JP2008127273A - Reduction type flake-like highly heterochromic titanium oxide composition and method of producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel reduction type flake-like highly heterochromic titanium oxide composition developing color in appearance on powder or on a coating surface layer by light interference, useful as a photo-functional material for cosmetics, ink, plastics, catalysts or the like and excellent in availability such as dense feeling, flip/flop property or extensibility and a method of producing the same. <P>SOLUTION: The reduction type flake-like highly heterochromic titanium oxide composition is obtained by forming a coating layer of a titanium composition on the surface of a flake-like substrate, reducing a flake like titanium composition obtained by peeling the coating layer from the surface of the substrate with a gaseous mixture of ammonia gas or hydrogen and an inert gas and coating the surface of the particle of the reduced flake-like titanium composition with a colorless metal oxide and/or a colorless metal hydroxide. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a reduced flaky high-iris titanium oxide composition, a method for producing the same, and various compositions using the same. Specifically, the surface of the flaky substrate is coated with a titanium composition, the titanium composition is peeled off, and the calcined gas is reduced to produce a novel flaky black iris titanium oxide composition and its production method, A novel flaky black-type iris-colored titanium oxide composition and a method for producing the same after coating the surface of a flaky substrate with a titanium composition, reducing the calcined gas of the titanium composition, and then peeling it off. Further, the surface of the powder appearance color and the layer on the coated surface coated with a colorless metal oxide and / or a colorless metal hydroxide on the surface of the particles of the flaky black iris titanium oxide composition obtained by peeling are light. The present invention relates to a novel reduced flaky high iris colored titanium oxide composition that develops an appearance color by interference and a method for producing the same. More specifically, it is a reducing flaky high-irradiation oxidation that is useful as a photo-functional material such as cosmetics, paints, inks, plastics, and catalysts, and has a good feeling of use such as flip-flop and extensibility. The present invention relates to a titanium composition.

A pearly luster pigment that has natural mica coated with a metal compound such as titanium oxide or iron oxide to give a pearly feeling has been conventionally known. This type of pearl luster pigment has the disadvantages of insufficient glitter, poor color development, and turbidity. Synthetic mica is a highly transparent product, and in that respect it can be said to be an excellent substrate for pearl luster pigments. However, since synthetic mica is hard and difficult to cleave and crush, it is inferior to natural mica in terms of particle surface smoothness and particle thickness in the usual method, but it is transparent because it contains less impurities, especially colored metals. Due to its high whiteness, it has come to be used as a substrate for pearl luster pigments covering thin films such as titanium oxide. Further, in order to increase the brightness of the interference color, it has been used as a pearly luster pigment for coating a thin film such as titanium oxide using plate-like aluminum oxide or plate-like silicon oxide as a substrate.

Titanium oxide is widely used as an additive to paints, cosmetics, and even resins or papers, taking advantage of its whiteness and UV-blocking properties. These are particulate fine particles produced by conventional methods. Since it was used, there were problems in applicability, adhesion, dispersibility and the like. Patent Document 1 is disclosed as a method for producing plate-like titanium oxide, which is titanium oxide having no gloss or interference color.

Originally, color is a very important factor that has a physiological and psychological impact on humans. In fact, it is a method to create a safe and functional working environment and a healthy and comfortable living environment by utilizing the physiological and psychological effects that color can have on humans, and color preparation technology is used in various fields. Has been.

Usually, various color pigments are used to give color to a substance. This colored pigment gives a desired color by utilizing a phenomenon such as light absorption and scattering, but the color pigment alone cannot meet the recent demand for sensitivity and design for the color. Accordingly, pearlescent pigments such as titanium dioxide-coated mica, which are pigments utilizing the interference phenomenon of light, in addition to the colored pigments, are provided. A major feature of this pearl pigment is that it can provide a “flip-flop effect” in which the color tone slightly changes depending on the glitter and the angle.

This pearlescent pigment is used in various fields such as paints, cosmetics, adhesives, printing inks, and resin kneading, but the following drawbacks are pointed out. For example, pearlescent pigments are made of flaky or plate-like particles such as natural mica, synthetic mica, alumina, silica, silicate glass, borate glass, etc., and this is coated with titanium dioxide. By controlling the brightness, it exhibits a pearly luster with various interference colors. For this reason, when such a pearlescent pigment is used as a pigment for an external composition in paints, cosmetics, printing inks, pressure-sensitive adhesives, resin kneadings, etc., since the particles are thick, the film as an ultra-thin film There are drawbacks such as inability to control pressure, lack of design effect due to “flip-flop effect” due to strong light scattering at the particle edge, and lack of “strong particle feeling” and denseness.

On the other hand, for the synthesis of titanium oxide plate-like particles, for example, flaky titanium oxide described in Patent Document 1 is a porous body having a large specific surface area, and cesium titanate is brought into contact with an acid aqueous solution to form layered crystals. It is a flaky titanium oxide obtained by exfoliation and heating. As a result of exfoliating a layered crystal made of titanic acid into one layer, a very thin titanium oxide having a nanometer level is obtained. However, this is a flaky titanium oxide that is too thin and has curled particles and no interference color.

In addition, the plate-like titanium oxide described in Patent Documents 2, 3, and 4 is prepared by attaching a sol-gel obtained by hydrolyzing titanium alcoholate to a drum and heating it to form an oxide, which is peeled off from the drum by a scraper and heated and fired. In this way, plate-like titanium oxide is obtained. This is because the particles are curled to be peeled off by a scraper and the thickness of the particles is on the order of microns. Absent.

Furthermore, the high iris color titanium oxide composition and the production method thereof described in Patent Document 5 are obtained by coating a titanium composition on the surface of a flaky substrate and peeling off the coating layer. This produces an interference color only when it is applied on a black background, but has a drawback that the interference color does not develop on the powder color or the white background due to the large amount of transmitted and scattered light.

