JP5437587B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic composition containing an acrylic copolymer having an oil-soluble cycloalkyl group. More specifically, the present invention relates to a hair cosmetic composition that is less susceptible to plastic effects due to polyhydric alcohols, has less stickiness, and is glossy. The present invention relates to a hair cosmetic that has a certain finish, has a supple and high setting power, is excellent in sustainability, and does not flake.

Conventionally, hair wax, hair milk, hair gel, hair spray, hair mousse, blow lotion, pomade, and the like have been used as hair cosmetics with hair styling properties. In these dosage forms, oily ingredients such as waxes and film-forming synthetic polymers have been used as ingredients for giving hairstyling properties. (Non-Patent Document 1)
For example, combination of wax and water-soluble polymer (Patent Document 1), combination of wax and isoparaffin, volatile oil (Patent Document 2), combination of wax, water-soluble polymer and volatile oil (Patent Document 3), acrylic A combination of a resin and polyvinyl alcohol (Patent Document 4) has been studied.
Japan Cosmetic Technology Society, “Advances and Future Prospects of Evaluation Technology for Cosmetics” Yakuji Nippo, March 31, 2001, pp. 374-383 JP 10-45546 A (pages 1 to 8) JP 2007-015935 A (page 1 to page 9) JP 2007-001887 A (page 1 to page 15) JP-A-11-199453 (pages 1 to 5)

However, it is difficult to obtain sufficient effects, and those using wax and the like have high hair styling power, but increase the stickiness peculiar to the raw material, resulting in weak hair styling holding power and a heavy and hard finish. It was. In addition, those using a film-forming synthetic polymer have a high hair-retaining power, but the finish feels stiff or the film-forming component peels off and dandruff (flaking) is seen, or The combination with other raw materials such as polyhydric alcohol has a plastic effect, and there are problems such as stickiness, insufficient setting power, and lack of glossiness on the hair.
For this reason, there has been a demand for the development of a hair cosmetic composition that has less stickiness, has a glossy finish, is non-sticky, has a high setting power, maintains the setting power, and does not flake.

  In view of such a situation, the present inventors have intensively studied. As a result, by using an acrylic copolymer containing a cycloalkyl group, the present invention is less susceptible to plastic effects due to polyhydric alcohols, has little stickiness, and is transparent. It has been found that a hair cosmetic product having a glossy (shiny) finish, having a smooth and non-sticky setting power, and having excellent properties that last for a long time can be obtained. Further, it has been found that the acrylic copolymer does not flake while having high transparency unique to the acrylic copolymer. Based on these findings, the present inventors have found that a hair cosmetic composition containing the acrylic copolymer and a volatile oil solves the above problems, and has completed the present invention.

That is, the present invention includes the following components (A) and (B):

(A) An acrylic copolymer containing a cycloalkyl group (B) A hair cosmetic comprising a volatile oil agent is provided.

  The hair cosmetic composition of the present invention is less susceptible to plastic effects due to polyhydric alcohol, etc., has little stickiness, has a transparent glossy finish, has a supple and high setting power, and does not flake. There is an advantage that the set power is excellent in sustainability.

  Among the monomers constituting the acryl-based copolymer containing a cycloalkyl group which is the component (A) of the present invention, the cycloalkyl group-containing acrylate and / or methacrylate of the component (a1) is a lipophilic polymerizable monomer. It forms a skeleton having water-resistant, transparent and hard film-forming ability. Specific examples include cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, tricyclodecyl acrylate, tricyclodecyl methacrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, and the like. 1 type, or 2 or more types can be used. In particular, cyclohexyl methacrylate is particularly preferable because it has a good radical polymerizability, a high yield, and a suitable glass transition point for forming a hard film.

  Among the monomers constituting the component (A) of the present invention, the acrylate and / or methacrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms of the component (a2) is a lipophilic polymerizable monomer. Gives flexibility and adhesion to the film and enhances solubility in light isoparaffin. Specific examples include octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isononyl acrylate, isononyl methacrylate, lauryl acrylate, lauryl methacrylate, and the like, and one or more of these can be used. However, 2-ethylhexyl methacrylate and lauryl methacrylate are preferable, and 2-ethylhexyl methacrylate is particularly preferable.

  Among the monomers constituting the component (A) of the present invention, the organopolysiloxane macromonomer containing a radically polymerizable group at one end of the component (a3) is an acrylic acid or methacrylic acid via a divalent hydrocarbon group. And ester compounds in which organopolysiloxanes are linked. The organopolysiloxane macromonomer containing a radically polymerizable group at one end of the component (a3) imparts water resistance to the film and increases the solubility in light isoparaffin. Specific examples include dimethylpolysiloxane macromonomer represented by the following general formula (1), and the degree of polymerization n indicating the repeating unit of the dimethylpolysiloxane group is preferably 0 to 200, more preferably 5 to 150. . Among these, 1 type, or 2 or more types can be used. Within this range, sufficient water resistance can be obtained, and a transparent and uniform film can be obtained.

