Pigment made of particles mainly composed of calcium titanium composite oxide and use thereof

Abstract

To provide a pigment that allows selective passage of light in a warm-color range, and can be used as an alternative material for titanium oxide.SOLUTION: This pigment is composed of particles having a lattice constant a of 5.4700-5.5100 Å and containing a calcium-titanium composite oxide as the main component. This pigment can be used for cosmetics, for example.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a pigment comprising particles containing calcium titanium composite oxide as a main component, and in particular to said pigment having a warm color light transmitting effect. [Background technology]

[0002] Conventionally, makeup cosmetics such as foundations have been used as cosmetics that change the skin tone by adding colorants such as titanium dioxide pigments, which have high coloring power, and other inorganic pigments and organic pigments in order to cover redness, dullness, spots, freckles, and the like caused by the skin and to create a uniform and beautiful looking skin.

[0003] In order to make the skin tone uniform, pigments with high coloring and hiding power are generally used for the titanium dioxide, and pigment-grade titanium dioxide with a rutile crystal form and a primary particle size of 0.1 μm to 0.3 μm is widely used. However, when applying makeup to the skin using a foundation containing this titanium dioxide, the intensity of the white scattered light tends to become too strong, causing the makeup finish to look pale and unnatural, which is a problem known as the white cast phenomenon.

[0004] One of the means for preventing the white cast phenomenon is to use rutile titanium dioxide of a specific shape to balance the coloring power, hiding power, and the intensity of the white scattered light. For example, Japanese Patent No. 4684970 (Patent Document 1) describes blending in cosmetics an aggregate of fan-shaped rutile titanium dioxide particles in which rod-shaped primary particles are aggregated and / or bonded. In addition, Japanese Patent No. 6258462 (Patent Document 2) describes blending in cosmetics a rutile titanium dioxide powder obtained by firing rutile titanium dioxide having needle-shaped protrusions on the particle surface.

[0005] Another method for preventing the white cast phenomenon is to utilize the scattering of light in the warm color region inside the skin. Patent No. 5363696 (Patent Document 3) describes that a study was conducted focusing on light propagating inside bare skin. Specifically, in a light scattering medium such as skin, a part of the light irradiated onto the skin is transmitted inside and reflected by an internal scatterer, so that it is emitted from a part different from the irradiated part. However, it describes that by using a coloring material with a low light absorption rate in the wavelength range of 630 nm to 700 nm in a skin cosmetic, the distribution of the above-mentioned emission parts becomes close to that of bare skin, and a natural texture can be obtained.

[0006] However, in recent years, the possibility of health damage from titanium dioxide (IV), including rutile-type titanium dioxide, cannot be denied, and there has been a growing trend, mainly in Europe, to reduce the amount of titanium dioxide used and to use alternative materials. JP-A-5-339121 (Document 4) proposes the use of compounds having a perovskite crystal structure, such as calcium titanate, strontium titanate, barium titanate, calcium zirconate, and strontium zirconate, as pigments other than rutile-type titanium dioxide. JP Patent No. 3464564 (Patent Document 5) also describes an ultraviolet protection cosmetic composition using particles of a complex oxide having a perovskite structure or a solid solution thereof. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 4684970 [Patent Document 2] Patent No. 6258462 [Patent Document 3] Patent No. 5363696 [Patent Document 4] Japanese Patent Application Publication No. 5-339121 [Patent Document 5] Patent No. 3464564 Summary of the Invention [Problem to be solved by the invention]

[0008] However, in Patent Document 4, only the smoothness, adhesion, and covering power are discussed, and the white cast phenomenon is not considered. Patent Document 4 also only describes blending a powder of a compound having a perovskite crystal structure, an average particle size of 0.05 to 15 μm, and particles having an equiaxed shape into a cosmetic, but does not describe a specific method for producing such a powder. Patent Document 5 also describes the synthesis of a double oxide powder represented by CaTiO3, but does not describe a specific example of blending this powder into a cosmetic, and although it describes the UV protection effect, safety, and stability of a cosmetic containing a double oxide having a perovskite crystal structure, it does not consider how to deal with the white cast phenomenon.

[0009] Although the development of titanium dioxide substitutes has progressed, the development of cosmetics that achieve a natural finish is still in its infancy. In particular, no titanium dioxide substitute has been obtained that utilizes the effect of selectively transmitting light in the warm color range.

[0010] An object of the present invention is to provide a pigment which selectively transmits light in the warm color region and can be used as an alternative material to titanium oxide. [Means for solving the problem]

[0011] The inventors focused on calcium titanium composite oxide as an alternative material to titanium oxide, and as a result of extensive research, discovered that a pigment composed of particles mainly composed of calcium titanium composite oxide having a specific crystal structure selectively transmits light in the warm color range.

[0012] The present invention includes, but is not limited to, the following: [1] A pigment having a lattice constant a of 5.4700 Å or more and 5.5100 Å or less, composed primarily of particles of calcium titanium oxide. [2] The pigment according to [1], wherein the calcium titanium composite oxide is an orthorhombic calcium titanium composite oxide. [3] The pigment according to [1] or [2], in which, when the height of the diffraction line of the (1 2 1) plane appearing in the diffraction angle range of 32.50° to 33.50° in X-ray diffraction measurement is taken as 100.0, the height of the diffraction line of the (2 0 2) plane appearing in the diffraction angle range of 46.75° to 47.75° is 50.0 or less. [4] Specific surface area is 3.0 m 2 / g or more. [5] The pigment according to any one of [1] to [4], wherein in X-ray diffraction measurement, when the integrated diffraction intensity of the (1 2 1) plane appearing in the diffraction angle range of 32.50° to 33.50° is taken as 100.0, no diffraction lines appearing in the diffraction angle range of 24.75° to 28.00° have an integrated diffraction intensity of more than 12.00. [6] The pigment according to any one of [1] to [5], having an inorganic and / or organic coating layer on at least a portion of the surface of the particle. [7] The pigment according to any one of [1] to [6], wherein the particle shape is approximately spherical. [8] The pigment according to any one of [1] to [6], wherein the particle shape is rectangular. [9] The pigment according to any one of [1] to [8], wherein the crystallite diameter of the particles is 250 Å or more and 600 Å or less.

[10] A cosmetic preparation comprising the pigment according to any one of [1] to [9].

[11] A film composition comprising the pigment according to any one of [1] to [9].

[12] A resin composition comprising the pigment according to any one of [1] to [9].

[13] A paint comprising the pigment according to any one of [1] to [9].

[14] An ink comprising the pigment described in any one of [1] to [9]. Effect of the Invention

[0013] The pigment obtained by the present invention, which is composed of particles containing calcium titanium composite oxide as a main component, can selectively transmit light in the warm color range. The pigment composed of particles containing the calcium titanium composite oxide as a main component obtained by the present invention, when used as an ingredient in cosmetics to be applied to the skin, such as foundation, can realize a natural finish by transmitting light in the warm color region that is scattered inside the skin.

[0014] The pigment obtained by the present invention can also be used as a substitute for titanium oxide. The calcium titanium composite oxide used in the pigment of the present invention has an ultraviolet ray shielding effect equivalent to that of titanium oxide, and can therefore be used in sun creams and the like.

[0015] The pigment obtained by the present invention can be used in a wide range of applications other than cosmetics by utilizing its function of transmitting light in the warm color region. Examples of such applications include, but are not limited to, adding the pigment to transparent materials to use them in parts of optical devices, adding the pigment to resins to form resin compositions having a warm color light transmitting effect, and adding the pigment to paints to use them in residential paints. [Brief description of the drawings]

[0016] [Figure 1] This is the X-ray diffraction pattern of calcium titanium composite oxide, represented by the chemical formula CaTiO3, registered on the PDF card. [Diagram 2] 1 is an X-ray diffraction pattern of the pigment composed of particles containing calcium titanium composite oxide as a main component obtained in Example 4. [Diagram 3] This is the portion of the X-ray diffraction pattern of calcium titanium composite oxide, represented by the chemical formula CaTiO3, registered on the PDF card, where the diffraction angle 2θ is between 45.0° and 50.0°. [Figure 4] Of the X-ray diffraction pattern of the pigment obtained in Example 4, this is the portion where the diffraction angle 2θ is 45.0° or more and 50.0° or less. [Diagram 5] 1 is a transmission electron microscope photograph of the pigment obtained in Example 4. [Figure 6] 1 is a transmission electron microscope photograph of the pigment obtained in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention relates to a pigment having a lattice constant a of 5.4700 Å or more and 5.5100 Å or less, which is composed of particles containing calcium titanium composite oxide as a main component. "A pigment composed of particles mainly composed of calcium titanium composite oxide" means that the individual particles constituting the pigment are mainly particles of calcium titanium composite oxide. Specifically, it means that 850 g / kg or more, preferably 900 g / kg or more of the individual particles constituting the pigment are particles of calcium titanium composite oxide. The individual particles constituting the pigment of the present invention may contain, in addition to calcium titanium composite oxide, unreacted materials during the synthesis reaction of calcium titanium composite oxide, unavoidable impurities derived from the raw materials, and inorganic and / or organic substances derived from the coating layer.

