Red inorganic pigment and cosmetic

Abstract

To provide a novel red inorganic pigment and a cosmetic comprising the red inorganic pigment.SOLUTION: A red inorganic pigment comprising CaCo1-xAxB2-yAlyO6 (where A is at least one selected from Fe, Mg, and Zn, B is at least one selected from Ge and Si, 0≤x≤0.9, and 0≤y≤0.1), and a cosmetic comprising the red inorganic pigment.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a red inorganic pigment and a cosmetic product. [Background technology]

[0002] Inorganic and organic pigments are used for coloring in various fields, such as paints, inks, and cosmetics. Organic pigments are excellent in that they offer a wide variety of colors, high saturation, and high transparency and coloring power, but they have problems with lightfastness and solvent resistance. Furthermore, they may cause pigmentation and allergies, raising safety concerns, particularly in cosmetics that are applied to the skin, lips, etc. Although inorganic pigments are inferior to organic pigments in saturation, coloring power, and transparency, they are excellent in hiding power, solvent resistance, durability, and safety, and are therefore suitable for use in coloring ceramics, glass, cosmetics, and the like.

[0003] Existing red inorganic pigments include red lead (Pb3O4), cinnabar (HgS), cadmium red (CdS·CdSe), red iron oxide (Fe2O3), and ultramarine pink (SiO2·Al2O3·Na2O·S). While red lead, cinnabar, and cadmium red have extremely high saturation and vibrant colors, they contain elements (Pb, Hg, and Cd) that are harmful to the human body and the environment, and their use is restricted or prohibited. Red iron oxide and ultramarine pink are safe and are used in cosmetics, but they have low saturation and a dark, dull color. Furthermore, red iron oxide has a strong yellowish tint, while ultramarine pink has a strong blueish tint. The present applicants also reported in Non-Patent Document 1 that (Li 1-x Na x )2MnO3 (where 0≦x≦0.10) has been reported, but the pigment was very yellowish. Therefore, there is a demand for a red inorganic pigment that is free from harmful elements, is highly safe, and exhibits high chroma and vivid red with reduced yellow and blue hues. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] R. Oka, K. Kusukami, and T. Masui, “Effect of [MnO6] Octahedra to the Coloring Mechanism of (Li1-xNax)2MnO3”, ACS Omega, 2020, 5, 13108-13114. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a novel reddish inorganic pigment and a cosmetic product containing the reddish inorganic pigment. [Means for solving the problem]

[0006] The means for solving the problems of the present invention are as follows. 1. CaCo 1-x A x B 2-y Al y A red inorganic pigment consisting of O6 (where A = one or more of Fe, Mg, or Zn, B = one or more of Ge or Si, 0≦x≦0.9, 0≦y≦0.1). 2.L * a * b * In the color system, a * 1. The red inorganic pigment according to 1, which exhibits a color tone specified by +25 or more. 3. Cosmetics containing the red inorganic pigment described in 1. or 2. [Effects of the Invention]

[0007] The present invention provides a novel reddish inorganic pigment. The reddish inorganic pigment of the present invention can adjust its color tone by its composition, and can exhibit a variety of red colors, such as red, bluish red, yellowish red, and vivid and dull shades thereof. [Brief explanation of the drawings]

[0008] [Figure 1]Powder X-ray diffraction pattern of the pigment obtained in Example 1. [Figure 2] Powder X-ray diffraction pattern of the pigment obtained in Example 10.

Mode for Carrying Out the Invention

[0009] The red inorganic pigment of the present invention is CaCo 1-x A x B 2-y Al y O6 (where A = any one or more of Fe, Mg, Zn, B = any one or more of Ge, Si, 0 ≦ x ≦ 0.9, 0 ≦ y ≦ 0.1). The red inorganic pigment of the present invention can exhibit various red colors with its color tone changing depending on its composition.

[0010] In the red inorganic pigment of the present invention, any one or more of Fe, Mg, Zn represented by A are optional and may not be contained (x = 0). When A is Fe, the higher the Fe content, the stronger the yellowish tone and the tendency for the color to fade. When A is Fe, 0 < x ≦ 0.1 is preferable, 0.005 ≦ x ≦ 0.08 is more preferable, 0.005 ≦ x ≦ 0.06 is further preferable, and 0.005 ≦ x ≦ 0.04 is even more preferable. When A is Mg, it shows a vivid color tone compared to the case when A is Fe and can be pinkish red. Also, the higher the Mg content, the stronger the yellowish tone and the tendency for the color to fade. When A is Mg, 0 < x ≦ 0.9 is preferable, 0.01 ≦ x ≦ 0.8 is more preferable, 0.01 ≦ x ≦ 0.7 is further preferable, and 0.01 ≦ x ≦ 0.6 is even more preferable.

