JP2003286690A - Colored article and coloring method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored article capable enhancing preventing effects on its forgery, ascertaining its genuineness, and highlighting itself and to provide a coloring method therefor. <P>SOLUTION: The colored article has two or more colored regions each of which is colored by each of two or more dyestuffs different from each other, wherein at least one of the used dyestuffs comprises such a dyestuff that brings about color change in a region colored by the dyestuff according to change of an angle of viewing the region. The dyestuff bringing about the color change in the colored region according to the change of the angle of viewing it comprises a film-coated powder having a coating film on the surfaces of base particles, and has such a spectrophotometric characteristic that a ratio of H/W (H is height of a peak; and W is a half-width value) is in a range of 0.5-5, when normal incidence reflectivity of the film-coated powder is measured and when a reflected spectrum thereof is plotted by expressing a width at 400 nm between 380 nm and 780 nm [definite range of wavelength (L)] and a normal height of the reflectivity [definite range of reflectivity (R)] in a ratio of 5 to 2. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring matter and a coloring method, and more particularly to a coloring effect that can prevent counterfeiting of banknotes, securities, etc. and can enhance the effect of making colors more vivid and conspicuous from the surroundings. And a coloring method.

[0002]

2. Description of the Related Art Conventionally, currency bills, other gift certificates, gift certificates, event tickets, securities, etc. are used for printing, coating, etc. in order to facilitate indicators of economic, distribution, and market value levels and their facilitation. Used in form. These printed materials, coated materials, etc. are usually items such as paper sheets, etc. showing the characteristics of the printed materials, printed, coated, etc., and are lightweight and small in size, and are convenient to carry, store and use. Is. However, since it uses materials that are familiar to ordinary people, such as pieces of paper, it was sometimes illegally copied or forged.

For the purpose of preventing such forgery, conventionally, a seal imprint of a seal, a handwriting with a signature, a watermark, and the like have been used as the identification means. However, these identification means are easily imitated by persons with special skills, copying / printing technology developed in recent years, and the like. It is still in use today, but its creditworthiness is actually declining. Further, in recent years, bar code markers and the like have also been used. However, since this bar code mark is an inorganic pattern diagram consisting of streaks, it has a drawback that it spoils the elegant image of the securities and is easily imitated by advanced image analysis / reproduction technology. There is also.

Further, a method is adopted in which the securities are printed as a printed matter using a magnetic card or magnetic ink and the magnetism is identified. However, printed materials using these magnetic cards and magnetic inks are easily counterfeited because the black or black-brown color tone that magnetic powders generally have impairs aesthetics and makes it easy to understand the use of the magnetic identification function. There was also a problem that Furthermore, a method has been adopted in which a fluorescent substance is included in printing ink to identify the visible fluorescent color of the printed matter. However, this method of identifying the visible fluorescent color is usually a method of irradiating with a fluorescent light and recognizing the color with the naked eye, and is not suitable for strict authenticity determination or forgery prevention.

Further, in recent years, it is sometimes desired to make an object more conspicuous than surrounding objects. For example, many people prefer to express their presence, identity, individuality, sensibility, etc. For that purpose, clothes, other belongings / carrying items, and signs are given design characteristics so that they stand out from the surroundings. However, since there are innumerable various personalities, it is no longer possible to obtain a sufficient conspicuous effect by imparting design characteristics as in the past.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a colored product and a coloring method capable of overcoming the above-mentioned drawbacks of the prior art and improving anti-counterfeiting, authenticity discrimination, and conspicuous effect. .

[0007]

As a result of earnest studies, the present inventors were able to solve the above problems by adopting the following constitution. That is, the present invention is as follows. (1) A colored product having a plurality of colored regions each colored with a plurality of different dyes, wherein at least one of the dyes is used.
A colored product characterized in that the seed causes a color change of a colored region using the dye depending on a viewing angle. (2) Reflection in the case where the dye that causes a color change in the colored region depending on the viewing angle is a film-coated powder having a coating film on the surface of substrate particles, and the vertical reflection of the film-coated powder is measured. 400 between 380 and 780 nm in the spectrum
When the width of nm <specified wavelength width L> and the vertical axis reflection height (reflectance specified width R) are displayed in a ratio of 5 to 2, the ratio of the peak height (H) to the half width (W) ( (H / W) has a spectrophotometric characteristic in the range of 0.5 to 5, and the colored product according to (1) above. (3) The colored product according to (1) above, wherein at least one of the dyes emits fluorescence. (4) The colored product according to (1) above, wherein at least one of the dyes has magnetism.

(5) The colored product according to (1) above, which is capable of preventing forgery and discriminating authenticity. (6) The above (1), which has a noticeable effect.
The colored product described. (7) The colored product according to (1), which is a printed product. (8) The colored product according to (1), which is a coated product. (9) The colored product according to (1) above, which is a molded product molded from a composition containing the dye.

(10) A coloring method of providing a plurality of colored regions respectively colored with a plurality of different dyes, wherein at least one of the dyes causes a color change of the colored region using the dye depending on a viewing angle. What is used is a coloring method. (11) A film-coated powder having a coating film on the surface of substrate particles as the dye that causes a color change in the colored region depending on the viewing angle, and reflection when the vertical reflection of the film-coated powder is measured. When the 400 nm width in the spectrum between 380 and 780 nm <wavelength specified width L> and the vertical axis reflection height (reflectance specified width R) are displayed in a ratio of 5 to 2, the peak height (H) and the half value width The ratio (H / W) with (W) is 0.5 to 5
The coloring method according to the above (10), wherein a coloring agent having a spectrophotometric characteristic in the range of 10 is used. (12) The coloring method according to (10) above, wherein at least one of the dyes is one that emits fluorescence. (13) The coloring method as described in (10) above, wherein at least one of the dyes has a magnetism. (14) The coloring method according to the above (10), which enables forgery prevention and authenticity discrimination.

(15) The coloring method according to the above (10), which is characterized by imparting a noticeable effect. (16) The above (1) characterized by being applied to a printed matter
0) The coloring method described. (17) The above (1) characterized in that it is applied to a coated article.
0) The coloring method described. (18) The coloring method as described in (10) above, which comprises molding a mixture containing the dye.

