JP2001254028A - Yellow colorant composition and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bright yellow colorant composition which contains a yellow powder, 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; both a production facility and an explosionproof apparatus are not needed; and the control of temperature and humidity is easy. SOLUTION: This colorant composition contains a yellow 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 550-850 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 yellow colorant composition and a method for producing the same, and more particularly, to a method for producing a yellow colorant composition by an inexpensive and safe method without using expensive raw materials or dangerous organic solvents. Can, ink, 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, pigments Compositions, pigment compositions and paints for arts such as crafts and ceramics, pigment compositions for multicolor paints,
Pigment composition for fiber coloring (carrier), paint for toys, decorative paper
Yellow color materials used for various purposes such as paints and fillers for decorative boards, paints and fillers for plastics and metals, pigment compositions for displays, paints for display media, paints for magnetic recording media, catalyst paints and pigment compositions for heat-resistant paints The present invention relates to a composition and a method for producing the composition.

[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 yellow color composition may be particularly important. Yellow is one of the three primary colors and is an important pigment that gives a person a psychologically warm, cheerful, and healthy feeling. Obtaining a color material composition having such a yellow 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 yellow 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-mentioned technique, and more specifically, a technique for producing a film coating powder exhibiting a vivid yellow color. An attempt was made to establish a range of conditions for developing color. The present inventors have conducted studies from such a viewpoint, and as a result, a plurality of coating films in which a coating film having a large refractive index and a coating film having a small refractive index are laminated adjacently on the surface of the base particles, An adhesive resin layer in which pigments and dyes are dispersed, and
By setting the conditions of the base particles and the coating film so as to show a reflection spectrum having a peak between 50 and 850 nm, a function having a yellow color tone and a compound function even in a one-component developing method can be obtained. It has been found that a viable color toner can be obtained (JP-A-11-24317).

[0006]

However, the yellow toner disclosed in Japanese Patent Application Laid-Open No. H11-24317 has a coating layer formed on the surface of base particles formed by a hydrolysis reaction of metal alkoxide. Met. Film forming method by hydrolysis reaction of metal alkoxide, using a highly flammable organic one as a solvent,
As a raw material, expensive metal alkoxides must be used. 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 yellow toner described in JP-A-11-24317 did not have sufficient lightness and had a dark color 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 can be obtained at a low price comprehensively. It is to provide a method. A further object of the present invention is to provide a yellow color material composition which can be used as a toner, ink or paint having a high lightness and a stable color tone, and which has a high level of characteristics (for example, magnetic characteristics) of base particles. In order to make use of the characteristics of the base particles, a yellow color material composition based on a yellow powder having a coating film capable of obtaining sufficient lightness even with a relatively small number of films and film thicknesses And a method of manufacturing the same. Still another object of the present invention is to provide a yellow magnetic toner capable of performing an excellent combined function even in a one-component developing system, and a yellow magnetic printing capable of exhibiting excellent magnetic properties and having excellent weather resistance. It is an object of the present invention to provide a yellow color material composition which can be applied to an ink for use, a yellow paint and the like, and a method for efficiently producing the same.

[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 yellow powder can be obtained by improving the lightness by scattering reflection, and the above object can be achieved.

That is, the yellow colorant composition of the present invention and the method for producing the same are as follows. (1) 550 to 8 having at least one coating film formed on the surface of the base particles by the reaction of a metal salt in an aqueous solvent.
A yellow color material composition containing a yellow powder exhibiting a reflection spectrum having a peak between 50 nm. (2) The yellow color according to the above (1), wherein the coating film formed by the reaction of the metal salt of the yellow powder in an aqueous solvent satisfies the following formula: 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 550 to 850 nm) κ: attenuation coefficient]

(3) The yellow color material composition according to (1), wherein the coating film on the surface of the base particles of the yellow powder is a multilayer film. (4) The yellow color material composition according to (3), wherein each of the multilayer films of the yellow powder is formed by a reaction of a metal salt in an aqueous solvent. (5) The yellow color material composition according to (3), wherein each of the multilayer films of the yellow powder satisfies the following condition.

Nd = mλ / 4 wherein N = n + iκ (i represents a complex number) n: refractive index of a substance constituting the film d: film thickness m: natural number λ: peak of the reflection spectrum of the powder (Where λ is 550 to 850 nm) κ: attenuation coefficient]

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

(11) The coating film formed as an aggregate of the crystallized fine particles is coated with the crystallized fine particles on the surface of the substrate powder in a liquid in which the crystallized fine particles and the base powder are dispersed. The yellow color material composition according to the above (6), wherein the composition is formed by adhering. (12) The coating film formed as an aggregate of crystallized fine particles having voids forms solid fine particles in a reaction solution for forming the coating film, and coats the solid fine particles. The yellow color material composition according to the above (6), which is formed by baking after being taken into the film. (13) The yellow colorant composition according to (12), wherein the reaction solution is an aqueous solution. (14) Before the baking, the coating film in 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 yellow colorant composition according to the above (12), which is characterized in that: (15) The yellow color material composition according to any one of (1) to (14), wherein the yellow powder is dispersed in a dispersion medium containing at least a binder resin. (16) A yellow ink composition comprising the yellow color material composition according to (15). (17) The yellow color material composition according to any one of (1) to (14), further including an adhesive resin layer on the yellow powder. (18) The yellow color material composition according to (17), wherein the adhesive resin layer contains an extender pigment. (19) A yellow toner comprising the yellow color material composition according to (17) or (18).

(20) In a method for producing a yellow color material composition containing a yellow powder, the surface of the base particles is coated so that the yellow powder exhibits a reflection spectrum having a peak between 550 and 850 nm. A method for producing a yellow color material composition, comprising forming at least one coating film by a reaction of a metal salt in an aqueous solvent. (21) The method for producing a yellow colorant composition according to (20), 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 550 to 850 nm) κ: attenuation coefficient]

(22) The method for producing a yellow color material composition as described in (20) above, wherein the coating film formed on the surface of the base particles is a multilayer film. (23) The method according to (22), wherein each of the multilayer films is formed by a reaction of a metal salt in an aqueous solvent.
The method for producing the yellow colorant composition described in the above. (24) The method for producing a yellow color material composition according to the above (22), 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 550 to 850 nm) κ: attenuation coefficient]

(25) The yellow color material composition as described in (20) 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. (26) The coating film, which is formed as an aggregate of crystallized fine particles having voids, is formed so that lightness can be imparted by scattering and reflection of light generated between the surface of the crystallized fine particles and the voids. The method for producing a yellow color material composition according to the above (20), wherein (27) The above-mentioned (25), 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 yellow colorant composition according to the above. (28) The method for producing a yellow colorant composition according to (25), wherein the coating film, which is formed as an aggregate of crystallized fine particles having voids, is a high refractive index film. (29) The method for producing a yellow colorant composition according to (27), wherein the dense film is a silica film. (30) A film-forming substance is added to a liquid in which the crystallized fine particles and the base powder are dispersed, and the crystallized fine particles are added to the base powder. 26. The method for producing a yellow colorant composition according to the above item 25, wherein the composition is formed by attaching the composition to a body surface. (31) 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 yellow color material composition according to the above (25), wherein the composition is formed by baking after being taken in. (32) The method for producing a yellow colorant composition according to (31), wherein the reaction solution is an aqueous solution.

(33) Before the baking, ultrafine particles capable of forming a dense film that closes the voids on the surface of the coating film on the coating film in which the solid phase fine particles are incorporated. The method for producing a yellow color material composition according to the above (31), which comprises coating. (34) The yellow powder is dispersed in a dispersion medium containing at least a binder resin.
The method for producing a yellow color material composition according to any one of 0) to (33). (35) A method for producing a yellow ink composition comprising the method for producing a yellow color material composition according to (34). (36) The method for producing a yellow color material composition according to any one of (20) to (33), wherein an adhesive resin layer is provided on the yellow powder. (37) The method for producing a yellow colorant composition according to (36), wherein an extender is contained in the adhesive resin layer. (38) A method for producing a yellow toner, comprising the method for producing a yellow color material composition according to (36) or (37).

