JP2003055574A - Coated composition of highly heterochromic titanium oxide composition, highly heterochromic titanium oxide composition, and method for producing the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly heterochromic titanium oxide composition exhibiting color clarity and new excellent brilliance having a color due to color interference and having no turbid complementary color. SOLUTION: The coated composition of the highly heterochromic titanium oxide composition is a coated composition obtained by forming a coat on the surface of a flaky substrate, wherein the plate shape of the flaky substrate has 50-800 μm size and has 0.05-0.6 μm thickness and the coat contains 70-95 wt.% titanium composition. The highly heterochromic titanium oxide composition is a composition obtained by treating off the coat of the titanium composition from the covered composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high iris color titanium oxide composition, a method for producing the same, and various compositions using the same, and more specifically, a titanium composition on a flaky substrate surface. The present invention relates to a novel titanium composition which is obtained by removing the coated titanium composition and a method for producing the same. More specifically, paints, cosmetics, inks, plastics,
The present invention relates to a flaky, highly iris-colored titanium oxide composition useful as a photofunctional material such as a catalyst.

[0002]

2. Description of the Related Art A pearl luster pigment that gives a pearl feeling by coating natural mica with a metal oxide such as iron oxide or titanium oxide is
It has been publicly known. The conventional pearl luster pigments of this kind have the drawbacks that the luster is insufficient, the colors are not vivid, and the residual color is turbid. Further, synthetic mica gives a product with extremely high transparency, and in this respect, it can be said that it is an excellent substrate for pearl luster pigments. However, because synthetic mica has hard crystals and is difficult to cleave, the surface smoothness is inferior to that of natural mica by the usual method, but the transparency and whiteness are high, so the pearl luster that coats a thin film such as titanium oxide is used. It has come to be used as a substrate for pigments. Further, it has been used as a pearl luster pigment for coating a thin film such as titanium oxide using plate-like aluminum oxide or plate-like silicon oxide as a substrate in order to enhance the brightness of interference color.

Titanium oxide is widely used as an additive for paints, cosmetics, resins, and papers due to its whiteness and ultraviolet ray shielding ability. These are manufactured by conventional methods. Since granular fine particles are used, there are problems in coating properties, adhesiveness, dispersibility and the like. Japanese Patent No. 2979132 and the like are disclosed as a method for producing plate-shaped titanium oxide, which was titanium oxide having no gloss or interference color.

By the way, originally, color is a very important factor that has a physiological and psychological effect on humans. Actually, it is a method to create a safe and efficient working environment and a healthy and comfortable living environment by utilizing the physiological and psychological effects that color can have on humans, and color adjustment technology is used in various fields. Has been done.

Usually, when imparting color to a substance,
Various color pigments are used. This color pigment gives a desired color by utilizing phenomena such as absorption and scattering of light. However, the color pigment alone cannot meet various sensitivities to colors and demands of design in recent years. Therefore, in addition to this coloring pigment, a pearlescent pigment such as titanium dioxide-coated mica, which is a pigment utilizing the phenomenon of light interference, is provided. A major feature of this pearl pigment is that it can impart a "flip-flop effect" in which the color tone changes slightly depending on the angle.

This pearlescent pigment is used in various fields such as cosmetics, paints, adhesives, printing inks and resin kneading, but the following drawbacks are pointed out. For example, pearlescent pigments have flaky or plate-like particles such as natural mica or synthetic mica, alumina, silica, silicate glass, and borate glass as cores, and coated with titanium dioxide,
By controlling the coating amount of titanium dioxide, it has a pearlescent luster with various interference colors. For this reason, when such a pearlescent pigment is used as a pigment of a composition for external use in cosmetics, paints, printing inks, pressure sensitive adhesives, resin kneading, etc., the thickness of the particles is large, resulting in an ultrathin film. There are drawbacks such as the inability to control the thickness and the lack of the design effect due to the "flip-flop effect" due to the strong light scattering at the edge of the particle.

On the other hand, regarding the synthesis of plate-like particles of titanium oxide, for example, the flaky titanium oxide described in Japanese Patent No. 2979132 is a porous body having a large specific area, and cesium titanate is contacted with an aqueous acid solution. It is a flaky titanium oxide obtained by peeling and heating the layered crystal, and the layered crystal composed of titanic acid was peeled to one layer, and as a result, a very thin titanium oxide having a nanometer level was obtained. There is. However, it is a flaky titanium oxide that is too thin to have an interference color.

