JP2001254029A - Cyan colorant composition and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bright cyan colorant composition which can be obtained generally at a low cost and has high functionality and sufficient brightness and to provide a method for producing the same wherein a method based on the hydrolysis of a metal alkoxide is not used; a high-priced metal alkoxide or a highly inflammable organic solvent is not used; a producion facility and an explosinproof apparatus are not needed; and the control of temperature and humidity is easy. SOLUTION: This colorant composition contains a cyan powder which has at least one layer of a covering film formed on the surface of each base particle by the reaction of a metal salt in an aqueous solvent and which exhibits a reflection spectrum having a peak in the range of 350-550 nm. Preferably, the at least one layer of a covering film is formed as an aggregate 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 cyan colorant composition and a method for producing the same.
Even without using expensive raw materials and dangerous organic solvents, it can be manufactured by cheap and safe methods, inks, fillers for plastics and paper, toners, inks for inkjet printers, inks and toners for anti-counterfeiting, general paints, Powder pigments and paints for automobiles, paints for electrostatic coating, cosmetics, hair decoration, pigment compositions, pigment compositions and paints for arts such as crafts and ceramics, pigment compositions for multicolor paints, fiber coloring Paint composition for toys, paint for toys, paint and filler for decorative paper and decorative board, paint and filler for plastic and metal, pigment composition for display, display medium, paint for magnetic recording medium, catalyst paint and The present invention relates to a cyan color material composition used for various purposes such as a pigment composition for a heat-resistant paint, 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 color material compositions, a cyan color may be particularly important. The cyan color is
It is one of the three primary colors and is an important pigment that gives a person psychological hope, a refreshing sensation, and a non-irritating and secure feeling. Obtaining a color material composition having such a cyan 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 a color image, it is necessary to use a magnetic toner or a magnetic ink that is colored in cyan or a vivid primary color in addition to black and that retains magnetic characteristics. 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 mentioned above can be given special functions 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 method is applied to a magnetic particle having base particles, light can be reflected to produce a white toner powder. So that the unit 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 coloring material composition having a desired specific color tone based on the above-described technique, and more specifically, a technique for obtaining a film coating powder exhibiting a vivid cyan color. An attempt was made to establish a range of conditions for developing color.
The present inventors have studied from such a viewpoint,
A coating film having a large refractive index film and a small refractive index film adjacently stacked on the surface of the base particles, and an adhesive resin layer in which pigments and dyes are dispersed outside the coating layer;
By setting the conditions of the base particles and the coating film so as to show a reflection spectrum having a peak between 550 nm and 550 nm, a cyan-based color tone and a combined function even in a one-component developing system are achieved. It has been found that the obtained color toner can be obtained (JP-A-11-38679).

[0006]

However, the cyan toner described in Japanese Patent Application Laid-Open No. 11-38679 has a film formed on the surface of the base particles by a hydrolysis reaction of a 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 cyan toner described in JP-A-11-38679 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 to produce without using a method by hydrolysis of a metal alkoxide and without using an expensive metal alkoxide or a highly flammable organic solvent. The facility does not require explosion-proof equipment, the temperature and humidity can be easily controlled, and the product price is low. It is to provide a method. A further object of the present invention is to provide a toner having a high lightness and a stable color tone, which can be used as a toner, an ink, or a paint, and furthermore, characteristics (eg, magnetic characteristics) of base particles.
A high level of cyan colorant composition, in particular,
Cyan color material composition based on cyan powder having a coating film capable of obtaining sufficient lightness even with a relatively small number of films and film thickness for making use of the characteristics of base particles, and production thereof It seeks to provide a way. Still another object of the present invention is to provide a cyan magnetic toner capable of performing an excellent combined function even in a one-component developing system, and a cyan magnetic print capable of exhibiting excellent magnetic properties and having excellent weather resistance. An object of the present invention is to provide a cyan color material composition applicable to an ink for use, a cyan 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 cyan powder can be obtained by improving the lightness by scattering reflection, and the above object can be achieved.

That is, the cyan colorant composition of the present invention and the method for producing the same are as follows. (1) At least one coating film formed on the surface of the base particles by the reaction of a metal salt in an aqueous solvent has a thickness of 350 to 5
A cyan coloring material composition containing a cyan powder exhibiting a reflection spectrum having a peak between 50 nm. (2) The cyan color according to (1), wherein the coating film formed by the reaction of the metal powder of the cyan 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: peak of the reflection spectrum of the powder (Where λ is 350 to 550 nm) κ: attenuation coefficient]

(3) The cyan colorant composition according to (1), wherein the coating film on the surface of the base particles of the cyan powder is a multilayer film. (4) The cyan colorant composition as described in (3) above, wherein each of the layers of the cyan powder multilayer film is formed by a reaction of a metal salt in an aqueous solvent. (5) The above (3), wherein each of the multilayer films of the cyan powder satisfies the condition of the following expression.
The cyan colorant composition described in 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: Peak of the reflection spectrum of the powder (Where λ is 350 to 550 nm) κ: attenuation coefficient]

(6) At least one layer of the coating film formed on the surface of the base particles of the cyan powder is formed as an aggregate of crystallized fine particles having voids. The cyan colorant composition according to 1). (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. The cyan colorant composition according to the above (6), which is characterized in that: (8) On the surface of the coating film constituted 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 cyan colorant composition according to (6) above. (9) The cyan colorant composition according to (6), wherein the coating film configured as an aggregate of crystallized fine particles having voids is a high refractive index film. (10) The cyan colorant 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 cyan color material composition according to the above (6), which is formed by baking after being taken into the coating film. (12) The cyan 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 cyan colorant composition according to the above (11), which is characterized in that: (14) The cyan color material composition according to any one of (1) to (13), wherein the cyan powder is dispersed in a dispersion medium containing at least a binder resin. (15) A cyan ink composition comprising the cyan color material composition according to (14). (16) The cyan color material composition according to any one of (1) to (13), further including an adhesive resin layer on the cyan powder. (17) The cyan colorant composition according to (16), wherein the adhesive resin layer contains an extender pigment. (18) A cyan toner comprising the cyan color material composition according to (16) or (17).

(19) In the method for producing a cyan color material composition containing a cyan powder, the cyan powder may be 35
A cyan colorant composition comprising: forming at least one coating film on a surface of a base particle by a reaction of a metal salt in an aqueous solvent so as to show a reflection spectrum having a peak between 0 and 550 nm. Method of manufacturing a product. (20) The method for producing a cyan colorant 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 substance constituting the film d: film thickness m: natural number λ: peak of the reflection spectrum of the powder (Where λ is 350 to 550 nm) κ: attenuation coefficient]

(21) The method for producing a cyan colorant composition as described in (19) above, wherein the coating film formed on the surface of the base particles is a multilayer film. (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 cyan colorant composition as described above. (23) The method for producing a cyan colorant 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: peak of the reflection spectrum of the powder (Where λ is 350 to 550 nm) κ: attenuation coefficient]

(24) The cyan colorant composition as described in (19) above, 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 constituted 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 cyan colorant composition according to (19) above. (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 cyan colorant composition as described above. (27) The method for producing a cyan colorant 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 cyan colorant 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 an 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 cyan colorant composition according to the above (24), wherein the composition is formed by baking after being taken in. (30) The method for producing a cyan colorant composition according to (29), wherein the reaction solution is an aqueous solution.