[0018] The calcium titanium composite oxide, which is the main component of the particles constituting the pigment of the present invention, is preferably an orthorhombic calcium titanium composite oxide. "Orthorhombic calcium titanium composite oxide" refers to a calcium titanium composite oxide in which the angles between two different crystal axes are all 90°.

[0019] The pigment of the present invention, which is made of particles mainly composed of calcium titanium composite oxide, is characterized by a larger lattice constant a than that of a general calcium titanium composite oxide whose chemical formula is CaTiO3, when the space group of the perovskite crystal structure is Pnma(62). The reason why the lattice constant a selectively transmits light in the warm color region as the lattice constant a increases is not clear, but it is thought to be for the following reason. When the lattice constant a increases, the crystal arrangement becomes disordered, and light in the low wavelength region in particular tends to attenuate. As a result, light in the long wavelength region (i.e., light in the warm color region) is selectively transmitted. The lattice constant a is preferably 5.4700 Å or more. It is more preferable that it is 5.4725 Å or more, and even more preferable that it is 5.4750 Å or more. On the other hand, when the lattice constant a increases further, the values ​​of the lattice constant b and the lattice constant a become closer, and the regularity of the crystal packing improves again, so the function of selectively transmitting light in the warm color region is lost. The lattice constant a is preferably 5.5100 Å or less, more preferably 5.5050 Å or less, and even more preferably 5.5030 Å or less.

[0020] Furthermore, in the pigment of the present invention, the lattice constant a is larger than that of a typical calcium titanium composite oxide whose chemical formula is CaTiO3, and as a result, the position of the diffraction lines of each crystal plane changes in X-ray diffraction measurement by the powder method. Specifically, the diffraction lines originating from the crystal plane with Miller indices (2 0 2) shift to the lower angle side. On the other hand, the diffraction lines originating from the crystal plane with Miller indices (0 4 0) do not shift. As a result, when the diffraction angle 2θ is between 46.75° and 47.75°, the diffraction lines of the (2 0 2) plane and the (0 4 0) plane, which are observed overlapping at the same position, are clearly separated, and the height of the highest part of the diffraction lines becomes smaller than before separation. Specifically, in the present invention, when the height of the diffraction line of the (1 2 1) plane, which is the maximum diffraction line of the calcium titanium composite oxide and appears in the range of a diffraction angle 2θ of 32.50° to 33.50°, is taken as 100.0, the height of the diffraction line of the (2 0 2) plane (hereinafter referred to as the "XRD diffraction line height ratio") is preferably 50.0 or less, more preferably 48.0 or less, and even more preferably 46.0 or less.

[0021] The pigment of the present invention preferably has a large specific surface area. Although the reason is not clear, it is thought to be as follows. The surface of the particles whose main component is calcium titanium composite oxide used in the present invention has irregularities and cracks. Light with short wavelengths is easily scattered by these irregularities and cracks, whereas light in the warm color region with long wavelengths is not significantly affected. Therefore, the more irregularities and cracks there are in the particles, the easier it is for light in the warm color region to selectively transmit through them. The specific surface area is 3.0 m 2 / g or more is preferable, and 3.5m 2 The specific surface area of ​​the pigment of the present invention is not particularly limited, but is preferably 200 m 2 / g or less is preferable because it provides advantages such as easier control of the properties of the cosmetic preparation since the oil absorption is not too large.

[0022] Since the pigment of the present invention, which is composed of particles mainly composed of calcium titanium composite oxide, may be used as an alternative material to cosmetics using titanium oxide, it is desirable that the content of titanium oxide is small. In order to calculate the exact content of titanium oxide in calcium titanium composite oxide, it is necessary to mix the calcium titanium composite oxide of the present invention with titanium oxide, perform X-ray diffraction measurement by powder method, and create a calibration curve, but this method requires a lot of time and cost. Therefore, as a simpler method for confirming that the content of titanium oxide is small, in X-ray diffraction measurement by powder method, the integrated diffraction intensity ratio of the diffraction line of the (1 2 1) plane, which has the highest integrated diffraction intensity and appears at 32.50° to 33.50° in calcium titanium composite oxide, and the diffraction line, which has the highest integrated diffraction intensity and appears at 24.75° to 28.00° in rutile, anatase, and brookite titanium oxide, is compared. From the viewpoint of a small titanium oxide content, in the present invention, when the integrated diffraction intensity of the diffraction line of the (1 2 1) plane appearing at 32.50° to 33.50° is taken as 100.0, it is preferable that no diffraction line with an integrated diffraction intensity of more than 12.00 appears in the range of 24.75° to 28.00°. When the integrated diffraction intensity of the diffraction line of the (1 2 1) plane appearing at 32.50° to 33.50° is taken as 100.0, the integrated diffraction intensity ratio of the diffraction line appearing at 24.75° to 28.00° (hereinafter referred to as "XRD titanium oxide integrated diffraction intensity") is more preferably 11.00 or less, and even more preferably 8.50 or less. In addition, the diffraction line of the (1 1 1) plane of calcium titanium composite oxide is present between 24.75° and 28.00°, and when the integrated intensity of the diffraction line of the (1 2 1) plane is taken as 100.0, the integrated diffraction intensity of this diffraction line of the (1 1 1) plane is about 3. Therefore, even if the sample does not contain any titanium oxide, the integrated diffraction intensity will not be zero.

[0023] The pigment obtained by the present invention is a particle shapeThe shape of the particles may be roughly spherical or rectangular. The term "roughly spherical" refers to particles in which the primary particles or secondary particles grow isotropically or form aggregates isotropically, as shown in FIG. 5, have an irregular or nearly spherical shape, and have a circularity of 0.790 or more as calculated by the method described below. For example, the term "roughly spherical" does not include particles that are rectangular, elongated, needle-like, or have protrusions with a length equal to or greater than the diameter of the center, as shown in FIG. 6. The term "rectangular" refers to particles in which the primary particles or secondary particles grow more in a specific axial direction than the other two axial directions, or form aggregates more in a specific axial direction, as shown in FIG. 6, have a shape close to a rectangular parallelepiped, and have a circularity of less than 0.790 as calculated by the method described below. The term "rectangular" does not necessarily mean that the particles are perfect rectangular parallelepipeds (all six faces are rectangular or square). Furthermore, the shape of the particle cross section perpendicular to the major axis direction does not have to be rectangular or square, and all cross sections do not have to have the same shape.

[0024] The phrase "particle shape is approximately spherical" or "particle shape is rectangular" means that 80% or more, and preferably 85% or more by number of the particles constituting the pigment of the present invention are approximately spherical or rectangular, respectively.

[0025] In general, when the crystallite size of the calcium titanium composite oxide, which is the main component of the particles constituting the pigment of the present invention, is small, the crystal growth tends to be insufficient and the characteristics tend to be unstable. Therefore, the crystallite size of the particles constituting the pigment by X-ray diffraction is preferably 250 Å or more, more preferably 300 Å or more. From the viewpoint of the touch when used in cosmetics, the upper limit of the crystallite size is preferably 600 Å or less. The crystallite size can be measured by the method described below.

[0026] The pigment of the present invention preferably has a small particle size distribution. If the particle size distribution is large, the particles become non-uniform, and the lubricity tends to deteriorate when used in a cosmetic. From the viewpoint of the lubricity when used in a cosmetic, the particle size distribution calculated by the method described below is preferably 10.00 or less, more preferably 8.00 or less, and even more preferably 5.00 or less.

[0027] The pigment of the present invention preferably has good lubricity. Pigments with a small particle size distribution tend to have good lubricity. In general, between rectangular parallelepiped and roughly spherical particles, roughly spherical particles tend to have better lubricity. Therefore, from the viewpoint of lubricity, it is preferable that the circularity of the particles is large.

[0028] The pigment of the present invention preferably has a warm color light transmission effect of 0.56 or more, calculated by the method described below. If the warm color light transmission effect is 0.56 or more, when used in a cosmetic, the reflection of the warm color region inside the skin is sufficient, and a natural finish is obtained. There is no particular upper limit for the warm color light transmission effect, but the theoretical maximum value of the warm color light transmission effect calculated by the evaluation method used in the present invention is 1.00.

[0029] The color of the pigment of the present invention is not particularly limited, however, since it may be used as a substitute for titanium oxide, it is preferably white like titanium oxide. The pigment of the present invention may have a coating layer made of an inorganic substance on the surface of the particle in order to impart hydrophobicity, optical properties, etc. Also, a coating layer made of an organic substance may be present. Two or more coating layers may be present, or both an inorganic layer and an organic layer may be included.

[0030] An example of the method for producing the pigment of the present invention will be described below. However, the method for producing the pigment of the present invention is not limited to the following. The pigment of the present invention, which is composed of particles mainly composed of calcium titanium composite oxide, is produced by a method called normal pressure heating reaction method, which includes mixing an acid peptized product of hydrolysis of titanium compound, a water-soluble compound containing calcium, and an alkali at normal pressure, and heating the mixture to 70°C to 100°C to synthesize calcium titanium composite oxide. The acid peptized product of hydrolysis of titanium compound is typically metatitanic acid obtained by a method called sulfuric acid method. After obtaining calcium titanium composite oxide by the above method, it is preferable to carry out a decalcification treatment.