The yellow powder in the yellow coloring material composition of the present invention suppresses the precipitation of a solid phase that does not become a film during the film-forming reaction by the following operations and actions, and the yellow powder is uniformly formed on the surface of the base particles. It is presumed that a coating having a thickness can be formed at a desired thickness. By using a buffer solution as a reaction solvent and adjusting the pH to a certain value, the influence of an acid or alkali is reduced, and erosion of the substrate surface is prevented;
Ultrasonic dispersion not only improves the dispersibility of magnetic particles such as base particles, especially magnetite powder, but also improves the diffusibility of the coating components, and further prevents the adhesion of the coatings to each other. The dispersibility of the body particles is also improved; the components of the coating are deposited at an appropriate reaction speed, and the deposition of a solid phase that does not become a coating is suppressed. By the above comprehensive action, the charge on the surface of the film-coated powder can be kept constant,
Due to the function of the overlay, dispersed particles are obtained without aggregation of the film-coated powder. In order to make full use of the function of the electric double layer, the pH is
It depends on the combination of the substance of the substrate and the type of metal compound formed in the liquid by the film forming reaction, and it is preferable to avoid the isoelectric point of both. Further, at least one layer of the coating film provided on the surface of the base particles is a film made of an aggregate of crystallized fine particles and crystallized fine particles having voids between the crystallized fine particles (hereinafter, simply referred to as a crystallized fine particle constituent film). ) To increase the refractive index difference between the surface of the crystallized fine particles and the voids to cause scattering and reflection of light, to enhance the reflection effect, and to provide a functional powder of yellow 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 yellow color material composition of the present invention obtained as described above is useful as a yellow-colored composite raw material powder which is used as a raw material for pigments, powder metallurgy, ceramic raw materials, electronic industries, and the like. It retains excellent performance that replaces the conventional pigments used for pigments for color inks and fillers for plastics and paper, 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-functionality and decorative or decorative products utilizing the reflected or transmitted colors, pottery, porcelain, glassware, for crafts and arts such as paintings, paints for 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. In other words, the present invention can be applied to yellow multifunctional inks, toners, paints, etc. 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. It is also possible to form a desired image as a toner on a supporting medium and determine the image by visual inspection or by a device.

Hereinafter, the crystallized fine particle constituting film of the present invention will be described in more detail with reference to the drawings. FIG.
Is a cross-sectional view of an example of the yellow colorant composition of the present invention having a crystallized fine particle constituting film 2 on the surface of a base particle 1,
FIG. 2 is an enlarged cross-sectional view of the crystallized fine particle constituting film 2 included in the yellow color material composition of FIG. 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 yellow, so care must be taken in its design. In particular, when the obtained film-coated powder has a strong monochromatic spectrum color like opal, the crystallized particle diameter in the film is uniform at a certain size (about one quarter to one wavelength of light wavelength). It is considered that interference has occurred due to the crystallized fine particles.

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

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

Further, in the yellow color material composition of the present invention, as shown in FIG. 2, the yellow powder contained in the yellow color material composition 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 yellow powder having a crystallized fine particle constituting 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 of No. 3 and the air gap is reduced to reduce 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. 4-269804 describes a colored powder having a coating layer of inorganic pigment particles on the surface. This colored powder has voids between the pigment particles.
It is filled with a mixture of a surface treatment agent and a resin, and does not generate scattering reflection as in the yellow color material composition of the present invention, but is colored in a desired color by the color of the pigment particles themselves. It is. In addition, this
In the colored powder described in JP-A-269804, 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.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the yellow color material composition of the present invention will be described in detail. The yellow color material composition of the present invention contains not only the above-mentioned crystallized fine particle constituting film on the surface of the base particles, but also a multilayer film-coated powder further having a film having another constitution capable of transmitting light. It is. When the metal hydroxide film or the metal oxide film is formed into a plurality of layers by the reaction of a metal salt or the like as the low-refractive-index light-transmitting coating film, the coating film (coating the base particles) is used. A special function can be imparted by adjusting the thickness of each layer of the layer which participates in light interference). For example, an alternating coating film having a different refractive index is provided on the surface of the base particles so that the refractive index n of a substance forming the coating film is satisfied so as to satisfy the following equation (1).
And an alternate film having a thickness d corresponding to an integer m times a quarter of the wavelength of visible light between 550 and 850 nm, the appropriate thickness and number of films provide a wavelength λ between 550 and 850 nm. (Using the interference reflection of Fresnel) is reflected or absorbed.

Nd = mλ / 4 (1)

Utilizing this effect, a film having a film thickness and a refractive index that satisfies the formula (1) is formed on the surface of the base particles at a target wavelength of 550 to 850 nm, Further, the coating with a film having a different refractive index is alternately repeated one or more times on the film.
A film having a reflection peak between 50 and 850 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 the range of 550 to 850 nm, a yellow-colored single-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 lighter, especially when coloring in a yellow 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, the reflection peak is set to 550, which is the target wavelength in the final target film number, using a spectrophotometer or the like.
It is necessary to find optimal conditions to be in the range of ８850 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 in a yellow color system. However, in the case of a curved surface, light incident on and reflected by the powder causes complicated interference. These interference waveforms are almost the same as a flat plate when the number of films is small. However, as the total number increases, the interference inside the multilayer film becomes more complicated. 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 with reference 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 550 to 850 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, solid phase deposition rate, substrate amount, and the like, the film thickness can be accurately controlled, a film having a uniform thickness can be formed, and a desired yellow color can be obtained. As described above, the reflection peak and the absorption bottom are 5 in the final target film number.
By finding optimum conditions while changing film forming conditions such as a film forming solution so as to have a target wavelength in the range of 50 to 850 nm, a yellow color 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. Thereby, the powder can be vividly colored into a desired yellow color system without using a dye or a pigment.

Hereinafter, the yellow color material composition of the present invention and the method for producing the same will be described in detail. In the yellow colorant composition and the method for producing the same according to the present invention, the base particles serving as a control for forming the metal oxide film and the like are
The material is not particularly limited, and may be an inorganic material containing a metal, an organic material, a magnetic material, a dielectric material, a conductor, an insulator, or the like. 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, for example, iron, nickel, chromium, titanium, aluminum, silicon, and the like, calcium, magnesium,
Oxides such as barium or composite oxides thereof may be used. Further, as metal compounds other than metal oxides,
Metal nitride, metal carbide, metal sulfide, metal fluoride,
Metal carbonate, metal phosphate and the like can be mentioned.

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

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

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

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

In the present invention, metals used as metal salts include iron, nickel, chromium, titanium, zinc, aluminum, cadmium, zirconium, silicon, tin, lead,
In addition to lithium, indium, neodymium, bismuth, cerium, antimony and the like, calcium, magnesium, barium and the like can be mentioned. Examples of the salts of these metals include salts of sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, carbonic acid and carboxylic acid. Furthermore, a chelate complex of the metal is also included. As the kind of the metal salt used in the present invention, a suitable metal salt is selected according to the property to be imparted to the surface of the substrate and the means to be applied in the production. The powder of the present invention basically forms a colorless and transparent film, and is formed by laminating films having different refractive indexes to be colored.The above-mentioned metals and salts thereof are mentioned, but only by interference coloration. If the reflection and absorption spectra do not have the desired color, the following metallic cobalt, yttrium,
Sulfur, europium, dysprosium, antimony,
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.
~ 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 of the present invention for producing a yellow color material composition containing a yellow powder, a multilayer coating film may be manufactured as a continuous process, or each coating film may be manufactured one by one. Alternatively, it can be manufactured by various methods such as a combination of a single-layer manufacturing and a multi-layer continuous manufacturing. The particle size of the yellow color material composition according to the present invention is not particularly limited and can be appropriately adjusted depending on the purpose. Usually, it is 0.1 μm to several mm, preferably 0.1 μm to 200 μm.
m.