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

The cyan powder in the cyan coloring material composition of the present invention is formed by the following operation and action during the film forming reaction.
It is presumed that the deposition of the solid phase that does not become a film is suppressed, and a film having a uniform thickness can be formed on the surface of the base particles with a desired thickness. Using a buffer solution as a reaction solvent,
By setting the pH to a certain level, the effect of acid or alkali is reduced, and the erosion of the substrate surface is prevented; the ultrasonic dispersion not only improves the dispersibility of the magnetic particles such as the substrate particles, particularly magnetite powder. In addition, it improves the diffusibility of the film components, further prevents the adhesion of the films, and improves the dispersibility of the magnetic particles formed by coating; the film components are deposited at an appropriate reaction speed. In addition, precipitation of a solid phase that does not form 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, causing scattering and reflection of light, enhancing the reflection effect, and providing a functional powder of cyan color tone having excellent lightness. It became possible to do.

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 cyan color material composition of the present invention obtained as described above is useful as a cyan-based composite raw material powder used as a raw material for pigments, powder metallurgy, ceramic raw materials, electronic industries, and the like. Pigments and plastics for color inks
It retains excellent performance in place of the conventional pigments used for paper fillers, and can have a stable color 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, multi-functional paints such as ornaments, pottery, porcelain, glassware, paintings and other crafts / arts, books, automobiles / bicycles, etc. Makes inks, toners, paints 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 cyan multifunctional inks, toners, paints, and the like having both the characteristics of the substrate and the characteristics of the film. In particular, a printing ink as a forgery-preventing pigment composition is obtained by combining any two or more of the above functions of magnetism, electric field, color, particle shape, fluorescence emission, phosphorescence emission, specific ultraviolet region reflection absorption and specific infrared reflection absorption. Forming a desired image on the support medium as a toner,
It is possible to make a determination by visual inspection or a determination target by a device. Having these excellent functions and utilizing a magnetic substance, a conductor or a dielectric as a base, an electric field,
Movement force by reacting by external factors such as magnetic field,
It has the function of generating additional functions such as rotation, movement, heat generation, etc.For example, when a magnetic material is applied as a base, it can also be used as a pigment for cyan or color magnetic toner or cyan or color magnetic ink without losing magnetism It is possible.

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 cyan color material composition of the present invention having a crystallized fine particle constituent film 2 on the surface of the base particles 1. FIG. FIG. 2 is an enlarged cross-sectional view of a film 2. 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. The brightness can be adjusted by adjusting 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 cyan, 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 diameter of the crystallized fine particles in the film is preferably 1 to 500 nm, more preferably 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, in the cyan color material composition of the present invention, the contained cyan powder is coated on the surface of the film 2 composed of the crystallized fine particles 3 having voids as shown in FIG.
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 on the surface. For example, when a cyan powder having a crystallized fine particle constituent film as the outermost layer as described above 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 voids and the crystallized fine particles. The difference in the refractive index between the surface and the air gap of No. 3 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 Patent Application Laid-Open No. Hei 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 treating agent and a resin, and does not generate scattering reflection as in the cyan color material composition of the present invention, but is colored in a desired color by the color of the pigment particles themselves. It is. Also, this Japanese Patent Laid-Open
In the colored powder described in JP-A-269804, the 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.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the cyan color material composition of the present invention will be described in detail. The cyan 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. As a light-transmitting coating film having a low refractive index, by reaction of a metal salt or the like,
When a metal hydroxide film or a metal oxide film is formed in a plurality of layers, the thickness of each layer of the coating film (a film that covers the base particles and participates in light interference) is adjusted. Function can be given. 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 substance forming the coating and 350 are satisfied so as to satisfy the following expression (1).
If an alternate film having a thickness d corresponding to an integer m times a quarter of the wavelength of visible light between 550 nm and 550 nm is provided with an appropriate thickness and number of films, light having a wavelength λ between 350 and 550 nm is obtained. (Using the interference reflection of Fresnel) is reflected or absorbed. nd = mλ / 4 (1)

Utilizing this action, a film having a film thickness and a refractive index that satisfies the formula (1) is formed on the surface of the base particles for a target wavelength between 350 and 550 nm, Further, the coating with a film having a different refractive index is alternately repeated once or more, thereby obtaining 3
A film having a reflection peak between 50 and 550 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 film thickness is measured and controlled as a reflection waveform using a spectrophotometer or the like to measure and control the change in the optical film thickness, which is the product of the film refractive index and the film thickness. 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 350 to 550 nm, a cyan colored powder 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 the attenuation coefficient κ is large, the phase shift at the mutual interface between the film material and the base material becomes large, and furthermore, all the layers of the multilayer film affect the optimum interference film thickness due to the phase shift.

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 cyan color system. In order to prevent this, the effect of the phase shift on all the films is taken into consideration, and 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, use a spectrophotometer, etc.
The reflection peak is the target wavelength of 350 to 5 which is the final target film number.
It is necessary to find the optimal conditions so as to be in the range of 50 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 also be designed to be cyan. 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. But,
As the total number increases, the interference inside the multilayer film becomes more complicated.
Even 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 the actual sample production, in order to correct these in the actual film by referring to the designed spectral curves, the film thickness is adjusted by a spectrophotometer or the like so that the reflection peak becomes the target wavelength in the range of 350 to 550 nm in the final target film number. It is necessary to find the optimal conditions while changing the conditions.

Even 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 multilayer film can be adjusted by the film thickness of each layer. By controlling the composition, the rate of solid phase deposition, 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 cyan color can be obtained. As described above, the reflection peak and the absorption bottom are 35 in the final target film number.
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 0 to 550 nm, a cyan powder can be obtained. 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. Thus, the powder can be vividly colored to a desired cyan color without using a dye or a pigment.

Hereinafter, the cyan colorant composition of the present invention and the method for producing the same will be described in detail. In the cyan color material composition and the method for producing the same of the present invention, the base particles serving as a 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 base is a metal, any metal such as iron, nickel, chromium, titanium, and aluminum may be used, but when using the magnetism, a magnetic material such as iron is preferable.
These metals may be alloys, and when having the above-mentioned magnetism, it is preferable to use ferromagnetic alloys. When the base of the powder is a metal compound, typical examples thereof include oxides of the above-mentioned metals. Examples of the metal oxide include iron, nickel, chromium, titanium, aluminum, silicon, and the like. , Magnesium, 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 by appropriately selecting the refractive index and the layer thickness of each coating layer. The powder can be colored cyan due to the interference color and exhibit a specific interference reflection peak outside the visible light region. As described above, a metal hydroxide film or a metal oxide film is deposited on the surface of the base particles by a reaction of a metal salt.
Using a buffer solution, precipitate at an appropriate rate at a certain pH.

