JP5026855B2 - Method for producing coloring structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily producing a colored structural form exhibiting multiple structural colors, with spherical particles arranged regularly. <P>SOLUTION: The method for producing the colored structural form comprises the following process: Using a solid material as the starting material comprising such a solid material(P) that a colored structure-forming thermoplastic resin(a) is dispersed with spherical particles(b) 5-800 nm in average size, whose particle size distribution's standard deviation is 20% or less of the average size and whose softening point is higher than that of the colored structure-forming resin(a) and the mixing weight ratio(a)/(b) is (1:0.01) to (1:10) and a second solid material(Q) differing in the mixing ratio(a)/(b) from the solid material(P), the solid material is rolled at a specific temperature. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a color developing structure having optical coherence.

Colors that exist in nature can be broadly divided into pigment colors and structural colors.
A pigment color is a substance that itself has a pigment, whereas a structural color does not have a pigment and has a fine structure with a wavelength of light in the visible region or less. It is a color that develops due to optical phenomena (interference, diffraction, scattering). Typical structural colors include morpho butterfly wings, luriiro damselfish skin, peacock wings, iridescent shells, opal play colors, and the like.

  For example, the structural color of opal is emitted by arranging naturally generated silica particles with uniform particle diameters. That is, the silica particles are self-assembled to form a close-packed crystal structure, and the distance between the particles at this time is exactly the same order as the wavelength (visible light), so that the light is diffracted by the periodic structure and exhibits a color.

In recent years, attempts have been made to artificially create a structural color. For example, attempts have been made to obtain a structural color by regularly arranging spherical particles.
Examples of such a method include a method of spontaneously sedimenting and depositing spherical particles, a method of producing a colloidal crystal thin film by pulling up, an electrophoresis method, a capillary method, and the like.
However, in these methods, the spherical particles are only stabilized by gravity, and the array of spherical particles (colloidal crystal structure) is easily destroyed by external stimulation. For such problems, various methods have been proposed for fixing spherical particles and maintaining the arrangement (colloidal crystal structure) of the spherical particles over a long period of time.

For example, Non-Patent Document 1 describes a method of aligning and immobilizing spherical particles by bonding a polymer monomer to the surface of spherical particles and then polymerizing. However, such a method requires a polymerization process and requires a long synthesis time.
Furthermore, since a liquid material such as a polymer monomer is used as a starting material, the liquid material is gelled and the spherical particles are fixed. Therefore, during the fixing process, at least a change in volume due to volatilization of volatile components occurs. is happening. Due to such subtle volume changes accompanying volatilization of volatile components, there is a possibility that the arrangement of the spherical particles may collapse, and there is a possibility that the color developing structure cannot be produced. Even if it can be manufactured, reproducibility is difficult to obtain, and it is difficult to easily obtain a plurality of structural colors.

Non-Patent Document 2 describes a method in which spherical particles are preliminarily deposited (arranged) on the substrate surface, and then a binder is poured into the particle gap and fixed. In this method, in order to arrange spherical particles on the substrate in advance, it is necessary to apply spherical particles to the substrate, evaporate the solvent, pour the binder component, cure the binder component, and perform a multi-step process.
In addition, since the binder component, which is a liquid material, is poured and cured, when the binder component is poured or cured, the arrangement of the spherical particles may be disturbed and the colloidal crystal state may be lost, and it is difficult to obtain a coloring structure. It is also difficult to easily obtain a plurality of structural colors.
Furthermore, since it is necessary to precisely arrange the spherical particles on the substrate, a long time is required and there is a problem in mass productivity.

