JP2010235489A - Water-containing cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-containing cosmetic which has good color development, good stability of the cosmetic itself, and good durability, and can give make-up effect, especially three-dimensional appearance, when used. <P>SOLUTION: This water-containing cosmetic comprises components (A) and (B): (A) an aqueous dispersion of a polymer; and (B) a dichroic pigment whose appearance color and interference color are different, prepared by forming a single layer of low oxidized titanium on plate-like particles. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a water-containing cosmetic, and more specifically, it has good stability and dispersibility, has vivid dichroism, can form a uniform cosmetic film, and has a three-dimensional cosmetic effect. Water-containing cosmetics.

  In addition to cosmetic effects when used, makeup cosmetics are required to have various functions such as good color development and stability of the cosmetics themselves. In addition, since moisture-containing cosmetics have the property of being easily removed by perspiration, good holding properties are also required as one of the important qualities. Among these, the cosmetic effect and color development vary greatly depending on the blending amount, color, and dispersibility of the pigment and pearl. For this reason, various pigments and pearls have been developed and studied for blending in order to exhibit cosmetic effects and good color development (see, for example, Patent Documents 1 and 2). In addition, with the aim of stabilizing the cosmetics and the cosmetics themselves, blending an aqueous polymer emulsion to improve the durability by forming a cosmetic film or adding viscosity to make the powder more stable and powdery. For example, Patent Documents 3 and 4 have been used.

  By the way, in order to produce a high cosmetic effect in coloring cosmetics, it is important to (1) make the coloring of the coloring clear, and in the dark coloring cosmetics such as mascara and eyeliner, the lightness is high. If it is low, it is effective to produce a three-dimensional effect by blending pearl with (2) pearls, which is rich in color such as eye color. Furthermore, it is also pointed out that (3) by improving the dispersibility of pigments and pearls and preventing agglomeration, it is possible to effectively produce color and make the film finish uniform and clean.

  Of these, if the amount of the coloring agent is small, the cosmetic effect is low, so interfering pearls are blended and the cosmetic effect is supplemented with the three-dimensional effect. The pearl itself is white, the makeup finish is blurred, and there is a problem that the color cannot be clearly displayed.

  Therefore, colored pearls may be used instead of interference pearls, but existing colored pearls coated with iron oxide have a problem that they are aggregated due to their magnetic properties, resulting in poor dispersibility. In addition, some existing colored pearls coated with dyes or bitumen have the problem of discoloration due to fluctuations in moisture and pH.

  It is possible to increase the saturation by using a high-saturation pigment without using pearl. In this case, however, the steric effect is inferior, and especially in the blue region, the blue pigment is unstable depending on the pH. Therefore, stable blending was difficult. In other words, examples of blue pigments include bitumen and ultramarine blue, but since bitumen is weak against alkalis and ultramarine blue is weak against acidity, it is difficult to mix stably, creating a highly saturated color. It was difficult.

WO05 / 028566 Japanese Patent Laid-Open No. 6-211521 JP-A-5-221825 JP-A-11-189513 Japanese Examined Patent Publication No. 43-025644 JP-A-60-060163

  Accordingly, as a water-containing makeup cosmetic, etc., a water-containing cosmetic that can give a cosmetic effect when used, particularly a three-dimensional effect, while having good color development, stability of the cosmetic itself, and good durability. Therefore, the present invention aims to provide such a water-containing cosmetic.

  The inventor has conducted extensive research to solve the above-mentioned problems. As a result, the specific pigment has excellent dichroism and is combined with a polymer aqueous dispersion (polymer emulsion). Thus, it is possible to obtain a water-containing cosmetic that has good usability, stability and dispersibility without forming lightness, and forms a uniform cosmetic film. The present invention was completed by finding that a feeling can be obtained and that a blue color having high saturation can be stably obtained even with a water-containing cosmetic.

That is, the present invention includes the following components (A) and (B):
(A) Aqueous dispersion of polymer (B) A pigment having a dichroism having different appearance color and interference color is formed by forming a monolayer of low-order titanium oxide on plate-like particles. A water-containing cosmetic is provided.

  Since the water-containing cosmetic of the present invention uses a polymer compound that forms a uniform cosmetic film and a pigment having vivid dichroism, it has good stability and dispersibility, high resistance to water, etc., and vivid It is a cosmetic that can impart a three-dimensional cosmetic effect due to its dichroism.

  Therefore, this is an O / W type, W / O type, water-based type, multilayer type water-containing cosmetic, mascara, eyeliner, eye color, foundation, makeup base, blusher, lipstick, sunscreen, body lotion Can be advantageously used as cosmetics.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a drawing schematically showing why a dichroic pigment having different appearance color and interference color can be obtained by providing a single layer of low-order titanium oxide in a dichroic pigment used in the present invention. It is drawing which shows the XRD measurement result about the precursor A used in manufacture example 1, and the obtained dichroic pigment. It is drawing which shows the XRD measurement result about the precursor B used in manufacture example 7, and the obtained dichroic pigment.

  The polymer aqueous dispersion (polymer emulsion) of the component (A) used in the present invention is a system in which polymer fine particles are stably dispersed in an aqueous solvent, and a monomer emulsified with a surfactant is polymerized. The liquid obtained by this and the milky sap which exists in nature are included, and can form a film | membrane on skin etc. Although the force which forms the film of this component (A) may not be so strong, what can provide a viscosity is preferable.

The polymer in this component (A) is 1 selected from acrylic acid, methacrylic acid, alkyl acrylate (C ₁ -C ₁₂ ), alkyl methacrylate (C ₁ -C ₁₂ ), vinyl acetate, styrene, vinyl pyrrolidone. Those formed from seeds or two or more monomers are preferred. Of these, there is the alkyl group of the alkyl acrylate or alkyl methacrylate, in one C ₁ -C _12, or may be two or more.

  More specifically, the polymer of component (A) includes acrylic acid / alkyl acrylate copolymer, acrylic acid / alkyl methacrylate copolymer, methacrylic acid / alkyl acrylate copolymer, methacrylic acid / alkyl methacrylate. Copolymer, alkyl acrylate copolymer, alkyl methacrylate copolymer, alkyl acrylate / vinyl acetate copolymer, alkyl methacrylate / vinyl acetate copolymer, styrene / alkyl acrylate copolymer, styrene / methacrylic acid Examples thereof include one or more selected from acid alkyl copolymers, vinyl acetate polymers, and vinylpyrrolidone / styrene copolymers.

  Among the polymers of component (A) described above, those obtained by polymerizing a monomer composition containing one or more monomers selected from acrylic acid and methacrylic acid are neutralized with an alkali agent together with film-forming properties. Therefore, it can be used particularly advantageously for the purpose of the present invention.

  The component (A) of the present invention can be obtained as a commercial product, but in this, the property of thickening by neutralization with an alkaline agent is stronger, and the film-forming property is more. There is something strong. For example, an acrylic acid / alkyl acrylate copolymer emulsion may be mentioned as a thickening agent by neutralization. This is an INCI (International Nomenclature Cosmetic Ingredient labeling names) name, and is called ACLYLATES COPOLYMER (Acrylates copolymer). As an example of a commercial product thereof, SALCARE SC81 (solid content 30%) (manufactured by CIBA SPECIALTY CHEMICALS), ACLYLATES COPOLYMER (alkyl acrylate copolymer): Aculin 33A (manufactured by Rohm Gmbh), ACLYLATES COPOLYMER (acrylate copolymer): Ultrazol V-280C (solid content 28%) (manufactured by Ganz Kasei Co., Ltd.) and the like.

  Further, examples of stronger film-forming properties include alkyl acrylate copolymer emulsions. This is ACLYLATES COPOLYMER (an alkyl acrylate copolymer ammonium) under the INCI name. Examples of commercially available products include iodosol GH800F (solid content 45%) (manufactured by NSC Japan), ACLLYLATES COPOLYMER (acrylic acid). Alkyl copolymer ammonium); Yodosol GH810F (solid content 46%) (manufactured by Nippon SC).

  Furthermore, the styrene / alkyl acrylate copolymer emulsion is SCYRENE / ACRYLATES COPOLYMER under the INCI name, and as an example of a commercially available product thereof, Yodosol GH41F (solid content 45%) (manufactured by NSC Japan) etc. The coalesced emulsion has an INCI name of POLTVINY ACEATE (polyvinyl acetate). As an example of a commercially available product, VINIBRAN GV-5651 (solid content 36%) (manufactured by Nissin Chemical Industry Co., Ltd.) is a vinylpyrrolidone / styrene copolymer emulsion. The INCI name is STYRENE / VP COPOLYMER (styrene / vinyl pyrrolidone) copolymer, and examples of commercially available products include ANTARA 430 (solid content 40%) (manufactured by ISP).

  In addition, as an aqueous dispersion of a polymer, a polymer obtained by a general polymerization method such as an emulsion polymerization method, a core-shell polymerization method, or a radical polymerization method can be used by being dispersed in an aqueous medium. The aqueous solvent here means a solvent containing water as a main component and may contain a polyhydric alcohol or the like.

  In the water-containing cosmetic of the present invention, the component (A) can be used alone or in combination of two or more thereof. In addition, a polymer obtained by using one or more monomers selected from acrylic acid and methacrylic acid (mainly having a property of thickening by neutralization with an alkali agent). In addition, it is more preferable to use in combination those which do not contain a polymer obtained by using these monomers (mainly those which form a film).

  The blending amount of the component (A) in the hydrated cosmetic composition of the present invention is preferably 0.01 to 30% by mass (hereinafter referred to as “%”) as the solid content, and more preferably 0.05 to 20%. % Is preferred. When the component (A) is used within this range, a good product can be obtained from the viewpoints of usability, usability, dispersibility, stability, good durability, and beauty of the cosmetic film.

  In the present invention, as the component (B), a pigment exhibiting dichroism having different appearance color and interference color by forming a single layer of low-order titanium oxide on the plate-like particles (hereinafter referred to as “dichroic pigment”). Is used).

  This dichroic pigment is obtained by forming a single layer of low-order titanium oxide on plate-like particles. More specifically, a method in which a pigment in which a plate-like particle base material is coated with titanium dioxide is reduced so that the titanium dioxide layer becomes a low-order titanium oxide layer, or a low-order titanium oxide composition is formed into a plate-like shape. It is obtained by a method of coating the particles, but preferably obtained by a method of reducing the pigment in which the base of the plate-like particles is coated with titanium dioxide to make the titanium dioxide layer a low-order titanium oxide layer. .

  Examples of the plate-like particles serving as the base material for the dichroic pigment include natural or synthetic mica, glass powder, and aluminum flakes. Of these, mica is not particularly limited to these materials, but may be a colored or colorless base material such as muscovite, phlogopite, biotite.

  A pigment in which titanium dioxide is coated on a plate-like particle base material is already commercially available and can be used. For example, as a commercially available product in which mica is coated with titanium dioxide, iridium (Merck) and flamenco sparkle gold (Engelhard) can be mentioned. Further, for example, as a commercial product in which glass powder is coated with titanium dioxide, there is Metashine (manufactured by Nippon Sheet Glass Co., Ltd.).

