JP2008189552A - Cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a cosmetic solving conventional defects and containing polyurethane gel particles. <P>SOLUTION: The cosmetic comprises three-dimensionally crosslinked polyurethane gel particles A and polyurethane gel particles C that cover the surfaces of the particles A and comprise polyurea colloidal particles B precipitated from a solution of polyurea colloid in a nonaqueous solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a cosmetic, and more particularly to a cosmetic containing polyurethane gel particles. The polyurethane gel particles used in the present invention have a high degree of circularity and a uniform particle diameter, and are excellent in mechanical strength, flex resistance, heat resistance, low temperature characteristics, wear resistance, chemical resistance, etc. Flexibility (soft touch feeling), slipperiness, moist feeling, elasticity, deformation recovery, permeability, light diffusion, moderate glossiness, extensibility to skin, medium resistance (swelling) required for cosmetics No), oil resistance (does not swell), oil absorption, sebum absorption and skin safety, etc. The polyurethane gel particles are useful as materials for makeup cosmetics, skin care and sunscreen cosmetics. is there.

  Conventionally, particles such as talc, kaolin, mica, and pigment are often used as particles used in cosmetics. Furthermore, examples of the organic particles include organic compounds such as nylon particles, crystalline cellulose particles, urethane particles, acrylic particles, silicone particles, polystyrene particles, polyethylene particles, and ethylene / methyl methacrylate copolymer particles.

  For organic particles obtained from various synthesis methods, the particles are spherical or non-spherical, porous spherical particles, changes in particle diameter, particle size distribution, specific gravity, hardness, surface treatment (surface properties), etc. Various materials are being considered.

  As for typical particles used in cosmetics, nylon 12 particles are excellent in extensibility, have a smooth feel due to their high hardness, are popular, and have a spherical and single particle size distribution. It has characteristics such as solvent resistance, chemical resistance, compression resistance, and non-thermal fluidity. However, the nylon 12 particles are high in cost, easily absorb preservatives such as parahydroxybenzoic acid esters, lose the antiseptic effect, and have problems with melting points when processed at high temperatures such as lipsticks. It causes problems such as fusing with cosmetic ingredients.

  Acrylic particles have low cost, good extensibility, good sliding feeling, and are used in makeup cosmetics, antiperspirants, lotions, etc., but the above acrylic particles are flexible, fit, and close to the skin There is also a problem that it has poor nature (with makeup).

  Silicone particles are used for make-up cosmetics because of their high hardness, good extensibility (low dynamic friction coefficient), water repellency, light diffusibility and hiding properties. However, the silicone particles have problems such as poor flexibility and poor sebum absorbability.

  Cosmetics containing true spherical organic particles are non-irritating to the skin and have no problems with the safety of the human body, as well as smooth and flexible touch, extensibility to the skin (rolling), sweat and Improves sebum absorbability and breathability, and exerts natural cover effect that produces natural skin that hides wrinkles and stains by utilizing optical properties such as permeability, light diffusibility, hiding effect, and glossiness It is used for purposes such as preventing shine, hiding uneven color, holding makeup, hiding small wrinkles and pores.

  Furthermore, in addition to its function as a cosmetic, the particles have good compatibility with, for example, volatile silicone oil, purified water, oils, preservatives, etc. Long-term stability is required with low absorbability of basic silicone oil, oil and preservatives.

  In addition, the moldability of the above-mentioned particles in each production method (dry method, wet method) is important for powder foundations, and lipsticks are processed at high temperatures, so they have low heat resistance (do not soften at the processing temperature) and polarity. The processability of cosmetics such as not sticking is required.

  As a method for solving such a problem, a method of blending spherical polyurethane particles in cosmetics has been proposed (Patent Document 1). This cosmetic has no problem in extensibility and touch, but has poor light diffusibility and hiding properties, which are required for the cosmetic, and is not satisfactory as optical properties.

Moreover, the method of mix | blending acrylic copolymer particle | grains with cosmetics is proposed (patent document 2). The cosmetic containing the acrylic copolymer particles has good extensibility and the like, but the particles themselves have a high hardness (a high glass transition temperature) and feel far from human skin. These conventional methods require flexibility close to human skin, which is currently mainstream, and cannot solve the problem that a natural cover effect close to nature cannot be obtained.
Japanese Patent Laid-Open No. 5-262622 JP 2001-151626 A

  Although the organic particles have excellent characteristics unique to each material in cosmetics, they have several problems and do not satisfy all the functions described above. In addition, there is a demand for organic particle materials and cosmetics that are more functional than conventional ones. Accordingly, an object of the present invention is to provide a cosmetic comprising polyurethane gel particles that has solved the above-mentioned drawbacks.

  The above object is achieved by the present invention described below. That is, the present invention relates to a three-dimensionally crosslinked polyurethane gel particle (hereinafter referred to as “particle A”) obtained by copolymerizing a polyisocyanate having at least one of three or more functional groups and a compound having an active hydrogen group in the molecule. And polyurethane gel particles (hereinafter also referred to as “particles B”) deposited from a polyurea colloid non-aqueous solvent solution covering the surface of the particles A. (Hereinafter, referred to as “particle C” in some cases).

