole, 2- [ 2-hydroxy-4- (2-methacryloyloxymethyl) phenyl ] benzotriazole, 2- [ 2-hydroxy-4- (3-methacryloyloxymethyl) phenyl ] benzotriazole Oxazole, 2- [ 2-hydroxy-4- (3-methacryloxypropyl) phenyl ] benzotriazole, phenyl salicylate, resorcinol monobenzoate, 2, 4-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate, octyl (3, 5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3, 5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3, 5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3, 5-di-tert-butyl-4-hydroxy) benzoate, octadecyl (3, 5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3, 5-di-tert-butyl-4-hydroxy) benzoate, 2-ethyl-2 ' -ethoxyoxanilide (2-ethyl-2 ' -ethoxyxanilide), 2-ethoxy-4 ' -dodecyloxanilide, resorcinol monobenzoate, 2-ethyl-2 ' -ethoxyxanilide, 2-dodecyl-4 ' -oxanilide, and mixtures thereof, Ethyl- α -cyano- β, β -diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, ethylhexyl methoxycinnamate, bisethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, various metal salts, metal chelating agents, and the like, and one or more kinds thereof may be used. The concentration of the ultraviolet absorber is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the cosmetic for hair treatment.

Examples of the solvent include: ethanol, isopropanol, butanol, isobutanol, acetone, ethyl acetate, ethylene glycol monoethyl ether, water, and the like, and one or more of these may be used. The concentration of the solvent is preferably 10 to 99% by mass, and more preferably 20 to 95% by mass, based on the total amount of the cosmetic for hair treatment.

The method for producing a polyurethane for a cosmetic material of the present invention is a method comprising: a method comprising reacting (A) a polyester polyol having two or more hydroxyl groups per molecule, (B) an aliphatic diol comprising an aliphatic hydrocarbon group having 3 to 8 carbon atoms and two hydroxyl groups, (C) a carboxyl group-containing diol having a carboxyl group in the molecule and a molecular weight of 100 to 300, and (D) a diisocyanate comprising at least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane-4, 4' -diisocyanate to produce a polyurethane prepolymer, and then reacting the polyurethane prepolymer with (E) a chain extender comprising at least one selected from the group consisting of water, ethylenediamine, and propylenediamine. The method for producing the polyurethane prepolymer is not particularly limited, and the polyurethane prepolymer can be produced by a known method. For example, a prepolymer mixing method can be used in which (a) a polyester polyol, (B) an aliphatic diol, (C) a carboxyl group-containing diol, and (D) a diisocyanate are reacted, added to a solvent containing a neutralizing agent and an emulsifying agent as needed, and dispersed.

The amount of each material used for producing the polyurethane prepolymer of the present invention is not particularly limited, and from the viewpoint of adjusting the molecular weight and balance of various properties of the obtained polyurethane for cosmetics, it is preferable that the ratio of the number of moles of hydroxyl groups of (a) polyester polyol to the number of moles of hydroxyl groups of (B) aliphatic diol to the number of moles of hydroxyl groups of (C) carboxyl group-containing diol in the material used is 1: 0.5 to 2.0: 0.5 to 6.0, more preferably 1: 0.6 to 1.8: 0.8 to 5.0, more preferably 1: 0.7 to 1.5: 1.0 to 4.5.

From the viewpoint of adjusting the balance between the molecular weight and various properties of the obtained polyurethane for cosmetics, the amount of each material used is preferably such that the number of moles of isocyanate groups contained in the diisocyanate (D) is 1.05 to 2.00 moles, preferably 1.10 to 1.60 moles, and preferably 1.15 to 1.40 moles, when the total number of hydroxyl groups of the polyester polyol (a), the aliphatic diol (B), and the carboxyl group-containing diol (C) in the material used is 1 mole.