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 yellow color material composition of the present invention is used as a film-forming reaction solvent at the time of film-forming reaction in the production method, particularly when the film-forming reaction is carried out in an aqueous solvent.
A film coating reaction is formed by a film forming reaction on the surface of a substrate under an ultrasonic dispersion condition using an aqueous solvent under a certain condition. 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, for particles which are difficult to be dispersed due to interparticle attraction such as a magnetic force, it is desirable to form a film after sufficiently dispersing by ultrasonic irradiation or to form a film while performing ultrasonic irradiation. As the ultrasonic dispersion conditions, various ultrasonic oscillators can be used, and 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 → XSi
O ₂ ⁺ 2Na + + 2OH ^-

Next, the crystallized fine particle constituting film of the yellow powder contained in the yellow color material composition of the present invention is:
Any material may be used as long as it can scatter and reflect light to increase the brightness, 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 sintering 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 preferable that the coating be performed after coating with ultrafine particles capable of forming a dense film for closing the voids on the surface, from the viewpoint of the film strength of the obtained yellow powder. Firing is 300
It is preferable to carry out at -1200 ° C.

In addition to the method of forming ultrafine particles that scatter and reflect visible light in a liquid by adjusting the solid phase deposition rate, existing particles can also be used. That is, in the buffer solution, after sufficiently uniformly dispersing the base particles and the crystallized ultrafine particles such as silica or titania in the buffer solution, a solution in which the raw material for coating the film such as silica or titania on the surface is dropped is dropped. By optimizing the solid phase deposition rate so that just a film is formed, the solid phase films deposited on both surfaces of the base particles and the crystallized ultrafine particles are fixed during the stirring, and the base particles are It is covered with crystallized ultrafine particles.

The powder formed in this manner is used in a range of 300 to 1
By baking at 200 ° C., the crystallized ultrafine particles become particles whose particles are covered with a film (particles having a fine particle film), the refractive index of the scattering ultrafine particles is high, and the particle size of the visible light scattering ultrafine particles is Preferably has a particle size that maximizes the scattering power. Especially in titania, 0.2-0.3 μm
The particle size is preferably When the refractive index of the base particles is smaller than the crystallized ultrafine particles, a high refractive index film is formed directly on the base particles, or the outermost layer is formed into a high refractive index film, and then the fine particle film is formed. It may be formed. Conversely, when the refractive index of the base particles is larger than that of the crystallized ultrafine particles, the fine particle film is formed with a film having a low refractive index. Is preferred for maximizing scattering.

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

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

The method for forming the metal compound film will be described below. As a film forming method, a method in which a vapor deposition method such as a PVD method, a CVD method, or a spray dry method is used to directly deposit the vapor on the surface of the base particles is possible. However, the above-mentioned Japanese Patent Application Laid-Open No.
Preferred are the metal alkoxide method described in JP 8604, JP-A-7-90310 or WO 96/28269, and the aqueous method described in 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 the case of producing a yellow color powder contained in the yellow color material composition of the present invention, which has a multilayer film on substrate particles. For example, if the base particles are made of a material having a high refractive index, a light-transmitting film having a low refractive index is provided thereon, and a particle-forming film having a high refractive index is further provided thereon. 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 is further formed thereon, a low-refractive-index light-transmitting film is further formed thereon, and a high-refractive-index particle forming film is further formed thereon. Are provided sequentially.

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

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

After the coating film is manufactured, the inclined cleaning is repeated while adding distilled water to remove the electrolyte, and 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 yellow color material composition according to the present invention, (1) yellow ink or paint-like composition (fluid) and (2) yellow toner, yellow dry ink-like composition (powder) Body) will be described. (1) In the present invention, as a medium (vehicle) of the yellow 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 yellow toner, the yellow dry ink, and the yellow dry paint-like composition (powder) are prepared by adding the yellow color material multilayer coating powder to a resin or, if necessary, a toning material. Is directly kneaded 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. Also, the powder coated with the yellow color material multilayer film can be made into a powdery yellow color material composition by using a polymerization method such as an emulsion polymerization method or a suspension polymerization method.

Further, an additive and a solvent such as a powder coated with a yellow multilayer film, a resin and a toning agent are added to a colloid mill or
It can also be liquefied with this roll to form a liquid yellow colorant composition such as an ink paint. Examples of the toning material for increasing the lightness include white pigments (coloring materials) such as titanium oxide, zinc oxide, tin oxide, silicon oxide, and antimony oxide.
Lead oxides or composite oxides thereof, and carbonates such as calcium carbonate, magnesium carbonate and barium carbonate;
Alternatively, sulfates such as barium sulfate and calcium sulfate, sulfides such as zinc sulfate, composite oxides obtained by sintering the above oxides, carbonates and sulfates, and composite hydrated oxides may be used. In order to adjust the saturation and hue, especially when used for color reproduction in full-color mixing, chromates (red-mouthed lead, chrome vermillion) such as lead, zinc and barium, and sulfurized Sulfides such as cadmium, yellow inorganic pigments such as complex oxide pigments such as titanium yellow, azo dyes and pigments such as Hansa Yellow, Naphthol Yellow, Pigment Yellow and Permanent Yellow, and first dyes such as First Yellow,
Yellow organic dyes and pigments such as oil dye pigments such as oil yellow, alcohol dye pigments such as methanol yellow, and oxides (red-mouthed yellow) such as lead chromate, and composites of chromic acid and lead sulfate (chromium) Vermillion) and other yellow organic dyes and pigments, azo pigments such as permanent orange, benzene orange, Hansa yellow, alcohol dyes such as methanol orange, oil dyes such as oil orange, etc. Is mentioned. However, the present invention is not limited only to these.

Further, in subtle color tone control, blue,
When it is necessary to perform toning using a pigment or dye such as reddish purple, it is preferable to add these pigments to obtain an optimum yellow color. In the case of the powdery yellow color material composition, (a) the resin produced by the above-mentioned pulverization method is not particularly limited, but polyamide, epoxy resin, polyester, melamine resin, polyurethane, vinyl acetate Resins, silicon resins, acrylates, methacrylates, polymers or copolymers of styrene, ethylene, butadiene, propylene and derivatives thereof, and the like. (B) In the case of 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 yellow color material composition of the present invention comprises (1) a yellow ink or a paint-like composition (fluid) and (2) a yellow toner or a yellow dry ink-like composition (powder). In the form of In the case of a fluid state, the ink is a yellow ink, a paint, etc .; the toning material; a resin which is slow to dry; a solidification accelerator; a thickener for increasing the viscosity; and a fluidizing agent for decreasing the 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 is used for the toning material and a resin that is slowly dried, and a fluidizing agent is used for reducing viscosity during kneading. In order to disperse the agent and the particles, components such as a dispersant, a charge controlling agent for fixing to paper or the like, and a wax can be included.
(B) When the polymerization method is used, the above-mentioned toning material, polymerization initiator, polymerization accelerator, thickener for increasing the viscosity, dispersant for dispersing the particles, fixing to paper, etc. And a component such as a wax for charge control.
The multilayer coating powder in the yellow color material composition of the present invention,
A single powder or a combination of multiple powders with different spectral characteristics can be applied to wet and dry color printing and wet and dry color magnetic printing. In addition, visible and invisible light using three primary color powders (Ultraviolet and yellow regions), fluorescence and magnetism, and electricity (electric field changes)
It can be applied to other uses that require a security function, such as a color magnetic ink for preventing forgery of printed matter, having the identification function of the above six combinations.

The yellow colorant composition of the present invention is applied to a substrate by printing, melt transfer or When applied to an object to be coated, the relationship between the content of the yellow color material multilayer film-coated powder and the resin in the yellow color material composition is 1: 0.5 to 1:15 by volume ratio. If the content of the medium is too small, the applied film does not adhere to the object to be coated. On the other hand, if the amount is too large, the color of the pigment becomes too light and cannot be said to be a good ink or paint. Further, the relationship between the amount of the solvent and the total amount of the yellow color material and the resin in the yellow ink or the coating composition is 1: 0.5 to 1:10, 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.