[0031] (Sulfuric acid method) Metatitanic acid, represented by the chemical formula TiO(OH)2, can be obtained by dissolving ilmenite ore in concentrated sulfuric acid and removing the resulting iron sulfate components.

[0032] (Normal pressure heating reaction method) An example of the acid peptized product of the hydrolyzate of a titanium compound is metatitanic acid. As metatitanic acid, it is preferable to use a compound having a sulfur content of 15 g / kg or less, preferably 10 g / kg or less in terms of SO3, as the hydrolyzate of a titanium compound, and to use the hydrolyzate which is peptized by adjusting the pH of the hydrolyzate to 0.8 to 1.5 using hydrochloric acid. This makes it possible to obtain calcium titanium composite oxide particles with a small particle size distribution. If the sulfur in metatitanic acid exceeds 15 g / kg in terms of SO3, peptization may not proceed. In addition to hydrochloric acid, nitric acid, hydrogen bromide, hydrogen iodide, formic acid, acetic acid, etc. can also be used. In addition, instead of the acid peptized product of the hydrolyzate of a titanium compound, the peptized product neutralized with an alkali can also be used.

[0033] The alkali to be mixed with the acid peptized product of the hydrolyzate of the titanium compound may be a caustic alkali, of which sodium hydroxide is preferred. The concentration of the alkali in the mixture in the normal pressure heating reaction method is preferably 0.1 mol / L or more, more preferably 0.5 mol / L or more and 3.6 mol / L or less.

[0034] Factors that affect the crystallinity and particle size of the pigment composed of particles mainly composed of calcium titanium composite oxide obtained by the normal pressure heating reaction method include the concentration and mixing ratio of the raw materials, the concentration of the alkali, the reaction temperature, and additives. The mixing ratio of the acid peptized product of the hydrolyzed titanium compound and the water-soluble compound containing calcium is preferably such that the amount of substance of calcium (Ca element) is 1.00 to 1.60 times the amount of substance of titanium (Ti element), more preferably 1.10 to 1.50 times. Since the acid peptized product of the hydrolyzed titanium compound has low solubility in water, when the amount of substance of calcium is smaller than the amount of substance of titanium, not only calcium titanium composite oxide particles but also unreacted titanium oxide tends to remain in the reaction product. The concentration of the acid peptized product of the hydrolyzed titanium compound in the mixture in the normal pressure heating reaction method is preferably 0.5 mol / L to 1.5 mol / L in terms of Ti, more preferably 0.7 mol / L to 1.4 mol / L.

[0035] The higher the reaction temperature, the better the crystallinity of the product. However, since a pressure vessel is required for a reaction at a temperature above 100°C, a practical range of 70°C to 100°C is appropriate, and a range of 70°C to less than 100°C is also acceptable.

[0036] When the particle shape is to be approximately spherical, one or more sugars selected from monosaccharides and disaccharides such as glucose and maltose may be added as additives during the normal pressure heating reaction. When such sugars are added, the total concentration of these sugars is preferably 0.0115 mol / mol or more and 0.0195 mol / mol or less relative to the amount of calcium added during the normal pressure heating reaction. When the concentration is 0. 0 If it is less than 115 mol / mol, the particles will not be approximately spherical, and 0. 0 If it is greater than 195 mol / mol, titanium oxide tends to remain. In general, the more sugar is added, the smaller the particles tend to be, but when used as a cosmetic, it is preferable that the particles are not too small, and for that reason the concentration of added sugar is set at 0. 0It is preferably 195 mol / mol or less.

[0037] During the normal pressure heating reaction, one or more compounds selected from aliphatic hydroxy acid compounds such as citric acid and isocitric acid may be added. When an aliphatic hydroxy acid compound is added, the aspect ratio of the particles increases. The amount of aliphatic hydroxy acid added is preferably 0.0180 mol / mol or less relative to the amount of calcium added during the normal pressure heating reaction.

[0038] (Calcium removal treatment) After synthesizing calcium titanium composite oxide by normal pressure heating reaction, it is preferable to carry out a decalcification treatment to prevent unreacted calcium from remaining and interfering with the surface treatment. The decalcification treatment involves adjusting the pH to 2.5 to 7.0, more preferably 4.5 to 6.0, using hydrochloric acid. In addition to hydrochloric acid, nitric acid, acetic acid, etc. may be used. If the pH is higher than 7.0, the unreacted calcium cannot be completely removed. On the other hand, if the pH is lower than 2.5, the calcium in the calcium titanium composite oxide may flow out into the acid, and titanium oxide may be partially generated.

[0039] (Surface coating treatment) In the present invention, the pigment consisting of particles mainly composed of calcium titanium composite oxide may have an inorganic coating layer such as a hydrous oxide or oxide of metals such as aluminum, silicon, zinc, titanium, zirconium, iron, cerium, and tin on at least a part of the particle surface for the purpose of improving the dispersion stability and durability in a dispersion medium when producing a cosmetic product. Metal salts other than those mentioned above may be used as the inorganic coating. In addition, an organic coating layer may be applied to at least a part of the particle surface of the pigment of the present invention in order to perform surface modification represented by hydrophobic treatment. Examples of organic coatings include silicone compounds such as dimethylpolysiloxane and methylhydrogenpolysiloxane, coupling agents such as silane-based, aluminum-based, titanium-based, and zirconium-based, fluorine compounds such as perfluoroalkyl phosphate compounds, hydrocarbons, lecithin, amino acids, polyethylene, wax, and metal soaps. A combination of these treatments may be performed, and the order of the treatments is not particularly limited.

[0040] (Pigment Uses) The pigment of the present invention can selectively transmit light in the warm color region, and when used as a cosmetic material to be applied to the skin, the transmitted light in the warm color region is scattered inside the skin, suppressing white cast and realizing a natural finish. Therefore, the pigment of the present invention can be suitably used as a cosmetic material. A cosmetic material containing the pigment of the present invention is one aspect of the present invention. From another perspective, the use of the pigment made of particles mainly composed of the calcium titanium composite oxide of the present invention as a cosmetic material is also one aspect of the present invention, and the use of the pigment made of particles mainly composed of the calcium titanium composite oxide of the present invention to suppress the white cast phenomenon in a cosmetic material is also one aspect of the present invention. Here, the "white cast phenomenon" refers to a phenomenon in which the finish of makeup looks pale and unnatural when the intensity of white scattered light is high when the cosmetic material is applied to the skin. "Suppressing the white cast phenomenon" refers to the fact that the pigment of the present invention blended in the cosmetic material selectively transmits light in the warm color region, and the transmitted light in the warm color region is scattered inside the skin, thereby suppressing, reducing, or mitigating the above-mentioned white cast phenomenon, resulting in a natural makeup finish. It should be noted that "light in the warm color range" refers to light with a wavelength of 570 nm or more and 780 nm or less.

[0041] The pigment of the present invention can also be used in a wide range of applications outside of cosmetics, taking advantage of its function of transmitting light in the warm color region. Examples of such applications include, but are not limited to, adding it to a transparent material to form a film for use in optical equipment parts, adding it to a resin to use in a sunroof, etc., and adding it to a paint to apply a coating that transmits light in the warm color region. The pigment obtained by the present invention can also be used as a substitute for titanium oxide.

[0042] (Cosmetics) When the pigment of the present invention is used as a cosmetic, typically, the surface is coated as described above, and then the pigment may be mixed with inorganic pigments and / or organic pigments according to a known method. The content of the pigment of the present invention in the cosmetic varies depending on the type of cosmetic, and is not particularly limited. For example, the pigment may be used in an amount of about 1 g / kg to 900 g / kg for powder-type cosmetics, 1 g / kg to 500 g / kg for oil-based cosmetics, and 1 g / kg to 150 g / kg for emulsion-type or cream-type cosmetics, but is not limited to these ranges.

[0043] When the pigment of the present invention is used as a cosmetic, inorganic pigments and / or organic pigments that can be mixed with the pigment of the present invention may be inorganic pigments and organic pigments that are used in ordinary cosmetic products, as necessary. Examples of such inorganic pigments include titanium oxide, zinc oxide, iron oxide such as red iron oxide, cerium oxide, alumina, zirconium oxide, magnesium oxide, chromium oxide, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium sulfate, magnesium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, talc, mica, surface-treated mica, micaceous synthetic pigments, sericite, zeolite, kaolin, bentonite, clay, silicic acid, boron nitride, bismuth oxychloride, hydroxyapatite, ultramarine, Prussian blue, and dehydrates and complexes thereof. Similarly, examples of organic pigments include silicone powder, silicone elastic powder, polyurethane powder, cellulose powder, nylon powder, urethane powder, silk powder, polymethyl methacrylate (hereinafter referred to as "PMMA") powder, polyethylene powder, starch, carbon black, metal soap such as zinc stearate, and complexes thereof. Tar dyes and various natural dyes can also be used.