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,
Sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, carbonic acid, and salts of carboxylic acids of metals such as samarium, copper, silver, gold, platinum, rhodium, iridium, tungsten, iron, and manganese are exemplified. 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%, and 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 such a metal salt may be formed in a plurality of layers. 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 for producing a cyan colorant composition containing a cyan powder of the present invention, 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 cyan color material composition according to the present invention is not particularly limited and can be appropriately adjusted depending on the purpose.
The range is from m to several mm, preferably from 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 forming 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.

As described above, the cyan colorant composition of the present invention is used as a film-forming reaction solvent in a water-based solvent having a constant pH when the film-forming reaction is performed in an aqueous solvent, particularly when the film-forming reaction is performed in an aqueous solvent. And at the same time, a film coating reaction is formed by a film forming reaction on the surface of the substrate under ultrasonic dispersion conditions. 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. The powder must be selected so as to be able to disperse the powder by the action of the electric double layer and to satisfy the conditions for forming a dense film by the above-mentioned gentle dropping reaction. 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 for 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 ₂ (SO ₄ ) ₂

The TiO ₂ content of titanyl sulfate is preferably from 5 g / l to 180 g / l, more preferably from 10 g / l to 160 g / l. 5g
If it is less than / g, it takes too much time to form a film, and the amount of powder to be treated is reduced, which is uneconomical. Both are unsuitable.

Subsequently, when a film of silicon dioxide or aluminum oxide is formed, the titania-coated particles are immersed and dispersed in a buffer solution of NaCl added to a KCl / H ₃ BO ₃ system or the like, and dispersed. Using metal salts such as aluminum such as sodium silicate and aluminum chloride as raw materials, an aqueous solution of these metal salts is slowly dropped into the reaction system to precipitate the generated metal hydroxide or metal oxide around the base particles. It can be done by doing. 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 → XS
iO ₂ ⁺ 2Na + + 2OH ^-

Next, the crystallized fine particle constituting film of the cyan color powder contained in the cyan color material composition of the present invention can scatter and reflect light, and can increase lightness.
Any material may be used, but a material having a high refractive index is preferable. 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 deposition 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 JP-A-11-131102. Solid-phase deposition method by reaction from metal salt in aqueous solution described in (Aqueous method)
And the like. In this case, the reaction solution is set so that the solid phase fine particles precipitate in the reaction solution at a higher rate than the rate at which the precipitate film grows on the surface of the substrate particles (linear growth rate). The concentration, the amount of catalyst added, and the amount of dispersion of the base particles 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 into 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 constituent 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 calcination may be performed after forming the coating film composed of the solid phase fine particles. However, the coating film is further formed on the coating film as a crystallized fine particle constituting film. In this case, it is desirable 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 cyan powder. Firing is 300 ~
It is preferably performed at 1200 ° C.

In the cyan colorant composition of the present invention, the film of the crystallized fine particles of the cyan powder contained therein is 2
It may have more than one layer. 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.

Hereinafter, a method of forming the metal compound film will be described. 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 JP-A-11-131102. 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 forming an organic film (resin film): a. A method of forming a resin film on particles by dispersing and emulsion-polymerizing the base particles in the liquid phase (polymerization method in the liquid phase); b. Film formation method in gas phase (CVD)
(PVD) and the like.

The following is an example of producing a cyan powder having a multilayer film on substrate particles as the cyan powder contained in the cyan color material composition of the present invention. 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. And light-transmitting films having a low refractive index are sequentially and alternately provided. If the base particles have a low refractive index, a high-refractive-index particle constituting film thereon, a low-refractive-index light-transmitting film thereon, and further thereon,
A high-refractive-index particle constituent film is sequentially provided.

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 the coating film is manufactured, the inclined washing is repeated while adding distilled water to remove the electrolyte. Then, a 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, in preparing the cyan color material composition according to the present invention, (1) cyan ink or paint-like composition (fluid) and (2) cyan toner, cyan dry ink-like composition (powder) Body) will be described. (1) In the present invention, as a medium (vehicle) of the cyan ink or the paint-like composition (fluid), a conventionally known varnish used for color printing, color magnetic printing, and color magnetic paint may be used. For example, a liquid polymer, a polymer or a monomer dissolved in an organic solvent, or the like can be appropriately selected and used depending on the type of powder, the application method of the ink, and the application.

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 cyan toner, the cyan dry ink, and the cyan dry paint-like composition (powder) are obtained by adding the cyan color material multilayer coating powder to a resin or, if necessary, a toning material. Is kneaded directly with a screw extruder, roll mill, kneader, etc., coarsely pulverized with a hammer mill, cutter mill, finely pulverized with a jet mill, etc., and classified into the required particle size with an elbow jet, etc. A colorant composition can be obtained. Further, the powder coated with the cyan color material multilayer film can be made into a powdery cyan color material composition by using a polymerization method such as an emulsion polymerization method or a suspension polymerization method. Furthermore, a liquid cyan coloring material composition such as an ink paint can be obtained by liquefying a cyan multi-layer coating powder, a resin, an additive such as a toning agent and a solvent with a colloid mill or a three-roll mill. 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.

In order to adjust the saturation and hue, the toning material particularly when used for color reproduction in a full-color mixture is as follows:
Lake pigments and lake pigments such as alkali blue lake, peacock lake and peacock lake blue, which are blue pigments (organic dyes / pigments), oil dyes such as oil blue, alcohol dyes such as alcohol blue, phthalocyanines such as phthalocyanine and copper phthalocyanine Pigments, (inorganic pigments) oxide sulfide composite pigments such as ultramarine, copper-based ultramarine blue pigments such as iron blue and miroly blue,
Cobalt oxide complex oxides such as cobalt blue and cerulean blue Blue pigments, blue organic dyes and pigments and blue inorganic pigments Lake dyes such as alkali blue lake and peacock blue lake, lake pigments, such as metal-free phthalocyanine and copper phthalocyanine Chromic oxides and hydrated oxides such as phthalocyanine dye pigments and green pigments such as chrome green, zinc green, chromium oxide and hydrated chromium (viridian), copper-based oxides such as emerald green, and cobalt-based oxides such as cobalt green Pigments, nitroso pigments such as pigment green and naphthol green, azo pigments such as green gold, phthalocyanine pigments such as phthalocyanine green and polychrome copper phthalocyanine, malachite green lake, acid pigments, etc. Rake system such as Dogreen rake,
Organic dyes and pigments such as oil dyes such as oil green and alcohol dyes such as alcohol 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 blue, yellow, or magenta in subtle color tone control, it is preferable to add these pigments to obtain an optimum cyan color.

