JP7366169B2 - Polyurethane resin for cosmetics and cosmetics containing polyurethane resin for cosmetics - Google Patents

Description

The present invention relates to a polyurethane resin for cosmetics and a cosmetic containing the polyurethane resin for cosmetics.

Makeup cosmetics are made of powder ingredients (talc, mica, titanium oxide, coloring pigments, etc.), oily ingredients (natural oils and fats, hydrocarbons, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, etc.), surfactants, It consists of polyhydric alcohols, polymer compounds, aqueous ingredients, etc., and there are a wide variety of types, including solid foundation, liquid foundation, eye shadow, blusher, lipstick, eyeliner, mascara, and sunscreen emulsion, as well as solid, non-aqueous, There are dosage forms such as W/O emulsion type and O/W emulsion type.

Conventionally, various film-forming resins have been used in makeup cosmetics in order to improve adhesion and prevent makeup from fading. Among these, film-forming resins such as ethyl acrylate/methacrylic acid copolymers, which have excellent makeup retention, are widely used. However, if an effective amount of film-forming resin is added to prevent makeup from fading, the film will feel taut, resulting in a poor feeling of use. It also causes insoluble lumps and aggregation of pigments.

In order to solve these problems, attempts have been made to provide makeup cosmetics containing film-forming resins with an excellent feeling of use and to improve the makeup's long-lasting effect. Specifically, emulsified makeup cosmetics containing a specific silicone graft copolymerized acrylic resin, a solid substance, and a hydrophobized powder (for example, see Patent Document 1) have been proposed.

Japanese Patent Application Publication No. 2002-212033

By using cosmetics containing the above-mentioned resins, it is possible to maintain the feeling of use and make-up durability to some extent, but the uniformity of the film upon application is still poor, and the film has poor ability to follow the movements of the skin. There is a problem in that makeup smudges due to sebum and the like, impairing the beauty of the film.
Therefore, the present invention focuses on urethane resin, which has a high affinity with sebum and is expected to prevent make-up from coming off and shine (sebum rises to the surface) caused by sebum, and improves the uniformity of the film and the movement of the skin. To provide a cosmetic that has excellent film followability and sebum resistance, and does not easily discolor even after long-term make-up.

The present inventors have made extensive studies to achieve the above object, and as a result, have arrived at the present invention. That is, the present invention provides a polyurethane resin (U) containing a polyol and a polyisocyanate (B) as essential constituent monomers, wherein the polyol (A) has a number average molecular weight of 500 to 5,000, and the polyol is Polyurethane resin for cosmetics containing polyfarnesene polyol (A1) and/or hydrogenated product of polyfarnesene polyol (A2); containing the polyurethane resin for cosmetics and water and/or solvent (S) A polyurethane resin composition for cosmetics; an aqueous polyurethane resin dispersion for cosmetics containing the polyurethane resin for cosmetics and water; a cosmetic containing the polyurethane resin for cosmetics.

The polyurethane resin for cosmetics of the present invention can provide a film with excellent film uniformity, ability to follow the movement of the skin, and sebum resistance, and can produce cosmetics that do not easily discolor even after long periods of use. It has the effect that it can be obtained.

The polyurethane resin for cosmetics of the present invention is a polyurethane resin (U) containing polyol (A) and polyisocyanate (B) as essential constituent monomers, wherein the polyol (A) has a number average molecular weight of 500 to 5. ,000, and the polyol (A) is a polyurethane resin for cosmetics containing a polyfarnesene polyol (A1) and/or a hydrogenated polyfarnesene polyol (A2).
In the present invention, by using a polyol containing a polyfarnesene polyol (A1) and/or a hydrogenated polyfarnesene polyol (A2) as the polyol (A), the molecular structure of the polyurethane resin (U) By having a part with high affinity for the skin and further using a polyol (A) with a number average molecular weight within the above range, uniformity during application, ability of the film to follow skin movements, and sebum resistance are improved. It was also discovered that an excellent film could be obtained.

<Polyol (A)>
In the present invention, the polyol (A) includes a polyfarnesene polyol (A1) and/or a hydrogenated polyfarnesene polyol (A2).
Polyfarnesene polyol (A1) means a polyol obtained by introducing a hydroxyl group into a polymer of farnesene-containing monomers.
Farnesene is one of the sesquiterpene hydrocarbons and is a bioraw material that can also be obtained from plants.
Examples of farnesene include α-farnesene represented by the following chemical formula (1) and β-farnesene represented by the chemical formula (2). One type of farnesene may be used, or two or more types may be used in combination.

Examples of the polyfarnesene polyol (A1) include polyols in which hydroxyl groups have been introduced into farnesene homopolymers, and polyols in which hydroxyl groups have been introduced into polyfarnesene copolymers obtained from farnesene and other vinyl monomers.
Other vinyl monomers include, for example, aliphatic unsaturated hydrocarbons other than farnesene [olefins having 2 to 36 carbon atoms (e.g., ethylene, propylene, 1-butene, 2-butene, isobutene, pentene, heptene, diisobutylene, octene); , dodecene, octadecene, triacosene, hexatriacocene, etc.) and dienes having 4 to 36 carbon atoms (e.g., isoprene, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, and 1,7-octadiene, etc.) etc.], alicyclic unsaturated hydrocarbons [e.g. cyclohexene, (di)cyclopentadiene, pinene, limonene, indene, vinylcyclohexene and ethylidene bicycloheptene, etc.], unsaturated hydrocarbons containing aromatic groups (e.g. styrene, α- Methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, vinylnaphthalene, divinylbenzene, divinyltoluene, divinylxylene and trivinylbenzene etc.) etc.
As other vinyl monomers, one type may be used, or two or more types may be used in combination.

The content of the farnesene-derived structural unit in the polyfarnesene polyol (A1) is determined based on the total weight of the monomers constituting the polyfarnesene polyol (A1). From the viewpoint of followability to the movement of The amount is 100% by weight, particularly preferably 70 to 100% by weight.
When farnesene is bio-derived, it is possible to reduce the dependence on petroleum in cosmetics, which is preferable from the viewpoint of carbon dioxide reduction and effective use of resources.

Polyfarnesene polyol (A1) is a polyol having repeating units derived from farnesene and two or more hydroxyl groups, and is prepared by polymerizing monomer components containing farnesene and, if necessary, other vinyl monomers other than farnesene. Examples include polyols obtained by a method of obtaining a polyfarnesene (co)polymer and then introducing a hydroxyl group to the terminal of the polyfarnesene (co)polymer. For example, a monomer component containing farnesene and other vinyl monomers other than farnesene is subjected to a living anionic polymerization reaction to obtain a polyfarnesene (co)polymer, and then the living end of the living polymer is connected to an alkylene oxide (e.g., carbon A polyol in which a hydroxyl group is introduced at each end of the chain part of the polymer (if it is a straight chain, a diol If it is a branched chain, it can be obtained by a method of obtaining a polyol having three or more hydroxyl groups.

The number average molecular weight (hereinafter abbreviated as Mn) of the polyfarnesene polyol (A1) is 500 to 5,000, preferably 1,000 from the viewpoint of the film's ability to follow skin movements and solvent solubility. ~3,000.
The weight average molecular weight (hereinafter abbreviated as Mw) of the polyfarnesene polyol (A1) is from 500 to 500, from the viewpoint of the ability of the polyurethane resin (U) film to follow the movement of the skin, uniformity of the film, and solvent solubility. It is preferably 10,000, more preferably 1,000 to 8,000.
The molecular weight distribution (Mw/Mn) of the polyfarnesene polyol (A1) is preferably 1.0 to 1.8 from the viewpoint of the film's ability to follow skin movements, film uniformity, and solvent solubility, and Preferably it is 1.0 to 1.5.
Mn, Mw, and molecular weight distribution of polyfarnesene polyol (A1) are measured by GPC (gel permeation chromatography) under the following conditions.
Equipment: High temperature gel permeation chromatograph
[“Alliance GPC V2000”, manufactured by Waters Co., Ltd.]
Detection device: Refractive index detector Solvent: Orthodichlorobenzene Reference material: Polystyrene Sample concentration: 3mg/ml
Column stationary phase: PLgel 10μm, MIXED-B 2 bottles in series
[Manufactured by Polymer Laboratories Co., Ltd.]
Column temperature: 135℃

The hydroxyl value (mgKOH/g) of polyfarnesene polyol (A1) is 18 to 225 mgKOH/g from the viewpoint of the ability of the polyurethane resin (U) film to follow the movement of the skin, uniformity of the film, and solvent solubility. is preferable, and more preferably 22 to 112 mgKOH/g.
In the present invention, the hydroxyl value is a value measured in accordance with JIS K0070-1992.
The glass transition temperature (hereinafter sometimes abbreviated as Tg) of the polyfarnesene polyol (A1) is -80 to -80 from the viewpoint of the ability of the polyurethane resin (U) film to follow the movement of the skin and the solubility in solvents. The temperature is preferably -10°C, more preferably -70 to -30°C.
In the present invention, the glass transition temperature is a value measured by a method specified in ASTM D3418-82 (DSC method) using, for example, DSC Q20 manufactured by TA Instruments Co., Ltd.