The coloring matter in the above (1) means a coloring matter by all coloring methods such as printing, coating, impregnation, papermaking, plastic coloring, coloring imparting a noticeable effect, and the present invention is particularly preferable. , Anti-counterfeit secret documents, for example banknotes,
Checks, check cards, stock certificates, credit cards, revenue stamps, stamps, railroad and airline tickets, telephone cards, prepaid cards, lottery tickets, gift certificates, travel and identification documents, etc. The present invention relates to a colored product capable of enhancing the effect of being noticeable from the surroundings and a method for coloring the same. Each of the colored materials can express a discrimination pattern on the entire surface of the material to be printed or the support, or on a specific range. In the present invention, the term “colorant” means a colorant such as a dye and / or a pigment used in a method for coloring a colored material, and a colorant (film-coated powder) that causes a color change in the following colored region. The dye that causes the color change of the colored region depending on the viewing angle in (2) is particularly preferably as described in Japanese Patent Application No. 2001-191294 by the present inventors, as described later. Based on our original technology, the number of films is preferably set to two or more to increase the film thickness, thereby increasing the reflectance at the peak in the reflection spectrum, thereby increasing the peak height (H) and the half width. By keeping the spectrophotometric characteristics where the ratio (H / W) with (W) is in the above specific range, it has an angle-dependent color change between strong interference colors and has a beautiful glow. It has a vivid color shift effect, has high brightness, has advantageous application characteristics, and has a red ~ blue ~
It is a film-coated powder that exhibits an angle-dependent color change of purple and is capable of expanding the range of coloring possibilities.

The colored product and the coloring method of the present invention are characterized in that at least one kind of dyes contains a dye which causes a color change of a colored region using the above-mentioned viewing angle, thereby changing the viewing angle. The feature is that the color difference between the portion using the color shift dye and the conventional dye can be easily identified, and the authenticity determination method can be easily and easily identified. That is, it is possible to perform visual identification under visible light, and a device for identifying a pattern by magnetism, an electric field, an electron beam, visible light, ultraviolet light, infrared light, or the like is not essential. In addition, since a latent image formed by the film-coated powder that undergoes color shift cannot be copied even if it is copied by a copying machine or an image is read by a scanner, a printed matter having an anti-counterfeiting effect can be obtained. Furthermore, by incorporating a fluorescent substance, a higher degree of forgery prevention is possible due to the combined effect of light emission by an ultraviolet light. When a magnetic substance, a conductor or a dielectric substance is used as a substrate, it reacts by an external factor such as an electric field or a magnetic field to generate an additional action such as a magnetic response, an electrical response, a moving force, a rotation, a movement, or heat generation. It is possible to provide a colored product having a color and a coloring method.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The colored product and the coloring method of the present invention will be described in detail below. The present invention is to provide a colored product and a coloring method capable of enhancing anti-counterfeiting, authenticity discrimination, and conspicuous effect. Recently, an imitation product obtained by printing an image of securities with a scanner and printing the same is used. In order to maximize the color change, which is an advantage of multi-colored powders, and to prevent counterfeiting with high practicality, to discriminate authenticity or to enhance the effect of conspicuousness, A coloring method is provided. As a solution, the color change of the polychromatic powder is visually expressed vividly by the following method. By providing the same color as the color viewed from a specific angle on the periphery, the difference between the colors is used to visually emphasize the polychromatic effect. By using the same color as seen from the front, it is possible to prevent forgery by eliminating the color difference when copying. Further, regarding the problem, by using a fluorescent multicolored powder, by using the same color as seen from the front,
By eliminating the color difference when copying and the combined effect of fluorescence emission, it is possible to further prevent forgery.

As described above, the colored product of the present invention is a colored product having a plurality of colored regions respectively colored with a plurality of different dyes, and at least one of the dyes uses the dye depending on the viewing angle. The powder contains a multilayer film-coated powder that causes a color change in the colored region.

The above-mentioned authenticity-determined colored product is particularly preferably a dye that causes a color change in the colored region depending on the viewing angle, as described in Japanese Patent Application No. 2001-191294 by the present inventors. An angle-dependent color between the strong interference colors described later in which the reflectance at the peak in the reflection spectrum is increased by increasing the film thickness by making the number of films preferably two or more based on the original technology. Has a change, has a beautiful glow, has a vivid color shift effect, has a high brightness, has advantageous application characteristics,
A color ink composition in which a film-coated powder, which exhibits an angle-dependent color change from red to blue to violet and is capable of expanding the range of coloring possibilities, is dispersed in an ink dispersion medium, particularly the base particles. A typical example is a printed matter printed with a color ink composition having magnetism.

The multilayer film-coated powder which is used in the colored product and the coloring method of the present invention and which causes the color change of the colored region using the dye according to the above viewing angle is a film-coated powder of the above-mentioned film coated powder on the surface of the substrate particles. When the vertical reflection is measured, the 400 nm width <wavelength specified width L> between 380 and 780 nm in the reflection spectrum and the vertical axis reflection height (reflectance specified width R) are 5
A multilayer film-coated powder having a spectrophotometric characteristic in which the ratio (H / W) of the peak height (H) and the half width (W) is in the range of 0.5 to 5 when displayed as a pair 2. It is contained. Ratio of peak height (H) and half width (W) (H /
W) is required to maintain the spectrophotometric characteristic in the range of 0.5 to 5, and preferably 1 / 1.5 to 1/0.
The range is 3 and more preferably the range is 1-2.
When the ratio (H / W) is less than 0.5, the width of the reflected color is wide and the color is not vivid, and when the ratio (H / W) is increased to 5 or more, the number of films to be coated is increased. It is necessary to increase the number of the particles so that the physical properties of the base particles are impaired and the manufacturing cost is increased.

When a metal hydroxide film or a metal oxide film is formed into a plurality of layers as a light-transmissive coating film by a reaction of a metal salt or the like, the above-mentioned coating film (base particles are coated A special function can be given by adjusting the thickness of each layer (the layer of the film that participates in interference). For example,
An alternating coating film having a different refractive index is provided on the surface of the base particle so that the following formula (1) is satisfied, the refractive index n of the material forming the film and an integer m times a quarter of the wavelength of visible light. If an alternating film having a thickness d corresponding to is provided with an appropriate thickness and number of films, light having a specific wavelength λ (using the Fresnel interference reflection) is reflected or absorbed.