In the case of this powdery cyan color material composition,
(A) The resin produced by the above pulverization method is not particularly limited, but may be polyamide, epoxy resin, polyester, melamine resin, polyurethane, vinyl acetate resin, silicon resin, acrylate, methacrylic acid. Esters, styrene, ethylene, butadiene,
Examples include a polymer or copolymer of propylene and their derivatives. (B) In the case of the polymerization method, polymerization is started from one or a mixture of one or more of an ester, urethane, vinyl acetate, organosilicon, acrylic acid, methacrylic acid, styrene, ethylene, butadiene, propylene and the like. These copolymers are formed.

As described above, the cyan colorant composition of the present invention comprises (1) a cyan ink or a paint-like composition (fluid) and (2) a cyan toner or a cyan dry ink-like composition (powder). In the form of In the case of a fluid, the ink is a cyan ink, a paint, etc., and the toning material, a solidifying accelerator for late drying resin, a thickening agent for increasing viscosity, and a fluidizing agent for decreasing viscosity. In addition, a component such as a dispersant may be included for dispersing the particles. on the other hand,
In the case of powder, (a) when powder is produced by a pulverization method, a solidification accelerator for the toning material and a resin that is slowly dried, and a fluidizing agent for decreasing the viscosity during kneading. A dispersant for dispersion of particles, a charge control agent for fixing to paper, etc.,
Components such as wax can be included. (B) When a polymerization method is used, the above-mentioned toning material, polymerization initiator, polymerization accelerator, thickener for increasing viscosity, dispersant for dispersing particles, fixing to paper, etc. Charge conditioner for
Components such as wax can be included. The multilayer coating powder in the cyan color material 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 the powders of the three primary colors, it has a function of identifying six combinations of visible light, invisible light (ultraviolet and cyan), fluorescent color and magnetism, and electricity (electric field change). The present invention can be applied to other applications that require a security function, such as color magnetic ink for preventing forgery.

The cyan colorant composition of the present invention may be prepared using a cyan ink or a paint-like composition or a cyan toner,
As a cyan dry ink-like composition, a cyan dry paint composition, when printed on a substrate, melt-transferred or applied to an object to be coated, the cyan color material multi-layer coating powder and resin in the cyan color material composition The relationship between the contents is 1: 0.5 to
1:15. 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. The relationship between the amount of the cyan ink or the total amount of the cyan coloring material and the resin in the coating composition and the amount of the solvent is 1: 0.5 to 1:10 in volume ratio, and the amount of the solvent is too small. And the viscosity of the paint is too high to apply 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.

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 cyan colorant multilayer film of the present invention on the object to be coated is 1 in area density when uniformly applied.
If the amount is 0.1 to 300 g per square meter, and preferably 0.1 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. It is uneconomical to make the coating film thicker than such a thickness, because the coating thickness exceeds the hiding power of the coating material, so that the coating effect is not obtained. 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. This is not the case even when a specific design or the like is partially formed.

[0077]

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] (Cyan color material composition 1 using a magnetic material,
Water-based two-layer coating) (Film formation of first-layer silica film) (1) Preparation of buffer solution A solution of 0.4M potassium chloride reagent and 0.4M boric acid in 1 liter of water was prepared. It was set to 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: 2.3 μm) as base particles was prepared in 189 ml in advance.
In a mixed solution of buffer solution 3 (pH: about 9.0) and 34 ml of pure water to obtain a dispersion. The container containing the dispersion is
Ultrasonic cleaner with water (made by Iuchi Seieido, Inc., US-
Placed in a water bath of 6-inch), 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, 148 ml of an aqueous sodium silicate solution also prepared in advance was added at a rate of 40 ml / min, and the mixture was gradually reacted and 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, put the silica film powder into the vat,
After separating by settling and discarding the upper solution, the solution was dried in air in a dryer for 150 minutes.
° C., then dried for 8 hours to obtain a silica-coated magnetite powder A _1.

(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.

[0080] (3) with respect to the powder A ₁ titania film-4g, slow衡溶solution 406Ml 4
(PH: about 8.4) and prepared pure water 48 ml, the mixture was powder A ₁ in the same manner as when the silica film, while ultrasonic dispersion, thoroughly dispersed in an ultrasonic bath did. Thereafter, while maintaining the temperature of the liquid at 50 to 55 ° C., a total of 48 ml of a 10% aqueous solution of titanium sulfate prepared in advance is dropped at 1.9 ml / min, and solid phase fine particles are precipitated in the liquid to make the liquid thin cloudy. I let it. 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 was 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.
Heat treatment (firing) was performed at 30 ° C. for 30 minutes to obtain a silica / titania-coated magnetite powder A ₂ having a smooth surface. This two-layer film-coated powder A ₂ was pale cyan, and its magnetization at 1 kOe was 36 emu / g. Maximum reflection peak of the two-layer film-coated powder A ₂ is 435 nm, was a bright cyan color.

The peak wavelength of the spectral reflection curve of the coated powder of the 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 cyan multilayer film-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 cyan-colored multi-layer coated powder A ₃ previously lipophilized in 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 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, 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 a cyan polystyrene-coated powder A. The resulting cyan powder A is spherical and has a magnetization of 17.1 em at a magnetic field of 1 kOe.
u / 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.

[0085]

[Table 1]

[Example 2] (Cyan 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: 2.3 μm) was prepared by using 231 prepared in advance.
ml of the buffer solution 3 (pH: about 9.0) and pure water 154
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. Also, 123m 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 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 Layer 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 15 g, slow衡溶solution 4 (pH: about 8.4) of 1313ml and prepared pure 1583Ml, the powder B ₁ on the slow衡溶solution 4, when the silica film Similarly to the above, the dispersion was sufficiently performed in the ultrasonic bath while the ultrasonic dispersion was being performed. Thereafter, while maintaining the temperature of the solution at 50 to 55 ° C., the titanium sulfate aqueous solution prepared in advance was added to 1.
The solution was slowly dropped at a constant rate of 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 a light cyan, a maximum reflection peak is 428 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 a third layer silica film, when the surface of the titania film is confined by a thin silica film) Preparation of buffer solutions 1 and 2 and aqueous solution of sodium silicate (water glass solution) in the same manner as in Example 1. Was done. A silica film was formed on 15 g of the powdered silica / titania-coated magnetite powder B ₂ . The amount of the buffer solution was the same as that for the first layer coating, except that the dropping rate of the aqueous sodium silicate solution was the same, and the dropping amount was 8 ml to form a film. After washing, heat treatment (baking) was performed in a rotary tube furnace at 500 ° C. for 30 minutes in a nitrogen atmosphere to obtain silica / titania-coated magnetite powder B ₃ .