The dichroic pigment is characterized in that a single layer made of low-order titanium oxide in a state where oxygen is partially lost from titanium dioxide is formed on the surface of the plate-like particles. This low-order titanium oxide has the following formula
TiOx
(In the formula, x means a number exceeding 1.0 and less than 2.0)
Can be expressed as The low-order titanium oxide single layer referred to in the dichroic pigment of the present invention is composed of a composition not containing titanium monoxide TiO and titanium dioxide TiO _2, and the composition of the single layer is expressed by the above formula. It consists of one or more types of titanium oxide compounds. The low-order titanium oxide single layer may contain titanium oxynitride in which part of oxygen in the low-order titanium oxide is replaced with nitrogen.

  When the amount of oxygen vacancies in the low-order titanium oxide layer increases and x in the above formula approaches 1.0, the light absorption becomes strong and the interference color becomes weak. On the other hand, when the amount of oxygen deficiency decreases and x approaches 2.0, the light absorption becomes weaker and the interference color becomes stronger. In addition, in the appearance color, when x approaches 1.0, the light absorption becomes strong and the appearance color becomes strong. Conversely, when x approaches 2.0, the light absorption becomes weak and the appearance color becomes weak.

  Since the composition of the low-order titanium oxide in the dichroic pigment is TiOx (1.0 <x <2.0) as described above, in order to replace the titanium dioxide on the plate-like particles with the low-order titanium oxide. It is necessary to appropriately adjust the amount of oxygen deficiency (oxygen deficiency) compared to titanium dioxide.

  The low-order titanium oxide layer is formed by using a material in which a titanium dioxide layer is coated on a plate-like particle, such as nitrogen, hydrogen, ammonia, carbon monoxide, nitric oxide, dinitrogen monoxide, hydrogen sulfide, or sulfur dioxide. Can be carried out by firing at 500 to 1500 ° C. in a gas atmosphere or mixed gas atmosphere or in a vacuum atmosphere.

  In addition, the material in which the titanium dioxide layer is coated on the plate-like particles at the time of firing is a compound containing titanium hydride, a titanium compound of titanium metal, or a hydride of sodium borohydride or lithium aluminum hydride as a reduction aid. It can also be added and reduced firing at 500-1500 ° C.

  On the other hand, the low-order titanium oxide layer can be formed on the plate-like particles by coating the plate-like particles with the low-order titanium oxide composition. As a coating method, it is possible to apply a low-order titanium oxide composition or use mechanochemical. At that time, the low-order titanium oxide particles can be sintered by heat treatment at 500 to 1500 ° C. in an inert atmosphere or a vacuum atmosphere to strengthen the coated low-order titanium oxide layer.

  The factor that determines the composition of the low-order titanium oxide monolayer is the degree of reduction, but this control can be performed by the firing temperature, the reduction aid to be added, and the amount thereof.

  Of these, the firing temperature can be set in the range of 500 to 1500 ° C., but to lower the reduction degree, the firing temperature is lowered to around 500 ° C., and to raise the reduction degree, the firing temperature is around 1500 ° C. Just raise it. That is, the oxygen deficiency reaction from titanium dioxide can be adjusted by adjusting the firing temperature.

  The degree of reduction can also be controlled by adding a reducing aid and adjusting the amount thereof. In the case of adding the reduction aid, the firing temperature is preferably not less than the decomposition temperature of the reduction aid and in the range of 500 to 1500 ° C. The amount of the reducing aid added is such that the substance that is the reducing component gas contained in the reducing aid is in the range of 0.001 to 30.0 mol (preferably 0.01 to 10.0 mol) with respect to 100 g of titanium dioxide. Range). Here, the reducing component gas is not particularly limited, but is hydrogen, nitrogen, ammonia, carbon monoxide, nitric oxide, dinitrogen monoxide, hydrogen sulfide, sulfur dioxide, or the like. It is possible to control the oxygen deficiency reaction by changing the amount of the reducing substance generated from the reducing aid relative to titanium dioxide.

  For example, if the addition amount of the reducing aid is 0.001 mol or less, the degree of reduction is low, the appearance color is close to white, the interference color may not be recognized significantly, and vivid dichroism is obtained. Absent. Further, when the addition amount of the reducing aid is 30.0 mol or more, the degree of reduction becomes too high, the interference color becomes weak, and only the color tone of the appearance color is lost. Absent.

  Further, the reduction degree can be controlled by using metallic titanium. In a reducing atmosphere, a material in which a titanium dioxide layer is coated on a plate-like particle and titanium metal are mixed and baked in a range of 500 to 1500 ° C. (preferably 900 to 1300 ° C.), whereby oxygen atoms of titanium dioxide are obtained. A part of is reduced by metal titanium to become low-order titanium oxide. On the other hand, metallic titanium combines with oxygen atoms of titanium dioxide to form low-order titanium oxide. The addition amount of the titanium compound is required to add 0.01 to 2.0 mol of titanium component with respect to 100 g of titanium dioxide.

  On the other hand, the control of the film thickness of the low-order titanium oxide layer can utilize the titanium dioxide film thickness control method described in Patent Document 5. For example, when the film thickness of the low-order titanium oxide single layer is 10 nm or less, a bright interference color cannot be obtained because the optical path difference in the low-order titanium oxide layer is reduced. Further, there is no particular limitation on the increase in the thickness of the low-order titanium oxide layer because the color tone is cyclically changed by the phase difference, but the light is attenuated and a vivid color tone cannot be obtained. . Therefore, the film thickness of the low-order titanium oxide layer is preferably 1000 nm or less, more preferably, by controlling the film thickness of the low-order titanium oxide in the range of 10 to 1000 nm (particularly preferably 10 to 600 nm), Bright dichroism with different interference colors can be obtained.

  The low-order titanium oxide layer of the dichroic pigment can be obtained by reducing the titanium dioxide layer, and the titanium dioxide layer contains titanium containing metatitanic acid, titanium hydroxide, oxytitanic acid, and titanium sulfate. Even a compound layer can be used because it changes to a low-order titanium oxide composition by heat treatment by reduction firing. Further, by using a compound containing nitrogen as a gas used for the reduction treatment and a compound containing nitrogen as a reducing aid, titanium oxynitride is also formed in the reduction firing. In this titanium oxynitride, a part of the oxygen in the low-order titanium oxide of the low-order titanium oxide single layer is modified by replacing nitrogen, but even if this is contained in the low-order titanium oxide single layer, light The relationship between the absorption and reflection of the light does not change, and the interference color and appearance color can be adjusted.

  The dichroic pigment of component (B) obtained as described above has a color tone different from that of a conventional pearlescent pigment in that it has a vivid dichroism with different appearance color and interference color. For example, conventional titanium dioxide-based interference pigments have Hunter's Lab color system, L values of 70 to 80, high brightness, and strong white appearance. Further, the black pearl luster pigment made of low-order titanium oxide had an L value of 25 or less and low brightness and an appearance close to black.

  However, the dichroic pigment used in the present invention exhibits dichroism different from the interference color and the appearance color at the lightness of L value 25 or more. Further, the b value of the Hunter Lab color system is a blue to yellow color value, and the saturation increases as the absolute value increases, but the dichroic pigment used in the present invention has this b value. It is possible to adjust to a range of −3.0 or less or 3.0 or more, and a color tone with high saturation can be obtained.

  Next, with reference to FIG. 1 schematically showing the reason why the dichroic pigment exhibits dichroism, it will be described that a bright appearance color and interference color are exhibited by adjusting the oxygen deficiency amount.

  The dichroic pigment as the component (B) is formed of plate-like particles (1) serving as a base material and a low-order titanium oxide layer (2) covering the plate-like particles (1). Low-order titanium oxide can adjust the amount of oxygen deficiency by changing the degree of reduction. And since visible light is an electromagnetic wave, a part of visible light is absorbed by the hole by oxygen deficiency.

  That is, as shown in the schematic diagram of FIG. 1, the reflected light (5) on the pigment surface has the incident light (3) absorbed at a specific wavelength by the low-order titanium oxide layer and develops a color tone as an appearance color. . The interference color is unique because the reflected light (5) interferes with the reflected light (6) reflected by the substrate (1) and the transmitted light (4) that has been absorbed by the low-order titanium oxide layer and has lost a specific wavelength. The color tone is emitted. A pigment having a vivid dichroic color tone can be obtained by the interference color composed of the reflected light of (5) and (6) and the appearance color of the low-order titanium oxide layer by the absorbed light. In this way, by adjusting the oxygen deficiency amount, it is possible to change the wavelength region to be absorbed and the absorption amount. Similarly, the wavelength of the reflected light can be controlled.

  Further, as described above, interference color is generated by interference of reflected light of (5) and (6). Therefore, by adjusting the film thickness of the low-order titanium oxide layer, the reflected light on the surface of the low-order titanium oxide layer ( 5) and the optical path difference of the reflected light (6) from the substrate (1) through the low-order titanium oxide layer can be changed. As a result, the wavelength phase can be changed and the interference color can be changed.

  As described above, the dichroic pigment of component (B) enables adjustment of reflected light and absorbed light by controlling the amount of oxygen deficiency and composition of the low-order titanium oxide layer, and the film of the low-order titanium oxide layer. It is a pigment having a wide variety of dichroic colors having an unprecedented bright interference color and appearance color that can adjust the interference color by changing the phase of the wavelength by controlling the thickness.

  Furthermore, the low-order titanium oxide used in the component (B) of the present invention is very stable, excellent in acid resistance and alkali resistance, and is also very stable thermally, and is in the atmosphere. It is a substance that can withstand 350 ° C heat. Accordingly, the dichroic pigment provided with the low-order titanium oxide layer can be used as a pigment that is acid-resistant, alkaline, and thermally stable.

  Although the compounding quantity of the said component (B) in the water-containing cosmetics of this invention is not specifically limited, 0.1-30% is preferable in the whole quantity, and also 0.1-20% is more preferable. When the component (B) is used within this range, a good one can be obtained from the viewpoints of usability, usability, and stereoscopic effect due to dichroism.

  Furthermore, the amount of water contained in the water-containing cosmetic of the present invention is 0.5 to 95%, preferably 3 to 90%. In addition, the quantity of water here is the quantity also including the water mix | blended as the dispersion medium, when a component (A) is an aqueous dispersion.

  In addition to the above essential components, the water-containing cosmetic of the present invention can contain optional components that are usually added to cosmetics.

  Such optional components include powder components for the purpose of feel adjustment and coloring, base materials, oily components as emollient components, aqueous components as moisturizing components, alkaline agents, powder dispersion, surfactants for feel control. , Ultraviolet absorbers, moisturizers, water-soluble film-forming resins, anti-fading agents, antioxidants, antifoaming agents, cosmetic ingredients, preservatives, fragrances, and the like, as long as the effects of the present invention are not impaired. It can mix | blend suitably.

