Pigment containing particles containing calcium titanium composite oxide as main component, method for producing the same, and use thereof

Abstract

Provided are a pigment mainly for cosmetic use, a method for manufacturing the same, and a method for using the same. The pigment preferentially transmits light in the warm color region and has a high hiding power. A pigment containing particles mainly composed of a perovskite composite oxide, wherein when observing the particles of the perovskite composite oxide in the pigment through a transmission electron microscope photograph at a magnification of 100,000 times, parts with a lighter color than the surroundings can be confirmed to be scattered in a spotted pattern within the particles, and the true density of the pigment is 3500 kg / m<supgt;3< / supgt> or more and 3790 kg / m<supgt;3< / supgt> or less.

Description

Technical Field

[0001] The present invention relates to a pigment containing particles with calcium titanium composite oxide as a main component, and in particular to the above-mentioned pigment having a warm light transmission effect and greater hiding power. Background Art

[0002] Conventionally, color cosmetics such as foundations were used to cover redness, dullness, spots, freckles, etc. of the skin to create an even and beautiful appearance by adding colorants such as titanium oxide pigments with strong coloring power and other inorganic and organic pigments to change the skin color.

[0003] Regarding the titanium oxide, a pigment with high hiding power is generally used to make the skin color uniform. When a pigment with low hiding power is used in cosmetics, a large amount of pigment needs to be mixed in order to exert sufficient hiding power, which deteriorates the usability of the cosmetics. Japanese Patent No. 2584562 (Patent Document 1) proposes a cosmetic with hiding power, which contains spherical or elliptical titanium dioxide.

[0004] However, when applying makeup on the skin using a foundation or concealer blended with titanium oxide having high covering power, there is a problem that the intensity of the white scattered light becomes too strong, and the finished makeup looks pale and unnatural, which is a so-called whitening phenomenon.

[0005] As one of the means to prevent the white floating phenomenon, the balance between the intensity of tinting power or hiding power and the scattered light of white can be listed by using rutile titanium oxide of a specific shape. For example, Japanese Patent No. 4684970 (Patent Document 2) records the mixing of the aggregate of fan-shaped rutile titanium oxide particles formed by the collection and / or combination of rod-shaped primary particles in cosmetics. In addition, Japanese Patent No. 6258462 (Patent Document 3) records the mixing of rutile titanium dioxide powder in cosmetics, which is obtained by roasting rutile titanium dioxide with needle-like protrusions on the particle surface.

[0006] As other means to prevent the whitening phenomenon, there is a method of utilizing the scattering of light in the warm color area inside the skin. Japanese Patent No. 5363696 (Patent Document 4) records the attention paid to the light propagating inside the skin under the bare face and conducted research. Specifically, it is recorded that: in a light scattering medium such as the skin, part of the light irradiated on the skin will be transmitted internally and reflected by the internal scatterer, so it will also be emitted from a part different from the irradiated part, but by using a coloring material with a small absorption rate of light at a wavelength of 630nm to 700nm for skin cosmetics, the distribution of the above-mentioned emission parts is close to the bare face itself, and a natural texture can be obtained.

[0007] However, in recent years, it is undeniable that titanium (IV) oxide including rutile titanium oxide may cause harm to health, so the trend of reducing the amount used or using alternative materials is expanding, centered on Europe. In Japanese Patent Publication No. 5-339121 (Patent Document 5), as pigments other than rutile titanium oxide, a scheme of using compounds having a perovskite crystal structure such as calcium titanate, strontium titanate, barium titanate, calcium zirconate, and strontium zirconate is proposed. Japanese Patent No. 3464564 (Patent Document 6) also records ultraviolet protection cosmetics using composite oxides having a perovskite structure or particles thereof as a solid solution.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent No. 2584562

[0011] Patent Document 2: Japanese Patent No. 4684970

[0012] Patent Document 3: Japanese Patent No. 6258462

[0013] Patent Document 4: Japanese Patent No. 5363696

[0014] Patent Document 5: Japanese Patent Application Laid-Open No. 5-339121

[0015] Patent Document 6: Japanese Patent No. 3464564 Summary of the invention

[0016] Problem that the invention aims to solve

[0017] However, Patent Document 5 only discusses lubricity, adhesion, and hiding power, and does not consider the response to the whitening phenomenon. In addition, Patent Document 5 only records that a powder containing particles having an average particle size of 0.05 to 15 μm and an equiaxed shape and composed of a compound having a perovskite crystal structure is mixed into cosmetics, but does not record a specific method for making such a powder. In addition, although Patent Document 6 records the synthesis of a composite oxide powder represented by CaTiO3, it does not record a specific example of mixing the powder into cosmetics. In addition, although it records the UV protection effect, safety, and stability of cosmetics containing a composite oxide having a perovskite crystal structure, there is no research on the response to the whitening phenomenon and hiding power.

[0018] Although some progress has been made in the research and development of titanium oxide alternative materials, the development of cosmetics that can achieve a natural look and high coverage is still underway.

[0019] The present invention aims to provide a pigment which can achieve a natural makeup by preferentially transmitting light in a warm color region, has a greater covering power, and can be used as a titanium oxide substitute material.

[0020] Solutions for solving problems

[0021] The present inventors have conducted intensive studies focusing on calcium titanium composite oxides as an alternative material to titanium oxide, and have found that a pigment containing particles having as a main component a calcium titanium composite oxide having a true density within a specific range, wherein a specific spotted pattern can be confirmed when the calcium titanium composite oxide is observed through a transmission electron microscope photograph, preferentially transmits light in a warm color region and has a greater hiding power.

[0022] The present invention includes but is not limited to the following aspects.

[0023] [1] A pigment comprising particles containing calcium titanium composite oxide as a main component, wherein:

[0024] When the particles of the calcium titanium composite oxide in the pigment were observed by a transmission electron microscope photograph at a magnification of 100,000 times, it was confirmed that portions lighter in color than the surrounding areas were scattered in spots within the particles.

[0025] The true density of the pigment is 3500 kg / m 3 Above and 3790kg / m 3 the following.

[0026] [2] The pigment according to [1], wherein the shape of the portion lighter in color than the surrounding area is a circle with a diameter of 1.5 nm to 15.0 nm or an ellipse with a major axis length of 1.5 nm to 15.0 nm, and

[0027] The portion with a lighter color than the surrounding area is equivalent to 1.0×10 4 nm 2 There are more than 100 and less than 200 in the range.

[0028] [3] The pigment according to [1] or [2], wherein the number average value of the diameter or the major axis length of the portion whose color is lighter than the surrounding area is 2.5 nm to 4.5 nm.

[0029] [4] The pigment according to any one of [1] to [3], wherein the particle size is 200 nm or more and 500 nm or less.

[0030] [5] The pigment according to any one of [1] to [4], wherein the width of the particle size distribution specified in JIS Z 8825:2013 is less than 10.00.

[0031] [6] A pigment according to any one of [1] to [5], wherein, in an X-ray diffraction measurement, when the integrated diffraction intensity of diffraction lines of the (121) plane appearing in the diffraction angle range of 32.50° to 33.50° is set to 100.0, the ratio of the integrated diffraction intensity of diffraction lines appearing in the diffraction angle range of 24.75° to 28.00° is 12.00 or less.

[0032] [7] The pigment according to any one of [1] to [6], which has an inorganic and / or organic coating layer on at least a portion of the surface of the particles.

[0033] [8] A method for producing the pigment according to any one of [1] to [7], comprising the following steps:

[0034] preparing an aqueous solution comprising a titanium source and a calcium source;

[0035] heating the aqueous solution to react the titanium source and the calcium source to generate a reactant;

[0036] Decalcifying the reactant, followed by solid-liquid separation to recover the solid component; and

[0037] The obtained solid content is heated.

[0038] [9] A method for producing the pigment according to any one of [1] to [7], comprising the following steps:

[0039] The acid deflocculant of the hydrolyzate of the titanium compound, the water-soluble compound containing calcium and the base are mixed and heated to a temperature of 70° C. to 100° C. at normal pressure to generate a reactant;

[0040] After cooling the obtained reaction product, the pH is kept below 7.0 for more than 1 hour;

[0041] Performing solid-liquid separation on the reaction product after the maintenance to recover the solid component; and

[0042] The solid component is calcined at 500°C or above.

[0043]

[10] A cosmetic comprising the pigment according to any one of [1] to [7].

[0044]

[11] A resin composition comprising the pigment according to any one of [1] to [7].

[0045]

[12] A coating material comprising the pigment according to any one of [1] to [7].

[0046]

[13] An ink comprising the pigment according to any one of [1] to [7].