In the present invention, the hydrogenated polyfarnesene polyol (A2) is one in which the carbon-carbon double bonds of the polyfarnesene polyol (A1) are partially or completely hydrogenated.
The number of carbon-carbon double bonds per 1000 carbon atoms of the hydrogenated polyfarnesene polyol (A2) is 0 to 200 from the viewpoint of the ability of the polyurethane resin (U) film to follow the movement of the skin. The number is preferably 0 to 100, and more preferably 0 to 100.
The number of double bonds can be determined from ^{the 1} H-NMR (nuclear magnetic resonance) spectroscopy spectrum of the hydrogenated polyfarnesene polyol (A2). That is, the peak in the spectrum is assigned, and the integral value derived from the double bond at 4.5 to 6 ppm of the hydrogenated product of polyfarnesene polyol (A2) and the hydrogenated product of polyfarnesene polyol (A2) From the integral value of the origin, calculate the relative value of the number of double bonds of the hydrogenated polyfarnesene polyol (A2) and the number of carbon atoms of the hydrogenated polyfarnesene polyol (A2), and calculate the relative value of the number of double bonds of the hydrogenated polyfarnesene polyol (A2). The number of double bonds per 1,000 carbons of the hydrogenated product (A2) is calculated.

The Mn of the hydrogenated polyfarnesene polyol (A2) is 500 to 5,000 from the viewpoint of the ability of the polyurethane resin (U) to follow the movement of the skin, the uniformity of the film, and the solvent solubility. , preferably 1,000 to 3,000.
The Mw of the hydrogenated product of polyfarnesene polyol (A2) is preferably 500 to 10,000, more preferably 1, 000 to 8,000.
The molecular weight distribution (Mw/Mn) of the hydrogenated polyfarnesene polyol (A2) is 1.0 to 1.8 from the viewpoint of the film's ability to follow skin movements, film uniformity, and solvent solubility. is preferable, and more preferably 1.0 to 1.5.
The Mn, Mw and molecular weight distribution (Mw/Mn) of the hydrogenated polyfarnesene polyol (A2) were determined by GPC (gel permeation chromatography) under the same conditions as the polyfarnesene polyol (A1). be measured.
The hydroxyl value (mgKOH/g) of the hydrogenated polyfarnesene polyol (A2) is preferably 18 to 225 mgKOH/g from the viewpoint of the film's ability to follow skin movements, film uniformity, and solvent solubility. , more preferably 22 to 112 mgKOH/g.
The glass transition temperature of the hydrogenated polyfarnesene polyol (A2) is preferably -80 to -10°C, more preferably -70 to - from the viewpoint of the film's ability to follow skin movements and solvent solubility. The temperature is 30°C.

As polyfarnesene polyol (A1) and hydrogenated polyfarnesene polyol (A2), "KRASOL F 3000 (polyfarnesene diol)" and "KRASOL F 3100 (hydrogenated polyfarnesene diol)" manufactured by Cray Valley Co., Ltd. farnesenediol), etc. are available.

In the present invention, as the polyol (A), in addition to the polyfarnesene polyol (A1) and the hydrogenated polyfarnesene polyol (A2), preferably a condensed polyester polyol (A3), a polylactone polyol ( A4), polycarbonate polyol (A5), polyether polyol (A6), poly(meth)acrylic polyol (A7), (hydrogenated) polybutadiene polyol (A8), castor oil polyol (A9) and silicone polyol (A10) It may contain at least one polyol selected from the group consisting of:

From the viewpoint of solvent solubility, the hydroxyl value (mgKOH/g) of the polyols (A3) to (A10) is preferably 22 to 225 mgKOH/g, more preferably 28 to 113 mgKOH/g.

Mn of the polyols (A3) to (A10) is from 500 to 5,000, more preferably from 900 to 4,000, from the viewpoint of the film's ability to follow skin movements and solvent solubility.
The Mn of the polyols (A3) to (A9) in the present invention can be measured by gel permeation chromatography (GPC), for example, under the following conditions.
Equipment: "Waters Alliance 2695" [manufactured by Waters]
Column: "Guardcolumn Super HL" (1 column), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected one each"
Sample solution: 0.25% by weight tetrahydrofuran solution Solution injection volume: 10μl
Flow rate: 0.6ml/min Measurement temperature: 40℃
Detection device: Refractive index detector Reference material: Standard polyethylene glycol

The condensed polyester polyol (A3) is obtained by condensation of a diol with Mn less than 500 and a dicarboxylic acid or its ester-forming derivative [acid anhydride, lower (1 to 4 carbon atoms) alkyl ester, acid halide, etc.] Examples include things that can be done.

Diols with Mn less than 500 include aliphatic dihydric alcohols having 2 to 8 carbon atoms [linear diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol); and 1,6-hexanediol) and diols with branched alkyl chains (1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propane) diol and 1,2-, 1,3- or 2,3-butanediol, etc.]; dihydric alcohol containing an alicyclic group having 6 to 10 carbon atoms [1,4-bis(hydroxymethyl)cyclohexane and 2, 2-bis(4-hydroxycyclohexyl)propane, etc.]; aromatic ring-containing dihydric alcohols having 8 to 20 carbon atoms [m- or p-xylylene glycol, bis(hydroxyethyl)benzene and bis(hydroxyethoxy)benzene]; AO adducts of bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.), AO adducts of dihydroxynaphthalene, bis(2-hydroxyethyl) terephthalate, etc.). Diols having Mn of less than 500 may be used alone or in combination of two or more.

Examples of dicarboxylic acids or their ester-forming derivatives include aliphatic dicarboxylic acids having 2 to 15 carbon atoms [oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.], carbon atoms 8 to 12 aromatic dicarboxylic acids [terephthalic acid, isophthalic acid, etc.] and their ester-forming derivatives [acid anhydrides, lower alkyl esters (dimethyl ester, diethyl ester, etc.), acid halides (acid chloride, etc.)], etc. can be mentioned. The dicarboxylic acids may be used alone or in combination of two or more.

Specific examples of the condensed polyester polyol (A3) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, and polyethylene butylene adipate diol. Diol, polybutylene hexamethylene adipate diol, poly(polyoxytetramethylene) adipate diol, poly(3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diols and polyneopentyl terephthalate diols.

Among the condensed polyester polyols (A3), polyester diols having a branched alkyl chain are preferred from the viewpoint of the ability of the polyurethane resin (U) to follow the movement of the skin and the solvent solubility, and polyneopentyl is particularly preferred. Adipate diols and poly(3-methylpentylene adipate) diols, most preferably poly(3-methylpentylene adipate) diols. (A3) may be used alone or in combination of two or more.

The polylactone polyol (A4) was prepared by ring-opening polymerization of lactone monomers (γ-butyrolactone, γ-valerolactone, ε-caprolactone, mixtures of two or more of these, etc.) using the diol having Mn of less than 500 as an initiator. Examples include things. Specific examples of the polylactone polyol (A4) include polybutyrolactone diol, polyvalerolactone diol, and polycaprolactone diol. The polylactone polyol (A4) may be used alone or in combination of two or more.

The polycarbonate polyol (A5) includes the aforementioned diol having an Mn of less than 500, and a low-molecular carbonate compound (for example, a dialkyl carbonate having an alkyl group having 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, and carbon Examples include polycarbonate diols produced by condensing a diaryl carbonate (having six to nine aryl groups) while performing a dealcoholization reaction. The polycarbonate polyol (A5) may be used alone or in combination of two or more.