[0018] nd = mλ / 4 (1)

By utilizing this action, a film having a film thickness and a refractive index satisfying the formula (1) for the target wavelength of visible light is formed on the surface of the substrate particles, and further on that. A film having a reflection peak in the visible light region is formed by alternately coating a film having a different refractive index once or more. At this time, the order of materials to be formed into a film is determined as follows. First, when the refractive index of the core substrate is high, the first layer is preferably a film having a low refractive index, and in the opposite case, the first layer is preferably a film having a high refractive index.

The film thickness is measured and controlled by a spectrophotometer or the like as a reflection waveform by changing the optical film thickness, which is the product of the film refractive index and the film thickness, so that the reflection waveform finally becomes the required waveform. Design the film thickness of each layer. For example, if the peak position of the reflection waveform of each unit coating constituting the multilayer film is precisely adjusted to a specific wavelength, it is possible to obtain a monochromatic colored powder such as blue, green, or yellow without using dyes or pigments. it can.

However, in the case of an actual substrate, the particle size of the substrate,
It is necessary to consider the shape, the phase shift at the interface between the film substance and the base particle substance, and the peak shift due to the wavelength dependence of the refractive index. For example, when the shape of the base particles is a parallel plate shape, the Fresnel interference due to the parallel film formed on the particle plane is designed under the condition that n in the above formula (1) is replaced with N in the following formula (2). To do. In particular, when the metal film is included even when the substrate has a parallel plate shape, 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.

[0022]         N = n + iκ (i represents a complex number) (2)

If this attenuation coefficient κ is large, the phase shift at the interface between the film substance and the substrate substance becomes large, and further, the optimum interference film thickness due to the phase shift affects all layers of the multilayer film.

As a result, the peak position is shifted even if only the geometrical film thickness is adjusted, and the color becomes light, especially when coloring in the cyan color system. In order to prevent this, the influence of the phase shift on all films is taken into consideration, and it is designed in advance by computer simulation to optimize the combination of film thicknesses. Furthermore, there is a phase shift due to the oxide layer on the surface of the substrate and a peak shift due to the wavelength dependence of the refractive index. To correct these, use a spectrophotometer, etc.
It is necessary to find the optimum conditions so that the reflection peak becomes the target wavelength at the final target film number.

The interference of a film formed on a curved surface such as a spherical powder occurs like a flat plate, and basically follows the Fresnel interference principle. Therefore, the coloring method can also be designed in a specific color system. However, in the case of a curved surface, the light incident on and reflected by the powder causes complicated interference. These interference waveforms are almost the same as the flat plate when the number of films is small. But,
As the total number increases, the interference inside the multilayer becomes more complicated.
Also in the case of a multilayer film, the reflection spectral curve can be designed in advance by computer simulation so that the combination of film thicknesses is optimal based on Fresnel interference. In particular, in the case of forming a film on the surface of the base particles, the influence of the phase shift on the surface of the base particles and all the films is taken into consideration, and it is designed in advance by computer simulation so that the combination of the film thicknesses is optimal. Furthermore, 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 also taken into consideration. In actual sample production, the designed spectroscopic curves are used as a reference, and in order to correct these in the actual film, the optimum conditions while changing the film thickness so that the reflection peak becomes the target wavelength at the final target film number with a spectrophotometer etc. You have to find out.

Also, when a metal or a core particle or a film having a large attenuation coefficient is used, a phase shift occurs such that the light reflected by the surface of the material having a large metal surface attenuation coefficient is elliptically polarized, and this interference occurs with the core particle. It is very complicated to optimize and obtain the target waveform for each of the multilayer films because it affects the mutual phase of the particles in the multilayer film. It is necessary to obtain the optical property values of the material of the film, and based on the optical property values, obtain the target film thickness and the combination of the film in advance by computer simulation.

Interference due to the multi-layered film also occurs when coloring the irregularly shaped powder, and the basic film design is performed with reference to the conditions of the interference multi-layered film of the spherical powder. The peak position of each unit film forming the above-mentioned multilayer film can be adjusted by the film thickness of each layer, and the film thickness depends on the raw material under the conditions for forming a solid phase component such as a metal oxide on the surface of the base particles. By controlling the composition, the solid phase deposition rate, the amount of the substrate, and the like, the film thickness can be accurately controlled, a film having a uniform thickness can be formed, and a desired color system can be colored. As described above, by finding optimum conditions while changing the film forming conditions such as the film forming solution so that the reflection peak and the absorption bottom become the target wavelength at the final target film number, it is possible to obtain powder of a specific color system. You can In addition, the color development due to the interference of the multilayer film can be adjusted by controlling the combination of the substances forming the multilayer film and the film thickness of each unit film. Thereby, the powder can be vividly colored in a desired color system without using a dye or a pigment.

Further, in order to maximize the color shift,
It is necessary to optimize the sharp reflection peak wavelength and the number of peaks, and the film thickness control of each layer is optimized. Especially when the reflection peak appears in the visible range by changing the viewing angle from outside the visible range, or conversely, when the reflection peak in the visible range appears by changing the viewing angle,
A sharp reflection peak is effective because the color can be changed at the same time by slightly changing the viewing angle.

In the film-coated powder used in the colored product and the coloring method of the present invention, the base particles as a reference for forming the metal oxide film or the like are not particularly limited, and may be an inorganic substance containing a metal or an organic substance. It may be a magnetic substance, a dielectric substance, a conductor or an insulator. When the substrate is a metal, it may be any metal such as iron, nickel, chromium, titanium, aluminum, etc. However, when utilizing its magnetism, a magnet such as iron is preferable. These metals may be alloys, and when they have the above-mentioned magnetism, it is preferable to use a ferromagnetic alloy. When the powder substrate is a metal compound, typical examples thereof include the above-mentioned metal oxides. Examples include iron, nickel, chromium, titanium, aluminum, silicon and the like, calcium. It may be an oxide of magnesium, magnesium, barium or the like, or a composite oxide thereof. Furthermore, examples of metal compounds other than metal oxides include metal nitrides, metal carbides, metal sulfides, metal fluorides, metal carbonates, metal phosphates, and the like.