Further, Patent Document 6 is a document in which high iris titanium oxide described in Patent Document 5 is blended as a cosmetic, and the characteristics as a powder are exactly the same.

On the other hand, the reduction method of titanium oxide is described in Patent Documents 7, 8, 9, 10, and 11. Patent Document 7 is a method for producing a colored mica titanium-based pigment by mixing metallic titanium with titanium mica coated with titanium dioxide. Patent Document 8 is a method for producing a colored mica titanium-based pigment by reducing titanium dioxide with silicon, titanium hydride, calcium hydride, and carbon. These patent documents describe a method for producing a colored mica titanium pigment by reducing titanium of mica titanium pigment with a metal. Patent Document 9 is a method for producing a colored mica titanium-based pigment obtained by reducing titanium dioxide with ammonia gas. Patent Document 10 is a method for producing a colored mica titanium pigment obtained by reducing titanium dioxide with aluminum oxide. Furthermore, Patent Document 11 is a method for producing a colored mica titanium-based pigment obtained by reducing titanium dioxide with metallic aluminum, manganese, iron, cobalt, nickel, and zinc. These methods for reducing titanium dioxide are known, but for the reduction of very thin flaky interference-colored titanium oxide that does not have a mica-like substrate, if the reducing agent is a metal, the thickness of the titanium oxide particles The particles of the reducing agent are large, and in the reduction process, the metal and titanium oxide are sintered to increase the size of the particles. Further, reduction with ammonia gas is very effective for mica titanium, but it has a drawback that it is difficult to control the degree of reduction and the reduction proceeds rapidly.
Japanese Patent No. 979132 Japanese Patent No. 2562875 JP-A-62-247834 JP-A-62-213833 JP 2003-055574 A JP 2004-067675 A Japanese Patent No. 1732810 JP-A-6-211521 JP-A-6-321540 JP-A-8-67830 Japanese Patent No. 3542388

The present invention is intended to solve such a conventional problem, and is a reduced type that expresses a new and excellent radiance and clearness of color tone in which the appearance color of the powder is an interference color and color development is recognized. It is an object of the present invention to provide a flaky high iris colored titanium oxide composition.

As a result of diligent research to solve the above problems, the present inventors formed a coating layer of a titanium composition on the surface of a flaky substrate when producing a powdered colored reduced flaky high-irradiated titanium oxide composition. Then, the flaky titanium composition obtained by peeling off the coating layer from the substrate surface is reduced with ammonia gas or a mixed gas of hydrogen and an inert gas, and a colorless metal is formed on the particle surface of the reduced flaky titanium composition. A novel reduced flaky high-irradiated titanium oxide composition was obtained that solved this problem by coating with an oxide and / or a colorless metal hydroxide.

Further, when producing a reduced flaky high-irradiated titanium oxide composition that has developed a powder color, a coating layer of the titanium composition is formed on the surface of the flaky substrate, and the titanium composition is added to ammonia gas or hydrogen and an inert gas. This is achieved by coating the particle surface of the reduced flaky titanium composition obtained by reducing the reduced coating layer from the substrate surface with a colorless metal oxide and / or a colorless metal hydroxide after reduction with a mixed gas. Thus, a novel reduced flaky high-irradiated titanium oxide composition 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, which is washed with water, filtered and dried. After reducing with ammonia gas or a mixed gas of hydrogen and an inert gas, or by adding an alkaline aqueous solution before the reduction, the thin plate-like titanium oxide composition obtained by peeling from the flaky substrate surface is converted to ammonia gas or hydrogen. And a flaky black iris titanium oxide composition can be obtained by reduction with a mixed gas with an inert gas. Further, by coating the surface of the particles of the flaky black iris titanium oxide composition with a colorless metal oxide and / or a colorless metal hydroxide, a desired glittering feeling in which the appearance color of the powder is colored with an interference color, It is provided as a reduced flaky high-iris titanium oxide composition that expresses color sharpness.

That is, the first coating composition according to the present invention is an oxidation coating on the particle surface of one or more flaky substrates selected from natural mica, synthetic mica, glass flakes, silica flakes, alumina flakes, and barium sulfate. A flaky black system in which a coating layer comprising a titanium composition and / or a titanium hydroxide composition is washed, filtered, dried and then reduced and peeled off with an alkaline aqueous solution, or the coating layer is peeled off with an alkaline aqueous solution and then reduced. Consists of an iris color titanium oxide composition. The second reduced flaky high iris colored titanium oxide composition according to the present invention is a colorless metal oxide and / or colorless metal on the particle surface of the first exfoliated reduced flaky black iris titanium oxide composition. It is coated with hydroxide.

Further, the coating layer comprising the titanium oxide composition and / or the titanium hydroxide composition coated on the particle surface of the flaky substrate is peeled off with an alkaline aqueous solution, and a colorless metal is coated on the particle surface of the peeled flaky titanium oxide composition. After obtaining a desired interference color by coating with oxide and / or colorless metal hydroxide, it is reduced with ammonia gas or a mixed gas of hydrogen and an inert gas, and the appearance color of the powder is colored with interference color It is provided as a reduced flaky high-iris color titanium oxide composition that expresses the sense of vividness and color tone.

The flaky black iris titanium oxide composition referred to here is a powder color tone before and after reduction, measured by the powder cell method using Minolta CM-2500D, and L, a, b, when converted. This means that the lightness L value has decreased by 40-60. Further, the flaky shape means that the ratio (aspect ratio) of the surface size and the particle thickness when observed with a scanning electron microscope S-2100B manufactured by Hitachi is 30 or more. Further, the iris color is the powder color tone before and after reduction measured by the powder cell method using the Minolta CM-2500D, and L, a, b, and the saturation (C) value when converted are (a ² + b ^2). ) When ^calculated as ^1/2 , the value before reduction is 3.5 or less, whereas the value after reduction is 7.0 or more. The reduced flaky high-irradiation titanium oxide composition is a powder cell tone color measurement using a Minolta CM-2500D with a flaky black-type iris-colored titanium oxide composition. a, b, the brightness (L) value and the saturation (C) value when converted are 5 or more.