Specific examples of the polycarbonate polyol (A5) include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, and poly(tetramethylene/hexamethylene) carbonate diol (for example, 1,4-butanediol and 1,4-butanediol). Diol obtained by condensing 6-hexanediol with a dialkyl carbonate while performing a dealcoholization reaction.

Examples of the polyether polyol (A6) include the above-mentioned AO adduct having 2 to 12 carbon atoms to the above-mentioned diol having an Mn of less than 500, and AO may be used alone or by block copolymerization of two or more types. Alternatively, random copolymerization may be performed.

Among the polyether polyols (A6), those having a branched alkyl chain are preferable from the viewpoint of solvent solubility, that is, those using a diol having a branched alkyl chain among diols with Mn less than 500 as raw materials, and AO. Examples include those using 1,2-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, and 3-methyltetrahydrofuran as AO in the adduct, and more preferred are those having a branched alkyl. Aliphatic polyether diols of dihydric alcohols, particularly preferred are polyoxypropylene glycols. The polyether polyol (A6) may be used alone or in combination of two or more.

Examples of the poly(meth)acrylic polyol (A7) include homopolymers and copolymers of (meth)acrylic acid esters having hydroxy groups. Poly(meth)acrylic polyol (A7) can also be obtained by copolymerizing a compound having a polymerizable unsaturated bond in addition to a (meth)acrylic acid ester having a hydroxy group.
In addition, in the present invention, "(meth)acrylic" means "methacrylic and/or acrylic".

The (meth)acrylic acid ester having a hydroxy group includes those having one (meth)acryloyl group, such as those having a hydroxyalkyl group having 2 to 20 carbon atoms {for example, (meth)acrylic acid -2-hydroxyethyl, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. hydroxyalkyl (meth)acrylic acid ester} and (meth)acrylic acid monoester of trihydric alcohol {for example, (meth)acrylic acid monoester of glycerin and (meth)acrylic acid monoester of trimethylolpropane} Can be mentioned.

The compound having a polymerizable unsaturated bond includes a compound having one polymerizable unsaturated bond, such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, ( n-butyl meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, lauryl (meth)acrylate, glycidyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. (meth)acrylic acid alkyl esters having 4 to 50 carbon atoms; unsaturated carboxylic acids having 3 to 50 carbon atoms such as (meth)acrylic acid, maleic acid, and itaconic acid; (meth)acrylamide, N-methylol (meth) Examples include unsaturated amides having 3 to 50 carbon atoms such as acrylamide and diacetone (meth)acrylamide; other polymerizable monomers such as styrene, vinyltoluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.

Examples of polymerization methods for the (meth)acrylic ester having a hydroxy group and the compound having a polymerizable unsaturated bond include emulsion polymerization, suspension polymerization, dispersion polymerization, and solution polymerization. The emulsion polymerization can also be carried out in stages.

Specific examples of the commercially available poly(meth)acrylic polyols (A7) include "ARUFON UH-2000, UH-2041, UH-2190 and UHE-2012" manufactured by Toagosei Co., Ltd. and "ARUFON UH-2000, UH-2041, UH-2190 and UHE-2012" manufactured by Soken Kagaku Co., Ltd. Examples include "Actflow UT-1001 and UMM-1001".

Among the poly(meth)acrylic polyols (A7), from the viewpoint of solvent solubility, the compounds having the polymerizable unsaturated bond are preferably n-butyl (meth)acrylate, isobutyl (meth)acrylate, ( A polyacrylic polyol using at least one member selected from the group consisting of n-hexyl (meth)acrylate, lauryl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, and more preferably (meth)acrylate. This is a polyacrylic diol using n-butyl acid and/or 2-ethylhexyl (meth)acrylate. The poly(meth)acrylic polyol (A7) may be used alone or in combination of two or more.

(Hydrogenated) polybutadiene polyols (A8) include polybutadiene polyols and hydrogenated reduction products of polybutadiene polyols (hydrogenated polybutadiene polyols).
In addition, in the present invention, "(hydrogenated) polybutadiene polyol" means "polybutadiene polyol and/or hydrogenated polybutadiene polyol".
The iodine value of the (hydrogenated) polybutadiene polyol (A8) is preferably in the range of 1 to 1000 g/100 g, more preferably in the range of 10 to 600 g/100 g, even more preferably in the range of 100 to 500 g/100 g. It is.
Note that the iodine value is measured according to JIS K3331 (1995).
Commercially available (hydrogenated) polybutadiene polyols (A8) include, for example, the "NISSO-PBG series" (G-1000, G-2000, G-3000, etc.) manufactured by Nippon Soda Co., Ltd., and the "Poly Bd" manufactured by ARCO in the United States. (registered trademark) series” (R-45M, R-15HT, R-45HT, CS-15, and CN-15, etc.) and CRAY VALLEY's KRASOL HLBP-H 1000, HLBP-H 2000, and HLBP-H 3000. .

The castor oil polyol (A9) is not particularly limited and includes, for example, castor oil and castor oil derivatives.

The castor oil derivatives include, for example, castor oil fatty acids; hydrogenated castor oil obtained by hydrogenating castor oil or castor oil fatty acids; transesterified products of castor oil and other fats and oils; reaction products of castor oil and polyhydric alcohols; Examples include esterification reaction products of castor oil fatty acids and polyhydric alcohols; compounds obtained by addition polymerization of alkylene oxide to these; and the like. Among the above castor oil polyols, it is preferable to use castor oil.

Examples of the hydrogenated castor oil include those disclosed in JP-A-2-298574. Note that hydrogenated castor oil is obtained by hydrogenation of the above-mentioned castor oil-based polyol.

Commercially available castor oil-based polyols (A9) include, for example, castor oil polyol [H-35, manufactured by Ito Oil Co., Ltd.] and [KSK polyol, manufactured by Toyokuni Oil Co., Ltd.].

Examples of the silicone polyol (A10) include those in which two or more hydroxy groups and/or hydroxy group-containing organic groups are introduced into the terminal and/or side chain of dimethylpolysiloxane, such as carbinol-modified silicone oil, Mention may be made of polyether-modified silicone oils and silanol-terminated silicone oils.
Commercially available silicone polyols (A10) include, for example, carbinol-modified silicone oil [KF-6000, KF-6001, KF-6002, KF-6003, etc. manufactured by Shin-Etsu Chemical Co., Ltd.] and polyether-modified silicone oil. Examples include "X-22-4952, X-22-4272, KF-6123, etc." manufactured by Shin-Etsu Chemical Co., Ltd.].

As the polyol (A), condensed polyester polyol (A3), polylactone polyol (A4), polycarbonate polyol (A5), polyether polyol (A6), poly(meth)acrylic polyol (A7), (hydrogenated) polybutadiene polyol ( A8), when using at least one polyol selected from the group consisting of castor oil polyol (A9) and silicone polyol (A10), hydrogenated products of the polyfarnesene polyol (A1) and polyfarnesene polyol. The ratio of the total weight of (A3) to (A10) to the total weight of (A2) is preferably 100% by weight or less, more preferably 10% by weight or less, from the viewpoint of uniformity of the film formed by the polyurethane resin (U) and solvent solubility. ~90% by weight.

<Polyisocyanate (B)>
The polyisocyanate (B) in the present invention includes a chain aliphatic diisocyanate (B1) having 4 to 22 carbon atoms, an alicyclic diisocyanate (B2) having 8 to 18 carbon atoms, and an aromatic diisocyanate (B2) having 8 to 26 carbon atoms. B3) and aromatic aliphatic diisocyanates having 10 to 18 carbon atoms (B4).

Examples of the chain aliphatic diisocyanate (B1) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Examples include lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, and bis(2-isocyanatoethyl) carbonate.

Examples of the alicyclic diisocyanate (B2) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl )-4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

Examples of the aromatic diisocyanate (B3) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), 4,4 '- or 2,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), polyaryl diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3, Examples include 3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, and m- or p-isocyanatophenylsulfonylisocyanate.

Examples of the aromatic aliphatic diisocyanate (B4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate.