[0044] The method for producing the cosmetic is not particularly limited, and a known method may be used. The formulation of the cosmetic is also not particularly limited, and may be, for example, any of powder, powder solid, cream, milky liquid, lotion, oily liquid, oily solid, paste, etc. For example, the cosmetic may be a makeup cosmetic, skin care cosmetic, hair care cosmetic, etc., such as a makeup base, foundation, concealer, face powder, control color, sunscreen cosmetic, lipstick, blusher, lip cream, lip color, lip gloss, eye shadow, eyeliner, mascara, cheek color, nail polish, body powder, perfume powder, baby powder, etc. In terms of maximizing the light transmission effect and smoothness of the warm color region due to the pigment of the present invention, it is preferable to use it in a makeup cosmetic to be applied to the skin.

[0045] In addition to the above-mentioned components, the cosmetic preparation of the present invention may contain other components in the quantitative and qualitative ranges that do not impair the effects of the present invention, depending on the purpose. For example, oily components, pigments, pH adjusters, moisturizers, thickeners, surfactants, dispersants, stabilizers, colorants, preservatives, antioxidants, sequestering agents, astringents, anti-inflammatory agents, UV absorbers, fragrances, some medicines, etc. may be appropriately blended depending on the purpose.

[0046] The pigment of the present invention can be used in fields other than cosmetics, such as film compositions, resin compositions, paints, and inks. That is, a film composition, resin composition, paint, or ink containing the pigment of the present invention is one aspect of the present invention. From another perspective, the use of the pigment consisting of particles mainly composed of the calcium titanium composite oxide of the present invention in a film composition, resin composition, paint, or ink is also one aspect of the present invention. For example, the use of the pigment consisting of particles mainly composed of the calcium titanium composite oxide of the present invention for producing a film composition, resin composition, paint, or ink that transmits light in the warm color region well can also be said to be one aspect of the present invention.

[0047] The pigment of the present invention can be used as one of the materials of the film composition. The film composition containing the pigment of the present invention can be used, specifically but not limited to, in optical instruments, solar power generation devices, etc. The film composition is mainly produced from resins such as polyethylene terephthalate, polypropylene, polyvinyl alcohol, and fluororesin, glass, porous materials, and biological materials. The film composition is produced by a known method. For example, a resin is dissolved in a solvent such as an organic solvent or water, mixed with the pigment of the present invention previously dispersed in the solvent, poured into a mold, and dried to obtain a film composition containing the material of the present invention. A dispersant, other pigments or colorants, antistatic agents, etc. can be used in combination. The pigment of the present invention is not limited to this range, but it is preferable to add it so that the amount of the pigment is 1 g / kg or more and 250 g / kg or less in the obtained film composition. By using the pigment of the present invention, a film composition that selectively transmits light in the warm color region can be obtained.

[0048] The pigment of the present invention can be used as one of the materials of a resin composition. The resin composition containing the pigment of the present invention can be used for sunroofs, resin containers, etc., but is not limited thereto. As the resin, any of thermoplastic resins such as polyethylene and polypropylene, and thermosetting resins such as polycarbonate can be used. The resin composition is produced by a known method. For example, a monomer and the pigment of the present invention are dispersed in a solvent such as an organic solvent or water, a polymerization initiator is added, and the mixture is heated, washed, and dried to obtain a resin composition containing the pigment of the present invention. A flame retardant, a filler, etc. can be used in combination with the pigment of the present invention. The pigment of the present invention is not limited to this range, but it is preferable to add the pigment to the obtained resin composition so that the amount of the pigment is 1 g / kg or more and 350 g / kg or less. By using the pigment of the present invention, a resin composition that transmits light in the warm color region or a white resin composition with warm light can be obtained.

[0049] The pigment of the present invention can be used as one of the materials for paints. The paint containing the pigment of the present invention can be used for residential paints in cold regions, but is not limited thereto. The pigment of the present invention can be used for both water-based paints and oil-based paints. The paint can be obtained from a resin such as an acrylic resin, a urethane resin, or a polyvinyl alcohol, a solvent such as toluene, ethanol, or water, and a colorant such as the pigment of the present invention. The paint is manufactured by a known method. For example, a paint containing the pigment of the present invention can be obtained by adding a hardener to a resin, and then adding the pigment obtained by the present invention and a solvent and stirring the mixture. An anti-settling agent, a preservative, and other pigments can be used in combination as desired. The pigment of the present invention is not limited to this range, but is preferably added so that the amount of the pigment is 1 g / kg or more and 700 g / kg or less in the dried coating film after use. By using the pigment of the present invention, a residential paint that transmits light in the warm color region well and makes it easier to raise the temperature inside the room can be obtained.

[0050] The pigment of the present invention can be used in ink. The ink containing the pigment of the present invention can be used in special inks for printing on films, glass surfaces, etc., but is not limited thereto. The ink can be obtained from a colorant, such as the pigment obtained in the present invention, a resin such as an acrylic resin, and a solvent such as a ketone, a hydrocarbon, or water. The ink is produced by a known method. For example, the ink can be obtained by dispersing and mixing the colorant, the resin, and the solvent. A pH adjuster, a surfactant, a preservative, and a pigment other than the pigment obtained in the present invention can be used in combination. The pigment of the present invention is not limited to this range, but it is preferable to add it to the obtained ink so that it is 1 g / kg or more and 600 g / kg or less. By using the pigment of the present invention, it is possible to print on a transparent substrate such as vinyl or glass, and to give it a beauty that has not been achieved with previous white pigments.

[0051] In addition to the above, the pigment of the present invention can be used in applications such as paper, toner additives, coating tools, textile products, packaging materials, films, and coating materials. Before describing the examples, the test methods used in the present invention will be described.

[0052] (Lattice constant a) X-ray diffraction measurements were performed using the powder method with an X-ray diffractometer RINT-TTR III manufactured by Rigaku Corporation. The amount of sample was crushed in a mortar and packed in a cell at approximately 1.5g ± 0.2g. The start angle was 5.0000°, the end angle was 90.0000°, the sampling width was 0.0100°, the scan speed was 10.0000° / min, the divergence slit was 0.5°, the scattering slit was 0.5°, the receiving slit width was 0.15mm, and the characteristic X-ray was generated using copper as the cathode and the wavelength was 0.15418nm. The obtained X-ray diffraction pattern was smoothed, background processed, and peaks were detected using analysis software MDI JADE7 manufactured by Material Data Corporation, and the lattice constant a was calculated.

[0053] (XRD diffraction line height ratio and XRD titanium oxide integrated diffraction intensity) The X-ray diffraction pattern measured by the above method was subjected to background processing, smoothing and peak detection using powder X-ray analysis software PDXL2 manufactured by Rigaku Corporation, and the height of the maximum part of the maximum diffraction line in the range of diffraction angle 2θ of 32.50° to 33.50° was calculated as 100.0, and this was defined as the XRD diffraction line height ratio. In addition, the integrated diffraction intensity of the maximum diffraction line appearing at a diffraction angle 2θ of 24.75° to 28.00° was calculated as the XRD titanium oxide integrated diffraction intensity, when the integrated diffraction intensity of the maximum diffraction line in the range of diffraction angle 2θ of 32.50° to 33.50° was set to 100.0.

[0054] (Crystallite size) The half-width of the diffraction line of the (1 2 1) plane obtained from the X-ray diffraction pattern measured by the above method was introduced into the following Sherrer equation to obtain the crystallite diameter D 121 was calculated: D 121 = kλ / βcosθ In the formula, the constant k is 0.9, λ is the wavelength of the X-ray, β is the half-width of the diffraction line of the (1 2 1) plane, and cos θ is a value based on the diffraction angle 2θ at which the diffraction line appears.

[0055] (specific surface area) The specific surface area was measured by the BET single point method using a Gemini VII 2390 manufactured by MICROMETORITICS.

[0056] (particle size distribution) The particle size distribution was measured using a Microtrac (registered trademark) MT3300EX II laser light diffraction scattering particle size analyzer manufactured by Microtrac Bell Co., Ltd., in accordance with a method conforming to JIS Z 8825:2013. Ion-exchanged water was used as the dispersion medium. After an appropriate amount of pigment was dropped into the ultrasonic dispersion tank of an automatic sample circulator attached to the measurement device, ultrasonic dispersion was performed for 360 seconds at an output of 40 W. After this, the measurement parameters were set to a refractive index of 1.33 for ion-exchanged water, reflection of the light transmittance of the particles to be measured, and a measurement time of 30 seconds, and the particle diameter (X10) corresponding to 10% of the cumulative particle size distribution (volume basis) and the particle diameter (X90) corresponding to 90% of the cumulative particle size distribution (volume basis) were measured, and X90 / X10 was used as an index of particle size distribution.