Embodiments of the present invention will be described below. The reduced flaky high-iris titanium oxide composition and the method for producing the same, wherein the appearance color of the powder according to the present invention is an interference color and expresses the brightness and color tone sharpness. A coating layer comprising a titanium composition of titanium hydroxide is formed, and the coating composition is reduced with ammonia gas or a mixed gas of hydrogen and an inert gas, and then peeled off with an alkaline aqueous solution, or the coating composition The product is peeled off with an alkaline aqueous solution and then reduced with ammonia gas or a mixed gas of hydrogen and an inert gas. The particle surface of the reduced release composition was coated with a colorless metal oxide and / or colorless metal hydroxide to develop a desired color tone, and the appearance color of the powder was an interference color. In which a process for producing a reduced flaky high-iris titanium oxide composition is disclosed. Furthermore, after peeling the composition to be coated with an alkaline aqueous solution and coating with a colorless metal oxide and / or a colorless metal hydroxide to develop a desired color tone, ammonia gas or hydrogen and an inert gas The present invention discloses a method for producing a reduced flaky high-irradiated titanium oxide composition that has been reduced with a mixed gas and has a bright appearance and a sharpness of the color tone of the appearance of the powder, which is an interference color. The difference from the prior art is that this is obtained by obtaining a titanium-based stripping composition that has been gas-reduced under predetermined conditions and a surface of the composition coated with a colorless metal oxide and / or a colorless metal hydroxide. When used in a wide range of applications such as paints, an unprecedented high iris color can be obtained by virtue of the glittering appearance and color tone of the powder as an appearance color.

The reduced flaky high-iris titanium oxide composition according to the present invention provides a glossy coating layer containing a metal oxide and / or metal hydroxide based on anatase type or rutile type on the surface of a flaky substrate. The composition is coated to a specific thickness of 0.05 to 0.6 μm, peeled off by gas reduction, and the particle surface is coated with a colorless metal oxide and / or a colorless metal hydroxide.

Alternatively, the surface of the flaky substrate is coated with a coating layer containing a metal oxide and / or metal hydroxide based on anatase type or rutile type to a specific thickness of 0.05 to 0.6 μm so that gloss can be obtained. This is a composition in which this is peeled off and gas-reduced, and the particle surface is coated with a colorless metal oxide and / or a colorless metal hydroxide.

Further, the surface of the flaky substrate is coated with a coating layer containing a metal oxide and / or metal hydroxide based on anatase type or rutile type to a specific thickness of 0.05 to 0.6 μm so that gloss can be obtained. Then, after peeling it off, it was further coated with a colorless metal oxide and / or colorless metal hydroxide and then gas-reduced.

The flaky substrate is rich in smoothness, and the plate size of the particles is preferably in the range of 50 to 800 μm in terms of laser diameter. When the thickness is 50 μm or less, the coated titanium oxide and / or titanium hydroxide is difficult to peel off and the interference gloss cannot be sufficiently exhibited. When the thickness is 800 μm or more, the interference gloss of the coated titanium oxide and / or titanium hydroxide can be sufficiently exerted, but the use application is limited because the mechanical strength of the peeled particles is weak. The most preferable particle diameter is in the range of 100 to 700 μm, and interference gloss can be sufficiently exhibited and peeling is easy.

Specific examples of the flaky substrate that easily enters the particle diameter include natural mica, synthetic mica, glass flakes, silica flakes, alumina flakes, and barium sulfate. Natural mica is relatively easy to control its shape and degree of surface smoothness, and it is also relatively easy to coat a uniform coating layer on the surface to a specific thickness that gives a gloss. In some respects, it is a preferred material for selection as a flaky substrate.

The thickness of the flaky substrate is not particularly limited, but is preferably in the range of 0.1 to 10 μm. When the particle thickness is 0.1 μm or less, the periphery of the substrate particle is curled round, and the interference gloss of the coated titanium oxide and / or titanium hydroxide cannot be sufficiently exhibited. Further, when the particle thickness is 10 μm or more, the titanium oxide and / or titanium hydroxide particles coated with the titanium oxide and / or titanium hydroxide coated in the thickness direction in the particle plane have different diameters depending on the plane and thickness. However, the overall interference gloss is insufficient.

The coating layer is a layer containing a titanium oxide and / or titanium hydroxide composition, and is coated to a specific thickness at which gloss is obtained. This is preferably obtained by hydrolysis of a soluble aqueous solution of titanyl sulfate or titanium tetrachloride or titanium alcoholate. Moreover, the coating layer can improve the mechanical strength of the light resistance / peeling composition by including a reinforcing agent such as silica and / or alumina, zirconia, titania and the like.

Furthermore, the present invention provides a method in which the above coating composition is reduced with ammonia gas or a mixed gas of hydrogen and an inert gas, and then peeled off with an alkaline aqueous solution, or after peeling off the coating composition with an alkaline aqueous solution, Reduction with a mixed gas of hydrogen and an inert gas. The appearance of the powder coated with the reduced coating composition with a colorless metal oxide and / or colorless metal hydroxide is an interference color that gives the appearance of high iris colors due to the brightness and color tone. Obtainable.

Furthermore, in the present invention, the above coating composition is stripped with an alkaline aqueous solution, and then coated with a colorless metal oxide and / or a colorless metal hydroxide, and the coating is coated with ammonia gas or hydrogen and an inert gas. Due to the brightness and the sharpness of the color tone, which is reduced by the mixed gas and the appearance color of the powder is an interference color, it is possible to obtain an unprecedented high iris color.

When obtaining a stripping composition before reduction, it is fired at 300 to 800 ° C. in the air in advance, and the coating layer is stripped from the thin plate substrate with an alkaline aqueous solution having a pH of 8 or more. A stripping composition can be obtained.