  As a result of intensive studies to solve the above problems, the present inventors have found that the particles C used in the present invention have mechanical strength, bending resistance, heat resistance, low temperature characteristics, wear resistance, chemical resistance, etc. It has excellent transparency, moderate transparency with a natural cover effect required as a cosmetic ingredient, moderate light diffusibility, moderate concealment, moderate gloss, anti-shine, concealing color irregularities, It has pore concealing effect and feel (flexibility (soft touch feeling), slipperiness, moist feeling), elasticity, deformation recovery, skin extensibility, oil absorption, sebum absorption, skin safety, etc. Excellent, especially flexibility (softness), deformation recovery ability and sebum (oleic acid) absorption performance is high, and since the particle size distribution is narrow and spherical, the particles C can be used as a cosmetic ingredient. , Found that the problems of the prior art are solved It was.

Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention.
In the particle C, the particle B covering the particle A is composed of a portion solvated with respect to the solvent and a non-solvated portion, and the particle size of the non-solvated portion is 0. 0.01 μm to 1.0 μm, and the particle B is a particle obtained by a reaction of an oil-modified polyol, a polyisocyanate, and a polyamine, and the non-solvated portion is formed of a hydrogen bond of a urea bond. Preferably, the particle C has a particle diameter in the range of 0.5 to 100 μm.

  Further, the particle C has a circularity (hereinafter, simply referred to as “circularity”) represented by [circularity = circumferential length of circle obtained from equivalent circle diameter / peripheral length of particle projection] 0.9 to 0.9. 1.0 is preferable. Here, the circularity is calculated by the above equation by the particle shape image analysis apparatus PITA-1 of Seishin Co., Ltd., and the circularity is equivalent to a circle-equivalent diameter (the same projected area as the perimeter actually captured). It is defined as a value obtained by dividing the perimeter calculated from the diameter of the perfect circle by the perimeter of the actually imaged particle, and becomes 1 for a perfect circle, and becomes a smaller value as the shape becomes more complex. For this reason, particles with extremely high sphericity with a circularity of 0.9 or more are preferable, and the dispersion in which the particles are dispersed in water or the like is very stably dispersed due to charge repulsion. Has dispersion stability and thickening effect. In addition, in the case of the particles C having a circularity of less than 0.9, the particles C are not spherical, and the stable dispersibility is lost, and the cosmetic containing the particles C gives a feeling of roughness and a squeak.

  Further, the compressive strength of the particles C is preferably 0.01 to 1.0 MPa, and the recovery rate is preferably in the range of 60 to 100%. Since the particle C is a polyuntan gel particle in which the particle A is coated with the particle B, a sufficient dry feeling can be obtained when the compressive strength is 0.01 MPa or more, and the softness (feel that is closer to the skin) From the viewpoint of obtaining a soft touch feeling, slipperiness, and moist feeling, the compressive strength of the particles C is preferably 1 MPa or less.

  Further, the recovery rate of the particles C is required to be restored to the original shape at the same time as the force is released when deformed by pressure, and is preferably in the range of 60 to 100%. Here, the compressive strength and the recovery rate are the load and particle diameter when the resin particles are subjected to a compression test with a microcompression tester MCT-W500 manufactured by Shimadzu Corporation and deformed by 10% with respect to the particle diameter. From the equation [compressive strength (MPa) = 2.8 × load (N) / {π × particle diameter (mm) × particle diameter (mm)}].

  Further, the recovery rate of the particle C is expressed by the equation [recovery rate (%) = L2 / L1 × 100] from the distance (L1) displaced when a pressure of 50 mN is applied to the particle and the distance (L2) displaced when the pressure is released. Is a value calculated by. The compressive strength and recovery rate of the resin particles can be adjusted by controlling the type and blending amount of the polyisocyanate that is a constituent of the particle A and the compound having an active hydrogen group in the molecule.

  Furthermore, the thermal softening point of the particles C is preferably 250 ° C. or higher. When the heat softening point is low, when the cosmetic composition containing the particles C is processed into a stick agent such as lipstick, problems such as melting of the particles C at a high temperature may occur. The thermal softening point of the particles C was measured by using a thermomechanical analyzer (TMA, Rigaku Corporation) to produce a sheet having the same resin composition as the particles.

  The above particles C are polymerized by emulsifying and dispersing a polyisocyanate as a raw material and a compound having an active hydrogen group in an inert solvent using a polyurea colloid solution (dispersion of particles B) described later as a dispersant. It is obtained with. At this time, the polyurea colloidal solution easily emulsifies the raw material polyisocyanate and the compound having active hydrogen groups in an inert solvent in a particulate form, and the compound having polyisocyanate and active hydrogen groups in this state. In a state where particles B precipitated from the polyurea colloid solution are uniformly attached around the generated particles A and the particles C are separated from the dispersion solvent. The particles A are uniformly coated with the particles B.

  Further, in the conventional process of synthesizing the particles A or C, a significant increase in viscosity usually occurs. However, when the particle A is synthesized in the presence of a polyurea colloid solution, a significant increase in the viscosity of the polymerization solution does not occur in the synthesis process. The produced particles C are characterized by maintaining excellent dispersion stability without agglomeration. This action is fundamentally different from conventionally known organic emulsifiers and dispersion stabilizers.

  The particles C used in the present invention can be obtained by the above-described method, but a preferable method is that a polyurea colloid solution is charged into an inert solvent in a jacket-type synthesis kettle equipped with a stirrer or an emulsifier, and at least one of them is contained therein. A method of synthesizing particles C by adding and emulsifying a polyisocyanate having one or more functional groups and a compound having an active hydrogen group in the molecule to an inert solvent solution and reacting these synthesis raw materials, or at least one of them A method in which polyisocyanate having a trifunctional or higher functional group and a compound having an active hydrogen group in the molecule are separately emulsified in an inert solvent in the presence of a polyurea colloid solution and reacted with each other.