From the viewpoint of adjusting the balance between the molecular weight and various properties of the obtained polyurethane for cosmetic materials, the amount of each material used is preferably such that the ratio of (a), (B) and (C) to (D) in the molar number of hydroxyl groups of (a) the polyester polyol, the molar number of hydroxyl groups of (B) the aliphatic diol, the molar number of hydroxyl groups of (C) the carboxyl group-containing diol, and the molar number of isocyanate groups of (D) the diisocyanate is 1: 0.5 to 2.0: 0.5 to 6.0: 2.5 to 10.0, more preferably 1: 0.6 to 1.8: 0.8 to 5.0: 3.5 to 9.0, still more preferably 1: 0.7 to 1.5: 1.0 to 4.5: 4.5 to 8.0, and still more preferably 1: 0.7 to 1.5: 0.5 to 0.5: 0.5 to 4.5: 4.5 to 8.0.0.

In addition, the amount of the chain extender (E) used in the reaction of the polyurethane prepolymer and the chain extender (E) containing at least one selected from the group consisting of water, ethylenediamine, and propylenediamine is preferably 1.0 time or more of the total mole number of the water molecules and the amino groups of the chain extender (E) relative to the mole number of the isocyanate groups remaining in the polyurethane prepolymer (the number obtained by subtracting the mole number of the hydroxyl groups of the polyester polyol (a), (B) and (C) from the mole number of the isocyanate groups of the diisocyanate (D) used). In the present invention, the molecular chain of the polyurethane prepolymer is extended by the chain extender, whereby the molecular weight of the obtained cosmetic polyurethane can be easily adjusted to a desired range. In the case where water is used as the (E) chain extender, water can be used as a solvent for the obtained polyurethane for cosmetics, and thus by adjusting the amount of water used, aqueous solutions or dispersions of polyurethanes for cosmetics having various concentrations can be obtained.

The above-mentioned reactions are not particularly limited as long as the reaction conditions of the raw materials are such that the raw materials react with each other, and the total amount of the raw materials may be charged together to cause the reaction to proceed, or the raw materials may be charged in several times to cause the reaction to proceed. Specifically, for example, the following methods are mentioned: the raw materials of each component are added into the reaction system once or several times, and mixed under the environment of pressurization, decompression or normal pressure at the temperature of 30-160 ℃, preferably 40-160 ℃, and the mixture is maintained for 30 minutes to 10 hours until the reaction is finished.

In the method for producing a polyurethane for a cosmetic material of the present invention, a neutralizing agent, an emulsifier, and a solvent may be used, if necessary. Examples of the neutralizing agent include: monofunctional organic amines such as ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, and triethanolamine; sodium hydroxide, potassium hydroxide, ammonia and other inorganic bases, which can be used in a sufficient amount to neutralize the carboxyl groups. When the neutralizing agent is used, the neutralizing agent may be added to the polyurethane prepolymer before the reaction with the chain extender, may be added simultaneously with the reaction of the polyurethane prepolymer with the chain extender, or may be added after the reaction of the polyurethane prepolymer with the chain extender. From the viewpoint of adjusting the balance between the molecular weight and various properties of the polyurethane for cosmetics, it is preferable to add a neutralizing agent to the polyurethane prepolymer before or simultaneously with the reaction with the chain extender, and in this case, it is more preferable to use an inorganic base as the neutralizing agent.

Examples of the emulsifier include known anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures of these surfactants. Examples of the solvent include: ethanol, propanol, butanol, hexane, toluene, ethyl acetate, butyl acetate, water, and the like.

In the above-mentioned respective reactions, a catalyst may be used for promoting the reactions. Examples of catalysts include: strong acids such as sulfuric acid and toluenesulfonic acid; metal halides such as titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride, tin chloride, and boron fluoride; hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium carbonate; alcoholates, carbonates; metal oxides such as aluminum oxide, calcium oxide, barium oxide, and sodium oxide; organometallic compounds such as tetraisopropyl titanate, dibutyltin dichloride, dibutyltin oxide and dibutyltin bis (2-ethylhexyl thioglycolate); soaps such as sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium caprylate, potassium caprylate, sodium laurate and potassium laurate. The amount of these catalysts is not particularly limited, and is about 0.01 to 1% by mass based on the total mass of the raw materials. The reaction proceeds without using a catalyst, but the reaction rate is increased by using a catalyst, and thus the reaction time can be shortened.