Further, as the base particles, other than metal,
It is a semi-metal or non-metal compound, particularly an oxide, a carbide or a nitride, and silica, glass beads or the like can be used. Other inorganic materials include inorganic hollow particles such as shirasu balloon (hollow silicic acid particles), fine carbon hollow spheres (cress spheres), fused alumina bubbles, aerosil, white carbon, silica fine hollow spheres, calcium carbonate fine hollow spheres, Calcium carbonate, perlite, talc, bentonite, mica such as synthetic mica and muscovite, kaolin and the like can be used.

Resin particles are preferred as the organic material. Specific examples of the resin particles include cellulose powder, cellulose acetate powder, polyamide, epoxy resin, polyester, melamine resin, polyurethane, vinyl acetate resin, silicon resin, acrylic ester, methacrylic ester, styrene, ethylene, propylene and these. Examples thereof include spherical or crushed particles obtained by polymerization or copolymerization of the derivative of. 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 a base, the heating temperature in drying must be below the melting point of the resin.

The shape of the substrate is a sphere, a subsphere, an isotropic body such as a regular polyhedron, a rectangular parallelepiped, a spheroid, a rhombohedron, a plate, a needle (a cylinder, a prism), or another polyhedron. It is also possible to use a completely amorphous powder such as a thing. These substrates are not particularly limited in particle size,
It is preferably in the range of 0.01 μm to several mm. Also,
The specific gravity of the base particles is in the range of 0.1 to 10.5, but when the obtained powder is used by dispersing it in a liquid or the like, it is 0 from the viewpoint of fluidity and floating property. 1 ~
It is preferably 5.5, more preferably 0.1 to 2.8, 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, so that it is necessary to make the film multi-layered or very thick, which is uneconomical. .
On the other hand, when it exceeds 10.5, the film for floating becomes thick, which is also uneconomical.

As described above, in the film-coated powder used in the colored product and the coloring method of the present invention, the powder base particles are provided with a plurality of coating layers having different refractive indexes, and the refractive index of each coating layer is changed. By appropriately selecting and coating the layer thickness, it is possible to obtain a powder that is colored in a specific color system due to the interference color and exhibits a color shift. As described above, the metal hydroxide film or the metal oxide film is deposited on the surface of the substrate particles by the reaction of the metal salt, but the buffer solution is used as the solvent for the solid phase deposition reaction, and the solution is kept at a certain pH. Precipitate at an appropriate rate.

In the present invention, the metal used as the metal salt is iron, nickel, chromium, titanium, zinc, aluminum, cadmium, zirconium, silicon, tin, lead,
Other than lithium, indium, neodymium, bismuth, cerium, antimony and the like, calcium, magnesium, barium and the like can be mentioned. Examples of salts of these metals include sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, carbonic acid and carboxylic acid salts. Furthermore, chelate complexes of the above metals are also included. The kind of metal salt used in the preparation of the film-coated powder is selected in accordance with the properties to be imparted to the surface of the substrate and the means applied in the production.

The film-coated powder used in the present invention basically forms a colorless and transparent film and is colored by laminating films having different refractive indexes. However, if the waveform of the reflection and absorption spectra does not become the desired color only by coloring due to interference, the following metal cobalt, yttrium, sulfur, europium, dysprosium, antimony, samarium, copper, silver, gold,
It is preferable to use sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, carbonic acid, carboxylic acid salts of metals such as platinum, rhodium, iridium, tungsten, iron and manganese. Further, chelate complexes of the above metals are also preferable. The content of these metals in the film is 10 ppm to 15%, preferably 10 ppm to 1
5%, and more preferably 50 ppm to 5%. When the content of these metals is small, coloring becomes insufficient, and when the content is too large, coloring becomes too strong to give a dark color, resulting in the inconvenience that a bright powder cannot be obtained.

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

In the method for producing a film-coated powder used in the colored product and the coloring method of the present invention, a multilayer coating film may be manufactured as a continuous process, or each coating film may be manufactured one layer at a time. Alternatively, it can be manufactured by various methods such as a combination of single-layer manufacturing and multi-layer continuous manufacturing. The particle size of the film-coated powder used in the present invention is not particularly limited and may be appropriately adjusted depending on the purpose, but is usually 0.1 μm.
To several mm are preferable, and more preferably 0.1 μm to 30
It is in the range of μm.

The preferable thickness range of one layer of the film-coated powder used in the present invention depends on the film substance and the size of the particles serving as the substrate. When the film substance is a substance having a large absorption coefficient such as a metal, an opaque metal oxide, or a metal sulfide, it is 0.00001 when the substrate particles are 0.1 μm to 1 μm.
The thickness is preferably 0.001 μm to 0.7 μm when the substrate particles are 1 μm to 10 μm, and 0.001 μm to 1.0 μm when the substrate particles are 10 μm or more. When the film material has a small absorption coefficient such as a transparent oxide, 0.01 μm when the substrate particles are 0.1 μm to 1 μm.
m to 1.5 μm, and the base particles are 1 μm to 10 μm, 0.
It is preferably from 0.01 μm to 3.0 μm, and from 0.01 μm to 5.0 μm when the substrate particles are 10 μm or more. Further, the preferable thickness range of the total film thickness of the film-coated powder used in the present invention also differs depending on the size of the particles serving as the base. When the base particles are 0.1 μm to 1 μm, 0.1 μm to 5
μm, 0.1 μm to 8 when the substrate particles are 1 μm to 10 μm
μm, when the base particles are 10 μm or more, 0.1 μm to 20 μm
It is preferably m.

As described above, the film-coated powder used in the present invention has a pH as a film-forming reaction solvent during the film-forming reaction in the production method, particularly when the film-forming reaction is carried out in an aqueous solvent.
A film-forming reaction is carried out by using a water-based solvent under constant conditions and simultaneously forming a film-coating reaction on the surface of the substrate under ultrasonic dispersion conditions. In the production of the film-coated powder, in order to keep the film-forming reaction constant, a buffering agent is added to an aqueous solvent to prepare a buffer solution, or a buffer solution prepared in advance is used. Further, during the film forming reaction, a film raw material other than the buffer solution is added to form the film. When performing film formation by adding film forming raw materials,
When the pH fluctuates greatly, it is desirable to add a buffer solution to prevent this. In the present invention, the constant pH means that the pH is within ± 2 of a predetermined pH, preferably within ± 1, and more preferably within ± 0.5.