  Although the synthesis temperature in the said synthesis method is not specifically limited, A preferable temperature is 40 to 140 degreeC. In addition, the polyurea colloid solution used at the time of synthesis is used in an amount of 0 per 100 parts by mass of each of the polyisocyanate and the compound having an active hydrogen group in the molecule, at least one of which is trifunctional or higher. .01 mass parts or more can be used, preferably 0.1 to 20 mass parts. When the amount used is less than 0.01 parts by mass, the stability of the generated particles C is insufficient, and large aggregates of the particles A are generated during the synthesis process, making it difficult to obtain a target particle C dispersion. On the other hand, when the amount used exceeds 20 parts by mass, there is no problem in the emulsifying properties of the polyurethane raw material, and the dispersion of particles C can be produced. Absent.

  The lower the concentration of the polyisocyanate and the compound having an active hydrogen group in the molecule in the inert solvent, the easier it is to obtain particles C having a smaller particle diameter. However, the preferred concentration is 20 to 70% by mass in terms of productivity.

  The polyol used as the compound having an active hydrogen group in the molecule used for the synthesis of the particles A is preferably a conventionally known short chain diol, polyhydric alcohol or polymer polyol conventionally used for the production of polyurethane. In addition, as the polyamine as a compound having an active hydrogen group in the molecule, a short chain diamine, a high molecular polyamine and the like conventionally used in the production of polyurethane can be used, but these are not particularly limited. Each compound used below is described.

  Examples of the short-chain diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6 -Aliphatic glycols such as hexamethylene glycol and neopentyl glycol and their alkylene oxide low molar adducts (number average molecular weight less than 500), 1,4-bishydroxymethylcyclohexane and 2-methyl-1,1-cyclohexanedimethanol, etc. Alicyclic glycol and its alkylene oxide low molar adduct (number average molecular weight less than 500), aromatic glycol such as xylylene glycol and its alkylene oxide low molar adduct (less than number average molecular weight 500), bisphenol A, thio Scan phenol and sulfonic bisphenol bisphenol and alkylene oxide low molar adducts such as (number average molecular weight of less than 500), and compounds such as alkyl dialkanolamine such as alkyl diethanolamine of C1~C18 thereof.

  Examples of the trifunctional or higher polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate, 1,1,1-trimethylolethane, and 1, 1,1-trimethylolpropane and the like can be mentioned. These can be used alone or in combination of two or more.

Examples of the polymer polyol include the following.
(1) Polyether polyols such as those obtained by polymerizing or copolymerizing alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) and / or heterocyclic ethers (tetrahydrofuran, etc.) are specifically exemplified. Are polyethylene glycol, polypropylene glycol, polyethylene glycol-polytetramethylene glycol (block or random), polytetramethylene ether glycol and polyhexamethylene glycol diol and / or polyether polyol having a tri- or higher functional hydroxyl group,

(2) Polyester polyols such as aliphatic dicarboxylic acids (eg succinic acid, adipic acid, sebacic acid, glutaric acid and azelaic acid) and / or aromatic dicarboxylic acids (eg isophthalic acid and terephthalic acid) And low molecular weight glycols (eg, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol and 1,4-bishydroxymethyl And the like, specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butylene acrylate. Petojioru, polyneopentyl / hexyl adipate diol, poly-3-methylpentane adipate diol, and polybutylene isophthalate diol of the diol and / or 3 polyester polyol having a functionality or more hydroxyl groups such as,

(3) Polylactone polyol, for example, polycaprolactone diol or diol such as polycaprolactone triol and / or poly-3-methylvalerolactone diol, and / or polylactone polyol having a hydroxyl group of three or more functional groups,
(4) Polycarbonate polyol, for example, a diol such as polyhexamethylene carbonate diol and / or a polycarbonate polyol having a trifunctional or higher functional hydroxyl group,

(5) Polyolefin polyol, for example, polybutadiene glycol and polyisoprene glycol, or a diol such as a hydride thereof and / or a polyolefin polyol having a trifunctional or higher functional hydroxyl group,
(6) Hydrogenated dimer polyol, diol such as castor polyol, and / or hydrogenated dimer polyol having a tri- or higher functional hydroxyl group,
(7) Polymethacrylate polyols such as α, ω-polymethylmethacrylate diol and α, ω-polybutylmethacrylate diol, and acrylic polyols having a tri- or higher functional hydroxyl group.

  Although the molecular weight of these polyols is not particularly limited, any of those that react with polyisocyanate can be used, and the number average molecular weight is usually preferably about 500 to 2,000. Moreover, these polyols can be used individually or in combination of 2 or more types. As the polyol, a polyol having two or more active hydrogen groups is preferable, and a polyol having three or more active hydrogen groups is particularly preferable.

  As polyisocyanate used for the synthesis | combination of the said particle | grain A, what is conventionally used for manufacture of a polyurethane can be used and it does not specifically limit. Preferred examples of the polyisocyanate include toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-Butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4′-methylenebis (phenylene isocyanate) (MDI), durylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate (XDI), 1,5 Aromatic diisocyanates such as naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate and 4,4′-diisocyanate dibenzyl, methylene di Aliphatic isocyanates such as socyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate and 1,10-decamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), Obtained by reacting 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as hydrogenated MDI and hydrogenated XDI, or these diisocyanates with low molecular weight polyols and polyamines so that the ends are isocyanates. Of course, polyurethane prepolymers can also be used.