Further, the plate-shaped titanium oxides described in JP-A-62-1237936, JP-A-62-124783 and JP-A-62-1213833 are oxidized by sol-gel of titanium alcoholate attached to a drum and heated. It is separated from the drum with a scraper and heated and baked to obtain a slightly pearl-like plate-shaped titanium oxide. This is because the particles are curled and the thickness of the particles is large because they are separated with a scraper. Since it is on the order of microns, no interference color can be developed.

[0009]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned conventional problems, and develops a novel and excellent glittering feeling and color sharpness in which colors due to interference colors can be recognized. In addition, it is an object of the present invention to provide a high iris color titanium oxide composition in which the residual color is not turbid.

[0010]

Means for Solving the Problems As a result of intensive research to solve the above problems, the present inventors have found that when producing a high iris titanium oxide composition, a flaky substrate surface is coated with the titanium composition. By forming a layer and peeling off the coating layer, a novel high iris titanium oxide composition that solves this problem was obtained.

More specifically, the surface of the flaky substrate is coated with a metal oxide and / or metal hydroxide based on anatase type or rutile type titanium oxide to form a coating layer. By adding an alkaline compound, a peeling composition peeled from the flaky substrate surface can be obtained. This release composition is provided as a composition that simultaneously develops a desired gloss and an interference color.

That is, the first coating composition according to the present invention comprises one or more flaky substrates selected from natural mica, synthetic mica, glass flakes, silica flakes, alumina flakes and barium sulfate, and the surface thereof. And a coating layer comprising a titanium oxide composition and / or a titanium hydroxide composition. The second aspect of the present invention
The release composition which is a high iris titanium oxide composition of
The titanium composition was peeled off from this coating composition of.

In terms of luster, the above-mentioned release composition was mixed with 30 parts of acrylic clear lacquer, 1 part, and applied on a black and white hiding rate test paper, JIS K5400 with a 4 mil applicator. The value obtained by measuring the gloss with a Horiba gloss checker IG-330 model is 55 to 90 at 60 °, and the coloring is a high iris titanium oxide composition that develops by light interference.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. FIG. 1 is a conceptual diagram of a coating composition relating to the high iris titanium oxide composition of the present invention, and FIG. 2 is a schematic diagram showing a method for producing the high iris titanium oxide composition of the present invention, and FIG. FIG. 4 is a graph of the analysis results of the coating composition of the present invention by X-ray diffraction, FIG. 4 is a micrograph showing the surface state of titanium oxide in the coating composition of the present invention, and FIG. FIG. 6 is a table showing the relationship between the interference color of a titanium oxide composition that is a release composition and the film thickness of a titanium layer, and FIG.
FIG. 8 is a micrograph of a titanium oxide composition that is a stripping composition, FIG. 7 is a micrograph of a titanium oxide composition that is a stripping composition, and FIG. 8 is a titanium oxide composition that is a stripping composition of the present invention. 3 is a graph showing the analysis results by the three-dimensional gloss meter of FIG.

The coating composition of the high iris color titanium oxide composition, the high iris color titanium oxide composition and the method for producing the same according to the present invention are a coating comprising a titanium oxide or titanium hydroxide titanium composition on a flaky substrate surface. A coating composition having a layer formed thereon, a peeling composition obtained by peeling only the coating layer from the coating composition, and a method for producing the same are disclosed. By obtaining a release composition under conditions, when using it for a wide range of applications such as paints, in the layer containing this release composition formed on the coated surface, an unprecedented high iris color due to light interference Can be obtained.

As shown in FIG. 1, the coating composition of the high iris titanium oxide composition according to the present invention comprises a metal oxide based on anatase type or rutile type titanium oxide on the surface of the flaky substrate 1 and / or Coating layer 2 containing metal hydroxide
Is coated to a specific thickness of 0.05 to 0.6 μm to obtain gloss.

The flaky substrate 1 is highly smooth, and the plate-like size of the particles is preferably in the range of 50 to 800 μm in terms of laser diameter. Titanium oxide exfoliated below 50 μm,
Even if the particle size of titanium hydroxide is too small and interference gloss can be sufficiently exhibited, titanium oxide is difficult to peel off. When the particle size of the particles is 800 μm or more, the interference gloss of titanium oxide and titanium hydroxide can be sufficiently exerted, but the mechanical strength of the exfoliated particles is weak, so that the use thereof is limited.

Most preferably, it is in the range of 100 to 700 μm. When a substrate having a thickness of 100 μm or less is used, the particles of the release composition, which will be described later, are too fine to weaken the color development of a high iris interference color. Further, when the particle size of the substrate is larger than 700 μm, the color of the interference color of high iris color due to the particles of the peeling composition becomes strong, but the particles have a grainy feeling, which is not preferable. Further, when it is 100 to 300 μm, the gloss is strong and the peeling is easy.