[0047] Effects of the Invention

[0048] The pigment obtained in the present invention, which contains particles containing calcium titanium composite oxide as a main component, preferentially transmits light in a warm color region and has a greater hiding power.

[0049] When the pigment obtained in the present invention contains particles mainly composed of calcium titanium composite oxide, the transmitted light in the warm color region is scattered inside the skin, especially when used as a material for cosmetics applied on the skin such as foundation, thereby achieving a natural makeup and a high covering power.

[0050] In addition, the pigment obtained in the present invention can also be used as a substitute material for titanium oxide. The calcium titanium composite oxide used in the pigment of the present invention has an ultraviolet shielding effect equivalent to that of titanium oxide, and can therefore be used in sunscreens and the like.

[0051] The pigment obtained in the present invention can be used in a wide range of applications, utilizing the function of transmitting light in the warm color range and the function of having a high hiding power, even in fields other than cosmetics. Such applications include, for example, adding the pigment to a resin to form a resin composition having a warm color light transmitting effect, adding the pigment to a coating to be used for residential coatings, etc., but are not limited thereto. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 This is a transmission electron microscope photograph of the pigment obtained in Example 5.

[0053] Figure 2 This is a transmission electron microscope photograph of the pigment obtained in Example 3.

[0054] Figure 3 This is a transmission electron microscope photograph of the pigment obtained in Comparative Example 3.

[0055] Figure 4 The transmission electron micrograph of the pigment obtained in Example 5 shows a region with an area of ​​1.0×10 4 nm 2 Rectangular figure. DETAILED DESCRIPTION

[0056] The present invention relates to a pigment comprising particles containing calcium titanium composite oxide as a main component, wherein when the calcium titanium composite oxide particles in the pigment are observed through a transmission electron microscope photograph with a magnification of 100,000 times, it can be confirmed that parts lighter in color than the surroundings are scattered in spots in the particles, and the true density of the pigment is 3500 kg / m 3 Above and 3790kg / m 3 the following.

[0057] "Pigment containing particles containing calcium titanium composite oxide as a main component" means that each particle constituting the pigment is mainly a particle of calcium titanium composite oxide. Specifically, it means that 850 g / kg or more, preferably 900 g / kg or more of each particle constituting the pigment is particles of calcium titanium composite oxide. As each particle constituting the pigment of the present invention, in addition to the calcium titanium composite oxide, it may also contain unreacted products during the synthesis reaction of the calcium titanium composite oxide, inevitable impurities derived from the raw materials, and inorganic and / or organic substances derived from the coating layer.

[0058] The calcium titanium composite oxide as the main component constituting the particles of 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 three different crystal axes are all 90°.

[0059] like Figure 1 and Figure 2 As shown in FIG. 1 , the particles of calcium titanium composite oxide in the pigment of the present invention are characterized in that, in a transmission electron microscope photograph, there are dark-colored parts and light-colored parts in the particles. Specifically, when observing through a transmission electron microscope photograph with a magnification of 100,000 times, it can be confirmed that light-colored parts are scattered in spots in the dark-colored parts. The inventors of the present invention have found that when the speckled pattern can be seen in the particles of calcium titanium composite oxide, the warm light transmission effect of the pigment is improved. The relationship between the speckled pattern and the warm light transmission effect is not yet clear, but the following speculation is made as to why the above-mentioned effect can be obtained:

[0060] The pigment of the present invention is believed to have generated pores inside the particles during the synthesis process. When the portion corresponding to the pores is observed with a transmission electron microscope, it becomes a portion with a lighter color than the surrounding. It is believed that since light with a short wavelength is easily scattered and reflected in such pores, light in the warm color region will be preferentially transmitted in the pigment of the present invention. It should be noted that, regarding the "pores", it is believed that there are both pores connected to other pores or the outside and unconnected pores.

[0061] The present inventors have found for the first time that it is possible to produce perovskite composite oxide particles having the above-mentioned spotted pattern when observed by transmission electron microscopy by the method described below. When commercially available perovskite composite oxide is observed by transmission electron microscopy, as shown in FIG. Figure 3 As shown, no speckled pattern was seen.

[0062] For the above-mentioned spotted pattern in the particles of the calcium titanium composite oxide in the pigment of the present invention, it is desirable to be evenly distributed in the whole particle. However, sometimes the light-colored part cannot be observed due to the reason that the particles overlap each other in the transmission electron microscope photo or the thickness of a part of the particles is particularly large. If there is no overlap of the particles, then at the outer edge of the particles, the thickness of the particles usually does not become particularly large. Therefore, the particles with spotted patterns in the present invention, when observed by the transmission electron microscope photo of a magnification of 100,000 times, can usually observe spotted patterns at least at their outer edges. On the other hand, when there is no overlap of the particles and even in the transmission electron microscope photo of a magnification of 100,000 times, the spotted pattern cannot be observed at the outer edge of the particles, it can be judged that the particles do not have a spotted pattern.

[0063] In addition, the pigment of the present invention has a characteristic of having a low true density as evaluated by the method described below. The true density of the pigment of the present invention is 3500 kg / m 3 Above and 3790kg / m 3 Below. When the above-mentioned spotted pattern can be observed and the true density is 3790kg / m 3 In the following cases, in addition to the warm light transmission effect, the hiding power can also be improved. The hiding power depends on the shape of the particles themselves. Specifically, it was found that although the rectangular particles described later tend to have a greater hiding power overall than the roughly spherical particles, when comparing particles of the same shape with each other, a spot-like pattern can be observed in a transmission electron microscope photograph at a magnification of 100,000 times. The true density is 3790kg / m 3 Although the relationship between true density and hiding power improvement is not yet clear, it is believed that when the true density is low, sufficient pores are formed inside the particles, so light becomes easier to scatter and reflect, and in addition to the warm light transmission effect, the hiding power can also be improved. If the true density is less than 3500kg / m 3 , the particles become easily disintegrated, and the usability as a cosmetic may deteriorate. Therefore, the true density is preferably 3500 kg / m 3 above.

[0064] The light-colored portions scattered in spots have a circular shape with a diameter of 1.5 nm to 15 nm or an elliptical shape with a major axis of 1.5 nm to 15 nm, and the light-colored portions are 1.0×10 4 nm 2When there are more than 100 and less than 200 particles within the range, when particles of the same shape are compared with each other, a further improvement in hiding power can be seen, so it is preferred. In addition, the number average value of the above diameter or major axis length (hereinafter also referred to as the "average diameter") is preferably more than 2.5nm and less than 4.5nm, more preferably more than 2.5nm and less than 4.2nm, and further preferably more than 3.0nm and less than 4.2nm. It is believed that if the average diameter of the particles is more than 2.5nm, the hiding power evaluated by the method described later is likely to become larger, and if it is less than 4.5nm, it is easy to obtain the structural stability of the particles. It should be noted that the above-mentioned "circular" is not limited to a perfect circle, but is intended to include shapes that are approximately circular; the same is true for "elliptical".

[0065] In addition, it is believed that the 1.0×10 4 nm 2 In the range of 100 or more, there are 100 or more parts with lighter colors than the surrounding parts, so that the scattering of short-wavelength light in the pores inside the particles can be fully generated, and preferential transmission of light in the warm color region can be obtained, and the hiding power of the pigment is improved. On the other hand, even if there are more than 200, the hiding power will not be further improved. In addition, if there are more than 200, there are many pores inside the particles, making the particles easy to disintegrate, and the usability as a cosmetic deteriorates. Therefore, it is preferable that the number of the above-mentioned light-colored parts is 200 or less.

[0066] Regarding the method for measuring the diameter or major axis length of a portion lighter than the surrounding area on a transmission electron micrograph at a magnification of 100,000 times and the equivalent of 1.0×10 4 nm 2 The specific method for measuring the number of parts in the range whose color is lighter than the surrounding areas will be described later.

[0067] The pigments obtained in the present invention include pigments having a substantially spherical particle shape and a rectangular parallelepiped particle shape. Figure 1 The primary particles or secondary particles shown are isotropically crystallized or are isotropically aggregated and have an irregular shape or a nearly spherical shape. Figure 2 The rectangular parallelepiped shape or the elongated needle shape shown in the figure, or the shape with protrusions having the same diameter as or longer than the center like a sea urchin, are not considered "substantially spherical". Figure 2The primary particles or secondary particles shown have more crystal growth in a specific axial direction than the other two axes or form more aggregates in a specific axial direction, thereby having an approximate rectangular parallelepiped shape. In the case of being referred to as "rectangular parallelepiped", it is not necessary to be a complete rectangular parallelepiped (all 6 faces are formed into a rectangle or a square). In addition, the shape of the particle cross section perpendicular to the major axis direction does not need to be a rectangle or a square, and the cross-sectional shapes of all cross sections do not need to be the same shape.