  Moreover, those having a polyfunctional isocyanate group in which these compounds are isocyanurate bodies, burette bodies, adduct bodies, and polymeric bodies, and conventionally known ones can be used and are not particularly limited. For example, dimer of 2,4-toluylene diisocyanate, triphenylmethane triisocyanate, tris- (p-isocyanatephenyl) thiophosphite, polyfunctional aromatic isocyanate, polyfunctional aromatic aliphatic isocyanate, polyfunctional aliphatic Examples thereof include blocked polyisocyanates such as isocyanate, fatty acid-modified polyfunctional aliphatic isocyanate, and blocked polyfunctional aliphatic isocyanate, and polyisocyanate prepolymers.

  Of these, it is possible to use either an aromatic or aliphatic type, preferably a modified product such as diphenylmethane diisocyanate and tolylene diisocyanate for an aromatic type, hexamethylene diisocyanate and isophorone diisocyanate for an aliphatic type, and a molecule. A urethane prepolymer obtained by reacting a polyisocyanate multimer or an adduct with another compound, or a low molecular weight polyol or polyamine so as to be a terminal isocyanate is preferable. Etc. are also preferably used. These are exemplified below with structural formulas, but are not limited thereto.

  The type, amount and use ratio of the polyisocyanate and the compound having an active hydrogen group are determined depending on the purpose of use of the resulting particles C, but any one of the components must be trifunctional or more. . For example, when the polyisocyanate is bifunctional, the compound having an active hydrogen group is trifunctional or more, and when the compound having an active hydrogen group is bifunctional, the polyisocyanate having trifunctional or more is It is necessary, and the number of functional groups used depends on the purpose of use. Of course, all the components may be trifunctional or more. The NCO / OH ratio of the raw material is determined by the performance required for the raw material compound to be used and the particles C to be obtained, and is preferably in the range of 0.5 to 1.2.

  The inert solvent used for the synthesis reaction of the particle C and forming the continuous phase of the dispersion of the generated particle C is substantially non-solvent for the generated particle A and has no active hydrogen group It is. Examples include pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, cyclohexane, methylcyclohexane, toluene, xylene, ethylcyclohexane, dimethylcyclohexane, etc. having the structure of alicyclic hydrocarbons. Hydrocarbon, dimethylpolysiloxane, etc. may be used alone or as a mixture, and these inert solvents have a boiling point of 150 ° C. or less in terms of productivity in the separation process of the particles C synthesized with the inert solvent. Is preferred. In the synthesis of the particles A, a known catalyst may be used at a low temperature, but a reaction temperature of 40 ° C. or higher is preferable from the work surface.

  The particles B in the polyurea colloid solution used as an emulsifier during the synthesis of the particles A are composed of a solvated part and a non-solvated part, and the particle size of the non-solvated part is preferred. Is a particle of 0.01 μm to 1.0 μm, and such a polyurea colloid solution is prepared by, for example, reacting an oil-modified polyol, a polyisocyanate (or a terminal NCO prepolymer comprising these compounds) and a polyamine in a non-aqueous solvent. It is obtained with.

  In this reaction, as the reaction proceeds, hydrogen bonds between urea bonds form an insoluble urea domain in the solvent, and at the same time, the oil-modified polyol chain is solvated in the solvent, thereby insoluble urea. The enlarging of the particle B due to domain aggregation or the like is prevented, and a stable polyurea colloid solution can be easily obtained.

  Furthermore, the oil-modified polyol used has less crystallinity in the non-aqueous solvent, and the polymer chain mainly composed of the oil-modified polyol can move to some extent in the solvent even in the process of polymerization that occurs as the reaction proceeds. Therefore, separation of the non-soluble crystal portion and the soluble non-crystalline portion is easily performed, and a urea domain having the non-soluble crystal portion due to hydrogen bonding between urea bonds as the center of the particle B is formed, and the periphery thereof is formed. The solvated polymer chains are regularly ordered outward. This is a fundamentally different action from the surfactant in a known method for producing a colloidal solution obtained by polymerization in the conventional micelle.

  The method for producing the polyurea colloid solution will be described more specifically. First, an oil-modified polyol and polyisocyanate are first reacted in a non-aqueous solvent or without a solvent to synthesize a prepolymer having an NCO group. Next, this prepolymer is charged into a jacket-type synthesis kettle equipped with a stirrer, and the concentration is adjusted by adding a non-aqueous solvent so that the concentration becomes 5 to 70% by mass. While stirring this solution, a polyamine solution adjusted to a concentration of 1 to 20% by mass in advance is gradually added to react to produce a polyurea colloid solution in the polyureaization reaction.

  In addition to the above method, the polyamine may be added by adding the prepolymer or a solution thereof to the polyamine solution. The temperature for polymer synthesis is not particularly limited, but a preferred temperature is 20 to 120 ° C. The reaction concentration for polymer synthesis, temperature, stirrer form, stirring power, polyamine solution and prepolymer or addition rate of the prepolymer are not particularly limited, but the reaction between the polyamine and the isocyanate group of the prepolymer is fast, It is preferable to control the reaction so that a rapid reaction is not performed.