Specific examples of the flaky substrate 1 that easily falls within this particle size range include natural mica, synthetic mica, glass flakes, silica flakes, alumina flakes, barium sulfate and the like. It is relatively easy to control the shape and the degree of smoothness of the surface of the silica flake, and it is also possible to coat the surface of the silica flake with a uniform coating layer 2 to a specific thickness at which gloss is obtained. It is a preferable material to be selected as the flaky substrate 1 in that it is easy to use.

The thickness of the particles of the flaky substrate 1 is not particularly limited, but is preferably in the range of 0.1 μm to 10 μm. When the thickness of the particles is 0.1 μm or less, the periphery of the substrate is curled round and the interference gloss of the coated titanium oxide or titanium hydroxide cannot be sufficiently exhibited. Further, when the thickness of the particles is 10 μm or more, the interference colors of titanium oxide and titanium oxide which are coated in the plane and the thickness direction of the particles and titanium oxide which is separated from the plane and the thickness of the titanium hydroxide are different, The interference gloss as a whole becomes insufficient.

The coating layer 2 is a layer containing a titanium oxide and / or titanium hydroxide composition, and is coated to a specific thickness at which gloss is obtained. It is preferably obtained from a soluble aqueous solution of titanyl sulphate or titanium tetrachloride or from the hydrolysis of titanium alcoholates. Further, the coating layer 2 can improve the crushing strength of the light resistance / peeling composition by containing silica and / or a reinforcing agent such as alumina, Zr, Ce, Zn or the like.

Each particle has a size of 0.01 to 0.05 μm.
m, preferably 0.02 to 0.04 μm, but 0.02 μ when the particle size of the substrate 1 is 300 μm.
The titanium oxide or titanium hydroxide composition (1) is most easily peeled off. When the particle size of the substrate 1 is 800 μm, the coating layer 2 can be peeled off with a small particle size of 0.01 μm, but when the particle size of the substrate 1 is 100 μm or less, the particles of the coating layer 2 are It cannot be peeled off unless the diameter is 0.05 μm. That is, the particle size of the substrate 1 and the particle size of the coating layer 2 are in inverse proportion.

In the present invention, first, the coating composition shown in FIG. 1 is formed, and then, as shown in FIG. 2, the coating layer 2 is peeled off from the coating composition, whereby the peeling composition 2a is obtained. Finally get. That is, the high iris titanium oxide composition according to the present invention is a release composition formed by removing the metal oxide or metal hydroxide that is the coating layer 2 of this coating composition from the surface of the flaky substrate 1. 2a.

As the flaky substrate 1, commercially available flaky powder can be used, but natural mica, synthetic mica, barium sulfate, silica flakes, alumina flakes and the like are used. For example, 80% natural mica from India in the air
It is calcined at a temperature of 0 ° C. for 2 hours, and the calcined chip-like natural mica is immersed in tap water for 5 days. This chip-shaped natural mica can be crushed with a mass colloider and classified to obtain it.

Further, before the peeling, water glass, organic silica, soluble aluminum salt or the like is used in advance to further coat the surface with a silica or alumina compound, and then the coating composition is peeled off to obtain good weather resistance, and A release composition that does not curl can be obtained.

In the coating composition, as described above, first, the surface of the flaky substrate 1 is coated with the titanium oxide or titanium hydroxide composition to a specific thickness at which gloss is obtained to form the coating layer 2. It is preferably obtained from a soluble aqueous solution of titanyl sulphate or titanium tetrachloride or from the hydrolysis of titanium alcoholates.

In order to obtain a release composition, this coating composition is previously calcined at 300 to 800 ° C. in an alkali (p.
By peeling the coating layer from the thin plate-like substrate with (H8 or more), a peeling composition having no curl and excellent smoothness can be obtained.

This improves the gloss and interference color of the release composition. When the firing temperature is lower than 300 ° C., the particles of the release composition curl, and when it is higher than 800 ° C., the titanium oxide or the titanium hydroxide of the release composition agglomerates, resulting in gloss and interference color after release. Becomes worse.

The peeling composition was filtered, washed with water and dried, and then 50
Bake at 0 to 900 ° C to maintain gloss and prevent curling. In addition, as post-treatment after peeling, iron oxide
The coating with cobalt / nickel / lithium / sodium / potassium or a coloring inorganic compound or the coating with an organic pigment to give an organic pigment colored product can be realized by a known method depending on various applications and embodiments.

