JP4936374B2 - Cosmetics - Google Patents

Description

The present invention relates to cosmetics containing a polysiloxane-modified polyurethane gel particles child. The polysiloxane-modified polyurethane gel particles contained in the cosmetic of the present invention have a uniform particle size, and have mechanical strength, flex resistance, heat resistance, low temperature characteristics, wear resistance, chemical resistance, water repellency and oxygen Excellent permeability, especially softness necessary for cosmetic ingredients (soft touch feeling), slipperiness, moist feeling, elasticity, deformation recovery, permeability, light diffusibility, moderate gloss, skin Excellent extensibility, medium resistance (does not swell), oil resistance (does not swell), oil absorption, sebum absorption and skin safety, etc., such as makeup cosmetics, skin care and sunscreen cosmetics It is useful as a component of cosmetics.

  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 copolymers.

  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 expensive and easily absorb preservatives such as parahydroxybenzoic acid ester and ethyl parahydroxybenzoate, thereby eliminating the antiseptic effect and high temperature processing such as lipstick. The problem of melting with the cosmetic ingredient is caused by the problem of the melting point.

  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 spherical organic particles are a material that is not irritating to the skin and has no problem with safety of the human body, and also has a smooth and flexible feel, extensibility to the skin (rolling property), sweat and sebum To provide natural absorbency, breathability, and natural cover effect that creates natural skin that hides wrinkles and stains by utilizing optical properties such as permeability, light diffusibility, hiding effect, glossiness, etc. It is used for purposes such as preventing shine, hiding uneven color, holding makeup, and hiding small wrinkles and pores.

  Furthermore, in addition to its function as a cosmetic, the above particles have good compatibility with, for example, volatile silicone oils, purified water, oils, preservatives and the like used in cosmetics, and are volatile. Long-term stability is required with little absorption of silicone oil, oil agent, and preservative.

  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 the 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 conventional problems described above resolved polysiloxane modified polyurethane gel particles child.

The above object is achieved by the present invention described below. That is, the present invention includes a polysiloxane-modified polyurethane gel (hereinafter, also simply referred to as “particle C”) having a particle size in the range of 0.5 to 100 μm and a cosmetic ingredient, C represents a polyisocyanate, a compound having an active hydrogen group in the molecule, a polysiloxane having an active hydrogen group in the molecule and / or a copolymer of the polysiloxane and a lactone (hereinafter simply referred to as “reactive polysiloxane”). The surface of a three-dimensionally crosslinked polysiloxane-modified polyurethane gel particle (hereinafter sometimes referred to simply as “particle A”) composed of a polyurea colloid particle (hereinafter referred to as “particle A” ) precipitated from a polyurea colloid non-aqueous solvent solution. it is covered by simply sometimes referred to as "particles B"), having a active hydrogen groups in the polyisocyanate and in the molecule Providing that reduction粧料to, wherein at least one compound is 3 or more functional groups.

  As a result of intensive studies to solve the above problems, the present inventors have found that the particles C of the present invention have mechanical strength, bending resistance, heat resistance, low temperature characteristics, wear resistance, chemical resistance, water repellency. It has excellent oxygen permeability, moderate transparency with a natural cover effect required as a cosmetic ingredient, moderate light diffusivity, moderate concealment, moderate gloss, anti-shine, color It has an effect of concealing unevenness, small wrinkles, and touch (softness (soft touch feeling), slipperiness, moist feeling), elasticity, deformation recovery, extensibility to the skin, oil absorption, sebum absorption, skin contact Excellent in safety, etc. Especially, since the flexibility (softness), deformation recovery power and sebum (oleic acid) absorption performance are high and the particle size distribution is narrow and spherical, the particles C are used as cosmetic ingredients. By using it, the problems of the prior art are solved. I found a door.