  Oily components include hydrocarbons, fats and oils, waxes, and hardened oils, regardless of the origin, such as animal oil, vegetable oil, synthetic oil, and the properties of solid oil, semi-solid oil, liquid oil, volatile oil, etc. Ester oils, fatty acids, higher alcohols, silicone oils, fluorinated oils, lanolin derivatives, oily gelling agents and the like. Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, polyisobutylene, polybutene, paraffin wax, ceresin wax, microcrystalline wax, polyethylene wax, ethylene / propylene copolymer, montan wax, Fischer-Tropsch wax, moscow, olive oil Oils such as castor oil, jojoba oil, mink oil, macadamian nut oil, waxes such as beeswax, carnauba wax, candelilla wax, gallow, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, myristic acid Octyldodecyl, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl triisostearate, diisostearyl malate, glyceride tribehenate , Esters of rosin acid pentaerythritol ester, neopentyl glycol dioctanoate, cholesterol fatty acid ester, N-lauroyl-L-glutamate (cholesteryl, behenyl, octyldodecyl), stearic acid, lauric acid, myristic acid, behen Acids, fatty acids such as isostearic acid, oleic acid, 12-hydroxystearic acid, higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol, low degree of polymerization dimethylpolysiloxane, high polymerization Dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, cross-linked organopolysiloxane, Silicones such as elementally modified polysiloxanes, fluorinated oils such as perfluorodecane, perfluorooctane and perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin derivatives such as lanolin alcohol, dextrin fatty acid ester, sucrose fatty acid Examples thereof include oily gelling agents such as esters, starch fatty acid esters, aluminum isostearate and calcium stearate.

  As a powder component, as long as it is a powder generally used in cosmetics, it is not particularly limited by the shape of a plate, spindle, needle, etc., particle diameter, particle structure such as porous, nonporous, etc. Inorganic powders, glitter powders, organic powders, pigment powders, composite powders and the like can be mentioned. Specifically, conger, ultramarine, bengara, yellow iron oxide, black iron oxide, titanium oxide, zinc oxide, titanium / titanium oxide sintered product, cerium oxide, magnesium oxide, zirconium oxide, antimony oxide, magnesium carbonate, calcium carbonate , Chromium oxide, chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, calcium silicate, barium silicate, magnesium aluminum silicate, magnesium magnesium metasilicate, mica, synthetic mica, synthetic sericite, sericite, talc , Muscovite, phlogopite, sauroite, biotite, kaolin, barium sulfate, bentonite, smectite, diatomite, hydroxyapatite, boron nitride and other inorganic powders, bismuth oxychloride, titanium mica, titanium dioxide coated oxychloride Bismuth, iron oxide coating Mica, iron oxide coated mica titanium, bitumen coated mica titanium, carmine coated mica titanium, organic pigment coated mica titanium, iron oxide / titanium oxide coated synthetic phlogopite, fish phosphorus foil, titanium dioxide coated glass flake, polyethylene terephthalate / aluminum / epoxy Laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / polymethyl methacrylate laminated film powder, etc., powder, polyamide resin, polyethylene resin, polyacrylic resin, polyester resin, fluorine resin, cellulose -Based resins, polystyrene-based resins, copolymer resins such as styrene-acrylic copolymer resins, polypropylene-based resins, organic polymer resin powders such as silicone resins and urethane resins, organic powders such as N-acyl lysine, starch, Natural powders such as clay powder, cellulose powder, pigment powders such as organic tar pigments, lake pigments of organic pigments, metal powders such as aluminum powder, gold powder, silver powder, particulate titanium oxide coated mica titanium, particulate oxidation Examples thereof include composite powders such as zinc-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, and zinc oxide-containing silicon dioxide, and these can be used alone or in combination. In addition, these powders may be used in combination of two or more, such as fluorine compounds, silicone compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, higher fatty acids, higher alcohols, esters, waxes, The surface treatment may be performed by a known method using one or more of wax, fats and oils, hydrocarbons, surfactants, amino acid compounds, water-soluble polymers and the like.

  The aqueous component may be any component that is soluble in water, for example, alcohols such as ethyl alcohol and isopropyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol. Glycerols such as glycerin, diglycerin, polyglycerin, saccharides such as sorbitol, maltitol, sucrose, starch sugar, lactitol, guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan, methylcellulose, hydroxy Water-soluble polymers such as ethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, salts Examples thereof include salts such as sodium chloride, magnesium chloride and sodium lactate, and plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender and rose.

  The alkali agent is not particularly limited as long as it has the property of neutralizing and thickening the aqueous dispersion of the polymer of component (A), and it is usually used in cosmetics. Any of them can be used. Examples thereof include inorganic alkali agents such as sodium hydroxide and potassium hydroxide, basic amino acids such as L-arginine, and organic alkali agents such as triethanolamine, ammonia and aminomethylpropanol. Although the addition amount of the alkali agent varies depending on the type, in the present invention, since the content of the polymer of the component (A) is such that an effect of 0.05 to 30% is obtained, the copolymer is neutralized. The amount is 0.01 to 30% when the amount is sufficient. This alkaline agent can be added by dissolving in water in advance or by directly mixing with a copolymer.

  As the surfactant, any surfactant that is generally used in cosmetics can be used. Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Is mentioned. Examples of the nonionic surfactant include glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol addition. Sorbitol fatty acid ester and its alkylene glycol adduct, polyalkylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyalkylene alkyl ether, glycerin alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene hydrogenated castor oil, lanolin alkylene Glycol adduct, polyoxyalkylene alkyl co-modified silicone, polyether-modified silicone And the like. Examples of the anionic surfactant include inorganic and organic salts of fatty acids such as stearic acid and lauric acid, alkylbenzene sulfate, alkyl sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate, and α-sulfonated fatty acid. Salt, acylmethyl taurate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, N-acyl amino acid salt , O-alkyl substituted malates, alkylsulfosuccinates and the like. Examples of the cationic surfactant include alkylamine salts, polyamines and alkanolamine fatty acid derivatives, alkyl quaternary ammonium salts, and cyclic quaternary ammonium salts. Examples of amphoteric surfactants include amino acid type and betaine type carboxylic acid types, sulfate ester types, sulfonic acid types, and phosphate ester types, and those that are safe for the human body can be used. For example, N, N-dimethyl-N-alkyl-N-carboxylmethyl ammonium betaine, N, N-dialkylaminoalkylene carboxylic acid, N, N, N-trialkyl-N-sulfoalkylene ammonium betaine, N, N-dialkyl -N, N-bis (polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine, lecithin and the like can be mentioned.

  Examples of ultraviolet absorbers include benzophenone-based, PABA-based, cinnamic acid-based, salicylic acid-based, 4-tert-butyl-4'-methoxydibenzoylmethane, and oxybenzone. Examples of humectants include protein, mucopolysaccharide, and collagen. , Elastin, keratin, etc., for example, α-tocopherol, ascorbic acid, etc., cosmetic ingredients, eg, vitamins, anti-inflammatory agents, herbal medicines, etc., antiseptics, eg, paraoxybenzoic acid esters, 1, 2 -Pentanediol, phenoxyethanol and the like.

  Moreover, when making the water-containing cosmetics of this invention into the cosmetics for eyelashes, the fiber for providing the effect which makes wrinkles look long can also be mix | blended. Examples of fibers that can be blended include synthetic fibers such as nylon and polyester, artificial fibers such as rayon, natural fibers such as cellulose, semi-synthetic fibers such as acetate silk, etc., but these are not particularly limited. It is not a thing and 1 type (s) or 2 or more types can be used as needed. In addition, those fibers treated with general oils, silicone oils, fluorine compounds, surfactants and the like can also be used. Among these, when nylon is used, the length is preferably 0.3 to 3 mm, the thickness is preferably 0.1 to 20 denier, and more preferably 0.5 to 10 denier. .

  Examples of the water-containing cosmetic of the present invention thus obtained include O / W type, W / O type, aqueous type, and multilayer type dosage forms. In addition, examples of the use include mascara, eyeliner, eye color, foundation, makeup base, cheeks, lipstick, sunscreen, body lotion and the like.

  EXAMPLES Next, although an Example and a manufacture example are given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.

In addition, evaluation of the dichroic pigment manufactured by the following manufacture examples was performed by the film thickness of the low order titanium oxide layer, the composition of the low order titanium oxide, and the color tone of the pigment. Among these, the cross-sectional SEM (Hitachi: S-4500) was used for the film thickness measurement, and the composition of the low-order titanium oxide was performed using a powder X-ray diffractometer (Science: RINT 2400). The color tone of the pigment was measured by a powder cell method using a colorimetric color difference meter (Tokyo Denshoku: TC-8600A). That is, 1 g of pigment is weighed into a quartz cell (diameter 35 mm, depth 15 mm, thickness 2 mm), and the pigment is uniformly pressed onto the top surface of the sample at a surface pressure of 25 g / cm ² and filled, and then the Hunter's Lab color The color tone was measured with the system.

  The appearance color and interference color of each pigment were evaluated by the following methods. That is, the pigment and water are mixed at a weight ratio of 1: 2 to make a uniform slurry with a stirrer, and 2 g is dropped on a transparent glass substrate (50 mm × 50 mm, thickness 1 mm). On top of that, the glass plates are put together, and the dropped slurry is stretched between the glass plates to orient the pigment. The appearance color and the interference color are evaluated by visually observing the glass plate sample with the pigment oriented. In this case, the sample is installed vertically from the white fluorescent lamp, the appearance color is visually observed from an angle of 90 degrees from the observation surface, and the interference color is visually observed from an angle of 45 degrees from the observation surface. It was a method.

Manufacturing example 1
A titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove an excess titanium compound, and a precursor A (thickness of titanium oxide layer: 140 nm) having a white appearance color and a light green interference color in which mica was coated with titanium dioxide was produced. Precursor A was measured by XRD and confirmed to be an anatase structure of titanium dioxide (FIG. 2).

To 100 g of this precursor A, 3.0 g of sodium borohydride was added as a reducing aid, the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was set to 100 ml / min, and 600 ° C. for 3 hours. Reduction firing was performed under the conditions. The color tone of the pigment obtained by this reduction treatment was dichroic, with the appearance color being green and the interference color being light blue. FIG. 2 shows the XRD analysis result of the obtained pigment. From this figure, it was shown that the titanium dioxide peak disappeared and low-order titanium oxide Ti ₄ O ₇ was produced.

Manufacturing example 2
A titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove an excess titanium compound, and a precursor A (thickness of titanium oxide layer: 140 nm) having a white appearance color and a light green interference color in which mica was coated with titanium dioxide was produced.

To 100 g of this precursor A, 7.0 g of sodium borohydride was added as a reducing aid, and the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was set to 100 ml / min. Reduction firing was performed under the conditions. The pigment obtained by this reduction treatment was recovered and measured for XRD diffraction. As a result, the titanium dioxide peak disappeared and low-order titanium oxide Ti ₂ O ₃ was produced (FIG. 2). As for the color tone, the appearance color was dark green and the interference color was blue.

