JP2010185073A - Dichroism pigment which has vivid appearance color and interference color - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment having a vivid dichroism with different color tone of an appearance color and an interference color. <P>SOLUTION: The pigment is obtained by forming single layers with different thicknesses and different compositions composed of lower titanium oxides TiO<SB>X</SB>(1.0<X<2.0) on a platy particles like mica, wherein the control of the composition and thickness of the single layer is carried out by controlling at least one of the atmosphere for titanium oxide burning, burning temperature or reduction auxiliary. The burning is carried out under the atmosphere of a gas, or a gas mixture of nitrogen, hydrogen, ammonia, carbon monoxide, nitrogen monoxide, dinitrogen monoxide, hydrogen sulfide, sulfur dioxide, etc., or under vacuum ambiance. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a pigment having a dichroic appearance color and interference color.
More specifically, the present invention provides a single layer of a composition composed of low-order titanium oxide or a part of low-order titanium oxide modified with nitrogen on a plate-like particle, the composition of the single layer, and the The present invention relates to a pigment having vivid dichroism in which the color tone of the appearance color and the interference color is changed by controlling the film thickness, and the color tone of the appearance color and the interference color is different.

Conventional interference pigments are coated with titanium dioxide on a base of natural or synthetic mica, glass powder, and aluminum flakes (Patent Document 1), thereby interfering with the optical path difference due to light reflection between the base and titanium dioxide layers. The color of the interference color is 10 to 200 nm.
The interference colors of silver, yellow, red, blue and green are developed by adjusting the optical path difference. However, the interference pigment coated with the titanium dioxide layer has a white appearance color, and thus the interference color cannot be recognized significantly.

In addition, an organic dye is added to an interference pigment of natural or synthetic mica, glass powder, and aluminum flakes coated with titanium dioxide on the surface in order to make the appearance and interference colors vivid (Patent Document 2). However, there are problems that organic dyes have poor weather resistance and stability and cannot maintain their color tone.

Furthermore, in the colored mica pigment coated with a titanium compound that needs to contain titanium dioxide and low-order titanium oxide, or low-order titanium oxide, or titanium oxynitride (Patent Documents 2 and 3),
In order to make the interference color of the raw material mica titanium stand out, low-order titanium oxide or titanium oxynitride, which is a colored layer, is provided, but the color of the obtained pigment depends on the interference color, and the appearance color matches the interference color. Only a monotonous color tone can be obtained. In addition, since the colored layer is formed as a mixture of titanium dioxide and a titanium compound containing low-order titanium oxide or titanium nitride, it is very difficult to control the abundance ratio of the above-mentioned mixture in production.

In addition, natural or synthetic mica coated with titanium dioxide as the outermost layer and low-order titanium oxide or titanium oxynitride as the intermediate layer, glass powder, pigments with vivid colors with interference flakes of aluminum flakes (Patent Documents 4 and 5) In adjusting the color tone, the outermost titanium dioxide film thickness is adjusted to obtain an appearance color and interference color of gold, blue, red and green.

Further, there is a colored mica titanium formed from a composite oxide layer made of titanium, iron, and nickel coated on a flaky mica substrate and a titanium dioxide layer coated on the composite oxide layer (Patent Document 6). However, these interference pigments are provided with a colored layer in the intermediate layer to enhance the color tone of the intermediate layer at an angle where no interference color is observed, and at the angle at which the interference color is generated, the interference color of the intermediate layer and the titanium dioxide layer. A method for producing a mixed color tone is disclosed. However, in order to form a multilayer on the base material, multi-step heat treatment and coating treatment steps are required, resulting in high cost and good color developability by adjusting the interference color by controlling the film thickness of the conventional titanium dioxide layer. The color tone is not obtained, and the texture is greatly influenced by the color tone of the appearance color as the intermediate layer.

In addition, the titanium dioxide coating immersed in an aqueous solution of titanyl sulfate and dried at 200 ° C. does not form a strong titanium oxide film on the base material or intermediate layer. By adding a share, the titanium dioxide layer peels off and it is difficult to use it as a stable pigment.

Furthermore, there is a black pearlescent powder pigment (Patent Document 7) by mixing titanium dioxide-coated powder with metallic titanium and subjecting it to a reduction heat treatment followed by an oxidation heat treatment to oxidize it. As shown, the coating layer is once subjected to strong reduction treatment to low-order titanium oxide,
The titanium dioxide layer is formed on the surface of the low-order titanium oxide layer by oxidizing it in the atmosphere to obtain pearl luster, but this titanium dioxide layer is the black color of the low-order titanium oxide layer of the intermediate layer. It is for giving luster to.

However, the pigment obtained here is a black agent that highlights black at an L value of 25 or less and only gives gloss to black, and may not provide vivid color development in the present invention.

Further, there is colored mica titanium (Patent Document 8) in which fine iron oxide having an average particle diameter of 60 to 150 nm is coated on titanium mica (Patent Document 8), but here, the purpose is to adjust the transmission interference color. Vivid color tone cannot be obtained, and fine iron oxide has poor stability, and particularly when dispersed in an aqueous solvent, there is a problem that deterioration occurs with time such as elution of iron and changing the solution color. there were.

As described above, a pigment having a brilliant appearance color and an interference color dichroism has not conventionally existed without adding an organic dye or providing a complicated multilayer.

Japanese Patent Publication No. 43-025644 JP 59-212422 A Japanese Unexamined Patent Publication No. 60-184570 JP 60-060163 A JP 60-170670 A Japanese Patent Laid-Open No. 11-189734 JP 2008-120914 A JP 2003-026537 A

The present invention solves the above-described conventional problems, and its object is to achieve vivid dichroism in which the color tone of the appearance color and the interference color are different without adding an organic dye or providing a complicated multilayer. It is to provide a chromatic pigment having excellent stability and a cosmetic containing the same.

The present invention relates to a conventional interference pigment in which white color stands out as seen in Patent Document 1, Patent Document 2
Unlike the pigments of monotone colors in which the appearance color and the interference color coincide with each other as seen in Patent Document 5 and the black pearlescent pigments mainly composed of black seen in Patent Document 7, the appearance is bright and has a high saturation and brightness. It is an object of the present invention to provide a chromatic pigment having dichroism of color and interference color.

The present invention is characterized in that a single layer consisting only of low-order titanium oxide is formed on the surface of the plate-like particles, and the low-order titanium oxide can be represented by TiOx (1.0 <x <2.0). This is a state in which oxygen is partially lost.

In other words, the principle of absorbing the incident light (electromagnetic wave) was formed by forming holes by causing oxygen to be lost in titanium oxide. The wavelength range to be absorbed can be adjusted by the amount of oxygen deficiency.

The composition of the low-order titanium oxide coated on the plate-like particles in the present invention is TiOx (1.0 <x <2.0), and the oxygen deficiency (X) needs to be appropriately adjusted. The low-order titanium oxide single layer referred to in the present invention is composed of a composition not containing titanium dioxide TiO _2, and the composition of the single layer is TiOx (1.0 <x
<2.0) is composed of one or more kinds of low-order titanium oxide compounds.

  When the oxygen deficiency X = 1.0 of the low-order titanium oxide layer is approached, the light absorption becomes strong and the interference color becomes weak. As X approaches 2.0, the light absorption becomes weaker and the interference color becomes stronger.

In addition, in the appearance color, when the value approaches X = 1.0, the absorption of light becomes strong and the appearance color becomes strong. X = 2.0
As it approaches, the light absorption becomes weaker and the appearance color becomes weaker.

  Therefore, the reflection and absorption of these light can be adjusted by adjusting the amount of oxygen vacancies within the range of TiOx (1.0 <x <2.0).

The change in interference color and appearance color due to light absorption described here is due to the adjustment of the light absorption wavelength region by the amount of oxygen deficiency due to the low-order titanium oxide layer. By adjusting the composition of the low-order titanium oxide layer (oxygen deficiency), it becomes possible to change the wavelength of light reflected and absorbed from the titanium layer, and the color tone of the appearance color and interference color can be changed. A pigment having vivid dichroism that is not present can be obtained.

In the present invention, the color tone is adjusted by adjusting the film thickness of the low-order titanium oxide layer within a range of 10 to 1000 nm by keeping the amount of oxygen deficiency in the low-order titanium oxide layer constant. The interference color can be adjusted by changing the optical path difference of light. Therefore, it is possible to further increase color tone variations by controlling the film thickness.

Furthermore, in the present invention, by adjusting the particle size of the plate-like particles coated with low-order titanium oxide,
It is possible to change the color tone. By increasing the particle diameter, the light reflected from the plate-like particles is in a collective direction, resulting in a glaring color tone that makes the interference color and appearance color stand out. When the particle diameter is reduced, the light reflected from the plate-like particles is scattered, the interference color and the appearance color are smoothly mixed, and a smooth glossy feeling can be given. In particular, the particle size of the plate-like particles is not limited, but dichroic color development is preferably 0.1 μm to 5,000 μm, and particularly preferably 1 μm to 500 μm. By controlling these particle sizes, it is possible to create different colors with the same interference color and appearance color.