Among these, alicyclic diisocyanate (B2) having 8 to 18 carbon atoms is preferable from the viewpoint of the ability of the polyurethane resin (U) film to follow the movement of the skin. IPDI is preferred from the viewpoint of the film's ability to follow movement.
The polyisocyanate (B) may be used alone or in combination of two or more.

Examples of the chain extender (C) having Mn or a chemical formula weight of less than 500 in the present invention include polyamine (C1), polyol (C2), water, and the like. The chain extender (C) may be used alone or in combination of two or more.

The polyamine (C1) includes diamines having 2 to 12 carbon atoms {for example, chain aliphatic diamines (ethylene diamine, propylene diamine, hexamethylene diamine, aminoethylaminoethanol, etc.), alicyclic diamines (isophorone diamine, norbornene diamine, Bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5, 5) undecane, etc.), aromatic diamines (toluenediamine, etc.) and piperazine, etc.)}, poly(n=2-6) alkylene (carbon number 2-6) poly(n=3-7) amines (diethylenetriamine, dipropylene) triamine, dihexylene triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, etc.) and hydrazine or its derivatives (for example, dibasic acid dihydrazide such as adipic acid dihydrazide).
Among these, alicyclic diamine is preferred, and isophorone diamine is more preferred from the viewpoint of the ability of the polyurethane resin (U) film to follow skin movements and solvent solubility.

Examples of the polyol (C2) include those similar to those exemplified as the diol having an Mn of less than 500, the polyol (C22) having an ionic polar group, and the like.
Among the diols exemplified above with Mn less than 500, 1,4-butanediol is preferred from the viewpoint of the ability of the polyurethane resin (U) to follow the movement of the skin and the solubility in solvents.

Examples of the polyol (C22) having an ionic polar group include a polyol (C221) having an anionic group and a polyol (C222) having a cationic group. The polyol (C22) having an ionic polar group may be used singly or in combination of two or more.

The anionic group in the polyol (C221) having an anionic group means an acid group and a neutralized acid anion group.
The polyol (C221) having an anionic group is, for example, a compound containing a carboxyl group as an anionic group and having 2 to 10 carbon atoms [dialkylolalkanoic acid (for example, 2,2-dimethylolpropionic acid, 2, 2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid and 2,2-dimethyloloctanoic acid), tartaric acid and amino acids (such as glycine, alanine and valine)], containing sulfonic acid groups as anionic groups. , a compound having 2 to 16 carbon atoms [3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid and sulfoisophthalic acid di(ethylene glycol) ester, etc.], containing a sulfamic acid group as an anionic group, Examples include compounds having 2 to 10 carbon atoms [N,N-bis(2-hydroxylethyl)sulfamic acid, etc.], and salts obtained by neutralizing these compounds with a neutralizing agent.

When the anionic group of the polyol (C221) having an anionic group is a neutralized acid anion group, examples of the neutralizing agent used to neutralize the acid anion group include ammonia, an amine having 1 to 20 carbon atoms, compounds or alkali metal hydroxides (sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.).
Examples of amine compounds having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine, and monoethanolamine; secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine, diisopropanolamine, and methylpropanolamine; Examples include amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine, and triethanolamine.

When the anionic group of the polyol (C221) having an anionic group is a neutralized acid anion group, as a neutralizing agent used for neutralizing the acid anion group, the storage stability of the polyurethane aqueous dispersion described below From this point of view, compounds having a high vapor pressure at 25°C are suitable. From this viewpoint, as the neutralizing agent, ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, and dimethylethylamine are preferable.
Regarding the amount of the neutralizing agent added, from the viewpoint of dispersion stability of the polyurethane resin (U) in water, it is preferable that the neutralization rate is 50 to 100% with respect to the amount of acidic groups possessed by the polyurethane resin (U). , more preferably 60 to 100%.
When the neutralization rate is 100% or less, the working environment is good, and when the neutralization rate is 50% or more, the dispersion stability of the polyurethane resin (U) in water is good.
In the present invention, the neutralization rate means the mol% of the neutralizing agent relative to the number of moles of anionic groups in the anionic group-containing polyol (C221) used for producing the polyurethane resin (U).

When the polyurethane resin (U) is used in the aqueous polyurethane resin dispersion for cosmetics described below, among the polyols (C221) having an anionic group, preferred from the viewpoint of dispersion stability of the aqueous polyurethane resin dispersion for cosmetics are , 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and salts thereof, and more preferred are 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid with ammonia or carbon. It is a neutralized salt with 1 to 20 amine compounds.

The cationic group in the polyol (C222) having a cationic group means a group in which a proton is added to a tertiary amino group, an unneutralized tertiary amino group, and a quaternary ammonium group.

The polyol (C222) having a cationic group includes, for example, a polyol having a tertiary amino group as a cationic group, and specifically, a diol containing a tertiary amino group having 3 to 20 carbon atoms [N-alkyldi Compounds such as alkanolamines (e.g. N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine) and N,N-dialkylmonoalkanolamines (e.g. N,N-dimethylethanolamine), etc. Examples include salts that have been neutralized with a neutralizing agent.

Examples of neutralizing agents used for polyols (C222) having a cationic group include monocarboxylic acids having 1 to 10 carbon atoms (such as formic acid, acetic acid, and propanoic acid), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride, Examples include benzyl chloride.

The neutralizing agent used for the polyol (C221) having an anionic group and the polyol (C222) having a cationic group can be used before the urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the water dispersion step, and during the water dispersion step. Although it may be added at any time during or after water dispersion, from the viewpoint of stability of the polyurethane resin (U) and stability of the polyurethane aqueous dispersion described later, it may be added before or during the water dispersion process. It is preferable to do so. Further, the neutralizing agent volatilized during the solvent removal may be additionally added after the solvent removal, and the type of neutralizing agent to be additionally added can be freely selected from those described above.

In obtaining the polyurethane resin (U), in addition to the essential components of the polyol (A), polyisocyanate (B), and chain extender (C), a reaction terminator is added for the purpose of adjusting the molecular weight of the polyurethane resin (U). (D) can be used.

As the reaction terminator (D), monoalcohols having 2 to 22 carbon atoms (ethanol, propanol, butanol, 2-ethylhexanol, lauryl alcohol, etc.) and monoamines having 2 to 22 carbon atoms [mono- or Dialkylamines (n-butylamine, di-n-butylamine, laurylamine, etc.), mono- or dialkanolamines having 2 to 6 carbon atoms (monoethanolamine, diethanolamine, propanolamine, etc.), and the like. Among these, monoalcohols or monoamines having 2 to 18 carbon atoms are preferred. The reaction terminator (D) may be used alone or in combination of two or more.

The amine value of the polyurethane resin (U) is preferably less than 2 mgKOH/g, more preferably less than 1 mgKOH/g. An amine value of 2 mgKOH/g or more is unfavorable from the viewpoint of skin irritation.
In the present invention, the amine value is a value measured in accordance with JIS K1557-7, and the amine value is a value measured in accordance with JIS K1557-7, and the amine value is a value measured in accordance with JIS K1557-7. It is derived from a group that indicates gender.

When using a reaction terminator (D) in obtaining the polyurethane resin (U), the weight ratio of the polyol (A), polyisocyanate (B), and chain extender (C) in the polyurethane resin (U) [(A) :(B):(C)] is preferably 100:(5 to 55):(1) from the viewpoint of the ability of the polyurethane resin (U) to follow the skin movement, uniformity of the film, and solvent solubility. ~30), more preferably 100:(9-35):(2-20).

The method for producing the polyurethane resin (U) is not particularly limited, and may include a one-shot method in which the polyol (A), polyisocyanate (B), chain extender (C), and if necessary a reaction terminator (D) are reacted at once; A multi-stage method in which a polyol (A), a polyisocyanate (B), and if necessary a chain extender (C) are reacted to form an isocyanate group-terminated prepolymer, and then the chain extender (C) and the necessary Any method such as a method in which a reaction terminator (D) is added and further reacted] may be used.

In producing the polyurethane resin (U), the molar ratio of the isocyanate group of the polyisocyanate (B), the polyol (A), and the active hydrogen-containing group of the optional component chain extender (C) and reaction terminator (D) is determined. (Isocyanate group: active hydrogen-containing group) is preferably 0.7:1 to 2.5:1, more preferably 0.9:1 from the viewpoint of uniformity and storage stability of the polyurethane resin (U) film. The ratio is 1 to 2:1.