  The oil-modified polyol used for the production of the polyurea colloid solution is a polyol having 2 or less functional groups, and a preferred molecular weight is 700 to 3,000, but is not limited thereto. Specific examples of the oil-modified polyol include, for example, various fats and oils by alcoholysis using a lower alcohol or glycol, a method of partially saponifying fats and oils, a method of esterifying a hydroxyl group-containing fatty acid with glycol, and the like. Those containing two or less hydroxyl groups are preferred, and examples of the hydroxyl group-containing fatty acid include ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, and the like.

  The reaction between the oil-modified polyol and the polyisocyanate is performed under the condition of 1 <NCO / OH ≦ 2, and the molecular weight of the solvated prepolymer chain is controlled. The molecular weight of the prepolymer synthesized in this way is not particularly limited, but a preferred range is about 500 to 15,000. Examples of the polyisocyanate used above include all known polyisocyanates. Particularly preferred are aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, water-added TDI, water-added MDI, isophorone diisocyanate, and hydrogenated XDI.

  As the non-aqueous solvent used in the production of the polyurea colloid solution, any non-aqueous solvent that dissolves the oil-and-fat-modified polyol, diisocyanate and polyamine used as raw materials and does not have an active hydrogen group can be used. Particularly preferred are pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, cyclohexane, methylcyclohexane, toluene, xylene, ethylcyclohexane and dimethylcyclohexane having an alicyclic hydrocarbon structure. A hydrocarbon, dimethylpolysiloxane or the like may be used alone or as a mixture. In the present invention, “dissolution” includes both dissolution at normal temperature and high temperature.

  Examples of the polyamine used for the production of the polyurea colloid solution include a short-chain diamine, an aliphatic polyamine, an alicyclic polyamine, an aromatic polyamine, and hydrazine. Short chain diamines and aliphatic polyamines include, for example, methylene diamine, ethylene diamine, diaminopropane, diaminobutane, trimethylene diamine, trimethyl hexamethylene diamine, hexamethylene diamine, octamethylene diamine, polyoxypropylene diamine and polyoxypropylene triamine. Aliphatic polyamines such as phenylenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether and 4,4′-diaminodiphenyl Aromatic polyamines such as sulfone, cyclopentanediamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, bis-amino Propyl piperazine, thiourea, methyl iminobispropylamine, and alicyclic diamines, such as norbornane diamine and isophorone diamine. Further, hydrazine such as hydrazine, carbohydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and phthalic acid dihydrazide can be used. These can be used alone or in combination of two or more.

  The purpose of controlling the size and stability of the particle B in the solvent used is the type, amount and ratio of the oil-modified polyol, polyisocyanate, polyamine and the resulting prepolymer used in the production of the polyurea colloid solution. Determined by That is, the particles B in the polyurea colloid solution are formed of a urea domain in a crystal part that is not solvated in the solvent and a polymer chain that extends from the urea domain and is solvated in the solvent.

  The size of the urea domain of particle B in the polyurea colloid solution and the size and morphology of the solvated polymer chain influence the properties of the polyurea colloid solution. Thus, the particle B formed of the urea domain and the solvated polymer chain is a polyurea colloidal solution that is stable in the solvent, and the particle size of the urea domain of the particle B in the solution is usually 0.00. The molecular weight of one solvated polymer chain is about 500 to 15,000, and the mass ratio of both is 0.5 for the urea domain (urea bond or polyamine) / polymer chain. A range of ˜30 is preferred. When the ratio of the urea bond is less than the above range, the non-solvating urea domain in the obtained particle B is hardly formed, the particle B is easily dissolved in the non-aqueous solvent, and a good polyurea colloid solution is not generated. On the other hand, when the ratio of the urea bond exceeds the above range, the non-solvating urea domain is increased, the stability of the resulting polyurea colloid solution is lowered, and the aggregation of the particles B is likely to occur.

  The form in the solvent of the particle | grains B used by this invention is imagined as shown in FIG. Regarding the control of the particle size of the particle B, it is possible to control both the size of the entire particle B including the solvated polymer portion and the urea domain, and the size of each of the solvated polymer portion and the urea domain. is there. The particle size of the particle B described above represents a urea domain portion.

  In order to produce a stably controlled polyurea colloidal solution, it is desirable that the solvated polymer part and the urea domain part are clearly phase-separated as shown in FIG. It is necessary to manufacture such that the chain and the urea domain of the crystal part are not mixed. For this purpose, a synthesis condition is required in which the polymer part solvated in the synthesis process and the urea domain part are easily separated.

  The synthesis of the polyurea colloidal solution gives better results as the concentration of both the prepolymer solution containing NCO groups and the polyamine solution is lower, and the addition rate of adding the other solution to one solution is lower, and the stirring is better. Propeller mixer agitation is sufficient. Further, when the concentration of the raw material solution is high or when the addition rate of the solution is high, it is preferable to synthesize while mixing with a high shearing force by using a homogenizer or the like. Although the reaction temperature is determined by the type of solvent used and the solubility of the urea domain in the solvent, the preferred temperature is 20 to 120 ° C. at which the synthesis can be easily controlled, but is not particularly limited to this temperature range. The formation of the urea domain may be a method of forming in the synthesis process, or a method of forming a synthesis at a high temperature in the cooling process.