[0068] “The particle shape is substantially spherical” or “the particle shape is rectangular parallelepiped” means that 80% by number or more, preferably 85% by number or more of the particles constituting the pigment of the present invention are substantially spherical or rectangular parallelepiped, respectively.

[0069] Although it cannot be generalized, pigments composed of roughly spherical particles are suitable for obtaining a smooth touch when used in cosmetics. On the other hand, pigments composed of rectangular particles tend to have greater hiding power than roughly spherical particles, and are suitable for obtaining cosmetics requiring hiding power.

[0070] When the pigment of the present invention is in a rectangular parallelepiped shape, it has the advantage of being able to obtain a greater hiding power than when it is in a substantially spherical shape, but the pigment of the present invention is not limited to a rectangular parallelepiped shape. For example, when it is desired to make the particle shape of the pigment substantially spherical according to the desired texture of the cosmetic, according to the present invention, by observing the particles of the calcium titanium composite oxide using a transmission electron microscope photograph with a magnification of 100,000 times, it can be confirmed that the particles are scattered in spots with a lighter color than the surrounding parts, and the true density is 3500 kg / m 3 Above and 3790kg / m 3 A pigment composed of substantially spherical particles having the characteristic of "below" has an advantage of being able to obtain greater hiding power than a pigment composed of substantially spherical particles not having such a characteristic.

[0071] The particle size of the pigment of the present invention is preferably 200 nm or more and 500 nm or less. When the particle size is within such a range, light scattering is easily generated, and a tendency to obtain a large hiding power is easily obtained. The method for measuring the particle size of the pigment will be described later.

[0072] The pigment of the present invention preferably has a small width of particle size distribution. When the width of particle size distribution is large, the particle size becomes uneven, the filling rate is reduced when used in cosmetics, and the hiding power is easily reduced. The width of particle size distribution is preferably 10.00 or less, more preferably 8.00 or less, and further preferably 5.00 or less. The method for measuring the width of the particle size distribution of the pigment will be described later.

[0073] The pigment of the present invention may be used as a substitute material for cosmetics obtained using titanium oxide, so it is expected that the content of titanium oxide is small. In order to calculate the strict content of titanium oxide in the calcium titanium composite oxide, it is necessary to mix the pigment of the present invention with titanium oxide, implement X-ray diffraction measurement based on the powder method, and prepare a standard curve, but this method requires a lot of time and cost. Therefore, as a simpler method to confirm that the content of titanium oxide is small, the following method can be listed; in the X-ray diffraction measurement based on the powder method, the diffraction line of the (121) plane appearing in the range of 32.50° or more and 33.50° or less with the largest integrated diffraction intensity in the calcium titanium composite oxide is compared with the diffraction line appearing in the range of 24.75° or more and 28.00° or less with the largest integrated diffraction intensity in rutile, anatase and brookite titanium oxides. In the present invention, when the integrated diffraction intensity of the diffraction line of the (121) plane appearing at 32.50° or more and 33.50° or less is set to 100.0, the ratio of the integrated diffraction intensity of the diffraction line appearing in the range of 24.75° or more and 28.00° or less (hereinafter referred to as "XRD titanium oxide integrated diffraction intensity") is preferably 12.00 or less. If such conditions are met, it can be considered that the content of titanium oxide in the pigment is small. The above-mentioned XRD titanium oxide integrated diffraction intensity is more preferably less than 11.00, and further preferably less than 8.50. It should be noted that there are diffraction lines of the (111) plane of the calcium titanium composite oxide in the range of 24.75° or more and 28.00° or less, and the integrated diffraction intensity of the diffraction line of the (121) plane when the integrated intensity is set to 100.0 is about 3, so even in the case of no titanium oxide at all, the above-mentioned integrated diffraction intensity will not be zero.

[0074] The color of the pigment of the present invention is not particularly limited, but is preferably white, the same as titanium oxide, because it can be used as a substitute for titanium oxide.

[0075] In order to impart hydrophobicity, optical properties, etc., the pigment of the present invention may also have a covering layer composed of an inorganic substance on the surface of the particle. In addition, a covering layer composed of an organic substance may also be present. There may be more than two covering layers, or both an inorganic layer and an organic layer may also be present.

[0076] The pigment of the present invention preferably has a warm light transmission effect calculated by the method described below of 0.580 or more. When the warm light transmission effect is 0.580 or more, when used in cosmetics, the reflection of the warm color area inside the skin becomes sufficient, and a natural makeup can be obtained. It should be noted that there is no particular upper limit on the warm light transmission effect, but the theoretical maximum value of the warm light transmission effect calculated by the evaluation method used in the present invention is 1.000.

[0077] The pigment obtained in the present invention preferably has a large hiding power. When the hiding rate as an index of hiding power is evaluated by the method described later, the pigment whose particles are roughly spherical preferably has a hiding rate of 0.690 or more. The pigment whose particle shape is roughly spherical and whose hiding rate is within the above range can give a smooth touch and hiding power to cosmetics. The pigment whose particles are rectangular parallelepiped preferably has a hiding rate of 0.730 or more. The pigment whose particle shape is rectangular parallelepiped and whose hiding rate is within the above range can give very large hiding power to cosmetics. It should be noted that the upper limit of the hiding rate is not particularly limited, but the theoretical maximum value of the hiding rate calculated by the evaluation method used in the present invention is 1.00.

[0078] An example of the method for producing the pigment of the present invention is shown below. It should be noted that the method for producing the pigment of the present invention is not limited to the following method.

[0079] The pigment of the present invention, which contains particles having the above-mentioned calcium titanium composite oxide as the main component, can be manufactured by the following process: heating an aqueous solution containing a titanium source and a calcium source, reacting the titanium source and the calcium source to generate a reactant, decalcifying the obtained reactant, performing solid-liquid separation to recover the solid component, and heating (calcining) the obtained solid component. The titanium source is preferably an acid deflocculated product of a hydrolyzate of a titanium compound, and a representative one is a deflocculated product of metatitanic acid obtained by a method called a sulfuric acid method. When reacting the titanium source and the calcium source, it is preferred to mix an alkali and heat to above 70°C and below 100°C at normal pressure (normal pressure heating reaction method). During the decalcification treatment, it is preferred to cool the reactant obtained by the normal pressure heating reaction method and keep it below pH 7.0 for more than 1 hour. The obtained solid component is preferably calcined at above 500°C.

[0080] (Sulfuric acid method)

[0081] By dissolving ilmenite with concentrated sulfuric acid, removing the generated iron sulfate component, and undergoing a hydrolysis process, titanic acid represented by the chemical formula TiO(OH)2 can be obtained.

[0082] (Normal pressure heating reaction method)

[0083] As a representative example of a titanium source, i.e., an acid deflocculated product of a hydrolyzate of a titanium compound, an acid deflocculated product of metatitanic acid can be cited. As metatitanic acid, it is preferred to use a compound having a sulfur content of 15 g / kg or less, preferably 10 g / kg or less, as a hydrolyzate of a titanium compound, and to use hydrochloric acid to adjust the hydrolyzate to a pH of 0.8 or more and 1.5 or less for deflocculation. By using the deflocculated product of metatitanic acid thus obtained as a titanium source, particles of calcium titanium composite oxide having a small width of particle size distribution can be obtained. If the sulfur in metatitanic acid exceeds 15 g / kg as SO3, deflocculation is sometimes impossible. 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 deflocculated product of the hydrolyzate of the titanium compound, a substance obtained by neutralizing the deflocculated product with an alkali can also be used.

[0084] The calcium source (water-soluble compound containing calcium) is not particularly limited, and examples thereof include calcium hydroxide and calcium carbonate.

[0085] As factors affecting the crystallinity and particle size of the pigment containing particles with calcium titanium composite oxide obtained by normal pressure heating reaction method as the main component, the concentration and mixing ratio of the raw materials, the concentration of the alkali, the reaction temperature and additives can be listed. The mixing ratio of the water-soluble compound containing titanium source and calcium source is preferably that the amount of calcium (Ca element) is 1.00 times or more and 1.60 times or less relative to the amount of titanium (Ti element), and more preferably 1.10 times or more and 1.50 times or less. The acid deflocculation product of the hydrolyzate of the titanium compound used as the titanium source has a small solubility in water. Therefore, when the amount of calcium is less than the amount of titanium, in the reaction product, not only calcium titanium composite oxide particles will remain, but also unreacted titanium oxide will easily remain. As the concentration of the acid deflocculation product of the hydrolyzate of the titanium compound in the mixture in the normal pressure heating reaction method, Ti is preferably 0.5mol / L or more and 1.5mol / L or less, and more preferably 0.7mol / L or more and 1.4mol / L or less.