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

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

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

Furthermore, the control of the degree of reduction, which determines the composition of the low-order titanium oxide monolayer on the plate-like particles necessary for exhibiting vivid dichroism with different appearance color and interference color, is controlled by the firing temperature and the reduction aid to be added. It can be carried out with a compound serving as an agent.

Furthermore, the firing temperature is set to 500 ° C. in a gas or mixed gas atmosphere such as nitrogen, hydrogen, ammonia, carbon monoxide, nitric oxide, dinitrogen monoxide, hydrogen sulfide, sulfur dioxide, or in a vacuum atmosphere.
It is possible to make it in the range of ~ 1500 ° C. Adjust the oxygen deficiency reaction from titanium dioxide by lowering the firing temperature to around 500 ° C to lower the degree of reduction, and adjusting the firing temperature by raising the firing temperature to around 1500 ° C to increase the degree of reduction. It is possible.

The degree of reduction in the pigment of the present invention can also be controlled by adjusting the amount of reduction aid added. The baking temperature in the case of adding the reducing aid needs to be higher than the decomposition temperature of the reducing aid.
The firing temperature is preferably in the range of 500 to 1500 ° C. The amount of the reducing aid added is such that the reducing component gas contained in the reducing aid is included in the range of 0.001 to 30.0 mol (preferably in the range of 0.01 to 10.0 mol) with respect to 100 g of titanium dioxide. It is necessary to be. Here, the reducing component gas refers to hydrogen, nitrogen, ammonia, carbon monoxide, nitrogen monoxide, dinitrogen monoxide, hydrogen sulfide, sulfur dioxide, and the like, but is not particularly limited thereto. It is possible to control the oxygen deficiency reaction by changing the amount of the reducing substance generated from the reducing aid relative to titanium dioxide. When the addition amount of the reducing aid is 0.001 mol or less, the degree of reduction is low, the appearance color is close to white, and the interference color cannot be recognized significantly, so vivid dichroism cannot be obtained.

In addition, when the amount of addition of the reduction aid is 30.0 mol or more, the degree of reduction becomes too high, the interference color becomes weak, and only the color tone of the appearance color is lost, which is not preferable because vivid dichroism is lost. .
Titanium metal can also be used to control the reduction degree. By firing in a reducing atmosphere in the range of 500 to 1500 ° C. (preferably 900 to 1300 ° C.), some of the oxygen atoms of titanium dioxide are reduced by titanium metal to form low-order titanium oxide. Combines with oxygen atoms to form low-order titanium oxide. The addition amount of the titanium compound is required to add 0.01 to 2.0 mol of titanium component with respect to 100 g of titanium dioxide.

Further, in the present invention, a method for controlling the thickness of titanium dioxide necessary for exhibiting vivid dichroism with different appearance color and interference color by controlling the thickness of the low-order titanium oxide single layer (Patent Document) It can carry out by using what is described in 1). When the film thickness is 10 nm or less, a bright interference color cannot be obtained because the optical path difference in the low-order titanium oxide layer is reduced. In addition, there is no particular limitation on the increase in the thickness of the low-order titanium oxide layer because the color tone is cyclically changed by the phase difference, but the light is attenuated and a vivid color tone cannot be obtained. The film thickness of the low-order titanium oxide layer is preferably 1000 nm or less. By controlling the film thickness of the low-order titanium oxide in the range of 10 to 1000 nm (preferably 10 to 600 nm), it becomes possible to adjust vivid dichroism with different appearance color and interference color.

Further, the low-order titanium oxide layer can be obtained by reducing the titanium dioxide layer, and the titanium dioxide layer is a titanium compound layer containing metatitanic acid, titanium hydroxide, oxytitanic acid, and titanium sulfate. In addition, it is possible to control to a low-order titanium oxide composition by heat treatment by reduction firing.

Since the heat treatment temperature is a high temperature of about 500 to 1500 ° C., low-order titanium oxides are sintered together, and a strong low-order titanium oxide layer can be formed on the base material. In addition, the pigment can be used in a dispersion treatment process that requires a high share in the cosmetics field. Further, titanium oxynitride is formed in the reduction firing by containing a compound containing nitrogen in the gas used for the reduction treatment or a compound containing nitrogen in the reducing aid. Titanium oxynitride is obtained by modifying a part of oxygen of low-order titanium oxide by replacing nitrogen. Even in the case of titanium oxynitride in which a part of low-order titanium oxide resulting from this modification is nitrided, the wavelength of light absorption and reflection can be controlled, and the interference color and appearance color can be adjusted.

Here, black iron (iron trioxide) has poor acid resistance, and is thermally oxidized to γ-iron oxide at about 150 ° C. and unstable. However, low-order titanium oxide is very stable and excellent in acid resistance and alkali resistance. It is a material that is also very stable thermally and maintains blackness even when heated to 350 ° C in the atmosphere. By providing the low-order titanium oxide layer, it is possible to synthesize an acid-resistant, alkaline, and thermally stable pigment.

It can also be obtained by coating a substrate of plate-like particles by a solid phase method using a low-order titanium oxide having a target composition [TiOx (1.0 <x <2.0)] as a raw material. 1 to 95 wt% of low-order titanium oxide in plate-like particles
Add and mix with mechanical shear to uniformly attach low-order titanium oxide on the substrate. Then, in order to increase the strength of the adhesion layer, in an inert gas atmosphere or a vacuum atmosphere,
By firing at a high temperature of about ˜1500 ° C., low-order titanium oxide was sintered to obtain a vivid dichroic pigment having a strong layer.
As the plate-like particles used in the present invention, natural or synthetic mica, glass powder, and aluminum flakes can be used, but are not particularly limited to these substances. In addition, by selecting the shape of the substrate, a pigment having the same hue and controlled light reflection can be obtained.
For example, in natural mica, terraces associated with cleavage are recognized, and the smoothness of the surface of the plate-like particles is not so high. On the other hand, the glass powder has high smoothness on the surface of the plate-like particles and the particle thickness is uniform, so if the thickness of the low-order titanium oxide layer and the degree of reduction are constant, natural mica is used as the base material. The glass-powder base material is more glaring and strong.

The dichroic pigment having different bright appearance color and interference color obtained in the present invention has a color tone different from that of the conventional pearlescent pigment.
In Hunter's Lab color system, conventional titanium dioxide-based interference pigments had a high L value of 70-80 and were white. In addition, for black pearlescent pigments made of low-order titanium oxide, the L value is 25
As below, the brightness was low and black.
However, in the present invention, by controlling the degree of reduction of the low-order titanium oxide layer and its film thickness,
It became possible to produce dichroic colors with different interference colors and appearance colors at brightness of 25 or more.
Further, the b value of Hunter's Lab color system is a color value of blue to yellow, and the greater the absolute value, the higher the saturation. In the present invention, by controlling the degree of reduction, the b value can be adjusted to a range of −3.0 or lower or 3.0 or higher, and a color tone with high saturation can be obtained.

Schematic diagram of pigment having vivid appearance color and interference color of the present invention XRD analysis results when the composition is changed by changing the reducing conditions (Examples 1 and 2 and Comparative Example 1) XRD analysis results of Examples 7 and 8 and Comparative Example 2

The pigment of the present invention is obtained by forming a monolayer of low-order titanium oxide on plate-like particles.
A method in which the base material of plate-like particles is coated with titanium dioxide is reduced, and the titanium dioxide layer is converted into a low-order titanium oxide layer, or the low-order titanium oxide composition is coated on the plate-like particles. However, a method obtained by reducing the pigment in which the base of the plate-like particles is coated with titanium dioxide to form a titanium dioxide layer as a low-order titanium oxide layer is preferable.

Examples of the plate-like particles used in the present invention include natural or synthetic mica, glass powder and aluminum flakes, and are not particularly limited to these substances. Colored and colorless base materials such as mica and biotite may be used.

The pigment having titanium dioxide coated on the plate-like particle base material can be a commercially available one.For example, as mica coated titanium dioxide, iridium (Merk) or flamenco sparkle gold (BASF) Can be used.
For example, for a glass powder coated with titanium dioxide, Metashine (Nippon Sheet Glass Co., Ltd.) can be used.

FIG. 1 is a schematic diagram of a pigment characterized by having a bright appearance color and interference color by adjusting the oxygen deficiency amount according to the present invention.

  The pigment is formed of plate-like particles (1) serving as a base material and a low-order titanium oxide layer (2).

Low-order titanium oxide can adjust the amount of oxygen deficiency by changing the degree of reduction. Here, since the visible light is an electromagnetic wave, a part of the visible light is absorbed by the hole due to oxygen deficiency.
Therefore, by adjusting the oxygen deficiency amount (X), it is possible to change the wavelength region to be absorbed and the absorption amount. Similarly, the wavelength of the reflected light can be controlled.

