JP2001207081A - Blue coloraing material composition and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a clear blue coloring material composition having high functionality, and preferably sufficient brightness which uses neither a method by the hydrolysis of a metal alkoxide nor an expensive metal alkoxide and a highly flammable organic solvent and requires neither production facilities nor explosion-proof facilities and is easy to control temperature and humidity to obtain products totally at a low cost. SOLUTION: The blue coloring material composition contains blue powder which has at least one layer of a coated film having been formed by the reaction of a metal salt in a water based solvent in the surface of the base particle and exhibits a reflective spectrum having a peak between 380 and 500 nm, and furthermore, it is preferred that at least one layer of the coated film is constituted as an assembly of crystallized fine particles having voids.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blue coloring material composition and a method for producing the same, and more particularly, to a method for producing a blue coloring material by an inexpensive and safe method without using expensive raw materials or dangerous organic solvents. Can be used for various purposes such as ink, filler for plastics and paper, toner, ink for inkjet printer, etc.
Pigment compositions and paints for toners, general paints, powder pigments and paints for automobiles, paints for electrostatic coating, cosmetics, hair decoration, pigment compositions, crafts and ceramics, and pigments for multicolor paints Compositions, pigment compositions for fiber coloring (carrier), paints for toys, paints and fillers for decorative paper and decorative boards, paints and fillers for plastics and metals, pigment compositions for displays, display media, magnetic recording media The present invention relates to a paint, a catalyst paint, a pigment composition for heat-resistant paint, a blue color material composition, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in the technical fields of electrophotography and printing, colorization of images to be handled has become common, and various studies have been made on techniques relating to colorization. In particular, toner in electrophotography and printing ink in printing are typical examples. Such toners and printing inks are sometimes collectively referred to as colorant compositions. In order to obtain a color image, among the above-mentioned coloring material compositions, a blue material may be particularly important. Blue is one of the three primary colors of light and is an important pigment that psychologically gives a person a sense of cleanliness, coolness, and security. Obtaining a coloring material composition having such a blue color tone and a specific function is of great industrial significance. For example, in a one-component developing method in which an electrophotographic toner itself has magnetism, a black magnetic toner is used in conventional monochrome copying and printing. Also, in the field of printing, a black magnetic ink may be contained by adding a magnetic powder in order to impart a magnetic identification function to a printed image. However, in copying and printing color images,
It is necessary to use a magnetic toner or a magnetic ink that is colored in blue or a vivid primary color in addition to black and that retains magnetic properties. In order to obtain a clear color image with this one-component color magnetic toner or color magnetic ink, it is necessary to color the coloring material composition itself such as the magnetic toner and ink into a vivid color. Since the body particles are generally black, even if a pigment or a dye is directly added to the coloring material composition or a coloring layer is directly provided on the surface of the magnetic material particles, the coloring material composition as a whole has a dark tone. There is a problem.

On the other hand, the present inventors have previously proposed a method of forming a metal film on substrate particles and whitening the powder by the reflection effect of the film (Japanese Patent Application Laid-Open No. 3-271376, JP-A-3-274278), by dispersing the base particles in a metal alkoxide solution and hydrolyzing the metal alkoxide to form a uniform 0.01 to 20 particles on the surface of the base particles.
Method for forming a metal oxide film having a thickness of μm
JP-A-228604), a thin film made of a metal oxide and a thin film made of a metal are alternately provided on the surface to form a functional powder (JP-A-7-90310). It has been proposed that a powder having a multilayer coating is heat-treated to produce a powder having a denser and more stable metal oxide multilayer film (WO 96/28269).

[0004] In particular, the powders provided with a plurality of metal oxide films or metal films as described above can be provided with a special function by adjusting the thickness of each layer. If a coating film having a different refractive index is provided on the surface of each particle at a thickness corresponding to a quarter wavelength of the incident light, a powder that reflects all the incident light can be obtained. When this is applied to a material having a magnetic substance as a base particle, light can be reflected to produce a white toner powder, and furthermore, each unit constituting the light interference multilayer film on the surface of the powder can be obtained. So that the coating layer has a specific same wavelength interference reflection peak,
It suggests that setting the film thickness enables a single-color powder to be obtained without using a dye or a pigment. In the methods described in JP-A-6-228604, JP-A-7-90310, and International Publication WO96 / 28269, the reflectance increases as the number or thickness of the films increases, so that the brightness increases. Characteristics become remarkable. However, as the number and thickness of the films increase, the characteristics of the base particles decrease. For example, when magnetic powder is used as the base particles, as the number and thickness of the films increase, the magnetic properties deteriorate. In other words, the colored powder obtained by the above method requires the number of films and the film thickness to be reduced in order to take advantage of the properties of the base particles. There was also a risk of not being able to get it.

The inventors of the present invention have developed a technique for obtaining a colorant composition having a desired specific color tone based on the above-mentioned technique, and in particular, the color of a film coating powder exhibiting a vivid blue color. An attempt was made to establish a range of conditions for developing the color. The present inventors have conducted studies from such a viewpoint, and as a result, a plurality of coating films in which a coating film having a large refractive index and a coating film having a small refractive index are laminated adjacently on the surface of the base particles, An adhesive resin layer in which pigments and dyes are dispersed;
By setting the conditions of the substrate particles and the coating film so as to show a reflection spectrum having a peak between 00 nm,
It has been found that a color toner having a blue color tone and capable of fulfilling a combined function even in a one-component developing system can be obtained (JP-A-11-24316).

[0006]

However, the blue toner disclosed in Japanese Patent Application Laid-Open No. 11-24316 has a coating layer formed on the surface of the base particles formed by a hydrolysis reaction of metal alkoxide. Met.
In the film forming method by the hydrolysis reaction of metal alkoxide, a highly flammable organic one must be used as a solvent, and an expensive metal alkoxide must be used as a raw material. In order to use an organic solvent having high flammability, a manufacturing facility is used as an explosion-proof facility, and temperature and humidity are strictly controlled, and the price of a product manufactured using the same is naturally high. Further, the blue toner described in JP-A-11-24316 does not have sufficient lightness,
It was of a dark tone.

Accordingly, an object of the present invention is to overcome the above-mentioned drawbacks of the prior art, and without using a method by hydrolysis of a metal alkoxide, without using an expensive metal alkoxide or an organic solvent having a high flammability, a production facility. No explosion-proof equipment is required, temperature and humidity can be easily controlled, and the overall price of the product can be obtained at low cost. To provide. A further object of the present invention is to provide a toner having a high brightness and a stable color tone, an ink, and a paint,
In addition, a blue color material composition that maintains the properties (eg, magnetic properties) of the base particles at a high level, in particular, a relatively small number of films and film thicknesses to take advantage of the properties of the base particles,
An object of the present invention is to provide a blue color material composition based on a blue powder having a coating film that can obtain sufficient brightness and a method for producing the same. Still another object of the present invention is to provide a blue magnetic toner capable of performing an excellent composite function even in a one-component developing system, and a blue magnetic printing ink capable of exhibiting excellent magnetic properties and having excellent weatherability. To provide a blue color material composition applicable to a blue paint and the like, and an efficient production method thereof.

[0008]

Means for Solving the Problems In view of this situation, the present inventors have conducted intensive studies and as a result, when producing a powder coated with a multilayer film, at least one layer of the coating film on the surface of the base particles was made of an aqueous material. It is formed by the reaction of a metal salt in a solvent, improves the combination of films, the thickness of each film, the method of controlling them, and the reaction conditions (pH, dispersion conditions, etc.). The range of wavelengths of values was limited to a specific range. In addition, at least one layer of the coating film is a coating film having voids made of crystallized fine particles,
The inventors have found that a bright blue powder can be obtained by improving the brightness by scattering reflection, and the above object can be achieved.

That is, the blue coloring material composition of the present invention and the method for producing the same are as follows. (1) The surface of the base particles has at least one coating film formed by the reaction of a metal salt in an aqueous solvent, and
A blue coloring material composition containing a blue powder exhibiting a reflection spectrum having a peak between 00 nm. (2) The blue coloring material according to (1), wherein the coating film formed by the reaction of the metal salt of the blue powder in an aqueous solvent satisfies the following condition: Composition. Nd = mλ / 4 [wherein, N = n + iκ (i represents a complex number) n: Refractive index of a substance constituting the film d: Film thickness m: Natural number λ: Wavelength of a peak in the reflection spectrum of the powder ( (Where λ is 380 to 500 nm) κ: attenuation coefficient] (3) The blue color material composition according to the above (1), wherein the coating film on the surface of the base particles of the blue powder is a multilayer film. object. (4) The blue colorant composition according to (3), wherein each of the layers of the blue powder multilayer film is formed by a reaction of a metal salt in an aqueous solvent. (5) The blue colorant composition according to (3), wherein each of the multilayer films of the blue powder satisfies the following condition. Nd = mλ / 4 [wherein, N = n + iκ (i represents a complex number) n: Refractive index of a substance constituting the film d: Film thickness m: Natural number λ: Wavelength of a peak in the reflection spectrum of the powder ( However, λ is 380 to 500 nm) κ: attenuation coefficient]

(6) At least one layer of the coating film on the surface of the base particles of the blue powder is formed as an aggregate of crystallized fine particles having voids. The blue colorant composition described in (1)). (7) The coating film configured as an aggregate of crystallized fine particles having voids can provide brightness by scattering and reflecting light generated between the surface of the crystallized fine particles and the voids. The blue colorant composition as described in (6) above, wherein (8) On the surface of the coating film configured as an aggregate of crystallized fine particles having voids, a dense coating film composed of ultrafine particles capable of closing the voids on the surface is provided. The blue colorant composition as described in (6) above. (9) The blue coloring material composition according to (6), wherein the coating film formed as an aggregate of crystallized fine particles having voids is a high refractive index film. (10) The blue coloring material composition according to (8), wherein the dense film is a silica film.

(11) The coating film formed as an aggregate of crystallized fine particles having voids forms solid phase fine particles in a reaction solution for forming the coating film, and the solid phase fine particles are formed. The blue coloring material composition according to the above (6), which is formed by baking after being taken into the coating film. (12) The blue colorant composition according to (11), wherein the reaction solution is an aqueous solution. (13) Before the baking, the coating film into which the solid phase fine particles are incorporated is coated with ultrafine particles capable of forming a dense film that closes the voids on the surface of the coating film. The blue colorant composition according to the above (11), wherein (14) The above (1), wherein the blue powder is dispersed in a dispersion medium containing at least a binder resin.
The blue coloring material composition according to any one of (13) to (13). (15) A blue ink composition comprising the blue colorant composition according to (14). (16) The blue coloring material composition according to any one of (1) to (13), further including an adhesive resin layer on the blue powder. (17) The blue coloring material composition according to (16), wherein the adhesive resin layer contains an extender pigment. (18) A blue toner comprising the blue coloring material composition according to (16) or (17).

(19) A method for producing a blue color material composition containing a blue powder, wherein the blue powder is 380 to 500 n
m, wherein at least one coating film is formed by a reaction of a metal salt in an aqueous solvent on the surface of the base particles so as to show a reflection spectrum having a peak between m. Production method. (20) The method for producing a blue color material composition according to (19), wherein the coating film formed by the reaction of the metal salt in an aqueous solvent is formed so as to satisfy the following formula: . Nd = mλ / 4 [wherein, N = n + iκ (i represents a complex number) n: Refractive index of a material constituting the film d: Film thickness m: Natural number λ: Wavelength of a peak of the reflection spectrum of the powder ( (Where λ is 380 to 500 nm) κ: Attenuation coefficient] (21) The production of the blue color material composition according to (19), wherein the coating film formed on the surface of the base particles is a multilayer film. Method. (22) The method according to (21), wherein all the films of the multilayer film are formed by a reaction of a metal salt in an aqueous solvent.
A method for producing the blue coloring material composition according to the above. (23) The method for producing a blue color material composition according to (21), wherein all the films of the multilayer film are formed so as to satisfy the following formula. Nd = mλ / 4 [wherein, N = n + iκ (i represents a complex number) n: Refractive index of a substance constituting the film d: Film thickness m: Natural number λ: Wavelength of a peak in the reflection spectrum of the powder ( However, λ is 380 to 500 nm) κ: attenuation coefficient]

(24) The blue color material composition according to the above (19), wherein at least one layer of the coating film formed on the surface of the base particles is constituted as an aggregate of crystallized fine particles having voids. Manufacturing method. (25) The coating film, which is formed as an aggregate of crystallized fine particles having voids, is formed so that lightness can be imparted by scattering and reflection of light generated between the surface of the crystallized fine particles and the voids. The method for producing a blue colorant composition according to the above (19). (26) The above-mentioned (24), wherein a dense film of ultrafine particles capable of closing the voids on the surface is formed on the surface of the coating film constituted as an aggregate of crystallized fine particles having voids. A method for producing the blue coloring material composition according to the above. (27) The method for producing a blue color material composition according to (24), wherein the coating film, which is formed as an aggregate of crystallized fine particles having voids, is a high refractive index film. (28) The method for producing a blue coloring material composition according to (26), wherein the dense film is a silica film. (29) Forming solid phase fine particles in a reaction solution for forming the coating film, wherein the coating film constituting the aggregate of crystallized fine particles having voids is formed by coating the solid phase fine particles with the coating film The method for producing a blue coloring material composition according to the above (24), wherein the composition is formed by baking after being taken in. (30) The method for producing a blue coloring material composition according to (29), wherein the reaction solution is an aqueous solution.