(Here, n represents an integer of 0 to 200, R ₁ represents hydrogen or a methyl group, and R ₂ represents an alkyl group having 1 to 5 carbon atoms.)

  The copolymer of the component (A) of the present invention can be obtained by polymerizing the component (a1), which is a monomer constituting the component (A), and the component (a2) and / or the component (a3). . That is, it can be obtained by polymerizing the component (a1) and the component (a2), the component (a1) and the component (a3), or the component (a1), the component (a2) and the component (a3).

  In order to obtain the copolymer of the component (A) of the present invention, polymerization is carried out using 50 to 90% by mass (hereinafter simply referred to as “%”) of the cycloalkyl group-containing acrylate and / or methacrylate of the component (a1). Preferably, it is 50 to 80%. If it is this range, the solubility to light isoparaffin and the film | membrane of sufficient hardness will be formed.

  Similarly, in order to obtain the copolymer of the component (A) of the present invention, the component (a2) is preferably polymerized using 10 to 50%, more preferably 15 to 45%. Within this range, the solubility in light isoparaffin is good, a uniform and supple film with sufficient hardness can be obtained, and it is preferable without stickiness.

The component (a3) is preferably polymerized using 10 to 50%, more preferably 15 to 45%. If it is this range, the solubility to light isoparaffin is favorable, there is no stickiness, a uniform and hard film | membrane is formed, and favorable setting force is exhibited, and it is preferable.
Furthermore, when the said component (a2) and component (a3) are used together, it is preferable that the sum total is 10 to 50%, More preferably, it is 15 to 45%. If it is this range, the solubility to light isoparaffin is favorable, a uniform and hard film | membrane without stickiness is formed, and the favorable setting force is exhibited and it is preferable.

  The acrylic copolymer containing a cycloalkyl group of the component (A) of the present invention is a polymerizable monomer other than the above components (a1) to (a3) as long as the effects of the present invention are not impaired. It can be added and polymerized as a constituent monomer. The amount added is preferably about 0.01 to 10% within a range of about 20% or less. The polymerizable monomer other than the components (a1) to (a3) is not particularly limited, but styrene, substituted styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylic esters and methacrylates other than the above, and maleic anhydride. , Maleic acid ester, fumaric acid ester, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, fluorinated olefin, acrylamide, methacrylamide, methyl acrylamide, methyl methacrylamide, dimethyl methacrylamide, N-isopropyl acrylamide, N- Vinylpyrrolidone, N-vinylacetamide, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylamide, - acrylamide-2-dimethyl propane sulfonic acid salts.

Although the weight average molecular weight of the acryl-type copolymer containing the cycloalkyl group of the component (A) of this invention is not limited, What is the range of 1.0 * 10 < ⁴ > -2.0 * 10 < ⁵ >. preferable. The weight average molecular weight is measured by liquid gel permeation chromatography (GPC) using tetrahydrofuran as an eluent and using a calibration curve prepared with a linear polystyrene standard and a refractive index detector. If it is this range, the melt viscosity in the solubility to light isoparaffin is moderate, a uniform and favorable film | membrane will be formed, and it will become the thing excellent in the flexible setting power, and is preferable.

  The acrylic copolymer containing a cycloalkyl group of the component (A) of the present invention can be polymerized by a known polymerization method using the constituent monomers of the components (a1) to (a3). For example, organic peroxides such as benzoyl peroxide and lauroyl peroxide, α, α′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis The polymerization may be carried out in the presence of a radical polymerization initiator such as an azo compound such as (2-methylbutyronitrile), a persulfuric polymerization initiator such as potassium persulfate or ammonium persulfate, and a solution polymerization method or emulsification A polymerization method, a suspension polymerization method, a bulk polymerization method, a precipitation polymerization method and the like can be used. Among these, the solution polymerization method is particularly preferable because it is easy to adjust the molecular weight of the obtained acrylic copolymer to the optimum range.

  Examples of the solvent used in the polymerization of the acrylic copolymer containing the cycloalkyl group of the component (A) of the present invention include aromatic hydrocarbons such as benzene, toluene and xylene, and ketones such as methyl ethyl ketone and methyl isobutyl ketone. And esters such as ethyl acetate and butyl acetate, and alcohols such as isopropanol, ethyl alcohol, and methanol, and these may be used alone or in combination. Moreover, it can also superpose | polymerize in paraffinic solvents, such as light isoparaffin, isododecane, and isohexadecane.

  The polymerization reaction temperature of the acrylic copolymer containing the cycloalkyl group of the component (A) of the present invention is not particularly limited as long as it is within the temperature range in which a normal radical polymerization initiator can be used, but usually 40 to 120. It is carried out in the range of ° C. While the reaction temperature varies depending on the radical polymerization initiator to be used, the type of monomer, and the reaction temperature, it is usually carried out for 2 to 24 hours. If it is this range, since the amount of residual monomers is low and it can be obtained with a high yield, it is more preferable. The acrylic copolymer containing the cycloalkyl group of component (A) thus obtained is soluble at least 30% in light isoparaffin at 25 ° C. When the solubility is 30% or more, a non-sticky film with a uniform and appropriate hardness is formed, and it is flexible and exhibits a good setting force.