Moreover, when obtaining a stripping composition after reduction, a stripping composition having no curling and excellent smoothness can be obtained by stripping the coating layer from the thin plate substrate with an alkaline aqueous solution having a pH of 8 or more.

The temperature of reduction with ammonia gas or a mixed gas of hydrogen and an inert gas is 500 to 900 ° C., and it is not reduced to black at temperatures lower than 500 ° C., and is reduced to black at temperatures higher than 900 ° C. Smoothness is lost and gloss is inferior. A more preferable reduction temperature is 600 to 800 ° C. Although the reduction time is not particularly specified, 2 to 4 hours is sufficient.

In order to make the reduction more uniform, a mixed gas of ammonia gas and nitrogen gas is preferable. The ratio of the mixed gas varies depending on the reduction temperature, but the ratio of ammonia gas to nitrogen gas is preferably in the range of 1/1 to 5/1.

As described above, three methods are disclosed for the reduction step, but the final powder characteristic according to the present invention is that the appearance color of the powder is colored with an interference color in any method. Unprecedented high iris color can be obtained by vividness and clarity of color tone. In addition, the reduced flaky high-iris titanium oxide composition has a thickness of 0.05 to 0.6 μm. This can be explained by the relationship between the geometrical film thickness exhibiting the iris color and the optical film thickness (film thickness × refractive index). In general, the geometric film thickness is 0.05 to 0.6 μm. It shows that it is preferable to select the thickness in the range of 0.1 to 1.5 μm.

If the composition is too thin, it is difficult to produce the 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 interference intensity decreases due to scattering of the thickness.

Table 1 shows the relationship between the powder appearance color of the reduced flaky high iris colored titanium oxide composition according to the present invention and the geometric film thickness of the composition.

As the particle size of the reduced flaky high-irradiated titanium oxide composition of the present invention becomes uniform, the saturation of the iris color increases. In other words, each of the particles of the flaky high iris color titanium oxide composition can obtain a desired interference color due to scattered light.

In the present invention, specifically, when the particle size of the reduced flaky high-iris titanium oxide composition and the shape of the thin plate are uniform, the average particle diameter Aμm of the laser diffraction scattering diameter is A ± 4 μm. The volume distribution in the range is 60% or more, preferably 70% or more, and the shape of the thin plate is obtained by observing particles with a scanning electron microscope and counting the number of particles at a magnification of 2000 times. It is desirable that the number of particles that are tangent to the particles and separated by 1.5 times or more of the thickness is less than 10%.

In order to maintain the uniformity of the particle size (shape), it is desirable to carefully pulverize and classify when preparing the smoothness of the flaky substrate. When natural mica is selected, it is desirable to select one having excellent uniformity by wet churning and crushing 2-8 mesh raw ore and elutriation.

Further, the surface of the flaky substrate having a smooth and uniform particle diameter is uniformly coated with the titanium composition, and the coated titanium composition is reduced with ammonia gas or a mixed gas of hydrogen and an inert gas and peeled off or It is preferable to peel and reduce in order to obtain a more uniform interference color.

The reduced flaky high-iris titanium oxide composition of the present invention is colored with little influence on the background color because the powder color is colored with interference color. The interference color is determined by controlling the thickness of the titanium oxide composition particles.

Hereinafter, specific production examples will be described. 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 calcined in the atmosphere at a temperature of 800 ° C. for 2 hours. I left it alone. This chip-like baked natural mica was placed in a 30 L-capacity ball mill pot, 40 kg of 15 mm alumina balls were added, 0.5 L of 10% hexametaphosphoric acid aqueous solution was added, and the mixture was pulverized for 36 hours at 30 rpm.

50 L of pulverized natural mica was placed in a pot tank and transferred to pot tank, and water was added to make the total volume 45 L. Stir with a propeller stirrer, and after standing for 5 minutes, transfer the supernatant to another container, repeat this operation 3 times, classify large particles of 0.1 mm or more, and leave the remaining supernatant with a sieve with an opening of 800 μm. Sieve classification was performed using a sieve having an opening of 203 μm, and particles having a particle size of 800 to 203 μm were filtered with a cloth to obtain 700 g of a wet product having a water content of 50%.

In a 20 L tank, 930 g of titanyl sulfate was weighed, 17.5 L of clean water was added thereto, and the mixture was stirred with a propeller to dissolve the titanyl sulfate. To this aqueous solution, 700 g of wet product of 50% water content pulverized and classified mica was added and heated with propeller stirring. The liquid was heated and hydrolyzed at 80 ° C. for 6 hours. After standing to cool, it was washed with water, filtered, and dried at 150 ° C. to obtain 720 g of a primary coated dry powder.

500 L of the above primary coating dry powder was put into a beaker, 4 L of clean water was added thereto, and a 10% aqueous sodium hydroxide solution was added to the solution while stirring with a propeller to adjust the pH to 11. After standing, the powder released in the supernatant liquid was classified by a decantation method, and the classified powder was filtered and washed with water to obtain 250 g of a primary peeling wet product having a water content of 60%.

100 g of the primary exfoliated wet product is dried at 150 ° C., the dry powder is put in a quartz crucible and set in a tubular electric furnace, and nitrogen gas is 2.1 dm ³ / hour and ammonia gas is 6.0 dm ³ / hour. The mixture was heated at a flow rate and reduced at 700 ° C. for 1 hour. After standing to cool, 38 g of powder having an interference color of a blackish-colored powder appearance color of magenta was obtained. The powder color tone before and after reduction was measured with Minolta CM-2500D. As a result, the L, a, and b values of the powder color before reduction are reduced to 91.7, -1.4, and 1.0 to 34.6, 8.6, and -10.2. As a result, the brightness decreased and the appearance color of the powder was vividly reddish purple.