(31) Before the baking, ultrafine particles capable of forming a dense film that closes the voids on the surface of the coating film on the coating film in which the solid phase fine particles are incorporated. The method for producing a blue coloring material composition according to the above (29), which comprises coating. (32) The above (19) to (19), wherein the blue powder is dispersed in a dispersion medium containing at least a binder resin.
(31) The method for producing a blue coloring material composition according to any of (31). (33) A method for producing a blue ink composition comprising the method for producing a blue colorant composition according to (32). (34) The method for producing a blue coloring material composition according to any one of (19) to (31), wherein an adhesive resin layer is provided on the blue powder. (35) The method for producing a blue coloring material composition according to (34), wherein an extender pigment is contained in the adhesive resin layer. (36) A method for producing a blue toner, comprising the method for producing a blue colorant composition according to (34) or (35).

The blue powder in the blue coloring material composition of the present invention suppresses the deposition of a solid phase that does not become a film during the film forming reaction by the following operation and action, and has a uniform thickness on the surface of the base particles. It is presumed that the coating can be formed in a desired thickness. By using a buffer solution as a reaction solvent and adjusting the pH to a certain level, the influence of an acid or alkali is reduced, and erosion of the substrate surface is prevented; by ultrasonic dispersion, particles of the substrate, particularly magnetite powder, etc. Not only improves the dispersibility of the magnetic material, but also improves the diffusibility of the film components, further prevents the adhesion of the films, and improves the dispersibility of the coated magnetic particles. The film components are deposited at a speed of 2. The deposition of the solid phase that does not become a film is suppressed. By the above-mentioned comprehensive action, the electric charge on the surface of the film-coated powder can be kept constant, and the function of the electric double layer does not cause aggregation of the film-coated powder, and thus dispersed particles can be obtained.
In order to make full use of the function of the electric double layer, the pH varies depending on the combination of the substance of the substrate and the type of metal compound formed in the liquid by the film forming reaction, and it is preferable to avoid the isoelectric point of both. Further, at least one layer of the coating film provided on the surface of the base particles is a film made of an aggregate of crystallized fine particles and crystallized fine particles having voids between the crystallized fine particles (hereinafter, simply referred to as a crystallized fine particle constituent film). To increase the refractive index difference between the surface of the crystallized fine particles and the voids to cause scattering and reflection of light, to enhance the reflection effect, and to provide a blue-colored functional powder having excellent lightness. It became possible.

According to the present invention, the film-coating powder does not agglomerate or adhere to each other even when a magnetic substance is used as a substrate, even though a water-soluble raw material is used, and the preferred film thickness control is achieved. Thus, it was possible to easily produce a film-coated powder capable of forming a film. In addition, it has become possible to provide a functional powder in which the characteristics (eg, magnetic characteristics) of the base particles are maintained at a high level. Further, by using water as a solvent, an effect is obtained that a film can be formed at a lower production cost than the alkoxide method.

The blue color material composition of the present invention obtained as described above is useful as a blue-based composite raw material powder used as a raw material for pigments, powder metallurgy, ceramic raw materials, electronic industries, and the like. It retains excellent performance in place of conventional pigments used for ink pigments and plastic / paper fillers, and can have a stable color tone even during long-term storage. Utilizing heat resistance, it can be used for painting, design, and decoration as a pigment composition for coloring ceramics, porcelain, glassware, crafts, arts, decorations, and the like. In addition, decorative products that are rich in design using polychromaticity and reflective or transmitted colors,
Pottery, porcelain, glassware, paintings and other crafts and arts,
Paints for books, automobiles, bicycles, etc.
Makes toner, paint, and cosmetics. Further, a titanium oxide film or the like having a catalytic action can provide a paint having excellent weather resistance and an environmental purification property such as air and water. That is, the present invention can be applied to blue multifunctional inks, toners, paints, and the like having both the characteristics of the substrate and the characteristics of the film. In particular, the function is magnetic,
Any one of the functions of electric field, color, particle shape, fluorescence emission, phosphorescence emission, specific violet ray reflection absorption and specific infrared reflection absorption
By combining more than one kind, it is possible to form a desired image on a support medium as a printing ink as a forgery-preventing pigment composition and a toner as a toner, and make it a target to be visually discriminated or discriminated by a device. In addition to having these excellent functions, if a magnetic, conductive or dielectric material is used as the base, additional effects such as moving force, rotation, movement, heat generation, etc. will be produced by reacting with external factors such as electric and magnetic fields. For example, when a magnetic substance is used as a substrate, it can be used as a pigment for a blue or color magnetic toner or a blue or color magnetic ink without losing magnetism.

Hereinafter, the crystallized fine particle constituting film of the present invention will be described in more detail with reference to the drawings. FIG.
FIG. 2 is a cross-sectional view of an example of the blue colorant composition of the present invention having a crystallized fine particle constituting film 2 on the surface of a base particle 1;
FIG. 2 is an enlarged cross-sectional view of a crystallized fine particle constituting film 2 included in the blue color material composition of FIG. 1. As shown in FIGS. 1 and 2, the crystallized fine particle constituting film 2 has a gap between the crystallized fine particles 3, thereby increasing the difference in the refractive index between the surface of the crystallized fine particle 3 and the gap. Scattered reflection of the powder, whereby a powder having high brightness can be obtained. The stronger the above-mentioned scattered reflection, the brighter the powder. The crystallized fine particles 3 contained in the film 2 preferably have a high refractive index, and more preferably have a non-uniform particle size. To adjust the brightness,
It can be adjusted by the amount and particle size of the crystallized fine particles in the film. However, depending on the particle size, scattering and interference occur simultaneously, and the interference may give a hue other than blue, so care must be taken in its design. In particular, when the obtained film-coated powder has a strong monochromatic spectrum color like opal, the crystallized particle diameter in the film is uniform at a certain size (about one quarter to one wavelength of light wavelength). It is considered that interference has occurred due to the crystallized fine particles.

In this case, the particle size of the crystallized fine particles in the film is preferably from 1 to 500 nm, more preferably from 1 to 500 nm.
00 nm, more preferably in the range of 1 to 100 nm. If the particle diameter is less than 1 nm, the constituent film may transmit light, so that the color of the underlying base particles may appear as it is. On the other hand, if it is larger than 500 nm, the interference coloring occurs due to the reflected light of a plurality of particles, or the film becomes brittle, and it is not preferable because the film is easily peeled. In addition, the crystallized fine particles in the film can be distinguished by the shape such as the grain boundary even if they are in contact with other fine particles or the film.

On the other hand, one layer of the crystallized fine particle constituting film
The preferred thickness range varies depending on the size of the base particles. 0.05 μm for substrate particles of 0.1 μm to 1 μm
m to 0.5 μm, and 0.1 μm when the substrate particles are 1 μm to 10 μm.
05 μm to 2 μm, 0.0 if the substrate particles are 10 μm or more.
It is preferably from 5 μm to 3 μm. Further, the preferable thickness range of the total film thickness of the crystallized fine particle constituting film also varies depending on the size of the particles serving as the substrate. Substrate particles 0.1μ
0.1 μm to 3 μm for m to 1 μm, 1 μm for base particles
0.1-10 μm, 0.1 μm-5 μm, base particles 10 μm
When it is more than m, the thickness is preferably 0.1 μm to 10 μm.

Further, as shown in FIG. 2, the blue coloring material composition according to the present invention has a blue powder on the surface of the film 2 composed of the crystallized fine particles 3 having voids. It is preferable to have a dense coating film (hereinafter, simply referred to as a dense film) composed of the ultrafine particles 4 capable of closing the voids. For example, when a blue powder having the above-described crystallized fine particle constituting film as the outermost layer is used as a pigment powder such as a toner or a paint, a vehicle of a resin or a paint of the toner enters the void and the crystallized fine particles 3 are formed. The difference in the refractive index between the surface and the air gap is reduced to weaken the scattering and reflection of light, and as a result, the brightness is also reduced. The above-described dense film is suitable for preventing the above-described decrease in brightness.

Japanese Unexamined Patent Publication (Kokai) No. 4-269804 describes a colored powder having a coating layer of inorganic pigment particles on the surface. This colored powder has voids between the pigment particles.
It is filled with a mixture of a surface treatment agent and a resin, and does not generate diffuse reflection as in the blue color material composition of the present invention, but is colored to a desired color by the color of the pigment particles themselves. It is. Also, Japanese Patent Application Laid-Open No. 4-26
In the colored powder described in Japanese Patent No. 9804, pigment particles may not be sufficiently fixed on the surface of the base particles. In such a case, the pigment particles adhering to the substrate are separated in the mixed solution of the solvent and the resin, and thus may not be applied to a paint or the like.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the blue color material composition of the present invention will be described in detail. The blue colorant composition of the present invention contains not only the above-mentioned crystallized fine particle constituting film on the surface of the base particles, but also a multilayer film-coated powder further having a film having another constitution capable of transmitting light. It is. When the metal hydroxide film or the metal oxide film is formed into a plurality of layers by the reaction of a metal salt or the like as the low-refractive-index light-transmitting coating film, the coating film (coating the base particles) is used. A special function can be imparted by adjusting the thickness of each layer of the layer which participates in light interference). For example, alternate coating films having different refractive indices are provided on the surface of the base particles so that the refractive index n of the material forming the coating is 380 to 5 so that the following formula (1) is satisfied.
When an alternate film having a thickness d corresponding to an integer m times a quarter of the wavelength of visible light between 00 nm and an appropriate number of films is provided, light having a wavelength λ between 380 and 500 nm ( Using the interference reflection of Fresnel) is reflected or absorbed. nd = mλ / 4 (1)

Utilizing this effect, a film having a film thickness and a refractive index that satisfies the formula (1) is formed on the surface of the base particles at a target wavelength of 380 to 500 nm, Further, by alternately repeating once or more times coating films having different refractive indices thereon, 3
A film having a reflection peak between 80 and 500 nm is formed. At this time, the order of the materials to be formed is determined as follows. First, it is preferable that the first layer be a film having a low refractive index when the refractive index of the base serving as a nucleus is high, and that the first layer be a film having a high refractive index in the opposite relationship.

The change in the optical film thickness, which is the product of the film refractive index and the film thickness, is measured and controlled as a reflected waveform by a spectrophotometer or the like. The thickness of each layer is designed. For example, when the peak position of the reflection waveform of each unit film constituting the multilayer film is precisely adjusted to a range of 380 to 500 nm, a single color powder of blue color can be obtained without using a dye or a pigment.

However, in the case of an actual substrate, the particle size of the substrate,
It is necessary to design in consideration of the shape, the phase shift at the mutual interface between the film material and the base particle material, the peak shift due to the wavelength dependence of the refractive index, and the like. For example, when the shape of the base particle is a parallel plate, the Fresnel interference by the parallel film formed on the particle plane is designed under the condition that n in the above formula (1) is replaced by N in the following formula (2). I do. In particular, in the case where a metal film is included even when the shape of the base is a parallel plate, the attenuation coefficient κ is included in the refractive index N of the metal of the formula (2). In the case of a transparent oxide (dielectric), κ is very small and can be ignored. N = n + iκ (i represents a complex number) (2) If this attenuation coefficient κ is large, the phase shift at the interface between the film material and the base material becomes large, and furthermore, interference due to the phase shift occurs in all the layers of the multilayer film. Affects optimum film thickness.

As a result, even if only the geometrical film thickness is adjusted, the peak position is shifted, so that the color becomes pale especially when coloring in a blue color system. In order to prevent this, the effects of the phase shift on all the films are taken into consideration, and a computer simulation is designed so that the combination of the film thicknesses is optimized in advance. Further, there is a phase shift due to the oxide layer on the substrate surface and a peak shift due to the wavelength dependence of the refractive index. To correct these, the reflection peak is 380 to 50, which is the target wavelength in the final target film number, using a spectrophotometer or the like.
It is necessary to find the optimal conditions so as to be in the range of 0 nm.