[0086] When heating the reaction at normal pressure, it is preferred to add an alkali on the basis of the titanium source and the calcium source. As the alkali, caustic alkali can be used, wherein sodium hydroxide is preferred. The concentration of the alkali in the mixture during the heating reaction at normal pressure is preferably 0.1 mol / L or more, more preferably in the range of 0.5 mol / L or more and 3.6 mol / L or less.

[0087] The higher the reaction temperature, the more crystalline the product will be. However, a reaction at a temperature greater than 100°C requires a pressure vessel, so in practical applications, a range of 70°C to 100°C is appropriate, and a range of 70°C to less than 100°C is also possible.

[0088] When the shape of the particles of calcium titanium composite oxide is roughly spherical, during the normal pressure heating reaction, as an additive, one or more than two of monosaccharides and disaccharides selected from glucose, maltose, etc. can be added. In the case of adding sugar as described above, relative to the amount of calcium added during the normal pressure heating reaction, the sum of the concentrations of these sugars is preferably more than 0.0115mol / mol and less than 0.0195mol / mol. When the concentration is less than 0.115mol / mol, the particles will not become roughly spherical, and when greater than 0.195mol / mol, there is a tendency for titanium oxide to remain easily. In addition, usually, if the addition amount of sugar is large, there is a tendency for the particle size to become smaller, but when used as a cosmetic, it is preferred that the particle size is not too small, and from this point of view, the concentration of the added sugar is preferably less than 0.195mol / mol.

[0089] 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 the aliphatic hydroxy acid compound is added, the aspect ratio of the particles of the calcium titanium composite oxide increases. When the aliphatic hydroxy acid is added, the amount of the 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.

[0090] (Decalcification treatment)

[0091] After synthesizing calcium titanium composite oxide by normal pressure heating reaction, in order to prevent unreacted calcium from remaining and hindering surface treatment, decalcification treatment is preferably performed. The decalcification treatment includes: after the reactants from the normal pressure heating reaction are cooled to below 55°C, the pH is adjusted to below 7.0 with an acid. It is more preferably below pH 6.0. The lower limit of pH is preferably above 2.5, and more preferably above 4.5. As the type of acid for adjusting pH, for example, hydrochloric acid, nitric acid, acetic acid, etc. can be listed. If the pH value is greater than 7.0, it may not be possible to remove unreacted calcium. On the other hand, if the pH is less than 2.5, the calcium in the calcium titanium composite oxide flows out into the acid, and titanium oxide may be partially generated.

[0092] (Roasting)

[0093] Preferably, after decalcification, solid-liquid separation is performed to recover the solid content, and the obtained solid content is calcined. The higher the calcination temperature, the higher the hiding power of the obtained pigment. However, if the calcination temperature is higher than 900°C, the pores inside the pigment particles may decrease, which is not preferred. The calcination temperature when manufacturing the pigment of the present invention is preferably 500°C or more and 900°C or less.

[0094] (Surface covering treatment)

[0095] As for the pigment of the present invention, for example, in order to improve the dispersion stability and durability in the dispersion medium when manufacturing cosmetics, an inorganic covering layer may be added to at least a portion of the surface of the particles in the pigment, for example, a hydroxide or oxide containing metals such as aluminum, silicon, zinc, titanium, zirconium, iron, cerium and tin. Metal salts other than the above may also be used as the covering of the inorganic substance. In addition, in order to implement surface modification represented by hydrophobic treatment on at least a portion of the surface of the particles, an organic covering layer may also be added. As the covering of the organic substance, organic silicon compounds such as polydimethylsiloxane, methyl hydrogen polysiloxane, coupling agents such as silane, aluminum, titanium and zirconium, fluorine compounds such as perfluoroalkyl phosphate compounds, hydrocarbons, lecithin, amino acids, polyethylene, wax, metal soaps, etc. may be listed. These treatments may be implemented in combination, and at this time, there is no particular restriction on the order of treatment.

[0096] (Purpose of pigments)

[0097] The pigment of the present invention can preferentially transmit light in the warm color region. When used as a material for cosmetics applied on the skin, the transmitted light in the warm color region is scattered inside the skin, thereby suppressing whitening and achieving a natural makeup. In addition, since the pigment of the present invention strongly scatters light outside the warm color region, when used as a material for cosmetics applied on the skin, it can cover the redness, dullness, spots, freckles, etc. caused by the skin and present a uniform and beautiful skin. Therefore, the pigment of the present invention can be suitably used as a material for cosmetics. Cosmetics containing the pigment of the present invention are one embodiment of the present invention. In addition, from another perspective, it can be considered that the use of the pigment of the present invention as a cosmetic is also one embodiment of the present invention, and the use of the pigment of the present invention for suppressing the whitening phenomenon in cosmetics is also one embodiment of the present invention. Among them, "whitening phenomenon" refers to the phenomenon that the finished makeup looks pale and unnatural when the intensity of the white scattered light is strong when the cosmetics are applied on the skin. "Suppressing whitening phenomenon" means that the pigment of the present invention mixed in the cosmetics preferentially 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 alleviating the above-mentioned whitening phenomenon, and the finished makeup looks natural. It should be noted that “light in a warm color region” refers to light having a wavelength of 570 nm to 780 nm.

[0098] The pigment of the present invention can also be used in a wide range of applications in fields other than cosmetics by utilizing the function of transmitting light in the warm color range. Such applications include, for example, adding the pigment to a resin for use in a sunroof of a car, and adding the pigment to a coating for transmitting light in the warm color range, but are not limited thereto. In addition, the pigment obtained in the present invention can also be used as a substitute material for titanium oxide.

[0099] (cosmetic)

[0100] When the pigment of the present invention is used as a cosmetic, it can be mixed with an inorganic pigment and / or an organic pigment etc. according to a known method after the surface is covered as described above. The content of the pigment of the present invention in the cosmetic varies according to the type of the cosmetic and is not particularly limited. For example, the amount of powder cosmetics can be more than 1g / kg and less than 900g / kg, the amount of oil cosmetics can be more than 1g / kg and less than 500g / kg, and the amount of emulsion or cream cosmetics can be more than 1g / kg and less than 150g / kg, but is not limited to this range.

[0101] As inorganic pigments and / or organic pigments that can be mixed when the pigment of the present invention is used as cosmetics, inorganic pigments, organic pigments, etc. used in common cosmetics can be used as needed. As such inorganic pigments, titanium oxide, zinc oxide, iron oxide represented by red iron oxide, cerium oxide, aluminum oxide, zirconium oxide, magnesium oxide, chromium oxide, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium sulfate, magnesium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, talc, mica, surface-treated mica, mica-shaped synthetic pigments, sericite, zeolite, kaolin, bentonite, clay, silicic acid, boron nitride, bismuth oxychloride, hydroxyapatite, ultramarine, cyanine and their dehydrates, complexes, etc. can be cited. Similarly as organic pigments, silicone powder, silicone elastic powder, polyurethane powder, cellulose powder, nylon powder, polyurethane powder, silk powder, polymethyl methacrylate (hereinafter referred to as "PMMA") powder, polyethylene powder, starch, carbon black, metal soaps such as zinc stearate, etc. and their complexes, etc. can be cited. In addition, tar pigment or various natural pigments can also be used.

[0102] The method for making the cosmetics is not particularly limited, and a known method can be used. The dosage form of the cosmetics is also not particularly limited, and can be, for example, any state of powder, powder solid, cream, emulsion, lotion, oily liquid, oily solid, paste, etc. For example, it can be made into makeup cosmetics such as primer, foundation, concealer, loose powder, CC cream, sunscreen cosmetics, lipstick, rouge, lipstick, lip glaze, lip gloss, eye shadow, eyeliner, mascara, blush, nail polish, body powder, scented powder, baby powder, skin care cosmetics, hair care cosmetics, etc. From the perspective of making the most of the transmission effect and covering power of the pigment of the present invention on the light in the warm color region, it is preferably used for makeup cosmetics applied on the skin.

[0103] It should be noted that, in addition to the above-mentioned ingredients, other ingredients may be blended in the cosmetics of the present invention according to the purpose within the range of quantity and quality that do not impair the effects of the present invention. For example, oily ingredients, pigments, pH adjusters, moisturizers, thickeners, surfactants, dispersants, stabilizers, colorants, preservatives, antioxidants, metal chelating agents, astringents, anti-inflammatory agents, ultraviolet absorbers, fragrances, some pharmaceuticals, etc. may be appropriately blended according to the purpose.