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 of the present invention, the particle B covering the particle A is composed of a part solvated with a solvent and a non-solvated part, and the particle size of the non-solvated part That the particle B is a polyurea colloidal particle obtained by the reaction of an oil-modified polyol, a polyisocyanate, and a polyamine, and the non-solvated portion is composed of a hydrogen bond of a urea bond. It is preferable that the particles C have a particle diameter in the range of 0.5 to 100 μm.

  The inventors of the present invention can easily prepare a polyurea colloid solution containing the particles B by mixing the polyisocyanate as a raw material of the particles A, a compound having an active hydrogen group in the molecule, and a reactive polysiloxane in an inert solvent. When emulsified in the form of particles and the raw material is subjected to a polymerization reaction in this state, polysiloxane-modified polyurethane gel particles (the particles A) are produced, and the polyurea precipitated from the polyurea colloid solution is formed around the produced particles A. The colloidal particles (the particles B) are uniformly attached, and the particles A are uniformly coated with the particles B in a state where the particles C are separated from the dispersion solvent.

  Furthermore, in the present invention, a significant increase in viscosity usually occurs in the process of synthesizing the polyurethane gel particles, but when the particle A is synthesized in the presence of the polyurea colloid solution, no significant increase in viscosity occurs 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 of the present invention can be obtained by the above-described method. In a preferred method, a polyurea colloid solution is charged in a jacket-type synthesis kettle equipped with a stirrer or an emulsifier in an inert solvent, and at least one of them is trifunctional. A method of synthesizing particles C by adding and emulsifying a polyisocyanate, a compound having an active hydrogen group in the molecule, and a reactive polysiloxane to an inert solvent solution and reacting these synthesis raw materials. A polyisocyanate having at least one of three or more functional groups, a compound having an active hydrogen group in the molecule, and a reactive polysiloxane are separately emulsified in an inert solvent in the presence of a polyurea colloid solution. And the like.

  Although the temperature at the time of synthesize | combining the particle | grains C of the said invention is not specifically limited, A preferable temperature is 40 to 140 degreeC. The polyurea colloid solution used at the time of synthesis is used in the form of a solid content, at least one of which is trifunctional or higher, polyisocyanate, compound having an active hydrogen group in the molecule, and reactive polysiloxane. 0.01 mass parts or more can be used per 100 mass parts of each, Preferably it is 0.1-20 mass parts. When the amount used is less than 0.01 parts by mass, the stability of the 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, if the amount used exceeds 20 parts by mass, there is no problem with the emulsifying properties of the polyurethane raw material, and the dispersion of particles C can be produced, but it is an excessive amount as an emulsifier and has no particular advantage. .

  The lower the concentration of the polyisocyanate, the compound having an active hydrogen group in the molecule, and the reactive polysiloxane in the inert solvent, the easier it is to obtain particles C having a smaller particle diameter. -70 mass%.

  The polysiloxane segment in the polyurethane resin constituting the particle C of the present invention is contained in a branched or branched state in the main chain of the polyurethane resin constituting the particle C. In other words, if the reactive polysiloxane used as a raw material is a double-end reactive type, the reactive polysiloxane may be a single-end or branched reactive type on the trunk portion that is the main chain of the polyurethane resin constituting the particles C. For example, the polysiloxane segment is contained in a state branched from the main chain of the polyurethane resin. The polysiloxane segment content in the polyurethane resin constituting the particles C is 0.01 to 80% by mass, preferably 1 to 35% by mass. When the polysiloxane segment content is less than the above range, it is not preferable in terms of water repellency, oxygen permeability, progressability to skin, deformation recovery, and the like, while when the polysiloxane segment content exceeds the above range, It is not preferable in that it cannot be taken out as particles because of a decrease in mechanical strength and an increase in softness.

As the reactive polysiloxane used for the synthesis of the particles C of the present invention, for example, the following compounds are preferably used (including epoxy-modified polysiloxane modified using active hydrogen groups). However, it is included because it reacts with the isocyanate group and is contained in the polyurethane resin). Examples of the active hydrogen group in the polysiloxane having an active hydrogen group in the molecule include a hydroxyl group (—OH), a carboxyl group (—COOH), an amino group (—NRH, —NH _2, etc.) and a thiol group (—SH). Among these, a hydroxyl group and an amino group are preferably used.