Comparative production example 1
A titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove an excess titanium compound, and a precursor A (thickness of titanium oxide layer: 140 nm) having a white appearance color and a light green interference color in which mica was coated with titanium dioxide was produced.

To 100 g of this precursor A, 10.0 g of sodium borohydride was added as a reducing aid, the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was set to 100 ml / min, and 600 ° C. for 3 hours. Reduction firing was performed under the conditions. The pigment obtained by this reduction treatment was recovered and measured for XRD diffraction. As a result, the titanium dioxide peak disappeared, and low-order titanium oxide TiO.Ti ₂ O ₃ was produced (FIG. 2). The color tone became a color tone in which the appearance color black was conspicuous.

  In Production Examples 1-2 and Comparative Production Example 1, the thickness of the low-order titanium oxide layer was made constant (140 nm), and the composition of the low-order titanium oxide was changed. FIG. 2 shows the analysis result of XRD that the composition of low-order titanium oxide changes by changing the reducing conditions. In this XRD measurement, the precursor and the pigment (reduced product) were each pulverized with an agate mortar, and were measured with a powder X-ray diffractometer. By changing the reducing conditions, the titanium dioxide peak disappeared completely, and only the low-order titanium oxide peak was obtained.

Table 1 below shows changes in color tone when the degree of reduction is changed. In the precursor, the interference color was only light, but the appearance color and interference color were changed by changing the titanium oxide layer to low-order titanium oxide, and a vivid color tone having dichroism could be obtained. Furthermore, by controlling the composition of the low-order titanium oxide, it was possible to change the colors of the interference color and the appearance color. In contrast, in the case of the TiO ₂ contained lower titanium oxide layer, the reflection of light by the TiO ₂ becomes strong, since the external color is close to white, vivid dichroic showed that the present invention Can't get. In order to have vivid dichroism, it is necessary to form a single layer having a composition composed of low-order titanium oxide not containing TiO ₂ .

In Comparative Production Example 1, the main composition is low-order titanium oxide TiO (x = 1) with a high degree of reduction, the absorption of incident light into the low-order titanium oxide is strong, the interference color cannot be recognized, and the appearance color Black color became distinctive. In the case of a low-order titanium oxide layer containing TiO, the absorption of light is strong, so that the reflected light becomes weak, the interference color as shown in the present invention cannot be obtained, and the appearance color stands out. In order to have vivid dichroism, it is necessary to form a single layer composed of a low-order titanium oxide composition that does not contain TiO. The monolayer on the plate-like particles, by controlling the composition of the low-order titanium oxide consisting of not including TiO ₂ and TiO [TiOx (1.0 <x < 2.0)], the absorption of the incident light Can be adjusted, and various appearance colors and interference colors can be obtained.

  In Patent Document 7, colored mica is obtained by making a low-order titanium oxide layer or a titanium compound layer containing low-order titanium oxide exist as an intermediate layer between mica that is the innermost layer and titanium dioxide that is the outermost layer. ing. And when all the intermediate layers are low-order titanium oxide or a mixture of low-order titanium oxide and titanium nitride, it is described that the appearance color / interference color is black. However, as a result of the study by the present inventors, it is possible to reflect incident light by controlling the composition of the low-order titanium oxide with TiOx (1.0 <x <2.0). It has been found that it is possible to control the absorption and develop dichroism with different interference colors and appearance colors.

Manufacturing example 3
A titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove an excess titanium compound, and a precursor having a white appearance color and a silver interference color (titanium oxide layer thickness: 30 nm) in which mica was coated with titanium dioxide was produced.

  To 100 g of this precursor, 1.0 g of sodium borohydride is added as a reducing aid, and the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) is set to 100 ml / min. Then, reduction firing was performed. As for the color tone of the pigment obtained by this reduction treatment, the appearance color was silver and the interference color was light yellow.

Manufacturing example 4
A titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor with a white appearance color and a yellow interference color (titanium oxide layer thickness: 70 nm) in which mica was coated with titanium dioxide was produced.

  To 100 g of this precursor, 1.7 g of sodium borohydride was added as a reducing aid, the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was set to 100 ml / min, and the conditions were 600 ° C. and 3 hours. Reduction firing was performed. The color tone of the pigment obtained by this reduction treatment was yellow in appearance color and dark green in interference color.

Manufacturing example 5
A titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove an excess titanium compound, and a precursor having a white appearance color and a red interference color (film thickness of the titanium oxide layer: 100 nm) in which mica was coated with titanium dioxide was produced.

  To 100 g of this precursor, 2.0 g of sodium borohydride was added as a reducing aid, the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was set to 100 ml / min, and the conditions were 600 ° C. and 3 hours. Reduction firing was performed. As for the color tone of the pigment product obtained by this reduction treatment, the appearance color was light red (pink) and the interference color was dark yellow.

Manufacturing Example 6
A titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor with a white appearance color and a blue interference color (titanium oxide layer thickness: 130 nm) in which mica was coated with titanium dioxide was produced.

  To 100 g of this precursor, 2.7 g of sodium borohydride was added as a reducing aid, the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was set to 100 ml / min, and the conditions were 600 ° C. and 3 hours. Reduction firing was performed. The color tone of the pigment obtained by this reduction treatment was blue in appearance color and purple in interference color.

In the said manufacture examples 3-6, the composition of the low order titanium oxide layer was made constant and the film thickness of the low order titanium oxide layer was changed. Table 2 below shows changes in color tone when the composition of the low-order titanium oxide layer is Ti ₄ O ₇ and the film thickness is 30 to 140 nm. By changing the film thickness, the interference color and appearance color could be changed significantly.

  As shown in these production examples 1 to 6, by controlling the composition and film thickness of the low-order titanium oxide layer, it is possible to synthesize pigments having dichroism with different types of bright appearance colors and interference colors that have never existed before. It became possible to do.

Manufacturing example 7
A titania sol was applied to the glass powder, and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, the excess titanium compound was removed by washing with water, and a precursor B (thickness of titanium oxide layer: 140 nm) having a white appearance color and a light green interference color with a glass powder coated with titanium dioxide was produced. This precursor B was confirmed to be an anatase structure of titanium dioxide by XRD measurement (FIG. 3).

To 100 g of this precursor B, 3.0 g of sodium borohydride was added as a reducing aid, and the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was 100 ml / min at 600 ° C. for 3 hours. Reduction firing was performed. The obtained reduction-treated product was recovered as a pigment, and the color tone of this product was green in appearance color and light blue in interference color. The XRD analysis result of this pigment is shown in FIG. 3. As is clear from this result, the peak of titanium dioxide disappeared and low-order titanium oxide Ti ₄ O ₇ was produced.

Manufacturing Example 8
A titania sol was applied to the glass powder, and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, the excess titanium compound was removed by washing with water, and a precursor B (thickness of titanium oxide layer: 140 nm) having a white appearance color and a light green interference color with a glass powder coated with titanium dioxide was produced.

7.0 g of sodium borohydride was added as a reducing aid to 100 g of this precursor B, the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was set to 100 ml / min, and conditions of 700 ° C. for 3 hours Then, reduction firing was performed. The obtained reduction-treated product was recovered as a pigment and measured for XRD diffraction. As a result, the titanium dioxide peak disappeared and low-order titanium oxide Ti ₂ O ₃ was produced (FIG. 3). As for the color tone, the appearance color was dark green and the interference color was blue.

Comparative production example 2
A titania sol was applied to the glass powder, and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove excess titanium compound, and a precursor B (thickness of the titanium oxide layer: 140 nm) having a white appearance color and a light green interference color with a glass powder coated with titanium dioxide was produced. .

To 100 g of this precursor B, 10.0 g of sodium borohydride as a reducing aid was added, the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was 100 ml / min, and the conditions of 800 ° C. for 3 hours Then, reduction firing was performed. The obtained reduction-treated product was recovered as a pigment and measured for XRD diffraction. As a result, the titanium dioxide peak disappeared, and low-order titanium oxide Ti · TiO · Ti ₂ O ₃ was produced (FIG. 3). The color tone was a color tone in which the appearance color black was conspicuous.

  Even in the pigments obtained by coating titanium dioxide on the glass powders of Production Examples 7 to 8, the same color tone was obtained by performing the reduction treatment in the same manner as Production Examples 1 and 2. Moreover, as shown in FIG. 3, the composition of the low-order titanium oxide also showed the same tendency as in Production Examples 1 and 2.

Manufacturing example 9
Reduction treatment was performed using a commercially available glass powder coated with titanium dioxide and having a white appearance color and a blue interference color (manufactured by Nippon Sheet Glass Co., Ltd .: Metashine (MC1080RB)). 2.7 g of sodium borohydride was added as a reducing aid to 100 g of the above glass powder to prepare a mixed raw material. This mixed material was subjected to reduction firing under conditions of 600 ° C. and 3 hours with a flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) being 100 ml / min. The color tone of the pigment obtained by this reduction treatment was blue in appearance color and purple in interference color.

Manufacturing example 10
Reduction firing was performed using commercially available titanium mica having a white appearance color and a blue interference color (Merck: Iridion 225) as a raw material. To 100 g of the above mica titanium, 2.7 g of sodium borohydride was added as a reduction aid to prepare a mixed raw material. This mixed raw material was subjected to reduction firing under conditions of 600 ° C. and 3 hours with a flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) being 100 ml / min. The color tone of the pigment obtained by this reduction treatment was blue in appearance color and purple in interference color.

Manufacturing Example 11
A titania sol was applied to the aluminum flakes and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove excess titanium compound, and a precursor (white thickness of the titanium oxide layer: 130 nm) having a white appearance color and a blue interference color was produced by coating the aluminum flakes with titanium dioxide.

  To 100 g of this precursor, 2.7 g of sodium borohydride was added as a reducing aid, the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was set to 100 ml / min, and the conditions were 600 ° C. and 3 hours. Reduction firing was performed. The color tone of the pigment obtained by this reduction treatment was blue in appearance color and purple in interference color.

  From Production Examples 9 to 10, it was found that a vivid dichroic pigment can be obtained by using a commercially available material and reducing it. Further, in Production Example 11, it was found that a pigment having vivid dichroism was obtained even when the raw material substrate was aluminum flakes.

Manufacturing example 12
Reduction treatment was performed using a commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass Co., Ltd .: Metashine (MC1080RB)). First, the titanium hydride powder was pulverized in an agate mortar, and the powder that passed through a sieve having an opening of 25 μm was recovered and used as a reduction aid. To 100 g of the above glass powder, 4.3 g of titanium hydride as a reducing aid was added and mixed uniformly with a mixer. The mixed raw material was subjected to reduction firing under conditions of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) at a flow rate of 100 ml / min at 600 ° C. for 3 hours. The obtained reduction-treated product was stirred with water and then subjected to a wet sieve having an opening of 25 μm to remove low-order titanium oxide formed from titanium hydride as a reducing aid. The pigment obtained as a recovered product had a blue appearance color and a purple interference color.