Further, the color density of the coating film when printing, melt-transferring, or applying a coating material to a substrate is determined by the amount of pigment per unit area of the substrate. After the paint is dried, the amount of the powder coated with the yellow color material multilayer film of the present invention on the object to be coated is 0.1 to 300 g per square meter in terms of area density when uniformly applied, and preferably 0.1 to 300 g. If it is 1 to 100 g, a good coating color can be obtained. If the area density is smaller than the above value, the ground color of the object to be coated appears, and if the area density is larger than the above value, the color density of the coating color does not change, which is uneconomical. That is, even if the pigment is placed on the object to be coated to a certain thickness or more, the light does not reach the pigment on the lower side of the coating film. 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. In addition, this does not apply to the case where a specific design is partially formed.

[0079]

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] (Yellow color material composition 1 using magnetic material, aqueous two-layer coating) (Film formation of first layer silica film) (1) Preparation of buffer solution 4 M potassium chloride reagent and 0.4 M boric acid were dissolved to prepare a buffer solution 1. 0.4 M sodium hydroxide was dissolved in 1 liter of water to obtain a buffer solution 2. 250 ml of the buffer solution 1 and 115 ml of the buffer solution 2 were mixed and homogenized to obtain a buffer solution 3. (2) Aqueous sodium silicate solution (water glass solution) The sodium silicate reagent was diluted with pure water, and the concentration was adjusted so that the SiO ₂ content became 10 wt%.

(3) Silica Film 15 g of magnetite powder (average particle size of 2.3 μm) was prepared as 146 ml of a substrate particle prepared in advance.
Was added to a mixture of buffer solution 3 (pH: about 9.0) and 134 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, 134 ml of an aqueous sodium silicate solution also prepared in advance was added at a rate of 40 ml / min, and the reaction was gradually decomposed to deposit a silica film on the surface. After the completion of the aqueous sodium silicate solution, the reaction was further continued for 2 hours, and all the unreacted raw materials were reacted. After the completion of the film forming reaction, the slurry containing the silica film forming powder was repeatedly decanted with sufficient water and washed. After washing, 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.

(3) Titania film 446 ml of buffer solution 4 _per 4 g of powder A1
(PH: about 8.4) prepared, the powder A ₁ to its slow衡溶solution 4, as in the case of the silica film, while ultrasonic dispersion was thoroughly dispersed in an ultrasonic bath. Thereafter, while maintaining the temperature of the solution at 50 to 55 ° C., a total of 52 ml of 10% titanium sulfate aqueous solution prepared in advance was added to 1.9 ml /
Minutes, the solid phase fine particles were precipitated in the solution, and the solution was thinly turbid. 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 has a pale yellow color and its 1 kOe
Was 33 emu / g. Maximum reflection peak of the two-layer film-coated powder A ₂ is 601 nm, was a bright yellow color.

The peak wavelength of the spectral reflection curve of the coating powder of the coating film, the reflectance at the peak wavelength, the refractive index and the film thickness of the coating film 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 yellow multilayer-coated powder A ₃ having been hydrophobic-treated.

(6) Adhesive resin layer (polystyrene composite powder, toner) A high-speed stirrer is used to disperse 100 g of the yellow-colored multi-layer coating powder A ₃ lipophilized in advance by the above surface treatment method into 100 g of styrene monomer. Stir and homogenize. A mixture of the styrene monomer and the particles was prepared by dissolving sodium n-dodecyl sulfate in 500 g of distilled water.
The mixture was charged with high-speed stirring, and the mixture was stirred until the emulsified particles became sufficiently fine. 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 yellow polystyrene-coated powder A. The obtained yellow powder A is spherical, and its magnetization at a magnetic field of 1 kOe is 15.
It was 7 emu / g. Table 1 shows the refractive index and film thickness of the first and second layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0087]

[Table 1]

[Example 2] (Yellow color material composition 2 using magnetic substance, aqueous three-layer coating) (Film formation of first layer silica film) (1) Silica film 15 g of spherical magnetite was used as the base particles. Powder (average particle size: 2.3 μm) was prepared in advance using 249 powder.
ml of the buffer solution 3 (pH: about 9.0) and 169 ml
In pure water to obtain 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, 600
The mixture was dispersed while stirring in a buffer solution 3 containing magnetite powder while applying ultrasonic waves in an ultrasonic bath of W. In addition, 133m prepared in advance
of sodium silicate aqueous solution at 40 ml / min,
The reaction was gradually decomposed to deposit a silica film on the surface.

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

(Formation of Second 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 mixture of purified water 1727Ml, the powder B ₁ to the mixed solution, the silica film As in the case of the above, while the ultrasonic dispersion was being performed, the dispersion was sufficiently performed in the ultrasonic bath. Thereafter, while maintaining the temperature of the solution at 50 to 55 ° C., the previously prepared 10% aqueous solution of titanium sulfate was gradually dropped at a constant rate of 1.8 ml / min. At the beginning of dropping, solid phase fine particles precipitated in the liquid,
It is fixed to the base particle surfaces, or even, its surface is covered by a small ultrafine grain size than the solid phase particles which are fixed to the base particle surfaces, to obtain a silica / titania-coated magnetite powder B _2. The two-layer film-coated powder B ₂ is light yellow, the maximum reflection peak is 622 nm, was the same as the powder A ₁ obtained in Example 1. The surface of the powder B ₂ has slightly uneven, convex portions of the partially titania particles were also observed.

(Formation of Third Layer Silica Film, When Titania Film Surface is Enclosed by Silica Thin Film) Preparation of Buffer Solutions 1 and 2 and Sodium Silicate Aqueous Solution (Water Glass Solution) as in Example 1. Was done. The film of the silica film was carried out in the powdered silica / titania-coated magnetite powder B _2. The volume of the buffer solution was the same as that of the first layer coating, but the film formation was carried out with the same dropping rate of the aqueous solution of sodium silicate and the dropping amount of 8 ml.
The reaction was carried out for a period of time, followed by washing in the same manner as described above, and after the washing, heat treatment (calcination) was performed at 500 ° C. for 30 minutes in a nitrogen atmosphere in a rotary tube furnace to obtain silica / titania-coated magnetite powder B ₃ .

[0092] The obtained powder B _3, during surface smooth silica film two layers, titania fine particles are crystallized, became pale light scattering is large yellow 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, crystallization of titania fine particles was observed between the two silica layers, and voids were present between the particles. Can be This three-layer film-coated powder B ₃
Had a maximum reflection peak of 602 nm.

(Adhesive Resin Layer, Polystyrene Composite Powder) Multilayer coating powder of yellow color material B ₃ 100 which was previously made lipophilic to 100 g of styrene monomer by the above-mentioned surface treatment method.
g was stirred with a high-speed stirrer until 10 g of lipophilic titanium oxide was dispersed and homogenized. A mixture of the styrene monomer and the particles was prepared by dissolving sodium n-dodecyl sulfate in 500 g of distilled water.
The mixture was charged with high-speed stirring, and the mixture was stirred until the emulsified particles became sufficiently fine. 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 yellow polystyrene-coated powder B. The powder of the obtained yellow color material composition B was spherical, and its magnetization under a magnetic field of 1 kOe was 15.7 emu / g. Table 3 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.

[0094]

[Table 2]

[Example 3] (Yellow color material composition 3 using a magnetic material, water-based
(Coating of Layer) (Formation of First Layer Silica Film) As base particles, 40 g of magnetite powder (average particle size: 0.7 μm) was prepared in the same manner as in Example 1 by 3615 g of buffer solution 3 prepared in advance. (pH: about 9.0) and the mixture was put dispersion of purified water 301ml, 28kH _Z, while applying an ultrasonic wave in an ultrasonic bath at 600W, further stirred in slow衡溶solution 3 containing magnetite powder While dispersing. To this, 1506 ml of an aqueous sodium silicate solution also prepared in advance was gradually added at 2.67 ml / min to deposit a silica film on the surface. After the completion of the aqueous sodium silicate solution, the reaction was further continued for 2 hours, and all the unreacted raw materials were reacted. After the completion of the film forming reaction, the slurry containing the silica film forming powder was repeatedly decanted with sufficient water and washed. After washing, put silica film powder in a vat, precipitation was separated, discarding the upper fluid, 0.99 ° C. in air in a drier, dried 8 hours to obtain a silica-coated magnetite powder C _1.