The interference of a film formed on a curved surface such as a spherical powder occurs similarly to a flat plate, and basically follows the Fresnel interference principle. Therefore, the coloring method can be designed to be blue. However, in the case of a curved surface, light incident on and reflected by the powder causes complicated interference. These interference waveforms are almost the same as a flat plate when the number of films is small. However, as the total number increases, the interference inside the multilayer film becomes more complicated. Also in the case of a multilayer film, the reflection spectral curve can be designed in advance by computer simulation based on the Fresnel interference so that the combination of the film thickness is optimized. In particular, in the case of forming a film on the surface of the substrate particles, the effect of the phase shift on the surface of the substrate particles and all the films is taken into consideration, and a computer simulation is designed so that the combination of film thicknesses is optimized in advance. Further, the peak shift due to the oxide layer on the surface of the base particles and the peak shift due to the wavelength dependence of the refractive index are taken into consideration. In actual sample production, the designed spectral curve is referred to, and in order to correct these in the actual film, the reflection peak is set to 38 in the final target film number using a spectrophotometer or the like.
The optimum conditions must be found while changing the film thickness so that the target wavelength is in the range of 0 to 500 nm.

In the case of coloring an irregularly shaped powder, interference by the multilayer film occurs, and a basic film design is performed with reference to the conditions of the interference multilayer film of the spherical powder. The peak position of each unit film constituting the above-mentioned multilayer film can be adjusted by the film thickness of each layer, and the film thickness can be adjusted in the film forming conditions for forming a solid phase component such as metal oxide on the surface of the base particles. By controlling the composition, the solid deposition rate, the amount of the substrate, and the like, the film thickness can be accurately controlled, a film having a uniform thickness can be formed, and a desired blue color can be obtained. As described above, the reflection peak and the absorption bottom are 380 to 380 in the final target film number.
A blue powder can be obtained by finding the optimum conditions while changing the film forming conditions such as the film forming solution so that the target wavelength is in the range of 500 nm. Further, by controlling the combination of the substances constituting the multilayer film and the thickness of each unit film, it is possible to adjust the color development due to the interference of the multilayer film. Thereby, the powder can be vividly colored to a desired blue color without using a dye or a pigment.

Hereinafter, the blue colorant composition of the present invention and the method for producing the same will be described in detail. In the blue color material composition and the method for producing the same of the present invention, the base particles serving as the control for forming the metal oxide film and the like are not particularly limited, and may be an inorganic substance containing a metal, an organic substance, a magnetic substance, a dielectric substance, Conductors and insulators may be used. When the substrate is metal, iron, nickel, chromium, titanium, aluminum, etc.
Any metal may be used, but those utilizing magnetism are preferably those having magnetism such as iron. These metals may be alloys, and when having the above-mentioned magnetism, it is preferable to use ferromagnetic alloys. Also,
When the base of the powder is a metal compound, examples thereof include oxides of the above-mentioned metals.Examples include iron, nickel, chromium, titanium, aluminum, silicon, and the like, and calcium and magnesium. And oxides of barium and the like, or composite oxides thereof. Furthermore, examples of metal compounds other than metal oxides include metal nitrides, metal carbides, metal sulfides, metal fluorides, metal carbonates, and metal phosphates.

Further, except for the metal as the base particles,
It is a semi-metallic or non-metallic compound, especially an oxide, carbide or nitride, and silica, glass beads or the like can be used. Other inorganic substances include inorganic hollow particles such as shirasu balloons (hollow silicate particles), fine carbon hollow spheres (Clekasphere), fused alumina bubbles, aerosil, white carbon, silica fine hollow spheres, calcium carbonate fine hollow spheres, Mica such as calcium carbonate, perlite, talc, bentonite, synthetic mica, muscovite, kaolin and the like can be used.

As the organic substance, resin particles are preferable. Specific examples of the resin particles include cellulose powder, cellulose acetate powder, polyamide, epoxy resin, polyester, melamine resin, polyurethane, vinyl acetate resin, silicon resin, acrylate, methacrylate, styrene, ethylene, propylene and these. Spherical or crushed particles obtained by polymerization or copolymerization of a derivative of the above. Particularly preferred resin particles are spherical acrylic resin particles obtained by polymerization of acrylic acid or methacrylic acid ester. However, when resin particles are used as the substrate, the heating temperature in drying must be lower than the melting point of the resin.

As the shape of the substrate, polyhedrons such as spheres, subspheres, isotropic bodies such as regular polyhedrons, rectangular parallelepipeds, spheroids, rhombohedrons, plate-like bodies, needle-like bodies (cylinders, prisms) and the like are further crushed. It is also possible to use a completely amorphous powder such as an object. These substrates are not particularly limited in terms of particle size,
Those having a range of 0.01 μm to several mm are preferred. Also,
The specific gravity of the substrate particles is in the range of 0.1 to 10.5. However, when the obtained powder is used by dispersing it in a liquid or the like, from the viewpoint of fluidity and buoyancy, it is considered to be 0. .1 to
5.5 is preferred, more preferably 0.1 to 2.8, and still more preferably 0.5 to 1.8. When the obtained powder is used by dispersing it in a liquid or the like, if the specific gravity of the substrate is less than 0.1, the buoyancy in the liquid is too large, and the film needs to be multi-layered or very thick, which is uneconomical. on the other hand,
If it exceeds 10.5, the film for floating becomes thicker,
Equally expensive.

In the present invention, as described above, the powder substrate particles are coated by using a plurality of coating layers having different refractive indices and appropriately selecting the refractive index and the layer thickness of each coating layer. A powder which is colored blue by the interference color and expresses a specific interference reflection peak outside the visible light region can be obtained. As described above, the metal hydroxide film or the metal oxide film is deposited on the surface of the base particles by the reaction of the metal salt. As a solvent for the solid phase deposition reaction, a buffer solution is used, and at a certain pH. Deposit at an appropriate rate.

In the present invention, metals used as metal salts include iron, nickel, chromium, titanium, zinc, aluminum, cadmium, zirconium, silicon, tin, lead,
In addition to lithium, indium, neodymium, bismuth, cerium, antimony and the like, calcium, magnesium, barium and the like can be mentioned. Examples of the salts of these metals include salts of sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, carbonic acid and carboxylic acid. Furthermore, a chelate complex of the metal is also included. As the kind of the metal salt used in the present invention, a suitable metal salt is selected according to the property to be imparted to the surface of the substrate and the means to be applied in the production. The powder of the present invention basically forms a colorless and transparent film, and is formed by laminating films having different refractive indexes to be colored.The above-mentioned metals and salts thereof are mentioned, but only by interference coloration. If the reflection and absorption spectra do not have the desired color, the following metallic cobalt, yttrium,
Sulfur, europium, dysprosium, antimony,
Examples include sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, carbonic acid, and carboxylic acid of metals such as samarium, copper, silver, gold, platinum, rhodium, iridium, and tungsten. Further, a chelate complex of the metal is also included. The content of these metals in the film is 10 ppm to 15%, preferably 10 ppm to 15%.
%, More preferably 50 ppm to 5%. When the content of these metals is small, the coloring becomes insufficient, and when the content is too large, the coloring becomes too strong and the color becomes dark, so that there is an inconvenience that the powder of the bright color which is the target of the present invention cannot be obtained.

A film of a metal oxide or the like made of these metal salts may be formed in a plurality of layers, and if necessary, a metal oxide or the like obtained by hydrolysis of a metal alkoxide may be formed on the film of the metal oxide or the like. Further, a film can be formed by another film forming method. In this way, a multilayer film can be formed on the substrate particles, and at this time, by setting the formation conditions so that the thickness of each layer has a predetermined thickness, the desired characteristics can be obtained. It is possible to obtain a multi-layered film of a metal oxide or the like using a metal salt, which is an inexpensive raw material, with a simple operation. In particular, it is an important advantage that a powder coated with a multilayer film can be obtained without using an expensive metal alkoxide as a raw material.

In the method of the present invention for producing a blue coloring material composition containing a blue powder, a multilayer coating film may be manufactured as a continuous process, or each coating film may be manufactured one by one. Alternatively, it can be manufactured by various methods such as a combination of a single-layer manufacturing and a multi-layer continuous manufacturing. The particle size of the blue coloring material composition according to the present invention is not particularly limited and can be appropriately adjusted depending on the purpose.
m, preferably in the range of 0.1 μm to 200 μm

In the present invention, the thickness of the metal oxide film formed at one time can be in the range of 5 nm to 10 μm, which can be made thicker than the conventional formation method. As the total thickness of the metal oxide film formed in a plurality of times, in the case of the color magnetic powder described above,
In order to form a metal oxide film having a good reflectance due to the interference, the thickness is preferably in the range of 10 nm to 20 μm, and more preferably in the range of 20 nm to 5 μm.
The thickness is preferably in the range of 0.02 to 2.0 μm in order to interfere and reflect visible light with a particularly thin film thickness, for example, when the particle size is limited.

The blue colorant composition of the present invention is, as described above,
During the film forming reaction in the manufacturing method, particularly when the film forming reaction is performed in an aqueous solvent, an aqueous solvent having a constant pH is used as the film forming reaction solvent, and the film coating reaction is simultaneously performed under ultrasonic dispersion conditions. It is formed by a film forming reaction on the surface. In the present invention, in order to make the membrane formation reaction constant, a buffer is added to an aqueous solvent to prepare a buffer solution, or a buffer solution prepared in advance is used. At the time of the film forming reaction, a film material other than the buffer solution is added to form a film. If the pH fluctuates greatly when the film is formed by adding the film forming raw material, it is desirable to add a buffer solution in order to prevent this from changing. The term “constant pH” as used in the present invention means that the pH is within ± 2, preferably within ± 1, more preferably within ± 0.5 of a predetermined pH.

As the buffer solution, various systems are used, and there is no particular limitation. First, it is important that the base particles can be sufficiently dispersed. It is necessary to select such that the powder can also be dispersed by the action of the electric double layer, and that the conditions for forming a dense film by the above-mentioned gentle dropping reaction are satisfied. Therefore, the method for producing a film-coated powder of the present invention is different from the conventional method of neutralizing by reaction of a metal salt solution, precipitating by isoelectric point, or decomposing by heating to precipitate.

Next, as the ultrasonic dispersion conditions, various ultrasonic oscillators can be used, for example, a water tank of an ultrasonic cleaner can be used, and there is no particular limitation. However, the ultrasonic dispersion conditions of the present invention vary depending on the size of the oscillator, the shape and size of the reaction vessel, the amount and volume of the reaction solution, the amount of the base particles, etc., and in each case, What is necessary is just to select appropriate conditions. The buffer solution used in the present invention depends on the solid phase component to be precipitated, and is not particularly limited. However, Tris, boric acid, glycine, succinic acid, lactic acid, acetic acid, tartaric acid, and hydrochloric acid are used. And the like.

Next, as an example, a method of forming an alternating multilayer film of a metal oxide having a high refractive index and a metal oxide having a low refractive index, particularly when a film forming reaction is performed in an aqueous solvent, will be specifically described. First, when forming a coating such as titanium oxide or zirconium oxide, the base particles are immersed in a buffer solution such as an acetic acid / sodium acetate system, dispersed by ultrasonic oscillation, and titanium sulfate, which is a metal salt such as titanium or zirconium. An aqueous solution of these metal salts is slowly dropped into a reaction system using zirconium sulfate or the like as a raw material, and the resulting metal hydroxide or metal oxide is deposited around the base particles. During this dropping reaction,
The pH is maintained at the pH of the buffer solution (5.4). After completion of the reaction, the powder is subjected to solid-liquid separation, washed and dried, and then subjected to a heat treatment. The drying means may be either vacuum drying or natural drying. Further, it is also possible to use a device such as a spray dryer in an inert atmosphere. When the film to be coated is titanium oxide, the formation of titanium oxide is represented by the following reaction formula. Ti (SO ₄ ) ₂ + 2H ₂ O → TiO ₂ + 4H
The TiO ₂ content of ₂ (SO ₄ ) ₂ titanyl sulfate is from 5 g / liter to 18
0 g / liter is preferable, and more preferably 10 g / liter to 160 g / liter. If the amount is less than 5 g / l, it takes too much time to form a film, and the amount of powder to be treated is reduced, which is uneconomical. If the amount exceeds 180 g / l, the diluting solution is hydrolyzed during the addition and does not become a film forming component. Are both unsuitable.

Subsequently, when a film of silicon dioxide or aluminum oxide is formed, KCl / H ₃ BO ₃
The titania-coated particles are immersed and dispersed in a buffer solution in which NaOH is added to a system or the like, and a metal salt of silicon or aluminum, such as sodium silicate or aluminum chloride, is used as a raw material, and an aqueous solution of these metal salts is reacted. It can be carried out by slowly dropping the solution into the system and depositing the resulting metal hydroxide or metal oxide around the base particles. During this dropping reaction, the pH is the pH of the buffer solution.
(9.0). After completion of the reaction, the powder is subjected to solid-liquid separation, washed and dried, and then subjected to a heat treatment. By this operation, the operation of forming two layers of metal oxide films having different refractive indices on the surface of the base particles is repeated, whereby a powder having a multilayer metal oxide film on the surface is obtained. In addition,
When the film to be coated is silicon dioxide, the formation of silicon dioxide is shown by the following reaction formula. Na ₂ Si _X O _{2X + 1} + H ₂ O → XSiO ₂ +
2Na ^{+ +} 2OH ^-

Next, the crystallized fine particle constituting film of the blue powder contained in the blue coloring material composition of the present invention can be any substance as long as it can scatter and reflect light and emit white light. May be used, but those made of a substance having a high refractive index are preferred. The substance having a high refractive index is not particularly limited, but oxides such as titanium oxide (titania), zirconium oxide, bismuth oxide, cerium oxide, antimony oxide, and indium oxide can be used. The most preferred is titanium oxide (titania).