Koji Yoshinaga, Tsuneada Kobayashi, Hiroyuki Karakawa, Kobunshi Ronbunsyu, Vol. 57, no. 4 (2000), pp. 244-250 Hiroshi Fudouzi, Youngan Xia, Advance Materials (2003), Vol. 15, no. 11, June 5, pp. 892 to 896

In order to solve the above-mentioned problems, the present invention has been intensively studied. As a result, in the color-forming structure-forming resin (a) having thermoplasticity, the average particle diameter is 5 nm to 800 nm, and the standard deviation of the particle diameter distribution is 20 of the average particle diameter. % Or less, and spherical particles (b) having a softening point higher than that of the colored structure-forming resin are dispersed, and the mixing ratio of (a) and (b) is from 1: 0.01 to 1:10 in weight ratio. A solid material (P), and a solid material (Q) having a mixing ratio of (a) and (b) different from the solid material (P), as a starting material,
By rolling this solid material at a specific temperature, it was found that a colored structure having a plurality of structural colors in which spherical particles are regularly arranged can be easily obtained, and the present invention has been completed. It was.

That is, the present invention has the following characteristics.
1. In the coloring structure forming resin (a) having thermoplasticity, the average particle diameter is 5 nm to 800 nm, the standard deviation of the particle diameter distribution is 20% or less of the average particle diameter, and the softening point is higher than that of the coloring structure forming resin. Particles (b) are dispersed, and the solid (P) in which the mixing ratio of (a) and (b) is 1: 0.01 to 1:10 by weight,
In the coloring structure forming resin (a) having thermoplasticity, the average particle diameter is 5 nm to 800 nm, the standard deviation of the particle diameter distribution is 20% or less of the average particle diameter, and the softening point is higher than that of the coloring structure forming resin. Solid particles having a mixing ratio different from that of the solid material (P), wherein the particles (b) are dispersed, and the mixing ratio of (a) and (b) is 1: 0.01 to 1:10 by weight ratio. Thing (Q) is mixed,
Rolling a mixture of the solid material (P) and the solid material (Q) at a temperature higher than the softening point of the colored structure-forming resin (a) and lower than the softening point of the spherical particles (b). A method for producing a color developing structure having optical coherence characterized by
2. 1. Spherical particles (b) are inorganic particles A method for producing a coloring structure having optical coherence described in 1.

  In the present invention, the coloring structure forming resin (a) having thermoplasticity has an average particle diameter of 5 nm to 800 nm, a standard deviation of the particle diameter distribution is 20% or less of the average particle diameter, and a softening point is the coloring structure forming resin. Higher spherical particles (b) are dispersed, and the solid (P) in which the mixing ratio of (a) and (b) is 1: 0.01 to 1:10 by weight, and has thermoplasticity. In the colored structure forming resin (a), spherical particles (b) having an average particle diameter of 5 nm to 800 nm, a standard deviation of the particle size distribution of 20% or less of the average particle diameter, and a softening point higher than that of the colored structure forming resin (b) ) Is dispersed, and the mixing ratio of (a) and (b) is 1: 0.01 to 1:10 by weight ratio, and has a mixing ratio different from that of the solid (P) (Q ) And starting the solid, and rolling the solid at a specific temperature And each of the spherical particles regularly arranged, it is possible to easily produce the coloring structure showing a plurality of colors structural color. According to the present invention, advantageous effects can be obtained in the production stability, reproducibility, mass productivity and the like of such a color structure.

  Hereinafter, the best mode for carrying out the present invention will be described.

The color developing structure of the present invention has an average particle size of 5 nm to 800 nm, a standard deviation of the particle size distribution of 20% or less of the average particle size, and a softening point in the color forming structure forming resin (a) having thermoplasticity. Spherical particles (b) higher than the structure-forming resin are dispersed, and the solid (P) in which the mixing ratio of (a) and (b) is 1: 0.01 to 1:10 by weight ,
In the coloring structure forming resin (a) having thermoplasticity, the average particle diameter is 5 nm to 800 nm, the standard deviation of the particle diameter distribution is 20% or less of the average particle diameter, and the softening point is higher than that of the coloring structure forming resin. Solid particles having a mixing ratio different from that of the solid material (P), wherein the particles (b) are dispersed, and the mixing ratio of (a) and (b) is 1: 0.01 to 1:10 by weight ratio. Thing (Q) is mixed,
The mixture of the solid product (P) and the solid product (Q) is rolled at a temperature higher than the softening point of the color forming structure-forming resin (a) and lower than the softening point of the spherical particles (b). It is obtained.