(1) Amino-modified polysiloxane

(2) Epoxy-modified polysiloxane

(3) Alcohol-modified polysiloxane

(4) Mercapto-modified polysiloxane

  The reactive polysiloxanes listed above are preferred compounds for use in the present invention, but the present invention is not limited to these exemplary compounds. Accordingly, not only the above-exemplified compounds but also other compounds that are currently commercially available and can be easily obtained from the market can be preferably used in the present invention. Particularly preferred reactive polysiloxanes in the present invention are polysiloxanes having two or more hydroxyl groups or amino groups.

  Besides these, polylactones (polyesters) -polysiloxanes modified with lactones of polysiloxanes having active hydrogen groups, polyethylene oxide-polysiloxanes modified with ethylene oxide or propylene oxide, and polypropylene oxide-polysiloxanes are also preferably used. . Particularly preferred is a compound obtained by modifying polysiloxane with lactone, and more preferred is a polylactone-polysiloxane obtained by modifying a reactive polysiloxane having two or more active hydrogen groups in the molecule with lactone.

  Preferred lactones used here are β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, 7-heptanolide, 8-octanolide, γ-valerolactone, γ-caprolactone and δ-caprolactone. .

  In the present invention, the polylactone-polysiloxane, that is, a polylactone-polysiloxane obtained by modifying a reactive polysiloxane having at least one active hydrogen group in the molecule with a lactone is one or two or more in the molecule. An active hydrogen atom group of a siloxane compound having an active hydrogen group such as an amino group, a hydroxyl group, or a carboxyl group is obtained by subjecting the lactone to ring-opening polymerization, and then subjecting it to a reduced pressure treatment.

  The polyol as the compound having an active hydrogen group used in the production of the particles C of the present invention is preferably a conventionally known polyol such as a short-chain diol, a polyhydric alcohol and a polymer polyol conventionally used in the production of polyurethane. Can be mentioned. Moreover, as a polyamine as a compound having an active hydrogen group, 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 polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate, 1,1,1-trimethylolethane, and 1,1,1- Examples include trimethylolpropane. 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 or / and a polyether polyol having a hydroxyl group of three or more functional groups,

(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 functional group or more hydroxyl groups such as,

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

(6) Hydrogenated dimer polyol, diol such as castor polyol, and / or dimer polyol having a hydroxyl group of three or more functional groups,
(7) Polymethacrylate polyols such as α, ω-polymethyl methacrylate diol and α, ω-polybutyl methacrylate diol, and acrylic polyols having a tri- or higher functional hydroxyl group are exemplified.

  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 compound having 2 or more active hydrogen groups is preferable, and a polyol compound having 3 or more active hydrogen groups is particularly preferable.

  As polyisocyanate used for the synthesis | combination of the said particle | grain C, what is used for manufacture of a conventionally well-known 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 Socyanates, 1,4-tetramethylene diisocyanate, aliphatic diisocyanates such as 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 or 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 types, usage amounts and usage ratios of the polyisocyanate, the compound having active hydrogen groups and the reactive polysiloxane used in the present invention are determined by the intended use of the resulting particles C. It is necessary that at least one of the components of the compound having a trifunctional or higher functionality. 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 Necessary, and for the reactive polysiloxane, the number of functional groups to be used is properly selected according to 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 compound used and the product, but is preferably in the range of 0.5 to 1.2.

  The inert solvent used for the reaction of all the compounds and forming the continuous phase of the dispersion of particles C is substantially non-solvent for the particles A or C to be produced 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 C of the present invention, a low temperature may be used if a known catalyst is used, 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 C 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 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 by.