Various systems may be used as the buffer solution, and the system is not particularly limited, but it is important that the substrate particles can be sufficiently dispersed, and at the same time, a metal hydroxide or a metal oxide film coated on the surface of the substrate is coated. The powder is also selected so that it can be dispersed by the action of the electric double layer and that the above condition that the dense coating film can be formed by the gentle dropping reaction.

Next, as ultrasonic dispersion conditions, various ultrasonic oscillators can be used, for example, a water tank of an ultrasonic cleaner can be used, and there is no particular limitation. However, the conditions of ultrasonic dispersion vary depending on the size of the oscillating device, the shape and size of the reaction container, the amount and volume of the reaction solution, the amount of substrate particles, and so on. Just select it. The buffer solution used in the film forming reaction depends on the solid phase component to be precipitated, and is not particularly limited, but Tris type, boric acid type, glycine type, succinic acid type, lactic acid type, acetic acid type, tartaric acid type, Examples thereof include hydrochloric acid type.

Next, as an example, a method of forming an alternating multilayer film of a metal oxide having a high refractive index and a metal oxide having a low refractive index will be specifically described when the film forming reaction is carried out particularly in an aqueous solvent. First, in the case of forming a film of titanium oxide or zirconium oxide, the base particles are immersed in a buffer solution of acetic acid / sodium acetate or the like and dispersed by ultrasonic oscillation to obtain titanium sulfate, which is a metal salt of titanium or zirconium. , Zirconium sulfate or the like as a raw material, an aqueous solution of these metal salts is slowly dropped into the reaction system, and the resulting metal hydroxide or metal oxide is precipitated around the base particles. During this dropping reaction
The pH is kept at the pH of the buffer solution (5.4). After the reaction is completed, this powder is subjected to solid-liquid separation, washed and dried, and then heat treated. The drying means may be vacuum drying or natural drying. 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 shown by the following reaction formula.

Ti (SO ₄ ) ₂ + 2H ₂ O → TiO ₂ + 2H ₂ (SO ₄ )

The TiO ₂ content of titanyl sulfate is preferably 5 g / liter to 180 g / liter, more preferably 10 g / liter to 160 g / liter. 5 g
If it is less than 1 liter / liter, the film formation takes too much time, and the amount of powder to be processed is reduced, which is uneconomical. If it exceeds 180 g / liter, the diluent causes hydrolysis during addition and does not become a film forming component. Both are unsuitable.

Subsequently, in the case of forming a film of silicon dioxide or aluminum oxide, the above titania-coated particles are dipped and dispersed in a buffer solution of NaOH added to a KCl / H ₃ BO ₃ system to obtain silicon or Using metal silicates such as aluminum, sodium silicate, aluminum chloride, etc. as a raw material, an aqueous solution of these metal salts is slowly dropped into the reaction system to deposit the produced metal hydroxide or metal oxide around the base particles. It can be done by During the dropping reaction, the pH is the pH of the buffer solution.
It is held at (9.0). After the reaction is completed, this powder is subjected to solid-liquid separation, washed and dried, and then heat treated. By this operation, a powder having a multi-layered metal oxide film on the surface thereof can be obtained by repeating the operation of forming a two-layered metal oxide film having different refractive indexes on the surface of the base particles. In addition,
When the film to be coated is silicon dioxide, the formation of silicon dioxide is shown in the following reaction scheme.

Na ₂ Si _X O _{2X + 1} + H ₂ O → XSiO ₂ +2
Na ^{+ +} 2OH ^-

The method for forming the metal compound film will be described below. As a film forming method, a vapor deposition method such as a PVD method, a CVD method, or a spray drying method may be used to directly deposit the particles on the surface of the base particles. However, the above-mentioned Japanese Patent Laid-Open No. 6-22 proposed by the present inventors has been proposed.
The metal alkoxide method described in JP-A-8604, JP-A-7-90310 or WO96 / 28269, and the aqueous method described in JP-A-11-131102 can also be preferably applied. In this case, the linear growth rate is made higher than the solid phase deposition rate, and the reaction conditions are adjusted so that an amorphous uniform film is formed.

As the film-coated powder, one using an organic film can be used. The organic substance is not particularly limited, but is preferably a resin. Specific examples of the resin, cellulose, cellulose acetate, polyamide, epoxy resin, polyester, melamine resin,
Examples thereof include polymers or copolymers of polyurethane, vinyl acetate resin, silicon resin, acrylic acid ester, methacrylic acid ester, styrene, ethylene, propylene and their derivatives. When forming an organic material film (resin film), a. A method of forming a resin film on the particles by dispersing and emulsifying the base particles in the liquid phase (polymerization method in the liquid phase); b. Film forming method in gas phase (C
VD) (PVD) and the like are adopted.

The following is an example of the case where the film-coated powder used in the present invention has a multi-layer film on the base particles. For example, when the base particles are made of a substance having a high refractive index, a light-transmitting film having a low refractive index is provided thereon, and a particle constituent film having a high refractive index is further formed on the light-transmitting film. And a light-transmitting film having a low refractive index are sequentially and alternately provided. If the base particles have a low refractive index, a high refractive index particle constituent film is formed thereon, a low refractive index light-transmitting film is formed thereon, and a high refractive index particle constituent film is formed thereon. And sequentially provide.

Next, specific raw materials used for film formation, particularly metal salts will be described. Raw materials used for forming a film having a high refractive index 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, etc. For indium oxide films such as salts, indium halides, sulfates and the like are preferable.
Further, as a raw material used for forming a film having a low refractive index, for a silicon oxide film, sodium silicate, water glass, a halide of silicon, an organosilicon compound such as an alkyl silicate and a polymer thereof, etc. , For aluminum oxide film,
For magnesium oxide films such as aluminum halides, sulfates and chelate complexes, magnesium sulfates and halides are preferable. Further, in the case of a titanium oxide film, for example, mixing titanium chloride with titanium sulfate has the effect of forming a rutile-type titanium oxide film having a high refractive index at a lower temperature.

A more complete oxide film can be manufactured by controlling the reaction temperature at the time of film coating to a temperature suitable for the kind of each metal salt and coating. When the film forming 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 of heating is excessive,
Since the reaction rate is too fast, the supersaturated solid phase does not form a film and precipitates in an aqueous solution to form gel or fine particles, making it difficult to control the film thickness.