In the present invention, it is preferable to use biomass-derived raw materials as the raw materials constituting the polyurethane resin (U) from the viewpoint of carbon dioxide reduction and effective use of resources, and the ratio of the weight of the biomass-derived raw materials to the total weight of the entire raw materials is: More preferably, it is 40% or more.

The urea group concentration of the polyurethane resin (U) in the present invention is preferably 1.5 mmol/g or less, more preferably 0.4 to 1.5 mmol/g, based on the weight of the polyurethane resin (U). .
In the present invention, polyfarnesene polyol (A1) and/or hydrogenated polyfarnesene polyol (A2) are used as the polyol (A), but the urea group concentration of the polyurethane resin (U) is 1.5 mmol. When it is below, the ability of the polyurethane resin (U) to follow the movement of the skin and the solvent solubility of the film will be even better.
In order to keep the urea group content in the polyurethane resin (U) within a desired range, the amino group content, water content, and isocyanate group content in the raw materials of (U) may be adjusted as appropriate.

The urethane group concentration of the polyurethane resin (U) in the present invention is based on the weight of the polyurethane resin (U) from the viewpoint of the ability of the polyurethane resin (U) to follow the movement of the skin, the uniformity of the film, and the solubility in solvents. It is preferably 0.6 to 1.4 mmol/g, more preferably 0.7 to 1.4 mmol/g.
In the present invention, the sum of the urethane group concentration and urea group concentration of the polyurethane resin (U) is determined by the weight of the polyurethane resin (U) from the viewpoint of the film's ability to follow skin movements, film uniformity, and solvent solubility. As a standard, it is preferably 0.6 to 2.7 mmol/g, more preferably 1.0 to 2.7 mmol/g.
The urethane group concentration and urea group concentration in the polyurethane resin (U) are determined by the N atom content determined by a nitrogen analyzer, the ratio of urethane groups and urea groups determined by ¹ H-NMR, and the content of allophanate groups and biuret groups. It can be calculated from the amount.

In the present invention, the urethane group concentration and urea group concentration of the polyurethane resin (U) can be measured as follows.

(Urethane group concentration and urea group concentration of polyurethane resin (U))
The urethane group concentration and urea group concentration of the polyurethane resin (U) are determined by the N atom content determined by a nitrogen analyzer [ANTEK7000 (manufactured by Antec Corporation)] and the ratio of urethane groups to urea groups determined by ¹ H-NMR. It is calculated from the allophanate group and biuret group contents described below.
¹ H-NMR measurement is carried out by the method described in "Structural research of polyurethane resins by NMR: Takeda Research Institute Bulletin 34 (2), 224-323 (1975)". That is, when ¹ H-NMR is measured and an aliphatic isocyanate is used, the urea group is determined from the ratio of the integral amount of hydrogen derived from the urethane group with a chemical shift of around 6 ppm and the integral amount of hydrogen derived from the urethane group with a chemical shift around 7 ppm. The weight ratio of urethane group and urethane group is measured, and the urethane group and urea group contents are calculated from the weight ratio, the above-mentioned N atom content, and allophanate group and biuret group content.
When aromatic isocyanate is used, the weight ratio of the urea group and the urethane group is calculated from the ratio of the integrated amount of hydrogen derived from the urea group with a chemical shift of around 8 ppm and the integrated amount of hydrogen derived from the urethane group with a chemical shift of around 9 ppm. The urethane group and urea group contents are calculated from the weight ratio, the N atom content, and the allophanate group and biuret group contents.

(Content of allophanate group and biuret group)
The total content of allophanate groups and biuret groups in the polyurethane resin (U) is calculated using a gas chromatograph [Shimadzu GC-9A {manufactured by Shimadzu Corporation}]. Prepare 50 g of DMF solution containing 0.01% by weight di-n-butylamine and 0.01% by weight naphthalene (internal standard).
Measure the sample into a test tube with a stopper, add 2 g of the above DMF solution, and heat the test tube in a constant temperature water bath at 90° C. for 2 hours. After cooling to room temperature, 10 μl of acetic anhydride was added and the mixture was shaken and stirred for 10 minutes. Furthermore, 50 μl of di-n-propylamine is added, and after shaking for 10 minutes, gas chromatography measurement is performed. A blank measurement is performed in parallel, the amount of amine consumed is determined from the difference from the test value, and the total content of allophanate groups and biuret groups is measured.
The blank measurement is the same as the sample measurement except that 2 g of the above DMF solution alone is added without measuring the sample into a test tube with a stopper, and the test tube is heated in a constant temperature water bath at 90° C. for 2 hours.
(Gas chromatograph conditions)
Equipment: Shimadzu GC-9A
Column: 10% PEG-20M on Chromosorb WAW DMLS 60/80mesh glass column 3mmφ x 2m
Column temperature: 160°C, sample introduction part temperature: 200°C, carrier gas: nitrogen (flow rate: 40ml/min), detector: FID, sample injection amount: 2μl
(Formula for calculating the total content of allophanate groups and biuret groups)
Total content of allophanate groups and biuret groups = {(BA)/B} x 0.00155/S
A: Sample (peak area of di-n-butylacetamide/peak area of naphthalene)
B: Blank (peak area of di-n-butylacetamide/peak area of naphthalene)
S: Polyurethane resin (U) collection amount (g)

The reaction between polyol (A) and polyisocyanate (B) is preferably carried out at a temperature of 20 to 140°C, more preferably 40 to 120°C.
The reaction temperature of the isocyanate group-terminated prepolymer obtained by reacting polyisocyanate (B) or polyol (A) with polyisocyanate (B) and chain extender (C) is preferably 0 to 100°C, more preferably The temperature is 0 to 80°C.

In the production of polyurethane resin (U), in order to accelerate the reaction of polyol (A), polyisocyanate (B), chain extender (C), and reaction terminator (D) used if necessary, urethane resin is generally used. Catalysts used in the reaction [amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin-based catalysts (dibutyltin dilaurate, dioctyltin dilaurate, tin octylate, etc.), and titanium-based catalysts (tetrabutyl titanate, etc.)] etc. may also be used. The amount of catalyst used is preferably 0.1% by weight or less based on the polyurethane resin (U).

Furthermore, in producing the polyurethane resin (U), the reaction may be carried out in a solvent (S), or the solvent (S) may be added during or after the reaction.
Examples of the solvent (S) include ketone solvents (acetone, methyl ethyl ketone, etc.), aliphatic hydrocarbon solvents (n-hexane, n-heptane, cyclohexane, etc.), and alcohol solvents (ethanol, n-propyl alcohol, isopropyl alcohol, etc.). (n-butanol, etc.), synthetic ester oils, and natural liquid oils and fats.

Examples of synthetic ester oils include ethyl acetate, triethylhexanoin, 2-ethylhexyl methoxycinnamate, isopropyl myristate, cetyl octoate, octyldodecyl myristate, cetyl palmitate, isopropyl palmitate, butyl stearate, and hexyl laurate. , myristyl myristate, decyl oleate, hexyldecyl dimethyloctoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, cetyl ethylhexanoate, di-2-ethylhexane acid ethylene glycol, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, Trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glycerin trioctanoate, glycerin triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate , 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl- L-glutamic acid-2-octyldodecyl ester, di-2-heptyl undecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-adipate Hexyldecyl, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, PEG-3 trimethylolpropane triisostearate, ethylhexyl palmitate, polyglyceryl-2 triisostearate, sucrose tetraisostearate, tri(capric/caprylic acid) ) glyceryl, glyceryl trioctanoate, and glyceryl triisopalmitate.

Examples of natural liquid oils include mineral oil, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, and castor oil. Oils such as linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnabar oil, Japanese tung oil, jojoba oil and germ oil.

Among these, ethyl acetate, acetone, methyl ethyl ketone, ethanol, n-propyl alcohol, isopropyl alcohol, ethylhexyl palmitate, cetyl ethylhexanoate, and the like are preferable from the viewpoint of uniformly dissolving the raw materials of the polyurethane resin (U). At least one type selected from the group consisting of tri(capric acid/caprylic acid) glyceryl. The solvent (S) may be used alone or in combination of two or more.