  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 little crystallinity in a 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 part and the soluble non-crystalline part is easily performed, and a urea domain having the non-soluble crystal part due to the hydrogen bond between urea bonds as the center of the particle is formed, and a solvent is formed around it. The summed polymer chains are regularly oriented outwardly. 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 150 ° 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 in the present invention 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, all non-aqueous solvents that do not have active hydrogen groups can be used, which dissolve oil-modified polyols, polyisocyanates, and polyamines that are raw materials 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. Examples of short-chain diamines and aliphatic polyamines include methylene diamine, ethylene diamine, diaminopropane, diaminobutane, trimethylene diamine, trimethyl hexamethylene diamine, hexamethylene diamine, octamethylene diamine, polyoxypropylene diamine, and polyoxypropylene triamine. Aliphatic polyamines, phenylenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether and 4,4′-diaminodiphenylsulfone Aromatic polyamines such as, cyclopentanediamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, bis-amino B pills 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, both the size of the entire particle including the solvated polymer portion and the urea domain and the size of each of the solvated polymer portion and the urea domain can be controlled. . 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 hydrophilicity, hydrophobic strength and inertness of polyisocyanate, a compound having an active hydrogen group and a reactive polysiloxane. Acts in correlation with solvent. As a result of considering these conditions, the particle size of particle C can be controlled by adjusting the amount of polyurea colloid solution added to polyisocyanate, compounds having active hydrogen groups and reactive polysiloxane. In this range, the larger the amount added, the smaller the particle size, and the smaller the amount, the larger the particle size.

  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, the particles C of the present invention can be obtained. 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 size of the particles C thus produced is 0.5 μm to 100 μm and is a true sphere. The control of the particle size depends on the emulsification type of the synthetic kettle (propeller type, saddle type, homogenizer, spiral band type, etc.) and the stirring force when the composition of the particle C is the same, especially in an inert solvent. The polyisocyanate, the concentration of the compound having an active hydrogen group and the concentration of the reactive polysiloxane, the type of polyurea colloid solution, and the amount added. The mechanical agitation and shearing force for emulsifying the polyisocyanate, the compound having an active hydrogen group and the reactive polysiloxane 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-cutting ingredients, collagen, stabilizers, antioxidants, UV absorbers, extender pigments, etc. to synthesize particles C to obtain particles C suitable for various applications. Is possible.

  These particles are almost perfectly spherical particles as shown in the electron micrograph (magnification 500 times) in FIG. 2, and as shown in the imaginary view of FIG. Since the particles B deposited from or adhered to the particles and the particles B are excellent in non-adhesiveness and heat resistance, the particles become extremely fluid by simply removing the particles from the dispersion solvent. In the particle formation, 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. .
The particle C of the present invention is useful as a component of cosmetics, and is used in applications requiring light diffusibility, blocking prevention, and impact resistance in the film field because of the properties of the particle C. Used for PC members. In the paint coating field, it is often used for matting and texture adjustment, and is useful for automobiles, homes, and home appliances. In addition, it is also useful for applications such as resin modification to shrinkage, wear and impact resistance.

  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 to dissolve 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.

[Synthesis Example 3]
100 parts of a monofunctional oil- and fat-modified polyol having a hydroxyl value of 157.8 (URIC H-31 manufactured by Ito Oil Co., Ltd.) was charged into a synthetic kettle equipped with a stirrer, and the temperature was controlled at 60 ° C. while stirring, and prepared in advance Tolylene diisocyanate (49.0 parts) was gradually added over 1 hour, and the reaction was conducted under these conditions for 5 hours to synthesize. Next, the concentration was adjusted to 60% with n-heptane to obtain a prepolymer solution (PP-3) containing 4.76% of NCO groups. The molecular weight of this product is 530.

  100 parts of the above PP-3 was charged into a synthetic kettle equipped with a stirrer, the temperature was controlled at 50 ° C. while stirring, and 89.7 parts of a 10% solution of n-heptane of trimethylhexamethylenediamine prepared in advance for 5 hours. The polyurea colloidal solution (solid content 36.4%) (C-3) of (polyamine / prepolymer chain) × 100 = 14.95% was obtained. This solution was a yellowish opalescent stable solution.