The high iris titanium composition of the present invention, which is the release composition thus obtained, has a thickness of 0.05 to 0.6 μm.
A thickness of m particles has been selected. This can be explained by the relationship between the geometrical film thickness that gives an iris color and the optical film thickness (film thickness × refractive index).
In m, it has been shown that it is preferable to select the thickness in the range of 0.1 to 0.9 μm optical thickness.

If the composition is too thin, it becomes difficult to produce a desired interference color, which is not preferable. On the other hand, if the composition is too thick, the interference color intensity is not preferable because the intensity of interference decreases due to scattering of the thickness.

Table 1 shows the relationship between the interference color and the geometrical thickness of the titanium composition when the high iris titanium composition according to the present invention is coated on a tape and the coated tape is placed on a black background. Is shown.

The particle size of the high iris titanium composition of the present invention is
The more aligned they are, the higher the saturation of the iris color will be. That is, it is possible to obtain a desired interference color by scattered light in each of the particles of the thin plate-shaped titanium composition of high iris color.

In the present invention, the fact that the particle size and the shape of the thin plate of the titanium composition of high iris color are specifically uniform means that the average particle size of the laser diffraction / scattering diameter is A μm, and the range is A ± 4 μm. The volume distribution is 60% or more, preferably 70% or more, and the shape of the thin plate is the thin plate when the particles are observed with a scanning electron microscope and the number of particles is counted at a magnification of 2,000. It is desirable that the shape be tangential to the particles and that the number of particles separated by at least 1.5 times the thickness be less than 10%.

In order to maintain the uniformity of the particle size (shape), it is desirable to carefully perform pulverization and classification when adjusting the smoothness of the flaky substrate. 2 when selecting natural mica
It is desirable to select an excellent ore by uniformly stirring and pulverizing a raw ore of ˜8 mesh and classifying with elutriation.

Further, it is preferable that the surface of the flaky substrate having a smooth and uniform particle size is uniformly coated with the titanium composition and the titanium composition is peeled off, because the interference color can be obtained more uniformly.

The high iris titanium oxide composition of the present invention, which is the release composition obtained as described above, has a specific thickness such that gloss can be obtained in the coating composition. When used for an application, the direct surface reflected light and the reflected light reflected when entering and transmitting interfere with each other to obtain a high iris color interference color due to a phase shift between them.

When a layer in which the highly iris-colored titanium oxide composition of the present invention is applied uniformly on the coating surface is exposed to light, the light reflected from the particle surface of the coating surface and the medium having a different refractive index The transmitted light of the particles of the titanium composition reflected by the light beams interfere with each other, and a color of a specific interference color is obtained. This interference color is determined by controlling the thickness of the coating layer in the coating composition.

(Comparative Example 1) FIG. 8 is a graph showing the results of analysis by a three-dimensional gloss meter of the titanium oxide composition which is the release composition of the present invention.

The release composition of the present invention was mixed with 30 parts of acrylic clear lacquer, 1 part, and coated on a black and white hiding rate test paper, JISK5400, with a 4 mil applicator. Original gloss meter GCM
S-4 type, incident angle 45 °, reflection angle (colorimetric angle) 0-75 °
The space was colored at 5 ° intervals, and the Lab was determined.

As comparative pigments, Iriodine (hereinafter abbreviated as IR) 225, 219 and 235 manufactured by Merck Ltd. were used. As a result of the analysis, it was found that the titanium oxide composition of the present invention exhibits interference color in a wide range.

Specific production examples will be described below.
The technical scope of the present invention is not limited by these production examples.

(Production Example 1) 1.0 kg of chip-shaped natural mica produced in India was burned for 2 hours at a temperature of 800 ° C. in the atmosphere, and after cooling, the chip-shaped calcined natural mica was immersed in 10 liters of tap water. It was left at room temperature for 5 days. The chip-shaped calcined natural mica was passed twice with a Masuko Sangyo Co., Ltd. mascoloyer with a gap of 500 μm, crushed, and 50 liters of the crushed calcined natural mica was transferred to a poly tank, where
A 02% aqueous hexametaphosphoric acid solution was added to make the total volume 45 liters.

After stirring with a propeller stirrer for 5 minutes after standing,
The supernatant was transferred to another container, this operation was repeated 3 times, and
Large particles of 1 mm or more are classified, and the supernatant is classified using standard mesh 10 mesh (800 μm) and 65 mesh (203 μm), and the particle size of 10 to 65 mesh is 150 g.
Obtained.