20 g of the above reduced powder, whose appearance color was reddish purple, was weighed and placed in a 500 ml beaker, and 400 ml of clean water and hydrochloric acid were added to adjust the pH to 2.0. After heating with propeller stirring and reaching 80 ° C., a titanium tetrachloride aqueous solution and a caustic soda aqueous solution were added dropwise while maintaining the pH. The titanium tetrachloride aqueous solution and the caustic soda aqueous solution were dropped while observing the color tone on the black fixed color dish, and the dropping was stopped when the color tone of the powder turned green. While cooling, the aqueous solution of sodium hydroxide was added dropwise to neutralize the pH to 7. Filtration, washing with water and drying were followed by baking for 2 hours at 800 ° C. in an argon stream. The powder developed a bright blue-green color, yielding 28 g. The powder color tone was measured with a Minolta CD-2500D. The L, a, and b values were 40.6, -4.8, and -16.0.

(Production Example 2) 100 g of the primary exfoliated wet product of 60% in Production Example 1 was put in a 1000 ml beaker, and 800 ml of clean water and hydrochloric acid were added to adjust the pH to 2.0. After heating with propeller stirring and reaching 80 ° C., a titanium tetrachloride aqueous solution and a caustic soda aqueous solution were added dropwise while maintaining the pH. The titanium tetrachloride aqueous solution and the caustic soda aqueous solution were dropped while observing the color tone on a black fixed color dish, and the dropping was stopped when the color tone of the powder turned reddish purple. While cooling, the aqueous solution of sodium hydroxide was added dropwise to neutralize the pH to 7. Filtration, washing and drying at 150 ° C. gave 55 g of a secondary titanium oxide-coated dry powder. The powder color was measured with a Minolta CD-2500D. The L, a, and b values were 91.5, -0.6, and 3.0 yellowish green.

40 g of the secondary titanium oxide-coated powder obtained above is put in a quartz crucible and set in a tubular electric furnace, with nitrogen gas at a flow rate of 2.1 dm ³ / hour and ammonia gas at a flow rate of 6.0 dm ³ / hour. The mixture was heated while flowing and reduced at 700 ° C. for 1 hour. After cooling, 38 g of powder having a blue-green interference color, which was vividly colored after cooling, was obtained. The powder color tone before and after reduction was measured with Minolta CD-2500D. As a result, the L, a, and b values of the powder color before reduction were reduced to 91, 5, -0.6, and 3.0, resulting in 42.6, -6.8, and -18.0. A colored blue-green powder was obtained.

(Production Example 3) Natural mica was pulverized and classified in Production Example 1, 200 g of dry powder primary coated with titanyl sulfate was placed in a 3 L beaker, and 2 L of clean water and hydrochloric acid were added to adjust the pH to 2.0. did. After heating with propeller stirring and reaching 80 ° C., a titanium tetrachloride aqueous solution and a caustic soda aqueous solution were added dropwise while maintaining the pH. The titanium tetrachloride aqueous solution and the caustic soda aqueous solution were dropped while observing the color tone with a black fixed color dish, and the dripping was stopped when the color tone of the powder turned blue-green. While cooling, the aqueous solution of sodium hydroxide was added dropwise to neutralize the pH to 7. Filtration, washing, and drying at 150 ° C. yielded 255 g of a secondary titanium oxide-coated dry powder. The powder color was measured with a Minolta CD-2500D. It was a reddish color with L, a, and b values of 87.9, 1.4, and 4.2.

200 g of the above-mentioned secondary titanium oxide-coated powder is put in a quartz crucible, set in a tubular electric furnace, and heated while flowing nitrogen gas at a flow rate of 2.1 dm ³ / hour and ammonia gas at a flow rate of 6.0 dm ³ / hour. And reduced at 650 ° C. for 2 hours. After standing to cool, 190 g of a powder that developed a bright red color was obtained.

180 g of the ammonia-reduced powder obtained above was placed in a beaker, 2 L of clean water was added thereto, and a 10% aqueous sodium hydroxide solution was added to the solution while stirring with a propeller to adjust the pH to 11. After standing, the powder released in the supernatant liquid was classified by a decantation method, and the classified powder was filtered and washed with water to obtain 150 g of a dry powder. The color tone of the obtained powder was measured with a Minolta CD-2500D. Vividly colored red powders having L, a, and b values of 45.7, 14.6, and 6.4 were obtained.

The present invention uses the reduced flaky high-irradiated titanium oxide composition produced as described above for the above-mentioned applications, and typical examples of the applications will be described below. In addition, the compounding quantity which mix | blends the composition of this invention by these uses can be suitably selected according to the objective etc., and should not be specifically limited, Usually 0.1 to 70 weight% according to a use. It mix | blends in the range of a grade.

Moreover, in the use of this invention, as long as the initial effect of this invention is not impaired, the surface may be processed. Moreover, the other component mix | blended for a normal use can be mix | blended.

For example, in the surface treatment, weather resistance and dispersibility treatment of silica, alumina, zirconia and the like. Hydrophobic treatment with an alumina or titanium coupling agent. Examples include hydrophobization treatment with a silicone oil, a fatty acid metal salt, an alkyl phosphoric acid, a fluorine compound having a perfluoroalkyl group, and the like.