As shown in the schematic diagram of FIG. 1, the reflected light (5) on the pigment surface is absorbed at a specific wavelength by the low-order titanium oxide layer and develops a color tone as an appearance color. The interference color is unique because the reflected light (5) interferes with the reflected light (6) reflected by the base material (1) and the transmitted light (4) absorbed by the low-order titanium oxide layer and losing a specific wavelength. The color tone is emitted. A pigment having a vivid dichroic color tone can be obtained by the interference color composed of the reflected light of (5) and (6) and the appearance color of the low-order titanium oxide layer by the absorbed light.

Also, by adjusting the film thickness of the low-order titanium oxide layer, the reflected light is reflected from the surface of the low-order titanium oxide layer (5) and reflected from the substrate (1) through the low-order titanium oxide layer. The optical path difference of the light (6) can be changed, and the interference color can be changed by changing the phase of the wavelength.

In the present invention, the amount of oxygen deficiency and the composition of the low-order titanium oxide layer can be controlled to adjust the reflected light and the absorbed light, and the wavelength phase can also be adjusted by controlling the film thickness of the low-order titanium oxide layer. It was possible to adjust the interference color by changing it, and it was possible to synthesize new pigments with a wide variety of dichroism having brighter interference colors and appearance colors than ever before.

Furthermore, by controlling the oxygen deficiency amount, composition and film thickness of the low-order titanium oxide layer, the same appearance color and interference color can be reproduced regardless of the type of plate-like particles used in the present invention.

In the present invention, the pigment was evaluated based on the film thickness of the low-order titanium oxide layer, the composition of the low-order titanium oxide, and the color tone of the pigment.
For the film thickness measurement, a low-order titanium oxide layer was measured using a cross-sectional SEM (Hitachi: S-4500).
The composition of the low-order titanium oxide was performed using a powder X-ray diffractometer (Science: RINT2400). The color tone of the pigment was measured using a Lab color system of a colorimetric color difference meter (Tokyo Denshoku: TC-8600A) Hunter.

The following methods are used for evaluating the appearance color and interference color of the pigment. A pigment and water are mixed at a weight ratio of 1: 2 to form a slurry, which is dropped onto a glass plate. On top of that, the glass plates are put together, and the dropped slurry is stretched between the glass plates to orient the pigment.
The appearance color and the interference color are evaluated by visually observing the glass plate sample with the pigment oriented.
The observation method is evaluated by installing the sample vertically from a white fluorescent lamp, visually observing the appearance color from an angle of 90 degrees from the observation surface, and visually observing the interference color from an angle of 45 degrees from the observation surface. did.

Further, in the cosmetic using the pigment of the present invention, when the appearance color of the decorative film and the interference color at the time of application were observed with the naked eye, those having excellent dichroism were obtained.

In the cosmetic using the pigment of the present invention, it has an excellent dichroism between the appearance color of the entire cosmetic film at the time of application and the interference color that appears to change the angle, thereby giving the cosmetic part a three-dimensional effect. It is possible to give a makeup effect such as emphasizing and making the makeup part stand out.
Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
Examples 1-31 are the pigments of the present invention themselves, and Examples 32-49 evaluate cosmetics using the pigments of the present invention.

[Example 1]
Titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, the excess titanium compound was removed by washing with water to prepare a precursor A (titanium oxide layer thickness: 140 nm) in which the appearance color was white and the interference color was light green in which mica was coated with titanium dioxide.
Precursor A was confirmed to have an anatase structure of titanium dioxide by XRD measurement (Table 1).
).

Sodium borohydride (3.0 g) was added as a reducing aid to 100 g of the precursor A, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was calcined at 600 ° C. for 3 hours at 100 ml / min.
The color tone of the obtained reduction-treated product was dichroic with the appearance color being green and the interference color being light blue.

Table 1 below shows the XRD analysis results of the product of Example 1 together with Precursor A, Example 2 and in comparison with Comparative Example 1.

FIG. 2 shows the XRD analysis results in Table 1.
According to the analysis result of FIG. 2, it can be seen that the titanium dioxide peak disappears and low-order titanium oxide Ti ₄ O ₇ is generated.

[Example 2]
Titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, the excess titanium compound was removed by washing with water to prepare a precursor A (titanium oxide layer thickness: 140 nm) in which the appearance color was white and the interference color was light green in which mica was coated with titanium dioxide. 7.0 g of sodium borohydride is added as a reducing aid to 100 g of precursor A, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1)
: 1) was calcined at 100 ml / min at 600 ° C. for 3 hours.
The obtained reduction-treated product was collected and subjected to XRD measurement. As shown in FIG. 2, the titanium dioxide peak disappeared and low-order titanium oxide Ti ₂ O ₃ was produced.
As for the color tone, the appearance color was dark green and the interference color was blue.

[Comparative Example 1]
Titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, the excess titanium compound was removed by washing with water to prepare a precursor A (titanium oxide layer thickness: 140 nm) in which the appearance color was white and the interference color was light green in which mica was coated with titanium dioxide. Add 10.0 g of sodium borohydride as a reducing aid to 100 g of the precursor A, and mix nitrogen and hydrogen (nitrogen: hydrogen =
1: 1) was calcined at 100 ml / min at 600 ° C. for 3 hours.
The obtained reduction-treated product was collected and subjected to XRD measurement. As shown in FIG. 2, the titanium dioxide peak disappeared and low-order titanium oxide TiO and Ti ₂ O ₃ were produced.
The color tone became a color tone in which the appearance color black was conspicuous.

[Examples 1 and 2] In [Comparative Example 1], the thickness of the low-order titanium oxide layer was kept constant at 140 nm, and the composition of the low-order titanium oxide was changed.

FIG. 2 shows the XRD analysis results when the composition is changed by changing the reducing conditions.
The XRD measurement was performed using a powder X-ray diffractometer after pulverizing the precursor and the reduction-treated product in an agate mortar. By changing the reducing conditions, the titanium dioxide peak disappeared completely, and only the low-order titanium oxide peak was obtained.

Table 1 shows the change in color tone when the reduction degree is changed.
In the precursor, the interference color was only light, but the appearance color and interference color were changed by changing the titanium oxide layer to low-order titanium oxide, and a vivid dichroic color tone could be obtained. Furthermore, by controlling the composition of the low-order titanium oxide, it was possible to change the colors of the interference color and the appearance color.

For TiO ₂ is included lower titanium oxide layer, the reflection of light is intensified by TiO _2, since the external color is close to white, it is impossible to obtain a vivid dichroic showed that the present invention . In order to have vivid dichroism, it is necessary to form a single layer having a composition composed of low-order titanium oxide not containing TiO ₂ .

In Comparative Example 1, the low-order titanium oxide TiO (x = 1) having a high degree of reduction has a strong absorption of incident light into the low-order titanium oxide, the interference color cannot be recognized, and the appearance color black becomes a conspicuous color tone. It was. In the case of a low-order titanium oxide layer containing TiO, since the light absorption is strong, the reflected light becomes weak, the interference color as shown in the present invention cannot be obtained, and the appearance color becomes conspicuous. In order to have vivid dichroism, it is necessary to form a single layer composed of a low-order titanium oxide composition that does not contain TiO. The monolayer on the plate-like particles, by controlling the not include TiO ₂ and TiO [TiOx (1.0 <x < 2.0)] The composition of the low-order titanium oxide consisting adjusts the absorption of the incident light It was possible to obtain bright and various appearance colors and interference colors.

In JP-A-60-060163, a low-order titanium oxide layer or a titanium compound layer containing low-order titanium oxide is present as an intermediate layer between mica that is the innermost layer and titanium dioxide that is the outermost layer. I have colored mica. In addition, it is described that when all the intermediate layers are low-order titanium oxide or a mixture of low-order titanium oxide and titanium nitride, the appearance color and the interference color are black. However, as a result of intensive studies in this study, reflection and absorption of incident light are controlled by controlling the composition of the low-order titanium oxide with TiOx (1.0 <x <2.0). Thus, it has been found that it is possible to develop dichroism having different interference colors and appearance colors.

Example 3
Titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor having a white appearance color and a silver interference color (titanium oxide layer thickness: 30 nm) in which mica was coated with titanium dioxide was produced. Add 100 g of sodium borohydride as a reducing aid to 100 g of the precursor, and add a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1).
Firing was performed at 100 ml / min at 600 ° C. for 3 hours.
Table 2 below shows the XRD analysis results of the product of Example 3 along with those of Examples 1 and 4-6.
Regarding the color tone of the obtained reduction-treated product, the appearance color was silver and the interference color was light yellow.

Example 4
Titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor having a white appearance color and a yellow interference color (titanium oxide layer thickness: 70 nm) in which mica was coated with titanium dioxide was produced. Add 1.7 g of sodium borohydride as a reducing aid to 100 g of the precursor, and add a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1)
Firing was performed at 100 ml / min at 600 ° C. for 3 hours.
Regarding the color tone of the obtained reduction-treated product, the appearance color was yellow and the interference color was dark green.