As a method of forming the crystallized fine particle constituting film as described above, a method of solid phase precipitation in a film forming reaction liquid phase or the like is used. Specifically, Japanese Patent Application Laid-Open Nos. 6-228604 and 7-903 previously proposed by the present inventors.
No. 10 and International Publication WO 96/28269, a solid phase precipitation method by hydrolysis of a metal alkoxide in an organic solvent (metal alkoxide method), and a specification attached to Japanese Patent Application No. 9-298717. And a solid phase precipitation method (aqueous method) by a reaction from a metal salt in an aqueous solution described in (1). In this case, in the film-forming reaction solution, the speed at which the solid phase fine particles precipitate in the reaction solution is higher than the speed at which the precipitate film grows on the surface of the base particles (linear growth speed).
The concentration of the reaction solution, the amount of the added catalyst, and the amount of the base particles dispersed are adjusted. As described above, the solid phase fine particles precipitated in the film forming reaction solution are adhered to the surface of the base particles to form a coating film composed of the solid state fine particles.

At this point, the solid fine particles incorporated in the film are amorphous, no voids are formed between the solid fine particles, no light scattering reflection occurs, and the mechanical strength of the film is low. Is also very low. Therefore, the coating film composed of the solid particles is fired. By this baking, the amorphous solid phase fine particles are crystallized, voids are formed between the crystallized fine particles, and the above-mentioned crystallized fine particle constituting film that scatters and reflects light is obtained.

In order to form the crystallized fine particle constituting film, the aqueous method is simpler than the above-mentioned metal alkoxide method to make the relationship between the linear growth rate and the solid phase deposition rate preferable. Therefore, it is preferable. Further, the metal alkoxide method requires an expensive metal alkoxide as a raw material and a relatively expensive and dangerous organic solvent as a reaction solvent. For this reason, the manufacturing apparatus or equipment must also be of explosion-proof type, and the cost performance is further deteriorated. From this viewpoint, the aqueous method is preferable to the metal alkoxide method. If the core particles are metals or oxides and are unstable with respect to water, the first layer is formed and stabilized by a metal alkoxide method so that the second and subsequent layers are formed by an aqueous method. Is preferred.

The sintering may be performed after forming the coating film composed of the solid phase fine particles. However, on the coating film, the coating film becomes a crystallized fine particle constituting film. In this case, it is preferable that the coating be performed after coating with ultrafine particles capable of forming a dense film for closing the voids on the surface, from the viewpoint of the film strength of the obtained blue powder. Baking is 300-12
It is preferably performed at 00 ° C.

In the blue coloring material composition of the present invention, the above-mentioned constituent film of the crystallized fine particles of the blue powder contained therein may have two or more layers. In that case, a light-transmitting coating film having a low refractive index is preferably present between the two layers of the crystallized fine particle constituent films. The low-refractive-index light-transmitting coating film is not particularly limited, and examples thereof include those made of a metal compound, an organic substance, and the like.

Examples of the metal compound include metal oxides, metal sulfides, metal selenides, metal tellurides, and metal fluorides. More specifically, zinc oxide, aluminum oxide, cadmium oxide, titanium oxide,
Zirconium oxide, tantalum oxide, silicon oxide, antimony oxide, neodymium oxide, lanthanum oxide, bismuth oxide, cerium oxide, tin oxide, magnesium oxide, lithium oxide, lead oxide, cadmium sulfide, zinc sulfide, antimony sulfide, cadmium selenide, tellurium Cadmium fluoride, calcium fluoride, sodium fluoride, trisodium aluminum fluoride, lithium fluoride, magnesium fluoride and the like can be suitably used.

The method for forming the metal compound film will be described below. As a film forming method, a method in which a vapor deposition method such as a PVD method, a CVD method, or a spray dry method is used to directly deposit the vapor on the surface of the base particles is possible. However, the above-mentioned Japanese Patent Application Laid-Open No.
Preferred are the metal alkoxide method described in JP 8604, JP-A-7-90310 or WO 96/28269, and the aqueous method described in Japanese Patent Application No. 9-298717. In this case, unlike the above-mentioned film formation of the crystallized fine particle constituent film, the linear growth rate is higher than the solid phase deposition rate, and the reaction conditions are adjusted so that an amorphous uniform film is formed.

The organic substance is not particularly limited, but is preferably a resin. Specific examples of the resin include cellulose, cellulose acetate, polyamide, epoxy resin, polyester, melamine resin, polyurethane, vinyl acetate resin, silicon resin, acrylate, methacrylate, styrene, ethylene, propylene and derivatives thereof. Polymers and copolymers are exemplified. (1) When an organic film (resin film) is formed, a. In the liquid phase, by dispersing the base particles and performing emulsion polymerization,
A method of forming a resin film on the particles (polymerization method in a liquid phase), b. Film forming method in gas phase (CVD) (PVD)
And so on.

The following is an example of producing a blue powder contained in the blue coloring material composition of the present invention having a multilayer film on substrate particles. For example, if the base particles are made of a material having a high refractive index, a light-transmitting film having a low refractive index is provided thereon, and a particle-forming film having a high refractive index is further provided thereon. A low-refractive-index light-transmitting film,
It is provided alternately in order. If the base particles have a low refractive index, a high-refractive-index particle-constituting film is further formed thereon, a low-refractive-index light-transmitting film is further formed thereon, and a high-refractive-index particle forming film is further formed thereon. Are provided sequentially.

Next, specific raw materials used for film formation in the present invention, in particular, metal salts will be described. Raw materials used to form a high refractive index film include titanium halides and sulfates for titanium oxide films, and zirconium halides, sulfates and carboxylic acids for zirconium oxide films. Salts, oxalates, chelate complexes, etc. for cerium oxide films, cerium halides, sulfates, carboxylates, oxalates, etc. For bismuth oxide films, bismuth halides, nitrates, carboxylic acids For indium oxide films such as salts, indium halides, sulfates, and the like are preferable. In addition, as a raw material used to form a low refractive index film, for silicon oxide film, sodium silicate,
Water glass, organosilicon compounds such as silicon halides and alkyl silicates and their polymers, etc., for aluminum oxide films, aluminum halides, sulfates, chelate complexes, etc.For magnesium oxide films, magnesium sulfate Salts and halides are preferred. In the case of a titanium oxide film, for example, mixing titanium chloride with titanium sulfate has the effect of producing a rutile type titanium oxide film having a higher refractive index at a lower temperature.

Further, by controlling the reaction temperature at the time of coating to a temperature suitable for the type of each metal salt and coating, a more complete oxide film can be manufactured. When the film formation reaction (solid phase deposition reaction) on the surface of the substrate in the aqueous solvent is too slow, the reaction system can be heated to accelerate the solid phase deposition reaction. However, if the heat treatment for heating is excessive, the reaction rate is too fast, and the supersaturated solid phase does not form a film, but precipitates in an aqueous solution to form gels or fine particles, making it difficult to control the film thickness.

After manufacturing the coating film, the inclined washing is repeated while adding distilled water to remove the electrolyte, and then heat treatment such as drying and baking is performed to remove water contained in the solid phase. It is preferable to use an oxide film. Further, by subjecting the powder after film formation to heat treatment in a rotary tube furnace or the like, sticking can be prevented and dispersed particles can be obtained. In order to form a hydroxide film or an oxide film and heat-treat it, heat treatment may be performed each time each layer is coated, or heat treatment may be performed last after completion of the target multilayer film. The heat treatment conditions vary depending on the reaction system, but the heat treatment temperature is 200 to 1300 ° C, preferably 400 to
1100 ° C. If the temperature is lower than 200 ° C., salts and water may remain. If the temperature is higher than 1300 ° C., the film and the substrate may react with each other to form another substance, which is inappropriate. The heat treatment time is 0.1 to 100 hours, preferably 0.5 to 50 hours.

Next, when preparing the blue color material composition according to the present invention, (1) a blue ink or a paint-like composition (fluid) and (2) a blue toner or a blue dry ink-like composition (powder) Each will be described. (1) In the present invention, as a medium (vehicle) of the blue ink or the paint-like composition (fluid), a medium for color printing,
Conventionally known varnishes used for color magnetic printing and color magnetic paints can be used.For example, a liquid polymer, a polymer or a monomer dissolved in an organic solvent can be used depending on the type of powder, the method of applying the ink, and the application. Can be appropriately selected for use.

Examples of the liquid polymer include dienes such as polypentadiene and polybutadiene, polyethylene glycols, polyamides, polypropylenes, waxes and knitted copolymers thereof. Polymers soluble in organic solvents include olefin polymers, acrylic resins such as oligoester acrylates, polyesters, polyamides, polyisocyanates, amino resins, xylene resins, ketone resins, diene resins. And rosin-modified phenolic resins, diene rubbers, chloroprene resins, waxes, and modified products and copolymers thereof. Examples of the monomer soluble in the organic solvent include styrene, ethylene, butadiene, propylene and the like. As the organic solvent, ethanol, isopropanol, alcohols such as normal propanol, ketones such as acetone, benzene, toluene, xylene,
Examples thereof include kerosene, benzene hydrocarbons, esters, ethers, and modified products and copolymers thereof.

(2) The blue toner, the blue dry ink, and the blue dry paint-like composition (powder) are obtained by screwing the powder coated with the blue color material multilayer film with a resin or, if necessary, a toning material. Powdered blue color material composition by directly kneading with a mold extruder, roll mill, kneader, etc., coarsely pulverizing with a hammer mill, cutter mill, finely pulverizing with a jet mill, etc. and classifying to the required particle size with an elbow jet etc. You can get things. Further, the powder coated with the blue color material multilayer film can be made into a powdery blue color material composition by using a polymerization method such as an emulsion polymerization method or a suspension polymerization method. Further, the blue multi-layer film-coated powder, a resin, an additive such as a toning agent, and a solvent may be liquefied by a colloid mill or a three-roll mill to form a liquid blue color material composition such as an ink paint. Examples of the toning material for increasing the lightness include white pigments (coloring materials), for example, titanium oxide, zinc oxide, tin oxide, silicon oxide, antimony oxide, lead oxide, and composite oxides thereof, and Calcium carbonate, magnesium carbonate, carbonates such as barium carbonate, or barium sulfate, sulfates such as calcium sulfate, sulfides such as zinc sulfate or composite oxides obtained by sintering the above oxides and carbonates and sulfates, Complex hydrated oxides are included. To adjust the saturation and hue, especially as a toning agent when used for color reproducibility with full color mixture, organic dyes that are blue pigments, and pigments such as alkali blue lake, peacock lake, peacock lake blue, etc. Dyes and lake pigments, oil blue, etc., oil dyes, oil pigments, alcohol dyes such as alcohol blue, phthalocyanine-based pigments such as phthalocyanine and copper phthalocyanine, and inorganic pigments such as oxide sulfide composite pigments such as urlamarine, iron blue, and milly blue And blue oxides of cobalt oxides such as cobalt blue and cerulean blue. However, the present invention is not limited only to these. Further, when it is necessary to perform toning using a pigment or a dye such as red, yellow, or magenta in delicate color tone control, it is preferable to use a pigment having an optimum blue color. In the case of this powdery blue color material composition, (a) the resin produced by the above-mentioned pulverization method is not particularly limited, but polyamide, epoxy resin, polyester, melamine resin, polyurethane, vinyl acetate Resins, silicon resins, acrylates, methacrylates, polymers or copolymers of styrene, ethylene, butadiene, propylene, and derivatives thereof, and the like. (B) In the case of a polymerization method, an ester, urethane,
Polymerization is started from one or a mixture of vinyl acetate, organosilicon, acrylic acid, methacrylic acid, styrene, ethylene, butadiene, propylene and the like to form a polymer or a copolymer thereof.