[0104] Except cosmetics, pigment of the present invention can also be used in fields such as resin combination, coating, ink.That is, the resin combination, coating or ink comprising the pigment of the present invention is a mode of the present invention.In addition, from another angle, the use of the pigment of the present invention in resin combination, coating or ink is also a mode of the present invention.In addition, for example, it can be considered that the use of the pigment of the present invention in the manufacture of resin combination, coating or ink is also a mode of the present invention.

[0105] The pigment of the present invention can be used as one of the materials of the resin composition. Specifically, the resin composition containing the pigment of the present invention can be used for automobile sunroofs, resin containers, etc., but is not limited to these. As the resin, any one of thermoplastic resins such as polyethylene, polypropylene, and thermosetting resins such as polycarbonate can be used. The resin composition is manufactured by a known method. For example, by dispersing monomers and the pigment of the present invention in a solvent such as an organic solvent or water, adding a polymerization initiator and heating, washing and drying, a resin composition containing the pigment of the present invention can be obtained. Flame retardants, fillers, etc. can be used in any combination. The pigment of the present invention is preferably added in a manner of more than 1g / kg and less than 350g / kg in the obtained resin composition, but is not limited to this range. By using the pigment of the present invention, a white resin composition with warm light can be obtained.

[0106] The pigment of the present invention can be used as one of the materials of coatings. Specifically, the coating containing the pigment of the present invention can be used for residential coatings in cold areas, but is not limited to this. The pigment of the present invention can be used for both water-based coatings and oil-based coatings. The coating can be obtained from resins such as acrylic resins, polyurethane resins, polyvinyl alcohol, solvents such as toluene, ethanol, water, and colorants represented by the pigment of the present invention. The coating is manufactured by a known method. For example, a curing agent is added to the resin, and then the pigment and solvent obtained in the present invention are added and stirred to obtain a coating containing the pigment of the present invention. Anti-settling agents, preservatives, other pigments, etc. can be used in any combination. The pigment of the present invention is preferably added to the dried coating film after use in an amount of more than 1g / kg and less than 700g / kg, but is not limited to this range. By using the pigment of the present invention, residential coatings that preferentially transmit light in warm color areas and easily increase indoor temperature can be obtained.

[0107] The pigment of the present invention can be used in ink. Specifically, the ink containing the pigment of the present invention can be used for special inks printed on thin films, glass surfaces, etc., but is not limited to these. The ink can be obtained from a colorant represented by the pigment obtained by the present invention, a resin such as an acrylic resin, a ketone, a hydrocarbon, a solvent, and the like. The ink is manufactured by a known method. For example, the ink is obtained by dispersing and mixing the colorant, the resin, and the solvent. pH adjusters, surfactants, preservatives, pigments other than the pigment obtained in the present invention, etc. can be used in any combination. The pigment of the present invention is preferably added in a manner of more than 1g / kg and less than 600g / kg in the obtained ink, but is not limited to this range. By using the pigment of the present invention, for example, printing on a transparent substrate such as plastic or glass, it is made to have a beauty that white pigments have not had so far.

[0108] In addition to the above, the pigment of the present invention can also be used for paper, toner external additives, coating tools, fiber products, packaging materials, coating films, coating materials and the like.

[0109] Before describing the examples, the test methods used in the present invention will be described.

[0110] (The diameter or major axis length of the part that is lighter than the surrounding area and the number of parts per unit area)

[0111] The pigment was photographed using a transmission electron microscope JEM-1400plus (hereinafter referred to as "TEM") manufactured by JEOL Ltd. at an accelerating voltage of 100 kV and a magnification of 100,000 times. Among the particles in the photograph, particles that have the same appearance as the surrounding particles were focused as much as possible, except for particles that overlapped with each other and particles whose thickness made it difficult to count the spot-like pattern, and the particles were photographed with clear contrast. In the photograph of the selected particles, Figure 4 As shown, the drawn area is 1.0×10 4 nm 2 Rectangular frame. In the area within the frame, measure the diameter or major axis length of the light-colored parts with a roughly circular or roughly elliptical appearance scattered in spots. Perform the same operation on more than 10 particles, and record the number average (average diameter) and maximum value (maximum diameter) of the diameter or major axis length of the light-colored parts scattered in spots within the range of 1.5nm to 15.0nm. In the case where the spots are connected to each other, for spots with an outer diameter of 1 / 2 or more that can be confirmed, the diameter is estimated based on the outer diameter of the particles. In addition, by visually counting the above-mentioned particles located at 1.0×10 4 nm 2The number of spot-like light-colored parts within the range of a diameter or a major axis length of 1.5 nm or more and 15.0 nm or less within the frame. It should be noted that the "light-colored parts" mentioned in the present invention refer to parts that are generally widely distributed inside the calcium titanium composite oxide particles in the pigment of the present invention and are lighter in color than the surroundings (usually white or light gray relative to the dark gray or black surroundings). It can be observed that in the above-mentioned particles of the present invention, the light-colored parts are generally scattered in the form of spots in a roughly circular or elliptical shape. Errors in TEM photos caused by the apparatus or instruments used in the evaluation, special de-whitening parts in the particles that present an appearance that is significantly different from other surrounding particles due to local foreign matter and particle defects, etc. are not included in the "light-colored parts" mentioned in the present invention.

[0112] When the entire particle is observed at a magnification of 100,000 times according to the above method and no light-colored portions are observed to be scattered in spots, it is determined that no spot-like pattern exists inside the particle.

[0113] (True density)

[0114] The measurement was performed according to method A of JIS K 5101-11-1: 2004. A 50 mL pycnometer 055520-050 manufactured by Shibata Scientific Co., Ltd. and SAJ special grade kerosene manufactured by Sigma Aldrich Japan Co., Ltd. were used as the replacement liquid. The true density was measured by using 2 g of a dry product as a sample and adjusting the temperature to 25°C.

[0115] (Width of particle size distribution)

[0116] The width of the particle size distribution was measured using a laser diffraction scattering particle size analyzer Microtrac (registered trademark) MT3300EXII manufactured by Microtrac MRB Co., Ltd. in accordance with a method based on 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 the automatic sample circulator attached to the measuring device, ultrasonic dispersion was performed for 360 seconds at a power of 40 W. Thereafter, with respect to each measurement parameter, the refractive index of the ion-exchanged water was set to 1.33, the light transmittance of the particles to be measured was measured by reflection, the measurement time was set to 30 seconds, and the particle size (X10) corresponding to 10% of the cumulative particle size distribution (volume basis) and the particle size (X90) corresponding to 90% of the cumulative particle size distribution (volume basis) were measured, and X90 / X10 was set as the width of the particle size distribution.

[0117] (Particle size)

[0118] The particle size is calculated by setting the area of ​​the particle when it is projected two-dimensionally to S and the equivalent diameter of the circle of equal area to R to 2×(S / π)^ 0.5The area S of the particle was obtained by photographing the particle with a TEM at an observation magnification of 10,000 times and calculating it using the image analysis software ImageJ. The average value of R of 200 or more particles was taken as the particle size.

[0119] (XRD titanium oxide integrated diffraction intensity)

[0120] X-ray diffraction measurement based on the powder method was performed using an X-ray diffraction device RINT-TTR III manufactured by Rigaku Co., Ltd. The sample was ground in a mortar and filled in a cuvette at about 1.5 g ± 0.2 g, the starting angle was set to 5.0000°, the ending angle was set to 90.0000°, the sampling width was set to 0.0100°, the scanning rate was set to 10.0000° / min, the divergence slit was set to 0.5°, the scattering slit was set to 0.5°, the width of the light receiving slit was set to 0.15 mm, copper was used as the cathode for the characteristic X-ray, and the wavelength was set to 0.15418 nm. For the obtained X-ray diffraction pattern, background processing, smoothing and peak detection were performed using the powder X-ray analysis software PDXL2 manufactured by Rigaku Corporation. The ratio of the integrated diffraction intensity of the diffraction line of the (121) plane appearing in the range of the diffraction angle 2θ being 32.50° to 33.50° was calculated to be 100.0, and the ratio was used as the XRD titanium oxide integrated diffraction intensity.

[0121] (Warm light transmission effect)

[0122] 3 mL of styrenated alkyd resin and 0.3 g of pigment were kneaded and coated using an H3 type automatic grinder manufactured by Toyo Seiki Seisaku-sho, Ltd. The resulting dispersion was applied to a black and white hiding test paper JIS-K5600-4-1 using a scraper of a 3-mill, and sintered at 130°C for 30 minutes to obtain a test sample. The reflectivity of the black matrix of the test sample at a wavelength of 380 nm or more and 780 nm or less was measured using a spectrophotometer SQ-2000 manufactured by Nippon Denshoku Industries (hereinafter referred to as "colorimeter"). The measured value was subtracted from 100% to calculate the transmittance at each wavelength. The total value of the transmittance at 380 nm or more and 780 nm or less was taken as the total transmitted light amount, the total value of the transmittance at 570 nm or more and 780 nm or less was taken as the warm color transmitted light amount, and the value of warm color transmitted light amount / total transmitted light amount was taken as the warm color light transmission effect.