Example 5
Titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor having a white appearance color and a red interference color (titanium oxide layer thickness: 100 nm) in which mica was coated with titanium dioxide was produced.
Sodium borohydride (2.0 g) was added as a reducing aid to 100 g of the precursor, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was calcined at 600 ° C. for 3 hours at 100 ml / min.
Regarding the color tone of the obtained reduction-treated product, the appearance color was pale red (pink) and the interference color was dark yellow.

Example 6
Titania sol was applied to mica and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor with a white appearance color and a blue interference color (titanium oxide layer thickness: 130 nm) in which mica was coated with titanium dioxide was produced.
Sodium borohydride (2.7 g) was added as a reducing aid to 100 g of the precursor, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was baked at 600 ° C. for 3 hours at 100 ml / min.
Regarding the color tone of the obtained reduction-treated product, the appearance color was blue and the interference color was purple.

In [Examples 3 to 6], the composition of the low-order titanium oxide layer was kept constant, and the film thickness of the low-order titanium oxide layer was changed.
Table 2 shows the change in color tone when the composition of the low-order titanium oxide layer is Ti ₄ O ₇ and the film thickness is 30 to 140 nm.
By changing the film thickness, the interference color and appearance color could be changed significantly.

As shown in these [Examples 3 to 6], by controlling the composition and film thickness of the low-order titanium oxide layer, a pigment having dichroism of different kinds of bright appearance colors and interference colors that has never existed before. Can be synthesized.

Example 7
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor B (thickness of titanium oxide layer: 140 nm) in which the appearance color was white and the interference color was light green in which the glass powder was coated with titanium dioxide was produced. XRD measurement was performed using the precursor B, and it was confirmed that it was an anatase structure of titanium dioxide (FIG. 3). Precursor B
To 100 g, 3.0 g of sodium borohydride was added as a reducing aid, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was calcined at 100 ml / min at 600 ° C. for 3 hours.

The obtained reduction-treated product was recovered and subjected to XRD measurement.
Table 3 below shows the XRD analysis results of the product of Example 7 together with Precursor B, Example 8 and in comparison with Comparative Example 2.
FIG. 3 illustrates the results of Table 3.
The titanium dioxide peak disappeared, and low-order titanium oxide Ti ₄ O ₇ was produced.
As for the color tone, the appearance color was green and the interference color was light blue.

Example 8
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor B (thickness of the titanium oxide layer: 140 nm) in which the appearance color was white and the interference color was light green in which the glass powder was coated with titanium dioxide was produced. Precursor B100g
7.0 g of sodium borohydride is added as a reduction aid to the mixture of nitrogen and hydrogen (nitrogen:
Firing was performed at 100 ml / min at 700 ° C. for 3 hours.
The obtained reduction-treated product was collected and subjected to XRD measurement.
The results are shown in FIG.
In the obtained pigment, the peak of titanium dioxide disappears as shown in FIG.
Ti ₂ O ₃ was produced.
As for the color tone, the appearance color was dark green and the interference color was blue.

[Comparative Example 2]
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor B (thickness of the titanium oxide layer: 140 nm) in which the appearance color was white and the interference color was light green in which the glass powder was coated with titanium dioxide was produced. Precursor B100g
Then, 10.0 g of sodium borohydride was added as a reducing aid, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was calcined at 800 ° C. for 3 hours at 100 ml / min.
The obtained reduction-treated product was recovered and subjected to XRD measurement (FIG. 3). As a result, the titanium dioxide peak disappeared, and low-order titanium oxide Ti, TiO, and Ti ₂ O ₃ were produced.
The color tone was a color tone in which the appearance color black was conspicuous.

Also in pigments [Examples 7 to 8] in which titanium dioxide is coated on the glass powder, [Examples 1 and 2]
], The same color tone was obtained by performing the reduction treatment. Moreover, as shown in FIG. 3, the composition of the low-order titanium oxide also showed the same tendency as [Examples 1-2].

Example 9
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor (titanium oxide layer film thickness: 30 nm) in which the appearance color was white and the interference color was silver with the glass powder coated with titanium dioxide was produced. Add 100 g of sodium borohydride as a reducing aid to 100 g of the precursor, and mix nitrogen and hydrogen (nitrogen: hydrogen =
1: 1) was calcined at 100 ml / min at 600 ° C. for 3 hours.
Regarding the color tone of the obtained reduction-treated product, the appearance color was silver and the interference color was light yellow.

Example 10
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor with a white appearance color and a yellow interference color (titanium oxide layer thickness: 70 nm) with titanium dioxide coated on the glass powder was prepared. 1.7 g of sodium borohydride is added as a reducing aid to 100 g of the precursor, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen =
1: 1) was calcined at 100 ml / min at 600 ° C. for 3 hours. As for the color tone of the obtained reduction-treated product, the appearance color was yellow and the interference color was dark green.

Example 11
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor (titanium oxide layer film thickness: 100 nm) in which the appearance color was white and the interference color was red with the glass powder coated with titanium dioxide was produced. Sodium borohydride (2.0 g) is added to 100 g of the precursor as a reducing aid, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen =
1: 1) was calcined at 100 ml / min at 600 ° C. for 3 hours. Regarding the color tone of the obtained reduction-treated product, the appearance color was pale red (pink) and the interference color was dark yellow.

Example 12
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor with a white appearance color and a blue interference color (titanium oxide layer thickness: 130 nm) coated with titanium dioxide on the glass powder was prepared. Add 2.7 g of sodium borohydride as a reducing aid to 100 g of the precursor, and mix nitrogen and hydrogen (nitrogen: hydrogen =
1: 1) was calcined at 100 ml / min at 600 ° C. for 3 hours. Regarding the color tone of the obtained reduction-treated product, the appearance color was blue and the interference color was purple.

In [Examples 7 and 9 to 12], the composition of the low-order titanium oxide layer was kept constant, and the film thickness of the low-order titanium oxide layer was changed.
Table 4 shows the change in color tone when the composition of the low-order titanium oxide layer is Ti ₄ O ₇ and the film thickness is 30 to 140 nm.
Similar to the mica substrate, by controlling the film thickness of the low-order titanium oxide layer, it became possible to synthesize pigments having dichroism with different vivid appearance colors and interference colors.

Example 13
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor with a white appearance color and a yellow interference color (titanium oxide layer thickness: 70 nm) with titanium dioxide coated on the glass powder was prepared.
Sodium borohydride (1.4 g) was added to 100 g of the precursor as a reducing aid, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was calcined at 600 ° C. for 3 hours at 100 ml / min.
Regarding the color tone of the obtained reduction-treated product, the appearance color was yellow and the interference color was light green.

Example 14
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor (titanium oxide layer film thickness: 100 nm) in which the appearance color was white and the interference color was red with the glass powder coated with titanium dioxide was produced.
Sodium borohydride (2.4 g) was added as a reducing aid to 100 g of the precursor, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was calcined at 600 ° C. for 3 hours at 100 ml / min.
Regarding the color tone of the obtained reduction-treated product, the appearance color was red and the interference color was dark yellow.

Example 15
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove excess titanium compound, and a precursor having a white appearance color and a red interference color (thickness of titanium oxide layer: 115 nm) in which titanium dioxide was coated on the glass powder was prepared.
To 100 g of the precursor, 1.8 g of sodium borohydride was added as a reducing aid, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was calcined at 600 ° C. for 3 hours at 100 ml / min.
Regarding the color tone of the obtained reduction-treated product, the appearance color was pale red (pink) and the interference color was purple.

Example 16
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor with a white appearance color and a blue interference color (titanium oxide layer thickness: 130 nm) coated with titanium dioxide on the glass powder was prepared.
Sodium borohydride (2.3 g) was added as a reducing aid to 100 g of the precursor, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was calcined at 600 ° C. for 3 hours at 100 ml / min.
As for the color tone of the obtained reduction-treated product, the appearance color was light green and the interference color was blue.

Example 17
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, the excess titanium compound was removed by washing with water to prepare a precursor (titanium oxide layer thickness: 140 nm) in which the appearance color was white and the interference color was green with the glass powder coated with titanium dioxide.
To 100 g of the precursor, 2.5 g of sodium borohydride was added as a reducing aid, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was calcined at 600 ° C. for 3 hours at 100 ml / min.
Regarding the color tone of the obtained reduction-treated product, the appearance color was yellow-green and the interference color was light blue.

In [Examples 13 to 17], various appearance colors and interference colors could be obtained by adjusting the composition and film thickness.
Table 5 shows changes in appearance color and interference color when the composition and thickness of the low-order titanium oxide layer are adjusted to 70 to 140 nm.
By controlling the composition and film thickness of the low-order titanium oxide layer, it was possible to adjust the change in appearance color and interference color, and the color tone.