[0057] (Circularity and average circularity) Circularity is the degree of circularity when a particle is projected onto a two-dimensional surface. of Let the area of ​​the particle be S and the measured perimeter of the particle be L, then (4π×S) / L 2 The particles were photographed at a magnification of 10,000 times using a JEM-1400plus transmission electron microscope manufactured by JEOL Ltd., and the circularity was calculated using the image analysis software ImageJ. The average circularity was calculated as the average value of the circularities of 200 particles.

[0058] (Warm light transmission effect) A paint was prepared by kneading 3 mL of styrenated alkyd resin and 0.5 g of pigment using a Toyo Seiki Seisakusho H3-type automatic Huber-Mallor. The resulting dispersion was applied to a black-and-white JIS-K5·400 opacity test paper using a 3-mil doctor blade and baked at 130°C for 30 minutes to obtain a test sample. The reflectance of the test sample on a black background at wavelengths of 380 nm to 780 nm was measured using a Nippon Denshoku Industries SQ-2000 spectrophotometer. The measured values ​​were subtracted from 100% to calculate the transmittance at each wavelength. The sum of the transmittances from 380 nm to 780 nm was taken as the total transmitted light amount, and the sum of the transmittances from 570 nm to 780 nm was taken as the warm color transmitted light amount, and the warm color transmitted light amount / total transmitted light amount was taken as the warm color transmitted light effect. EXAMPLES

[0059] The present invention will be described in detail below with reference to examples. However, the following examples are presented merely for illustrative purposes and are not intended to limit the scope of the invention. In addition, in the stirring operations described in the Examples and Comparative Examples, the rotation speed is appropriately adjusted to ensure that the entire liquid is mixed uniformly and that droplets are not scattered around, taking into consideration the properties related to the behavior of the liquid during stirring, such as the liquid volume, viscosity of the liquid, and shape of the container. In addition, when the same effect can be obtained by using any company's product as long as it is a general commercially available product, such as sodium hydroxide, the names of the manufacturer and distributor are omitted.

[0060] [Example 1] Metatitanic acid obtained by the sulfuric acid method was bleached to remove iron, and then an aqueous sodium hydroxide solution was added to adjust the pH to 9.0, followed by desulfurization. The solution was then neutralized to pH 5.8 with hydrochloric acid, filtered, and washed to obtain a metatitanic acid cake with a sulfur content of 9.3 g / kg calculated as SO3. Water was added to the washed cake to make a slurry of 2.13 mol / L in terms of Ti, and hydrochloric acid was added to adjust the pH to 1.4, followed by peptization. 2.25 mol of the treated slurry was collected as TiO2 and placed in a reaction vessel with a capacity of 3000 mL. Calcium hydroxide was added to this so that the amount of calcium as Ca was 1.15 times the amount of titanium as Ti, 0.36 mol of sodium hydroxide was added, and water was added to make the total volume 2.0 L, and the mixed solution was stirred for 30 minutes using HEIDON600G manufactured by Shinto Scientific Co., Ltd.

[0061] The slurry was further stirred and mixed, while being heated to 95°C using a BE type mantle heater manufactured by Tokyo Technical Research Institute, and stirring was continued for 18 hours to complete the reaction (normal pressure heating reaction). The stirred slurry was allowed to cool to 50°C, hydrochloric acid was added until the pH reached 5.0, and stirring was continued for another hour (calcium removal treatment). The resulting precipitate was washed by decantation, separated by filtration, and then dried in air at 120°C for 10 hours using a Perfect Oven PHH-202 manufactured by Espec Corporation. The dried product was pulverized using an Ishikawa type stirring and crushing machine AGA type manufactured by Ishikawa Factory Co., Ltd. (hereinafter referred to as "automatic mortar") to obtain a white pigment. When the pigment was evaluated using the above test method, the lattice constant a was 5.4924 Å, the XRD diffraction line height ratio was 37.3, and the specific surface area was 12.2 m 2 / g, XRD titanium oxide integrated diffraction intensity was 6.07, the particles were rectangular parallelepiped, the crystallite diameter was 389 Å, the particle size distribution was 2.81, the average circularity was 0.720, and the warm color light transmittance was 0.64.

[0062] [Example 2] Except for changing the amount of sodium hydroxide added after the addition of calcium hydroxide to 1.80 mol, the normal pressure heating reaction, calcium removal treatment, washing, filtration, drying and pulverization were carried out under the same conditions as in Example 1 to obtain a white pigment. The lattice constant a of the pigment was 5.5022 Å, the XRD diffraction line height ratio was 38.3 and the specific surface area was 6.1 m. 2 / g, XRD titanium oxide integrated diffraction intensity was 5.85, the particles were rectangular parallelepiped, the crystallite diameter was 420 Å, the particle size distribution was 2.92, the average circularity was 0.698, and the warm color light transmittance was 0.58. [Example 3] Except for changing the amount of sodium hydroxide added after the addition of calcium hydroxide to 7.20 mol, the normal pressure heating reaction, calcium removal treatment, washing, filtration, drying and pulverization were carried out under the same conditions as in Example 1 to obtain a white pigment. The lattice constant a of the pigment was 5.4924 Å, the XRD diffraction line height ratio was 37.8 and the specific surface area was 4.4 m 2 / g, XRD titanium oxide integrated diffraction intensity was 4.24, the particles were rectangular parallelepiped, the crystallite diameter was 377 Å, the particle size distribution was 4.26, the average circularity was 0.692, and the warm color light transmittance was 0.56.

[0063] [Example 4] The amount of sodium hydroxide added after the addition of calcium hydroxide was changed to 3.60 mol, and 0.0193 mol of glucose was added per mol of Ca after the addition of sodium hydroxide. The normal pressure heating reaction, calcium removal treatment, washing, filtration, drying and pulverization were carried out under the same conditions as in Example 1 to obtain a white pigment. The lattice constant a was 5.4809 Å, the XRD diffraction line height ratio was 33.2 and the specific surface area was 27.4 m. 2 / g, XRD titanium oxide integrated diffraction intensity was 3.14, the particles were nearly spherical, the crystallite diameter was 339 Å, the particle size distribution was 2.71, the average circularity was 0.835, and the warm color light transmission effect was 0.63.

[0064] [Example 5] The normal pressure heating reaction, calcium removal treatment, washing, filtration, drying and pulverization were carried out under the same conditions as in Example 4, except that the amount of glucose added was changed to 0.0077 mol per 1 mol of Ca, to obtain a white pigment. The lattice constant a of the pigment was 5.4907 Å, the XRD diffraction line height ratio was 38.0 and the specific surface area was 5.5 m. 2 / g, XRD titanium oxide integrated diffraction intensity was 5.31, the particles were rectangular parallelepiped, the crystallite diameter was 533 Å, the particle size distribution was 3.02, the average circularity was 0.740, and the warm color light transmission effect was 0.59.

[0065] [Example 6] The normal pressure heating reaction, calcium removal treatment, washing, filtration, drying and pulverization were carried out under the same conditions as in Example 5, except that 0.0166 mol of citric acid was added per mol of Ca after the addition of glucose, to obtain a white pigment. The lattice constant a of the pigment was 5.4907 Å, the XRD diffraction line height ratio was 40.9 and the specific surface area was 8.0 m. 2 / g, XRD titanium oxide integrated diffraction intensity was 8.42, the particles were rectangular parallelepiped, the crystallite diameter was 539 Å, the particle size distribution was 2.67, the average circularity was 0.614, and the warm color light transmittance was 0.58.

[0066] [Example 7] The normal pressure heating reaction, calcium removal treatment, washing, filtration, drying and pulverization were carried out under the same conditions as in Example 4, except that the amount of glucose added was changed to 0.0039 mol per 1 mol of Ca, to obtain a white pigment. The lattice constant a of the pigment was 5.5007 Å, the XRD diffraction line height ratio was 45.7, and the specific surface area was 3.6 m. 2 / g, XRD titanium oxide integrated diffraction intensity was 5.22, the particles were rectangular parallelepiped, the crystallite diameter was 277 Å, the particle size distribution was 3.51, and the average circularity was 0.699. The warm color light transmission effect was 0.56.

[0067] [Example 8] A white pigment was obtained in the same manner as in Example 1, except that the amount of the slurry collected after the peptization treatment was changed to 1.50 mol in terms of TiO2, the amount of sodium hydroxide added was changed to 0.60 mol, the time held at 95°C was changed to 4 hours, the temperature for drying after separation by filtration was changed to 60°C, and the drying time was changed to 2 hours. The lattice constant a of the pigment was 5.5021 Å, the XRD diffraction line height ratio was 41.5, and the specific surface area was 9.4 m 2 / g, XRD titanium oxide integrated diffraction intensity was 5.33, the particles were rectangular parallelepiped, the crystallite diameter was 355 Å, the particle size distribution was 2.44, and the average circularity was 0.689. The warm color light transmission effect was 0.59.

[0068] [Example 9] The pigment obtained in Example 8 was dried and then calcined in air at 300°C using a Motoyama SUPER-CC-2035D (hereinafter referred to as the "calcining furnace") to obtain a white pigment. The lattice constant a of the pigment was 5.4759 Å, the XRD diffraction line height ratio was 41.7, and the specific surface area was 8.2 m. 2 / g, XRD titanium oxide integrated diffraction intensity was 4.85, the particles were rectangular parallelepiped, the crystallite diameter was 423 Å, the particle size distribution was 2.52, and the average circularity was 0.655. The warm color light transmission effect was 0.59.