Furthermore, as other compounding ingredients, for example, in cosmetics, petroleum jelly, solid paraffin, lanolin, beeswax, whale wax, cholesterol, cetanol, behenyl alcohol, palmitic acid, stearic acid, perfluoropolyether, fluorine-based oil, silicone Oil, silicone derivative, sorbitan fatty acid ester, glyceryl fatty acid ester, polyoxyethylene (hereinafter abbreviated as POE) sorbitan fatty acid ester, POE glyceryl fatty acid ester, POE alkyl ether, POE polyoxypropylene ether, POE polyoxypropylene copolymer, POE alkyl Phenyl ether, POE hydrogenated castor oil, polyethylene glycol fatty acid ester, decaglycerin fatty acid ester, alkyl diethanolamide, alkyl sulfate, PO Alkyl ether sulfate, POE alkyl ether acetate, alkyl phosphate, POE alkyl ether sulfate, POE alkyl ether acetate, higher fatty acid salt, higher fatty acid hydrolyzed collagen salt, amino acid anionic surfactant, sulfosuccinic acid interface Activator, olefin sulfonate, lecithin, betaine acetate, imidazolinium betaine, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylbenzylammonium chloride, ethanol, propanol, benzyl alcohol, 1,3-butylene glycol, Propylene glycol, glycerin, polyethylene glycol, sorbitol, polyvinyl pyrrolidone, acrylic resin alkanolamine, methyl vinyl ether-maleic acid monoa Kill ester copolymer, diethyl sulfate Binirupirori bowl -N, hydroxyethyl cellulose, xanthan gum, and the like.

In addition, powders usually blended in cosmetics, for example, red No. 104, red No. 201, yellow No. 4, blue No. 1, black No. 401, yellow No. 4 Al lake, yellow No. 203 Ba lake, nylon powder, silk Powder, urethane powder, teflon powder, silicone powder, cellulose powder, silicone elastomer, chitin, chitosan, calcium alginate, yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, carbon black, ultramarine, bitumen, titanium oxide, oxidation Zinc, cerium oxide, talc, mica, sericite, kaolin, barium sulfate, aluminum oxide, silicon oxide, calcium carbonate, magnesium carbonate, aluminum silicate, magnesium silicate, particulate titanium oxide, particulate zinc oxide, particulate cerium oxide, mica Titanium, bentonite, Mekutaito, and the like.

Furthermore, cosmetics can be produced according to conventional methods, such as basic cosmetics such as lotions, emulsions and creams, powder white powder, solid white powder, face powder, powder foundation, oily foundation, creamy foundation, liquid foundation, It can be used as makeup cosmetics such as concealer, lipstick, lip balm, blusher, eyeliner, eye shadow and eyebrow.

It can also be blended for coatings, for example, coating film forming elements such as polymer oils, natural or synthetic resins, polymer materials such as cellulose and rubber derivatives, etc .; plasticizers, desiccants, Film forming aids such as curing agents, anti-skinning agents, fluidity modifiers, anti-sagging agents, antiseptics, rust inhibitors, UV absorbers, etc .; other than the reduced flaky high-iris titanium oxide composition of the present invention A pigment or the like can be blended in the coating composition of the present invention.

Moreover, the solvent which melt | dissolves said coating-film formation element can also be selected suitably, and can be used. In the coating composition of the present invention, various interference colors are recognized in the layer that is applied to the application surface and the appearance color formed on the application surface is colored with the interference color.

The paint composition of the present invention includes various paints such as building material paints, stone paints, vehicle paints, ships, ship bottom paints, wood paints, equipment paints, marker paints, electrical insulating paints, conductive / semiconductive paints, chemical resistant paints, It can be widely used for anticorrosion paint, heat resistant paint, fireproof paint, temperature indicating paint, luminescent paint, insecticidal paint and the like.

When the reduced flaky high iris colored titanium oxide composition of the present invention is a printing ink composition: A printing ink composition is an image defined by a manuscript or a plate on the surface of a substrate by printing means. It is a composition used as an image forming material to be formed and fixed.

This printing ink composition is distinguished from the above-mentioned coating composition in that it has “printing suitability” which is a characteristic necessary for producing a printed matter without any trouble in the printing process.

In such a printing ink composition, color materials such as pigments and dyes are blended, and the above-mentioned color pigments are often used as these colorants.

However, from the need to provide more diverse printing, the use of an iris color pigment as a colorant has been studied in the same manner as the coating composition described above.

The reduced flaky high iris colored titanium oxide composition of the present invention is excellent as a colorant for printing ink compositions in terms of imparting various interference colors to the object, and further, it develops appearance with interference colors. Therefore, the printed matter provided using the printing ink composition using this as a colorant is excellent in terms of color development and light resistance of printing.

Thus, the present invention also provides a printing ink composition as the aforementioned coloring composition.

Further, in the printing ink composition of the present invention, in addition to the reduced flaky high iris colored titanium oxide composition of the present invention, elements that can usually be incorporated in the printing ink composition have the initial effects of the present invention. It can be blended as long as it is not impaired.

Specifically, as a colorant, pigments or dyes other than the reduced flaky high-irradiated titanium oxide composition of the present invention: as a vehicle, oil (vegetable oil such as linseed oil, persimmon oil, ink oil, solvent, etc.) Mineral oils, etc.), resins (natural resins such as gilsonite and rosin, rosin-modified phenolic resins, maleic acid resins, petroleum resins, alkyd resins, ester gums, etc.), plasticizers, waxes, solvents, etc .: drying control agents as auxiliaries (Dryers, anti-skinning agents, etc.), viscosity control agents (compounds, thickeners, waist-cutting agents, etc.), dispersibility control agents (dispersants, anti-coloring agents, stabilizers, etc.), color adjusters (toners, Matting agents, etc.), reactive agents (photopolymerization initiators, catalysts, crosslinking agents, etc.), etc., in addition, wetting agents, antifoaming agents, fungicides, etc. can be blended in the printing ink composition of the present invention.

In the printing ink composition of the present invention, the reduced flaky high-iris titanium oxide composition formed on the coated surface after being applied to the coated surface and then through the printing process is colored with an interference color. By doing so, a clear interference color is recognized.

This printing ink composition of the present invention can be widely used as various printing inks, for example, lithographic printing ink, gravure printing ink, relief printing ink, screen printing ink, flexographic printing ink, intaglio printing ink, various printing inks, etc. is there.

The specific formulation of the printing ink composition of the present invention is described in the following examples.

These reduced flaky high iris colored titanium oxide compositions of the present invention were used in the following examples and the like. Further, the blending amount is mass% unless otherwise specified.