After the coating film is manufactured, gradient washing is repeated while adding distilled water to remove the electrolyte, and then heat treatment such as drying and firing is performed to remove the water contained in the solid phase to completely remove the electrolyte. It is preferable to use an oxide film. Further, by heat-treating the powder after film formation in a rotary tube furnace or the like, sticking can be prevented and dispersed particles can be obtained. 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 after the target multilayer film is completed, heat treatment may be performed last.
The heat treatment conditions vary depending on the reaction system, but the heat treatment temperature is 200 to 1300 ° C., preferably 40.
It is 0-1100 degreeC. At temperatures below 200 ° C, salts and water may remain, and above 1300 ° C,
The film and the substrate may react with each other to form another substance, which is not suitable. The heat treatment time is 0.1 to 100 hours, preferably 0.5 to 50 hours.

Next, a representative example of a coloring material composition containing the film-coated powder used in the coloring matter and coloring method of the present invention,
(1) Each specific color ink or paint-like composition (fluid)
And (2) each specific color toner and each specific color dry ink-like composition (powder) will be described. (1)
As a medium (vehicle) for the specific color ink or paint-like composition (fluid), conventionally known varnishes used for color printing, color magnetic printing, and color magnetic paint can be used. For example, liquid polymer A polymer or monomer dissolved in an organic solvent can be appropriately selected and used according to the type of powder, the ink application method, and the application.

Examples of the liquid polymer include dienes such as polypentadiene and polybutadiene, polyethylene glycols, polyamides, polypropylenes, waxes, and modified copolymers thereof. Polymers that are soluble in organic solvents include olefin polymers, acrylic resins such as oligoester acrylates, polyesters, polyamides, polyisocyanates, amino resins, xylene resins, ketone resins, and diene resins. , 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. Examples of the organic solvent include alcohols such as ethanol, isopropanol and normal propanol, ketones such as acetone, benzene, toluene, xylene,
Examples thereof include kerosene, benzine hydrocarbons, esters, ethers, and modified products and copolymers thereof.

(2) The specific color toner, the specific color dry ink, and the specific color dry paint-like composition (powder) are prepared by adjusting the specific color multi-layer film-coated powder with a resin or if necessary. Color materials are directly kneaded with a screw extruder, roll mill, kneader, etc., coarsely crushed with a hammer mill, cutter mill, finely crushed with a jet mill, etc., and then classified by an elbow jet etc. A body-colored cyan colorant composition can be obtained. Further, the specific color type multilayer film-coated powder can be made into a powdery specific color type coating composition by using a polymerization method such as an emulsion polymerization method or a suspension polymerization method. Further, the powder for coating a specific color type multi-layer film, a resin, an additive such as a toning agent, and a solvent may be liquefied by a colloid mill or a three-roll mill to obtain a liquid specific color type coating composition such as an ink coating material.

As a toning material for increasing the lightness, a white pigment (color-developing material) such as titanium oxide, zinc oxide, tin oxide, silicon oxide, antimony oxide, lead oxide, etc., or a composite oxide of these is used. Or a carbonate such as calcium carbonate, magnesium carbonate or barium carbonate, or a sulfate such as barium sulfate or calcium sulfate, a sulfide such as zinc sulfate, or a composite obtained by sintering the oxide, carbonate or sulfate. Examples thereof include oxides and complex hydrous oxides.

As a toning material for adjusting saturation and hue, particularly as a toning material when used for color reproduction in full color mixing
Blue pigments (organic dyes / pigments) Alkaline blue lake, peacock lake, peacock lake blue etc. lake dye and lake pigment, oil blue etc. oil dye pigment, alcohol blue etc. alcohol dye, phthalocyanine, copper phthalocyanine etc. phthalocyanine -Based pigments, (inorganic pigments) oxide sulfide composite pigments such as ultramarine, copper-based group blue navy blue pigments such as iron blue and milory blue,
Cobalt blue, cobalt oxide-based complex oxides such as cerulean blue, blue pigments, blue organic dyes and pigments and blue inorganic pigments such as alkali blue lake, peacock blue lake, lake dyes, lake pigments metal-free phthalocyanine, copper phthalocyanine, etc. Phthalocyanine-based dyes and green pigments such as chrome green, zinc green, chromium oxide, chromium oxides and hydrous oxides such as hydrous chromium (viridian), copper-based oxides such as emerald green, cobalt-based oxidation such as cobalt green. Pigments, nitroso pigments such as pigment green and naphthol green, azo pigments such as green gold, phthalocyanine green, phthalocyanine pigments such as polychrome copper phthalocyanine, malachite green lake, acid Rake system such as de green rake,
Organic dyes and pigments such as oil dye pigments such as oil green, alcohol dye pigments such as alcohol blue, and the like. However, the present invention is not limited to these.

Further, in delicate color tone control, blue,
When it is necessary to use toning with a pigment or dye such as yellow or magenta, it is preferable to add these pigments to obtain an optimum specific color. In the case of this powdery specific color coating composition, (a) the resin to be produced by the pulverization method is not particularly limited, but may be polyamide, epoxy resin, polyester, melamine resin, polyurethane, acetic acid. Examples thereof include polymers or copolymers of vinyl resins, silicon resins, acrylic acid esters, methacrylic acid esters, styrene, ethylene, butadiene, propylene and their derivatives. (B) In the case of the polymerization method, the polymerization is started from one or a mixture of a plurality of ester, urethane, vinyl acetate, organic silicon, acrylic acid, methacrylic acid, styrene, ethylene, butadiene, propylene, etc. These copolymers and the like are formed.

Typical examples of the coloring material composition containing the film-coated powder used in the present invention are (1) each specific color ink or paint-like composition (fluid) and (2) as described above.
Each specific color toner and each specific color dry ink-like composition (powder) are formed. In the case of a fluid, it is a specific color ink, paint, etc., a solidification accelerator for the toning material, a resin that dries slowly, a thickener for increasing the viscosity, and a fluidization for decreasing the viscosity. Ingredients such as a dispersant may be included to disperse the agent and particles. On the other hand, in the case of powder,
(A) When a powder is produced by a pulverization method, the above-mentioned toning material,
For resins that dry slowly, solidification accelerators, fluidizers for lowering viscosity during kneading, dispersants for dispersing particles, charge control agents for fixing to paper, wax, etc. Ingredients can be included. (B) When a polymerization method is used, the above-mentioned toning agent, polymerization initiator, polymerization accelerator, thickener for increasing viscosity, dispersant for dispersing particles, fixing to paper, etc. A component such as a charge control agent, a wax or the like can be included. The film-coated powder can be applied to wet and dry color printing or wet and dry color magnetic printing by using a single powder or a combination of a plurality of powders having different spectral characteristics, and powders of three primary colors are used. It has the identification function of 6 kinds of combination of visible light, invisible light (UV region and cyan region), fluorescent color and magnetism, and electricity (change of electric field), and security function such as color magnetic ink for preventing forgery of printed matter. It can be applied to other uses as needed.