  The important factors of the particles B in the polyurea colloid solution are the type and concentration of the surface groups, and further the dispersibility and the dispersed particle size in an inert solvent. That is, the action as an emulsifier of the polyurea colloid solution is a W / O, O / O type emulsifier, and the correlation between the hydrophilicity and hydrophobicity of the polyisocyanate and the compound having an active hydrogen group and the inert solvent. Act on. As a result of considering these conditions, it is possible to control the particle size of the particles C by adjusting the amount of polyurea colloid solution added to the polyisocyanate and the compound having an active hydrogen group. The larger the amount added in the range, the smaller the particle size, and the smaller the amount, the larger the particle size.

  The particles C are obtained by separating the inert solvent from the dispersion solution of the particles C obtained from the raw materials as described above under normal pressure or reduced pressure. Any known device such as a spray dryer, a vacuum dryer with a filtration device, a vacuum dryer with a stirring device, a shelf dryer, etc. can be used as a device for particle formation, and the preferred drying temperature is the vapor pressure of an inert solvent, gel particles Although it is influenced by the softening temperature, particle size, etc., it is preferably 40 to 130 ° C. under reduced pressure.

  The particle C thus produced has a true particle size of 0.5 μm to 100 μm and a circularity of 0.9 to 1.0. The control of the particle size depends on the emulsification type (propeller type, saddle type, homogenizer, spiral band type, etc.) of the synthetic kettle and the stirring force when the polyurethane composition is the same. It is influenced by the concentration of the polyisocyanate and the compound having an active hydrogen group, the type of polyurea colloid solution and the amount added. The mechanical agitation and shearing force for emulsifying the polyisocyanate and the compound having an active hydrogen group are determined at the initial stage of emulsification, and the stronger this is, the smaller the particle size of the dispersion. Subsequent stirring and shear forces are not significantly affected. On the other hand, if the force is too strong, aggregation of the dispersions is promoted, which is not preferable.

  In the present invention, in the production of the above particles C, at least a part or all of the raw material is a colorant such as a dye or pigment, mica, pearl, moisturizing component, vitamin component, antioxidant component, blood circulation promoting component, ultraviolet absorption And / or mixing various additives such as UV-blocking ingredients, collagen, stabilizers, antioxidants, UV absorbers, extender pigments, etc. to synthesize polyurethane and obtain particles C suitable for various cosmetic applications. Is also possible.

  These particles C are almost perfectly spherical particles as shown in the electron micrograph (magnification 500 times) in FIG. 2, and polyurea colloids are formed on the surfaces of the individual particles A as shown in the imaginary view of FIG. Particles B deposited from the solution are adhered or coated, and particles B are excellent in non-adhesiveness and heat resistance. Therefore, the particles C are extremely fluid by simply removing the particles C from the dispersion solvent. In the formation of particles, there are various advantages such as no complicated and costly pulverization process and classification operation as in the prior art.

  The cosmetic of the present invention is obtained by blending the above-mentioned particles C as an essential component with other conventionally known cosmetic ingredients. Examples of other cosmetic ingredients include, for example, when the cosmetic is a cream, silicone surfactants, squalane, volatile silicones, 1,3-butanediol, purified water, and the like. , And used in the range of 1.0 to 90% by mass of the entire cosmetic. Further, when the cosmetic is a liquid foundation, a silicone-based surfactant, volatile silicone, dimethyl silicone, titanium oxide, petal, yellow iron oxide, talc, propylparaben (preservative), 1,3-butane Examples include glycol, vitamin E, and purified water. Further, when the cosmetic is a powder foundation, talc, sericite, titanium oxide, petal, yellow iron oxide, black iron oxide, mica, squalane, stearyl alcohol, beeswax and the like are exemplified, but not limited thereto. .

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples, but the present invention is not limited thereto. Moreover, in the following sentence, “part” indicates mass part, and “%” indicates mass%.

(Preparation of polyurea colloid solution)
[Synthesis Example 1]
100 parts of a bifunctional oil- and fat-modified polyol having a hydroxyl value of 119.5 (URIC Y-202 manufactured by Ito Oil Co., Ltd.) and 100 parts of n-octane were charged into a synthetic kettle equipped with a stirrer, and the polyol was dissolved. While stirring, the temperature was controlled at 50 ° C., 47.3 parts of isophorone diisocyanate prepared in advance so that NCO / OH = 2 was gradually added over 1 hour, and the reaction was continued for 3 hours under these conditions. The reaction was performed at 3 ° C. for 3 hours. Next, the concentration was adjusted to 50% with n-octane to obtain a prepolymer solution (PP-1) containing 3.0% of NCO groups. The molecular weight of this product is 1,383.

  40 parts of the above PP-1 and 60 parts of n-octane were charged into a synthesis kettle equipped with a stirrer and dissolved. While controlling the temperature at 70 ° C. while stirring, 24.3 parts of a 10% solution of n-octane of isophoronediamine prepared in advance was gradually added over 5 hours to complete the reaction, and (polyamine (urea bond part) ) / Prepolymer chain) × 100 = 12.15% polyurea colloid solution (solid content 18.0%) (C-1) was obtained. This solution was a blue opalescent stable solution.

[Synthesis Example 2]
100 parts of a bifunctional oil- and fat-modified polyol having a hydroxyl value of 119.5 (URIC Y-202 manufactured by Ito Oil Co., Ltd.) and 100 parts of n-octane were charged into a synthetic kettle equipped with a stirrer, and the polyol was dissolved. While stirring, the temperature was controlled at 50 ° C., 26.0 parts of isophorone diisocyanate prepared in advance so that NCO / OH = 1.1 was gradually added over 1 hour, and the reaction was continued for 3 hours under these conditions. Further, the reaction was carried out at 80 ° C. for 4 hours for synthesis. Next, the concentration was adjusted to 50% with n-octane to obtain a prepolymer solution (PP-2) containing 0.36% of NCO groups. The molecular weight of this product is 11,834.