Production Example 13
Reduction treatment was performed using a commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass Co., Ltd .: Meta Shine (MC1080RB)). First, the titanium powder was pulverized in an agate mortar, and the powder that passed through a sieve having an opening of 25 μm was recovered and used as a reduction aid. To 100 g of the above glass powder, 3.8 g of titanium as a reducing aid was added and mixed uniformly with a mixer. The mixed raw materials were subjected to reduction firing under conditions of 700 ° C. and 3 hours at a flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 2) of 100 ml / min. The obtained reduction-treated product was stirred with water and then subjected to a wet sieve having an opening of 25 μm to remove low-order titanium oxide formed from titanium hydride as a reducing aid. The pigment obtained as a recovered product had a blue appearance color and a purple interference color.

Production Example 14
A commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass Co., Ltd .: Metashine (MC1080RB)) was used, and reduction treatment was performed using lithium aluminum hydride as a reduction aid. First, 2.7 g of lithium aluminum hydride is added as a reducing aid to 100 g of the glass powder to prepare a mixed raw material. This mixed raw material was subjected to reduction firing under conditions of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) at a flow rate of 100 ml / min at 600 ° C. for 3 hours. The color tone of the pigment obtained by this reduction treatment was blue in appearance color and purple in interference color.

Production Example 15
Using commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass Co., Ltd .: Metashine), reduction firing is performed with a mixed gas of hydrogen and nitrogen. 20 g of metashine (MC1080RB) was put in an atmosphere furnace, and the flow rate of a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 3) was set to 100 ml / min, and reduction firing was performed at 1000 ° C. for 8 hours. As for the color tone of the obtained reduced fired product, the appearance color was blue and the interference color was purple.

  Production Examples 12 to 13 show that vivid dichroic pigments can be obtained by using titanium hydride and metal titanium as the reducing aid. Further, Production Example 14 shows that a vivid dichroic pigment can be obtained even when lithium aluminum hydride is used as the reducing aid, and Production Example 15 shows a mixed gas of nitrogen and hydrogen. It shows that a vivid dichroic pigment can also be obtained by reducing the mixture ratio.

Production Example 16
Reduction treatment was performed using commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass Co., Ltd .: Metashine (MC1080RB)). First, 2.7 g of sodium borohydride and 0.2 g of guanidine were added as reducing aids to 100 g of the above glass powder to prepare a mixed raw material. This mixed raw material was subjected to reduction firing under conditions of a flow rate of a mixed gas of nitrogen and hydrogen (ammonia: hydrogen = 1: 1) of 100 ml / min at 600 ° C. for 3 hours. As for the color tone of the pigment obtained by this reduction treatment, the appearance color was magenta and the interference color was blue.

Manufacturing Example 17
Reduction treatment was performed using a commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass Co., Ltd .: Metashine (MC1080RB)). 2.7 g of sodium borohydride was added as a reducing aid to 100 g of the above glass powder to prepare a mixed raw material. Reduction firing was carried out at a flow rate of a mixed gas of ammonia and hydrogen (ammonia: hydrogen = 2: 1) of 100 ml / min at 600 ° C. for 3 hours. The color tone of the pigment obtained by this reduction treatment was brown in appearance color and purple in interference color.

  Production Example 16 is an example using a compound containing nitrogen in the reducing aid. Production Example 17 is an example in which a mixed gas of ammonia and hydrogen is used for the reduction treatment. In these examples, a part of each low-order titanium oxide layer was replaced with nitrogen and modified, but even in that case, a vivid dichroic pigment could be obtained.

Manufacturing Example 18
The mica is coated with particles having a low-order titanium oxide composition of Ti ₃ O ₄ and a particle diameter of 10 to 30 nm. In this coating, low-order titanium oxide particles are uniformly dispersed in an aqueous solvent, and mica is added to suspend, and then mica particles coated with the low-order titanium oxide particles are collected, dried at 105 ° C., This was done by removing

  The mica coated with the low-order titanium oxide was heat-treated at 800 ° C. for 3 hours in a vacuum atmosphere. The color tone of the obtained reduction-treated product was dichroic with the appearance color being green and the interference color being light blue.

Comparative production example 3
A titania sol was applied to the glass powder, and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound to obtain a glass powder coated with titanium dioxide, which had a white appearance color and a green interference color (thickness of the titanium dioxide layer: 140 nm). .

Comparative production example 4
Based on Example 1 of JP-A-60-060163 (Patent Document 6), 500 parts of ion-exchanged water is added to 50 parts of mica, and the resulting slurry is sufficiently stirred. %) Was added in an amount of 208.5 parts, followed by stirring with heating for 6 hours. After standing to cool, it was washed with filtered water and fired at 900 ° C. to obtain mica coated with titanium dioxide. The mica coated with titanium dioxide was subjected to reduction treatment at 800 ° C. for 4 hours at a flow rate of 3 L / min of ammonia gas. When the XRD analysis of the obtained product was conducted, it was a mixture of TiO and TiO ₂ , and its appearance color and interference color were blue.

Table 8 below shows data relating to the appearance of those obtained in Comparative Production Examples 1 to 4. In the comparative production examples 1 and 2, when the reduction degree of the low-order titanium oxide TiO (x = 1) is high, the absorption of the incident light into the low-order titanium oxide becomes strong, the interference color is seen, and the appearance color is changed. Only black. On the other hand, in Comparative Production Example 3, the composition was TiO ₂ (x = 2) and the appearance color was white, so that the color of the interference color could not be recognized significantly.

Further, those obtained in Comparative Production Example 4, although the coating composition is a mixture of TiO and TiO _2, when lower titanium oxide is such a coating composition is a mixture of TiO and TiO ₂ TiO absorbs light strongly, and reflected light becomes weak. Therefore, the reflected light is only blue emitted from TiO ₂ , and TiO gives only the effect of making it stand out (effect as a background color) and has a monotone color tone.

  In the present invention, as shown in the embodiment, a single layer of low-order titanium oxide having a reduction degree of TiOx (1.0 <x <2.0) that can reflect light is provided in FIG. The resulting light is reflected and absorbed, and dichroism with different appearance color and interference color can be obtained.

Example 1
Liquid eye color:
Liquid eye colors, which are water-containing cosmetics, of the present invention products 1 to 6 and comparative products 1 to 7 were prepared by the composition shown in Table 9 below and the following production method. About the obtained liquid eye color, each of the items of “dispersibility”, “stereoscopic effect due to dichroism”, “uniform cosmetic film”, “transparency” and “stability over time” are shown below. It was evaluated by. The results are also shown in Table 9.

( Production method )
A: Components (1) to (8) are mixed uniformly.
B: Components (9) to (12) are added to component A and mixed uniformly.
C: B was filled into a container with an applicator to obtain a product.

(Evaluation)
The following evaluation items were evaluated by the following methods.
<Evaluation items and evaluation methods>
B) Dispersibility For dispersibility, a thin film was drawn on a glass plate using a 400 μm thick applicator for each sample and dried sufficiently, and then the presence or absence of aggregates and unevenness was visually observed. This observation result was evaluated in the following three stages. In addition, the thing of a two-layer state was used shaking 10 times before evaluation.

( Evaluation criteria )
State: Judgment Uniformity without aggregation and unevenness. : ○
Aggregation and unevenness are slightly seen. : △
Aggregation or unevenness is clearly observed. : ×

(B) Three-dimensional effect due to dichroism For the three-dimensional effect due to dichroism, one panel used for each sample was applied to a bag, and the state after this application was evaluated in seven stages according to the following evaluation criteria. Evaluation and a score were given, and the average value was calculated from the total score of all the evaluation panels of each sample, and judged according to the following four-step criteria. In addition, after application, when viewed from the front, front, front, 45 ° angle of the top, bottom, right, left, whether the three-dimensional effect is obtained, whether the color change is felt by the angle and vividness Whether or not there is an important point in the evaluation. In addition, the two-layer state was used by shaking 10 times before evaluation.

C) Uniform cosmetic film and transparency For the uniform cosmetic film and transparency, each sample is subjected to a usage test by 20 specialist panels, and each panel evaluates it according to the following evaluation criteria and gives a score. The average value was calculated from the total score of all the panels of each sample, and judged according to the following four-step criteria. In addition, the two-layer state was used by shaking 10 times before evaluation.

(1) Evaluation criteria Evaluation: Rating Very good: 6
Good: 5
Slightly good: 4
Normal: 3
Slightly bad: 2
Bad: 1
Very bad: 0

(2) Criteria:
Average score: 5 or more judgments: ◎
3.5 points or more and less than 5 points: ○
1.5 points or more and less than 3.5 points: △
Less than 1.5 points: ×

D. Stability over time Stability over time was determined by allowing the samples to stand for 6 weeks at room temperature, then shaking and mixing each sample twice, and evaluating the appearance at that time according to the following three-stage criteria.

( Evaluation criteria )
State: Judgment Uniformity without aggregation and unevenness. : ○
Aggregation and unevenness are slightly seen. : △
Aggregation or unevenness is clearly observed. : ×

  As is apparent from the results in Table 9, the eye colors of the inventive products 1 to 6 are more dispersible, three-dimensional due to dichroism, film uniformity and stability over time than the eye colors of comparative products 1 to 7. All were excellent. In contrast, Comparative Product 1 using a water-soluble resin rather than an emulsion (polymer aqueous dispersion) is slow in drying and lacks uniformity in the film, and is satisfactory in the effect of stereoscopic effect due to dichroism. Was not obtained. Further, in Comparative products 2, 4 to 6 containing black iron oxide-coated mica instead of the dichroic pigment, satisfactory results were not obtained particularly in dispersibility, film uniformity, transparency, and stability. Further, in Comparative product 3 in which mica titanium was blended in place of the dichroic pigment, a satisfactory appearance was not obtained in terms of the effect of three-dimensional effect due to dichroism and transparency in view of the white appearance. Furthermore, the comparative product 7 containing the black low-order titanium oxide pigment shown in Comparative Production Example 1 in place of the dichroic pigment does not give a satisfactory three-dimensional effect and transparency, and has no transparency. As a result, there appeared to be uneven color, and the uniformity of the film was insufficient.

  The dichroic pigments obtained in Production Examples 1 to 5 and Production Examples 7 to 18 were used in place of the dichroic pigment obtained in Production Example 6 used in Product 1 of the present invention. A color was prepared. These were also evaluated in the same manner as described above, and all of them were excellent. The results are shown in Table 10. The following Examples 2 to 22 were also evaluated in the same manner as in Example 1.

Example 2
Oil-in-water mascara:
An oil-in-water mascara that is a water-containing cosmetic was prepared by the following composition and production method.