[0090] Powder B ₃ obtained, while the surface is smooth silica film two layers, titania fine particles are crystallized and became light scattering is large pale cyan powder. The surface of B ₃ are eliminated irregularities, substantially smooth and holes and cracks were not like depressions. In observation with a transmission electron microscope, the silica layer 2
It is probable that titania fine particles were crystallized between the layers, and voids were present between the particles, so that the scattering reflection increased between the particles and the voids. Maximum reflection peak of the three-layer film-coated powder B ₃ was 428 nm.

(Adhesive resin layer, polystyrene composite powder) 100 g of styrene monomer, 100 g of a cyan color material multilayer coating powder B ₃ lipophilized in advance by the surface treatment method described above.
The mixture was stirred with a high-speed stirrer until 45 g of lipophilic titanium oxide was dispersed in the same manner as in Example 1 to obtain a uniform mixture. 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, 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 a filter paper to obtain a cyan polystyrene-coated powder B. The powder of the obtained cyan color material composition B is spherical and has a magnetization of 17 at a magnetic field of 1 kOe.
emu / g. 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.

[0092]

[Table 2]

[Example 3] (Cyan color material composition 3 using a magnetic material, water-based four-layer coating when scattering particles are attached to the surface) (Formation of first-layer silica film) 40 g as base particles Of magnetite powder (average particle size 0.7 μm) in a mixed solution with 2800 g of buffer solution 3 (pH: about 9.0) and 233 ml of pure water prepared in advance in the same manner as in Example 1. Liquid. 28KH _Z, while applying an ultrasonic wave in an ultrasonic bath at 600W, further were dispersed with stirring in slow衡溶solution 3 containing magnetite powder. To this, 1167 ml of an aqueous sodium silicate solution prepared in advance was also 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.

[0094] For the powder C ₁ of 40 g (deposition of the second layer Titania films), the slow衡溶liquid 3 4,667mlml
Providing a pure water of 4,667ml and, C ₁ to the pure water
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.
1890 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 terminated while the liquid was slightly clouded. 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 the film formation reaction,
The decantation was repeated with sufficient pure water to remove the unreacted portion, excess sulfuric acid, and sulfuric acid formed by the reaction. Solid-liquid separation was performed, followed by drying with a vacuum drier to obtain a dry powder. The obtained dried powder was subjected to heat treatment (firing) at 650 ° C. for 30 minutes in a rotary tube furnace to obtain silica / titania-coated magnetite powder C ₂ . The two-layer film-coated powder C ₂ is a light cyan color, the maximum reflection peak was at 422 nm.

[0095] 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 3,360ml that had been prepared in advance (pH: About 9.0) and 280 ml of pure water.
8KH _Z, while applying an ultrasonic wave in an ultrasonic bath at 600W, further dispersed with stirring in a mixture containing magnetite powder. To this, 1,400 ml of an aqueous sodium silicate solution prepared in advance was also added for 2.6 times.
The mixture was gradually added at 7 ml / min to precipitate 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. Then, the film was dried in a dryer at 150 ° C. for 8 hours in air to obtain silica-coated magnetite powder C ₃ .

[0096] For the powder C ₃ of 40 g (deposition of the fourth layer Titania membranes) prepared pure water slow衡溶liquid 4 and pure water 5,600Ml of 5,600Ml, flour To the mixture solution Body C
₃ was sufficiently dispersed in an ultrasonic bath while being ultrasonically dispersed in the same manner as in the silica film formation. Thereafter, while maintaining the temperature of the solution at 50 to 55 ° C., 2,268 ml of an aqueous solution of titanyl sulfate (TiO ₂ ,
15 w%) was gradually dropped at a constant rate of 1.25 ml / min, and the dropping was completed while depositing 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. .

[0097] The obtained dry powder is put in a rotary tube furnace.
Heat treatment (firing) was performed at 650 ° C. for 30 minutes to obtain silica / titania-coated magnetite powder C ₄ . This four-layer film-coated powder C ₄ is cyan and has a maximum reflection peak of 432 n.
m.

(Preparation of Cyan Ink Composition) The silica / titania-coated magnetite powder C thus obtained
₄ , 30 g, 2.5 g of acrylic polymer (Technovit, manufactured by Kulzer) in 80 g of ethanol in advance
Is dispersed in a solution in which is dissolved, and a mixed solution obtained by adding 20 g of titanium oxide (silicone hydrophobic treated product: coloring material) and 3.2 g of hydroxypropylcellulose is subjected to a dispersion treatment for 8 hours by a zirconia ball mill to obtain a cyan coloring material. A paint dispersion CL of the composition was obtained.

(Coating and Spectral Characteristics) The dispersion liquid CL of the cyan color material composition was coated on a plastic film for thermal transfer by a blade coater. The application amount (after drying) of the cyan color material composition was 60 g / m ² . After drying, the color of the obtained coated paper C has a maximum reflection peak wavelength of 430 nm,
A bright cyan color with a reflectance of 67% was obtained. The magnetization at 1 kOe per 1 m ^{2 of the} coating C was 1,140.
emu / cm ² . Each refractive index of the first to fourth layers,
Table 3 shows the film thickness, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0100]

[Table 3]

[Example 4] (Cyan color material composition 4 using magnetic material, three-layer coating by hydrolysis of metal alkoxide) (Film formation of first layer silica film) 10 g of carbonyl iron powder made by BASF (average) The magnetization at a particle size of 1.8 μm and 10 kOe is 2
After dispersing 03 emu / g in a solution prepared by dissolving 6.3 g of silicon ethoxide in 158.6 g of ethanol in advance, 6.3 g of aqueous ammonia (29%) prepared in advance with stirring and 6.3 g of aqueous ammonia (29%) were added. A mixed solution of 8.4 g of deionized water 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, use a rotary tube furnace in a nitrogen atmosphere for 8 hours.
00 ° C. subjected to 30 minutes (baking), the was cooled to obtain a silica-coated iron powder D _1.

[0102] In (second layer Titania film of film) In a separable flask, the silica-coated powder D ₁ of the 10 g, submerged plus titanium isopropoxide 8.1g of ethanol previously 198.3g 4.9 g of pure water prepared in advance 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 5 hours. After the reaction, the resultant was diluted and washed with sufficient ethanol, filtered, and dried in a vacuum drier at 110 ° C. for 3 hours to obtain silica / titania-coated iron powder D ₂ . When the state of particles in the dried titania layer was observed using a transmission electron microscope, the particle size was 1 to 10 n.
m titanium oxide solid particles were found, but there were no gaps between the particles inside the film and the film was uniformly filled. The titanium oxide film had an average thickness of 76 nm, had a peak wavelength of a spectral reflection curve at 411 nm, and was bright cyan.