Example 18
A glass powder coated with commercially available titanium dioxide (manufactured by Nippon Sheet Glass: Metashine) is used to reduce the raw material whose appearance color is white and interference color is blue. A mixed raw material is prepared by adding 2.7 g of sodium borohydride as a reducing aid to 100 g of Metashine (MC1080RB). Firing was performed at 600 ° C. for 3 hours with a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) at 100 ml / min.
Table 6 below shows the XRD analysis results of the product of Example 18 along with the results obtained in Examples 19 and 20.
The color tone of the pigment obtained in this example was blue in appearance color and purple in interference color.

Example 19
Reduction firing was performed using a commercially available titanium mica (MERK: Iridion225) with a white appearance color and a blue interference color. A mixed raw material is prepared by adding 2.7 g of sodium borohydride as a reducing aid to 100 g of the raw material. A mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) at 600 ml at 100 ml / min, 3
Time firing was performed.
As for the color tone, the appearance color was blue and the interference color was purple.

Example 20
Titania sol was applied to aluminum flakes and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, the excess titanium compound was removed by washing with water, and a precursor having a white appearance color and a blue interference color (thickness of the titanium oxide layer: 130 nm) in which aluminum dioxide was coated with titanium dioxide was produced.
Sodium borohydride (2.7 g) was added as a reducing aid to 100 g of the precursor, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was calcined at 600 ° C. for 3 hours at 100 ml / min. Regarding the color tone of the obtained reduction-treated product, the appearance color was blue and the interference color was purple.

In [Examples 18 to 19], a vivid dichroic pigment could also be obtained by reduction treatment using a commercially available material.
In [Example 20], a pigment having vivid dichroism could be obtained even when the raw material substrate was aluminum flakes.

Example 21
Reduction treatment is performed using commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass: Metashine). The titanium hydride powder was pulverized in an agate mortar, and the powder that passed through a sieve having an opening of 25 μm was collected and used as a reduction aid. Titanium hydride added to Metashine 100g (MC1080RB) 4.
3 g was added and mixed uniformly with a mixer. The mixed raw material is mixed with nitrogen and hydrogen (nitrogen:
Hydrogen = 1: 1) was calcined at 100 ml / min at 600 ° C. for 3 hours. The obtained reduction-treated product was stirred with water and subjected to wet sieving with an opening of 25 μm to remove low-order titanium oxide formed from titanium hydride as a reducing aid.

Table 7 below shows the XRD analysis results of the product of Example 21 together with the analysis results of Examples 22-24.
The recovered material thus obtained had a blue appearance color and a purple interference color.

[Example 22]
Reduction treatment is performed using commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass: Metashine). Titanium powder was pulverized in an agate mortar, and the powder that passed through a sieve having an opening of 25 μm was collected and used as a reducing aid. 3.8 g of titanium was added to 100 g of Metashine (MC1080RB) and mixed uniformly with a mixer.
The mixed raw material was mixed with nitrogen and hydrogen (nitrogen: hydrogen = 1: 2) at 100 ml / min at 700 ° C., 3
Time firing was performed.
The obtained reduction-treated product was stirred with water and subjected to wet sieving with an opening of 25 μm to remove low-order titanium oxide formed from titanium powder as a reducing aid.
The resulting product was blue in appearance color and purple in interference color.

Example 23
A commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass: Metashine) is used, and lithium aluminum hydride is used as a reducing aid. A mixed raw material is prepared by adding 2.7 g of lithium aluminum hydride as a reducing aid to 100 g of Metashine (MC1080RB).
Firing was performed in a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) at 100 ml / min at 600 ° C. for 3 hours. As for the color tone, the appearance color was blue and the interference color was purple.

Example 24
Using glass powder coated with commercially available titanium dioxide (manufactured by Nippon Sheet Glass: Metashine), reduction firing is performed with a mixed gas of hydrogen and nitrogen. 20 g of Metashine (MC1080RB) was placed in an atmosphere furnace, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 3) was baked at 1000 ° C. for 8 hours at 100 ml / min.
As for the color tone of the obtained reduced fired product, the appearance color was blue and the interference color was purple.

In [Examples 21 to 24], a vivid dichroic pigment could also be obtained by using titanium hydride and titanium metal as the reducing aid. Further, in [Example 23], a vivid dichroic pigment could be obtained even when lithium aluminum hydride was used as the reducing aid. In [Example 24], a vivid dichroic pigment could also be obtained by performing a reduction treatment with a mixed gas of nitrogen and hydrogen.

Example 25
Reduction treatment is performed using commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass: Metashine). Metashine (MC1080RB) 100g sodium borohydride as a reducing aid 2.
Add 7g and 0.2g of guanidine to make a mixed raw material.
Firing was performed in a mixed gas of nitrogen and hydrogen (ammonia: hydrogen = 1: 1) at 100 ml / min at 600 ° C. for 3 hours.
Table 8 below shows the XRD analysis result of the product of Example 25 together with the analysis result of Example 26.
As for the color tone, the appearance color was magenta and the interference color was blue.

Example 26
Reduction treatment is performed using commercially available glass powder coated with titanium dioxide (manufactured by Nippon Sheet Glass: Metashine). Metashine (MC1080RB) 100g sodium borohydride as a reducing aid 2.
Add 7g to make a mixed raw material.
Firing was performed in a mixed gas of ammonia and hydrogen (ammonia: hydrogen = 2: 1) at 100 ml / min at 600 ° C. for 3 hours.
As for the color tone, the appearance color was brown and the interference color was purple.

In Example 25, a compound containing nitrogen was used in the reducing aid.
In [Example 26], a mixed gas of ammonia and hydrogen was used for the reduction treatment. A part of each low-order titanium oxide layer was modified by replacing nitrogen.
Also in [Examples 25 to 26], a vivid dichroic pigment could be obtained.

Example 27
The mica is coated with particles having a composition of low order titanium oxide Ti ₄ O ₇ and a particle size of 10 to 30 nm.
For coating, low-order titanium oxide particles were uniformly dispersed in an aqueous solvent, and mica was added and suspended. Thereafter, mica particles coated with low-order titanium oxide particles were collected and dried at 105 ° C. to remove moisture. The dried mica was heat-treated at 800 ° C. for 3 hours in a vacuum atmosphere.
Table 9 below shows the XRD analysis results of the product of Example 27.
The color tone of the obtained reduction-treated product was dichroic with the appearance color being green and the interference color being light blue.

[Comparative Example 3]
A titania sol was applied to the glass powder and heat-treated at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and the appearance color in which the glass powder was coated with titanium dioxide was white and the interference color was green (the thickness of the titanium dioxide layer: 140 nm).
Table 10 below shows the results obtained in Comparative Example 3 together with those obtained in other Comparative Examples (1, 2, 4).

In [Comparative Examples 1-2], when the low-order titanium oxide TiO (x = 1) has a high degree of reduction, the absorption of incident light into the low-order titanium oxide becomes strong, the interference color becomes weak, and the appearance color is black. It became only.
In Comparative Example 3, since the composition was TiO ₂ (x = 2) and the appearance color was white, the interference color was not significantly recognized.

[Comparative Example 4]
Based on Example 1 of JP-A-60-060163, 208.5 parts of an aqueous solution of titanyl sulfate (40 wt%) is added to a slurry obtained by sufficiently stirring 500 parts of ion-exchanged water with respect to 50 parts of mica, followed by stirring with heating. 6
Went for hours. After standing to cool, it was washed with filtered water and fired at 900 ° C. to obtain mica coated with titanium dioxide. The mica coated with titanium dioxide was subjected to reduction treatment at 800 ° C. for 4 hours with 3 L / min of ammonia gas.
As a result of XRD analysis of the obtained product, it was a mixture of TiO and TiO ₂ , and the appearance color and interference color were blue.

In Comparative Example 4, the coating compositions is a mixture of TiO and TiO _2. Low-order titanium oxide is TiO and Ti
When it is a mixture of O ₂ , TiO absorbs light strongly, and reflected light becomes weak.
Therefore, the reflected light is only blue emitted from TiO ₂ , and TiO gives only the effect of making it stand out (effect as the base color) and has a monotone color tone.
As a result of intensive studies in the present invention, as shown in the examples, a single layer of low-order titanium oxide having a reduced degree of TiOx (1.0 <x <2.0) that can reflect light is provided in FIG. Reflected and absorbed light was generated, and dichroism with different appearance color and interference color could be obtained.

[Example 28]
Titania sol was applied to mica having a plate-like particle diameter of 1-15 μm, and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor with a white appearance color and a blue interference color (titanium oxide layer thickness: 130 nm) in which mica was coated with titanium dioxide was produced. Add 2.7 g of sodium borohydride as a reducing aid to 100 g of the precursor, and mix nitrogen and hydrogen (
Firing was performed at 100 ml / min at 600 ° C. for 3 hours with nitrogen: hydrogen = 1: 1).
As for the color tone, the appearance color was blue, the interference color was purple, and a smooth gloss was obtained.