Next, to 150 g of classified mica, 400 g of titanyl sulfate and 7.5 liters of tap water were added, and the titanyl sulfate was dissolved while stirring with a propeller. After the titanyl sulfate was dissolved, it was heated with stirring and hydrolyzed at a temperature of 90 ° C. or higher for 4 hours. After standing to cool, wash with water, filter, 150 ° C
Dried in. Further, it was baked at 300 ° C. for 2 hours. One part was taken for observing the surface condition and observed with a Hitachi S-2100B electron microscope (SEM) at 20,000 times. As a result, as shown in FIG. 4, the particle size of the coating composition was 0.0
The aggregate was 2 μm.

Further, 10% of a loading soda aqueous solution was added to the water-washed powder to adjust the pH to 11, followed by immersion and standing.
The powder floating in the supernatant was classified by a decantation method, and the classified powder was filtered and washed with water. An aqueous solution prepared by dissolving 8.325 g of aluminum sulfate in 5 liters was added to the washed and classified powder, and 4 g of zirconium oxychloride and 18 urea were further added.
Added gram. The mixture was heated with stirring with a propeller and hydrolyzed at 80 ° C. or higher for 5 hours. After allowing to cool, it was washed with water, filtered, and dried at 150 ° C. This dry powder is 700 ℃ in the air
It was baked for 2 hours. The powder obtained was 140 grams.

This powder was measured with an X-ray diffractometer, Miniflex, manufactured by Rigaku Denki. As shown in FIG. 3C, the X-ray diffraction pattern was broad, but it was anatase of titanium oxide. In addition, scanning electron microscope (SE
M) As a result of 2,000 times and 20,000 times, as shown in FIG. 6, in the form of flakes, the average plate diameter was 10 μm, and the plate thickness was 0.24 μm. 1g of this product is mixed with 30 parts of acrylic clear lacquer, and black and white concealment rate test paper J
The ISK5400 was coated with an applicator of 4 mil, and the gloss was measured with a gloss checker IG-330 type manufactured by Hokuba on a black background, and the value was 85 at 60 °.

Further, in order to investigate the color tone angle dependence of the black background, a three-dimensional gloss meter GCMS-4 type manufactured by Murakami Color Research Laboratory was used, and the incident angle was 45 ° and the colorimetric take-out angle was 5 ° at 5 °.
Coloring was performed at intervals, L-a-b conversion was performed, and ab plots, which are hues, were plotted. As shown in FIG. 8, the results showed a wide range of changes from green to blue-green and blue.

To determine the composition of this product, 0.2 grams was accurately weighed, sulfuric acid and ammonium sulfate were added,
It was heated and dissolved. After cooling, water and hydrochloric acid were added, metallic aluminum was added to reduce titanium, and after cooling, potassium thiocyanate solution was used as an indicator and titrated with ammonium iron (III) sulfate solution to determine the amount of titanium oxide (percentage). It was As a result, the titanium oxide content was 95.0%. Further, in order to quantify aluminum and zirconium, a wavelength dispersion type fluorescent X-ray analyzer ZSX100e type manufactured by Rigaku Denki Co., Ltd. was used, and aluminum was 394.40n.
m and zirconium were quantified by a calibration curve method using a peak height of 343.82 nm. As a result, aluminum is 1.15% as aluminum oxide, and
Zirconium was 1.08% as zirconium oxide. That is, the composition of this product is titanium oxide 9
The composition was 5.0 percent, 1.15 percent aluminum oxide, and 1.08 percent zirconium oxide.

(Production Example 2) Synthetic mica (manufactured by Topy Industries)
Laser diameter 150-650 μm Average diameter 300 μm, 1
0 kg was placed in a 600 liter glass lining tank with a jacket, and 400 liters of tap water, 175 g of stannic chloride and a 1 mol / liter sulfuric acid aqueous solution were added to adjust pH to 1.9. Heat with stirring,
After reaching a temperature of 80 ° C., a 1/3 mol / liter titanium tetrachloride hydrochloric acid aqueous solution and a 15% loading soda aqueous solution are used, while maintaining the pH, the titanium tetrachloride hydrochloric acid aqueous solution is added dropwise at a flow rate of 0.12 kg / min. Then, they were reacted for 10 hours.

After cooling, the stirring was stopped and the supernatant was decanted. To the remaining powder, 400 liters of tap water was added and stirred, and a 15% loading soda aqueous solution was added to adjust the pH to 6.5 to 7.5, followed by filtration and washing with water.
It was dried at ° C. The dry powder was calcined in air at 800 ° C. for 2 hours. As in Production Example 1, the surface condition was observed by SEM and the size of the coated particles was an aggregate of 0.016 μm.