  In the present invention, at the time of rolling, two or more kinds of solid materials having different mixing ratios of the color structure-forming resin and the spherical particles are used as starting materials, and the solid material is higher than the softening point of the color structure-forming resin, It is obtained by rolling at a temperature lower than the softening point of the spherical particles. At this time, at the time of rolling, the colored structure-forming resin is in a softened state (a state close to a liquid state), and the degree of freedom of the spherical particles is relaxed to some extent. By rolling in such a state, it becomes easy to close-pack the spherical particles, and accordingly, the spherical particles are regularly arranged to obtain a colored structure.

  When rolling at a temperature lower than the softening point of the color-forming structure-forming resin, the degree of freedom of the spherical particles is restricted and they are not regularly arranged. In addition, when rolling at a temperature higher than the softening point of the spherical particles, the spherical particles are softened, the shape is broken and no color is developed.

In the present invention, since a solid material is used as a starting material, it is easy to handle and can be easily manufactured by rolling. In particular, since there is almost no volatilizing substance during rolling and there is almost no volume change before and after rolling, turbulence of spherical particles due to volume change can be suppressed.
Therefore, it is possible to easily obtain a structure in which spherical particles are uniformly arranged, that is, a structure exhibiting a structural color having excellent optical coherence.

  In the production method of the present invention, the color structure of the present invention is mainly composed of spherical particles having an average particle diameter of 5 nm to 800 nm and a standard deviation of the particle diameter distribution of 20% or less of the average particle diameter. It is expressed by using. If the average particle size of the spherical particles is not within the scope of the present invention, structural color development cannot be expressed, and if the standard deviation of the particle size distribution of the spherical particles is larger than 20% of the average particle size, the particles are regularly arranged. The structural color development cannot be expressed.

  In addition, the color of the coloring structure exhibits different structural coloring mainly depending on the mixing ratio of the coloring structure forming resin and the spherical particles. In other words, the interparticle distance between the spherical particles is determined by the mixing ratio of the color forming structure forming resin and the spherical particles. For example, the system can be set to blue, green for an interval of about 200 nm to 230 nm, yellow for an interval of about 240 nm to 260 nm, and red for an interval of about 270 nm to 290 nm. In the present invention, the color of the coloring structure can also be set by the average particle diameter of the particles, the degree of dispersion of the particles, the form of the particles, and the like.

  In the production method of the present invention, the color of the coloring structure can be set mainly by the mixing ratio of the coloring structure-forming resin and the spherical particles. In the present invention, the coloring structure-forming resin and the spherical particles are specified by a specific ratio. Since a solid material (P) having a mixing ratio and a solid material (Q) having a mixing ratio of the color forming structure forming resin and the spherical particles different from the solid material (P) is used as a starting material. The structural color of the coloring structure obtained from the solid product (P) and the structural color of the coloring structure obtained from the solid product (Q) are combined to exhibit excellent design properties showing a plurality of structural colors. be able to.

  The solid product (P) in the present invention has an average particle size of 5 nm to 800 nm and a standard deviation of the particle size distribution of 20% or less of the average particle size in the color forming structure-forming resin (a) having thermoplasticity. Are formed by dispersing spherical particles (b) that are higher than the colored structure-forming resin.

The color forming structure-forming resin (a) is not particularly limited as long as it has thermoplasticity and softens during rolling, and various resins can be used.
Examples of the coloring structure forming resin (a) include acrylic resin, polyester resin, polyether resin, vinyl resin, polyamide resin, phenol resin, urethane resin, fluororesin, vinyl acetate resin, vinyl chloride resin, acrylic-styrene resin, acetic acid Vinyl-versaic acid vinyl ester resin, polyvinyl pyrrolidone resin, polyvinyl caprolactam resin, polyvinyl alcohol resin, cellulose resin, epoxy resin, acrylic-silicon resin, silicone resin, alkyd resin, melamine resin, etc. A solvent type, a solvent soluble type, an NAD type, a water soluble type, a water dispersion type, or the like can be used.