In the present invention, the ratio of the amounts of the materials (a) to (D) used is adjusted as described above, and the molecular weight is adjusted to a specific range by producing a polyurethane prepolymer and reacting the polyurethane prepolymer with the chain extender (E), so that a polyurethane for cosmetics having excellent various properties can be obtained.

In the method for producing a cosmetic polyurethane of the present invention, other raw materials (except for the neutralizing agent) that can react with the above-mentioned materials (a) to (E) may be used, but from the viewpoint of the effect of the present invention, it is preferable to react only the above-mentioned polyester polyol (a), aliphatic diol (B), carboxyl group-containing diol (C), diisocyanate (D), and chain extender (E). More specifically, it is preferable to produce a polyurethane prepolymer from the materials consisting of only the above (a) to (D), and to produce the cosmetic polyurethane of the present invention by reacting only the polyurethane prepolymer with the above (E). The carboxyl group present in the polyurethane prepolymer may be neutralized by adding a neutralizing agent to the polyurethane prepolymer as desired.

[ examples ]

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited thereto. In the following examples and the like,% is based on mass unless otherwise specified.

< example 1: production of polyurethane 1 for cosmetic Material

341.9g of a polyester polyol (manufactured by ADEKA, Inc., ADEKA NEWACE YG-108) having a molecular weight of 1000 and two hydroxyl groups in one molecule, which was obtained by reacting isophthalic acid, adipic acid and hexane diol and was used as (A) the polyester polyol, was charged into a glass reaction vessel having a stirrer, a cooling tube and a nitrogen introduction tube; 37.4g of neopentyl glycol as (B) an aliphatic diol; 143.3g of dimethylolpropionic acid as (C) a carboxyl group-containing diol; and 477.3g of isophorone diisocyanate as (D) diisocyanate, and they were reacted at 80 ℃ for 4 hours to produce a polyurethane prepolymer. In this case, the ratio of the hydroxyl group of the (A) polyester polyol to the hydroxyl group of the (B) aliphatic diol to the hydroxyl group of the (C) carboxyl group-containing diol to the isocyanate group of the (D) diisocyanate is 1: 3: 6, assuming that the molar number of the hydroxyl group of the (A) polyester polyol is 1 mol. After the reaction, 1611.0g of water as (E) a chain extender and a solvent and 41.0g of potassium hydroxide as a neutralizing agent were further added, and the mixture was reacted at 40 ℃ for 2 hours, and NCO-free absorption was confirmed by infrared absorption spectroscopy to complete the reaction, thereby producing a polyurethane 1 for cosmetics. The weight average molecular weight of the resulting polyurethane for cosmetics 1 was 137000 in terms of styrene, as measured by Gel Permeation Chromatography (GPC).

< comparative example 1: production of polyurethane 2 for cosmetic preparation

In the method for producing the cosmetic polyurethane 1, the cosmetic polyurethane 2 was produced by the same method except that the amount of each raw material used was changed so that the ratio of the hydroxyl group of (a) the polyester polyol to the molar number of the hydroxyl group of (B) the aliphatic diol to the hydroxyl group of (C) the carboxyl group-containing diol to the isocyanate group of (D) the diisocyanate was 1: 2: 3: 6, and (E) the chain extender was not used. The weight average molecular weight of the resulting polyurethane 2 for cosmetics was 30000 in terms of styrene, as measured by Gel Permeation Chromatography (GPC).

Comparative example 2: production of polyurethane 3 for cosmetic Material

A commercially available polyurethane (trade name: LUVISE P.U.R., 30% aqueous solution, manufactured by BASF corporation) was used as the polyurethane 3 for cosmetics. The polyurethane was a copolymer composed of isophthalic acid, adipic acid, hexanediol, neopentyl glycol, dimethylolpropionic acid, and isophorone diisocyanate, and a weight average molecular weight of 16000 as measured by Gel Permeation Chromatography (GPC) and calculated in terms of styrene.