[Example 29]
Titania sol was applied to mica having a plate-like particle diameter of 10-60 μm, and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor having a white appearance color and a blue interference color (titanium oxide layer thickness: 130 nm) in which mica was coated with titanium dioxide was produced.
Sodium borohydride (2.7 g) was added as a reducing aid to 100 g of the precursor, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was baked at 600 ° C. for 3 hours at 100 ml / min.
As for the color tone, the appearance color was blue, the interference color was purple, and a smooth gloss was obtained.

[Example 30]
Titania sol was applied to mica having a plate-like particle size of 20-180 μm, and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor having a white appearance color and a blue interference color (titanium oxide layer thickness: 130 nm) in which mica was coated with titanium dioxide was produced.
Sodium borohydride (2.7 g) was added as a reducing aid to 100 g of the precursor, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was baked at 600 ° C. for 3 hours at 100 ml / min.
As for the color tone, the appearance color was blue, the interference color was purple, and an extremely fine glossy gloss was obtained.

[Example 31]
Titania sol was applied to mica having a plate-like particle size of 20 to 500 μm, and heat treatment was performed at 600 ° C. in an air atmosphere. After the heat treatment, it was washed with water to remove the excess titanium compound, and a precursor having a white appearance color and a blue interference color (titanium oxide layer thickness: 130 nm) in which mica was coated with titanium dioxide was produced.
Sodium borohydride (2.7 g) was added as a reducing aid to 100 g of the precursor, and a mixed gas of nitrogen and hydrogen (nitrogen: hydrogen = 1: 1) was baked at 600 ° C. for 3 hours at 100 ml / min.
As for the color tone, the appearance color was blue, the interference color was purple, and the interference color and the appearance color had a lustrous glossiness.

In [Examples 28 to 31], the particle diameter was changed while keeping the composition and film thickness of the low-order titanium oxide layer constant. Table 11 shows the change in color tone depending on the particle diameter when the composition of the low-order titanium oxide layer is Ti ₄ O ₇ and the film thickness is 130 nm. By reducing the particle size, the reflected light was scattered, and the interference color and the appearance color were mixed smoothly to give a smooth gloss. In addition, by increasing the particle size, it was possible to give a glare feeling that made the interference color and appearance color stand out.
The color tone can be adjusted by the particle size of these particles with other low-order titanium oxide compositions and film thicknesses, and the glossiness can be changed with the same appearance color and interference color by controlling the particle size.

By blending the pigment of the present invention with other cosmetic ingredients such as an oily component, an aqueous component, and a powder component to make a cosmetic, the vivid dichroism of the present invention can be utilized even on the skin. it can. It can be applied not only to makeup cosmetics but also to skin care cosmetics and hair cosmetics.

Cosmetics having the compositions shown below were prepared by the following production methods, and each item of “three-dimensional effect” and “uniform uniform film” was evaluated by the evaluation methods shown below.

(Evaluation item)
A, three-dimensional feeling, uniform makeup film

(Evaluation methods)
Each sample is subjected to a usage test by 20 specialist panels, and each panel member evaluates it according to the following absolute evaluation and gives a score. The average value is calculated from the total score of all the panel members of each sample. Judgment was made based on the stage judgment criteria.
The evaluation of A is based on whether the appearance color of the entire cosmetic film at the time of application and the interference color that appears by changing the angle have excellent dichroism and a three-dimensional effect can be felt at the makeup site. did.

(1) Evaluation criteria (Evaluation): (Score)
Very good: 6
Good: 5
Slightly good: 4
Normal: 3
Somewhat bad ： 2
Bad: 1
Very bad: 0
(2) Criteria:
(Average score): (Judgment)
5 points or more: Very good 3.5 points or more and less than 5 points: Excellent 1.5 points or more and less than 3.5 points: Inferior Less than 1.5 points: Very inferior

[Example 32] Stick lipstick (ingredient) (%)
(1) Polyethylene wax * 1 5
(2) Ceresin wax 5
(3) Candelilla wax 5
(4) Liquid paraffin 10
(5) Glyceryl tri-2-ethylhexanoate Residual amount (6) Diglyceryl triisostearate 30
(7) Silicic anhydride * 2 1
(8) Silylated silicic acid * 3 1
(9) Calcium carbonate 1
(10) Red No. 202 0.5
(11) Yellow No. 4 0.1
(12) Bengala 1
(13) Dichroic pigment * 4 5
(14) Dichroic pigment * 5 1
(15) Rosemary extract 0.1
* 1 PERFORMALENE 500 (manufactured by New Phase Technology)
* 2 AEROSIL 200 (manufactured by Nippon Aerosil Co., Ltd.)
* 3 AEROSIL R972 (manufactured by Nippon Aerosil Co., Ltd.)
* 4 Example 19
* 5 Example 11

(Production method)
A. Components (1) to (6) are uniformly heated and dissolved (95 ° C.).
B. Components (7) to (15) are uniformly mixed with A.
C. B is heated and filled in a container (85 ° C.) and cooled to obtain a product.

The stick lipstick obtained by the above manufacturing method has a dichroic appearance color and interference color (the appearance color is red,
The interference color was purple) and both “three-dimensional appearance” and “uniform makeup film” were very excellent.

In place of the dichroic pigment * 4 of the component (13) of the stick lipstick of Example 32 and the dichroic pigment * 5 of the component (14), Comparative Example 1 (mica) and Comparative Example 3 (glass powder) were used. The obtained product did not have dichroism, “stereoscopic appearance” was very inferior, and “uniform cosmetic film” was inferior.

[Example 33] Liquid rouge (component) (%)
(1) Residual amount of isododecane (2) Trimethylsiloxysilicic acid * 6 10
(3) Decamethylcyclopentasiloxane 10
(4) Dimethyl distearyl ammonium hectorite * 7 5
(5) Dichroic pigment * 8 10
(6) Dichroic pigment * 9 1
(7) Dichroic pigment * 10 0.5
(8) Silicic anhydride * 11 3
(9) Silicone-treated titanium dioxide * 12 1
(10) Fragrance 0.1
* 6 Silicon KF-7312J (manufactured by Shin-Etsu Chemical Co., Ltd., 50% solution of decamethylcyclopentasiloxane)
* 7 BENTON 38 (made by Elementis)
* 8 Example 18
* 9 Example 1
* 10 Example 10
* 11 Silysia 550 (Fuji Silysia)
* 12 Dimethylpolysiloxane 2% treatment

(Production method)
A. Ingredients (1) to (3) are uniformly dissolved.
B. Ingredients (4) to (10) are uniformly mixed with A.
C. Fill B into a container to make a product.

The liquid rouge obtained by the above manufacturing method has dichroic appearance color and interference color (appearance color is blue, interference color is purple), and both “three-dimensional effect” and “uniform makeup film” are very It was excellent.

Instead of the dichroic pigment * 8 of the component (5) of the liquid rouge of Example 33, the dichroic pigment * 9 of the component (6), and the dichroic pigment * 10 of the component (7), Comparative Example 3 (Glass powder), Comparative Example 4 (
Mica) and Comparative Example 3 (glass powder) are white blurred and inferior in dichroism.
Was very inferior, and the “uniform cosmetic film” was inferior.

[Example 34] Lip Balm (Component) (%)
(1) Vaseline remaining amount (2) Liquid paraffin 10.0
(3) Dichroic pigment * 13 0.1
(4) Dichroic pigment * 14 0.5
(5) Dichroic pigment * 15 0.01
(6) Mica titanium * 16 1
(7) Honey 0.1
* 13 Example 2
* 14. Example 21
* 15 Example 9
* 16 Timilon Super Red (Merck)

(Production method)
A. Ingredients (1) and (2) are uniformly dissolved.
B. Ingredients (3) to (7) are uniformly mixed with A.
C. Fill B into a container to make a product.

The lip balm obtained by the above manufacturing method has dichroism of appearance color and interference color (appearance color is light blue, interference color is light purple). It was very good.

In place of the dichroic pigment * 13 of the component (3) of the lip balm of Example 34, the dichroic pigment * 14 of the component (4), and the dichroic pigment * 15 of the component (5), Comparative Example 4 (Mica), Comparative Example 3 (Glass Powder), and Comparative Example 3 (Glass Powder) use white blurring and inferior in dichroism.
Was very inferior, and the “uniform cosmetic film” was inferior.

[Example 35] Mascara (component) (%)
(1) Residual amount of isododecane (2) Trimethylsiloxysilicic acid * 6 10
(3) Decamethylcyclopentasiloxane 10
(4) Dimethyl distearyl ammonium hectorite * 7 5
(5) Dichroic pigment * 17 30
(6) Dichroic pigment * 18 5
(7) Black iron oxide 1
(8) Talc 3
(9) Nylon fiber * 19 1
(10) Tocopherol acetate 0.1
* 17 Example 3 treated with 2% methylphenylpolysiloxane * 18 Example 16
* 19 10 denier, 2mm

(Production method)
A. Ingredients (1) to (3) are uniformly dissolved.
B. Ingredients (4) to (10) are uniformly mixed with A.
C. Fill B into a container to make a product.

The mascara obtained by the above manufacturing method has dichroism of appearance color and interference color (appearance color is silver, interference color is light yellow), and both “three-dimensional effect” and “uniform makeup film” are very It was excellent.