The blue coloring material composition of the present invention is, as described above,
It takes the form of (1) a blue ink or paint-like composition (fluid) and (2) a blue toner, a blue dry ink-like composition (powder). In the case of a fluid, it is a blue ink, paint, etc., the toning material, a solidification accelerator for the resin that is slow to dry, a thickener to increase the viscosity, a fluidizing agent to reduce the viscosity, Components such as a dispersant can be included for dispersion of the particles. On the other hand, in the case of powder, (a) when powder is produced by a pulverization method, a solidification accelerator is used for the toning material and a resin that is slowly dried, and a fluidizing agent is used for reducing viscosity during kneading. In order to disperse the agent and the particles, components such as a dispersant, a charge controlling agent for fixing to paper or the like, and a wax can be included. (B) When the polymerization method is used, the above-mentioned toning material, polymerization initiator, polymerization accelerator, thickener for increasing the viscosity, dispersant for dispersing the particles, fixing to paper, etc. And a component such as a wax for charge control. The powder coated with a multilayer film in the blue colorant composition of the present invention can be applied to wet and dry color printing and wet and dry color magnetic printing by using a single powder or a combination of a plurality of powders having different spectral characteristics. In addition, using powder of three primary colors, it has the function of identifying 6 types of combinations of visible light, invisible light (ultraviolet and infrared), fluorescent coloring and magnetism, and electricity (change of electric field). The present invention can be applied to other uses requiring a security function, such as color magnetic ink for forgery prevention.

The blue colorant composition of the present invention is printed on a substrate as a blue ink or a paint-like composition or a blue toner, a blue dry ink-like composition, or a blue dry paint composition.
In the case of melt transfer or application to a body to be coated, the relationship between the content of the resin coated with the blue coloring material multilayer film in the blue coloring material composition and the content of the resin is 1: 0.5 to 1:15 by volume ratio. If the content of the medium is too small, the applied film does not adhere to the object to be coated.
On the other hand, if the amount is too large, the color of the pigment becomes too light and cannot be said to be a good ink or paint. Further, the relationship between the amount of the solvent and the total amount of the blue coloring material and the resin in the blue ink or the coating composition is 1: 0.5 to 1:10, and if the amount of the solvent is too small, The viscosity of the paint is so high that it cannot be applied uniformly. On the other hand, if the amount of the solvent is too large, it takes time to dry the coating film, and the efficiency of the coating operation is extremely reduced.

Further, the color density of the coating film when printing, melt-transferring, or applying a coating material to a substrate is determined by the amount of pigment per unit area of the substrate. After the paint is dried, the amount of the powder coated with the blue color material multilayer film of the present invention on the object to be coated is 0.1 to 300 g per square meter in area density when uniformly applied, and preferably 0.1 to 300 g. If it is 1 to 100 g, a good coating color can be obtained. If the area density is smaller than the above value, the ground color of the object to be coated appears, and if the area density is larger than the above value, the color density of the coating color does not change, which is uneconomical. That is, even if the pigment is placed on the object to be coated to a certain thickness or more, the light does not reach the pigment on the lower side of the coating film. To make the coating thicker than this thickness,
Since the thickness exceeds the hiding power of the paint, there is no effect of the paint and it is uneconomical. However, this is not the case when thick coating is performed because the thickness of the coating is reduced in consideration of the abrasion of the coating.
Also, this is not limited to the case where a specific design or the like is partially formed.

[0063]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, of course, are not intended to limit the scope of the present invention. [Example 1] (Blue color material composition 1 using magnetic material, aqueous two-layer coating) (Film formation of first layer silica film) (1) Preparation of buffer solution 4 M potassium chloride reagent and 0.4 M boric acid were dissolved to obtain a buffer solution 1. 0.4 M sodium hydroxide was dissolved in 1 liter of water to obtain a buffer solution 2. 250 ml of the buffer solution 1 and 115 ml of the buffer solution 2 were mixed and homogenized to obtain a buffer solution 3. (2) Aqueous sodium silicate solution (water glass solution) The sodium silicate reagent was diluted with pure water, and the concentration was adjusted so that the SiO ₂ content became 10 wt%.

(3) Silica Film 15 g of magnetite powder (average particle size of 2.3 μm) was prepared as base particles in 190 ml of a previously prepared material.
In a mixed solution of buffer solution 3 (pH: about 9.0) and 150 ml of pure water to obtain a dispersion. The container containing the dispersion is filled with a water-washed ultrasonic cleaner (Uchi Seikeido Co., Ltd., U.S.A.).
Placed in a water bath of S-6 _type), 28kH Z, while applying an ultrasonic wave in an ultrasonic bath at 200 W, further, was dispersed with stirring magnetite powder in loose衡溶solution 3. To this, 120 ml of an aqueous sodium silicate solution also prepared in advance was added at a rate of 40 ml / min, and the reaction was gradually decomposed to deposit a silica film on the surface. After the completion of the aqueous sodium silicate solution, the reaction was further continued for 2 hours, and all the unreacted raw materials were reacted. After the completion of the film forming reaction, the slurry containing the silica film forming powder was repeatedly decanted with sufficient water and washed. After washing, the silica film powder was put into a vat, sedimented and separated, and the upper solution was discarded. The resultant was dried in air at 150 ° C. for 8 hours using a drier, and silica-coated magnetite powder A was dried.
₁ was obtained.

(Formation of Second Layer Titania Membrane) (1) Preparation of Buffer Solution For 1 liter of deionized water, 0.3 M acetic acid and 0.1 M acetic acid were added.
9M sodium acetate was dissolved to obtain a buffer solution 4. (2) Titanium sulfate aqueous solution Titanium sulfate was added to water so as to have a concentration of 0.6 M / liter, and dilution was adjusted to obtain a titanium sulfate aqueous solution.

[0066] (3) with respect to the powder _{A 1} titania film-4g, slow衡溶solution 400 ml 4
(PH: about 8.4) prepared, pure water 47ml and powder A ₁ to its slow衡溶solution 4, as in the case of the silica film, while ultrasonic dispersion, sufficient in an ultrasonic bath Dispersed. Thereafter, while maintaining the temperature of the solution at 50 to 55 ° C., an aqueous solution of titanium sulfate prepared in advance was dropped at 1.9 ml / min to precipitate solid phase fine particles in the solution to make the solution thinly cloudy. Then, for fixing the solid phase particulates in a powder A ₁ surface, decreasing the dropping speed of 1.5 ml / min, it was gradually precipitate unreacted. As a result, the solid fine particles precipitated in the liquid were fixed on the surface of the base particles, and the surface was further covered with ultrafine particles having a smaller particle diameter than the solid fine particles fixed on the surface of the base particles.

(4) Washing and drying After completion of the film forming reaction, decantation is repeated with pure water.
Unreacted components, excess sulfuric acid, and sulfuric acid formed by the reaction were removed, solid-liquid separation was performed, and a dried powder was obtained after drying with a vacuum dryer. The obtained dried powder is subjected to 650 in a rotary tube furnace.
℃ 30 minutes heat treatment performed (fired), to obtain surface-smoothed silica / titania-coated magnetite powder A _2. The two-layer film-coated powder _{A 2} is a pale blue, the magnetization at 1kOe was 37emu / g. Maximum reflection peak of the two-layer film-coated powder _{A 2} is 408 nm, was a light blue.

The peak wavelength of the spectral reflection curve of the coated powder of the above coating film, the reflectance at the peak wavelength, the refractive index of the coating film, and the film thickness were measured by the following methods. 1) The spectral reflection curve was obtained by packing a powder sample into a glass holder using a spectrophotometer with an integrating sphere manufactured by JASCO Corporation and measuring the reflected light. The measuring method was measured according to JISZ8723 (1988). 2) The refractive index and the film thickness were evaluated by fitting the measurement result of the spectral reflection curve of a sample having a film thickness prepared under different conditions to a curve calculated by an instrument based on an interference equation.

(5) Surface Hydrophobizing Treatment of Multilayer Film-Coated Powder 10 g of the obtained silica-titania-coated powder A ₂ was dissolved in an ethanol solution 2 in which 0.2 g of silicon ethoxide was dissolved.
The solution was dispersed in 00 ml, and the temperature of the solution was kept at 55 ° C. by heating the container in an oil bath. Add ammonia water (29%
Was added concentration) 3 g, After stirring for 3 h, filtered, and dried for 2 hours at 100 ° C. in a vacuum dryer, to obtain a blue multilayer-coated powder A ₃ having been hydrophobic-treated.

(6) Adhesive resin layer (polystyrene composite powder, toner) A high-speed stirrer is used to disperse 100 g of the blue-colored multi-layer coating powder A ₃ lipophilized in advance by the above-mentioned surface treatment method into 100 g of styrene monomer. Stir and homogenize. This mixture of styrene monomer and particles was added to a solution of sodium n-dodecyl sulfate dissolved in 500 g of distilled water while maintaining the temperature at 70 ° C. while stirring at a high speed, and the mixture was stirred until the emulsified particles were sufficiently formed into fine particles. 10% aqueous solution of ammonium persulfate 1
0 g was added, and the mixture was stirred and reacted for 4 hours. After completion of the reaction, the mixture is diluted with 2 liters of distilled water, and the supernatant is discarded by slant washing, and the precipitate is collected. The precipitate was dried on filter paper to obtain blue polystyrene-coated powder A. The resulting blue powder A was spherical, and its magnetization at a magnetic field of 1 kOe was 17.6 emu / g. Table 1 shows the refractive index and film thickness of the first and second layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0071]

[Table 1]

[Example 2] (Blue color material composition 2 using magnetic material, aqueous three-layer coating) (Film formation of first layer silica film) (1) Silica film 15 g of spherical magnetite was used as base particles. Powder (average particle size of 2.3 μm) was prepared from 225 prepared in advance.
ml of the buffer solution 3 (pH: about 9.0) and 150 parts of pure water.
The resulting mixture was placed in a mixed solution with the same to prepare a dispersion. The vessel containing the dispersion was placed in a water bath filled with water ultrasonic cleaning machine (Co. Iuchi Ltd., US-6 _type), 26kH _Z, 600W
While applying ultrasonic waves in an ultrasonic bath, and further dispersed in a buffer solution 3 containing magnetite powder while stirring. In addition, 120m prepared in advance
of sodium silicate aqueous solution at 40 ml / min,
The reaction was gradually decomposed to deposit a silica film on the surface.

After the completion of the addition of the aqueous solution of sodium silicate, the reaction was further continued for 2 hours, and all the unreacted raw materials were reacted. After the completion of the film forming reaction, the slurry containing the silica film forming powder was repeatedly decanted with sufficient water and washed. After washing, the silica film powder is put into a vat, settled and separated, and the upper solution is discarded. After drying in a dryer at 150 ° C. for 8 hours in air, heat treatment at 500 ° C. for 30 minutes in a nitrogen atmosphere (calcination) ) to obtain a silica-coated magnetite powder B _1.

(Formation of Second Titania Film) In the same manner as in Example 1, a buffer solution 4 and an aqueous solution of titanium sulfate were prepared and prepared. To the powder _{B 1} of 40 g, slow衡溶solution 4 (pH: about 8.4) of 1313ml and prepared mixed solution of pure water 1541Ml, the powder _{B 1} to the mixed solution, manufactured by the silica As in the case of the membrane, the dispersion was sufficiently performed in the ultrasonic bath while the ultrasonic dispersion was being performed. Thereafter, while keeping the temperature of the liquid at 50 to 55 ° C., a 15 wt% aqueous solution of titanium sulfate prepared in advance and a total amount of 181 ml were gradually dropped at a constant rate of 1.8 ml / min. At the beginning of the dropping, solid fine particles precipitated in the liquid, but were fixed on the surface of the base particles, and the surface was covered with ultrafine particles having a smaller particle diameter than the solid fine particles fixed on the surface of the base particles. , to obtain a silica / titania-coated magnetite powder _{B 2.} The two-layer film-coated powder B ₂ is bright blue, the maximum reflection peak 410
a nm, was the same as the powder A ₁ obtained in Example 1. The surface of the powder B ₂ has slightly uneven, convex portions of the partially titania particles were also observed.

(Formation of Third Layer Silica Film, When Titania Film Surface is Enclosed by Silica Thin Film) Preparation of Buffer Solutions 1 and 2 and Sodium Silicate Aqueous Solution (Water Glass Solution) in the same manner as in Example 1. Was done. The film of the silica film was carried out in the powdered silica / titania-coated magnetite powder B _2. The volume of the buffer solution was the same as that of the first layer coating, but the film formation was carried out with the same dropping rate of the aqueous solution of sodium silicate and the dropping amount of 8 ml.
By the time reaction wherein a washed as, after washing with a rotary tubular furnace, 30 min heat treatment at 500 ° C. in a nitrogen atmosphere performed (fired), to obtain a silica / titania-coated magnetite powder B _3.

[0076] Powder B ₃ obtained, while the surface is smooth silica film two layers, titania fine particles are crystallized, became pale light scattering is large blue powder. B ₃ is the surface, there is no unevenness, substantially smooth and holes and cracks were not like depressions. In observation with a transmission electron microscope, crystallization of titania fine particles was observed between the two silica layers, and voids were present between the particles. Can be This three-layer film-coated powder B ₃
Had a maximum reflection peak of 416 nm.