Cosmetic: Solid powdery foundation Ingredients Ingredient Amount (% by mass)
1, Silicone treatment composition of Production Example 3 of the present invention 10
2. Silicone-treated sericite 15
26
3. Silicone-treated mica 15
4. Silicone-treated talc 13
5, Silicone-treated spherical silica 5
6, boron nitride 2
7. Silicone-treated titanium oxide 10
8. Silicone-treated fine particle titanium oxide 5
9. Silicone-treated red iron oxide 0.2
10. Silicone-treated yellow iron oxide 1
11. Silicone-treated black iron oxide 0.1
12. Silicone-treated zinc oxide 7
13. Dimethylpolysiloxane 5
14, methylphenylpolysiloxane 2
Cetyl 15,2-ethylhexanoate 2
16, Octyl methoxycinnamate 2
17. Sorbitan sesquiisostearate 1
18, Paraben appropriate amount 19, Antioxidant appropriate amount 20, Fragrance appropriate amount The ingredients of “Production method” 1-12 were mixed and pulverized, then the mixture of 13-20 ingredients was added, stirred and mixed, and further pulverized. The thing was filled and molded into a container to obtain a solid powdery foundation.

Instead of compounding component 1 in the solid powdery foundation of Example 1 (silicone treatment composition of Production Example 3 of the present invention), 10% by mass of Mercy Cimilon Super Red was blended and compared in the same manner as above. The solid powdery foundation of Example 1 was obtained.

Test for actual use of cosmetics Test method: Smoothness at the time of application, elongation to the skin, correction effects of skin defects (texture, uneven color, etc.), evaluation items of finish feeling (beauty) by 20 specialist panels An actual use test was conducted.

(Evaluation criteria)
5 points: Excellent 4 points: Excellent 3 points: Normal 2 points: Inferior 1 point: Very inferior (Evaluation criteria were 5 points for all items, and the total score was corrected to 100 points) When points)
◎: Total score is 80 or more ○: Total score is 60 or more and less than 80 △: Total score is 40 or more and less than 60 ×: Total score is less than 40

この表２から、実施例１の固形パウダリーファンデーションは塗布時が滑らかで肌への伸びも良く肌の欠点を見えにくくして化粧肌の仕上がりも美しかった。The actual use test results of Example 1 and Comparative Example 1 are shown in Table 2.

From Table 2, the solid powdery foundation of Example 1 was smooth when applied, stretched to the skin well, made it difficult to see the skin defects, and the finish of the makeup skin was also beautiful.

Cosmetics: Emulsification foundation Blending ingredients Blending amount (% by mass)
1, Composition of Production Example 3 of the present invention 10
2, Sericite 5
3, Kaolin 3
4, spherical silica 7
5, Red iron oxide 0.1
6, Yellow iron oxide 0.7
7. Black iron oxide 0.1
8. Liquid paraffin 5
9, Decamethylcyclopentasiloxane 12
10, Polyoxyethylene modified silicone 3
11, 1,3 Butylene glycol 6
12. Ion exchange water 48.1
13, Paraben appropriate amount 14, perfume appropriate amount “Production method” After heating and stirring the above 11 to 13 at 70 ° C., 1 to 7 were added thereto and homomixed at 70 ° C. Furthermore, what mixed 8-10 and 14 at 70 degreeC was added to this homomixer processed material, and the homomixer process was further performed at 70 degreeC. This was cooled with stirring to obtain the desired emulsified foundation.

The emulsification foundation of Example 2 showed a light elongation to the skin and an effect of making the skin look beautiful.

Cosmetics: Eye shadow Ingredients Ingredients (mass%)
1, Composition of Production Example 3 of the present invention 15
2, Talc 25
3, mica 10
4, Sericite 7
5, spherical PMMA powder 9
6, plate-like barium sulfate 8
7. Boron nitride 2
8. Yellow iron oxide 1
9. Liquid paraffin 7
10, Dimethylpolysiloxane 5
11. Sorbitan sesquioleate 4
12, Paraben appropriate amount 13, Antioxidant appropriate amount 14, Perfume appropriate amount "Production method" 1-8 and 12 above are mixed well in a mixer, and the remaining components are uniformly dissolved, and this is pulverized by a pulverizer. Thus, the desired eye shadow was obtained by compression molding.

The eye shadow of Example 3 had a good feel during application, and was excellent in appearance color appearance after application.

Coating composition Formulation component Formulation amount (% by mass)
1, Thermoplastic acrylic resin 80
2, Composition of Production Example 1 of the present invention 10
3, Toluene 10
“Manufacturing method” The thermoplastic acrylic resin and the composition of Production Example 1 of the present invention were mixed and then diluted with toluene to obtain a coating composition.

The coating composition of Example 4 was applied to a 1 mm mild steel plate with a bar coater so as to have a film thickness of 30 to 35 μm, allowed to stand at room temperature for 10 minutes, and then baked at 135 ° C. for 20 minutes. The obtained coating film was colored vivid blue-green.

Ink composition for printing Compounding ingredients Compounding amount (% by mass)
1, Composition of Production Example 2 of the present invention 10
2, Ethylene-vinyl acetate copolymer resin 7.2
3, Polypropylene chloride 5.8
4, Toluene 60
5, ethyl acetate 13
6, Isopropyl alcohol 3
7. Polyethylene wax 0.8
8. Antistatic agent 0.2
[Production Method] The above components were mixed and kneaded with a sand mill to obtain a printing ink composition.

When the printing ink composition of Example 5 was used to print on white paper with a coating thickness after drying of 50 μm, the coated body had a clear blue-green interference color.

Ink composition for printing Compounding ingredients Compounding amount (% by mass)
1, Composition of Production Example 3 of the present invention 10
2, Acrylic resin 20
3, Naphtha 40
4, Butyl cellosolve 30
[Production Method] The above components were mixed and kneaded with a sand mill to obtain a printing ink composition.