Further, the color forming structure-forming resin (a) preferably contains a resin that forms a crosslinked network as long as it has thermoplasticity and softens during rolling. By forming a crosslinked network, it is possible to prevent only the arrangement of the spherical particles, maintain the structural color for a longer period, and improve physical properties such as durability and water resistance.
Examples of the resin that forms such a crosslinked network include those having the reactivity of the reactive functional groups shown below. Examples of combinations of reactive functional groups include carboxyl groups and metal ions, carboxyl groups and carbodiimide groups, carboxyl groups and epoxy groups, carboxyl groups and aziridine groups, carboxyl groups and oxazoline groups, hydroxyl groups and isocyanate groups, carbonyl groups and hydrazides. Groups, epoxy groups and hydrazide groups, combinations of epoxy groups and amino groups, hydrolyzable silyl groups, and the like.
Such crosslinking of the reactive functional group may be a reaction between the reactive functional groups present in the above-described resin, or a crosslinking agent having a reactive functional group may be newly added.
The amount of the reactive functional group is such that the monomer having the reactive functional group forming the resin is 50% by weight or less, further 0.5% by weight, based on the total amount of the resin forming the color forming structure. The content is preferably 40% by weight or less, more preferably 1% by weight or more and 30% by weight or less. When it is more than 50% by weight, it is difficult to soften during rolling, and it is difficult to obtain a structure in which spherical particles are uniformly arranged.

  The softening point of the color structure-forming resin (a) in the present invention is preferably about 50 ° C. to 300 ° C. (preferably 80 ° C. to 200 ° C.). When the softening point of the color forming structure-forming resin (a) is lower than 50 ° C., the structure can be colored by rolling, but it is softened at room temperature, and the arrangement of the spherical particles may be disturbed and the structural color may not be exhibited. There is sex.

  The softening point of the color structure-forming resin (a) is a value calculated by measuring with a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min.

  The refractive index of the color forming structure-forming resin (a) in the present invention is not particularly limited, but it may be about 0.8 to 1.8.

  The spherical particles (b) are not particularly limited as long as they finally exhibit a structural color, but in order to exhibit a structural color, the average particle diameter of the spherical particles (b) is 5 nm to 800 nm (preferably 10 nm to 500 nm).

In the present invention, since the spherical particles (b) are more uniform in size, a structural color can be obtained. Specifically, the standard deviation of the particle size distribution of the spherical particles (b) is 20 times the average particle size. % Or less (further 10% or less, further 5% or less), the spherical particles (b) can be regularly arranged and can exhibit an excellent structural color.
In addition, the average particle diameter in this invention is a number average value by observation with an electron microscope. The particle size distribution is obtained from measurement by a centrifugal sedimentation method or the like.
The aspect ratio of the spherical particles (b) is preferably 1.0 or more and less than 1.2 (more preferably 1.0 or more and 1.15 or less, and further preferably 1.0 or more and 1.1 or less). Within such a range, the spherical particles (b) can be regularly arranged and exhibit a more excellent structural color. The aspect ratio mentioned here is a value represented by b / a which is the ratio of the length b in the longitudinal direction of the particle to the length a in the lateral direction.

  Examples of the spherical particles (b) include silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, tantalum pentoxide, gadolinium oxide, yttrium oxide, barium oxide, iron oxide, cobalt oxide, chromium oxide, vanadium oxide, and oxidation. Hafnium, magnesium oxide, strontium oxide, calcium carbonate, zinc carbonate hydroxide, potassium titanate, iron hydroxide oxide, barium sulfate, barium carbonate, carbon black and other inorganic particles, polystyrene beads, acrylic beads, polyolefin beads and other organic particles Among these, these can be used alone or in combination of two or more. In the present invention, inorganic particles are particularly preferable, and silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, tantalum pentoxide, gadolinium oxide, yttrium oxide and the like are particularly preferable among the inorganic particles.