(Adhesive Resin Layer, Polystyrene Composite Powder) In 100 g of styrene monomer, 10 g of lipophilic titanium oxide as well as 100 g of blue coloring material multi-layer coating powder B ₃ previously lipophilized by the above surface treatment method is dispersed. The mixture was stirred with a high-speed stirrer until uniform. This mixture of styrene monomer and particles is treated with sodium n-dodecyl sulfate in distilled water 5
The solution dissolved in 00 g was added while maintaining the temperature at 70 ° C. and stirring at a high speed, and stirred until the emulsified particles were sufficiently turned into fine particles. 10% ammonium persulfate solution
g was added and stirred for 4 hours to react. After the reaction,
Dilute with 2 liters of distilled water, discard the upper solution by slant washing, and collect the precipitate. The precipitate was dried on filter paper to obtain blue polystyrene-coated powder B. The powder of the obtained blue color material composition B is spherical, and has a magnetization of 176 emu / g at a magnetic field of 1 kOe.
Met. Table 2 shows the refractive index, the film thickness of the first to third layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0078]

[Table 2]

[Example 3] (Blue color material composition 3 using magnetic material, water-based four-layer coating when scattering particles adhered to the surface) (Film formation of first layer silica film) 40 g as base particles Of magnetite powder (average particle size: 0.7 μm) in a mixed solution of 2400 g of buffer solution 3 (pH: about 9.0) and 200 ml of pure water prepared in the same manner as in Example 1. a dispersion, sonicating in an ultrasonic bath at 28kH _{Z, 600W,} further were dispersed with stirring in slow衡溶solution 3 containing magnetite powder. To this, 1,000 ml of an aqueous sodium silicate solution also prepared in advance was gradually added at 2.67 ml / min to deposit a silica film on the surface. After the completion of the aqueous sodium silicate solution, the reaction was further continued for 2 hours, and all the unreacted raw materials were reacted. After the completion of the film forming reaction, the slurry containing the silica film forming powder was repeatedly decanted with sufficient water and washed.
After washing, put silica film powder in a vat, precipitation was separated, discarding the upper fluid, 0.99 ° C. in air in a drier, dried 8 hours to obtain a silica-coated magnetite powder C _1.

[0080] For the powder _{C 1} of 40 g (deposition of the second layer Titania films), prepared pure water slow衡溶solution and 200ml of 2400 g, the _{C 1} to the mixed solution, the silica film As in the case of the above, the dispersion was sufficiently performed in the ultrasonic bath with the ultrasonic dispersion. Thereafter, while maintaining the temperature of the liquid at 50 to 55 ° C., 1.25 ml of a previously prepared 1620 ml aqueous solution of titanyl sulfate (TiO ₂ , 15 w%) was prepared.
The solution was gradually dropped at a constant rate of 1 / min. After the completion of the dropwise addition, the reaction was further performed for 3 hours, the unreacted portion was gradually precipitated, and the particles were taken into the film. After completion of the film-forming reaction, decantation was repeated with sufficient pure water to remove unreacted components and excess sulfuric acid and sulfuric acid formed by the reaction, to perform solid-liquid separation, and to obtain a dried powder after drying with a vacuum dryer. . The resulting dry powder, a rotary tube furnace, for 30 minutes heat treatment (baking) at 650 ° C., to obtain a silica / titania-coated magnetite powder C _2.
The two-layer film-coated powder C ₂ is Obikimidori blue, the maximum reflection peak was at 418 nm.

[0081] For the silica / titania-coated magnetite powder _{C 2} of 40 g (deposition of the third layer silica film), as in the first layer, slow衡溶liquid 3 of 2880g which had been prepared in advance (pH: about 9 .0) and added to a mixed solution of pure water 280 _ml, while applying an ultrasonic wave in an ultrasonic bath at 28kH Z, 600W, further it was dispersed with stirring in slow衡溶solution 3 containing magnetite powder. To this, 1200 ml of an aqueous sodium silicate solution also prepared in advance was gradually added at 2.67 ml / min to deposit a silica film on the surface. After the completion of the aqueous sodium silicate solution, the reaction was further continued for 2 hours, and all the unreacted raw materials were reacted. After the completion of the film forming reaction, the slurry containing the silica film forming powder was repeatedly decanted with sufficient water and washed. After washing, put silica film powder in a vat, precipitation was separated, discarding the upper fluid, 0.99 ° C. in air in a drier, dried 8 hours to obtain a silica-coated magnetite powder C _3.

[0082] For the powder _{C 3} of 40 g (deposition of the fourth layer Titania films), slow衡溶solution 4 of 4800ml of pure water 48
And a mixed solution of powder C _{3 in the} mixture.
The same as the above-mentioned silica film, while dispersing ultrasonic waves,
Dispersed well in an ultrasonic bath. After that, the temperature of the liquid is reduced to 5
While keeping it at 0-55 ° C, it was prepared in advance.
1944 ml of titanyl sulfate aqueous solution (TiO ₂ , 15 w
%) Was gradually dropped at a constant rate of 1.25 ml / min, and the dropping was completed while precipitating solid phase fine particles and making the liquid slightly cloudy. After the completion of the dropping, the reaction was further performed for 3 hours, and the unreacted portion was gradually precipitated as solid fine particles, and the fine particles were incorporated into the film. After completion of the film-forming reaction, decantation was repeated with sufficient pure water to remove unreacted components and excess sulfuric acid and sulfuric acid formed by the reaction, to perform solid-liquid separation, and to obtain a dried powder after drying with a vacuum dryer. .

The obtained dried powder was placed in a rotary tube furnace.
For 30 minutes heat treatment (baking) at 650 ° C., to obtain a silica / titania-coated magnetite powder _{C 4.} This 4-layer film-coated powder _{C 4} are light blue, the maximum reflection peak 410nm
Met.

(Preparation of Blue Ink Composition) The silica / titania-coated magnetite powder C ₄ thus obtained,
30 g was previously dispersed in a solution prepared by dissolving 2.5 g of an acrylic polymer (Technovit, manufactured by Kulzer) in 80 g of ethanol, and then 20 g of titanium oxide (hydrophobic silicone treated product: coloring material) and 3.2 g of hydroxypropyl cellulose. Was dispersed in a zirconia ball mill for 8 hours to obtain a coating dispersion CL of a blue colorant composition.

(Coating and Spectral Characteristics) The dispersion liquid CL of the above blue color material composition was applied to a plastic film for thermal transfer using a blade coater. The application amount (after drying) of the blue coloring material composition was 60 g / m ² . After drying, the color of the obtained coated paper C was bright blue with a maximum reflection peak wavelength of 410 nm. In addition, 1 m ^{2 of} this coating C
The magnetization at kOe was 1,260 emu / cm ² . Table 3 shows each refractive index and film thickness of the first to fourth layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.
Shown in

[0086]

[Table 3]

[Example 4] (Blue color material composition 4 using magnetic material, three-layer coating by hydrolysis of metal alkoxide) (Film formation of first layer silica film) 20 g of carbonyl iron powder manufactured by BASF (average) The magnetization at a particle size of 1.8 μm and 10 kOe is 2
03 emu / g) was previously dispersed in a solution of 12.0 g of silicon ethoxide dissolved in 158.6 g of ethanol, and then, with stirring, 12.0 g of aqueous ammonia (29%) prepared in advance. And 16.0 g
Of deionized water was added. 5 hours after addition,
The reaction was performed at room temperature. After the reaction, the reaction mixture was diluted and washed with sufficient ethanol, filtered, and dried in a vacuum drier at 110 ° C. for 3 hours. After drying, using a rotary tube furnace, 30 min heat treatment at 800 ° C. in a nitrogen atmosphere subjected to (firing), and cooled to obtain a silica-coated iron powder D _1.

[0088] In (second layer Titania film of film) In a separable flask, the silica-coated powder _{D 1} of the 20g, submerged plus titanium isopropoxide 9.4g of ethanol previously 198.3g After dispersing in water, 16 g of pure water prepared in advance was added to 47.
A solution mixed with 9 g of ethanol was added dropwise over 1 hour. After the addition, the reaction was carried out at room temperature for 5 hours. After the reaction, the mixture is diluted and washed with sufficient ethanol, filtered, and dried with a vacuum dryer.
Dry at 10 ° C for 3 hours, silica / titania-coated iron powder D
₂ was obtained. When the state of the particles in the dried titania layer was observed using a transmission electron microscope, titanium oxide solid fine particles of 1 to 10 nm were observed. Had been filled. This titanium oxide film had an average thickness of 74 nm, had a peak wavelength of a spectral reflection curve at 411 nm, and was blue.

[0089] The silica / titania-coated iron powder _{D 2} of 20 g (deposition of the third layer silica film), previously 158.6g
After dispersing in a solution prepared by dissolving 2.0 g of silicon ethoxide in ethanol, mixing with 2.0 g of ammonia water (29%) and 3.0 g of deionized water prepared in advance while stirring. The solution was added. After the addition,
The reaction was performed for 1 hour at room temperature. After the reaction, the reaction mixture was diluted and washed with sufficient ethanol, filtered, and dried in a vacuum drier at 110 ° C. for 3 hours. After drying, further at 500 ° C. in a nitrogen atmosphere for 30
Subjected to partial heat treatment (baking), and cooled to obtain a silica / titania-coated iron powder D _3. Observation of the particle state in the titania layer after the heat treatment using a transmission electron microscope showed that the titania layer was 10%.
Titanium oxide crystallized fine particles of about 150 nm were observed, and a gap of about 10 to 50 nm was observed between the respective particles. However, the silica layer was dense, free of particles, and smooth. Further, voids existed at the interface with titania.

[0090] maximum reflection peak wavelength of the powder _{D 3} is 40
At 9 nm, it became bright blue. From this Example 4, crystal particles of titania particles were formed depending on the presence or absence of heat treatment (calcination), and voids between the particles and the silica film accompanying the particle formation were observed. Due to the scattering reflection effect accompanying these particles, It is considered that bluing was achieved. Another characteristic of the blue color material powder of Example 4 is that a dense film is formed on the final coating layer. The void is covered with a dense film that does not affect interference and scattering, not limited to a high refractive index film as in the last layer. In the prior art, when the obtained powder is used as a pigment such as a toner or a paint, a resin or a vehicle enters the voids, and the difference in the refractive index between interference and scattering particles is reduced, and the Fresnel reflectance is reduced. was there. However, the final layer is a dense film that does not affect interference and scattering, and covers the voids of the particle constituent film,
It is possible to prevent the decrease in the scattered reflection.

(Adhesive Resin Layer, Polystyrene Composite Powder) A high-speed stirrer is used until 100 g of styrene monomer and 100 g of a blue-colored material multi-layer coating powder (silica / titania-coated iron powder D ₃ ) and 45 g of the lipophilic titanium oxide are dispersed. And homogenized. This mixture of styrene monomer and particles was added to a solution of sodium n-dodecyl sulfate dissolved in 500 g of distilled water while maintaining the temperature at 70 ° C. while stirring at a high speed, and the mixture was stirred until the emulsified particles were sufficiently formed into fine particles.
10 g of a 10% aqueous solution of ammonium persulfate was added thereto, and the mixture was stirred and reacted for 4 hours. After completion of the reaction, distilled water 2
Dilute with liter and discard the upper solution by decantation and collect the precipitate. The precipitate was dried on a filter paper to obtain a blue polystyrene-coated powder D. The powder of the blue color material composition D obtained was spherical, and the magnetization at a magnetic field of 1 kOe was 104 emu / g.
The magnetization at a magnetic field of 10 kOe was 173.6 emu / g. Table 4 shows each refractive index and thickness of the first to third layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0092]

[Table 4]

Example 5 (Blue Color Material Composition 5 Using Magnetic Material, Five-Layer Coating by Hydrolysis of Metal Alkoxide) (Formation of First Layer Silica Film) 20 g of Carbonyl Iron Powder from BASF (average) The magnetization at a particle size of 1.8 μm and 10 kOe is 8
0emu / g) was previously dispersed in a solution of 12.0 g of silicon ethoxide in 158.6 g of ethanol, and then, with stirring, 16.0 g of ammonia water (29%) prepared in advance. And 16.0
g of deionized water mixed solution was added. After the addition, the reaction was carried out at room temperature for 5 hours. After the reaction, the reaction mixture was diluted and washed with sufficient ethanol, filtered, and dried in a vacuum drier at 110 ° C. for 3 hours. After drying, further using a rotary tube furnace, 30 min heat treatment at 600 ° C. in a nitrogen atmosphere subjected to (firing), and cooled to obtain a silica-coated iron powder E _1.