[0123] (Coverage)

[0124] The hiding power of the pigment is measured by using a colorimeter to measure the brightness index L at the black background of the test sample prepared by the method described in the column of the warm light transmission effect. band the brightness index L at the white background w , L b / L w The value of is taken as the coverage rate.

[0125] Example

[0126] Hereinafter, the present invention will be specifically described by way of examples. However, the following examples are merely illustrative and do not limit the scope of the invention.

[0127] It should be noted that, in the stirring operation described in the embodiments and comparative examples, the rotating speed is appropriately adjusted in such a way that the liquid as a whole is uniformly mixed and the foam does not scatter around, taking into account the properties related to the state of the liquid during stirring, such as the amount of the liquid, the viscosity of the liquid, and the shape of the container. In addition, if it is a common commercial product such as sodium hydroxide, when the same effect can be obtained regardless of which company's commercial product is used, the company name of the manufacturer and the distributor is omitted.

[0128] [Example 1: Rectangular particles]

[0129] After the titanic acid obtained by the sulfuric acid method is subjected to a de-ironification and bleaching treatment, a sodium hydroxide aqueous solution is added to adjust the pH to 9.0 for desulfurization treatment, and then it is neutralized with hydrochloric acid to a pH of 5.8, filtered and washed with water to obtain a titanic acid filter cake (hydrolysis product of titanium compound) with a sulfur content of 9.3 g / kg in terms of SO3. Water is added to the washed filter cake to make a slurry with a Ti content of 2.13 mol / L, and hydrochloric acid is added to adjust the pH to 1.4 for deflocculation treatment to obtain an acid deflocculation product of the hydrolysis product of the titanium compound (titanic acid). 2.25 mol of the treated slurry in terms of TiO2 is extracted and placed in a reaction vessel with a capacity of 3000 mL. Calcium hydroxide was added thereto so that the mass of calcium in the form of Ca was 1.15 times the mass of titanium in the form of Ti, 0.36 mol of sodium hydroxide was added, water was added so that the total volume was 2.0 L, and the mixed solution was stirred for 30 minutes using HEIDON600G manufactured by Shintoko Co., Ltd.

[0130] While further stirring and mixing the above slurry, the BE type heating jacket made by Tokyo Institute of Technology was used to heat to 95°C, and the reaction was terminated after continuous stirring for 18 hours (normal pressure heating reaction). The stirred slurry was naturally cooled to 50°C, hydrochloric acid was added to pH 5.0, and further stirring was continued for 1 hour (decalcification treatment). The obtained precipitate was decanted and washed, and after separation by filtration, it was dried at 120°C for 10 hours in the atmosphere using a thermostat PHH-202 made by EPOCH. The dried product was roasted in the atmosphere for 1 hour in a SUPER-C C-2035D (hereinafter referred to as "roasting furnace") made by Motoyama at 500°C. The roasted product was crushed with an Ishikawa-type stirring crushing machine AGA type (hereinafter referred to as "automatic mortar") made by Ishikawa Factory Co., Ltd. to obtain a white pigment. The shape of the particles constituting the pigment is mainly rectangular. The pigment was evaluated by the above test method, and it was confirmed that the part with lighter color than the surrounding area in the transmission electron microscope photo existed in the form of spots inside the particle. The part with lighter color than the surrounding area was circular or elliptical, with a maximum diameter or major axis length of 10.0nm and a number average of 4.1nm. In addition, the true density was 3760kg / m 3 In addition, the part with lighter color than the surrounding area is within 1.0×10 4 nm 2 There are 165 in the range of . The particle size of the pigment is 294nm, the width of the particle size distribution is 2.25, and the XRD titanium oxide integrated diffraction intensity is 5.23. In addition, the warm light transmission effect is 0.586 and the hiding rate is 0.731.

[0131] [Example 2: Rectangular particles]

[0132] Except that the setting temperature of the baking oven is changed to 700 ℃, under the same conditions as Example 1, normal pressure heating reaction, decalcification treatment, cleaning, filtration, drying and pulverization are carried out to obtain white pigment. The shape of the particles constituting the pigment is mainly rectangular. Confirm that the part with a color lighter than the surrounding in the transmission electron microscope photo of the pigment exists in a spot-like manner inside the particle, and the part with a color lighter than the surrounding is circular or elliptical. Each measurement result is as shown in Table 2.

[0133] [Example 3: Rectangular shaped particles]

[0134] Except that the setting temperature of the baking oven is changed to 900 ℃, under the same conditions as Example 1, normal pressure heating reaction, decalcification treatment, cleaning, filtration, drying and pulverization are carried out to obtain white pigment. The shape of the particles constituting the pigment is mainly rectangular. Confirm that the part with color lighter than the surrounding in the transmission electron microscope photo of the pigment exists in the particle interior as a spot, and the part with color lighter than the surrounding is circular or elliptical. Each measurement result is as shown in Table 2.

[0135] [Comparative Example 1: Rectangular Particles]

[0136] Except not carrying out the roasting based on roasting furnace, carry out normal pressure heating reaction, decalcification treatment, cleaning, filtration, drying and pulverization under the condition identical with embodiment 1, obtain white pigment.The shape of the particle constituting pigment is mainly cuboid.Confirm that in the transmission electron microscope photo of this pigment, color is than the part that is shallow around in particle interior with spot shape, and this color is than the part that is shallow around is circular or oval.Each measurement result is as shown in table 2.

[0137] [Example 4: roughly spherical particles]

[0138] Except the amount of the sodium hydroxide that will add after adding calcium hydroxide is changed into 3.60mol, adding sodium hydroxide and adding 0.0193mol glucose relative to the Ca of 1mol, under the condition identical with Example 1, carry out normal pressure heating reaction, decalcification, cleaning, filtration, drying and pulverizing, obtain white pigment.The shape of the particle that constitutes pigment is mainly roughly spherical.Confirm that color exists with spotty inside particle than the part that is shallow around in the transmission electron microscope photo of this pigment, and this color is circular or elliptical than the part that is shallow around.Each measurement result is as shown in table 2.

[0139] [Example 5: roughly spherical particles]

[0140] Except that the setting temperature of the baking furnace is changed to 700 ℃, under the same conditions as Example 4, normal pressure heating reaction, decalcification treatment, cleaning, filtration, drying and pulverization are carried out to obtain white pigment. The shape of the particles constituting the pigment is mainly roughly spherical. Confirm that the part with lighter color than the surrounding in the transmission electron microscope photo of the pigment exists in the particle interior as a spot, and the part with lighter color than the surrounding is circular or elliptical. Each measurement result is as shown in Table 2.

[0141] [Example 6: roughly spherical particles]

[0142] Except that the setting temperature of the baking furnace is changed to 900 ℃, under the same conditions as Example 4, normal pressure heating reaction, decalcification treatment, cleaning, filtration, drying and pulverization are carried out to obtain white pigment. The shape of the particles constituting the pigment is mainly roughly spherical. Confirm that the part with lighter color than the surrounding in the transmission electron microscope photo of the pigment exists in the particle as a spot, and the part with lighter color than the surrounding is round or oval. Each measurement result is as shown in Table 2.

[0143] [Comparative Example 2: Approximately spherical particles]

[0144] Except not carrying out the roasting based on roasting furnace, carry out normal pressure heating reaction, decalcification treatment, cleaning, filtration, drying and pulverization under the same condition as Example 4, obtain white pigment.The shape of the particle constituting pigment is mainly roughly spherical.Confirm that in the transmission electron microscope photo of this pigment, color is lighter than surrounding part in particle interior with spot shape, and this color is round or oval than surrounding part.Each measurement result is as shown in table 2.

[0145] [Comparative Example 3: Commercially available product]

[0146] A commercially available calcium titanium composite oxide reagent CAF04PB manufactured by a high-purity chemical research institute was used as comparative example 3. The appearance of this reagent was light pink, and in the transmission electron microscope photograph, the color tone inside the particles was roughly the same, and no spot-like pattern could be confirmed. The measurement results are shown in Table 2.

[0147] Table 1 shows the production conditions of the pigments of Examples and Comparative Examples, and Table 2 shows the measurement results of the properties of the pigments obtained in Examples and Comparative Examples.