Such a spherical particle (b) has a softening point higher than that of the color forming structure-forming resin (a) having thermoplasticity. For example, the softening point of the spherical particles (b) is preferably 20 ° C. or higher, more preferably 50 ° C. or higher, than the softening point of the color forming structure-forming resin (a) having thermoplasticity.
Specifically, the softening point of the spherical particles (b) may be 80 ° C. or higher (more preferably 100 ° C. or higher). The upper limit of the softening point of the spherical particles (b) is not particularly limited, but is preferably 1500 ° C. or lower (more preferably 1000 ° C. or lower).

In addition, the softening point of the inorganic particles is a value calculated by measuring with a temperature increase rate of 10 ° C./min using a differential thermal analyzer (TG-DTA).
The softening point of the organic particles is a value calculated by measuring at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC).

  In the present invention, it is particularly preferable to use inorganic particles as the spherical particles (b). Since the inorganic particles are excellent in durability and the like, they can improve the durability of the obtained coloring structure and can maintain an excellent color over a long period of time. In addition, the inorganic particles have a very high softening point compared to the color forming structure forming resin (a). Therefore, the limitation of the heating temperature at the time of rolling is relaxed, and the limitation of the color structure-forming resin (a) that can be used is relaxed, which is preferable.

  Although the refractive index of the spherical particles in the present invention is not particularly limited, it may usually be about 0.8 to 4.5. The difference in refractive index between the color forming structure-forming resin (a) and the spherical particles (b) is preferably about 0.01 to 2.7, more preferably about 0.02 to 1.8. If it is in the range, an excellent color can be expressed.

The mixing ratio of the color forming structure-forming resin (a) and the spherical particles (b) is 1: 0.01 to 1:10 (more 1: 0.05 to 1: 8, more preferably 1: 0. 1-1: 5). With such a ratio, light in the visible light region is efficiently diffracted, and can be recognized as a color for human vision, and a structural color can be easily presented. Further, by controlling the mixing ratio of the coloring structure forming resin (a) and the spherical particles (b), the distance between the spherical particles in the coloring structure can be controlled, and the coloring structure having various colors. Can be obtained.
When the number of spherical particles (b) is too small, the distance between the arranged spherical particles (b) becomes too long and becomes longer than the wavelength of visible light, and the color is not recognized by human vision. Therefore, it is difficult to obtain a coloring structure. In addition, when there are too many spherical particles (b), the spherical particles are easily aggregated, and it becomes difficult to fix the spherical particles, so that the colloidal crystals are not self-supporting.

In addition to the spherical particles (b), non-spherical particles having an average particle diameter of 600 nm or less and a softening point higher than that of the color forming structure-forming resin are preferably added as components constituting the solid material (P). By adding such non-spherical particles, the color structure of the finally obtained color structure becomes clearer. The effect of improving color developability can be confirmed visually, but can also be confirmed by measuring an ultraviolet-visible absorption spectrum or an absolute reflectance.
Although the mechanism of action for obtaining such a color development improving effect is not clear, it is contributed that non-spherical particles enter the gaps between the spherical particles at regular intervals, thereby suppressing the disorder of the arrangement of the spherical particles during rolling. It is thought that.

As such non-spherical particles, those having an average particle diameter of 600 nm or less are used, and those having an average particle diameter of 50 to 600 nm are more preferable. If the average particle size is larger than 600 nm, the transparency and gloss of the color developing structure may be impaired.
Furthermore, as the non-spherical particles, acicular or scaly particles having an aspect ratio of 1.2 to 600 (preferably 1.5 to 500) are suitable. The aspect ratio mentioned here is a value represented by b / a which is the ratio of the length b in the longitudinal direction of the particle to the length a in the lateral direction.