[0094] In (second layer Titania film of film) In a separable flask, the silica-coated powder _{E 1} of 20g, submerged plus titanium isopropoxide 9.4g of ethanol previously 198.3g After stirring, 16.0 g of pure water prepared in advance was added to 4 parts with stirring.
A solution mixed with 7.9 g of ethanol was taken for 1 hour,
It was dropped. After the addition, the reaction was carried out at room temperature for 3 hours. After the reaction, it was diluted and washed with sufficient ethanol, filtered, 100 ° C. in a vacuum dryer, and dried for 8 hours to obtain a silica / titania-coated iron powder E _2. The average thickness of this titanium oxide film is 75 n.
m, a peak wavelength of a spectral reflection curve at 410 nm, and a bright blue color.

[0095] The silica / titania-coated iron powder _{E 2} of 20 g (deposition of the third layer silica film), previously 158.6g
After dispersing in a solution prepared by dissolving 15.6 g of silicon ethoxide in ethanol, 15.6 g of ammonia water (29%) and 20.8 g of deionized water prepared in advance were mixed with stirring. The solution was added. After the addition, the reaction was carried out at room temperature for 5 hours. After the reaction, the mixture is diluted and washed with sufficient ethanol, filtered, and dried at 110 ° C. in a vacuum drier at 3 ° C.
Dried for hours. After drying, further using a rotary tube furnace, 30 minutes at 500 ° C. in a nitrogen atmosphere (baking) the applied, and cooled to obtain a silica / titania-coated iron powder E _3.

[0096] In (fourth layer Titania film deposition of) separable flask, the silica-coated powder _{E 3} of 20g, submerged plus titanium isopropoxide 12.2g of ethanol previously 198.3g Then, while stirring, a solution prepared by mixing 20.8 g of pure water in 60.0 g of ethanol prepared in advance was added dropwise over 1 hour. After the addition, the reaction was carried out at room temperature for 4 hours. After the reaction, it was diluted and washed with sufficient ethanol, filtered, 100 ° C. in a vacuum dryer, and dried for 8 hours to obtain a silica / titania-coated iron powder E _4.

20 g of silica / titania-coated iron powder E₄
Was added to 158.6 g of ethanol in advance of 2.5 g of
After dispersing in a solution in which silicon ethoxide is dissolved,
While stirring, prepare the 3.0 g
Mixing of Monia water (29%) and 3.0 g of deionized water
The solution was added. After the addition, the reaction was carried out at room temperature for 5 hours.
After the reaction, dilute and wash with sufficient ethanol, filter, and vacuum
It was dried at 110 ° C. for 3 hours in a drier. After drying, repeat
Using a rolled tube furnace at 600 ° C in a nitrogen atmosphere
0 minute heat treatment (heat treatment), cool, silica / titani
Acoat iron powder E ₅I got Average thickness of this titanium oxide film
Was 11 nm. In addition, this iron powder E₅Is 410 nm
Had a peak wavelength of a spectral reflection curve and was light blue.

(Preparation of Blue Ink Composition) 30 g of the silica / titania-coated iron powder E ₅ thus obtained was obtained.
Was previously dispersed in a solution of 2.5 g of an acrylic polymer (Technovit, manufactured by Kulzer) in 80 g of ethanol, and 20 g of titanium oxide (hydrophobic silicone treated product: coloring material) and 3.2 g of hydroxypropyl cellulose were added. The added mixed solution was subjected to a dispersion treatment for 8 hours by a zirconia ball mill, and a blue color material composition coating dispersion E was prepared.
L was obtained.

(Coating and Spectral Characteristics) The dispersion EL of the above fluorescent pigment composition was applied to art paper using a blade coater. The application amount (after drying) of the blue colorant composition is 60 g / m
^{And 2} . After drying, the color of the obtained coated paper E was 411 nm at the peak wavelength, and was bright blue. The magnetization of the coating E at a magnetic field of 1 kOe was 28.1 emu / m.
^2, the magnetization in the magnetic field 10kOe is 9360emu /
m ² . Table 5 shows the refractive index, film thickness, peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength of the first to fifth layers.

[0100]

[Table 5]

The blue coloring material compositions of the examples of the present invention each obtained satisfactory results. In addition, by providing two layers (second layer and fourth layer) of the titania coating layer having voids due to crystallization of the titania particles rather than one layer (second layer), a high degree of blue coloration was achieved.

[Example 6] (Blue color material composition 5 using a dry coating magnetic substance, aqueous three-layer coating) (Formation of first layer titania film) 1 kg of iron powder having an average particle size of 1.8 microns 1.5 kg of titanium oxide particles having an average particle size of 0.2 μm were dry-mixed and pulverized three times for 5 minutes using a meso-fusion device manufactured by Hosokawa Micron to confirm that a film was formed. F coated iron powder
₁ was obtained.

(Formation of Second Layer Silica Membrane) To 190 ml of the same buffer solution 3 prepared in Example 1, 150 ml of pure water also prepared in advance was mixed, and 10 g of F ₁ was added. After mixing, 120 ml of a water glass solution having a mixing ratio of SiO ₂ of 10 wt% was gradually added dropwise with stirring over 3 hours while stirring, and then the reaction was continued for 1 hour. After the reaction, solid-liquid separation is performed by decantation.
After drying for 5 hours, use a rotary tube furnace in a nitrogen atmosphere for 5 hours.
Heat treatment was performed at 00 ° C. for 30 minutes to obtain a silica / titania film-coated iron powder F ₂ .

(Formation of Third Layer Titania Film) Further, 4 g of the silica / titania film-coated iron powder F _{2 was} added to buffer solutions 4 and 4.
After fully dispersing in 40 ml, titanyl sulfate TiO ₂ 15%
An aqueous solution, 31 ml, was added dropwise over 4 hours, and after the addition, the mixture was reacted for 1 hour to eliminate unreacted raw materials. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried with a vacuum drier for 8 hours.
Heat treatment in 30 minutes to obtain a silica / titania film-coated iron powder F _3. The peak of this powder was 409 nm, the reflectance was 47%, and the powder was deep blue. The magnetic field of this powder is 1 kOe.
Has a magnetization of 36.2 emu / g and a magnetization of 10 kOe has a value of 1
It was 18 emu / g. Table 6 shows the refractive index, film thickness, peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength of the first to third layers.

[0105]

[Table 6]

(Tonerization) A solution prepared by dissolving 0.3 g of oil blue in 100 g of styrene monomer and 30 ml of xylene was mixed and then lipophilized F ₃ powder obtained in advance.
00g and 10 g of titanium oxide were added and mixed uniformly. Next, the mixture of the styrene monomer and the particles was put into a solution by a stirrer in which 3 g of 70C sodium dodecyl sulfate was dissolved in distilled water, and then the mixture was subjected to 10,000 rpm with a homogenizer.
While stirring at 5000 rpm.
10 g of a 10% aqueous solution of ammonium persulfate was added and reacted for 3.5 hours. Thereafter, the solid content was filtered and washed three times with warm water to obtain a blue polystyrene-coated powder FP. The magnetic field magnetization of this powder at 1 kOe was 18.1 emu / g, and the magnetization at 10 kOe was 45.2 emu / g.

Example 7 (Blue color material composition 7 using plate magnetic material, three-layer coating with metal alkoxide hydrolysis and aqueous system) (Ink) (First layer coating) Average particle size of 2.8 μm After sufficiently dispersing in 79.5 g of ethanol with respect to 10 g of plate-like Ba-based ferrite, 6 g of silicon ethoxide is added and mixed, and further,
6 g of water and 6 g of aqueous ammonia were added and reacted for 3 hours while stirring at room temperature. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried under vacuum and then dried for 8 hours, and then heat-treated at 500 ° C. for 30 minutes in a nitrogen atmosphere using a rotary tube furnace to obtain silica film-coated Ba-based ferrite particles G ₁ . Obtained.

[0108] (second layer coating color) the silica film-coated Ba ferrite particles G _1, 10 g was added titanium isopropoxide 4.8g were thoroughly dispersed in ethanol 159 g, after thorough mixing, to prepare further advance 8.1 water
g, and a mixed solution of 24 g of ethanol was dropped and reacted for 5 hours. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried under vacuum and dried for 8 hours, and then heat-treated at 650 ° C. for 30 minutes in a nitrogen atmosphere using a rotary tube furnace.
To obtain a titania film-coated Ba ferrite particles G _2. The peak of this powder was 411 nm, the reflectance was 44%, and it was deep blue. The magnetization of this powder at 10 kOe was 25.
It was 2 emu / g, and the residual magnetization was 16.4 emu / g.

[0109] (third layer scattering film coating) G ₂ powders buffer solution A500ml prepared in advance with respect, also mixed with a buffer solution 3,875 ml prepared in advance, the average particle size of 0.2 microns and this _{G 2} powder 10g After 5 g of titanium oxide (rutile type) powder particles were added and mixed well, the mixture was stirred for 1 hour while stirring with 146 ml of a 10 wt% water glass solution. After decantation was repeated 20 times and sufficiently washed, the resultant was dried at 120 ° C. for 8 hours using a dryer. The powder after drying using a rotary tube furnace, and heat-treated for 30 minutes at 500 ° C. in a nitrogen atmosphere to obtain a titania-scattering layer-silica film-coated Ba ferrite particles G _3. The peak of this powder was 408 nm, the reflectance was 70%, and the powder was pale blue. In addition, 10 kOe of this powder
Has a magnetization of 18.9 emu / g and a residual magnetization of 12.4 em
u / g. Table 7 shows the refractive index, the film thickness of the first to third layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0110]

[Table 7]

[0111] For (inked) the G ₃ flour 30g, pre acrylic resin 1.5g hydroxypropyl cellulose 2.3g, dispersed in ethanol 80 g, liquid to increase the viscosity to evaporate the alcohol with stirring I got GL. This GL was formed into a striped pattern on a plastic film for thermal transfer by a small printer PG10 manufactured by Riso Kagaku.

[0112] In the detection device provided with the (coated material) after drying the magnetic head, was scanned over the film, but the magnetic response was detected in the printed portion of the magnetic powder G _3, the magnetic-blank portion There was no reaction. The coating material was blue when viewed from above, but when viewed obliquely at an angle of 30 degrees, it appeared purple and polychromatic.

[Example 8] (Blue color material composition using plate-like mineral, three-layer coating by metal alkoxide hydrolysis)
(Coating film) (First layer coating coloring) 20 g of plate-like muscovite mica powder having an average particle diameter of 12 μm was sufficiently dispersed in 160 g of ethanol, and 4.8 g of titanium isopropoxide was added thereto. A prepared mixed solution of 8.2 g of water and 30 g of ethanol was added dropwise and reacted for 5 hours. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried in a vacuum drier for 8 hours and then heat-treated at 500 ° C. for 30 minutes in a nitrogen atmosphere using a rotary tube furnace to obtain a titania film-coated plate-like muscovite mica powder H _1. I got The peak of this powder was 420 nm, the reflectance was 44%, and the powder was deep blue.

(Second Layer Coating) After sufficiently dispersing 20 g of titania-coated plate-like muscovite powder H ₁ in 80 g of ethanol,
Add 8 g of silicon ethoxide, mix and add 8 g of water.
g and 10.5 g of aqueous ammonia, and reacted at room temperature with stirring for 3 hours. After the reaction, solid-liquid separation was carried out by decantation, and the powder was dried in vacuum and then dried for 8 hours. Got _two .

(Third-layer colored film coating) Silica / titania film-coated plate-like muscovite powder H ₂ , 20 g, ethanol g 16
After sufficient dispersion in 0 g, 6.2 g of titanium isopropoxide.
Was added and mixed well, and a mixed solution of 10.6 g of water and 30 g of ethanol prepared in advance was added dropwise and reacted for 5 hours. Solid-liquid separation by decantation after the reaction, after 8 hours drying the powder after vacuum drying, using a rotary tube furnace, and heat-treated for 30 minutes at 500 ° C. in a nitrogen atmosphere, a silica / titania film-coated muscovite powder H ₃ I got The peak of this powder was 415 nm, the reflectance was 66%, and the powder was pale blue. Table 8 shows the refractive index, the film thickness of the first to third layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0116]

[Table 8]

(Applying) While stirring and dispersing 15 g of powder H ₃ , an ethanol solution (50 g of ethanol) in which 2.2 g of an acrylic resin was dissolved was added and dissolved. When a part of the solvent was dispersed and the viscosity was increased, the dispersion was spread on a flat glass plate and further uniformly attached to a rubber roller.
The viscous fluid HL was applied to the thermal transfer film of the plate and left for one day to dry. The resulting powder-coated film shows a pale blue band when viewed vertically, and when the plate is tilted toward the sun and the viewing angle is changed, the plate turns back to the sun (almost vertical light).
Was pale red, but when viewed from the plate so that the angle between the sun and the plate (incident angle) was 40 degrees, the color was purplish red and polychromatic. This property is a polychromatic display medium,
It can be used for cosmetics, ornaments, or flip-flop method.