[0011] In the red inorganic pigment of the present invention, one or more of Ge and Si represented by B may be partially substituted by Al. However, Al is optional and may not be contained (y = 0). When B is Ge, it tends to have a vivid color tone, and when B is Si, it tends to have a dull color tone. Also, the higher the Al content, the stronger the yellowish tone tends to be.

[0012] L * a * b * In the color system, a * represents the degree of red or green, and a * The larger the absolute value of the positive value, the redder the color tends to be, and the larger the absolute value of the negative value, the greener the color tends to be. * represents the degree of yellow or blue, and b * The larger the absolute value of the positive value, the yellower the color tends to be, and the larger the absolute value of the negative value, the bluer the color tends to be. Hue angle h is L * a * b * Color space a * and b * Therefore, the value is expressed by the following formula (1) and has a value in the range of −180° to +180°. Equation (1) h=tan -1 (b * / a * ) The inorganic pigment of the present invention is red, * ≧5 and −45≦h≦45.

[0013] The red inorganic pigment of the present invention is L * a * b * In the color system, a * The color tone of the red inorganic pigment of the present invention is preferably defined as a * ≧+27 is more preferable, and a * ≧+29 is more preferable, and a * ≧+31 is even more preferred, * ≧+33 is even more preferred, * ≧+35 is even more preferred, * ≧+37 is even more preferred, * ≧+39 is even more preferred, * ≧+41 is even more preferred, * ≧+43 is even more preferred, * Even more preferred is ≧+45.

[0014] The red inorganic pigment of the present invention is L* a * b * The hue angle h in the color system is -45≦h≦45. The color tone of the reddish inorganic pigment of the present invention preferably exhibits a color tone in which the hue angle h is specified as -45≦h≦40, more preferably -45≦h≦30, even more preferably -40≦h≦30, still more preferably -40≦h≦25, and even more preferably -35≦h≦25.

[0015] L * a * b * In the color system, L * is the brightness, which ranges from 0 for black to 100 for white. The red inorganic pigment of the present invention has a lightness of 40≦L * ≦80, and 45≦L * ≦75, more preferably 49≦L * ≦70, and more preferably 51≦L * Even more preferably, 53≦L * Even more preferably, it is ≦70.

[0016] Saturation C * L * a * b * Color space a * and b * Therefore, the value is expressed by the following formula (2). Formula (2) C * =(a 2 +b 2 ) 0.5 The red inorganic pigment of the present invention has a chroma of C * ≧25, and C * ≧30 is more preferable, C * ≧35 is more preferable, and C * ≧40 is even more preferred, and C * ≧45 is even more preferred, and C * ≧50 is even more preferred, and C * ≧55 is even more preferred, and C *Even more preferred is ≧60.

[0017] The method for producing the red inorganic pigment of the present invention is not particularly limited, and it can be produced by a conventionally known method, such as a solid phase method, a citric acid complex method, a coprecipitation method, a hydrothermal synthesis method, or a thermal decomposition method.

[0018] The use of the red inorganic pigment of the present invention is not particularly limited, and it can be used, for example, to color cosmetics, paints, cement, resins, rubber, etc. When using the red inorganic pigment of the present invention, it may be subjected to a known surface treatment for the purpose of improving dispersibility, water resistance, oil resistance, etc. Examples of the surface treatment include general oil treatment, metal soap treatment, silicon compound treatment, alkyl phosphate treatment, compound treatment having a perfluoroalkyl group, amino acid treatment, lecithin treatment, collagen treatment, etc.

[0019] The reddish inorganic pigment of the present invention can be used in any cosmetic colored with an inorganic pigment, including, for example, lipstick, lip gloss, eye shadow, eye liner, mascara, powder foundation, cream foundation, etc. When the reddish inorganic pigment of the present invention is blended in cosmetics, it can be blended by mixing with known agents depending on the type of cosmetic. In this case, the reddish inorganic pigment of the present invention can also be mixed with other inorganic pigments or organic pigments. However, from the viewpoint of safety, it is preferable that the other pigments to be mixed are inorganic pigments. [Example]

[0020] Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples, and various modifications are possible within the technical concept of the present invention.