The calcined powder was treated with an aqueous sodium carbonate solution PH12.
It was immersed in 400 liters of the above solution. After immersion for 5 days, the propeller was sufficiently dispersed by stirring, and 2 liter of a 2% aqueous solution of sodium hexamer phosphate was added and stirred. After being sufficiently dispersed, the fine powder in the supernatant was separated by the decantation method.
This operation was repeated to collect the powder in the supernatant.

The powder in the supernatant was washed with water and filtered. The filtered powder was immersed in 400 liters of a pH 9.2 solution of a loading soda solution and dispersed by stirring with a propeller. PH 9.2
While maintaining the temperature at 80 ° C., a 3 mol / liter aqueous solution of water glass and a 6N hydrochloric acid aqueous solution were added to the aqueous solution of water glass at a flow rate of 0.085 liters / min for 2 hours. After further aging for 2 hours, it was allowed to cool. After filtration and washing with water, it was dried at 150 ° C. to obtain 18 kg of powder.

X-ray diffraction was measured with the same device as in Production Example 1. As a result of X-ray diffraction, it was rutile type titanium oxide. SE
As shown in FIG. 7, the M observation was in the form of flakes, and the average plate diameter was 15 μm and the plate thickness was 0.45 μm.

Black and white concealment ratio test paper JIS as in Production Example 1
Color measurement with K5400 and a three-dimensional gloss meter, and composition analysis were performed. As a result, the gloss check value was 80 at 60 °, and the color tone angle dependence of the color measurement changed in a wide range from yellow green to green and turquoise. As a result of composition analysis, titanium oxide was 88.5% and silica was 1%.
It was 0.3 percent.

(Production Example 3) Laser diameter is 50 to 200 μm.
1 kg of glass flakes (RCF140 manufactured by Nippon Sheet Glass Co., Ltd.) having an average size of 140 μm were placed in a 40-liter enamel container, 17 liters of 10% titanyl sulfate aqueous solution, and 5 liters of 0.06 mol / liter sulfuric acid aqueous solution, and urea. 100 g and further 10 liters of tap water were added, and the mixture was heated with stirring with a propeller and hydrolyzed at a temperature of 90 ° C. or higher for 6 hours.

After allowing to cool, decantation was repeated to wash with water. A 10% loading soda and 30 liters of tap water were added to adjust the pH of the solution to 8.8 and heated to 80 ° C. While maintaining pH and temperature, 0.85 liters of a 1 mol / liter aqueous solution of water glass and 1N hydrochloric acid aqueous solution were added for 1 hour at a flow rate of 0.014 liters of water glass aqueous solution per minute. Aged for another 3 hours.

After allowing to cool, the surface condition was SE as in Production Example 1.
When observed with M, the size of the coated particles was as large as 0.04 μm.

A 1 mol / liter sodium carbonate aqueous solution was added to the aged dispersion to obtain PH12, which was left for 4 days. After standing, the propeller was stirred, and after standing still, the powder in the supernatant was separated by decantation. This operation was repeated to collect the powder in the supernatant. The recovered powder is washed with water, filtered, and 150 ℃
It was dried at. After drying, the product was further baked in the air at 300 ° C. for 1 hour to obtain 650 g of powder.

As a result of X-ray diffraction, the obtained powder was a fairly broad anatase type. As a result of SEM observation, it has a thin plate shape with an average plate diameter of 8 μm and a thickness of 0.05 μm.
Met.

Physical property tests were conducted in the same manner as in Production Example 1. As a result, when the gloss checker value was 60 °, the color tone angle dependence of the color measurement changed in a wide range from magenta to red / yellow at 60. As a result of compositional analysis, titanium oxide was 70%, silica was 2.8%, and the others were water.

The present invention uses the release composition produced as described above for the above-mentioned uses, and typical examples of the uses will be described below. The technical scope of the present invention is not limited by these applications.

(Application Example 1) Cosmetic powder foundation The following 1 to 6 were mixed in a Henschel mixer, and 7 to
A mixture obtained by heating and dissolving 11 was added and mixed, and then pulverized, and this was molded into an intermediate dish to obtain a desired powder foundation. Blending ingredients Blending amount (parts by weight) 1. Release composition powder of Production Example 3 of the present invention 20.0 2. Talc 21.0 3. Muscovite 44.2 4. Red iron oxide 0.7 5. Yellow iron oxide 1.0 6. Black iron oxide 0.1 7. Dimethyl polysiloxane 1.0 8. Cetyl 2-ethylhexanoate 9.0 9. Sorbitan sesquioleate 1.0 10. Paraben suitable amount 11. Perfume Appropriate amount The powder foundation of this application example has a light elongation,
The effect of improving the skin color beautifully was recognized by the action of the pigment color and the interference color generated from the composite powder of the present invention.