(Formation of Third Layer Silica Film) 10 g of silica / titania-coated iron powder D ₂ was previously dispersed in a solution of 1.0 g of silicon ethoxide in 80 g of ethanol, and then stirred. 1.0 g of ammonia water (29%) prepared in advance and 1.1 g
Of deionized water was added. 1 hour 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, a heat treatment (calcination) was further performed at 500 ° C. for 30 minutes in a nitrogen atmosphere, followed by cooling to obtain silica / titania-coated iron powder D ₃ . When the state of particles in the heat-treated titania layer was observed using a transmission electron microscope,
Titanium oxide crystallized fine particles of 0 nm were observed, and a gap of about 10 to 50 nm was observed between each particle. However, the silica layer was dense, free of particles, and smooth. Further, voids existed at the interface with titania.

The maximum reflection peak wavelength of this powder D ₃ is 40
At 9 nm, a bright cyan color was obtained. From this Example 4, crystal particles of titania particles are formed depending on the presence or absence of heat treatment (calcination), and voids between the particles and the silica film accompanying the particle formation are observed. Due to the scattering and reflection effect accompanying these particles, It is considered that cyanization was achieved. Another feature of the cyan 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 using the obtained powder as a pigment such as toner or paint,
In some cases, the resin or the vehicle enters the voids, and the difference in the refractive index between the particles and the interference or scattering particles becomes small, resulting in a decrease in the Fresnel reflectance. However, by lowering the final layer as a dense film having no influence on interference and scattering and covering the voids of the particle-constituting film, it is possible to prevent the above-mentioned reduction in scattering reflection.

(Adhesive resin layer, polystyrene composite powder) High-speed stirrer until 100 g of styrene monomer and 100 g of cyan-colored material multi-layer coating powder (silica / titania-coated iron powder D ₃ ) and 10 g of the lipophilic titanium oxide are dispersed. And homogenized. The mixture of the styrene monomer and the particles is mixed with sodium n-dodecyl sulfate in 500 g of distilled water.
The temperature was kept at 70 ° C. while stirring at a high speed, and the mixture was stirred until the emulsified particles were sufficiently turned 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, 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 a filter paper to obtain a cyan polystyrene-coated powder D. The powder of the obtained cyan color material composition D is spherical, and its magnetization at a magnetic field of 1 kOe is 170 emu /
g, and the magnetization at a magnetic field of 10 kOe is 170 emu / g.
Met. 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.

[0106]

[Table 4]

Example 5 (Cyan Coloring 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
0 emu / g) was previously dispersed in a solution prepared by dissolving 4.4 g of silicon ethoxide in 158.6 g of ethanol, and then 8.0 g of ammonia water (29%) prepared in advance with stirring. And a mixed solution of 8.0 g of deionized water 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, heat treatment (sintering) was further performed at 600 ° C. for 30 minutes in a nitrogen atmosphere using a rotary tube furnace, followed by cooling.
To obtain a silica-coated iron powder E _1.

[0108] In (second layer Titania film of film) In a separable flask, the silica-coated powder E ₁ of 20g, submerged plus titanium isopropoxide 8.1g of ethanol previously 198.3g After stirring, 6.3 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, the peak wavelength of the spectral reflection curve at 410 nm, and a bright cyan color.

(Formation of Third Layer Silica Film) 158.6 g of silica / titania-coated iron powder E ₂ was previously prepared in an amount of 208.6 g.
After dispersing in a solution prepared by dissolving 3.7 g of silicon ethoxide in ethanol, 8.0 g of ammonia water (29%) and 8.0 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 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,
A heat treatment (calcination) was performed at 500 ° C. for 30 minutes in a nitrogen atmosphere, and the mixture was cooled to obtain silica / titania-coated iron powder E ₃ .

(Formation of Fourth Layer Titania Film) In a separable flask, 20 g of the silica / titania coat powder E
₃ in advance to 8.8 g of ethanol in 198.3 g of ethanol
After dispersing in a solution containing titanium isopropoxide of
While stirring, a solution prepared by mixing 6.0 g of pure water and 47.9 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, the mixture was diluted and washed with sufficient ethanol, filtered, and dried in a vacuum drier at 100 ° C. for 8 hours to obtain silica / titania-coated iron powder E ₄ .

(Formation of Fifth Layer Silica Film) 20 g of silica
/ Titania coated iron powder E_Four158.6g in advance
Dissolve 2.5 g of silicon ethoxide in ethanol
After dispersing in a mixed solution, prepare
3.0 g of aqueous ammonia (29%) and
A mixed solution of 3.0 g of deionized water was added. After the addition,
The reaction was carried out at room temperature for 5 hours. After the reaction, sufficient ethanol
Diluted with, filtered and dried in a vacuum dryer at 110 ° C for 3 hours
Dried. After drying, using a rotary tube furnace,
Heat treatment (heat treatment) at 600 ° C for 30 minutes in a nitrogen atmosphere
And cool, silica / titania-coated iron powder E _FiveI got
This iron powder E_FiveIs the peak wavelength of the spectral reflection curve at 410 nm
And a pale cyan color.

(Preparation of Cyan Ink Composition) 30 g of the silica / titania-coated iron powder E ₅ thus obtained
Was dispersed in a solution in which 2.5 g of an acrylic polymer (Technovit, manufactured by Kulzer) was dissolved 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 mixture was subjected to a dispersion treatment for 8 hours using a zirconia ball mill to obtain a coating dispersion EL of a cyan colorant composition.

(Coating and Spectral Characteristics) The dispersion EL of the cyan color material composition was applied to art paper using a blade coater. The application amount (after drying) of the cyan colorant composition is 5
It was 1 g / m ² . After drying, the color of the obtained coated paper E was 431 nm at the peak wavelength, and was bright cyan. The magnetization of the coated paper E at a magnetic field of 1 kOe is 3,
It was 570 emu / m ² and the magnetization at a magnetic field of 10 kOe was 8,925 emu / 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.

[0114]

[Table 5]

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

(Formation of Second Layer Silica Film) To 3,193 ml of the same buffer solution as prepared in Example 1, pure water and 152 ml of the same solution prepared in advance were mixed, and 10 g of F ₁ was added. After mixing, the mixing ratio of SiO ₂ is 10 wt%
Was gradually added dropwise over 3 hours while stirring, and the reaction was continued for 1 hour. 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 iron powder F ₂ Obtained.

(Formation of Third Layer Titania Film) Further, 4 g of the silica / titania film-coated iron powder F _{2 was} added to a buffer solution 4,40.
After sufficiently dispersing in 6 ml, titanyl sulfate TiO ₂ , 1
A 5 wt% aqueous solution, 32 ml, was added dropwise over 4 hours. After the addition, the mixture was allowed to react for 1 hour to eliminate unreacted raw materials. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried in a vacuum dryer 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 / titania film-coated iron powder F ₃ Obtained. The peak of this powder was 435 nm, the reflectance was 47%, and the powder was dark greenish blue. The magnetization of this powder at a magnetic field of 1 kOe was 37.5 emu / g and
The magnetization of kOe was 117 emu / g.