(Formation of Second Layer Titania Film)
Powder C₁In comparison, 6025 g of buffer solution and 6025 ml
Of pure water, and C₁The above silica
As in the case of the membrane, while dispersing the ultrasonic waves,
Dispersed in minutes. After that, keep the temperature of the liquid at 50-55 ° C.
While preparing 2400 ml of sulfuric acid
Titanyl acid aqueous solution (TiO _Two, 15w%) is 1.25m
1 / min.
The dropping was completed while the solution was dropped. After dropping is completed, it is
Reaction, the unreacted components are gradually precipitated, and the particles are
I took it inside. After the film formation reaction, decant with sufficient pure water.
The unreacted portion and excess sulfuric acid and reaction
Remove the sulfuric acid formed by
After drying with a dryer, a dried powder was obtained. Rotate the obtained dry powder
Heat treatment (firing) at 650 ° C for 30 minutes in a tube furnace
Performed, silica / titania coated magnetite powder C_TwoGet
Was. This two-layer film-coated powder C_TwoIs pale yellow and has maximum reflection
The peak was at 602 nm.

[0097] For the silica / titania-coated magnetite powder C ₂ of 15 g (deposition of the third layer silica film), as in the first layer, slow衡溶liquid 3 of 4338g which had been prepared in advance (pH: about 9 .0) and added to a mixed solution of pure water 361 ml, while applying an ultrasonic wave in an ultrasonic bath at 28kH _Z, 600W, further it was dispersed with stirring in slow衡溶solution 3 containing magnetite powder. To this, 1807 ml of an aqueous sodium silicate solution also prepared in advance was gradually added at 2.67 ml / min to deposit a silica film on the surface. After the completion of the aqueous sodium silicate solution, the reaction was further continued for 2 hours, and all the unreacted raw materials were reacted. After the completion of the film forming reaction, the slurry containing the silica film forming powder was repeatedly decanted with sufficient water and washed. After washing, 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 .

(Formation of Fourth Layer Titania Membrane) For 40 g of the above powder C ₃ , 7230 ml of buffer solution 4 and 7230 ml were used.
ml of pure water was prepared, and the powder C ₃ was sufficiently dispersed in the mixed solution in an ultrasonic bath while being subjected to ultrasonic dispersion in the same manner as in the above-described silica film formation. Thereafter, the temperature of the liquid is raised to 50-55.
2928 prepared in advance while maintaining at
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 precipitating solid phase fine particles and making the liquid slightly cloudy. After the completion of the dropping, the reaction was further performed for 3 hours, and the unreacted portion was gradually precipitated as solid fine particles, and the fine particles were incorporated into the film. After completion of the film-forming reaction, decantation was repeated with sufficient pure water to remove unreacted components and excess sulfuric acid and sulfuric acid formed by the reaction, to perform solid-liquid separation, and to obtain a dried powder after drying with a vacuum dryer. .

[0099] 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 was yellow and had a maximum reflection peak of 598 nm.

(Preparation of Yellow Ink Composition) 30 g of the silica / titania-coated magnetite powder C ₄ thus obtained was previously added to 80 g of ethanol and 2.5 g of an acrylic polymer (Technobit, manufactured by Kulzer).
Is dispersed in a solution in which is dissolved, and a mixed solution obtained by adding 20 g of titanium oxide (hydrophobic silicone 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 yellow coloring material. A paint dispersion liquid CL of the composition was obtained.

(Coating and Spectral Characteristics) The dispersion liquid CL of the yellow ink composition was applied to art paper using a blade coater. The coating amount (after drying) of the yellow color material composition was 60 g / m ² . After drying, the obtained coated paper C
Has a maximum reflection peak wavelength of 598 nm and is a bright yellow color. The magnetization of the coated paper C at kOe per 1 m ² was 1020 emu / cm ² .
Table 3 shows the refractive index and film thickness of the first to fourth layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0102]

[Table 3]

[Example 4] (Yellow 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 manufactured by BASF The magnetization at 1.8 μm and 10 kOe is 2
03 emu / g) was previously dispersed in a solution in which 8.8 g of silicon ethoxide was dissolved in 158.6 g of ethanol, and then, with stirring, 8.8 g of aqueous ammonia (29%) prepared in advance. And 11.7g
Of deionized water was added. 5 hours after addition,
The reaction was performed at room temperature. After the reaction, the reaction mixture was diluted and washed with sufficient ethanol, filtered, and dried in a vacuum drier at 110 ° C. for 3 hours. After drying, using a rotary tube furnace, 30 min heat treatment at 800 ° C. in a nitrogen atmosphere subjected to (firing), and cooled to obtain a silica-coated iron powder D _1.

[0104] In (second layer Titania film of film) In a separable flask, the silica-coated powder D ₁ of the 20g, submerged plus titanium isopropoxide 8.1g of ethanol previously 198.3g After stirring, 6.0 g of pure water prepared in advance was added to 4 parts with stirring.
A solution mixed with 7.9 g of ethanol was taken for 1 hour,
It was dropped. After the addition, the reaction was carried out at room temperature for 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 average thickness of this titanium oxide film was 93 nm, had a peak wavelength of a spectral reflection curve at 600 nm, and was pale yellow.

(Formation of Third Layer Silica Film) 158.6 g of silica / titania-coated iron powder D ₂ was previously prepared in an amount of 158.6 g.
After dispersing in a solution prepared by dissolving 11.4 g of silicon ethoxide in ethanol, 11.4 g of ammonia water (29%) and 15.2 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 1 hour. After the reaction, the mixture is diluted and washed with sufficient ethanol, filtered, and dried at 110 ° C. in a vacuum drier at 3 ° C.
Dried for hours. After drying, 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 observing the particle state in the layer of the titania layer after the heat treatment using a transmission electron microscope,
Titanium oxide crystallized fine particles of 10 to 150 nm are seen,
Voids of about 10 to 50 nm were observed between the particles. However, the silica layer is dense, without particles,
It was smooth. Further, voids existed at the interface with titania.

The maximum reflection peak wavelength of this powder D ₃ is 60
At 0 nm, it became pale yellow. From Example 4, the crystal particles of the titania particles are changed according to the presence or absence of heat treatment (calcination).
Voids were observed between the particles and the silica film due to the particle formation, and it is considered that yellowing was achieved due to the scattering and reflection effect accompanying the particle formation. One of the features of the yellow color material powder of Example 4 is that a dense film is formed on the final coating layer. The void is covered with a dense film that does not affect interference and scattering, not limited to a high refractive index film as in the last layer. In the prior art, when the obtained powder is used as a pigment such as a toner or a paint, a resin or a vehicle enters the voids, and the difference in the refractive index between interference and scattering particles is reduced, and the Fresnel reflectance is reduced. was there. However, 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) A high-speed stirrer is used until 100 g of styrene monomer and 100 g of yellow-colored-colored-material-coated powder (silica / titania-coated iron powder D ₃ ) and 45 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 filter paper to obtain yellow polystyrene-coated powder D. The powder of the obtained yellow color material composition D is spherical, and has a magnetization of 16.6 e at a magnetic field of 1 kOe.
mu / g, and the magnetization at a magnetic field of 10 kOe is 50.5 e.
mu / g. Refractive index, film thickness of the first to third layers,
Table 4 shows the peak wavelength of the spectral reflection curve of the coated powder and the reflectance at the peak wavelength.