(Composition) (%)
(1) Stearic acid 3
(2) Carnauba wax 1
(3) Beeswax 7
(4) Paraffin wax 1
(5) Self-emulsifying glyceryl monostearate 1
(6) Sucrose fatty acid ester 2
(7) Polyoxyethylene sorbitan monooleate 1.3
(8) Sorbitan sesquioleate 0.5
(9) Black iron oxide 5
(10) Dichroic pigment (obtained in Production Example 4) 3
(11) Alkyl acrylate copolymer emulsion ^{* 1} 2.5
(12) Silicic anhydride 2
(13) Triethanolamine 1.6
(14) 1,3-butylene glycol 8
(15) Preservative (phenoxyethanol) 0.2
(16) Preservative (1,2-pentanediol) 0.1
(17) Alkyl acrylate copolymer emulsion ^{* 2} 28
(18) Vinyl acetate copolymer emulsion ^{* 4} 0.5
(19) Residual amount of purified water
* 1 Above
* 2 〃
*Four 〃

(Production method)
A. Components (1) to (8) are dissolved by heating at 85 ° C., and components (9) and (10) are added,
Mix evenly.
B. Components (11) to (19) are heated to 85 ° C. and mixed uniformly.
C. Add B to A and emulsify.
D. C is cooled to room temperature and filled into a container to obtain a product.

  The oil-in-water mascara obtained as described above was excellent in volume effect, color development, makeup effect such as gloss, and its sustainability.

Example 3
Water-in-oil eyeliner:
A water-in-oil eyeliner that is a water-containing cosmetic was prepared by the following composition and production method.

(Composition) (%)
(1) Light liquid isoparaffin remaining amount (2) Black iron oxide 15
(3) Organically modified bentonite ^{* 11} 5
(4) Dextrin palmitate 1
(5) Polyisobutylene 2
(6) Purified water 2
(7) Sodium chloride 5
(8) Preservative (paraoxybenzoic acid ester) 0.2
(9) Preservative (1,2-pentanediol) 0.1
(10) Alkyl acrylate copolymer emulsion ^{* 2} 2
(11) Vinyl acetate copolymer emulsion ^{* 4} 5
(12) Dichroic pigment (obtained in Production Example 12) 5
* 2 Above
*Four 〃
* 11 BENTONE38V BC (manufactured by ELEMENTIS)

(Production method)
A. Ingredients (1) to (5) are heated and mixed at 90 ° C., cooled and allowed to cool at room temperature.
And mix evenly.
B. Fill A into a container to make a product.

  The water-in-oil eyeliner obtained as described above was excellent in steric makeup effect due to dichroism, and excellent in uniformity and stability of the cosmetic film.

Example 4
Oil-in-water eyeliner:
An oil-in-water eyeliner that is a water-containing cosmetic was prepared by the following composition and production method.

(Composition) (%)
(1) Partially cross-linked organopolysiloxane polymer solution ^{* 12} 15
(2) Methylphenylpolysiloxane 5
(3) Decamethylcyclopentasiloxane 5
(4) Alkyl acrylate copolymer emulsion ^{* 2} 3
(5) Sodium hydroxide 1
(6) Residual amount of purified water (7) Glycerin 10
(8) Preservative (paraoxybenzoic acid ester) 0.3
(9) Silica 10
(10) Black titanium oxide 5
(11) Black iron oxide 5
(12) Dichroic pigment (obtained in Production Example 2) 5
* 12 Silicon KSG-16 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 2 Above

(Production method)
A. The components (1) to (3) are mixed and dissolved.
B. Components (4) to (8) are mixed, and components (9) to (12) are added and mixed uniformly.
C. A is added to B and emulsified.
D. Fill the container with C to make a product.

  The oil-in-water eyeliner obtained as described above was excellent in steric makeup effect due to dichroism and excellent in uniformity and stability of the cosmetic film.

Example 5
Water-based eyeliner:
A water-based eyeliner was prepared by the following composition and production method.

(Composition) (%)
(1) Purified water remaining amount (2) 1,3-butylene glycol 5
(3) Red No. 202 1
(4) Carboxyvinyl polymer 0.1
(5) Sodium hydroxide 0.1
(6) Preservative (paraoxybenzoic acid ester) 0.1
(7) Alkyl acrylate copolymer emulsion ^{* 2} 10
(8) Dichroic pigment (obtained in Production Example 9) 5
* 2 Above

(Production method)
A. Mix components (1) to (8) uniformly.
B. Fill A into a container to make a product.

  The water-based eyeliner obtained as described above was excellent in the three-dimensional cosmetic effect due to dichroism, and was excellent in the uniformity and stability of the decorative film.

Example 6
Oil-in-water emulsified eyebrow (liquid):
A liquid oil-in-water eyebrow was prepared by the following composition and production method.

(Composition) (%)
(1) Stearic acid 3
(2) Cetanol 2
(3) Glyceryl monostearate 0.5
(4) Candelilla resin ^{* 13} 10
(5) Sucrose fatty acid ester ^{* 14} 1.5
(6) Black iron oxide 1
(7) Silicic anhydride 1
(8) Purified water remaining amount (9) 1,3-butylene glycol 5
(10) Sodium hydroxide 0.2
(11) Preservative (paraoxybenzoic acid ester) 0.1
(12) Alkyl acrylate copolymer emulsion ^{* 2} 10
(13) Dichroic pigment (obtained in Production Example 17) 5
* 2 Above
* 13 Candelilla resin E-1 (Nippon Natural Products)
* 14 Sugar wax S-10E (Daiichi Kogyo Seiyaku Co., Ltd.)

(Production method)
A. Components (1) to (5) are heated and dissolved at 110 ° C., and (6) is added and mixed uniformly.
B. Ingredients (7) to (13) are mixed uniformly and heated to 80 ° C.
C. Add B to A and emulsify.
D. C is cooled to room temperature and filled into a container to obtain a product.

  The oil-in-water emulsified eyebrow obtained as described above was excellent in the three-dimensional cosmetic effect due to dichroism, and excellent in the uniformity and stability of the decorative film.

Example 7
Oil-in-water emulsified eye color (cream):
A creamy oil-in-water emulsified eye color was prepared by the following composition and production method.

(Composition) (%)
(1) Stearic acid 1
(2) Cetanol 1
(3) Glyceryl monostearate 0.5
(4) Ethylene glycol monostearate (40E.O.) 0.5
(5) Candelilla resin ^{* 13} 8
(6) Red No. 202 1
(7) Purified water remaining amount (8) 1,3-butylene glycol 5
(9) Triethanolamine 0.2
(10) Preservative (paraoxybenzoic acid ester) 0.1
(11) Alkyl acrylate copolymer emulsion ^{* 2} 10
(12) Vinylpyrrolidone / vinyl acetate copolymer ^{* 15} 3
(13) Ethyl alcohol 3
(14) Anhydrous silicic acid ^{* 16} 2
(15) Mica titanium 10
(16) Dichroic pigment (obtained in Production Example 12) 5
(17) Fragrance 0.5
* 2 Above
*13 〃
* 15 PVP / VAE-735 (made by ISP)
* 16 AEROSIL 300 (Nippon Aerosil Co., Ltd.)

(Production method)
A. Components (1) to (5) are heated and dissolved at 110 ° C., and (6) is added and mixed uniformly.
B. Ingredients (7) to (17) are mixed uniformly and heated to 80 ° C.
C. Add B to A and emulsify.
D. C is cooled to room temperature and filled into a container to obtain a product.

  The oil-in-water emulsified eye color obtained as described above was excellent in steric cosmetic effect due to dichroism, and excellent in uniformity and stability of the cosmetic film.

Example 8
Aqueous foundation:
An aqueous foundation was prepared by the following composition and production method.

(Composition) (%)
(1) Fluorine compound-treated titanium oxide ^{* 17} 7.5
(2) Fluorine compound-treated talc ^{* 17} 5
(3) Sericite treated with fluorine compound ^{* 17} 3.1
(4) Fluorine compound-treated bengara ^{* 17} 0.2
(5) Fluorine compound-treated yellow iron oxide ^{* 17} 1.1
(6) Fluorine compound-treated black iron oxide ^{* 17} 0.1
(7) Dichroic pigment (obtained in Production Example 17) 3
(8) Ethyl alcohol 10
(9) (Acrylic / alkyl acrylate) copolymer 1
Emulsion ^{* 18}
(10) Triethanolamine 1
(11) 1,3-butylene glycol 5
(12) Silicic anhydride 0.2
(13) Purified water remaining amount (14) Glycerin 7
(15) Preservative (paraoxybenzoic acid ester) 0.1
(16) Hydroxypropyl methylcellulose 0.2
* 17 All treated with 3% fluoroalkyltriethoxysilane
* 18 Ultrazol V-280C (solid content 28%) (manufactured by Gantz Kasei)

(Production method)
A: Components (1) to (11) are mixed uniformly.
B: Components (12) to (13) are mixed uniformly.
C: A and B and components (14) to (16) are mixed uniformly.
D: C is degassed and filled into a container to obtain a product.

  The aqueous foundation obtained as described above was excellent in the cosmetic effect of the three-dimensional effect due to dichroism, and was excellent in the uniformity and stability of the decorative film.

Example 9
Oil-in-water foundation:
An oil-in-water foundation that is a water-containing cosmetic was prepared by the following composition and production method.

(Composition) (%)
(1) Fluorine compound-treated titanium oxide ^{* 19} 9
(2) Fluorine compound-treated talc ^{* 19} 5
(3) Fluorine compound-treated sericite ^{* 19} 3.1
(4) Fluorine compound-treated bengara ^{* 19} 0.2
(5) Fluorine compound-treated yellow iron oxide ^{* 19} 0.8
(6) Fluorine compound-treated black iron oxide ^{* 19} 0.2
(7) Dichroic pigment (obtained in Production Example 5) 3
(8) Ethyl alcohol 8
(9) (Acrylic / alkyl acrylate) copolymer 1
Emulsion ^{* 20}
(10) Triethanolamine 1.2
(11) 1,3-butylene glycol 12
(12) Sorbitan sesquioleate 0.3
(13) Polyoxyethylene sorbitan monooleate (20E.O.) 0.5
(14) Preservative (paraoxybenzoic acid ester) 0.2
(15) Purified water remaining amount (16) Carboxyvinyl polymer ^{* 21} 0.1
(17) Triethanolamine 0.1
(18) Stearic acid 1
(19) Cetostearyl alcohol 0.6
(20) Sorbitan sesquioleate 0.2
(21) Polyoxyethylene sorbitan monooleate (20E.O.) 1
(22) Squalane 7
* 19 All treated with 5% fluoroalkyltriethoxysilane
* 20 SALCARE SC81 (solid content 30%)
* 21 CARBOPOL 940 (manufactured by LUBRIZOL ADVANCED MATERIALS A)

(Production method)
A: Components (1) to (14) are heated and mixed at 80 ° C.
B: Components (15) to (17) are added to A by heating to 80 ° C., and mixed and dispersed.
C: Components (18) to (22) are added to B by heating to 80 ° C. and emulsified.
D: C is cooled to room temperature, degassed, and filled into a container to obtain a product.

  The oil-in-water type foundation obtained as described above was excellent in the cosmetic effect of the three-dimensional effect due to dichroism, and was excellent in the uniformity and stability of the decorative film.

Example 10
Water-based blusher A water-based blusher was prepared by the following composition and production method.