When the printing ink composition of Example 6 was used to print on white paper so that the film thickness upon drying was 50 μm, the coated body had a bright red interference color.

The invention's effect

The present invention provides a highly versatile powder that can be used in various fields because the appearance color of the powder is an interference color, and uses the interference color of this powder. A coloring composition for the purpose of coloring an object is provided. This coloring composition can take various forms of external compositions such as cosmetics, coating compositions, and printing ink compositions.

Moreover, this invention provides the usage method of these powder and coloring composition in order to exhibit the function of said powder and coloring composition to the maximum.

Claims (27)

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 peeled off from the surface of the substrate. A flaky black-type iris-colored titanium oxide composition, which is a flaky titanium composition to be formed and wherein the exfoliated titanium composition is further reduced. 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 titanium composition is reduced to form a black titanium composition. A flaky black iris titanium oxide composition, which is a flaky black titanium composition formed by peeling off the black titanium composition layer from the substrate surface. 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 peeled off from the surface of the substrate. A reduced flaky titanium composition to be formed, wherein the particle surface of the exfoliated titanium composition is further coated with a colorless metal oxide and / or a colorless metal hydroxide, and the coating composition is reduced. Type flaky high iris colored titanium oxide composition. The flaky black iris titanium oxide composition according to claim 1 or 2, wherein the stripping composition is reduced with ammonia gas or a mixed gas of hydrogen and an inert gas. The flaky black iris titanium oxide composition according to claim 1 or 2, wherein the stripping composition contains 60 to 95% by weight of titanium dioxide and / or reduced titanium oxide. A reducing flaky high iris color of a coating composition, wherein the particle surface of the flaky black iris titanium oxide composition of the release composition is coated with a colorless metal oxide and / or a colorless metal hydroxide. Titanium oxide composition. The reduced flaky high-iris titanium oxide composition of a coating composition according to claim 6, wherein the metal of the colorless metal oxide and / or the colorless metal hydroxide is selected from silica, alumina, zirconia, and titanium. A reduced flaky high-irradiated titanium oxide composition of a coating composition, wherein the coating composition has a thickness of 0.05 to 2 µm. 6. The reduced flaky high-iris titanium oxide composition according to claim 5, wherein the flaky high-iris titanium oxide composition is colored in appearance by light interference in the powder color and the layer on the coated surface. 10. The reduced flaky high iris titanium oxide composition according to claim 9, wherein the flaky high iris titanium oxide composition has a uniform particle size in the powder and the layer on the coated surface. 10. The reduced flaky high iris colored titanium oxide composition according to claim 6, 7, 8, or 9, wherein the reduced flaky high iris colored titanium oxide composition is a cosmetic. 10. The reduced flaky high iris colored titanium oxide composition according to claim 6, 7, 8 or 9, wherein the reduced flaky high iris colored titanium oxide composition is a paint or a printing ink. The reduced flaky high iris colored titanium oxide composition according to claim 6, 7, 8 or 9, wherein the reduced flaky high iris colored titanium oxide composition is an external composition. The reduced flaky high-iris titanium oxide composition according to claim 6, 7, 8, or 9, wherein the flaky high-iris titanium oxide composition is an adhesive composition. 10. The reduced flaky high iris colored titanium oxide composition according to claim 6, 7, 8, or 9, wherein the reduced flaky high iris colored titanium oxide composition is a resin kneaded composition. . The reduced flaky high iris titanium oxide composition according to claim 5, 6, 7 or 8, wherein the reduced flaky high iris titanium oxide composition is a photocatalyst. 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 peeled off from the surface of the substrate. A process for producing a flaky black iris titanium oxide composition, characterized in that it is a flaky titanium composition to be formed, and the stripped titanium composition is further reduced with a mixed gas of ammonia gas or hydrogen and an inert gas. . 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 titanium composition is mixed with ammonia gas or hydrogen and an inert gas. A flaky black rainbow characterized in that it is a flaky black titanium composition formed by reducing with a gas to form a black titanium composition, and further peeling off the black titanium composition layer from the substrate surface. A method for producing a colored titanium oxide composition. The method for producing a flaky black iris titanium oxide composition according to claim 17 or 18, wherein the stripping composition contains 60 to 95% by weight of titanium dioxide and / or reduced titanium oxide. The method for producing a flaky black-type iris-colored titanium oxide composition according to claim 18, wherein the stripping composition is stripped by hydrolysis of a soluble titanium salt aqueous solution or titanium alcoholate. 21. The flaky black iris titanium oxide composition according to claim 20, wherein the stripping composition is baked at 300 to 800 ° C. after filtration, washing with water, and drying to reduce after stripping or stripping after reduction. Manufacturing method. The method for producing a flaky black iris titanium oxide composition according to claim 21, wherein the stripping composition is stripped in an alkaline aqueous solution. 23. The flaky black iris titanium oxide composition according to claim 22, wherein the stripping composition is stripped in an aqueous solution having a pH of 8 or more of an aqueous alkali solution of soluble carbonate, hydroxide and ammonium salt. The manufacturing method. A reducing flaky high iris color of a coating composition, wherein the particle surface of the flaky black iris titanium oxide composition of the release composition is coated with a colorless metal oxide and / or a colorless metal hydroxide. A method for producing a titanium oxide composition. 25. The process for producing a reduced flaky high-iris titanium oxide composition for a coating composition according to claim 24, wherein the metal of the colorless metal oxide and / or colorless metal hydroxide is selected from silica, alumina, zirconia, and titanium. 26. The reduced flaky high-iris titanium oxide composition according to claim 25, wherein the colorless metal oxide and / or the metal of the colorless metal hydroxide is coated with a soluble salt aqueous solution or alcoholate hydrolysis. Manufacturing method. 27. The process for producing a reduced flaky high-iris titanium oxide composition according to claim 26, wherein the coating composition is baked at 300 to 800 [deg.] C. in vacuum or in an inert gas after filtration, washing and drying. .