(Application Example 2) Ink composition for printing The following components were mixed and kneaded with a sand mill to obtain an ink composition for printing. Blending ingredients Blending amount (parts by weight) 1. Peeling composition powder of Production Example 2 of the present invention 15.0 2. Acrylic resin 20.0 3. Naphtha 35.0 4. Butyl Cellosolve 30.0 Using the printing ink composition of this application example, when printing was performed on black paper with a coating thickness (after drying) of 50 μm, the coated body changed its color from yellow green to green / turquoise depending on the angle. It had a vivid interference color that changed.

(Application Example 3) Coating composition The thermoplastic acrylic resin and the release composition powder of the present invention were mixed and diluted with toluene to obtain the following coating composition. Blending ingredients Blending amount (parts by weight) 1. Thermoplastic acrylic resin 90.0 2. Release composition powder of Production Example 1 of the present invention 10.0 3. Toluene 10.0 The coating composition of this application example 3 was applied on a 0.8 mm mild steel plate with a bar coater to a film thickness of 30 to 35 μm, left at room temperature for 10 minutes, and then baked at 80 ° C. for 20 minutes. .
The resulting coating is green to bluish green. It had a vivid interference color that changed its color depending on the angle and blue.

Further, this release composition was added to a silicone coating material "Fresselera NA" manufactured by Matsushita Electric Works, Ltd. to prepare a coating composition. Here, it was added so that the ratio to the total solid content was 80% by weight. The coating composition thus prepared has a coating thickness of 10
The surface of the glass plate was spray-coated so as to have a thickness of μm to obtain a coated product.

The photocatalyst performance of this coated article was evaluated as follows. First, 300 pieces of 25 cm2 coated product
It was put in a transparent container of cc, injecting acetaldehyde so that the concentration in the container was about 50 ppm, and irradiating it with black light to evaluate the photocatalytic performance by the half-life of the acetaldehyde concentration, the half-life was 42 minutes. It was possible to obtain high photocatalytic activity.

[0068]

Industrial Applicability As described above, the present invention provides a novel iris-colored titanium oxide composition which exhibits a novel and excellent luster and color sharpness in which a color due to an interference color can be recognized, and in which a residual color does not become turbid. It was possible to provide.

[Brief description of drawings]

FIG. 1 is a conceptual diagram of a coating composition related to the high iris titanium oxide composition of the present invention.

FIG. 2 is a schematic view showing a method for producing a high iris titanium oxide composition of the present invention.

FIG. 3 is a graph of the analysis results of the coating composition of the present invention by X-ray diffraction.

FIG. 4 is a micrograph showing the surface state of titanium oxide in the coating composition of the present invention.

FIG. 5 is a table showing the relationship between the interference color and the film thickness of the titanium layer of the titanium oxide composition that is the release composition of the present invention.

FIG. 6 is a micrograph of a titanium oxide composition that is a release composition.

FIG. 7 is a micrograph of a titanium oxide composition that is a release composition.

FIG. 8 is a graph showing the results of analysis of a titanium oxide composition that is a release composition of the present invention using a three-dimensional gloss meter.

[Explanation of symbols]

1 Flaky substrate 2 coating layer 2a Release composition

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI Theme Coat (reference) C09D 11/00 C09D 11/00 201/00 201/00 (72) Inventor Iku Yagaku Ichiban, Tachikawa, Tokyo 6-1, 2 Machi, Nikko Kogyo Co., Ltd. (72) Inventor Yukio Ii 6-1, 1-2, Ichibancho, Tachikawa, Tokyo Nihon Koken Kogyo (72) Inventor Fukuji Suzuki Tokyo 6-1, Ichibancho, Tachikawa-shi Nihon Koken Kogyo Co., Ltd. F-term (reference) 4C083 AB171 AB172 AB221 AB232 AB351 AB431 AB432 AC342 AC442 AD152 CC01 CC11 CC12 DD17 EE06 EE07 EE11 FF01 4G073 BA20 BD15 BD22 CM22 GA11 GA34 UA01 UB14 UB16 UB19 UB25 UB31 4J037 AA08 AA09 AA18 AA25 AA26 CA09 DD05 DD10 EE03 EE26 EE43 FF02 FF03 4J038 EA011 HA216 HA376 HA446 HA486 HA546 KA08 KA15 KA20 4J039 BA14 BA15 BA21 BA25 BE01 EA20

Claims (27)