Mn of the polyurethane resin (U) is preferably 5,000 to 100,000. When Mn is 5,000 or more, the film formed by the polyurethane resin (U) has good followability to skin movement and mechanical strength, and when Mn is 100,000 or less, cosmetics containing the polyurethane resin (U) are obtained. The storage stability of the polyurethane resin composition for use in cosmetics and cosmetics containing the composition is improved.
Further, when the polyurethane resin composition for cosmetics containing the polyurethane resin (U) is a non-dispersed material, it is more preferable that the Mn of the polyurethane resin (U) is 10,000 to 32,000. When the Mn of the polyurethane resin is within this range, the film's ability to follow skin movements, mechanical strength, and storage stability will be even better.
In addition, a non-dispersed body means a composition having a uniform phase in which the polyurethane resin (U) and water and/or solvent (S) contained in the composition cannot be visually distinguished, and is a liquid. It may be solid or gel-like.
In addition, Mn of the polyurethane resin (U) is measured under the same conditions as for the polyfarnesene polyol (A1).

<Polyurethane resin composition for cosmetics>
The polyurethane resin composition for cosmetics of the present invention is a composition containing the polyurethane resin (U) and water and/or a solvent (S).
The polyurethane resin composition for cosmetics may be a dispersion containing polyurethane resin (U) as a dispersoid and water and/or a solvent (S) as a dispersion medium, or a polyurethane resin (U) and water and a solvent (S) as a dispersion medium. The composition may have a uniform phase that cannot be visually distinguished from S). Moreover, the polyurethane resin composition for cosmetics may be in liquid form, solid form, or gel form.
Examples of the solvent (S) contained in the polyurethane resin composition for cosmetics include the same solvents (S) that can be used in the production of the polyurethane resin (U) described above; Preferred from the viewpoint of solubility are ethanol, ethylhexyl palmitate, cetyl ethylhexanoate, and tri(caprylic/capric)glyceride.
When the polyurethane resin composition for cosmetics of the present invention contains a solvent (S), it may be obtained by producing the polyurethane resin (U) in a solvent (S), or after producing the polyurethane resin (U). It may also be obtained by dissolving it in a solvent (S).

The content of the polyurethane resin (U) in the polyurethane resin composition for cosmetics of the present invention is determined from the viewpoint of handling properties of the polyurethane resin composition for cosmetics, based on the weight of the polyurethane resin composition for cosmetics. It is preferably from 50% by weight, more preferably from 20 to 40% by weight.
The polyurethane resin (U) in the polyurethane resin composition for cosmetics of the present invention has good film uniformity and has the ability to follow the movement of the skin, and furthermore, the polyurethane resin (U) in the polyurethane resin composition for cosmetics of the present invention Since the resin composition has excellent storage stability, by using the polyurethane resin composition for cosmetics of the present invention, the film has good uniformity, has the ability to follow the movement of the skin, and is storage stable. Cosmetics with excellent properties can be obtained.

The polyurethane resin composition for cosmetics of the present invention may be in liquid, solid, or gel form. Gel is something that has almost lost its fluidity, and if the concentration of polyurethane resin (U) to solvent (S) is low, it will become a polyurethane resin solution at room temperature, and the concentration of polyurethane resin (U) to solvent (S) will be high. It becomes a gel at room temperature, but the boundary between the concentration of the polyurethane resin solution and the gel varies depending on the composition of the polyurethane resin and the type of solvent.
For example, when the solvent (S) does not contain alcohol, the polyurethane resin composition for cosmetics can be made into a gel by setting the urethane group concentration of the polyurethane resin (U) to 15% or more, and the solvent (S) In the case where alcohol is included as the alcohol, the polyurethane resin composition for cosmetics can be made into a gel by setting the urethane group concentration of the polyurethane resin (U) to 55% or more.
When the polyurethane resin composition for cosmetics of the present invention is a gel, it is preferable that the viscosity as measured by a B-type viscometer at room temperature of 25° C. is smaller than 100,000 mPa·s.

<Polyurethane resin aqueous dispersion for cosmetics>
The aqueous polyurethane resin dispersion for cosmetics of the present invention is a dispersion containing a polyurethane resin (U) and water, and is obtained by dispersing the polyurethane resin (U) in a medium containing water (aqueous medium). It is something. Aqueous medium means water or a mixture of water and a solvent.

The aqueous polyurethane resin dispersion for cosmetics can be produced, for example, by the following method.
(1) A solution (for example, a solvent solution described below) of a polyurethane prepolymer (P) having an isocyanate group at the end and containing polyol (A) and polyisocyanate (B) as constituent monomers is prepared.
Next, water, and if necessary, a solvent, a chain extender (C), and a neutralizing agent are added, followed by phase inversion emulsification, and if necessary, the solvent is distilled off to obtain a polyurethane resin aqueous dispersion for cosmetics. .
(2) A solution (for example, an organic solvent solution described below) of a polyurethane prepolymer (P) having an isocyanate group at the terminal and containing polyol (A) and polyisocyanate (B) as constituent monomers is prepared.
Next, a mixture of water, a solvent, a neutralizing agent, and a chain extender (C) is added as necessary, and dispersed using a known dispersing machine.If necessary, the solvent is distilled off to form a polyurethane resin for cosmetics. An aqueous dispersion is obtained.

(3) A solution (for example, a solvent solution described below) of a polyurethane prepolymer (P) having an isocyanate group at the terminal and containing polyol (A) and polyisocyanate (B) as constituent monomers is prepared.

Next, after dispersing the mixture containing the solution of the polyurethane prepolymer (P) and water using a known disperser, if necessary, a neutralizing agent and a reaction terminator (D) are added, and further, if necessary, The solvent is distilled off to obtain an aqueous polyurethane resin dispersion for cosmetics.
(4) A solvent solution of polyurethane resin (U) containing polyol (A) and polyisocyanate (B) as constituent monomers is prepared.
Next, water is added and dispersed, for example, using a dispersing machine, and if necessary, the solvent is distilled off to obtain an aqueous polyurethane resin dispersion for cosmetics.

In addition, in the step of obtaining the aqueous polyurethane resin dispersion for cosmetics, in addition to the polyurethane prepolymer (P), a solvent, a neutralizing agent, a chain extender (C), water, and a reaction terminator (D), if necessary, Known anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants (for example, the emulsifier (F) described in JP-A-2015-131889) may be used.

Examples of the solvent include organic solvents such as ketone solvents (e.g. acetone and methyl ethyl ketone), ester solvents (e.g. ethyl acetate), alcohol solvents (e.g. ethanol and isopropyl alcohol), and aromatic hydrocarbon solvents (e.g. toluene). It will be done.

The aqueous polyurethane resin dispersion for cosmetics is made by dispersing the polyurethane resin (U) in a medium containing water, but the medium may contain the above-mentioned solvent. The content of the above-mentioned solvent in the medium is preferably 30% by weight or less, more preferably 5% by weight or less from the viewpoint of the working environment.

From the viewpoint of dispersion stability, the volume average particle diameter (Dv) of the particles of the polyurethane resin (U) in the aqueous polyurethane resin dispersion for cosmetics of the present invention is preferably 0.01 to 1 μm, more preferably 0.02 ~0.7 μm, particularly preferably 0.03 to 0.4 μm. When (Dv) is 0.01 μm or more, the viscosity is appropriate and handling property is good, and when it is 1 μm or less, the dispersion stability of the particles of the polyurethane resin (U) is good.
The volume average particle diameter (Dv) in the present invention can be measured with a light scattering particle size distribution analyzer [LA950 V2 "manufactured by Horiba, Ltd.]".

The volume average particle diameter (Dv) can be controlled by the ionic polar group in the polyurethane resin (U) and the type and operating conditions of the disperser used in the dispersion step. Specifically, the volume average particle diameter (Dv) can be reduced by increasing the amount of ionic polar groups in the polyurethane resin (U), and the amount of ionic polar groups in the polyurethane resin (U) can be reduced. The volume average particle diameter (Dv) can be increased by decreasing the amount.