[0108]

[Table 4]

[Example 5] (Yellow coloration of magnetite powder particles, aqueous four-layer coating, use of existing titania particles) (First layer silica film formation) As in Example 1, buffer solutions 1, 2 and Sodium silicate aqueous solution (water glass solution)
Was prepared. (1) Silica film Spherical magnetite powder (average particle size 2.3 μm) 15 g
Put in 680 ml of buffer solution prepared in advance,
While applying ultrasonic waves in a 26 kHz, 600 W ultrasonic bath, it is further dispersed while stirring in a buffer solution containing magnetite powder. To this, 203 ml of an aqueous sodium silicate solution (40 ml /
Min), and the reaction was slowly decomposed 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 is repeatedly decanted with sufficient water to be washed. After washing, the silica film powder is put into a vat, sedimented and separated, and the upper solution is discarded. The resultant is dried in a dryer at 150 ° C. for 8 hours in air and heat-treated at 500 ° C. for 30 minutes in a nitrogen atmosphere to coat the silica. to obtain a magnetite powder E _1.

(Second Layer Titania Film Formation) (1) Titania Film Formation A buffer solution 4 and an aqueous solution of titanium sulfate were prepared and prepared in advance in the same manner as in Example 1. E obtained
_{1 For} 4.0 g, 250 ml of buffer solution and 250 m of pure water
1 and then, while ultrasonically dispersing E ₁ in the solution, sufficiently dispersing it in an ultrasonic dispersion tank, and keeping the temperature of the solution at 60 ° C., a titanium sulfate aqueous solution prepared in advance. 67 g is gradually dropped at a constant rate of 1.5 ml / min. At the beginning of the dropping, fine particles in the liquid were precipitated, but were fixed on the surface of the core powder, and the surface was covered with fine particles having a larger particle diameter of 0.01 to 0.5 μm.

(2) Washing and drying After the completion of the film forming reaction, decantation was carried out with pure water to remove unreacted components, excess sulfuric acid and sulfuric acid formed by the reaction.
After performing solid-liquid separation and drying with a vacuum drier, a dried powder was obtained.
The obtained dried powder is heated at 650 ° C. in a rotary tube furnace for 3 hours.
It performed 0 min heating process (baking), to obtain a silica / titania-coated magnetite powder E _2. The color of the resulting E ₂ is light yellow, the reflection peaks of the two-layer coating was 602 nm. The surface of the E ₂ is slightly has irregularities, also the convex portion of the partially titania fine seen.

(Formation of Third-Layer Silica Dense Film) (When the Film Surface is Enclosed by a Thin Silica Film) As in Example 1, the preparation of buffer solutions 1 and 2 and an aqueous solution of sodium silicate (water glass solution) were performed in advance. went. (1) Silica film 15 g of titania / silica coated powder E ₂ was put into 80 ml of a buffer solution prepared in advance, and the dropping rate of the silica raw material solution was the same as in the case of the first layer coating. The membrane was formed with a volume of 19 ml, and reacted for 2 hours until no unreacted substance was found. After the completion of the film forming reaction, the slurry containing the silica film forming powder is repeatedly decanted with sufficient water to be 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., dry 8 hours to obtain a silica-coated magnetite powder E ₃ was heat-treated for 30 minutes at 500 ° C. in a nitrogen atmosphere. This three-layer film-coated powder E ₃ was pale yellow, and its magnetization at 1 kOe was 38 emu / g. The resulting silica / titania-coated magnetite powder E _{3 has} a titania coating film thickness of 72.
nm. The reflection peak of this three-layer coating is 604n.
m, and the reflectance at the peak wavelength was 47%.

(Fourth Layer Crystallized Fine Particle Constituent Film (Scattering Film)
As in Example 1, a buffer solution 4 and an aqueous solution of titanium sulfate were prepared and prepared in advance. To 10 g of the obtained E _{3, 7} g of ultrafine titanium oxide crystal particles (CR-5 manufactured by Ishihara Sangyo Co., Ltd.) was added to 800
The mixture was added to the mixture and dispersed well. The container containing the suspension, 200 W, placed in a water bath of an ultrasonic cleaning tank 28kH _Z ((Ltd.) Iuchi Ltd., US-6 type) and stirred. Ultrasonic waves were oscillated and dispersed at the same time as the stirring was started. Next, 1
30 ml of a 0% by weight aqueous sodium silicate solution was added to 40 ml
/ Minute, and the reaction was gradually decomposed to deposit a silica film on the surface. After the completion of the dropwise 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 ion-exchanged water and washed. After the washing operation, the silica film powder was put into a vat, sedimented and separated, and the upper solution was discarded.
After drying at 0 ° C. for 8 hours, heat treatment was performed in air at 500 ° C. for 30 minutes to obtain a silica-coated magnetite powder E ₄ .

(Fifth Layer Silica Dense Film Forming) To 37 g of silica / titania-coated magnetite powder E ₄ , put in a previously prepared mixed solution of 460 ml of buffer solution 1 and 500 ml of pure water, and apply 28 kHz, 600 W While applying ultrasonic waves in an ultrasonic bath, and further stirring and dispersing in a buffer solution containing magnetite powder. To this was added 14 ml (4 ml / min) of an aqueous solution of sodium silicate that had been prepared in advance, and the mixture was gradually decomposed by reaction 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 is repeatedly decanted with sufficient water to be washed. After washing, the silica / titania film powder was put into a vat, sedimented and separated, and the upper liquid was discarded. The dried product was dried in a dryer at 150 ° C. for 8 hours in air, and 500 ° C. in a nitrogen atmosphere.
In to obtain a silica / titania-coated magnetite powder E ₅ was heat-treated for 30 minutes. This five-layer film-coated powder E ₅ is pale yellow,
Its magnetism was 18 emu / g at 1 kOe. The thickness of the obtained silica / silica film of titania-coated magnetite powder E ₅ is was 9 nm. The reflection peak of this five-layer coating is 604 nm, and the reflectance at the peak wavelength is 91.
%Met.

(Adhesive resin layer, polystyrene composite powder) Multilayer coating powder of yellow color material E ₅ 100 which was previously made lipophilic to 100 g of styrene monomer by the surface treatment method described above.
g was stirred with a high-speed stirrer until 45 g of lipophilic titanium oxide was dispersed, and the mixture was homogenized. A mixture of the styrene monomer and the particles was prepared by dissolving sodium n-dodecyl sulfate in 500 g of distilled water.
The mixture was charged with high-speed stirring, and the mixture was stirred until the emulsified particles became sufficiently fine. 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 yellow polystyrene-coated powder E. The powder of the obtained yellow color material composition E was spherical, and its magnetization under a magnetic field of 1 kOe was 9.1 emu / g. 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.

[0117]

[Table 5]

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

(Second Layer Silica Film Forming) To 212 ml of buffer solution 3 prepared in the same manner as in Example 1, 212 ml of pure water also prepared in advance was mixed, and 15 g of powder F was prepared.
After adding ₁ and mixing well, the mixing ratio of SiO ₂ is 10 wt%.
Of water glass solution 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.

(Third Layer Titania Film Forming) Further, 4 g of the silica / titania film-coated iron powder F ₂ was sufficiently dispersed in 446 ml of the buffer solution 4 and then 35 ml of a 15 wt% TiO ₂ aqueous solution of titanyl sulfate was added for 4 hours. The mixture was allowed to react for 1 hour after the addition to remove unreacted raw materials. After the reaction, solid-liquid separation is performed by decantation, and the powder is dried for 8 hours with a vacuum dryer.
Using a rotary tube furnace, 30 minutes at 500 ° C in a nitrogen atmosphere
Was separated heat-treated, to obtain a silica / titania film-coated iron powder F _3.
The peak of this powder was 601 nm, the reflectance was 46%, and the powder was deep yellow. The magnetization of this powder at a magnetic field of 1 kOe was 34.1 emu / g, and the magnetization at 10 kOe was 10 emu / g.
It was 5 emu / g.

(Formation of toner) 100 g of styrene monomer,
After mixing a liquid in which 0.3 g of oil green 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 added to 7
After adding 3 g of sodium dodecyl sulfate at 0 C to the solution with a stirrer dissolved in distilled water, the homogenizer was used to add 10.0 g of sodium dodecyl sulfate.
The mixture was stirred at 00 rpm, and while 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 yellow polystyrene-coated powder FP. The magnetic field of this powder at 1 kOe was 16.2 emu / g, and the magnetization at 10 kOe was 50.0 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.