(Composition) (%)
(1) Fluorine compound-treated talc ^{* 22} 0.2
(2) Fluorine compound-treated bengara ^{* 22} 0.5
(3) Fluorine compound-treated yellow iron oxide ^{* 22} 0.3
(4) Dichroic pigment (obtained in Production Example 5) 3
(5) Ethyl alcohol 1
(6) (Acrylic / alkyl acrylate) copolymer 0.05
Emulsion ^{* 20}
(7) Triethanolamine 0.1
(8) 1,3-butylene glycol 5
(9) Silicic anhydride 0.2
(10) Purified water remaining amount (11) Glycerin 10
(12) Preservative (paraoxybenzoic acid ester) 0.1
(13) Hydroxypropyl methylcellulose 0.5
* 20 Above
* 22 All treated with 1.5% fluoroalkyltriethoxysilane

(Production method)
A: Components (1) to (8) are mixed uniformly.
B: Components (9) to (10) are mixed uniformly.
C: A and B and components (11) to (13) are mixed uniformly.
D: C is degassed and filled into a container to obtain a product.

  The water-based cheeks obtained as described above were excellent in the three-dimensional cosmetic effect due to dichroism, and excellent in the uniformity and stability of the decorative film.

Example 11
Oil-in-water sunscreen An oil-in-water sunscreen that is a water-containing cosmetic was prepared according to the following composition and production method.

(Composition) (%)
(1) Fluorine compound-treated titanium oxide ^{* 19} 16.5
(2) Fluorine compound-treated talc oxide ^{* 19} 10
(3) Fluorine compound-treated bengal oxide ^{* 19} 0.5
(4) Fluorine compound-treated yellow iron oxide ^{* 19} 3
(5) Dichroic pigment (obtained in Production Example 15) 0.5
(6) Ethyl alcohol 20
(7) (Acrylic / alkyl acrylate) copolymer 3
Emulsion ^{* 20}
(8) Triethanolamine 3
(9) 1,3-butylene glycol 5
(10) Silicic anhydride 1
(11) Residual amount of purified water (12) Kojic acid 0.5
(13) Citric acid 0.1
(14) Sodium citrate 0.1
(15) Disodium edetate 0.1
(16) Hydroxymethoxybenzophenone sodium sulfonate 0.2
(17) Glycerin 5
(18) Preservative (paraoxybenzoic acid ester) 0.2
(19) Stearic acid 2
(20) Cetostearyl alcohol 1
(21) Glyceryl monostearate 0.5
(22) Sorbitan sesquioleate 0.3
(23) Polyoxyethylene sorbitan monooleate (20E.O.) 0.5
(24) Glyceryl tri-2-ethylhexanoate 10
* 19 Above
* 20 〃

(Production method)
A: Components (1) to (9) are heated to 80 ° C. and mixed uniformly.
B: Ingredients (10) to (18) are added to A by heating to 80 ° C., and uniformly mixed and dispersed.
C: Components (19) to (24) are added to B by heating to 80 ° C. and emulsified.
D: C is cooled to room temperature and defoamed to obtain a product.

  The oil-in-water sunscreen obtained as described above was excellent in steric makeup effect due to dichroism, and excellent in uniformity and stability of the cosmetic film.

Example 12
Base Cosmetic A base cosmetic that is a water-containing cosmetic was prepared by the following composition and production method.

(Composition) (%)
(1) Locust bean gum 0.5
(2) Acrylic acid / alkyl methacrylate (C10-30) 0.2
Copolymer ^{* 23}
(3) (Acrylic / alkyl acrylate) copolymer 0.5
Emulsion ^{* 20}
(4) Residual amount of purified water (5) Triethanolamine 0.2
(6) Silicic anhydride 5
(7) Nylon powder 5
(8) Fluorine compound-treated titanium oxide ^{* 17} 2
(9) Fluorine compound-treated bengara ^{* 17} 0.1
(10) Fluorine compound-treated yellow iron oxide ^{* 17} 0.5
(11) Fluorine compound-treated black iron oxide ^{* 17} 0.1
(12) Fluorine compound treated talc ^{* 17} 2
(13) Dichroic pigment (obtained in Production Example 17) 3
(14) Preservative (paraoxybenzoic acid ester) 0.1
(15) 1,3-butylene glycol 15
(16) Ethyl alcohol 5
(17) Polyoxyethylene 20 mol addition sorbitan trioleate 1
(18) Soy lecithin 0.4
(19) Liquid paraffin 1
(20) Fragrance appropriate amount
* 17 Above
* 20 〃
* 23 CARBOPOL 1342 (LUBRIZOL ADVANCED MATERIALS A)

(Production method)
A: Swell and mix (1) to (4), and neutralize with (5).
B: (6) to (18) are mixed uniformly.
C: B is added to A and mixed, and (19) to (20) are added and mixed.
D: C is filled into a container to obtain a product.

  The base cosmetic obtained as described above was excellent in the effect of stereoscopic effect due to dichroism, and excellent in uniformity and stability of the decorative film.

Example 13
Water-based gel eye color:
An aqueous gel eye color was prepared by the following composition and production method.

(Composition) (%)
(1) Gellan gum 0.5
(2) Acrylic acid / alkyl methacrylate (C10-30) 0.2
Copolymer ^{* 23}
(3) (Acrylic / alkyl acrylate) copolymer 0.5
Emulsion ^{* 20}
(4) Xanthan gum 0.5
(5) Residual amount of purified water (6) Triethanolamine 0.2
(7) Silicic anhydride 5
(8) Dichroic pigment (obtained in Production Example 10) 3
(9) Dichroic pigment (obtained in Production Example 16) 3
(10) Fluorine compound-treated black iron oxide ^{* 19} 0.02
(11) Preservative (paraoxybenzoic acid ester) 0.1
(12) 1,3-butylene glycol 10
(13) Polyoxyethylene 20 mol addition sorbitan monooleate 1
(14) Sorbitan sesquioleate 0.3
(15) Dimethylpolysiloxane (100CS) 0.5
(16) Perfluoropolyether ^{* 24} 1
(17) Fragrance proper amount
* 19 Above
* 20 〃
* 23 Above
* 24 Fomblin HC / 04 (Solvay Solexis)

(Production method)
A: Swell and mix (1) to (5), and neutralize with (6).
B: (7) to (14) are mixed uniformly.
C: B is added to A and mixed, and (15) to (17) are added and mixed.
D: C is filled into a container to obtain a product.

  The obtained water-based gel-like eye color was excellent in a three-dimensional cosmetic effect due to dichroism, and was excellent in the uniformity and stability of the cosmetic film.

Example 14
Aqueous mascara:
An aqueous mascara was prepared by the following composition and production method.

(Composition) (%)
(1) Carboxymethylcellulose 3
(2) Carboxyvinyl polymer ^{* 21} 0.1
(3) Triethanolamine 0.1
(4) Alkyl acrylate copolymer emulsion ^{* 2}
(5) Residual amount of purified water (6) Sodium hydroxide 2
(7) Ethyl alcohol 2
(8) Polyvinyl alcohol 5
(9) Nylon fiber ^{* 25} 10
(10) Dichroic pigment (obtained in Production Example 1) 2
(11) Dichroic pigment (obtained in Production Example 7) 2
(12) Phenoxyethanol 0.5
* 2 Above
*twenty one 〃
* 25 Thickness 6.3T (decitex), length 2mm

(Production method)
A: (1) to (7) are uniformly mixed.
B: (8) to (12) are added to A and dispersed uniformly.
C: B is filled into a container to obtain a product.

  The mascara obtained as described above was excellent in the three-dimensional cosmetic effect due to dichroism, and excellent in the uniformity and stability of the decorative film.

Example 15
Water-in-oil eyebrow:
A water-in-oil eyebrow was prepared by the following composition and production method.

(Composition) (%)
(1) Ozoquelite wax 3
(2) Carnauba wax 1
(3) Beeswax 3
(4) Candelilla wax 1
(5) Candelilla resin ^{* 13} 8
(6) Lecithin 1
(7) Black iron oxide 10
(8) Dichroic pigment (obtained in Production Example 4) 1
(9) Organically modified bentonite ^{* 11} 3
(10) Light liquid isoparaffin remaining amount (11) Dextrin palmitate 1
(12) 1,3-butylene glycol 2
(13) Purified water 20
(14) Alkyl acrylate copolymer emulsion ^{* 2} 5
(15) Preservative (paraoxybenzoic acid ester) 0.2
* 2 Above
* 11 〃
*13 〃

(Production method)
A: (1) to (11) are heated at 110 ° C. and mixed uniformly.
B: (12) to (15) are mixed uniformly.
C: B is added to A and emulsified at room temperature.
D: C is filled into a container to obtain a product.

  The eyebrow obtained as described above was excellent in the three-dimensional cosmetic effect due to dichroism, and was excellent in the uniformity and stability of the cosmetic film.

Example 16
Water-based eyebrow:
An aqueous eyebrow was prepared by the following composition and production method.

(Composition) (%)
(1) Carboxymethylcellulose 3
(2) Carboxyvinyl polymer ^{* 21} 0.1
(3) Triethanolamine 0.1
(4) Alkyl acrylate copolymer emulsion ^{* 2} 1
(5) Purified water remaining amount (6) Sodium hydroxide 1
(7) Ethyl alcohol 2
(8) Polyvinyl alcohol 5
(9) Dichroic pigment (obtained in Production Example 5) 1
(10) Phenoxyethanol 0.5
* 2 Above
*twenty one 〃

(Production method)
A: (1) to (8) are uniformly mixed.
B: (9) and (10) are added to A and dispersed uniformly.
C: B was filled into a container to obtain a product.

  The aqueous eyebrow obtained as described above was excellent in the three-dimensional cosmetic effect due to dichroism, and was excellent in the uniformity and stability of the decorative film.

Example 17
Water-in-oil eye color:
A water-in-oil eye color was prepared by the following composition and production method.

(Composition) (%)
(1) Silicone-treated talc ^{* 26} 3
(2) Silicone-treated titanium oxide ^{* 26} 1
(3) Silicone-treated iron oxide ^{* 26} 2
(4) Dichroic pigment (obtained in Production Example 11) 5
(5) Dichroic pigment (obtained in Production Example 3) 5
(6) Blue No. 404 0.5
(7) Hydrophobic-treated fumed silicic acid ^{* 27} 0.2
(8) Neopentyl glycol dioctanoate 5
(9) Organically modified bentonite ^{* 11} 1
(10) Decamethylpentasiloxane 25
(11) Alkyl acrylate / dimethicone copolymer ^{* 28} 5
(12) Cetyl dimethicone copolyol ^{* 29} 2.7
(13) Nylon powder 1.5
(14) 1,3-butylene glycol 2
(15) Ethyl alcohol 7
(16) Residual amount of purified water (17) Sodium chloride 0.5
(18) Alkyl acrylate copolymer emulsion ^{* 2} 1
(19) Preservative (paraoxybenzoic acid ester) 0.05
* 2 Above
* 11 〃
* 26 3% dimethylpolysiloxane treatment
* 27 AEROSIL R972 (Nippon Aerosil Co., Ltd.)
* 28 Silicon KP-545 (Decamethylcyclopentasiloxane 30% solution)
(Shin-Etsu Chemical Co., Ltd.)
* 29 ABIL EM90 (Gold Schmidt)

(Production method)
A: (1) to (12) are mixed uniformly.
B: Components (13) to (19) are mixed uniformly.
C: Add B to A and emulsify at room temperature.
D: C is filled into a container to obtain a product.