In the aqueous polyurethane resin dispersion for cosmetics, the volume average particle diameter (Dv) of the particles of the polyurethane resin (U) is determined by the amount of polyol (C22) having an ionic polar group used, the amount of ions in the polyurethane resin (U). The content of the polar group is preferably 0.5 to 5.0% by weight, more preferably 0.5 to 4.8% by weight, particularly preferably 0.5% by weight, based on the weight of the polyurethane resin (U). It can be adjusted to 4.5% by weight.
Note that the content of ionic polar groups in the present invention means the weight percent of unneutralized cationic groups or anionic groups, and does not include the weight of counter ions. For example, in the case of triethylamine salt of 2,2-dimethylolpropionic acid, the content of ionic polar groups in the polyol (C221) having anionic groups is calculated by dividing the weight% of carboxyl groups (-COOH) into 3-( In the case of the triethylamine salt of 2,3-dihydroxypropoxy)-1-propanesulfonic acid, it means the weight percent of sulfo groups (-SO ₃ H). Moreover, the content of ionic polar groups in the polyol (C222) having a cationic group means the weight % of only the nitrogen atoms in the tertiary amino group.

<Cosmetics>
The method for producing the cosmetic of the present invention is not particularly limited, and can be produced by mixing by a known method. Specifically, the above-mentioned polyurethane resin (U) for cosmetics or polyurethane resin composition for cosmetics and other known raw materials for cosmetics are mixed using a known mixing/stirring device such as a disper mixer or a paddle mixer. The present invention is not limited to these manufacturing methods.
If the cosmetic is an emulsion-type cosmetic, the cosmetic can be obtained by emulsifying separately prepared aqueous and oil phases, but the aqueous and oil phases may be prepared in one step or in multiple steps. This may be done by adjustment. If the material contains powder, add the powder-containing mixture gradually to prevent agglomeration.

Known additives used in cosmetics may be appropriately blended within the range that does not impede the effects of the present invention.
Examples of the additives include pigments, fragrances, hormones, vitamins, photosensors, plant and animal extracts, thickeners, alkalis, ultraviolet protection agents, antioxidants, preservatives and disinfectants, and antiperspirants and deodorants. Agents etc. can be added.
The weight ratio of the additives described above can be appropriately selected depending on the purpose within a range that does not impair the effects of the present invention.

The cosmetics of the present invention are suitable for makeup cosmetics such as solid foundations, liquid foundations, eye shadows, blushers, lipsticks, eyeliners, cosmetic creams, and cosmetic emulsions, and skin care cosmetics such as lotions, emulsions, and serums. It is particularly suitable for liquid foundations, cosmetic creams, and cosmetic emulsions because it has good uniformity of the film upon application and good followability of the film to the movement of the skin. The properties of the cosmetic of the present invention are not particularly limited, and may be liquid or cream.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. In the following, "parts" indicate parts by weight.

<Example 1>
Polyfarnesene polyol (A1-1) manufactured by CRAY VALLEY (Mn = 3,000, Tg = -65°C, hydroxyl value = 37.4 mgKOH/g) was placed in a simple pressurized reaction device equipped with a stirring device and a heating device. [Product name: Krasol F-3000, manufactured by CRAY VALLEY] 235 parts, 3.08 parts of 1,4-butanediol (C2-1) and 46.6 parts of IPDI (C2-2) were charged, and the mixture was heated at 110°C under a nitrogen atmosphere. The reaction was carried out for 6 hours to obtain a urethane prepolymer having an NCO content of 2.52% by weight. After cooling to 40°C, 600 parts of 2-ethylhexyl palmitate (S-1) was added to form a homogeneous solution. Next, 100 parts of ethanol (S-2) was added and stirred until homogeneous, and then 13.91 parts of isophoronediamine (C1-1) (chemical formula weight 170) and 3.03 parts of laurylamine (D-1) were added. , and reacted at 40° C. for 1 hour to obtain a polyurethane resin solution for cosmetics containing the polyurethane resin (U-1) of the present invention. The viscosity of the polyurethane resin solution for cosmetics containing the polyurethane resin (U-1) at 20° C. was 800 mPa·s, and the Mn of the polyurethane resin (U-1) was 15,000.

<Examples 2 to 9, Comparative Examples 1 to 2>
In Example 1, the reaction was carried out in the same manner as in Example 1 except that the raw materials used were changed to the types and amounts listed in Table 1, and polyurethane resins (U-2) to (U-9) and (U'-1 ) to (U'-2) A polyurethane resin solution for cosmetics was obtained. The results are shown in Table 1.

<Example 10>
(Preparation of urethane prepolymer)
In a simple pressure reaction apparatus equipped with a stirrer and a heating device, 272 parts of polyfarnesene polyol (A1-1) manufactured by CRAY VALLEY, 3.32 parts of 1,4-butanediol (C2-1), and 2.2 parts of polyfarnesene polyol (A1-1) manufactured by CRAY VALLEY were added. - 17.0 parts of dimethylolpropionic acid (C2-5), 82.7 parts of IPDI (C2-2), and 125 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) were charged, and the mixture was stirred at 85°C for 10 hours to undergo a urethanization reaction. A MEK solution (P-1) of urethane prepolymer was produced.
(Manufacture of polyurethane resin aqueous dispersion for cosmetics)
500 parts of the MEK solution (P-1) of the obtained urethane prepolymer was charged into a simple pressure reaction apparatus equipped with a stirrer and a heating reaction apparatus, and while stirring at 50°C, 237 parts of MEK and 12 parts of triethylamine (neutralizing agent) were added. 8 parts of ion-exchanged water was added and homogenized for 30 minutes at 60 rpm, the temperature was maintained at 50° C., and 581 parts of ion-exchanged water was gradually added while stirring at 500 rpm to emulsify. 0 parts (C1-3) was added, and MEK was distilled off under reduced pressure at 65° C. for 12 hours to obtain a polyurethane resin aqueous dispersion for cosmetics containing polyurethane resin (U-10).

<Examples 11 to 13, Comparative Example 3>
In Example 9, the reaction was carried out in the same manner as in Example 9 except that the raw materials used were changed to the types and amounts listed in Table 2, and polyurethane resins (U-11) to (U-13) and (U'-3 ) was obtained. An aqueous polyurethane resin dispersion for cosmetics was obtained. The results are shown in Table 2.

In addition to those described in Examples and Comparative Examples, the raw materials used in Table 2 are as follows.
<Polyol (A)>
・(A1-1): Biomass-derived polyfarnesene polyol manufactured by CRAY VALLEY (Mn = 3,000, Tg = -65°C, hydroxyl value = 37.4 mgKOH/g) [Product name: Krasol F-3000, CRAY Made by VALLEY]
・(A2-1): CRAY VALLEY hydrogenated polyfarnesene polyol derived from biomass (Mn=3,000, Tg=-56°C, hydroxyl value=37.4mgKOH/g) [Product name: Krasol F-3100 , made by CRAY VALLEY]
・(A3-1): Poly(3-methyl-1,5 pentane adipate) diol (Mn=2,000) [Product name: Kuraray Polyol P-2010, manufactured by Kuraray Co., Ltd.]
・(A5-1): Polyhexamethylene carbonate diol (Mn=2,000) [Product name: Ethanachol UH-200, manufactured by Ube Industries, Ltd.]
・(A6-1): Poly(oxypropylene) glycol (Mn=3,000) [Product name: SANNIX PP-3000, manufactured by Sanyo Chemical Industries, Ltd.]
・(A6-2): Poly(oxytetramethylene) glycol (Mn=2,000) [Product name: PTMG2000, manufactured by Mitsubishi Chemical Corporation]
・(A8-1): Hydrogenated polybutadiene diol (Mn=2,000) [Product name: NISSO-PB GI-2000, manufactured by Nippon Soda Co., Ltd.]
・(A9-1): Biomass-derived castor oil diol (Mn=920) [Product name: HS 2G-120, manufactured by Toyokuni Oil Co., Ltd.]
・(A10-1): Carbinol-modified silicone oil (Mn=930) [Product name: KF-6000, manufactured by Shin-Etsu Chemical Co., Ltd.]
<Diisocyanate (B)>
・(B2-2): 1,5-pentamethylene diisocyanate derived from biomass [Product name: Stabio PDI, manufactured by Mitsui Chemicals, Inc.]
<Chain extender (C2)>
・(C1-2): Diethylenetriamine (chemical formula weight 103)
・(C1-3): 5% by weight diethylenetriamine aqueous solution: Diethylenetriamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was mixed with ion-exchanged water (1 μS/cm or less manufactured using a cartridge water purifier G-10C manufactured by Organo Co., Ltd.) (C1-4): 5% by weight ethylenediamine aqueous solution: Ethylenediamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) diluted to 5% by weight with ion-exchanged water (cartridge water purifier manufactured by Organo Co., Ltd.) (C2-1): 1,4-butanediol (chemical formula weight 90) diluted to 5% by weight with ion-exchanged water of 1 μS/cm or less produced by G-10C type
・(C2-2): 1,3-propanediol derived from biomass (chemical formula weight 76) [Product name: Susterra Propanediol, manufactured by DuPont Tate & Lyle Bio Products Company]
・(C2-3): Biomass-derived neopentyl glycol (chemical formula weight 104) [Product name: Neeture N-40, manufactured by Perstorp]
・(C2-4): Ion-exchanged water [Product name: Ion-exchanged water of 1 μS/cm or less manufactured with a cartridge deionizer G-10C manufactured by Organo Co., Ltd.]