[0069] [Comparative Example 1] A pigment mainly composed of calcium titanium composite oxide was synthesized by a general calcination method. Specifically, metatitanic acid, which is the peptized product described in Example 1, and calcium carbonate were added so that the amount of calcium as Ca was 1.15 times the amount of titanium as Ti, and the mixture was rehydrated to a solid concentration of 200 g / L, and the pH was adjusted to 10.0 with sodium hydroxide, and then the mixture was dispersed and mixed in an Ultra Apex Mill UAM-015 (hereinafter referred to as "beads mill") manufactured by Hiroshima Metal & Machinery Co., Ltd. The slurry was filtered to separate the solids, and then dried in air at 120°C for 10 hours. The dried product was calcined in a calcination furnace in air at 1100°C for 1 hour, and then pulverized in an automatic mortar to obtain a light pink pigment. The lattice constant a of the pigment was 5.4465 Å, the XRD diffraction line height ratio was 54.0, and the specific surface area was 4.7 m 2 / g, XRD titanium oxide integrated diffraction intensity was 2.63, the particles were almost spherical because they were partially melted and fused together by firing at high temperatures, the crystallite diameter was 383 Å, the particle size distribution was 19.92, and the average circularity was 0.818. The warm color light transmission effect was 0.51.

[0070] [Comparative Example 2] The pigment obtained in Example 1 was calcined for 1 hour in a calcining furnace at 1100°C, and then pulverized in an automatic mortar to obtain a light ochre pigment. The lattice constant a of the pigment was 5.4436 Å, the XRD diffraction line height ratio was 53.2, and the specific surface area was 6.7 m 2 / g, XRD titanium oxide integrated diffraction intensity was 2.55, the particles were nearly spherical, the crystallite diameter was 373 Å, the particle size distribution was 63.54, and the average circularity was 0.838. The warm color light transmission effect was 0.53.

[0071] [Comparative Example 3] The pigment obtained in Example 4 was calcined for 1 hour in a calcining furnace at 1100°C, and then pulverized in an automatic mortar to obtain a light ochre pigment. The lattice constant a of the pigment was 5.4514 Å, the XRD diffraction line height ratio was 52.2, and the specific surface area was 5.4 m 2 / g, XRD titanium oxide integrated diffraction intensity was 2.05, the particles were nearly spherical, the crystallite diameter was 415 Å, the particle size distribution was 100.82, and the average circularity was 0.822. The warm color light transmission effect was 0.55.

[0072] [Comparative Example 4] The commercially available calcium titanium composite oxide reagent CAF04PB manufactured by Kojundo Chemical Laboratory was used as Comparative Example 4. The appearance of the reagent was pale pink, the lattice constant a was 5.4420 Å, the XRD diffraction line height ratio was 52.3, and the specific surface area was 2.5 m 2 / g, XRD titanium oxide integrated diffraction intensity was 3.72, the particles were nearly spherical, the crystallite diameter was 556 Å, the particle size distribution was 13.19, and the average circularity was 0.791. The warm color light transmission effect was 0.53.

[0073] Table 1 shows the production conditions for the pigments of the Examples and Comparative Examples, and Table 2 shows the properties of the pigments obtained in the Examples and Comparative Examples. As shown in Table 2, the pigments of Examples 1 to 9, which have a lattice constant a of 5.4700 Å or more and 5.5100 Å or less, have a warm color light transmission effect of 0.56 or more, and can be said to be pigments that selectively transmit light in the warm color region. On the other hand, the pigments of Comparative Examples 1 to 4, which have a lattice constant a smaller than 5.4700 Å, have a small warm color light transmission effect of 0.55 or less.

[0074] As described above, the pigment of the present invention is capable of selectively transmitting light in the warm color region. When used as a raw material for cosmetics, the pigment of the present invention can achieve a natural finish.

[0075] [Table 1]

[0076] [Table 2]

[0077] Next, the powder foundations prepared using the pigments obtained in the Examples and Comparative Examples were subjected to a sensory evaluation by the following method. (Sensory evaluation of powder foundation) Each pigment obtained in the examples and comparative examples was surface-treated with methylhydrogenpolysiloxane, and then sold by HANIL Electric. Co., Ltd. in the blending ratio shown in Table 3. t The mixture was mixed uniformly using a Lab.MIXER LM-110T manufactured by Tokyo Atomizer Manufacturing Co., Ltd. (hereafter referred to as the "mixer"). The mixture was then pulverized using a Sample Mill TASM-1 manufactured by Tokyo Atomizer Manufacturing Co., Ltd. (hereafter referred to as the "sample mill"), after which a specified amount was placed in a metal dish and compression molded to produce a powder foundation.

[0078] [Table 3]

[0079] Ten panelists were instructed to apply each of the obtained powder foundations to the arms and face, particularly to areas with dullness or blemishes, until the dullness, blemishes, etc. were no longer noticeable, and the natural finish and smoothness were evaluated.

[0080] (Natural finish) The impression of the area where foundation was not used was visually compared to that of an area where foundation was not used and evaluated according to the following criteria, and the "natural finish" was determined by the average score of the 10 panelists. The higher the score, the less the foundation looked "white and cast" and the more "natural finish" was achieved. The results of the sensory evaluation are shown in Table 4. (Evaluation Criteria) 5 points: Even when viewed up close, it is indistinguishable from an unpainted area. 4 points: When viewed from a distance of 1m, it is indistinguishable from an unpainted area. 3 points: No discomfort when viewed from a distance of 1m. 2 points: Looks white when viewed from close up. 1 point: White enough to be noticeable from a distance. (Judgment criteria) 4.0 points or more and 5.0 points or less: A; 3.0 points or more and less than 4.0 points: B; 2.0 points or more and less than 3.0 points: C; 1.0 points or more and less than 2.0 points: D.

[0081] (Smoothness) The feel of the foundation when spread with a finger was evaluated according to the following criteria, and the "smoothness" was determined by the average score of 10 panelists. The higher the score, the better the smoothness of the foundation. Table 4 shows the results of the sensory evaluation. (Evaluation Criteria) 5 points: Can be spread thinly and smoothly over the skin. 4 points: Can be spread smoothly over a wide area. 3 points: Can be stretched without discomfort. 2 points: Poor stretch. 1 point: Feels rough when spread on skin. (Judgment criteria) 4.0 points or more and 5.0 points or less: A; 3.0 points or more and less than 4.0 points: B; 2.0 points or more and less than 3.0 points: C; 1.0 points or more and less than 2.0 points: D.

[0082] [Table 4]

[0083] As a result of the sensory evaluation, all of the foundations prepared using the pigment of the present invention had a natural bare skin feel and were excellent in smoothness, compared to those containing the pigments of the comparative examples. Thus, by incorporating the pigment of the present invention into cosmetics, it was possible to provide cosmetics that produce a natural bare skin feel and are excellent in smoothness.

[0084] [Example 10] (Powder foundation manufacturing) Components 1 to 13 below were mixed and uniformly ground (Step A), and then components 15 to 17 were mixed uniformly and added to the mixed and ground product obtained in Step A and homogenized (Step B). Component 14 was then added and the mixture was press molded in a mold to obtain a powder foundation (Step C).

[0085] It was confirmed that the obtained powder foundation did not produce a white cast when applied to the skin, gave a natural bare skin finish, and also had good smoothness. (Ingredients) Mixing ratio (g / kg) 1. Caprylylsilane-treated mica (note 1) 400 2. Caprylylsilane-treated pigment described in Example 6 (Note 1) 50 3. Silicone-treated talc (Note 2) Residual 4. Silicone-treated pigment-grade titanium dioxide (Note 2) 50 5. Silicone-treated titanium dioxide microparticles (Note 2) 50 6. Silicone-treated barium sulfate (Note 2) 100 7. Silicone-treated red iron oxide (Note 2) 4 8. Silicone-treated yellow iron oxide (Note 2) 20 9. Silicone-treated amber (Note 2) 4 10. Silicone-treated black iron oxide (Note 2) 1 11. Phenyl-modified hybrid silicone composite powder (Note 3) 20 12. Spherical polymethylsilsesquioxane powder (Note 4) 5 13. Preservatives (appropriate amount) 14.Fragrance (appropriate amount) 15. Crosslinked dimethylpolysiloxane (Note 5) 40 16. Glyceryl trioctanoate 20 17. Squalane 10 (Note 1) Surface treated with Shin-Etsu Chemical Co., Ltd.'s AES-3083 (Note 2) Surface treated with Shin-Etsu Chemical Co., Ltd.'s KF-9909 (Note 3) Shin-Etsu Chemical Co., Ltd. KSP-300 (Note 4) Shin-Etsu Chemical Co., Ltd. KMP-590 (Note 5) KSG-16 manufactured by Shin-Etsu Chemical Co., Ltd.