[0122]

[Table 6]

Example 7 (Yellow color material composition 7 using plate magnetic material, three-layer coating with metal alkoxide hydrolysis and water 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, 8.8 g of silicon ethoxide is added and mixed, and 8.8 g of water and 11.7 g of aqueous ammonia are further added. 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 Coloring) 10 g of silica-coated Ba-based ferrite particles G ₁ were sufficiently dispersed in 159 g of ethanol, 6.9 g of titanium isopropoxide was added, mixed well, and further prepared in advance. Water 1
A mixed solution of 1.7 g and 30 g of ethanol was dropped and reacted for 5 hours. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried by vacuum drying for 8 hours, and then heat-treated at 650 ° C. for 30 minutes in a nitrogen atmosphere using a rotary tube furnace to obtain silica-titania film-coated Ba ferrite particles G ₂ I got
The peak of this powder was 606 nm, the reflectance was 44%, and the powder was deep yellow. The magnetization of this powder at 10 kOe was 19.2 emu / g and the residual magnetization was 12.1 emu / g.
mu / g.

[0125] For (third layer scattering film coating) prepared beforehand G ₂ powders buffer solution A500ml, was also prepared in advance 8
75 ml of the buffer solution 3 was mixed, 10 g of G ₂ powder and 5 g of titanium oxide (rutile type) powder particles having an average particle size of 0.2 μm were added thereto and mixed well. The solution was stirred for 1 hour with stirring for 135 ml. After repeating decantation 20 times and thoroughly washing,
It dried at 120 degreeC with a dryer for 8 hours. The dried powder was heat-treated 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 600 nm, the reflectance was 68%, and the powder was pale yellow. In addition, 1 of this powder
The magnetization at 0 kOe was 13.1 emu / g, and the residual magnetization was 8.6 emu / g. Table 7 shows the refractive index, the film thickness of the first to third layers, the peak wavelength of the spectral reflection curve of the coated powder, and the reflectance at the peak wavelength.

[0126]

[Table 7]

[0127] 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.

[0128] In the detection device provided with the (coated material) after drying the magnetic head, it was scanned over the film, but in the printed portion of the magnetic powder G ₃ are magnetically reaction was detected,
There was no magnetic reaction in the blank area. The coated product was yellow when viewed from above, but when viewed obliquely at an angle of 30 degrees, it appeared blue-green and exhibited polychromaticity.

[Example 8] (Yellow color material composition using plate-like mineral, three-layer coating by metal alkoxide hydrolysis)
(Coating film) (First layer coating and coloring) After sufficiently dispersing 20 g of plate-like aluminum powder coated with an average particle diameter of 12 μm in 160 g of ethanol, 7.0 g of titanium isopropoxide was added and mixed well, and further prepared in advance. A mixed solution of 12.0 g of water and 30 g of ethanol was dropped and allowed to react for 5 hours.
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 to obtain a titania film-coated plate-like aluminum powder H _1. I got The peak of this powder is 6
At 05 nm, the reflectance was 43%, and it was deep yellow.

(Second Layer Coating) After sufficiently dispersing 20 g of titania-coated plate-like aluminum powder H ₁ in 80 g of ethanol, 11.7 g of silicon ethoxide was added and mixed, and 11.7 g of water and 15 g of aqueous ammonia were further added. After adding 0.5 g, the mixture was reacted for 3 hours while stirring at room temperature. After the reaction, solid-liquid separation was carried out 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 silica-titania-coated plate-like aluminum powder H _2. I got

(Third Layer Colored Film Coating) 20 g of silica / titania-coated plate-like aluminum powder H _{2 was} mixed with 160 g of ethanol.
After sufficiently dispersing the mixture, 9.2 g of titanium isopropoxide was added thereto, and the mixture was sufficiently mixed. Then, a mixed solution of 15.6 g of water and 30 g of ethanol prepared in advance was added dropwise and reacted for 5 hours. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried 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 a silica / titania film-coated aluminum powder H _3. I got The peak of this powder was 610 nm, the reflectance was 63%, and the powder was pale yellow. 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.

[0132]

[Table 8]

(Application) While stirring and dispersing 15 g of the powder H _3, an ethanol solution (50 g of ethanol) in which 2.2 g of an acrylic resin was dissolved was added and dissolved. When a part of the solvent was dispersed and the viscosity was increased, the dispersion was spread on a flat glass plate and further uniformly attached to a rubber roller.
The viscous fluid HL was applied to the thermal transfer film of the plate and left for one day to dry. When the powder coated film obtained is viewed vertically, a pale yellow band is seen. In addition, when the plate is tilted toward the sun and the viewing angle is changed, when the sun is turned back (almost vertical light)
Was pale yellow, but when viewed at an angle of 40 degrees between the sun and the plate (incident angle), the color took on a bluish green color, indicating polychromaticity. This property is a polychromatic display medium,
It can be used for cosmetics, ornaments, or flip-flop method.

Example 9 (Yellow color material composition using plate-shaped conductor, three-layer coating by metal alkoxide hydrolysis)
(Coating) (First layer coating and coloring) After sufficiently dispersing 18 g of plate-like aluminum powder coated with an average particle diameter of 12 μm in 160 g of ethanol, 7.0 g of titanium isopropoxide was added, and the mixture was sufficiently mixed and further prepared in advance. A mixed solution of 12.0 g of the saved water and 160 g of ethanol was dropped and reacted for 5 hours. After the reaction, solid-liquid separation was performed by decantation, and the powder was dried in vacuum and then dried for 8 hours.
Heat treated for 30 minutes at 500 ° C. in a nitrogen atmosphere to obtain a titania film-coated plate-shaped aluminum powder I _1. The peak of this powder was 609 nm, the reflectance was 43%, and the powder was deep yellow.

(Second Layer Coating) After sufficiently dispersing 18 g of titania-coated plate-like aluminum powder I ₁ in 160 g of ethanol, 11.7 g of silicon ethoxide was added and mixed.
Further, 11.7 g of water and 15.5 g of aqueous ammonia were added, and the mixture was 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

(Coating of Colored Film of Third Layer) To 18 g of silica / titania-coated plate-like aluminum powder I _2, g was sufficiently dispersed in 160 g of ethanol, and then titanium isopropoxide was added.
After adding 2 g and mixing well, a mixed solution of 15.6 g of water and 60 g of ethanol prepared in advance was further added dropwise and reacted for 5 hours. After the reaction, solid-liquid separation was carried out 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 a silica / titania film-coated plate-like aluminum powder I. _Three
I got This powder has a peak at 612 nm and a reflectance of 66.
%, Pale yellow. 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.

[0137]

[Table 9]

(Coating) A double-sided adhesive tape was applied to a white vinyl chloride plate having a width of 3 mm and a length of 80 mm, a single side of 57 mm and a thickness of 1.5 mm.
Seven strips each having a length of 57 mm and a length of 57 mm were prepared, and one sheet was stuck at the center in parallel with a single side of the plate, and then stuck in parallel from the center strip tape at an interval of 3 mm. Thereafter, 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 pale yellow band was observed, and polychromaticity was recognized as in Example 8.

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

As is clear from Tables 9 to 10, all of the yellow color material compositions of Examples of the present invention had a high brightness and a bright yellow color. In particular, the powder of Example 5 used the existing fine particles as the fine particles of the crystallized fine particle constituting film, so that the particle diameter of the fine particles was relatively large and the scattering reflection was large, and satisfactory results were obtained.

[0141]

As described above, the yellow colorant composition of the present invention can be produced at a lower production cost than the alkoxide method by using water as a solvent during the film forming reaction in the production method. It is possible to obtain an effect that a film can be formed, an organic solvent having high flammability is not used, a manufacturing facility does not require explosion-proof equipment, and temperature and humidity can be easily controlled. Further, the yellow color material composition and the method for producing the same of the present invention have a coating film on the surface of the base particles, and at least one layer of the coating film has a gap between the crystallized fine particles and the crystallized fine particles. By forming a layer consisting of an aggregate of crystallized fine particles having, by increasing the refractive index difference between the crystallized particle surface and the voids, scatter and reflect light, enhance the reflection effect, and have excellent brightness It has become possible to provide a yellow colorant composition containing a functional powder. In addition, in forming a crystallized ultrafine particle constituent film, in addition to a method of forming ultrafine particles that scatter and reflect visible light in a liquid by adjusting a solid phase deposition rate, existing particles are incorporated into the film to manufacture. By forming a film, the crystallized ultrafine particles contained in the film tend to have a relatively large particle size, so that the degree of scattered reflection increases, and a yellow color material composition having higher lightness can be obtained.