  The acrylic copolymer containing the cycloalkyl group of the component (A) is dissolved in a volatile oil agent when reacted or, if necessary, an oil agent such as other hydrocarbon, ester, triglyceride or the like. Dilution can also be performed, and solvent substitution to other oil agents can also be performed. Further, the solvent of the solution can be removed to take out the component (A) as a solid, and the acrylic copolymer is obtained by dissolving the resulting acrylic copolymer in a volatile oil such as light isoparaffin. It can also be used as a solution. The acrylic copolymer of component (A) and its solution may be used as a mixture of two or more.

  Although the compounding quantity of the acryl-type copolymer containing the cycloalkyl group of the component (A) to the hair cosmetics of this invention is not specifically limited, 0.1 to 5% is preferable, More preferably, it is 1-3. %. Within this range, there is no stickiness at the finish like other resins and polymers, a transparent and glossy film is formed, it can be set flexibly without being stiff, no flaking, A product with excellent sustainability of setting power can be obtained.

  The volatile oil of component (B) used in the hair cosmetic composition of the present invention serves as a solvent for the acrylic copolymer containing the cycloalkyl group of component (A), facilitating blending into the system, and finishing. Reduce stickiness and improve the sustainability of set power.

  Examples of the volatile oil of component (B) used in the hair cosmetic composition of the present invention include light isoparaffin, cyclic silicone, and volatile dimethylpolysiloxane. In particular, a mixture of hydrocarbons composed of light isoparaffins is preferable. Specifically, it is a saturated hydrocarbon having 9 to 12 carbon atoms having a side chain, and having a 95% by volume distillation temperature in a distillation test of JIS-K2254 of 200 ° C. or less. Is mentioned. Examples of commercially available products include IP solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.).

  Although the compounding quantity of the volatile oil agent of the component (B) to the hair cosmetics of this invention is not specifically limited, 1-90% is preferable, More preferably, it is 1-60%. If it is this range, the stickiness of a finish will be suppressed and the thing with the sustainability of a setting power will be obtained.

  In the hair cosmetic composition of the present invention, water and / or a lower alcohol can be further blended as the component (C). By blending component (C), the stickiness of the finish can be further suppressed, and a product that is easy to extend to the hair and has good usability can be obtained. As the water of component (C), in addition to purified water, mineral water, deep water, hot spring water, or steam distilled water of plants such as lavender and rose can be used. Examples of the lower alcohol include alcohols such as ethyl alcohol and propanol. Component (C) may be used alone or in combination of two or more thereof.

  Although the compounding quantity of the component (C) to the hair cosmetics of this invention is not specifically limited, 1-95% is preferable, More preferably, it is 20-80%. If it is this range, the stickiness of a finish will be suppressed, it will be easy to extend to hair, and the thing of favorable usability will be obtained.

  Moreover, in the hair cosmetics of this invention, a polyhydric alcohol can also be mix | blended as a component (D). By blending the polyhydric alcohol of component (D), the finish becomes more smooth and smooth.

  The polyhydric alcohol of component (D) is not particularly limited as long as it is usually blended as a cosmetic. Specifically, 1,3-butylene glycol, propylene glycol, dipropylene glycol, 1,2-pentylene. Glycol, 1,2-hexylene glycol, isoprene glycol, 1,2-octylene glycol, glycerin, diglycerin, polyethylene glycol, etc. may be mentioned, and these may be used alone or in combination of two or more. Can do.

  Although the compounding quantity of the polyhydric alcohol of the component (D) to the hair cosmetics of this invention is not specifically limited, 1 to 30% is preferable, More preferably, it is 1 to 15%. If it is this range, the thing with a smooth finish with a smoothness is obtained.

  In addition to the above essential components (A) to (D), the hair cosmetic composition of the present invention is usually used in preparations such as cosmetics, quasi-drugs, and external medicines as long as the effects of the present invention are not impaired. Components other than component (B), oil agent, surfactant, metal soap, gelling agent, powder, water-soluble polymer, film-forming agent, resin other than component (A), clathrate compound, moisturizer, Antibacterial agents, fragrances, deodorants, salts, pH adjusters, refreshing agents, plant extracts, vitamins, amino acids, peptides, and other beauty components for hair care can be blended.