Each specific color ink or paint-like composition or each specific color toner, each specific color dry ink-like composition, each specific color dry paint composition is printed, melt-transferred or transferred onto a substrate. When applied to a coated body, the relationship between the content of each specific color type multilayer coating powder and the resin in the coating composition is 1: 0.5 to 1:15 by volume ratio. If the content of the medium is too small, the applied film will 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 it cannot be said to be a good ink or paint. Further, the relationship between the total amount of each color-based colorant and resin in each color-based ink or coating composition and the amount of solvent is 1: 0.5 to 1:10 in volume ratio, and the amount of solvent is small. If it is too much, the viscosity of the paint is too high to apply it uniformly. Further, 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, melting transfer or coating material is applied to the substrate is determined by the amount of pigment placed per unit area of the object. The amount of each color type multi-layer film coating powder of the present invention on the coated object after the coating material is dried is 0.1 to 300 g per square meter in an area density when uniformly applied, and preferably 0. 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 background color of the object to be coated appears, and if it 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 with a certain thickness or more, the light does not reach the pigment below the coating film. To make the coating thicker than this thickness,
Since the thickness exceeds the hiding power of the paint, it is uneconomical because there is no painting effect. However, this is not the case when a thick coating is applied in consideration of abrasion of the coating film, because the thickness of the coating film is worn away.
This is also not the case when a specific design or the like is partially formed.

Fluorescent coloring can be imparted to the color shift portion of the colored product of the present invention. The applying method is not particularly limited, but for powders that undergo color shifting,
There is a method of further providing a coating layer containing a fluorescent substance as disclosed in JP-A-2000-87103, and a method of mixing a powder for color shift and a fluorescent substance to form a coloring material composition.

The method for determining the authenticity of a colored product colored by the above-described coloring method of the present invention has an angle-dependent color change between strong interference colors, has a beautiful glow, and has a vivid color shift (color). Because it uses a film-coated powder that has the effect of
When the viewing angle is changed, the color difference between the part using the color shift dye and the part using the conventional dye can be easily identified. That is, under visible light, it is possible to identify with the naked eye,
An apparatus for identifying patterns by magnetism, electric field, electron beam, visible light, ultraviolet light, infrared light, etc. is not essential. The colored product and the coloring method of the present invention are characterized by the fact that the authenticity determination method is easy and can be easily identified as described above. In addition, since a latent image formed by the film-coated powder that undergoes color shift cannot be copied even if it is copied by a copying machine or an image is read by a scanner, a printed matter having an anti-counterfeiting effect can be obtained. Further, by incorporating a fluorescent substance, a higher degree of forgery prevention can be achieved due to the combined effect of light emission by an ultraviolet light.

[0064]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto. [Example 1] (Method for clarifying color change) Fourth of Example 6 of Japanese Patent Application No. 2001-191294
Permalloy powder (average particle size 2
0 μm) as the base powder, and in the visible region in the multilayer film, 4
A multilayer film-coated powder having an interference reflection peak at 50 nm and a vertical color as viewed from the front which was blue, and which was tilted at 40 degrees to change to magenta was prepared. A color shift printing ink was prepared by using 30 parts of acrylic and 40 parts of alcohol for 15 parts of the multilayer film-coated powder. Further, 30 parts of an acrylic resin and alcohol were mixed with 13 parts of blue pigment oil blue to prepare a blue ink having a color tone visually similar to that of the color shift printing ink.

Character "CHANNGE" was printed with the above color shift printing ink using PG10 manufactured by Ideal Science Co., Ltd., and the surrounding area of this character was printed with the above blue ink to obtain a printed matter P for discrimination. When the printed matter P was tilted by 10 degrees, the character color was bluish-purple as in the background as shown in FIG. 1, but when viewed from the front, as shown in FIG.
The letters "NNGE" changed to blue and the surroundings remained bluish purple. Further, as shown in FIG. 3, when tilted at 40 degrees, the letters "CHANNGE" changed to red and the surrounding area remained bluish purple. In this way, it is possible to obtain a printed matter that can be easily visually discriminated from forgery prevention.

[Embodiment 2] (Copy protection characteristic for hiding color:
Latent image) No. 5 of Example 6 of Japanese Patent Application No. 2001-191294
Permalloy powder (average particle size 2
0 μm) as the base powder, and the visible region in the multilayer film as 3
A multilayer film-coated powder which has interference reflection peaks at 82 nm and 821 nm and whose vertical color when viewed from the front is blue and which is inclined 40 degrees to change to magenta was prepared. A color shift printing ink was prepared by using 20 parts of acrylic resin and 65 parts of xylene for 15 parts of the multilayer film-coated powder. Further, 20 parts of acrylic resin and 69 parts of xylene were mixed with 11 parts of reddish purple pigment lake red to prepare a reddish purple ink having a color tone visually similar to that of the above color shift printing ink.

A pattern (concentric circle) shown in FIG. 4 is printed on the coated paper with the above color shift printing ink using PG10 manufactured by Ideal Science Co., Ltd., and the circumference of the concentric circle is printed using the above-mentioned magenta ink to make a printed matter for discrimination. (FIG. 4) was obtained. Also, separately, as a comparison, a comparative printed matter obtained by solid printing on the same contour as the discriminating printed matter with the above-described red-purple ink alone.
(Fig. 5) was obtained.

In the printed matter P (FIG. 4), when viewed from the front, the concentric circle pattern was the same red purple as that of the base, as in FIG. 5, but when the viewing angle was tilted at 40 degrees, the concentric circle pattern became It turned green and the surrounding area remained reddish purple.
As is clear from the comparison between FIGS. 4 and 5, when the viewing angle is changed, the color difference between the portion using the color shift printing ink and the conventional magenta ink can be identified. When the above-mentioned FIG. 4 and FIG. 5 are copied by a copier or an image is read by a scanner, the printed matter P and the comparative printed matter are copied in the same manner, and the color-shifted latent image in FIG. 4 cannot be copied. A printed matter is obtained.