When a magnetic substance, a conductive substance or a dielectric substance is used as the base of the yellow powder contained in addition to having these excellent functions, it reacts by an external factor such as an electric field or a magnetic field, and thereby has a moving force and a rotational force. Has a function of exerting an additional action such as movement, heat generation, etc. For example, when a magnetic substance is applied as a base, a yellow color material composition applicable to a color magnetic toner, a color magnetic ink, a yellow paint, and the like, and its efficient It is possible to provide a manufacturing method. In addition, it is used for decorative goods, pottery, porcelain, glassware, paintings and other crafts and arts, paints for books, automobiles and bicycles, etc. Functional inks, toners, paints, cosmetics can be made, and a paint with excellent weather resistance and environmental purification properties such as air and water can be made by the catalytic titanium oxide film.
In addition, the present invention can be applied to yellow multifunctional inks, toners, paints, etc. 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 functions of magnetism, electric field, color, particle shape, fluorescence emission, phosphorescence emission, specific ultraviolet region reflection absorption and specific infrared reflection absorption. It is possible to provide a yellow color material composition and a method for producing the same, which can form a desired image on a support medium as a toner, and can be visually discriminated and discriminated by a device, and can contribute to the industry. Is big.

[Brief description of the drawings]

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

FIG. 2 is an enlarged cross-sectional view of a crystallized fine particle constituting film 2 included in a yellow powder contained in the yellow 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-machi, Nishitama-gun, Tokyo Inside the Iron Mining Co., Ltd. (72) Inventor Katsuto Nakatsuka 4-chome, Moiwadai, Taihaku-ku, Sendai City, Miyagi Prefecture 5 1403 F term (reference) 4J037 AA04 AA09 AA14 AA18 AA19 AA22 AA25 AA26 AA27 AA30 CA05 CA14 CA18 CA20 CB09 CC02 CC12 CC13 CC15 CC16 CC22 CC23 CC24 CC26 CC27 CC28 DD02 EE04 EE08 EE13 FE1 FE1 001 CB DA021 DA041 DA101 DA111 DD001 DF021 DG291 DH001 HA066 HA076 HA106 HA186 HA216 HA296 HA316 HA356 HA406 HA446 HA486 HA526 HA536 HA546 HA556 KA08 KA15 NA01 NA03 4J039 AB12 AD01 AD09 AD15 AE01 AE02 AE03 AE04 AE06 BA25 BA18 BA36 BA37 BA38 BE01 CA07 DA02 EA17 EA34 GA13 GA24

Claims (34)

[Claims] 1. A coating film formed on a surface of a base particle by a reaction of a metal salt in an aqueous solvent, and
A yellow color material composition containing a yellow powder exhibiting a reflection spectrum having a peak between 550 and 850 nm. 2. The yellow coating according to claim 1, wherein the coating film formed by the reaction of the metal salt of the yellow 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 550 to 850 nm) κ: attenuation coefficient] 3. The coating film of the yellow powder on the surface of the base particles is a multilayer film.
The yellow colorant composition described in the above. 4. The multi-layer film of the yellow powder,
The yellow colorant composition according to claim 3, wherein the composition is formed by a reaction of a metal salt in an aqueous solvent. 5. Each of the multilayer films of the yellow color powder is:
4. The yellow color material composition according to claim 3, wherein all of the following conditions are satisfied. 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 550 to 850 nm) κ: attenuation coefficient] 6. The method according to claim 1, wherein at least one layer of the coating film on the surface of the base particles of the yellow powder is formed as an aggregate of crystallized fine particles having voids. The yellow 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. 7. The yellow 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 yellow coloring material composition according to claim 6, wherein 9. The yellow coloring material composition according to claim 6, wherein the coating film formed as an aggregate of crystallized fine particles having voids is a high refractive index film. 10. The yellow color material composition according to claim 8, wherein said dense film is a silica film. 11. The coating film formed as an aggregate of crystallized fine particles adheres the crystallized fine particles to the surface of the base powder in a liquid in which the crystallized fine particles and the base powder are dispersed. The yellow colorant composition according to claim 6, wherein the composition is formed by causing the colorant to be colored. 12. 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 forms the solid phase fine particles. 7. The yellow color material composition according to claim 6, wherein the composition is formed by baking after being taken into a coating film. 13. The yellow colorant composition according to claim 12, wherein the reaction solution is an aqueous solution. 14. 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 yellow colorant composition according to claim 12, wherein 15. The yellow color material composition according to claim 1, wherein the yellow powder is dispersed in a dispersion medium containing at least a binder resin. 16. The yellow color material composition according to claim 1, further comprising an adhesive resin layer on the yellow powder. 17. The yellow color material composition according to claim 16, wherein the adhesive resin layer contains an extender pigment. 18. A method for producing a yellow color material composition containing a yellow powder, wherein the yellow powder comprises 5
A yellow 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 50 and 850 nm. Method of manufacturing a product. 19. The production of a yellow color material composition according to claim 18, wherein the coating film formed by the reaction of the metal salt in an aqueous solvent is formed so as to satisfy the following formula: Method. Nd = mλ / 4 [wherein, N = n + iκ (i represents a complex number) n: Refractive index of a substance constituting the film d: Film thickness m: Natural number λ: Wavelength of a peak in the reflection spectrum of the powder ( However, λ is 550 to 850 nm) κ: attenuation coefficient] 20. The method for producing a yellow color material composition according to claim 18, wherein the coating film formed on the surface of the base particles is a multilayer film. 21. The method for producing a yellow color material composition according to claim 20, wherein each of the multilayer films is formed by a reaction of a metal salt in an aqueous solvent. 22. The multilayer film according to claim 20, wherein each of the films is formed so as to satisfy the following condition.
The method for producing the yellow 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: Wavelength of a peak in the reflection spectrum of the powder ( However, λ is 550 to 850 nm) κ: attenuation coefficient] 23. The production of a yellow color material composition according to claim 18, 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. 24. The method according to claim 24, wherein the coating film formed as an aggregate of crystallized fine particles having voids is formed so that lightness can be imparted by scattering and reflection of light generated between the surface of the crystallized fine particles and the voids. A method for producing a yellow colorant composition according to claim 23. 25. A dense film formed 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. 24. The method for producing a yellow colorant composition according to 23. 26. The method for producing a yellow colorant composition according to claim 23, wherein the coating film formed as an aggregate of crystallized fine particles having voids is a high refractive index film. 27. The method for producing a yellow colorant composition according to claim 25, wherein the dense film is a silica film. 28. The coating film formed as an aggregate of crystallized fine particles, a film-forming substance is added to a liquid in which the crystallized fine particles and a base powder are dispersed, and the crystallized fine particles are dispersed in the liquid. 24. The method for producing a yellow colorant composition according to claim 23, wherein the method is formed by attaching the composition to a substrate powder surface. 29. 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. 24. The method for producing a yellow colorant composition according to claim 23, wherein the composition is formed by baking after being taken into the covering film. 30. The method for producing a yellow colorant composition according to claim 29, wherein the reaction solution is an aqueous solution. 31. 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. 30. The method for producing a yellow color material composition according to claim 29, wherein: 32. The method for producing a yellow coloring material composition according to claim 18, wherein the yellow powder is dispersed in a dispersion medium containing at least a binder resin. 33. The method for producing a yellow color material composition according to claim 18, wherein an adhesive resin layer is provided on the yellow powder. 34. The method for producing a yellow colorant composition according to claim 33, wherein an extender is contained in the adhesive resin layer.