  20 parts of the above PP-2 and 80 parts of n-octane were charged into a synthetic kettle equipped with a stirrer and dissolved in the prepolymer. While controlling the temperature at 70 ° C. while stirring, 14.4 parts of a 1% solution of n-octane of isophoronediamine prepared in advance was gradually added over 8 hours to complete the reaction, and (polyamine / prepolymer chain) ) × 100 = 1.44% polyurea colloid solution (solid content: 8.9%) (C-2) was obtained. This solution was a blue opalescent stable solution.

(Production of polyurethane gel particles C)
[Synthesis Example 3] (Example 1)
20 parts of polybutylene adipate diol having an average molecular weight of 1,000 is dissolved at 60 ° C., and isocyanurate polyisocyanate of hexamethylene diisocyanate represented by the following structural formula (Duranate TPA-100 manufactured by Asahi Kasei Kogyo Co., Ltd., NCO% = 23.1) 7.3 parts were added and mixed uniformly. This product was gradually added to a mixed solution of 5.0 parts of polyurea colloid solution (C-1) of Synthesis Example 1 and 25 parts of n-octane prepared in advance in a 1 liter stainless steel container, and emulsified with a homogenizer for 15 minutes. . This emulsion was a stable emulsion having an average dispersoid particle size of 5 μm and no separation.

  Next, this was charged into a reaction kettle equipped with a vertical stirrer, the temperature was raised to 80 ° C. while rotating at 400 rpm, the reaction for 6 hours was completed, and a solution of polyurethane gel particles (particle C) was obtained. This solution was vacuum-dried at 100 Torr to separate n-octane to obtain particles C (1). This was a spherical white powder having an average particle diameter of 5 μm and a circularity of 0.92. The compressive strength was 0.35 MPa and the recovery rate was 89%.

[Synthesis Example 4] (Example 2)
In a 500 ml separable flask, 4 parts of polyurea colloid solution (C-2) and 150 parts of isooctane were charged and mixed. Next, 100 parts of a trifunctional polylactone polyol having an average molecular weight of 785, which was preheated to 50 ° C., was gradually added and emulsified while mixing this solution with a homomixer. Furthermore, 68.3 parts of hexamethylene diisocyanate adduct polyisocyanate represented by the following structural formula (Duranate 24A-100 manufactured by Asahi Kasei Kogyo Co., Ltd., NC 0% = 23.5) was gradually added.

  Next, while rotating the homomixer, the temperature was raised to 80 ° C., and after reaction for 3 hours, 0.005 part of dibutyltin dilaurate was added as a reaction catalyst, and the reaction was further performed for 4 hours to obtain a dispersion of particles C. . Particle C (2) was obtained from this dispersion in the same manner as in Example 1. This was a spherical white powder having an average particle diameter of 15 μm and a circularity of 0.94. The compressive strength was 0.60 MPa, and the recovery rate was 92%.

[Synthesis Example 5] (Comparative Example 1)
In a 1,000 ml separable flask equipped with a stirrer and a reflux condenser, 50 parts of methyl methacrylate, 35 parts of ethyl acrylate, 5 parts of propylene glycol diacrylate, 10 parts of ethylene glycol dimethacrylate and 0.3 part of benzoyl peroxide In addition, 30 parts of a 5% aqueous solution of polyvinyl alcohol (GH-17, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and 250 parts of ion-exchanged water are added, and dispersed at 4,000 to 6,000 rpm for 10 minutes with a homomixer. The dispersion (1) was prepared by treatment. Further, the dispersion (1) was radically polymerized at 80 ° C. for 5 hours with stirring in a nitrogen atmosphere. The resulting acrylate-based particle dispersion was dehydrated, washed and dried, then crushed and sieved to obtain acrylic particles (3). This was a spherical white powder having an average particle diameter of 10 μm and a circularity of 0.93. The compressive strength was 7.1 MPa and the recovery rate was 45%.

[Synthesis Example 6] (Comparative Example 2)
Silica particles having a mean particle size of 3.9 μm and a circularity of 0.74 were used as silica particles. The compressive strength was 15.5 MPa, and the recovery rate was 0% because it was destroyed.

(Cosmetic evaluation of each particle of Examples 1 and 2 and Comparative Examples 1 and 2)
<Dispersibility>
5 g of each particle was added to 100 g of IPA (isopropyl alcohol) in a dissolver stirrer (1,000 rpm), and the dispersibility after 20 seconds was confirmed.
Evaluation criteria;
○: Uniformly dispersed.
Δ: Some agglomerates were present.
X: Not dispersed.

<Oil absorption measurement>
It measured according to JIS-K5101. Linseed oil is considered to have less absorbability because it can no longer exhibit its effect when it absorbs oils, preservatives and the like used in cosmetics. Oleic acid was measured as an alternative material for human sebum components. The higher the absorption of oleic acid, the better it is because it absorbs human sebum. Absorption of oils and preservatives used in cosmetics is low, and absorption of sebum (oleic acid) is required.

<Dispersion stability test>
10 g of each particle was added to 100 g of 1,3-butane glycol, volatile silicone, and IPA, and the dispersion stability when mixed by hand stirring was confirmed.
Evaluation criteria;
○: After being easily dispersed, after 3 days, a stable solution without aggregation / sedimentation can be maintained.
Δ: Although easily dispersed, agglomeration and sedimentation are partially observed after 3 days.
X: Not dispersed.