(Formation of toner) 100 g of styrene monomer,
After mixing a liquid in which 0.3 g of oil blue was dissolved in 30 ml of xylene, 100 g of lipophilized F ₃ powder obtained in advance and 10 g of titanium oxide were added and uniformly mixed.
Next, the mixture of the styrene monomer and the particles was subjected to 70C
3 g of sodium dodecyl sulfate was added to the solution with a stirrer in which distilled water was dissolved, and then 10,000 g with a homogenizer.
While stirring at rpm, and further stirring at 5,000 rpm, 10 g of a 10 wt% ammonium persulfate aqueous solution was added, and the mixture was reacted for 3.5 hours. Thereafter, the solid content was filtered and washed three times with warm water to obtain a greenish blue polystyrene-coated powder FP. The magnetic field magnetization at 1 kOe of this powder was 17.7 emu / g, and the magnetization at 10 kOe was 55.7 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.

[0119]

[Table 6]

[Example 7] (Cyan 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 the plate-shaped Ba-based ferrite, 6.3 g of silicon ethoxide is added and mixed, 6.3 g of water and 8.4 g of aqueous ammonia are further added, and the mixture is added at room temperature. The mixture was reacted for 3 hours while stirring. Solid-liquid separation by decantation after the reaction, after the powder 8 hours drying after vacuum drying, using a rotary tube furnace, and heat-treated for 30 minutes at 500 ° C. in a nitrogen atmosphere, the silica film-coated Ba ferrite particles G ₁ Obtained.

(Second Layer Coating and Coloring) After sufficiently dispersing 10 g of Ba-based ferrite particles G ₁ coated with silica film in 159 g of ethanol, 4.9 g of titanium isopropoxide was added.
After thorough mixing, further prepare 8.4 of prepared water.
g and 30 g of ethanol were added dropwise and reacted for 5 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.
To obtain a titania film-coated Ba ferrite particles G _2. The peak of this powder was 428 nm, the reflectance was 44%, and the powder was dark greenish blue. The magnetization of this powder at 10 kOe was 24.6 emu / g, and the remanent magnetization was 15.5 emu / g.
u / g.

[0122] (third layer scattering film coating) to a prepared G ₂ powders buffer solution A500ml, mixed well buffer solution 3,875 ml prepared in advance, the average particle size of 0.2 and this G ₂ 10 g After 5 g of micron 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 dried powder was subjected to a heat treatment at 500 ° C. for 30 minutes in a nitrogen atmosphere using a rotary tube furnace to obtain a titania scattering film / silica film-coated Ba-based ferrite particle G ₃ . The peak of this powder was 450 nm, the reflectance was 68%, and the powder was pale greenish blue. In addition, 1 of this powder
The magnetization at 0 kOe was 18.2 emu / g, and the residual magnetization was 12.0 emu / g.

[0123] For (inked) the G ₃ flour 30g, pre acrylic resin 1.5g hydroxypropyl cellulose 2.3g, dispersed in ethanol 80 g,
The alcohol was evaporated while stirring to obtain a liquid GL whose viscosity was increased. This GL can be converted into a small printing machine PG1
0, a stripe pattern was formed on the plastic film for thermal transfer.

(Applied Material) After drying, the film was scanned with a detection device equipped with a magnetic head. As a result, a magnetic reaction was detected in the printed portion of the magnetic powder GL.
There was no magnetic reaction in the blank area. The coating material was greenish blue when viewed from above, but when viewed obliquely at an angle of 30 degrees, it appeared blue-purple and polychromatic. The first
Table 7 shows the refractive index, film thickness of each of the three layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0125]

[Table 7]

[Example 8] (Cyan color material composition using plate-like mineral, three-layer coating by hydrolysis of metal alkoxide) (coating) (first-layer coating coloring) Plate-shaped white cloud coated with an average particle diameter of 12 microns After sufficiently dispersing 20 g of the mother powder in 160 g of ethanol, 5.0 g of titanium isopropoxide was added and thoroughly mixed, and a mixed solution of 8.6 g of water and 30 g of ethanol prepared in advance was added dropwise for 5 hours. Reacted. After the reaction, solid-liquid separation was performed by decantation, the powder was dried under vacuum, dried for 8 hours, and then heat-treated at 500 ° C. for 30 minutes in a nitrogen atmosphere using a rotary tube furnace. ₁ was obtained. The peak of this powder was 440 nm, the reflectance was 43%, and the powder was dark greenish blue.

(Second Layer Coating) After sufficiently dispersing 20 g of titania-coated plate-like muscovite mica powder H ₁ in 80 g of ethanol, 8.4 g of silicon ethoxide was added and mixed, and further 8.4 g of water and aqueous ammonia were added. After adding 11.1 g, the mixture was reacted for 3 hours while stirring at room temperature. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried in 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 / titania-coated plate-like muscovite mica powder H
Got _two .

(Third Layer Colored Film Coating) g of ethanol / 160 g of silica / titania-coated plate-like muscovite mica powder H _{2 was} added to 20 g of H _2.
6.6 g of titanium isopropoxide was added thereto, and the mixture was sufficiently mixed. Then, a mixed solution of 11.2 g of water and 30 g of ethanol prepared in advance was added dropwise.
Allowed to react for 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.
A silica / titania-coated plate-like muscovite mica powder H ₃ was obtained. The peak of this powder was 436 nm, the reflectance was 64%, and the powder was pale greenish blue.

(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 increased, the dispersion was spread on a flat glass plate, and evenly adhered to a rubber roller. Then, the viscous fluid HL was applied to the A4 size thermal transfer film and left for one day. Dried. When the powder coating film obtained is viewed vertically, a light greenish greenish blue band is observed. In addition, when the plate is tilted toward the sun and the viewing angle is changed, the plate faces the sun (almost vertical light).
Was pale green, but when viewed from the plate so that the angle between the sun and the plate (incident angle) was 40 degrees, the color was tinged with bluish purple and polychromaticity was recognized. This property is a polychromatic display medium,
It can be used for cosmetics, ornaments, or flip-flop method. 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.

[0130]

[Table 8]

[Example 9] (Cyan color material composition using plate-like conductor, three-layer coating by hydrolysis of metal alkoxide) (paint) (first-layer coating coloring) Plate-shaped aluminum coated with an average particle diameter of 12 microns After 18 g of the powder was sufficiently dispersed in 160 g of ethanol, 5.0 g of titanium isopropoxide was added and mixed well, and a mixed solution of 8.6 g of water and 30 g of ethanol prepared in advance was added dropwise and reacted for 5 hours. I let it. 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 434
The reflectivity in nm was 44%, and it was a dark greenish blue.

(Second Layer Coating) After sufficiently dispersing 18 g of titania-coated plate-like aluminum powder I ₁ in 160 g of ethanol, 8.4 g of silicon ethoxide was added and mixed, and 8.4 g of water and 11 g of aqueous ammonia were added. .1 g 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) Ethanol 16 was added to 18 g of silica / titania-coated plate-like aluminum powder I _2.
0 g and then 6.6 g of titanium isopropoxide.
Was added and mixed well, and a previously prepared mixed solution of 11.2 g of water and 160 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 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. Got _three . The peak of this powder is 436 nm and the reflectance is 70.
%, Pale greenish blue.