[Example 3] (A fluorescent property was added to a color hiding copy protection property: a fluorescent latent image) The thickness of the final layer of the film forming method of Example 4 of JP-A-2000-160050 was used as the raw material composition. A 32/40 permalloy powder (average particle size 20 μm) was used as the base powder, and the multilayer film had an interference reflection peak at 558 nm in the visible region, and the vertical color when viewed from the front was green. A multilayer film-coated powder that changes color to blue by tilting was prepared. A color shift printing ink was prepared by using 30 parts of acrylic and 40 parts of alcohol for 20 parts of the multilayer film-coated powder. Furthermore, 30 parts of acrylic resin and xylene were mixed with 11 parts of pigment oil blue to prepare a magenta ink having a color tone visually similar to that of the color shift printing ink.

Using PG10 manufactured by Ideal Science Co., Ltd., the above color shift printing ink was applied to the coated paper as shown in FIG.
The pattern shown in the hatched portions of (A) and (B) is printed, the white portion is printed with the above green ink, and when viewed from the front, the entire green printed matter as shown in FIGS. 6 (C) and (D). P was obtained.

When viewed from the front, both of the printed materials P and P were green on the entire surface as shown in FIGS. 6C and 6D, but when the viewing angle was inclined to 40 degrees, Also changes to blue in the pattern portions as shown in FIGS. 6A and 6B, and both have a color shift effect. Further, in the pattern shown in the white part of FIG. 6 (F), the printed matter P emitted light by an ultraviolet light, but the printed matter P was
No light emission was observed as shown in FIG.

[0072]

As described above, according to the coloring matter and the coloring method of the present invention, when the viewing angle is changed, the color difference between the portion using the color shift printing ink and the conventional ink can be easily distinguished. It is possible to make a distinction with the naked eye under visible light, and the authenticity determination method is easy and easy. In addition, since a latent image formed by the film-coated powder that undergoes color shift cannot be copied even if it is copied by a copying machine or an image is read by a scanner, a printed matter having an anti-counterfeiting effect can be obtained. Furthermore, by incorporating a fluorescent substance, a higher degree of forgery prevention can be achieved due to the combined effect of light emission by an ultraviolet light. In addition, it is possible to make the colors look vivid and enhance the effect of being conspicuous from the surroundings.

[Brief description of drawings]

FIG. 1 is a diagram showing an image pattern (visible light pattern) of a printed matter P of Example 1 as viewed by tilting it by 10 degrees.

FIG. 2 is a diagram showing an image pattern of the printed matter P of Example 1 as viewed from the front.

FIG. 3 is a diagram showing an image pattern when the printed matter P of Example 1 is tilted at 40 degrees.

FIG. 4 is a diagram showing an image pattern of a printed matter P of Example 2 as viewed by being tilted at 40 degrees.

FIG. 5 is a diagram showing an image pattern of a printed material P of Example 2 viewed from the front and an image pattern of a comparative printed material.

FIG. 6 is a diagram showing each image pattern of a printed matter P of Example 3.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) B44F 1/12 B44F 1/12 D21H 21/28 D21H 21/28 B 21/30 21/30 21/40 21 / 40 G03G 21/04 G03G 21/00 550 F term (reference) 2C005 HA02 HA04 HB01 HB04 HB10 HB12 HB13 HB20 JA09 JB14 JB17 KA40 KA51 KA57 2H134 NA06 4L055 AG15 AG71 AG94 AG98 AH37 AH50 AJ04 BE07 BE08 BE07 BE08

Claims (18)

[Claims] 1. A colored product having a plurality of colored regions, each of which is colored with a plurality of different dyes, wherein at least one of the dyes causes a color change of the colored region using the dye depending on a viewing angle. A colored product characterized by being. 2. The case where the dye that causes a color change in the colored region depending on the viewing angle is a film-coated powder having a coating film on the surface of a substrate particle, and the vertical reflection of the film-coated powder is measured. When the width of 400 nm between the wavelengths of 380 to 780 nm <specified wavelength width L> and the height of vertical axis reflection (reflectance specified width R) are displayed in a ratio of 5 to 2, the peak height (H) is The ratio (H / W) to the half width (W) is 0.5
The colored product according to claim 1, which has a spectrophotometric characteristic in the range of -5. 3. The colored product according to claim 1, wherein at least one of the dyes emits fluorescence. 4. The colored product according to claim 1, wherein at least one of the dyes has magnetism. 5. The colored product according to claim 1, which is capable of preventing forgery and determining authenticity. 6. The colored product according to claim 1, which has a noticeable effect. 7. The colored product according to claim 1, which is a printed product. 8. The colored product according to claim 1, which is a coated product. 9. The colored product according to claim 1, which is a molded product molded from a composition containing the dye. 10. A coloring method for providing a plurality of colored regions respectively colored with a plurality of different dyes, wherein at least one kind of the dyes causes a color change of the colored regions using the dye depending on a viewing angle. A coloring method characterized by using. 11. A film-coated powder having a coating film on the surface of base particles as the dye that causes a color change in the colored region depending on a visual angle,
When the vertical reflection of the film-coated powder was measured, the 400 nm width <wavelength specified width L> between 380 and 780 nm in the reflection spectrum and the vertical axis reflection height (reflectance specified width R) were 5
When displayed as a pair 2, the ratio (H / W) of the peak height (H) and the full width at half maximum (W) is in the range of 0.5-5. The coloring method according to claim 10. 12. The coloring method according to claim 10, wherein a fluorescent substance is used as at least one of the dyes. 13. The coloring method according to claim 10, wherein one having magnetism is used as at least one of the dyes. 14. The coloring method according to claim 10, wherein forgery prevention and authenticity discrimination are enabled. 15. The coloring method according to claim 10, wherein a conspicuous effect is imparted. 16. The coloring method according to claim 10, which is applied to a printed matter. 17. The coloring method according to claim 10, which is applied to a coated product. 18. The coloring method according to claim 10, wherein a mixture containing the dye is molded.