  As the oil agent, oily components such as higher alcohols, hydrocarbon oils, ester oils, fatty acids, fats and oils other than the volatile oil of component (B) described above can be used. For example, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol , Higher alcohols such as sitosterol, lanosterol, monostearyl glycerol ether (batyl alcohol), hydrocarbons such as ozokerite, squalane, squalene, ceresin, paraffin, paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax, petrolatum, etc. , Diisobutyl adipate, 2-hexyldecyl adipate, adipic acid 2-heptylundecyl, monoisostearic acid-alkyl glycol, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, tri-2-ethylhexanoate tri Methylolpropane, tetra-2-ethylhexanoic acid pentaerythritol, cetyl octoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate , Amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, milk Myristyl, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearylate, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, Ester oils such as myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, diisostearyl malate, waxes such as beeswax, carnauba wax, candelilla wax, whale wax, beef tallow, beef leg fat, Beef bone fat, hardened beef fat, hardened oil, turtle oil, pork fat, horse fat, mink oil, liver oil, egg yolk oil and other animal oils, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid Lanolin derivatives such as isopropyl, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, arachidonic acid, docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid Low-polymerization dimethylpolysiloxane, high-polymerization dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, polyether-modified polysiloxane, polyoxyalkylene, alkylmethylpolysiloxane, methylpoly Siloxane copolymer, alkoxy-modified polysiloxane, alkyl-modified polysiloxane, cross-linked organopolysiloxane, fluorine-modified polysiloxane, amino-modified polysiloxane, glycerin Modified polysiloxane, higher alkoxy-modified silicones, higher fatty acid-modified silicones, silicone resins, silicone rubber, silicone resin and the like.

  As the surfactant, nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxy Propylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor Oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol , Polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, polyoxyalkylene / alkyl co-modified organopolysiloxane, lauric acid diethanolamide, coconut oil fatty acid diethanolamide , Coconut oil fatty acid monoethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide, lauric acid monoisopropanolamide, coconut oil fatty acid monoisopropanolamide, polyoxyprolene coconut oil fatty acid monoisopanolamide, alkanolamide, sugar ether, Examples thereof include sugar amides. Anionic surfactants include higher fatty acid salts such as sodium laurate, potassium laurate and potassium coconut fatty acid; sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl ether ammonium sulfate, polyoxyethylene lauryl ether sulfate triethanolamine Polyoxyethylene alkyl ether sulfates such as sodium lauryl sulfate, alkyl sulfates such as triethanolamine lauryl sulfate; α-olefin sulfonates such as sodium tetradecenesulfonate and potassium tetradecenesulfonate; dodecane-1,2 -Hydroxy ether carboxylates such as sodium diol acetate; sulfosuccinic acid such as sodium sulfosuccinate and the like. Cationic surfactants include cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium chloride, behenyl trimethyl ammonium bromide, behenyl trimethyl ammonium methyl sulfate, distearyl chloride Quaternary ammonium salts such as dimethylammonium, dioleyldimethylammonium bromide, cetylbehenyldimethylammonium sulfate, stearyldimethylbenzylammonium chloride, stearoyl lysine butyl ester / hydrochloride, N-coconut oil fatty acid acyl L-arginine ethyl DL -Mono-N-long chain acyl bases such as pyrrolidone carboxylate, lauroyl-ornithine propyl ester, acetate Amino lower alkyl ester salts, decyl guanidine acetate, 2-guanidino-ethyl lauramide hydrochloride, a guanidine derivative, such as 2-guanidino-butyl stearamide · DL-pyrrolidone carboxylic acid salt. Amphoteric surfactants include cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium chloride, behenyl trimethyl ammonium bromide, behenyl trimethyl ammonium methyl sulfate, distearyl dimethyl chloride Quaternary ammonium salts such as ammonium, dioleyl dimethyl ammonium bromide, cetyl behenyl dimethyl ammonium methyl sulfate, stearyl dimethyl benzyl ammonium chloride, stearoyl lysine butyl ester / hydrochloride, N-coconut oil fatty acid acyl L-arginine ethyl DL- Mono-N-long chain acyl basic amino acids such as pyrrolidone carboxylate, lauroyl-ornithine propyl ester and acetate Acid lower alkyl ester salts, decyl guanidine acetate, 2-guanidino-ethyl lauramide hydrochloride, a guanidine derivative, such as 2-guanidino-butyl stearamide · DL-pyrrolidone carboxylic acid salt.

  Metal soaps include: aluminum isostearate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, sodium cetyl phosphate, zinc laurate, undecylenate Zinc etc. are mentioned.

  Gelling agents include amino acid derivatives such as α, γ-di-n-butylamine, dextrin palmitate, dextrin stearate, dextrin fatty acid ester such as dextrin 2-ethylhexanoate palmitate, sucrose palmitate Sucrose fatty acid esters such as sucrose stearate, benzylidene derivatives of sorbitol such as monobenzylidene sorbitol, dibenzylidene sorbitol, organically modified clay minerals such as dimethylbenzyl dodecyl ammonium montmorillonite clay, dimethyl dioctadecyl ammonium montmorillonite clay, etc. .