[0148] As shown in Table 2, in the transmission electron microscope photograph, the pigment containing particles mainly composed of calcium titanium composite oxide particles whose color is lighter than the surrounding area and which is present in the form of spots inside the particles has a greater warm light transmission effect than the pigment in which no spot pattern is confirmed (Comparative Example 3). 3 Above and 3790kg / m 3 The following pigments also have greater hiding power when compared with pigments of the same particle shape (comparison of Examples 1 to 3 with Comparative Example 1 and comparison of Examples 4 to 6 with Comparative Example 2). These pigments are believed to be pigments that preferentially transmit light in the warm color range and have greater hiding power.

[0149] As described above, it is believed that the pigment of the present invention preferentially transmits light in the warm color range and has a high hiding power. By using the pigment of the present invention as a raw material for cosmetics, a cosmetic that realizes a natural makeup and has a high hiding power can be obtained.

[0150] [Table 1]

[0151]

[0152] [Table 2]

[0153]

[0154] Next, sensory evaluation was performed on the pressed powders produced using the pigments obtained in Examples and Comparative Examples according to the following method.

[0155] (Sensory evaluation of pressed powder)

[0156] Each pigment obtained in the examples and comparative examples was surface treated with methyl hydrogen polysiloxane and uniformly mixed using LAB.MIXER LM-110T manufactured by HANIL Electric.Co., Lid (hereinafter referred to as "mixer") at the mixing ratio shown in Table 3. The mixture was pulverized using a sample mill TASM-1 manufactured by Tokyo Atomizer Manufacturing Co., Ltd. (hereinafter referred to as "sample mill"), and a prescribed amount was filled into a metal dish and compression molded to prepare a powder cake.

[0157] [Table 3]

[0158]

[0159] Ten panelists were asked to apply each of the obtained pressed powders on their arms and faces, particularly on areas with dark spots and blemishes, and evaluate the natural finish and coverage.

[0160] (Natural makeup)

[0161] The following criteria were used to evaluate the impression of visual comparison with the area without foundation, and the average score of 10 panelists was used to determine the "natural makeup face". The higher the score, the less "white" the foundation was, and the more "natural makeup face" was achieved. Table 4 shows the results of the sensory evaluation.

[0162] (Evaluation Criteria)

[0163] 4 points: Even at a very close distance (30 cm), the area cannot be distinguished from the unapplied area.

[0164] 3 points: From a very close distance, you can tell that the paint has been applied, but it gives a natural impression.

[0165] 2 points: It gives a whitish impression when viewed from a very close distance.

[0166] 1 point: Even when viewed from a distance (1m), the image appears whitish.

[0167] (Hiding power)

[0168] The impression of applying foundation on spots or dark spots was evaluated according to the following criteria, and the "covering power" was determined based on the average score of 10 panelists. The higher the score, the better the covering power of the foundation. Table 4 shows the results of the sensory evaluation.

[0169] (Evaluation Criteria)

[0170] 4 points: Even when viewed from a very close distance (30 cm), the presence of spots or dark spots is not apparent.

[0171] 3 points: When viewed from a very close distance, spots or dark spots can be seen, but they are not noticeable.

[0172] 2 points: Spots or dark spots can be seen from a very close distance.

[0173] 1 point: Spots or dark spots can be discerned at the same distance as when no application is made.

[0174] (Comprehensive evaluation criteria)

[0175] The total score of the natural makeup and the coverage is 7 points or more: A; 5 points or more and less than 7 points: B; 3 points or more and less than 5 points: C; less than 3 points: D

[0176] [Table 4]

[0177]

[0178] The results of the sensory evaluation show that when a foundation made of a pigment with particles having a spot-like pattern as the main component is used, there is less white floating and the makeup is natural. In addition, when comparing pigments with the same particle shape (comparison of Examples 1 to 3 with Comparative Example 1 and comparison of Examples 4 to 6 with Comparative Examples 2 and 3), it can be seen that the pigments of the present invention have greater hiding power than the pigments of the comparative examples. In addition, compared with pigments with rectangular particles, the pigments of Examples 4 to 6 with roughly spherical particles have a smooth touch. It can be seen that by mixing the pigment of the present invention into cosmetics, a cosmetic that presents a natural makeup and has excellent hiding power can be provided.

[0179] [Example 7]

[0180] (Manufacturing of pressed powder)

[0181] After mixing and uniformly grinding the following components 1 to 13 (step A), components 15 to 17 are uniformly mixed and added to the mixed and ground product obtained in step A to make it uniform (step B). Component 14 is then added and pressed in a mold to obtain a powder cake (step C).

[0182] It was confirmed that the obtained pressed powder did not cause whitening when applied on the skin, and the makeup had a natural bare face feeling and good covering power.

[0183]

[0184] (Note 1) The surface was treated with AES-3083 manufactured by Shin-Etsu Chemical Co., Ltd.

[0185] (Note 2) The surface was treated with KF-9909 manufactured by Shin-Etsu Chemical Co., Ltd.

[0186] (Note 3) KSP-300 manufactured by Shin-Etsu Chemical Co., Ltd.

[0187] (Note 4) KMP-590 manufactured by Shin-Etsu Chemical Co., Ltd.

[0188] (Note 5) KSG-16 manufactured by Shin-Etsu Chemical Co., Ltd.

[0189] [Example 8]

[0190] (Manufacture of pressed powder)

[0191] After mixing and grinding the following components 1 to 7 (process A), the mixed and ground product is transferred to a mixer, and components 8 to 12 are added and stirred uniformly (process B), and then ground with a sample mill and pressed into an aluminum pan to obtain a pressed powder cake (process C).

[0192] It was confirmed that the obtained pressed powder did not cause whitening when applied on the skin, and the makeup had a natural bare face feeling and good covering power.

[0193]

[0194] (Note 1) Matsumoto microsphere M-100, 7 μm, manufactured by Matsumoto Oil & Fats Pharmaceutical Co., Ltd.

[0195] (Note 2) Sunlovely C manufactured by Dokai Chemical Industry Co., Ltd.

[0196] [Example 9]

[0197] (Manufacturing of loose powder)

[0198] After mixing and grinding the following components 1 to 7 (step A), the mixed and ground product is transferred to a mixer, and components 8 to 10 are added and uniformly stirred and mixed (step B). Next, the mixture obtained in step B is ground with a sample mill and filled to obtain loose powder (step C).

[0199] It was confirmed that the obtained loose powder did not cause whitening when applied on the skin, and the makeup had a natural bare face feeling and good covering power.

[0200]

[0201] (Note 1) Matsumoto Microsphere S-100, 10 μm, manufactured by Matsumoto Oil & Fats Pharmaceutical Co., Ltd.

[0202] [Example 10]

[0203] (Manufacturing of oily foundation)

[0204] The following components 1 to 6 are mixed with a mixer and pulverized uniformly (step A), components 7 to 16 are heated to 85°C to dissolve, the mixed pulverized product obtained in step A is added, and the mixture is stirred uniformly (step B). After degassing, the solid component is added to a tray and slowly cooled to room temperature to obtain an oily foundation (step C).

[0205] It was confirmed that the obtained oil-based foundation did not cause whitening when applied on the skin, had a natural bare-faced look, and had good covering power.

[0206]

[0207] (Note 1) The surface was treated with KF-96A-50cs manufactured by Shin-Etsu Chemical Co., Ltd.

[0208] [Example 11]

[0209] (Manufacture of foundation stick)

[0210] Mix the following ingredients 12 to 16 using a mixer (process A). In addition, weigh ingredients 1 to 11 in a container that can hold the total amount, heat to 85°C, and dissolve them (process B). In addition, weigh ingredients 17 to 21 in another container and dissolve them (process C). Then, add the mixture obtained in process A to the heated solution obtained in process B, disperse it with a stirrer until it is visually uniform, and then add the heated solution obtained in process C to emulsify (process D). After degassing, inject the solid component into the mold, slowly cool it to room temperature, and obtain a foundation stick (process E).

[0211] It was confirmed that the obtained foundation stick did not cause whitening when applied on the skin, and the makeup surface had a natural bare face feeling and good covering power.

[0212]

[0213] (Note 1) The surface was treated with KF-99P manufactured by Shin-Etsu Chemical Co., Ltd.

[0214] [Example 12]

[0215] (Manufacturing of W / O emulsified foundation)

[0216] After mixing the following components 12 to 14 with a mixer (step A), components 1 to 11 are added and dispersed with a stirrer until visually uniform (step B). On the other hand, components 15 to 19 are dissolved by heating in another container (step C). Then, the heated dissolved substance obtained in step C is added to the dispersion obtained in step B to emulsify, and then cooled to room temperature to obtain a W / O emulsified foundation (step D).

[0217] It was confirmed that the obtained W / O emulsified foundation did not cause whitening when applied on the skin, had a natural bare-faced look, and had good covering power.