Dichroic pigment * 17 of component (5) of mascara of Example 35, dichroic pigment * 1 of component (6)
In place of 8, Comparative Example 1 (Mica) and Comparative Example 3 (Glass Powder) are inferior in dichroism, inferior in “three-dimensional effect”, and inferior in “uniform cosmetic film”. there were.

[Example 36] Mascara substrate (component) (%)
(1) Residual amount of isododecane (2) Trimethylsiloxysilicate * 6 10.0
(3) Decamethylcyclopentasiloxane 10.0
(4) Dimethyl distearyl ammonium hectorite * 7 5.0
(5) Dichroic pigment * 4 0.05
(6) Dichroic pigment * 20 0.01
(7) Black iron oxide 0.01
(8) Mica 3
(9) Ultramarine 0.1
(10) Tocopherol acetate 0.1
* 20 Example 7

(Production method)
A. Ingredients (1) to (3) are uniformly dissolved.
B. Ingredients (4) to (10) are uniformly mixed with A.
C. Fill B into a container to make a product.

The mascara obtained by the above manufacturing method has dichroic appearance color and interference color (appearance color is light blue, interference color is light purple), and both “three-dimensional effect” and “uniform makeup film” are very It was excellent.

Dichroic pigment * 4 of the component (5) of the mascara base of Example 36, Dichroic pigment * 4 of the component (6)
In the case of using Comparative Example 3 (glass powder) and Comparative Example 2 (glass powder) in place of 20, white blurring and inferior dichroism, “stereoscopic effect” is extremely inferior, and “uniform makeup film” "Was inferior.

[Example 37] Liquid eyeliner (component) (%)
(1) Light liquid isoparaffin remaining amount (2) Carnauba wax 5.0
(3) Decamethylcyclopentasiloxane 10.0
(4) Sorbitan sesquioleate 3.0
(5) Dichroic pigment * 21 6.0
(6) Dichroic pigment * 22 0.5
(7) Black iron oxide 1.0
(8) Zinc oxide 0.1
(9) Purified water 10.0
(10) Fragrance 0.1
* 21 Example 4 treated with 5% perfluoropolyether * 22 Example 12

(Production method)
A. Components (1) to (4) are uniformly dissolved, and components (5) to (8) are mixed uniformly.
B. Ingredients (9) to (10) are uniformly mixed with A.
C. Fill B into a container to make a product.

The liquid eyeliner obtained by the above process has dichroism of appearance color and interference color (appearance color is yellow, interference color is green). It was excellent.

Instead of the dichroic pigment * 21 of component (5) and the dichroic pigment * 22 of component (6) of the liquid eyeliner of Example 37, Comparative Example 1 (mica) and Comparative Example 3 (glass powder) were used. What I used
White blurring was inferior in dichroism, “stereoscopic” was very inferior, and “uniform cosmetic film” was inferior.

[Example 38] Pencil eyeliner (component) (%)
(1) Light liquid isoparaffin 25.0
(2) Carnauba wax 30.0
(3) Decamethylcyclopentasiloxane 10.0
(4) Liquid paraffin 10.0
(5) Dichroic pigment * 23 18.0
(6) Black iron oxide 2.0
(7) Sericite 5.0
* 23 Example 5

(Production method)
A. Ingredients (1) to (4) are uniformly dissolved.
B. Ingredients (5) to (7) are uniformly mixed with A.
C. B is molded into a core to make a product.

The pencil eyeliner obtained by the above method has dichroism of appearance color and interference color (appearance color is pale red, interference color is yellow). It was very good.

Instead of the dichroic pigment * 23 of component (5) of the pencil eyeliner of Example 38, the one using Comparative Example 4 (mica) is white blurred, and the “three-dimensional effect” is very inferior. Uniform makeup film "
Was inferior.

[Example 39] Pencil eyebrow (component) (%)
(1) Light liquid isoparaffin remaining amount (2) Candelilla wax 20.0
(3) Decamethylcyclopentasiloxane 10.0
(4) Liquid paraffin 8.0
(5) Dichroic pigment * 24 14.0
(6) Dichroic pigment * 25 0.1
(7) Dichroic pigment * 26 0.2
(8) Black iron oxide 1.0
(9) Bengala 1.0
* 24 Example 6
* 25 Example 13
* 26 Example 14

(Production method)
A. Ingredients (1) to (4) are uniformly dissolved.
B. Components (5) to (9) are uniformly mixed with A.
C. B is molded into a core to make a product.

The pencil eyebrow obtained by the above manufacturing method has the dichroic appearance color and interference color (appearance color is light blue, interference color is light purple). It was very good.

Instead of the dichroic pigment * 24 of component (5) of the pencil eyebrow of Example 39, the dichroic pigment * 25 of component (6), and the dichroic pigment * 26 of component (7), Comparative Example 4 ( Mica), Comparative Example 2 (
Glass powders) and Comparative Example 3 (glass powder) were white-blurred and inferior in dichroism, “stereoscopic” was very inferior, and “uniform cosmetic film” was inferior.

[Example 40] Beautiful nail preparation (component) (%)
(1) Butyl acetate Residual amount (2) Ethyl acetate 15.0
(3) Nitrocellulose 15.0
(4) Alkyd resin 3.0
(5) Dimethyl distearyl ammonium hectorite * 7 5.0
(6) Dichroic pigment * 27 10.0
(7) Dichroic pigment * 28 5.0
(8) Dichroic pigment * 29 1.0
(9) Red 220 No. 0.01
(10) Shikonin 0.1
(11) Mica 0.1
* 27 Example 7 treated with 3% methylhydrogenpolysiloxane * 28 Example 20
* 29 Example 31

(Production method)
A. Ingredients (1) to (4) are uniformly dissolved.
B. Ingredients (5) to (11) are uniformly mixed with A.
C. Fill B into a container to make a product.

The nail polish obtained by the above method has dichroism of appearance color and interference color (appearance color is blue-green, interference color is purple). It was very good.

Dichroic pigment * 27 of component (6) of the beauty nail preparation of Example 40, dichroic pigment * 28 of component (7)
In place of the dichroic pigment * 29 of component (8), Comparative Example 3 (glass powder), Comparative Example 4 (mica),
In Comparative Example 4 (mica), white blurring was inferior in dichroism, “stereoscopic” was very inferior, and “uniform cosmetic film” was inferior.

[Example 41] Beauty nail preparation (component) (%)
(1) Purified water 83.0
(2) Carboxymethylcellulose 3.0
(3) Polyvinylpyrrolidone 5.0
(4) Polyvinyl alcohol 1.0
(5) Nylon fiber * 30 0.5
(6) Dichroic pigment * 31 1.0
(7) Dichroic pigment * 32 5.0
(8) Dichroic pigment * 4 1.0
(9) Blue No. 1 0.4
(10) Red No. 106 0.1
* 30 0.5 denier, 0.5mm
* 31 Example 8
* 32 Example 18

(Production method)
A. Ingredients (1) to (4) are uniformly dissolved.
B. Components (5) to (10) are uniformly mixed with A.
C. Fill B into a container to make a product.

The nail polish obtained by the above method has dichroism of appearance color and interference color (appearance color is blue, interference color is purple), and both “three-dimensional appearance” and “uniform makeup film” are very It was excellent.

Dichroic pigment * 31 of component (6) of the beauty nail preparation of Example 41, dichroic pigment * 32 of component (7)
In place of the dichroic pigment * 4 of component (8), Comparative Example 4 (Mica), Comparative Example 3 (Glass Powder), and Comparative Example 3 (Glass Powder) were used as a white blurring two-color Inferior in properties, “stereoscopic” was very inferior, and “uniform cosmetic film” was inferior.

[Example 42] Eye color (component) (%)
(1) Ethanol 20.0
(2) Purified water remaining amount (3) Hydroxypropyl methylcellulose 3.0
(4) Polyvinylpyrrolidone 1.0
(5) Polyoxyethylene hydrogenated castor oil 1.0
(6) Bismuth oxychloride 5.0
(7) Dichroic pigment * 33 5.0
(8) Dichroic pigment * 4 5.0
(9) Dichroic pigment * 34 1.0
(10) Yellow iron oxide 1.0
* 33 Example 22
* 34. Example 28

(Production method)
A. Ingredients (1) to (5) are uniformly dissolved.
B. Ingredients (6) to (10) are uniformly mixed with A.
C. Fill B into a container to make a product.

The eye color obtained by the above process has dichroism of appearance color and interference color (appearance color is green, interference color is purple), and both “three-dimensional effect” and “uniform makeup film” are very It was excellent.

Dichroic pigment * 33 of eye color component (7) of Example 42, dichroic pigment * of component (8)
4. In place of the dichroic pigment * 34 of component (9), Comparative Example 3 (glass powder), Comparative Example 4 (mica)
In Comparative Example 4 (mica), white blurring was inferior in dichroism, “stereoscopic” was very inferior, and “uniform cosmetic film” was inferior.