[0021] <Synthesis of inorganic pigments> Example 1 0.5884 g of CaCO3, 0.7341 g of CoCO3, and 1.2299 g of GeO2 were weighed out and mixed in an agate mortar for 30 minutes, then placed in an alumina boat (SSA-H boat #5 SSAHBOAT-5, AS ONE Corporation) and fired in air at 1200°C for 6 hours. After firing, the mixture was pulverized in the agate mortar to obtain an inorganic pigment. The resulting inorganic pigment was subjected to powder X-ray diffraction (XRD) measurement using a powder X-ray diffractometer (Ultima IV, Rigaku Corporation), which confirmed that a single CaCoGe2O6 phase had been obtained. The resulting powder X-ray diffraction pattern is shown in Figure 1.

[0022] Examples 2-9, Comparative Examples 1 and 2 CaCO3, CoCO3, Fe2O3, GeO2, MgO, and NiO were weighed as shown in Table 1, and inorganic pigments were obtained by the same synthesis method as in Example 1.

[0023] [Table 1]

[0024] Example 10 Weighed out 0.9404 g of Ca(NO3)2·4H2O, 1.1587 g of Co(NO3)2·6H2O, 1.6589 g of (C2H5O)4Si, and 3.0596 g of citric acid, which is 1 equivalent of the total amount of metal ions. The metal nitrates and (C2H5O)4Si were dissolved in 45 cm of ethanol. 3 and 5 cm of deionized water 3 The mixture was dissolved in a mixed solvent, citric acid was added, and the mixture was heated and stirred at 80°C to obtain a gel. The resulting gel was dried at 80°C for 12 hours, after which the sample was placed in an alumina crucible (Alumina 99 crucible ARC-30, AS ONE Corporation) and calcined in air at 500°C for 6 hours. After calcination, the resulting sample was placed in an alumina boat (SSA-H boat #5 SSAHBOAT-5, AS ONE Corporation) and fired in air at 1100°C for 6 hours. After calcination, the sample was crushed in an agate mortar to obtain an inorganic pigment. The obtained inorganic pigment was subjected to powder X-ray diffraction (XRD) measurement using a powder X-ray diffractometer (Ultima IV, manufactured by Rigaku Corporation), and it was confirmed that a single phase of CaCoSiO was obtained. The obtained powder X-ray diffraction pattern is shown in Figure 2.

[0025] Examples 11 and 12 Ca(NO3)2·4H2O, Co(NO3)2·6H2O, Zn(NO3)2·6H2O, Mg(NO3)2·6H2O, (C2H5O)4Si, and citric acid were weighed as shown in Table 2, and inorganic pigments were obtained using the same synthesis method as in Example 10.

[0026] [Table 2]

[0027] Examples 13-22 CaCO3, CoCO3, Fe2O3, GeO2, Al2O3, and MgO were weighed as shown in Table 3, and inorganic pigments were obtained by the same synthesis method as in Example 1. [Table 3]

[0028] <Hue evaluation (L * a * b * Color system)> 0.15 g of the obtained inorganic pigment was uniformly packed into a 20 mm × 20 mm square glass cell (glass sample plate, manufactured by Rigaku Corporation), and the color difference was measured using a colorimeter (CR-400, manufactured by Konica Minolta, Inc.) The measurement results are shown in Tables 4 and 5.

[0029] [Table 4]

[0030] [Table 5]

[0031] The pigments obtained in Comparative Examples 1 and 2 were * was smaller than 5, and h was not in the range of -45≦h≦45, and the pigments were not reddish. Specifically, the pigment obtained in Comparative Example 1 was white, and the pigment obtained in Comparative Example 2 was light green. The inorganic pigments obtained in Examples 1 to 22 were * ≧5 and -45≦h≦45, and it was a reddish inorganic pigment. It was also confirmed that various reddish colors can be obtained depending on the pigment composition. The pigment obtained in Example 1 had the highest chroma C * It was high and vivid.

Claims

1. CaCo １－ｘ A ｘ B ２－ｙ Al ｙ O ６ (wherein A=one or more of Fe, Mg, and Zn; B=one or more of Ge and Si; 0≦x≦0.9; 0≦y≦0.1).

2. L ＊ a ＊ b ＊ In the color system, a ＊ 2. The reddish inorganic pigment according to claim 1, which exhibits a color tone defined as +25 or greater.

3. A cosmetic comprising the reddish inorganic pigment according to claim 1 or 2.

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