[0218]

[0219] (Note 1) Product with HLB value 4.5

[0220] (Note 2) RHEOPEARL (registered trademark) ISK manufactured by Chiba Flour Milling Co., Ltd.

[0221] (Note 3) The surface was treated with KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd.

[0222] [Example 13]

[0223] (Manufacturing of O / W emulsified foundation)

[0224] Heat and dissolve the following components 1 to 7 at 85°C (process A). In addition, mix and grind components 8 to 10 (process B). In addition, heat components 11 to 15 to 85°C and dissolve and mix them (process C). Then, add the mixed and ground product obtained in process B to the heated dissolved product obtained in process A, disperse it with a stirrer until it is visually uniform, slowly add the dissolved mixture obtained in process C to emulsify it, and stir and cool it to room temperature. Next, fill it into a suitable container to obtain an O / W emulsified foundation (process D).

[0225] It was confirmed that the obtained O / W emulsified foundation did not cause whitening when applied on the skin, had a natural bare-faced look, and had good covering power.

[0226]

[0227]

[0228] [Example 14]

[0229] (Manufacturing of W / O liquid foundation)

[0230] After uniformly mixing the following components 8 to 12 (process A), a portion of component 4 is mixed with component 13, added to the mixture obtained in process A, and dispersed with a stirrer until visually uniform (process B). In addition, components 1 to 3, the remainder of component 4 and components 5 to 7 are mixed, and dispersed with a stirrer until visually uniform (process C). In addition, components 14 to 18 and component 20 are mixed, and dispersed with a stirrer until visually uniform (process D). Under stirring, the mixture obtained in process C is slowly added to the mixture obtained in process D for emulsification, and the dispersion obtained in process B and component 19 are further added to obtain a W / O liquid foundation (process E).

[0231] It was confirmed that the obtained W / O liquid foundation did not cause whitening when applied on the skin, and the makeup had a natural bare face feeling and had good covering power.

[0232]

[0233]

[0234] (Note 1) KSG-210 manufactured by Shin-Etsu Chemical Co., Ltd.

[0235] (Note 2) KSG-15 manufactured by Shin-Etsu Chemical Co., Ltd.

[0236] (Note 3) KF-6028P manufactured by Shin-Etsu Chemical Co., Ltd.

[0237] (Note 4) 6mm 2 / sec (25℃)

[0238] (Note 5) The surface was treated with KF-9909 manufactured by Shin-Etsu Chemical Co., Ltd.

[0239] (Note 6) KP-575 manufactured by Shin-Etsu Chemical Co., Ltd.

[0240] (Note 7) 20g / kg aqueous solution

[0241] [Example 15]

[0242] (Manufacture of sunscreen)

[0243] In order to confirm the ultraviolet blocking ability of the pigment of the present invention, a sunscreen was prepared. Component 7 was added to a part of the following component 5 and homogenized, and components 8 and 9 were added and dispersed with a bead mill (process A). In addition, components 1 to 4, the remainder of component 5 and component 6 were uniformly mixed (process B). In addition, components 10 to 12 and component 14 were dispersed with a stirrer until visually uniform (process C). Next, the mixture obtained in process C was added to the mixture obtained in process B for emulsification, and the dispersion obtained in process A and component 13 were added to obtain a sunscreen (process D).

[0244] It was confirmed that the obtained sunscreen had the same ultraviolet shielding ability as titanium oxide, and did not cause whitening when applied to the skin, giving a natural look.

[0245]

[0246]

[0247] (Note 1) KSG-240 manufactured by Shin-Etsu Chemical Co., Ltd.

[0248] (Note 2) KSG-15 manufactured by Shin-Etsu Chemical Co., Ltd.

[0249] (Note 3) KF-6038 manufactured by Shin-Etsu Chemical Co., Ltd.

[0250] (Note 4) KP-575 manufactured by Shin-Etsu Chemical Co., Ltd.

[0251] (Note 5) The surface was treated with AES-3083 manufactured by Shin-Etsu Chemical Co., Ltd.

[0252] [Example 16]

[0253] (Manufacture of resin composition)

[0254] Prepare a resin composition containing the pigment of the present invention. Distill component 1 and bubble with nitrogen for 30 minutes (process A). Mix components 5 and 6 and disperse them with a bead mill (process B). Add the liquid obtained in process A and components 2 to 4 to component 7, stir and heat, and after the temperature reaches 65°C, add the dispersion obtained in process B after 5 minutes, keep stirring at 65°C (process C). After 10 hours, add component 8 for neutralization (process D), filter, and wash to obtain a resin composition (process E).

[0255] It was confirmed that when the obtained resin composition was placed under sunlight, the ratio of the transmitted light in the warm color region was significantly large, and that the resin composition had a warm color light transmitting effect.

[0256]

[0257]

[0258] [Example 17]

[0259] (Manufacture of paint)

[0260] A coating material containing the pigment of the present invention is prepared by mixing components 1 to 4 in a mixer for 30 minutes to 120 minutes (step A), and then dispersing them in a bead mill (step B).

[0261] It was confirmed that when the obtained coating material was applied on a transparent glass substrate and placed under light, the proportion of transmitted light in the warm color region was significantly large, and it had a warm color light transmission effect.

[0262]

[0263] (Note 1) Contains polymerization initiator

[0264] [Example 18]

[0265] (Ink Manufacturing)

[0266] An ink containing the pigment of the present invention was prepared by mixing components 1 to 4 in a mixer for 30 minutes to 120 minutes (step A), and then dispersing the mixture in a bead mill for 24 hours (step B).

[0267] It was confirmed that when the obtained ink was applied on a glass plate and placed under light, the proportion of transmitted light in the warm color region was significantly large, and that the ink had a warm color light transmission effect.

[0268]

[0269] (Note 1) HOMOGENOL (registered trademark) L-18 manufactured by Kao Corporation

[0270] (Note 2) Orgonite (registered trademark)-T manufactured by Japan Organoclay Co., Ltd.

Claims

1. A pigment comprising particles containing calcium titanium composite oxide as a main component, wherein: When the particles of the calcium titanium composite oxide in the pigment were observed by a transmission electron microscope photograph at a magnification of 100,000 times, it was confirmed that portions lighter in color than the surrounding areas were scattered in spots within the particles. The true density of the pigment is 3500 kg / m 3 Above and 3790kg / m 3 the following.

2. The pigment according to claim 1, wherein The shape of the portion whose color is lighter than the surrounding is a circle with a diameter of 1.5 nm to 15.0 nm inclusive or an ellipse with a major axis length of 1.5 nm to 15.0 nm inclusive, and The portion with a lighter color than the surrounding area is equivalent to 1.0×10 4 nm 2 There are more than 100 and less than 200 in the range.

3. The pigment according to claim 1 or 2, wherein The number average value of the diameter or the major axis length of the portion whose color is lighter than the surrounding area is 2.5 nm or more and 4.5 nm or less. The pigment according to claim 1 or 2, which has a particle size of 200 nm to 500 nm.

5. The pigment according to claim 1 or 2, wherein The width of the particle size distribution defined in accordance with JIS Z 8825: 2013 is less than 10.

00.

6. The pigment according to claim 1 or 2, wherein In the X-ray diffraction measurement, when the integrated diffraction intensity of the diffraction line of the (121) plane appearing in the range of the diffraction angle of 32.50° to 33.50° is set to 100.0, the ratio of the integrated diffraction intensity of the diffraction line appearing in the range of the diffraction angle of 24.75° to 28.00° is less than 12.

00. 7 . The pigment according to claim 1 , which has a coating layer of an inorganic substance and / or an organic substance on at least a part of the surface of the particles.

8. A method for producing a pigment according to any one of claims 1 to 7, wherein: The manufacturing method comprises the following steps: preparing an aqueous solution comprising a titanium source and a calcium source; heating the aqueous solution to react the titanium source and the calcium source to generate a reactant; Decalcifying the reactant, followed by solid-liquid separation to recover the solid component; and The obtained solid content is heated.

9. A method for producing a pigment according to any one of claims 1 to 7, wherein: The manufacturing method comprises the following steps: The acid deflocculant of the hydrolyzate of the titanium compound, the water-soluble compound containing calcium and the base are mixed and heated to a temperature of 70° C. to 100° C. at normal pressure to generate a reactant; After cooling the obtained reaction product, the pH is kept below 7.0 for more than 1 hour; Performing solid-liquid separation on the reaction product after the maintenance to recover the solid component; and The solid component is calcined at 500°C or above.

10. A cosmetic comprising the pigment according to any one of claims 1 to 7. 11 . A resin composition comprising the pigment according to claim 1 .

12. A coating comprising the pigment according to any one of claims 1 to 7.

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

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