  The eye color obtained as described above was excellent in the three-dimensional cosmetic effect due to dichroism, and was excellent in the uniformity and stability of the decorative film.

Example 18
Water-in-oil foundation (milky liquid):
An emulsion water-in-oil foundation was prepared by the following composition and production method.

(Composition) (%)
(1) Bengala 0.5
(2) Yellow iron oxide 2
(3) Black iron oxide 0.2
(4) Titanium oxide 5
(5) Dichroic pigment (obtained in Production Example 5) 3
(6) Sericite 5
(7) Synthetic phlogopite 5
(8) Inulin stearate ^{* 30} 1
(9) Neopentyl glycol dicaprate 15
(10) Decamethylcyclopentasiloxane 20
(11) Octyl methoxycinnamate 3
(12) Fragrance appropriate amount (13) Polyoxyethylene methyl polysiloxane copolymer ^{* 31} 2
(14) Nylon powder 1
(15) Preservative (paraoxybenzoic acid ester) 0.1
(16) Ethyl alcohol 7
(17) Purified water remaining amount (18) Sodium chloride 0.2
(19) Alkyl acrylate copolymer emulsion ^{* 2} 1
(20) Dipropylene glycol 1
* 2 Above
* 30 Leopard ISK2 (Chiba Flour Mills)
* 31 KF-6019 (Shin-Etsu Chemical Co., Ltd.)

(Production method)
A: (8) to (9) are heated to 80 ° C. and dissolved.
B: (1) to (7) are added to A and mixed and dispersed uniformly.
C: (10) to (13) are added to B and mixed.
D: (15) to (20) are mixed and dissolved, and (14) is added and mixed and dispersed.
E: D is added to C and emulsified at room temperature.
F: E is filled into a container to obtain a product.

  The foundation obtained as described above was excellent in the cosmetic effect of the three-dimensional effect due to dichroism, and was excellent in the uniformity and stability of the decorative film.

Example 19
Double-layer eye color:
An aqueous two-layer eye color was prepared by the following composition and production method.

(Composition) (%)
(1) Preservative (paraoxybenzoic acid ester) 0.1
(2) Glycerin 6
(3) Hydroxypropyl methylcellulose 0.2
(4) 1,3-butylene glycol 10
(5) Residual amount of purified water (6) Ethyl alcohol 15
(7) Silicone-treated iron oxide ^{* 26} 0.5
(8) Silicone titanium oxide ^{* 26} 1
(9) Synthetic phlogopite 3
(10) Silicone-treated mica titanium ^* 262
(11) Dichroic pigment (obtained in Production Example 8) 5
(12) Dichroic pigment (obtained in Production Example 15) 5
(13) Fragrance appropriate amount (14) (Acrylic / alkyl acrylate) copolymer 0.2
Emulsion ^{* 20}
(15) Triethanolamine 0.05
(16) Blue No. 205 0.002
* 20 Above
* 26 〃

(Production method)
A: (1) to (3) are mixed uniformly.
B: (4) to (16) are uniformly mixed and dispersed.
C: A and B are mixed uniformly.
E: Fill C into a container to make a product.

  The eye color obtained as described above was excellent in the three-dimensional cosmetic effect due to dichroism, and was excellent in the uniformity and stability of the decorative film.

Example 20
Water-in-oil lipstick (cream):
A creamy water-in-oil lipstick was prepared by the following composition and production method.

(Composition) (%)
(1) Dextrin palmitate ^{* 32} 6
(2) Diisostearyl malate 10
(3) Liquid paraffin 15
(4) Heavy liquid isoparaffin 10
(5) Tree 2 Triglyceryl ethyl hexanoate Residual amount (6) Dimethylpolysiloxane (10 cs) 20
(7) Preservative (paraoxybenzoic acid ester) 0.1
(8) Cetyl dimethicone copolyol ^{* 29} 1
(9) Dimethylpolysiloxane (100 cs) 2
(10) Silicone-treated mica titanium ^* 262
(11) Silylated Anhydrous Silicic Acid ^{* 27} 2
(12) Dichroic pigment (obtained in Production Example 5) 0.5
(13) Red No. 226 8
(14) Silicone-treated yellow iron oxide ^{* 26} 0.2
(15) Silicone-treated black iron oxide ^{* 26} 0.05
(16) Polyoxyethylene methylsiloxane
Polyoxypropylene oleylmethyl 2
Siloxane / dimethylsiloxane copolymer ^{* 33}
(17) Alkyl acrylate copolymer emulsion ^{* 2} 0.1
(18) Purified water 15
* 2 Above
* 26 〃
* 27 〃
* 29 〃
* 32 Leo Pearl KL2 (Chiba Flour Mills)
* 33 KF-6026 (Shin-Etsu Chemical Co., Ltd.)

(Production method)
A: (1) to (9) are heated and mixed at 90 ° C.
B: (10) to (16) are added to A and mixed and dispersed uniformly.
C: (17) and (18) are added to B and emulsified at room temperature.
D: A container was filled with C to obtain a product.

  The lipstick obtained as described above was excellent in the three-dimensional makeup effect due to dichroism, and excellent in the uniformity and stability of the cosmetic film.

Example 21
Water-based eyeliner:
A water-based eyeliner was prepared by the following composition and production method.

(Composition) (%)
(1) Polyoxyethylene alkyl (12-15) ether phosphoric acid 3
(2) Polyoxyethylene cetyl ether 0.1
(3) L-arginine 0.1
(4) Preservative (paraoxybenzoic acid ester) 0.1
(5) 1,3-butylene glycol 2
(6) Residual amount of purified water (7) Black iron oxide 5
(8) Dichroic pigment (obtained in Production Example 8) 5
(9) Dichroic pigment (obtained in Production Example 14) 10
(10) Silicic anhydride 3
(11) Alkyl acrylate copolymer emulsion ^{* 1} 2
(12) L-arginine 0.5
(13) Alkyl acrylate copolymer emulsion ^{* 2} 20
(14) Phenoxyethanol 0.2
(15) Ethyl alcohol 2
* 1 Above
* 2 〃

(Production method)
A: (1) to (6) are uniformly mixed.
B: (7) to (10) are added to A and dispersed uniformly.
C: (11) to (15) are added to B and mixed uniformly.
D: A container was filled with C to obtain a product.

  The eyeliner obtained as described above was excellent in the three-dimensional cosmetic effect due to dichroism, and excellent in the uniformity and stability of the decorative film.

Example 22
Water-in-oil mascara:
A water-in-oil mascara was prepared by the following composition and production method.

(Composition) (%)
(1) Pentaerythridic acid rosin acid 20
(2) Dextrin palmitate ^{* 32} 1
(3) Carnauba wax 3
(4) Organically modified bentonite ^{* 11} 4
(5) Light liquid isoparaffin remaining amount (6) Lecithin 0.3
(7) Black iron oxide 8
(8) Talc 5
(9) Dichroic pigment (obtained in Production Example 12) 5
(10) Preservative (paraoxybenzoic acid ester) 0.5
(11) Alkyl acrylate copolymer emulsion ^{* 2} 1
(12) Vinyl acetate polymer emulsion ^{* 4} 1
(13) Purified water 3
* 2 Above
*Four 〃
* 11 〃
* 32 〃

(Production method)
A: Components (1) to (6) are mixed at 110 ° C., and components (7) to (10) are added and mixed uniformly.
B: Components (11) to (13) are added to A and emulsified at room temperature.
C: B is filled into a container to obtain a product.

  The water-in-oil mascara obtained as described above was excellent in steric cosmetic effect due to dichroism, and excellent in uniformity and stability of the decorative film.

  The water-containing cosmetic of the present invention is stable in terms of physical properties because the water-containing cosmetic of the present invention uses a polymer compound that forms a uniform cosmetic film and a pigment having high water resistance and vivid dichroism. It is a cosmetic that is highly dispersible and dispersible, and that can impart a stereoscopic effect due to vivid dichroism in terms of makeup effect.

  Therefore, this product can be used for various types of water-containing cosmetics such as O / W type, W / O type, water-based type, multilayer type, mascara, eyeliner, eye color, foundation, makeup base, blusher, lipstick, tan. It can be advantageously used as a cosmetic such as a stopper or body lotion.

1 ... Plate-like particle base material (mica, glass powder, aluminum flakes)
2… Low-order titanium oxide layer 3…… Incident light (visible light)
4 ... Transmitted light (light that lost a specific wavelength)
5 ... Reflected light (reflected light from the surface of the lower titanium oxide layer)
6 ... Reflected light (light in which transmitted light 4 is reflected by substrate 1)
7…… Absorbed light (light absorbed by the lower titanium oxide layer)

Claims (11)

The following components (A) and (B):
(A) Aqueous dispersion of polymer (B) A pigment having a dichroism having different appearance color and interference color is formed by forming a monolayer of low-order titanium oxide on plate-like particles. Water-containing cosmetics. The low-order titanium oxide monolayer of the component (B) has the following composition formula
TiO _X
(Where X means a number greater than 1.0 and less than 2.0)
The water-containing cosmetic according to claim 1, which is a low-order titanium oxide represented by the formula:   The water-containing cosmetic according to claim 1 or 2, wherein the low-order titanium oxide single layer of component (B) is a single layer containing titanium oxynitride.   The water-containing cosmetic according to any one of claims 1 to 3, wherein the plate-like particles of the component (B) are natural or synthetic phlogopite, aluminum flakes or glass powder.   The hydrated cosmetic according to any one of claims 1 to 4, wherein the dichroic pigment of the component (B) has an L value of 25 or more in Hunter's L, a, b color system.   The dichroic pigment of the component (B) has a b value of -3.0 or less or 3.0 or more in Hunter's L, a, and b color systems. Water-containing cosmetics.   The water-containing cosmetic according to any one of claims 1 to 6, wherein the polymer aqueous dispersion of the component (A) has a property of forming a film.   The water-containing cosmetic according to any one of claims 1 to 7, wherein the polymer aqueous dispersion of the component (A) has a property of thickening by neutralization with an alkali agent.   The polymer of component (A) was obtained by polymerizing one or more monomers selected from acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, vinyl acetate, styrene and vinyl pyrrolidone. The water-containing cosmetic according to any one of claims 1 to 8, which is a product.   The polymer of component (A) is one or more selected from alkyl acrylate copolymers, styrene / alkyl acrylate copolymers, vinyl acetate polymers, and vinylpyrrolidone / styrene copolymers. Item 10. A water-containing cosmetic according to any one of Items 1 to 9.   The polymer of the component (A) is obtained by polymerizing one or more monomers selected from acrylic acid and methacrylic acid. Water-containing cosmetics as described in 1.

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