<How to adjust cosmetics (emulsified foundation)>
According to the formulation shown in Table 3, the oily component 1) whose temperature had been adjusted in advance at 70°C and the cosmetic polyurethane resin solution were added to a container equipped with a stirrer (HOMOGENIZING DISPER Model 2.5, manufactured by PRIMIX) at 600 rpm for 5 minutes. It was stirred with The oily component 2) was gradually added thereto and stirred. After stirring at 600 rpm for 5 minutes, the aqueous component was gradually added and emulsified by stirring at 3000 rpm. Thereafter, by defoaming, cosmetics (Y-1) to (Y-9) and comparative cosmetics (Y'-1) to (Y'-2) were obtained. Table 3 shows the test results of film uniformity and sebum resistance of the obtained cosmetics and comparative cosmetics immediately after application and after 8 hours. The uniformity test of the film after 8 hours was conducted to confirm the ability of the film to follow the movement of the skin.

The raw materials listed in Table 3 are as follows.
・Sorbitan sesquioleate [Product name: NIKKOL SO-15V, manufactured by Nikko Chemicals Co., Ltd.]
・2-Ethylhexyl palmitate [Product name: Koyo COC, manufactured by Koyo Fine Chemical Co., Ltd.]
・Polyurethane powder [Product name: Dynamic Beads CM, manufactured by Dainichiseika Kagyo Co., Ltd.]
・Polyglyceryl polyricinoleate [Product name: NIKKOL Hexaglyn PR-15, manufactured by Nikko Chemicals Co., Ltd.]
・Fine particle titanium oxide (ultraviolet protection agent) [Product name: MT-100TV, manufactured by Teika Co., Ltd.]
・Zinc oxide (ultraviolet protection agent) [Product name: MZ-300, manufactured by Teika Co., Ltd.]
・Titanium oxide (white pigment) [Product name: MP-1133, manufactured by Teika Co., Ltd.]
・Iron oxide (red iron oxide) [Product name: TAROX R-516HP, manufactured by Titan Industries Co., Ltd.]
・Yellow iron oxide [Product name: TAROX LL-100HP, manufactured by Titan Kogyo Co., Ltd.]
・Black iron oxide [Product name: TAROX BL-100HP, manufactured by Titan Industries Co., Ltd.]
- Reagents manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. were used for tocopherol, sodium chloride, 1,2-pentanediol, and 1,3-butylene glycol.

<How to adjust cosmetics (eyeliner)>
In a container equipped with a stirrer (HOMOGENIZING DISPER Model 2.5, manufactured by PRIMIX), according to the formulation shown in Table 4, a pigment component, purified water, an aqueous component, and an aqueous urethane resin dispersion for cosmetics prepared by the above method were added. Cosmetics (Y-10) to (Y-13) and comparative cosmetics (Y'-3) were obtained by blending and stirring at 600 rpm for 10 minutes at room temperature. Table 4 shows the test results of film uniformity of the obtained cosmetics and comparative cosmetics immediately after application and after 8 hours. The uniformity test of the film after 8 hours was conducted to confirm the ability of the film to follow the movement of the skin.

The raw materials listed in Table 4 are as follows.
・Carbon black water dispersion [Product name: WD-CB2, manufactured by Daito Kasei Kogyo Co., Ltd., carbon black content 25% by mass]
・Isoprene glycol [Product name: IPG-S, manufactured by Kuraray Co., Ltd.]
- For phenoxyethanol and 1,3-butylene glycol, reagents manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. were used.

<Method for evaluating uniformity of cosmetic film>
Cosmetics (Y-1) to (Y-9) and cosmetics (Y'-1) to (Y'-2) were applied to the inside of the forearm using fingers and air-dried at room temperature for 10 minutes. The thickness unevenness due to subsequent convergence of the film was sensory evaluated using the following criteria.
For cosmetics (Y-10) to (Y-13) and cosmetics (Y'-3), use a makeup brush to draw a line about 10 cm on the inside of the forearm, and after air drying at room temperature for 10 minutes. The thickness unevenness due to film convergence was sensory evaluated using the following criteria.
The evaluation results in the table were sensory evaluated by five expert evaluators on the following five levels, and the total scores of the five were listed in Tables 3 and 4.
The higher the total score, the better the uniformity of the film.
Further, 8 hours after application, thickness unevenness due to film twisting was also sensory-evaluated using the same criteria.
(Evaluation criteria)
5 points: A uniform film was obtained with no thickness unevenness.
4 points: Slight unevenness in thickness was observed.
3 points: Thickness unevenness was slightly noticeable.
2 points: Thickness unevenness was noticeable.
1 point: Thickness unevenness was quite noticeable.

<Method for evaluating sebum resistance of cosmetics>
The emulsified foundation was applied to the inside of the forearm with a finger, and the presence or absence of greasiness 8 hours after application was evaluated according to the following criteria.
The evaluation results in the table were sensory evaluated by five expert evaluators on the following five levels, and the total scores of the five were listed in Table 3.
The higher the total score, the better the sebum resistance.
5 points: A uniform film was obtained without greasiness.
4 points: Slight oiliness was observed.
3 points: Oiliness was slightly noticeable.
2 points: Oiliness was noticeable.
1 point; Greasiness was quite noticeable.

As shown in Tables 3 and 4, the cosmetic of the present invention has sufficient uniformity of the film upon application and ability of the film to follow the movement of the skin, and is superior to the skin cosmetic of the comparative example. The results were as follows.

The cosmetic composition of the present invention can be applied to make-up cosmetics because the uniformity of the film upon application and the ability of the film to follow the movement of the skin are sufficient and excellent.

Claims (6)

A polyurethane resin (U) containing polyol (A) and polyisocyanate (B) as essential constituent monomers, wherein the polyol (A) has a number average molecular weight of 500 to 5,000, and the polyol (A) is a polyurethane resin for cosmetics containing a polyfarnesene polyol (A1) and/or a hydrogenated product of polyfarnesene polyol (A2), wherein the polyol (A) further contains a condensed polyester polyol (A3). , polylactone polyol (A4), polycarbonate polyol (A5), polyether polyol (A6), poly(meth)acrylic polyol (A7), (hydrogenated) polybutadiene polyol (A8), castor oil polyol (A9), and silicone It contains at least one polyol selected from the group consisting of polyols (A10), and is based on the total weight of the polyfarnesene polyol (A1) and the hydrogenated polyfarnesene polyol (A2). A polyurethane resin for cosmetics in which the total weight ratio of A3) to (A10) is (126/173)×100 % by weight or less. The polyurethane resin for cosmetics according to claim 1, wherein the polyurethane resin (U) further contains a chain extender (C) having a number average molecular weight or chemical formula weight of less than 500 as a constituent monomer. The polyurethane resin for cosmetics according to claim 1 or 2, wherein the polyurethane resin (U) has a urea group concentration of 0.1 to 1.5 mmol/g. A polyurethane resin composition for cosmetics, comprising the polyurethane resin for cosmetics according to any one of claims 1 to 3, and water and/or a solvent (S). An aqueous polyurethane resin dispersion for cosmetics, comprising the polyurethane resin for cosmetics according to any one of claims 1 to 3 and water. A cosmetic containing the polyurethane resin for cosmetics according to any one of claims 1 to 3.