[Example 9] (Blue color material composition using plate-shaped conductor, three-layer coating by metal alkoxide hydrolysis)
(Coating) (First layer coating coloring) 18 g of plate-like aluminum powder having an average particle diameter of 12 μm was sufficiently dispersed in 160 g of ethanol, and 4.8 g of titanium isopropoxide was added. A mixed solution of 8.2 g of water and 160 g of ethanol was dropped and allowed to react for 5 hours. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried for 8 hours after vacuum drying, and then heat-treated at 500 ° C. for 30 minutes in a nitrogen atmosphere using a rotary tube furnace to obtain titania film-coated plate-like aluminum powder I ₁ . Obtained. The peak of this powder is 42
At 0 nm, the reflectance was 44% and it was a deep blue color.

(Second Layer Coating) After sufficiently dispersing 18 g of titania-coated plate-like aluminum powder I ₁ in 160 g of ethanol, 8.1 g of silicon ethoxide was added and mixed, followed by 8.1 g of water and 6 ammonia 10.5 g of water was added and reacted for 3 hours while stirring at room temperature. Solid-liquid separation by decantation after the reaction, after 8 hours drying the powder after vacuum drying, using a rotary tube furnace, and heat-treated for 30 minutes at 500 ° C. in a nitrogen atmosphere, silica / titania coated platelets aluminum powder I ₂ I got

(Third Layer Colored Film Coating) 18 g of silica / titania-coated plate-like aluminum powder I _{2 was} added to ethanol 160
After sufficiently dispersing the mixture in gram, 6.3 g of titanium isopropoxide was added and mixed well, and a mixed solution of 10.5 g of water and 160 g of ethanol prepared in advance was added dropwise and reacted for 5 hours. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried in a vacuum for 8 hours after vacuum drying, and then heat-treated at 500 ° C. for 30 minutes in a nitrogen atmosphere using a rotary tube furnace to obtain silica / titania film-coated aluminum powder I ₃ . Obtained. The peak of this powder was 420 nm, the reflectance was 70%, and the powder was pale blue. Table 9 shows each refractive index and film thickness of the first to third layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0121]

[Table 9]

(Coating) A double-sided adhesive tape was applied to a white vinyl chloride plate having a width of 3 mm and a length of 80 mm, a single side of 57 mm and a thickness of 1.5 mm.
Seven strips each having a length of 57 mm and a length of 57 mm were prepared, and one sheet was stuck at the center in parallel with a single side of the plate, and then stuck in parallel from the center strip tape at an interval of 3 mm. Thereafter, H ₃ was applied uniformly to the plate on which the tape was stuck.
Furthermore, this white vinyl chloride plate is placed horizontally and 10c on each side
m, placed on a 1 cm thick iron plate, put the same plate on top, sandwich it between two plates, and place a 1 kg weight at the center of the plate.
Left for hours. After 1 hour, the board was removed and the powder that had not adhered was brushed off. When the obtained plate was viewed vertically, a light blue band was observed, and polychromaticity was recognized as in Example 8.

(Physical Properties) As a result of scanning a Wheatstone bridge, a power supply and a search coil equipped with an ammeter perpendicularly to a single side of this plate, the ammeter changed in the coated portion, but changed in no portion. I couldn't. Detection by an electric field is also possible. This property can be used for multicolor display media, cosmetics and ornaments, or flip-flop methods.

As is clear from Tables 1 to 9, the blue coloring material compositions of the examples of the present invention each obtained satisfactory results. Further, the number of the titania coating layers having voids due to the crystallization of the titania particles is two (second layer) rather than one (second layer).
Layer and the fourth layer), a high degree of bluing was achieved.

[0125]

As described above, the blue colorant composition of the present invention is less expensive than the alkoxide method by using water as a solvent during the film forming reaction in the production of the contained blue powder. The effect that the film can be formed at a low production cost can be obtained. Also, at least one layer of the coating film on the surface of the base particles is a film composed of crystallized fine particles and an aggregate of crystallized fine particles having voids between the crystallized fine particles (hereinafter simply referred to as a crystallized fine particle constituent film). To increase the refractive index difference between the crystallized particle surface and the void,
It has become possible to provide a blue color material composition containing a functional powder having a blue color tone, which causes scattering and reflection of light, enhances the reflection effect, and has excellent lightness.

The blue coloring material composition of the present invention obtained as described above, when a magnetic substance is used as the base of the contained blue powder, the properties (eg, magnetic properties) of the base particles are brought to a high level. The retained functional powder, for example, a blue magnetic toner capable of performing an excellent combined function even in a one-component developing system, and excellent magnetic properties can be exhibited. In addition, it is a multi-functional paint for crafts and arts such as ornaments, pottery, porcelain, glassware, painting, etc., and books, automobiles, bicycles, etc. Ink, toner, paint, and cosmetics can be made. In addition, a titanium oxide film with a catalytic action has excellent weather resistance, and a paint with environmental purification properties such as air and water can be obtained. It can be applied to blue multifunctional inks, toners and paints. In particular, the above function is printed as a forgery prevention pigment composition by combining any two or more of the functions of magnetism, electric field, color, particle shape, fluorescence emission, phosphorescence emission, specific violet reflection absorption and specific infrared reflection absorption. Forming a desired image on a support medium as ink or toner,
It has become possible to provide a blue color material composition that can be visually distinguished and can be distinguished by a device, and a method for efficiently producing the same. Having these excellent functions and utilizing a conductor or dielectric as the base of the contained blue powder, it reacts due to external factors of the electric field, so that additional force such as moving force, rotation, movement, heat generation etc. It is possible to provide a blue color material composition having a function of exerting an action and an efficient production method thereof, which greatly contributes to the industry.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a blue powder contained in a blue coloring material composition of the present invention.

FIG. 2 is an enlarged cross-sectional view of a crystallized fine particle constituting film 2 of a blue powder contained in the blue colorant composition of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base particle 2 Crystallized fine particle constituent film 3 Crystallized fine particle 4 Ultra fine particle

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) // A61K 7/02 B41J 3/04 101Y 5E040 (72) Inventor Takashi Niiko Hirai Hiraicho, Nishitama-gun, Tokyo 8-1, 1st Iron Mining Co., Ltd. (72) Inventor Kiyoshi Hoshino Tokyo, Nishitama-gun, Hinodecho Hirai 8-1, 1st Iron Mining Co., Ltd. No. 1403 No. 3F F-term (Reference) 2C056 EA13 EB30 EC07 EC38 EC41 EC42 ED01 ED03 FA04 FA10 FC02 4C083 AB172 AB242 AB432 AD022 BB25 CC01 FF01 4D075 DA11 EA02 EA06 EC01 4G002 AA04 AB05 AE01 AE05 4A03 BC02 BC08 CA07 HB14 NN06

Claims (32)

[Claims] 1. A method comprising: a substrate having at least one coating film formed on a surface of a base particle by a reaction of a metal salt in an aqueous solvent;
A blue coloring material composition containing a blue powder exhibiting a reflection spectrum having a peak between 80 and 500 nm. 2. The blue color according to claim 1, wherein the coating film formed by the reaction of the metal salt of the blue powder in an aqueous solvent satisfies the following condition. Material composition. Nd = mλ / 4 [wherein, N = n + iκ (i represents a complex number) n: Refractive index of a substance constituting the film d: Film thickness m: Natural number λ: Wavelength of a peak in the reflection spectrum of the powder ( However, λ is 380 to 500 nm) κ: attenuation coefficient] 3. The blue coloring material composition according to claim 1, wherein the coating film formed on the surface of the base particles of the blue powder is a multilayer film. 4. The blue colorant composition according to claim 3, wherein each of the multilayer films of the blue powder is formed by a reaction of a metal salt in an aqueous solvent. 5. The blue coloring material composition according to claim 3, wherein each of the multilayer films of the blue powder satisfies the following condition. Nd = mλ / 4 [wherein, N = n + iκ (i represents a complex number) n: Refractive index of a substance constituting the film d: Film thickness m: Natural number λ: Wavelength of a peak in the reflection spectrum of the powder ( However, λ is 380 to 500 nm) κ: attenuation coefficient] 6. The method according to claim 1, wherein at least one layer of the coating film on the surface of the base particles of the blue powder is formed as an aggregate of crystallized fine particles having voids. Blue colorant composition. 7. The coating film configured as an aggregate of crystallized fine particles having voids can provide lightness by scattering and reflecting light generated between the surface of the crystallized fine particles and the voids. 7. The blue coloring material composition according to claim 6, wherein 8. A method according to claim 1, wherein the surface of the coating film formed as an aggregate of crystallized fine particles having voids has a dense coating film made of ultrafine particles capable of closing the voids on the surface. The blue colorant composition according to claim 6, characterized in that: 9. The blue coloring material composition according to claim 6, wherein the coating film formed as an aggregate of crystallized fine particles having voids is a high refractive index film. 10. The blue coloring material composition according to claim 8, wherein said dense film is a silica film. 11. The coating film formed as an aggregate of crystallized fine particles having voids forms solid phase fine particles in a reaction solution for forming the coating film, and the solid phase fine particles are formed. The blue coloring material composition according to claim 6, wherein the composition is formed by baking after being taken into the coating film. 12. The blue colorant composition according to claim 11, wherein the reaction solution is an aqueous solution. 13. Before the baking, the coating film in which the solid phase fine particles are taken in is coated with ultrafine particles capable of forming a dense film that closes the voids on the surface of the coating film. The blue colorant composition according to claim 11, wherein: 14. The blue colorant composition according to claim 1, wherein the blue powder is dispersed in a dispersion medium containing at least a binder resin. 15. The blue coloring material composition according to claim 1, further comprising an adhesive resin layer on the blue powder. 16. The blue color material composition according to claim 15, wherein said adhesive resin layer contains an extender pigment. 17. A method for producing a blue coloring material composition containing a blue powder, wherein the blue powder exhibits a reflection spectrum having a peak between 380 and 500 nm, and the surface of the base particles is coated with an aqueous solvent. Forming a coating film of at least one layer by the reaction of the metal salt in step (a). 18. The production of a blue color material composition according to claim 17, wherein the coating film formed by the reaction of the metal salt in an aqueous solvent is formed so as to satisfy the following formula: Method. Nd = mλ / 4 [wherein, N = n + iκ (i represents a complex number) n: Refractive index of a substance constituting the film d: Film thickness m: Natural number λ: Wavelength of a peak in the reflection spectrum of the powder ( However, λ is 380 to 500 nm) κ: attenuation coefficient] 19. The method for producing a blue coloring material composition according to claim 17, wherein the coating film formed on the surface of the base particles is a multilayer film. 20. The method for producing a blue coloring material composition according to claim 19, wherein each of the multilayer films is formed by a reaction of a metal salt in an aqueous solvent. 21. A method according to claim 19, wherein each of the multilayer films is formed so as to satisfy the following condition.
A method for producing the blue coloring material composition according to the above. Nd = mλ / 4 [wherein, N = n + iκ (i represents a complex number) n: Refractive index of a substance constituting the film d: Film thickness m: Natural number λ: Wavelength of a peak in the reflection spectrum of the powder ( However, λ is 380 to 500 nm) κ: attenuation coefficient] 22. The production of the blue color material composition according to claim 17, wherein at least one layer of the coating film formed on the surface of the base particles is constituted as an aggregate of crystallized fine particles having voids. Method. 23. The method according to claim 23, wherein the coating film formed as an aggregate of the crystallized fine particles having voids is formed so as to provide lightness by scattering and reflection of light generated between the surface of the crystallized fine particles and the voids. The method for producing a blue coloring material composition according to claim 22, characterized in that: 24. A dense film made of ultrafine particles capable of closing the voids on the surface of the coating film formed as an aggregate of crystallized fine particles having voids. 23. The method for producing a blue colorant composition according to item 22. 25. The method for producing a blue coloring material composition according to claim 22, wherein the coating film formed as an aggregate of crystallized fine particles having voids is a high refractive index film. 26. The method for producing a blue coloring material composition according to claim 24, wherein the dense film is a silica film. 27. The coating film, which is formed as an aggregate of crystallized fine particles having voids, is formed into solid phase fine particles in a reaction solution for forming the coating film. The method for producing a blue colorant composition according to claim 22, wherein the composition is formed by baking after being taken into the covering film. 28. The method for producing a blue colorant composition according to claim 27, wherein the reaction solution is an aqueous solution. 29. Before the baking, the coating film in which the solid-phase fine particles are taken in is coated with ultrafine particles capable of forming a dense film that closes the voids on the surface of the coating film. 28. The method for producing a blue colorant composition according to claim 27, wherein: 30. The blue powder is dispersed in a dispersion medium containing at least a binder resin.
30. The method for producing a blue colorant composition according to any one of 7 to 29. 31. The method for producing a blue colorant composition according to claim 17, wherein an adhesive resin layer is provided on the blue powder. 32. The method for producing a blue color material composition according to claim 31, wherein the adhesive resin layer contains an extender pigment.