(Production of lactone-modified polysiloxane)
[Synthesis Examples 4 to 6]
A reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a reflux condenser was substituted with nitrogen gas, and then the lactone compound and siloxane compound described in Table 1 were added to predetermined concentrations, and 100 ° C. under a nitrogen stream. The mixture was stirred until uniform. Subsequently, predetermined tetra-n-butyl titanate was added and reacted for 10 hours at a temperature of 180 ° C. under a nitrogen stream. As the reaction proceeds, the viscosity of the reactant increases. Thereafter, the reaction was continued at 180 ° C. under a reduced pressure of 5 mmHg for 1 hour to complete the reaction, and the non-reactive siloxane compound and unreacted substances contained in the starting siloxane compound were completely removed. Table 1 shows the composition and properties of the obtained polycaprolactone-modified polysiloxane.

The polysiloxane (a) in Table 1 has the following structure.

(Production of polysiloxane-modified polyurethane gel particles)
[Example 1]
16 parts of polybutylene adipate diol having an average molecular weight of 1,000 and 4 parts of lactone-modified polysiloxane (Synthesis Example 4) are dissolved at 60 ° C., and isocyanurate polyisocyanate of hexamethylene diisocyanate represented by the following structural formula (Asahi Kasei Kogyo) DURANATE TPA-100, NCO% = 23.1) and 6.16 parts were added and mixed uniformly. This product was gradually added to a mixed solution of 3.0 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 in 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 polysiloxane-modified polyurethane gel particles was obtained. This solution was vacuum-dried at 100 Torr to separate n-octane to obtain polysiloxane-modified polyurethane gel particles (1) of the present invention. This was a spherical white powder having an average particle diameter of 5 μm.

[Example 2]
In a reaction vessel equipped with a vertical stirrer, 70 parts of polytetramethylene adipate diol having an average molecular weight of 2,000 and 30 parts of the lactone-modified polysiloxane of Synthesis Example 5 were charged, dissolved at 70 ° C. with stirring, and diphenylmethane diisocyanate (MDI). 20.9 parts was gradually added, and the reaction was carried out for 5 hours to obtain a prepolymer of NCO / OH = 2. To this, 3.7 parts of trimethylolpropane was added and mixed.

  25 parts of this product was gradually added to a mixed solution of 12 parts of polyurea colloid solution (C-2) of Synthesis Example 2 and 50 parts of n-heptane prepared in advance in a 1 liter stainless steel container, and emulsified with a homogenizer for 25 minutes. did. This emulsion was a stable emulsion having an average dispersoid particle size of 8 μm and no separation. Next, this was charged into a reaction kettle equipped with a vertical stirrer, the temperature was raised to 100 ° C. while rotating at 500 rpm, and the reaction for 5 hours was completed to obtain a solution of polysiloxane-modified polyurethane gel particles. The polysiloxane-modified polyurethane gel particles (2) of the present invention were obtained from this solution in the same manner as in Example 1. This was a spherical white powder having an average particle diameter of 8 μm.

[Example 3]
In a 500 ml separable flask, 12 parts of the polyurea colloid solution (C-3) of Synthesis Example 3 and 150 parts of isooctane were charged and mixed. Next, 70 parts of a trifunctional polylactone polyol having an average molecular weight of 785 and 30 parts of the lactone-modified polysiloxane of Synthesis Example 6 which were heated to 50 ° C. in advance while mixing with a homomixer were added and gradually added to emulsify. I let you. Further, 48.6 parts of an adduct polyisocyanate of hexamethylene diisocyanate represented by the following structural formula (Duranate 24A-100, NC 0% = 23.5, manufactured by Asahi Kasei Kogyo Co., Ltd.) was gradually added.