[Example 43] Eye color (component) (%)
(1) Sericite 8.9
(2) Remaining talc (3) Mica 10.0
(4) Dichroic pigment * 35 40.0
(5) Dichroic pigment * 36 5.0
(6) Dichroic pigment * 37 2.0
(7) Methyl paraoxybenzoate 0.1
(8) Bengala 0.5
(9) Squalane 10.0
(10) Phenoxyethanol 0.5
* 35 Example 23 treated with 5% liquid paraffin * 36 Example 30
* 37 Example 29

(Production method)
A. Ingredients (1) to (8) are mixed uniformly.
B. Ingredients (9) to (10) are uniformly mixed with A.
C. Fill B into a container to make a product.

The eye color obtained by the above process has dichroism of appearance color and interference color (appearance color is blue, interference color is purple), and both “three-dimensional effect” and “uniform makeup film” are very It was excellent.

Dichroic pigment * 35 of eye color component (4) of Example 43, dichroic pigment * 5 of component (5)
36. Instead of the dichroic pigment * 37 of component (6), those using Comparative Example 3 (glass powder), Comparative Example 4 (mica), and Comparative Example 4 (mica) are white-blown and two-color Inferior in properties, “stereoscopic” was very inferior, and “uniform cosmetic film” was inferior.

[Example 44] Teak color (ingredient) (%)
(1) Sericite remaining amount (2) Talc 30.0
(3) Mica 1.0
(4) Dichroic pigment * 38 10.0
(5) Dichroic pigment * 39 0.1
(6) Methyl paraoxybenzoate 0.1
(7) Conger 0.1
(8) Liquid paraffin 10.0
(9) Polybutene 0.9
* 38 Example 24
* 39 Example 17

(Production method)
A. Ingredients (1) to (7) are mixed uniformly.
B. Components (8) to (9) are uniformly mixed with A.
C. Fill B into a container to make a product.

The cheek color obtained by the above manufacturing method has dichroism of appearance color and interference color (appearance color is blue, interference color is purple), and both “three-dimensional effect” and “uniform makeup film” are very It was excellent.

Instead of the dichroic pigment * 38 of the cheek color component (4) of Example 44 and the dichroic pigment * 39 of the component (5), Comparative Example 3 (glass powder) and Comparative Example 2 (glass powder) were used. What was used was white blurring and inferior in dichroism, “stereoscopic” was very inferior, and “uniform cosmetic film” was inferior.

[Example 45] Teak color (component) (%)
(1) Stearic acid 3.0
(2) Liquid paraffin 15.0
(3) Sorbitan sesquioleate 3.0
(4) Dichroic pigment * 40 10.0
(5) Dichroic pigment * 41 0.5
(6) Glycerin 10.0
(7) Purified water remaining amount (8) Sodium hydroxide 0.5
(9) Ethanol 10.0
* 40 Example 25
* 41 Example 15

(Production method)
A. Components (1) to (3) are uniformly heated and dissolved (80 ° C.).
B. Ingredients (4) to (9) are mixed uniformly.
C. Add A to B and emulsify (80 ° C)
D. Fill the container with C to make a product.

The cheek color obtained by the above manufacturing method is a dichroic appearance color and interference color (the appearance color is magenta,
The interference color was blue), and both “three-dimensional effect” and “uniform makeup film” were very excellent.

Instead of the dichroic pigment * 40 of the cheek color component (4) of Example 45 and the dichroic pigment * 41 of the component (5), Comparative Example 3 (glass powder) and Comparative Example 2 (glass powder) were used. What was used was white blurring and inferior in dichroism, “stereoscopic” was very inferior, and “uniform cosmetic film” was inferior.

[Example 46] Interesting (ingredient) (%)
(1) Talc 58.4
(2) Sericite 20.0
(3) Mica 10.0
(4) Dichroic pigment * 42 0.1
(5) Ethyl paraoxybenzoate 0.5
(6) Titanium dioxide 0.5
(7) Titanium mica * 43 10.0
(8) Fragrance 0.5
* 42. Example 26
* 43 TIMICA EXTRA BRIGHT 1500 (manufactured by BASF)

(Production method)
A. Ingredients (1) to (8) are mixed uniformly.
B. Fill A into a container to make a product.

The funnel obtained by the above process has dichroism of appearance color and interference color (appearance color is light brown, interference color is light purple), and both “three-dimensional effect” and “uniform makeup film” are very It was excellent.

In place of the dichroic pigment * 42 of the interesting component (4) of Example 46, Comparative Example 3 (glass powder) used was white-blurred and “stereoscopic” was very inferior. The “film” was inferior.

[Example 47] Foundation (component) (%)
(1) Sericite 42.4
(2) Talc 30.0
(3) Mica 10.0
(4) Dichroic pigment * 4 1.0
(5) Methyl paraoxybenzoate 0.1
(6) Bengala 1.0
(7) Yellow iron oxide 2.0
(8) Titanium dioxide 3.0
(9) Squalane 10.0
(10) Oxybenzidione 0.5

(Production method)
A. Ingredients (1) to (8) are mixed uniformly.
B. Ingredients (9) to (10) are uniformly mixed with A.
C. Fill B into a container to make a product.

The foundation obtained by the above manufacturing method has dichroic appearance color and interference color (appearance color is skin color, interference color is light purple), and both “three-dimensional effect” and “uniform makeup film” are very It was excellent.

In place of the dichroic pigment * 4 of the component (4) of the foundation of Example 47, the one using titanium mica is white blurred, “stereoscopic” is very inferior, and “uniform cosmetic film” is inferior. It was a thing.

[Example 48] Makeup base (ingredient) (%)
(1) Stearic acid 3.0
(2) Liquid paraffin 15.0
(3) Sorbitan sesquioleate 3.0
(4) Dichroic pigment * 4 1.0
(5) Glycerin 10.0
(6) Purified water 67.5
(7) Sodium hydroxide 0.5

(Production method)
A. Components (1) to (3) are uniformly heated and dissolved (80 ° C.).
B. Ingredients (4) to (7) are mixed uniformly.
C. Add A to B and emulsify (80 ° C)
D. Fill the container with C to make a product.

The makeup base obtained by the above process has dichroism of appearance color and interference color (appearance color is light blue, interference color is light purple). It was very good.

In place of the dichroic pigment * 4 of the makeup base component (4) of Example 48, the one using titanium mica is white blurred, the “three-dimensional effect” is very inferior, and the “uniform makeup film” is It was inferior.

[Example 49] Body gel (component) (%)
(1) Carboxymethylcellulose 0.5
(2) Purified water 79.4
(3) Triethanolamine 0.1
(4) Dichroic pigment * 4 9.0
(5) Dichroic pigment * 44 1.0
(6) Glycerin 10.0
* 44 Example 27

(Production method)
A. Ingredients (1) to (6) are mixed uniformly.
B. Fill A into a container to make a product.

The body gel obtained by the above process has dichroism of appearance color and interference color (appearance color is blue, interference color is purple), and both “three-dimensional effect” and “uniform makeup film” are very It was excellent.

In place of the dichroic pigment * 4 of the component (4) and the dichroic pigment * 44 of the component (5) of the body gel of Example 49, those using titanium mica are white blurred, Is very inferior,
“Uniform cosmetic film” was inferior.

Claims (11)

A pigment characterized by vivid dichroism having different appearance color and interference color by forming a single layer of low-order titanium oxide on plate-like particles. The single layer of low-order titanium oxide formed on the plate-like particles is a composition composed of low-order titanium oxide with TiO _X (where 1.0 <X <2.0), and the composition of the single layer and its film thickness The pigment according to claim 1, wherein the pigment is controlled. The pigment according to claim 1 or 2, wherein the composition and film thickness of the single layer are controlled by at least one of an atmosphere for firing titanium oxide, a firing temperature, or a reducing aid. The firing atmosphere is characterized by being in a gas or mixed gas atmosphere such as nitrogen, hydrogen, ammonia, carbon monoxide, nitric oxide, dinitrogen monoxide, hydrogen sulfide, sulfur dioxide, or a vacuum atmosphere. The pigment according to any one of claims 1 to 3. The pigment according to any one of claims 1 to 4, wherein the firing temperature is 500 to 1500 ° C. The reduction aid is selected from a compound containing a hydride selected from titanium hydride, titanium compound selected from titanium metal, sodium borohydride, lithium aluminum hydride, and the like. Item 5. The pigment according to any one of Items 1 to 5. The pigment according to any one of claims 1 to 6, wherein the plate-like particles are selected from natural or synthetic mica, aluminum flakes or glass powder. The pigment according to any one of claims 1 to 7, wherein the low-order titanium oxide monolayer is modified with titanium oxynitride. The pigment according to any one of claims 1 to 8, wherein the L value of the Hunter's L, a, b color system is 25 or more. The color tone is additionally changed by changing the particle diameter.
The pigment according to any one of   A cosmetic comprising the pigment according to any one of claims 1 to 10.