[Claims] 1. A coating composition in which a coating layer is formed on the surface of a flaky substrate, wherein the flaky substrate has a plate size of 50 to 8.
High iris color titanium oxide composition having a thickness of 00 μm and a coating layer thickness of 0.05 to 0.6 μm, and the coating layer contains 70% by weight to 95% by weight of the titanium composition. Coating composition. 2. The highly iris-colored titanium oxide composition according to claim 1, wherein the flaky substrate is selected from natural mica, synthetic mica, glass flake, silica flake, alumina flake, and barium sulfate. Coating composition. 3. The coating composition for a high iris-colored titanium oxide composition according to claim 1, wherein the coating layer is a titanium composition selected from titanium dioxide and titanium hydroxide. 4. The coating composition for a high iris titanium oxide composition according to claim 1, wherein the particles of the titanium composition have a uniform particle size. 5. The coating composition of the high iris titanium oxide composition according to claim 1, wherein the coating layer contains 5 to 20% by weight of a reinforcing agent. 6. The coating composition of a high iris titanium oxide composition according to claim 5, wherein the reinforcing agent is selected from silica, alumina and zirconium. 7. A coating layer of a titanium composition having a thickness of 0.05 to 0.6 μm is formed on the surface of a flaky substrate having a size of 50 to 800 μm, and the coating layer of the titanium composition is formed from the coating composition. A high iris color titanium oxide composition, which is a release composition formed by removing. 8. The high iris colored titanium oxide composition according to claim 7, wherein the release composition contains 70 to 95% by weight of titanium dioxide or titanium hydroxide. 9. The high iris titanium oxide composition according to claim 5, wherein said release composition contains 5 to 20% by weight of a reinforcing agent. 10. A coating composition of a high iris titanium oxide composition according to claim 7, wherein said reinforcing agent is selected from silica, alumina and zirconium. 11. The release composition has a thickness of 0.05 to 0.
The coating composition of the high iris titanium oxide composition according to claim 7, which has a thickness of 6 μm. 12. The release composition is obtained by mixing 30 parts of acrylic clear lacquer with 1 part of black and white hiding test paper,
Apply to JISK5400 with a 4 mil applicator,
HORIBA's gross checker I on a black background of the masking rate test paper
The high iris color titanium oxide composition according to claim 7, wherein the value of gloss measured with G-330 type is 55 to 90 at 60 °. 13. The highly iris-colored titanium oxide composition according to claim 7, wherein the release composition develops color by light interference in a layer on the coated surface. 14. The high iris titanium oxide composition according to claim 7, wherein the release composition has a uniform particle size in the layer on the coated surface. 15. The high iris color titanium oxide composition is a cosmetic material.
A high iris colored titanium oxide composition as described. 16. The high-iris color titanium oxide composition according to claim 13 or 14, wherein the high-iris color titanium oxide composition is a paint or a printing ink. 17. The high iris color titanium oxide composition according to claim 13, wherein the high iris color titanium oxide composition is an external composition. 18. The high iris color titanium oxide composition according to claim 13 or 14, wherein the high iris color titanium oxide composition is an adhesive composition. 19. The high iris titanium oxide composition according to claim 13 or 14, wherein the high iris titanium oxide composition is a resin kneading composition. 20. The high iris titanium oxide composition is a photocatalyst, wherein the composition is a photocatalyst.
A high iris colored titanium oxide composition as described. 21. A thickness of 0.05 to 0.6 μm and 70 to 95 on the surface of a flaky substrate having a size of 50 to 800 μm.
A method for producing a high iris-colored titanium oxide composition, which comprises forming a coating layer containing a titanium composition by weight% and peeling the coating layer from the coating composition. 22. The method for producing a highly iris titanium oxide composition according to claim 21, wherein the coating layer contains 5 to 20% by weight of a reinforcing agent. 23. The method for producing a highly iris-colored titanium oxide composition according to claim 22, wherein the reinforcing agent is selected from silica, amina and zirconium. 24. The method for producing a highly iris-colored titanium oxide composition according to claim 21, wherein the exfoliation composition is exfoliated by hydrolysis of a soluble titanium salt aqueous solution or titanium alcoholate. 25. The method for producing a high iris-colored titanium oxide composition according to claim 21, wherein the peeling composition is filtered, washed with water, dried and then baked at 300 to 800 ° C. to be peeled off. 26. The method for producing a highly iris-colored titanium oxide composition according to claim 21, wherein the peeling composition is peeled in an alkaline aqueous solution. 27. The high iris oxidation according to claim 21, wherein the stripping composition is stripped in an aqueous solution of an alkaline aqueous solution of a soluble carbonate, hydroxide or ammonium salt having a pH of 8 or more. Method for producing titanium composition.