  If the powder is used in ordinary cosmetics, its shape (spherical, needle-like, plate-like, etc.), particle size (smoke-like, fine particles, pigment grade, etc.), particle structure (porous) Any inorganic powder can be used, for example, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, synthetic mica. , Mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, Barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hydrite, montmorillonite, z Light, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, etc .; organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder, polymethyl Benzoguanamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk powder, nylon powder, 12 nylon, 6 nylon, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol Resin, fluororesin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder, Lauro Luridine, etc .; as colored pigments, inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as γ-iron oxide, yellow inorganic oxides such as yellow iron oxide and loess, black iron oxide, Inorganic black pigments such as carbon black, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as bitumen and ultramarine, tar Dye raked, natural dye raked, composite powder made by combining these powders, etc .; pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide Coated bismuth oxychloride, titanium oxide coated talc, fish scale foil, titanium oxide coated colored mica, etc .; -Powder, stainless steel powder, etc. As tar pigments, Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227 , Red 228, Red 230, Red 401, Red 505, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 204, Yellow 401, Blue 1, Blue 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207, etc .; A powder selected from acids, laccaic acid, calsamine, bradylin, crocin, etc., and these powders are compounded or surface treated with oils, silicones, or fluorine compounds It may be carried out powder.

  The water-soluble polymer is not particularly limited as long as it is used in ordinary cosmetics. Specifically, cationized cellulose, cationized guar gum, cationized starch, dimethyldiallylammonium chloride / acrylamide copolymer, Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer, cationic polymer such as polydimethylmethylenediperinium chloride, methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer, (octylacrylamide / hydroxypropyl acrylate) / Butylaminoethyl methacrylate) copolymer, amphoteric polymers such as acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, chondroitin sulfate, hyaluronic acid, mucin, dermatan sulfate, heparin and Mucopolysaccharides selected from keratan sulfate and salts thereof, gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, algae colloid, trant gum, locust bean gum, galactomannan, etc. Molecules, microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, starch polymers such as starch, carboxymethyl starch, methylhydroxypropyl starch, methylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropyl Cellulose of cellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder Polymers, sodium alginate, alginic acid polymers such as propylene glycol alginate, vinyl polymers such as carboxyvinyl polymers and alkyl-modified carboxyvinyl polymers, polyoxyethylene polymers, polyoxyethylene polyoxypropylene copolymer systems Examples include polymers, acrylic polymers such as sodium polyacrylate and polyacrylamide, and inorganic water-soluble polymers such as polyethyleneimine, bentonite, laponite, and hectorite. Also included are film forming agents such as polyvinyl alcohol and polyvinyl pyrrolidone.

  Antibacterial agents include benzoic acid, sodium benzoate, salicylic acid, coalic acid, sorbic acid, potassium sorbate, paraoxybenzoic acid ester, parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitive And silicon, bis (2-pyridylthio-1-oxide) zinc, phenoxyethanol, isopropylmethylphenol, polyaminopropyl biguanide and the like.

  Examples of pH adjusters include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, malic acid, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide, triethanolamine, monoethanolamine, Examples of the refreshing agent include l-menthol and camphor.

  Vitamins such as vitamin A and derivatives thereof, vitamin B and derivatives thereof, vitamin C and derivatives thereof, vitamin D and derivatives thereof, vitamin E and derivatives thereof, linolenic acid and derivatives thereof; phytonadione, menaquinone, Vitamin Ks such as menadione and menadiol; vitamins P such as eriocitrin and hesperidin; and biotin, carcinine, ferulic acid and the like.

Examples of amino acids include glycine, alanine, valine, isoleucine, serine, threonine, aspartic acid, glutamic acid, asparagine, glutamine, lysine, hydroxylysine, arginine, cystine, cysteine, acetylcysteine, methionine, phenylalanine, tyrosine, proline, hydroxy Examples include proline, ortinin, citrulline, theanine, creatine, and creatinine. As amino acid derivatives, N-lauroyl-L-glutamate di (phytosteryl 2-octyldodecyl), N-lauroyl-L-glutamate di (cholesteryl behenyl octyldodecyl), N-lauroyl-L-glutamate di (cholesteryl Octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl, behenyl, 2-octyldodecyl), N-lauroyl-L-glutamate di (2-octyldodecyl), N-acylglutamate lysine condensate and the like. Peptides may be derived from animals, fish, shellfish, plants, and specifically, collagen and derivatives thereof or hydrolysates thereof, elastin and derivatives thereof or hydrolysates thereof, keratin and derivatives thereof or the like. Degradation products, wheat proteins and derivatives thereof or hydrolysates thereof, soybean proteins and derivatives or hydrolysates thereof, and the like. Examples of the saccharide include sorbitol, erythritol, maltose, maltitol, xylitol, xylose, trehalose, inositol, glucose, mannitol, pentaerythritol, fructose, sucrose and esters thereof, dextrin and derivatives thereof, honey, brown sugar extract and the like. . In addition, compositions containing ceramide and derivatives thereof, hair lipid components such as 18-methyleicosanoic acid, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingophospholipids and the like, or the like Products, that is, soybean lecithin, egg yolk lecithin, or hydrogenated products thereof, and also a phospholipid such as a homopolymer of 2-methacryloyloxyethyl phosphorylcholine or a copolymer of 2-methacryloyloxyethyl phosphorylcholine and a hydrophobic monomer And beauty derivatives useful for hair care such as moisturizing and repairing hair. One or two or more of these may be appropriately selected or combined.