(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, it was about to descend so as to be uniform in a plate with the tape is adhered to I _3.
Furthermore, this white vinyl chloride plate is placed horizontally, 10 c 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 greenish greenish blue band was observed, and polychromaticity was recognized as in Example 8.

(Physical properties) As a result of scanning a Wheatstone bridge, a search coil equipped with a power supply and an ammeter perpendicularly to a single side of this plate, the ammeter changed in the coated portion, but changed in the non-applied 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. 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.

[0136]

[Table 9]

As is clear from Tables 1 to 9, the cyan colorant compositions of the examples of the present invention each obtained satisfactory results. In addition, by providing the titania coating layer having voids due to the crystallization of titania particles in two layers (second layer and fourth layer) rather than one layer (second layer), high cyan coloration was achieved. .

[0138]

As described above, the cyan colorant composition of the present invention can be produced by using water as a solvent during the film-forming reaction in the production of the cyan powder to be contained, and can be used as compared with the alkoxide method. The effect is obtained that the film can be formed at a low production cost. Further, 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 voids, causing scattering and reflection of light, enhancing the reflection effect, and producing a cyan-colored functional powder having excellent lightness. It has become possible to provide a cyan colorant composition containing the same.

In the cyan color material composition of the present invention obtained as described above, when a magnetic substance is used as the base of the cyan powder to be contained, the characteristics (for example, magnetic characteristics) of the base particles are increased to a high level. , For example, a cyan magnetic toner capable of performing an excellent composite function even in a one-component developing system, and excellent magnetic properties. In addition, it uses polychromatic and reflective or transmissive colors for decorative products, pottery, porcelain, glassware, paintings and other crafts and arts, books, automobiles and bicycles, etc. Functional inks, toners, paints, cosmetics,
Furthermore, a multifunctional cyan ink, toner, and paint that has excellent weather resistance and cleanability of the environment such as air and water due to its catalytic action, such as titanium oxide film, and has both the properties of the substrate and the properties of the film. Applicable to In particular, the above-mentioned function is a pigment composition for preventing forgery by combining any two or more of the functions of magnetism, electric field, color, particle shape, fluorescence emission, phosphorescence emission, specific ultraviolet reflection absorption and specific infrared reflection absorption. It has become possible to provide a cyan color material composition that can form a desired image on a support medium as ink or toner, and that can be visually identified and identified by a device, and a method for efficiently producing the same. Having these excellent functions and utilizing a conductor or a dielectric as the base of the contained cyan powder, the electric field, reacting due to external factors of the movement force, rotation, movement,
It is possible to provide a cyan colorant composition having a function of generating an additional action such as heat generation and a method for efficiently producing the same, which greatly contributes to the industry.

[Brief description of the drawings]

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

FIG. 2 is an enlarged cross-sectional view of a crystallized fine particle constituting film 2 of a cyan powder contained in the cyan color material 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 Continuing on the front page (72) Inventor Kiyoshi Hoshino 8-1, Hirai-machi, Hinode-cho, Nishitama-gun, Tokyo Inside the Iron Mining Co., Ltd. (72) Inventor Katsuhito Nakatsuka 4-chome Modaidai, Taihaku-ku, Sendai City, Miyagi Prefecture No. 1403 No. F3 term (reference) 2H005 AA21 AB02 CA01 CA21 CB07 CB13 4J037 AA04 AA08 AA09 AA15 AA18 AA19 AA22 AA25 CA09 CA14 CA24 CA25 DD02 DD05 DD30 EE04 EE14 EE26 EE43 EE46 FF08 4J0 001 001 001 EA011 KA06 KA08 KA15 NA01 NA19 4J039 AB12 AD01 AD03 AD10 AD15 AE01 AE02 AE03 AE04 AE06 AE07 AE08 AF01 BE01 CA04 DA05 EA16

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 cyan color material composition containing a cyan powder that exhibits a reflection spectrum having a peak between 50 and 550 nm. 2. The cyan film according to claim 1, wherein the coating film formed by the reaction of the metal powder of the cyan powder in an aqueous solvent satisfies the following condition. Color 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 350 to 550 nm) κ: attenuation coefficient] 3. The cyan colorant composition according to claim 1, wherein the coating film on the surface of the base particles of the cyan powder is a multilayer film. 4. The cyan color material composition according to claim 3, wherein each of the multilayer films of the cyan powder is formed by a reaction of a metal salt in an aqueous solvent. . 5. The cyan color material composition according to claim 3, wherein each of the layers of the cyan powder multilayer film 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 350 to 550 nm) κ: attenuation coefficient] 6. A method according to claim 1, wherein at least one layer of the coating film on the surface of the base particles of the cyan powder is constituted as an aggregate of crystallized fine particles having voids. The cyan colorant composition described in the above. 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. The cyan colorant composition according to claim 6, wherein 8. A method in which a dense coating film composed of ultra-fine particles capable of closing the voids on the surface is provided on the surface of the coating film configured as an aggregate of crystallized fine particles having voids. The cyan colorant composition according to claim 6, characterized in that: 9. The cyan colorant composition according to claim 6, wherein said coating film formed as an aggregate of crystallized fine particles having voids is a high refractive index film. 10. The cyan colorant 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 cyan colorant composition according to claim 6, wherein the composition is formed by baking after being taken into the coating film. 12. The cyan 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 cyan colorant composition according to claim 11, wherein 14. The cyan color material composition according to claim 1, wherein the cyan powder is dispersed in a dispersion medium containing at least a binder resin. 15. The cyan color material composition according to claim 1, further comprising an adhesive resin layer on the cyan powder. 16. The cyan color material composition according to claim 15, wherein said adhesive resin layer contains an extender pigment. 17. The method for producing a cyan coloring material composition containing a cyan powder, wherein the cyan powder is 350 to
A cyan colorant composition characterized in that 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 550 nm. Production method. 18. The production of a cyan colorant 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 condition. 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 350 to 550 nm) κ: attenuation coefficient] 19. The method for producing a cyan colorant 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 cyan colorant 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 cyan colorant composition as described 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 350 to 550 nm) κ: attenuation coefficient] 22. The production of a cyan colorant 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 cyan colorant 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 cyan colorant composition according to 22. 25. The method 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 cyan colorant 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 cyan 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 cyan 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 cyan colorant composition according to claim 27, wherein: 30. The method for producing a cyan colorant composition according to claim 17, wherein the cyan powder is dispersed in a dispersion medium containing at least a binder resin. 31. The method for producing a cyan colorant composition according to claim 17, wherein an adhesive resin layer is provided on the cyan powder. 32. The method for producing a cyan colorant composition according to claim 31, wherein the adhesive resin layer contains an extender pigment.