[0086] [Example 11] (Pressed powder manufacturing) After mixing and grinding ingredients 1 to 7 below (step A), the mixture was transferred to a mixer, ingredients 8 to 12 were added and stirred until homogeneous (step B), and the mixture was ground in a sample mill and press molded into an aluminum dish to obtain a pressed powder (step C). The obtained pressed powder did not cast a white cast when applied to the skin, had a natural bare-skin finish, and was confirmed to have good smoothness. (Ingredients) Mixing ratio (g / kg) 1. Talc Residue 2.PMMA (Note 1) 100 3. Sericite 300 4. Scaly silica (Note 2) 30 5. Pigment described in Example 7 60 6. Preservatives: appropriate amount 7.Color material appropriate amount 8. Octyl methoxycinnamate 30 9. Squalane 20 10. Preservatives (appropriate amount) 11. Antioxidants (appropriate amount) 12.Fragrance (appropriate amount) (Note 1) Matsumoto Microsphere M-100, 7 μm, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd. (Note 2) Sun Lovely C manufactured by Dokai Chemical Industry Co., Ltd.

[0087] [Example 12] (Loose powder manufacturing) After mixing and grinding the following components 1 to 7 (step A), the mixed and ground product was transferred to a mixer, and components 8 to 10 were added and stirred and mixed to be uniform (step B). Furthermore, the mixture obtained in step B was ground in a sample mill, and this was filled to obtain a loose powder (step C).

[0088] The obtained loose powder did not produce a white cast when applied to the skin, gave a natural bare skin finish, and was confirmed to have good smoothness. (Ingredients) Mixing ratio (g / kg) 1. Talc Residue 2. Pigment 10 described in Example 7 3. Amihope LL 30 4.PMMA (Note 1) 80 5. Preservatives (appropriate amount) 6. Appropriate amount of coloring material 7. Squalane 10 8. Preservatives (appropriate amount) 9. Antioxidants (appropriate amount) 10.Fragrance (appropriate amount) (Note 1) Matsumoto Microsphere S-100, 10 μm, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.

[0089] [Example 13] (Manufacture of oil-based foundation) Components 1 to 6 below were mixed in a mixer and pulverized uniformly (Step A). ​​Components 7 to 16 were then heated to 85°C to dissolve, and the mixed and pulverized product obtained in Step A was added and stirred uniformly (Step B). After degassing, the solids were poured into a tray and slowly cooled to room temperature to obtain an oil-based foundation (Step C).

[0090] The obtained oil-based foundation did not produce a white cast when applied to the skin, gave a natural, bare-skin feel, and was confirmed to have good smoothness. (Ingredients) Mixing ratio (g / kg) 1. Silicone-treated talc (Note 1) 53 2. Silicone treatment Pigment described in Example 4 (Note 1) 150 3. Silicone-treated sericite (Note 1) 282 4. Silicone-treated red iron oxide (Note 1) 5 5. Silicone-treated yellow iron oxide (Note 1) 18 6. Silicone-treated black iron oxide (Note 1) 2 7. Candelilla Row 10 8. Carnauba Wax 10 9. Ceresin 15 10. Decamethylcyclopentasiloxane 140 11. Isononyl isononanoate residue 12. Polyglyceryl diisostearate 20 13. Dextrin Palmitate 10 14. Octyl methoxycinnamate 30 15. Preservatives (appropriate amount) 16. Antioxidants (appropriate amount) (Note 1) The surface has been treated with KF-96A-50cs manufactured by Shin-Etsu Chemical Co., Ltd.

[0091] [Example 14] (Stick foundation manufacturing) Components 12 to 16 below were mixed in a mixer (Step A). ​​Components 1 to 11 were weighed out in a container that could hold the entire amount, heated to 85°C, and dissolved (Step B). Components 17 to 21 were weighed out in a separate container and dissolved (Step C). Thereafter, the mixture obtained in Step A was added to the heated and dissolved product obtained in Step B, dispersed with a stirrer until visually uniform, and the heated and dissolved product obtained in Step C was further added to emulsify (Step D). After degassing, the solids were poured into a mold and slowly cooled to room temperature to obtain a stick foundation (Step E).

[0092] The obtained stick foundation did not produce a white cast when applied to the skin, gave a natural, bare-skin feel, and was confirmed to have good smoothness. (Ingredients) Mixing ratio (g / kg) 1. Dimethylpolysiloxane 180 2. Decamethylcyclopentasiloxane 300 3. Octyl methoxycinnamate 50 4. Diisostearyl malate 40 5. Candelilla Wax 60 6. Hydrogenated Jojoba Esters 40 7. Cetyl Dimethicone Copolyol 20 8. Sorbitan Sesquiisostearate 5 9. Antioxidants (appropriate amount) 10. Preservatives (appropriate amount) 11.Fragrance (appropriate amount) 12. Silicone-treated coloring agent (Note 1) 5 13. Silicone treatment Pigment described in Example 1 (Note 1) 85 14. Silicone-treated talc (Note 1) 60 15. Silicone-treated mica (Note 1) 20 16. Polymethylmethacrylate 20 17.Purified water remainder 18. Sodium Citrate 3 19. 1,3-Butylene glycol 30 20. Glycerin 20 21. Preservatives (appropriate amount) (Note 1) The surface has been treated with Shin-Etsu Chemical's KF-99P.

[0093] [Example 15] (Manufacture of W / O emulsion foundation) After mixing components 12 to 14 below with a mixer (step A), components 1 to 11 were added and dispersed with a stirrer until visually uniform (step B). Meanwhile, components 15 to 19 were heated and dissolved in a separate container (step C). After that, the heated and dissolved product obtained in step C was added to the dispersion obtained in step B to emulsify, and then cooled to room temperature to obtain a W / O emulsion foundation (step D).

[0094] The obtained W / O emulsion foundation did not produce a white cast when applied to the skin, gave a natural, bare-skin feel, and was confirmed to have good smoothness. (Ingredients) Mixing ratio (g / kg) 1. POE modified silicone (Note 1) 8 2. Polyglyceryl Polyricinoleate 5 3. Neopentyl glycol dicaprylate 30 4. Squalane 10 5. Pentaerythrityl tetraisopropyl ester 20 6. Inulin stearate (Note 2) 10 7. Octyl methoxycinnamate 40 8. Decamethylcyclopentasiloxane 154 9. Preservatives (appropriate amount) 10. Antioxidants (appropriate amount) 11.Fragrance (appropriate amount) 12. Silicone treatment Pigment described in Example 5 (Note 3) 80 13. Silicone-treated talc (Note 3) 57 14. Silicone-treated coloring agent (Note 3) 10 15.Purified water remainder 16.1,3-Butylene glycol 60 17. Glycerin 10 18. Sodium Chloride 10 19. Preservatives (appropriate amount) (Note 1) HLB value 4.5 (Note 2) Leopearl (registered trademark) ISK manufactured by Chiba Flour Mills (Note 3) The surface has been treated with Shin-Etsu Chemical Co., Ltd.'s KF-9901.

[0095] [Example 16] (Manufacture of O / W emulsion foundation) Components 1 to 7 below were heated and dissolved at 85°C (Step A). ​​Components 8 to 10 were mixed and ground (Step B). Components 11 to 15 were heated to 85°C and mixed (Step C). The ground mixture obtained in Step B was then added to the heated and dissolved product obtained in Step A, and dispersed using a stirrer until visually uniform. The dissolved mixture obtained in Step C was gradually added thereto to emulsify, and the mixture was stirred and cooled to room temperature. The mixture was then filled into a suitable container to obtain an O / W emulsion foundation (Step D).

[0096] The obtained O / W emulsion foundation did not cast a white cast when applied to the skin, gave a natural, bare-skin feel, and was confirmed to have good smoothness. (Ingredients) Mixing ratio (g / kg) 1. Stearic acid 4 2. Isostearic acid 3 3. Cetyl 2-ethylhexanoate 40 4. Liquid Paraffin 110 5. Polyoxyethylene (10) stearyl ether 20 6. Cetyl Alcohol 3 7. Preservatives 2 8. Talc 150 9. Coloring agent 40 10. Pigment described in Example 1 30 11. Triethanolamine 4 12. Propylene glycol 50 13.Purified water 541 14. Preservatives 2 15.Antioxidants 1.

[0097] [Example 17] (W / O liquid foundation manufacturing) After components 8 to 12 below were mixed uniformly (step A), a part of component 4 and component 13 were mixed, and the mixture obtained in step A was added and dispersed using a stirrer until it was visually uniform (step B). Components 1 to 3, the remainder of component 4, and components 5 to 7 were mixed and dispersed using a stirrer until it was visually uniform (step C). Furthermore, components 14 to 18 and component 20 were mixed and dispersed using a stirrer until it was visually uniform (step D). Under stirring, the mixture obtained in step D was gradually added to the mixture obtained in step C to emulsify, and the dispersion obtained in step B and component 19 were further added to obtain a W / O liquid foundation (step E).