< evaluation of resistance to Hot Water >

The produced polyurethanes 1 to 3 for cosmetics were applied to a glass plate, and dried, thereby forming a film of polyurethane for cosmetics having a thickness of 100 μm on the glass plate. Next, the glass plate on which the film was formed was immersed in warm water at 40 ℃ for 30 seconds and then taken out, and the state of the film after further drying at room temperature for 12 hours was observed. As a result, the film formed using the cosmetic polyurethane 1 remained in the film state, but the films formed using the cosmetic polyurethane 2 and the cosmetic polyurethane 3 were completely dissolved in warm water, and no film remained. From this, it is understood that the polyurethane for cosmetics of the present invention is excellent in heat resistance.

< preparation of Hair treatment agent >

Using the produced polyurethanes 1 to 3 for cosmetic preparations, hair treatment agents 1 to 6 containing the components (% by mass) shown in Table 1 below were produced. The amount of the cosmetic polyurethane in each hair treatment agent is the amount of each cosmetic polyurethane except for a solvent such as water.

[ Table 1]

< evaluation of smoothness and holding ratio of set >

The smoothness of hair strands (length: 35cm) after drying at 50 ℃ for 1 hour was evaluated according to the following evaluation criteria by applying 1g of each of the hair treatment agents 1 to 6 to 3g of hair strands (length: 35 cm). Further, each hair bundle was evaluated for the style Retention ratio (Curl Retention ratio) by the following evaluation method. The evaluation results are shown in table 1.

(evaluation criteria for smoothness)

O: has softness and smooth touch.

X: no softness and no smoothness perceived.

(method of evaluating fixation Retention)

The hair bundle after drying was curled by using a cylindrical curler (curler) having a curl diameter of 2cm, hung on a plate with a scale, and the length (L) of the hair bundle after drying at 50 ℃ for 1 hour was measured₁). Subsequently, the hair bundle after the curl formation was suspended on a graduated plate and placed in a thermostat having a temperature of 30 ℃ and a humidity of 90% RH, and allowed to stand for 1 hour. Then, the length (L) of the hair bundle after standing for 1 hour was measured₂) The retention of fixed form (%) was determined according to the following formula. The closer the set retention rate is to 100%, the stronger the holding power indicating curl, and the more excellent the set holding power and moisture resistance of the hair treatment agent, and the set retention rate of 30% or more indicates practicality.

Fixation retention ratio (%) { (35-L)₂)/(35－L₁)}×100

< evaluation of shape memory >

The hair tresses treated with the hair treatment agents 1 and 3 were evaluated for shape memory. Specifically, 3g of hair strands (length 35cm) were coated with 1g of each of the hair treatment agents 1 and 3, dried at 50 ℃ for 1 hour, curled with a cylindrical curler having a curl diameter of 2cm, hung on a graduated plate, and the length (L) of the hair strands after drying at 50 ℃ for 1 hour was measured₃). Then, the lengths (L) of the hair bundles were measured after suspending a 100g weight at the lower end of the bundle of curly hair for 1 minute, 3 minutes, 5 minutes, and 20 minutes, respectively₄) The shape memory value at each load time is calculated according to the following equation. The results are shown in Table 2. The closer the shape memory value is to 100%, the stronger the holding force of the curl against the load is, and the more excellent the setting holding force of the hair treatment agent is. Further, the load time of 0 minute corresponds to the length of the hair bundle before the weight is hung.

Shape memory value (%) { (35-L)₄)/(35－L₃)}×100

[ Table 2]

From the above results, it is understood that the polyurethane for a cosmetic of the present invention is excellent in water resistance and also excellent in smoothness and set retention when used as a hair treatment agent. The conventional polyurethane produced in the comparative example was not smooth and was not suitable for use as a cosmetic material, although the hair treatment agent contained a high concentration of the polyurethane, which increased the style retention. Thus, the cosmetic polyurethane of the present invention is excellent in flexibility, strength, stability and the like of the coating film, and is excellent in various properties when used in a cosmetic.