  Next, while rotating the homomixer, the temperature was raised to 80 ° C., and after 3 hours of reaction, 0.005 part of dibutyltin dilaurate was added as a reaction catalyst, and the reaction was further continued for 4 hours to disperse the polysiloxane-modified polyurethane gel particles. A liquid was obtained. The polysiloxane-modified polyurethane gel particles (3) of the present invention were obtained from this dispersion in the same manner as in Example 1. This was a spherical white powder having an average particle diameter of 3 μm.

[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 (4). This was a spherical white powder having an average particle diameter of 10 μm.

[Comparative Example 2]
As silica particles, Silicia 350 (Fuji Silysia Chemical Co., Ltd.) average particle size of 3.9 μm was used.

(Cosmetic evaluation of each particle of Examples 1 to 3 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 aggregates were present.
X: Not dispersed.

<Oil absorption measurement>
It measured according to JIS-K5101.
Linseed oil is considered to have less absorbability because it will not be effective when absorbing oils, preservatives, etc. 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.

<Compatibility 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;
○: Dispersed easily, and a stable solution without aggregation / sedimentation can be maintained after 3 days.
(Triangle | delta): Although it disperse | distributes easily, aggregation and sedimentation are seen in part 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.

<Heat resistance>
The thermal behavior (softening temperature) of each particle was confirmed by thermomechanical analysis (TMA) measurement.

(Cosmetic application of each particle of Examples 1 to 3 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 Cosmetic evaluation was performed according to the prescription.

<Flexibility>
An appropriate amount was applied to the back of the hand and evaluated in a dry state.
○: Soft.
Δ: Soft property 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 extensibility was good.
○: Extensive.
Δ: Less extensibility
X: There is 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 concealing 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 polysiloxane-modified polyurethane gel particles C having a controlled particle size.
2. The resulting polysiloxane-modified polyurethane gel particles C are spherical, and the polyurea colloid particles B precipitated from the polyurea colloid solution are uniformly attached or coated on the surface of the polysiloxane-modified polyurethane gel particles C. The particles C are extremely excellent in fluidity and easy to handle, and can be used in various applications particularly as cosmetic ingredients.
3. From the above effects, the polysiloxane-modified polyurethane gel particle C of the present invention is particularly 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 polysiloxane modified polyurethane gel particle C of this invention. The imaginary figure of the section of polysiloxane modification polyurethane gel particle C of the present invention.

Explanation of symbols

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

Claims (6)

Containing a polysiloxane-modified polyurethane gel (particle C) having a particle size in the range of 0.5 to 100 μm, and a cosmetic ingredient,
The particle C is three-dimensionally cross-linked consisting of polyisocyanate, a compound having an active hydrogen group in the molecule, a polysiloxane having an active hydrogen group in the molecule and / or a copolymer of the polysiloxane and a lactone. surface of the polysiloxane-modified polyurethane gel particles (particles a) is made is coated with a polyurea colloid aqueous solvent solution polyurea colloid particles precipitated from (particles B),
Cosmetics, characterized in that at least one is trifunctional or more compounds having active hydrogen groups in the polyisocyanate and in the molecule. The cosmetic according to claim 1, wherein the content ratio of the particles C is 1.0 to 90 mass%. The polysiloxane is at least one selected from the group consisting of (1) amino-modified polysiloxane, (2) epoxy-modified polysiloxane, (3) alcohol-modified polysiloxane, and (4) mercapto-modified polysiloxane. Item 3. A cosmetic according to item 1 or 2. The proportion of polysiloxane segment occupied in the particles C are cosmetic according to any one of claims 1 to 3 is 0.01 to 80 mass%. The particle B is composed of a solvated portion and a non-solvated portion with respect to the solvent,
The cosmetic according to any one of claims 1 to 4, wherein the particle size of the unsolvated portion is 0.01 µm to 1.0 µm. The particles B are polyurea colloidal particles obtained by a reaction of an oil-modified polyol, a polyisocyanate, and a polyamine,
The cosmetic according to any one of claims 1 to 5, wherein the unsolvated part is a hydrogen bond of a urea bond.