  The hair cosmetic composition of the present invention may be aqueous, solubilized, O / W emulsified, W / O emulsified, oily, etc. as a dosage form, and may be liquid, emulsion, cream, gel, solid The shape and other properties may be any. It can also be used as foam type with aerosol foam or pump foam container with propellant, hair milk, hair cream, hair gel, hair wax, hair mousse, hair spray, pomade, hair lotion, hair It can be used as a color, shampoo, conditioner, hair pack, hair oil, hair colon, hair essence, hair straightener, permanent agent, and the like.

  Next, the present invention will be described in more detail with reference to examples. The present invention is not limited at all by these.

Production Example 1: Synthesis of cycloalkyl group-containing acrylic copolymer 1 In a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stirrer, 22.5 g of cyclohexyl methacrylate and 2-ethylhexyl methacrylate 7.5 g and 70 g of toluene were added, and nitrogen gas was introduced to make a nitrogen atmosphere sufficiently. Then, the mixture was heated to 100 ° C., 0.15 g of AIBN was added and refluxed for 3 hours for polymerization. Methanol was injected into the resulting reaction product to precipitate an acrylic copolymer, and the precipitate was filtered off and dried under vacuum to obtain 27.4 g of a solid content of cycloalkyl group-containing acrylic copolymer. The weight average molecular weight in terms of polystyrene was 3.8 × 10 ⁴ . Moreover, what mixed 70 mass parts of light isoparaffins (IP solvent 1620 (made by Idemitsu Kosan Co., Ltd.)) and mixed this with 30 mass parts melt | dissolved well in 25 degreeC, and became transparent.

Production Example 2 Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer 2 In a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirrer, 22.5 g of cyclohexyl methacrylate, the following general formula ( 2) 7.5 g of dimethylpolysiloxane macromonomer and 70 g of toluene were added, and nitrogen gas was introduced to make a nitrogen atmosphere sufficiently. Then, the mixture was heated to 100 ° C. and α, α′-azobisisobutyronitrile ( Hereinafter, 0.15 g of AIBN) was added, and the mixture was refluxed for 8 hours for polymerization. Toluene was distilled off from the obtained reaction product by evaporation, followed by vacuum drying to obtain 26.6 g of a cycloalkyl group-containing acrylic copolymer solid content. The weight average molecular weight in terms of polystyrene was 6.7 × 10 ⁴ . Further, as in Production Example 1, 30 parts by mass of light isoparaffin (IP solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.)) 70 parts by mass was mixed and dissolved well at 25 ° C. and became transparent. It was.

Production Example 3 Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer 3 A four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirrer was charged with 15 g of cyclohexyl methacrylate, 15 g of 2-ethylhexyl methacrylate and After adding 70 g of toluene and introducing nitrogen gas to make it sufficiently nitrogen atmosphere, the mixture was heated to 100 ° C., 0.15 g of AIBN was added and refluxed for 3 hours for polymerization. Methanol was injected into the obtained reaction product to precipitate an acrylic copolymer, and the precipitate was filtered off and dried under vacuum to obtain 25.5 g of a cycloalkyl group-containing acrylic copolymer solid content. The weight average molecular weight in terms of polystyrene was 3.7 × 10 ⁴ . Further, as in Production Example 1, 30 parts by mass of light isoparaffin (IP solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.)) 70 parts by mass was mixed and dissolved well at 25 ° C. and became transparent. It was.

Production Example 4: Synthesis of Acrylic Copolymer 4 Containing Cycloalkyl Group 4. 21 g of cyclohexyl methacrylate and 2-ethylhexyl methacrylate were added to a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stirrer. 5 g, 4.5 g of the dimethylpolysiloxane macromonomer of the above general formula (2) and 70 g of toluene were added, nitrogen gas was introduced and the atmosphere was sufficiently nitrogen, then heated to 80 ° C., and 0.15 g of AIBN was added. The mixture was refluxed for 5 hours for polymerization. Methanol was injected into the obtained reaction product to precipitate an acrylic copolymer, and the precipitate was filtered off and dried under vacuum to obtain 20.5 g of a solid content of cycloalkyl group-containing acrylic copolymer. The weight average molecular weight in terms of polystyrene was 6.2 × 10 ⁴ . Further, as in Production Example 1, 30 parts by mass of light isoparaffin (IP solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.)) 70 parts by mass was mixed and dissolved well at 25 ° C. and became transparent. It was.

Example 1: Invention products 1 to 4 and comparative products 1 to 4: Hair styling materials Hair styling materials shown in Table 1 were prepared by the following production method, and the finish was “non-sticky” and “glossy” (transparent glossy ”),“ Supple setting power ”,“ sustainability of setting power ”, and“ no flaking ”were determined by the following evaluation method and criteria, and the results are also shown in Table 1.