<Swelling test>
After each particle was immersed in IPA for 24 hours, the change in particle diameter was compared.

<Optical characteristics>
For the test piece, each particle was added to a nitrocellulose solution at a concentration of 10 phr, and the optical properties of a sample coated and dried to a film thickness of 20 μm during drying were measured.
Transmittance: Total light transmittance, diffusion = diffuse transmittance was measured. If the transmittance is high, it is said that natural skin with transparency may be produced. Further, the diffuse transmittance is required to have an appropriate value (30 to 50), and has an effect of hiding small wrinkles, stains and the like by the light diffusion effect.

<Thermal softening point>
Using thermomechanical analysis (TMA, Rigaku Corporation), a sheet having the same resin composition as each particle was prepared, and the load was 10 g and the heating rate was 10 ° C./min. The measurement was performed by the needle approach method under the following conditions.

(Cosmetic application of each particle of Examples 1 and 2 and Comparative Examples 1 and 2)
<Cream formula>
・ Each particle 12.0 parts ・ Silicone surfactant 1.0 part ・ Squalane 12.0 parts ・ Volatile silicone 12.0 parts ・ 1,3-BG 5.0 parts ・ Purified water 58.0 parts The following cosmetics evaluation was performed by prescription.

<Flexibility>
An appropriate amount was applied to the back of the hand and evaluated in a dry state.
○: Soft.
Δ: Softness is weak.
X: Hardness is strong.
When the softness is high, it is a feeling that approximates human skin and is evaluated.

<Extensible (rolling)>
An appropriate amount was applied to the back of the hand, and it was confirmed that the extensibility was good.
○: Extensive.
Δ: Less extensibility ×: No extensibility

<Pore concealment effect>
Appropriate amount was applied to the back of the hand, and it was visually observed and evaluated whether the pores were hidden.
○: Pore concealment effect.
Δ: Pore concealment effect is low.
X: No pore concealing effect.

<Liquid foundation prescription>
・ Each particle 10.0 parts ・ Silicone surfactant 1.5 parts ・ Volatile silicone 23.0 parts ・ Dimethyl silicone 5.0 parts ・ Titanium oxide 9.0 parts ・ Valve 0.6 parts ・ Yellow iron oxide 0.2 parts, talc 2.0 parts, propylparaben (preservative) 0.5 parts, 1,3-BG 10.0 parts, vitamin E 0.2 parts, purified water 38.0 parts

<Powder foundation prescription>
・ Each particle 3.0 parts ・ Talc 35.0 parts ・ Sericite 20.0 parts ・ Titanium oxide 9.0 parts ・ Valve 2.0 parts ・ Yellow iron oxide 3.5 parts ・ Black iron oxide 0.5 parts・ Mica 15.0 parts ・ Squalane 6.0 parts ・ Stearyl alcohol 3.0 parts ・ Beeswax 3.0 parts

The present invention has the following effects.
1. It is possible to provide a cosmetic containing polyurethane gel particles C having a controlled particle size.
2. The obtained polyurethane gel particles C are spherical (the degree of circularity is 0.9 to 1.0), and the polyurea colloid particles B precipitated from the polyurea colloid solution are uniformly attached to the surface of the polyurethane gel particles C. Since the particles C are coated, the particles C are extremely excellent in fluidity and easy to handle, and can be applied in various ways as ingredients of cosmetics.
3. From the above effects, the polyurethane gel particle C is useful as a cosmetic ingredient.

The imaginary figure of the cross section of the polyurea colloid particle B in the polyurea colloid solution used by this invention. The photograph of the polyurethane gel particle C used by this invention. The imaginary figure of the cross section of the polyurethane gel particle C used by this invention.

Explanation of symbols

1: Solvated polymer chain (oil segment)
2: Unsolvated urea domain 3: Polyurethane gel particle A
4: Polyurea colloidal particle B

Claims (7)

  Three-dimensionally crosslinked polyurethane gel particles (particle A) obtained by copolymerizing a polyisocyanate having at least one of three or more functional groups and a compound having an active hydrogen group in the molecule, and the surface of the particle A A cosmetic comprising polyurethane gel particles (particles C) comprising polyurea colloid particles (particles B) deposited from a polyurea colloid non-aqueous solvent solution.   The makeup according to claim 1, wherein the particles B are composed of a solvated portion and a non-solvated portion with respect to the solvent, and the particle size of the non-solvated portion is 0.01 µm to 1.0 µm. Fee.   The cosmetic according to claim 1, wherein the particles B are polyurea colloidal particles obtained by a reaction between an oil-modified polyol, a polyisocyanate, and a polyamine, and the non-solvated portion is a hydrogen bond of a urea bond.   The cosmetic according to claim 1, wherein the particle diameter of the particles C is in the range of 0.5 to 100 µm. The cosmetic according to claim 1, wherein the circularity of the particle C represented by the following formula is in the range of 0.9 to 1.0.
Circularity = Circle circumference obtained from equivalent circle diameter / circumference of particle projection   The cosmetic according to claim 1, wherein the compression strength of the particles C is in the range of 0.01 to 1.0 MPa, and the recovery rate is in the range of 60 to 100%.   The cosmetic according to claim 1, wherein the heat softening temperature of the particles C is 250 ° C or higher.