[0098] The obtained W / O liquid foundation did not produce a white cast when applied to the skin, gave a natural, bare-skin feel, and was confirmed to have good smoothness. (Ingredients) Mixing ratio (g / kg) 1. Cross-linked polyether modified silicone (Note 1) 30 2. Crosslinked dimethylpolysiloxane (Note 2) 50 3. Branched polyether modified silicone (Note 3) 20 4. Decamethylcyclopentasiloxane 211 5. Cetyl isooctanoate 50 6. Dimethylpolysiloxane (Note 4) 65 7. Dimethyl distearyl ammonium hectorite 12 8. Silicone-treated pigment described in Example 1 (Note 5) 50 9. Silicone-treated pigment-grade titanium dioxide (Note 5) 50 10. Silicone-treated red iron oxide (Note 5) 4 11. Silicone-treated yellow iron oxide (Note 5) 10 12. Silicone-treated black iron oxide (Note 5) 1 13. Acrylic silicone resin solution (Note 6) 20 14. 1,3-Butylene glycol 50 15. Xanthan gum (note 7) 50 16. Sodium Citrate 2 17. Sodium Chloride 5 18. Preservatives (appropriate amount) 19.Fragrance (appropriate amount) 20.Purified water 320 (Note 1) Shin-Etsu Chemical Co., Ltd. KSG-210 (Note 2) Shin-Etsu Chemical Co., Ltd. KSG-15 (Note 3) Shin-Etsu Chemical Co., Ltd. KF-6028P (Note 4) 6mm 2 / second (25℃) product (Note 5) Surface treated with Shin-Etsu Chemical's KF-9909 (Note 6) Shin-Etsu Chemical Co., Ltd. KP-575 (Note 7) 20g / kg aqueous solution.

[0099] [Example 18] (Manufacture of Sun Cut Cream) In order to confirm the ultraviolet shielding ability of the pigment of the present invention, a sun-cut cream was prepared. Component 7 was added to a part of component 5 below to make it uniform, and then components 8 and 9 were added and dispersed using a bead mill (step A). ​​Components 1 to 4, the remainder of component 5, and component 6 were mixed uniformly (step B). Furthermore, components 10 to 12 and component 14 were dispersed using a stirrer until they were visually uniform (step C). Next, the mixture obtained in step C was added to the mixture obtained in step B and emulsified, and the dispersion obtained in step A and component 13 were added to obtain a sun-cut cream (step D).

[0100] The obtained sun cream was confirmed to have high ultraviolet shielding ability, no white cast when applied to the skin, a natural bare skin finish, no sensation of grains touching the skin when applied, and good smoothness. (Ingredients) Mixing ratio (g / kg) 1. Cross-linked polyether modified silicone (Note 1) 30 2. Crosslinked dimethylpolysiloxane (Note 2) 20 3. Alkyl-modified branched polyether-modified silicone (Note 3) 10 4. Neopentyl glycol dioctanoate 50 5. Decamethylcyclopentasiloxane 175 6. Octyl methoxycinnamate 60 7. Acrylic silicone resin solution (Note 4) 100 8. Caprylylsilane-treated fine zinc oxide (note 5) 200 9. Caprylylsilane-treated pigment described in Example 2 (Note 5) 30 10. 1,3-Butylene glycol 20 11. Sodium Citrate 2 12. Sodium Chloride 5 13.Fragrance (appropriate amount) 14.Purified water 298 (Note 1) Shin-Etsu Chemical Co., Ltd. KSG-240 (Note 2) Shin-Etsu Chemical Co., Ltd. KSG-15 (Note 3) Shin-Etsu Chemical Co., Ltd. KF-6038 (Note 4) Shin-Etsu Chemical Co., Ltd. KP-575 (Note 5) The surface has been treated with Shin-Etsu Chemical Co., Ltd.'s AES-3083.

[0101] [Example 19] (Production of film composition) A film composition containing the pigment of the present invention was prepared. A part of component 3 was added to component 1, and dispersed in a bead mill (step A). ​​Component 2 and the remaining part of component 3 were mixed, heated, and stirred at 95°C for 10 minutes (step B). The dispersion obtained in step A was added, and after stirring for 5 minutes, heating was stopped and the mixture was poured into a mold (step C). The mixture was dried to obtain a film composition (step D).

[0102] When the obtained film composition was held up to sunlight, the proportion of warm color region in the transmitted light was significantly large, confirming that the composition has a warm color light transmitting effect. (Ingredients) Mixing ratio (g / kg) 1. Pigment described in Example 4 100 2. Polyvinyl alcohol (Note 1) 100 3.Purified water 800 (Note 1) Polyvinyl alcohol 500 manufactured by Kishida Chemical Co., Ltd.

[0103] [Example 20] (Production of resin composition) A resin composition containing the pigment of the present invention was prepared. Component 1 was distilled and then bubbled with nitrogen for 30 minutes (step A). ​​Component 5 and component 6 were mixed and dispersed using a bead mill (step B). The liquid obtained in step A and components 2 to 4 were added to component 7 and heated with stirring. Five minutes after the temperature reached 65°C, the dispersion obtained in step B was added and stirring was continued while maintaining the temperature at 65°C (step C). After 10 hours, component 8 was added to neutralize (step D), and the mixture was filtered and washed to obtain a resin composition (step E).

[0104] When the obtained resin composition was held up to sunlight, the proportion of warm color region in the transmitted light was significantly large, and it was confirmed that the resin composition had a warm color light transmitting effect. (Ingredients) Mixing ratio (g / kg) 1. Methyl methacrylate 600 2. Azoisobutyronitrile 0.3 3. Sodium chloride 1 4. Calcium phosphate 6 5. Methylhydrogenpolysiloxane surface treatment Pigment described in Example 4 200 6. Toluene 140 7. Purified water (appropriate amount) 8. Hydrochloric acid, appropriate amount.

[0105] [Example 21] (Paint manufacturing) A paint containing the pigment of the present invention was prepared by mixing components 1 to 4 in a mixer for 30 to 120 minutes (step A) and then dispersing the mixture in a bead mill (step B).

[0106] When the obtained paint was applied to a transparent glass substrate and held up to the light, the proportion of warm color regions in the transmitted light was significantly large, confirming that the paint has a warm color light transmitting effect. (Ingredients) Mixing ratio (g / kg) 1. Acrylic resin 300 2. Methylhydrogenpolysiloxane surface treatment Pigment described in Example 4 300 3. Toluene 200 4. Isophorone 200.

[0107] [Example 22] (Ink manufacturing) An ink containing the pigment of the present invention was prepared by mixing components 1 to 4 in a mixer for 30 to 120 minutes (step A) and then dispersing the mixture in a bead mill for 24 hours (step B).

[0108] When the obtained ink was applied to a glass plate and held up to the light, the proportion of warm color areas in the transmitted light was significantly large, confirming that the ink had a warm color light transmission effect. (Ingredients) Mixing ratio (g / kg) 1. Acrylic resin 75 2. Methylhydrogenpolysiloxane surface treatment Pigment described in Example 4 495 3. Methylcyclohexane 400 4. Dispersant (Note 1) 10 5. Gelling agent (note 2) 20 (Note 1) Homogenol (registered trademark) L-18 manufactured by Kao Corporation (Note 2) Organite (registered trademark)-T manufactured by Nippon Organic Viscosity Co., Ltd.

Claims

1. The lattice constant a is 5.4700 Å or more and 5.5100 Å or less, The specific surface area is 3.0 m 2 / g or more, The individual particles constituting the pigment account for 850 g / kg or more of calcium titanium composite oxide particles, A pigment, wherein the calcium titanium composite oxide is an orthorhombic calcium titanium composite oxide.

2. 2. The pigment according to claim 1, wherein, when the height of the diffraction line of the (1 2 1) plane appearing in the diffraction angle range of 32.50° to 33.50° in X-ray diffraction measurement is taken as 100.0, the height of the diffraction line of the (2 0 2) plane appearing in the diffraction angle range of 46.75° to 47.75° is 50.0 or less.

3. 3. The pigment according to claim 1, wherein in X-ray diffraction measurement, when the integrated diffraction intensity of the (1 2 1) plane appearing in the diffraction angle range of 32.50° to 33.50° is taken as 100.0, no diffraction line appears in the diffraction angle range of 24.75° to 28.00° with an integrated diffraction intensity of more than 12.

00.

4. The pigment according to claim 1 , which has an inorganic and / or organic coating layer on at least a portion of the surface of the particle.

5. The pigment according to claim 1 , wherein the particle shape is approximately spherical.

6. The pigment according to claim 1 , wherein the particle shape is a rectangular parallelepiped.

7. 7. The pigment according to claim 1, wherein the crystallite diameter of the particles is from 250 Å to 600 Å.

8. A cosmetic preparation comprising the pigment according to any one of claims 1 to 7.

9. A film composition comprising the pigment according to any one of claims 1 to 7.

10. A resin composition comprising the pigment according to claim 1 .

11. A paint comprising the pigment according to any one of claims 1 to 7.

12. An ink comprising the pigment according to any one of claims 1 to 7.

Images