(Production method)
A: 1 to 8 and 11 are mixed by heating (70 ° C.) and uniformly dissolved.
B: Heat (70 ° C.) to mix 12-16 to dissolve uniformly.
C: C is added to B and emulsified.
D: After cooling C, add 9,10.

〔Evaluation method〕
20 panelists specializing in cosmetics evaluation use the hair-styling products of the present invention and comparative products, and evaluate the “no stickiness”, “feel of gloss”, and “flexible set power” at the finish, After 3 hours of normal life, each of them evaluated the “sustainability of set power” and “no flaking”.
“No stickiness”, “Glossy”, “Flexible setting power”, “Sustainability of setting power” are evaluated according to the following evaluation criteria 1, and the average score of each item and all panels is evaluated. The determination was made according to the following criteria 1.
“No flaking” was evaluated according to the following evaluation criteria 2, and the average score of all panels was determined according to the following criteria 2.

Evaluation criteria 1: Evaluation of “no stickiness”, “glossiness (transparent glossiness)”, “flexible setting power”, “sustainability of setting power” [Evaluation result]: [rating]
Very good: 5 points Good: 4 points Normal: 3 points Somewhat bad: 2 points Bad: 1 point Criteria 1:
[Average score]: [Judgment]
4.5 or more: ◎
3.5 or more and less than 4.5: ○
1.5 or more and less than 3.5: △
Less than 1.5: ×

Evaluation criteria 2: Evaluation of “no flaking” [Evaluation result]: [Score]
No problem: 4 points Flaking is seen only slightly: 3 points Flaking is seen slightly: 2 points Flaking is found in the whole hair: 1 point Criterion 2:
[Average score]: [Judgment]
3.5 or more: ◎
3.0 or more to less than 3.5: ○
2.0 or more and less than 3.0: △
Less than 2.0: ×

The hair styling products of the present invention products 1 to 4 blended with the acrylic copolymer containing a cycloalkyl group of Production Example 1 or 2 are all non-sticky, glossy, supple setting power, and setting power. It was an excellent hair styling product in all of its sustainability and lack of flaking. In particular, the products 1 and 2 of the present invention exhibited the effects of an acrylic copolymer containing a cycloalkyl group sufficiently, and were extremely excellent in a smooth finish with no stickiness.
On the other hand, the comparative product 1 in which the copolymer (A) was not blended with the hairdressing composition was not satisfactory as a hairdressing composition because the finished glossiness, the supple setting power, and the durability of the setting power were not obtained. Moreover, in the comparative product 2 which mix | blended the (vinyl pyrrolidone / vinyl acetate) copolymer as another copolymer instead of the copolymer of (A), it receives a plastic effect, such as a polyhydric alcohol, and becomes sticky. Lack of gloss and set power, flaking also occurred, and it was not satisfactory in all aspects. Similarly, Comparative Product 3 containing another acrylate silicone instead of the copolymer of (A) is not satisfactory because it feels sticky to the finish and does not provide a firm and flexible setting force. It was. Furthermore, comparative product 4 in which non-volatile liquid paraffin is blended in place of the volatile oil of (B) is a non-uniform system in which component (A) does not dissolve, and even if it is forcibly applied to hair It was not satisfactory because it was sticky, glossy and inferior in setting.

Example 2: Hair wax Hair wax was prepared by the following composition and production method.

(composition)
(Component) (%)
(1) Stearic acid 2
(2) Paraffin 8
(3) Cetostearyl alcohol 3
(4) Liquid paraffin 2
(5) Triethylhexanoin 2
(6) Triphenylmethylpolysiloxane 1
(7) Light isoparaffin * 1 5
(8) Acrylic copolymer containing a cycloalkyl group * 3 2
(9) Purified water remaining amount (10) 1,3-butylene glycol 10
(11) Polyethylene glycol 1
(12) 2-Methacryloyloxyethyl phosphorylcholine / methacrylic acid copolymer 1
(13) 1,2-pentylene glycol 1
(14) Triethanolamine 1
(15) Amino-modified silicone emulsion * 5 3
* 5: SM8904 COSMETIC EMULSION (Toray Dow Corning)

(Production method)
A: 1 to 8 are heated (70 ° C.) and mixed to dissolve uniformly.
B: 9 to 14 are heated (70 ° C.) and mixed to dissolve uniformly.
C: C is added to B and emulsified.
D: After cooling C, add 15

  The hair wax of Example 2 obtained as described above is an excellent hair wax in all of the glossiness of the finish, non-stickiness of the finish, supple setting power, durability of the setting power, and no flaking. became. In particular, the acrylic copolymer containing a cycloalkyl group used in this is excellent in water resistance, and is excellent in non-stickiness and sustainability of setting power even in high humidity environments such as rainy days. It was something that demonstrated.

Example 3: Hair oil Hair oil was prepared by the following composition and production method.

(composition)
(Component) (%)
(1) Light isoparaffin * 1 Remaining amount (2) Acrylic copolymer containing cycloalkyl group * 6 2
(3) Dimethylpolysiloxane 40
(4) Dimethiconol 10
(5) Phenyl glycol 0.5
(6) Jojoba oil 1
(7) Phytosterol 0.1
* 6: Acrylic copolymer containing cycloalkyl group of Production Example 3

(Production method)
A: 1 and 2 are mixed and uniformly dissolved.
B: 3-7 are uniformly dissolved, and A is added thereto to make it uniform.

  The hair oil of Example 3 obtained as described above was an excellent hair oil in all of the glossiness of finish, non-stickiness of finish, supple setting power, durability of setting power, and lack of flaking. .

Example 4:
A hair spray was prepared by the following composition and production method.

(composition)
(Component) (%)
(1) Ethyl alcohol Residual amount (2) Methyl paraoxybenzoate 0.3
(3) Octyl palmitate 25
(4) Isopropyl myristate 15
(5) Light isoparaffin * 1 10
(6) Acrylic copolymer containing a cycloalkyl group * 7 3
(7) Behenyl alcohol 1
(8) Propylene glycol dicaprate 0.5
(9) Paramethoxycinnamic acid-2-ethylhexyl 0.1
(10) Fragrance Appropriate amount * 7: Acrylic copolymer containing the cycloalkyl group of Production Example 4

(Production method)
A: 1 and 2 are mixed and uniformly dissolved.
B: 3-10 are uniformly dissolved, and A is added thereto to make it uniform to obtain a stock solution.
C: A 40% aerosol can is filled with propellant (dimethyl ether) with respect to 60% of the stock solution of B to obtain a hair spray.

  The hair spray of Example 4 obtained as described above was an excellent hair spray in all of the finish non-stickiness, glossiness, supple setting power, durability of setting power, and lack of flaking. .

Claims (10)

The following components (A) and (B);
(A) Acrylic copolymer containing a cycloalkyl group (B) A hair cosmetic blended with light isoparaffin, wherein the acrylic copolymer containing a cycloalkyl group of component (A) is ,
An acrylic copolymer composed of the following components (a1) and (a2);
(A1) cyclo hexyl acrylate and / or cyclohexyl methacrylate (a2) acrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms and / or methacrylate or the following components (a1), composed of (a3) Acrylic copolymer;
(A1) an organopolysiloxane macromonomer or the next component containing cyclo hexyl acrylate and / or cyclohexyl methacrylate (a3) one terminal radical polymerizable group (a1), (a2), acrylic composed of (a3) Copolymer;
(A1) organosilane containing cyclo hexyl acrylate and / or cyclohexyl methacrylate (a2) a linear or acrylate containing a branched alkyl group and / or the radical polymerizable group in methacrylate (a3) one end of 8 to 12 carbon atoms A hair cosmetic characterized by being a polysiloxane macromonomer.   The acrylic copolymer containing a cycloalkyl group of component (A) is an acrylic copolymer obtained by polymerizing component (a1) at 50 to 90 mass% and component (a2) at 10 to 50 mass%. The hair cosmetic composition according to claim 1, wherein the hair cosmetic composition is provided.   The acrylic copolymer containing a cycloalkyl group of component (A) is an acrylic copolymer obtained by polymerizing component (a1) at 50 to 90% by mass and component (a3) at 10 to 50% by mass. The hair cosmetic composition according to claim 1, wherein the hair cosmetic composition is provided.   The acrylic copolymer containing a cycloalkyl group of component (A) is an acrylic copolymer obtained by polymerizing component (a1) at 50 to 90% by mass, component (a2), and component (a3). The hair cosmetic composition according to claim 1, wherein the hair cosmetic composition is provided. The component (a3) of the component (A) is a dimethylpolysiloxane macromonomer represented by the general formula (1)
(Here, n represents an integer of 0 to 200, R ₁ represents hydrogen or a methyl group, and R ₂ represents an alkyl group having 1 to 5 carbon atoms.)
The hair cosmetic composition according to claim 1, wherein the hair cosmetic composition is an acrylic copolymer.   The hair cosmetic composition according to any one of claims 1 to 5, wherein the component (a1) of the component (A) is an acrylic copolymer which is cyclohexyl methacrylate. The weight average molecular weight in terms of polystyrene measured by liquid gel permeation chromatography of the acrylic copolymer containing a cycloalkyl group as the component (A) is 1.0 × 10 ^{4 to} 2.0 × 10 ^5. The hair cosmetic composition according to any one of claims 1 to 6. The hair cosmetic composition according to any one of claims 1 to 7 , further comprising water and / or a lower alcohol as component (C). Furthermore, the hair cosmetics in any one of the Claims 1 thru | or 8 which mix | blend a polyhydric alcohol as a component (D). The hair cosmetic composition according to any one of claims 1 to 9 , wherein the hair cosmetic composition is a hair styling composition.