  The non-spherical particles preferably have a softening point higher than the softening point of the color-forming structure-forming resin, particularly 20 ° C. or higher, more preferably 50 ° C. or higher than the softening point of the color-forming structure-forming resin. Specifically, the softening point of the non-spherical particles may be 80 ° C. or higher (more preferably, 100 ° C. or higher). The upper limit of the softening point of the non-spherical particles is not particularly limited, but is usually 1500 ° C. or lower (preferably 1000 ° C. or lower).

  Inorganic particles are suitable as the non-spherical particles in the present invention. If the non-spherical particles are inorganic particles, the durability of the coloring structure is increased, and the initial coloring performance can be maintained for a long time. Furthermore, since the inorganic particles have a very high softening point as compared with the color-forming structure-forming resin, the limitation of the heating temperature during rolling is relaxed, and the range of applicable color-forming structure-forming resins is expanded.

  As such non-spherical particles, the same material as the spherical particles can be used, but in the present invention, for example, scaly silica, acicular titanium oxide, acicular zinc oxide, acicular iron oxide, hydroxide oxidation Iron, zinc carbonate, titanium oxide, iron oxide, aluminum oxide, zirconium oxide, tantalum pentoxide, gadolinium oxide, yttrium oxide, barium oxide, cobalt oxide, chromium oxide, vanadium oxide, hafnium oxide, magnesium oxide, strontium oxide, Examples include inorganic particles such as calcium carbonate, potassium titanate, barium sulfate, barium carbonate, clay, kaolin, porcelain clay, china clay, talc, carbon black, white carbon, diatomaceous earth, bentonite, hydrotalcite, etc. And two or more types can be used in combination.

  The mixing ratio of the color forming structure-forming resin and the non-spherical particles is usually 1: 0.0001 to 1: 0.01, preferably 1: 0.0001 to 1: 0.005 by weight. When the addition amount of the non-spherical particles is within such a range, a sufficient color development improving effect can be obtained.

In the present invention, in addition to the above-mentioned spherical particles and non-spherical particles, other particles (for example, particles having a standard deviation of the particle size distribution of more than 20% or an average particle size of 600 nm to the extent that the effects of the present invention are not impaired). Or particles less than 50 nm, etc.).
The other particles also preferably have a softening point higher than the softening point of the color forming structure-forming resin, particularly 20 ° C. or higher, more preferably 50 ° C. or higher than the softening point of the color forming structure-forming resin. Specifically, the softening point of the other particles may be 80 ° C. or higher (more preferably 100 ° C. or higher). The upper limit of the softening point of the other particles is not particularly limited, but is usually 1500 ° C. or lower (preferably 1000 ° C. or lower).

  In the present invention, it is particularly preferable to include particles (spherical particles, non-spherical particles, other particles) having a diffuse reflectance of 60% or less (preferably 30% or less, more preferably 10% or less). By including such particles, the transmitted light of the coloring structure is suppressed, and the reflected light of the coloring structure is recognized more clearly, which is preferable.

Particularly in the present invention, particles having a diffuse reflectance of 60% or less are 0.01% by weight or more and 80% by weight or less (preferably 0.01% by weight or more and 50% by weight or less, more preferably 0% of all particles). 0.02 wt% or more and 10 wt% or less).
Furthermore, in the present invention, the non-spherical particles are preferably particles having a diffuse reflectance of 60% or less. By using particles having a diffuse reflectance of 60% or less as non-spherical particles, the reflected light of the coloring structure can be made clearer and excellent structural coloration by the spherical particles can be exhibited.

  The diffuse reflectance is a value obtained by measuring the diffuse reflectance spectrum of each powder in the visible light region (in the present invention, wavelength: 550 nm) using a self-spectrophotometer.

  In the present invention, it is also preferable to include particles having luminous properties (spherical particles, non-spherical particles, and other particles). By including particles having phosphorescent properties, light emitted from the particles passes through the structural color body, and in combination with the hue of the structural color, excellent aesthetics can be obtained. Further, by adjusting the content of the phosphorescent particles, it is possible to clearly confirm the color of the structural color during the daytime, and it is possible to exhibit the color derived from the phosphorescent particles at night.

Examples of the phosphorescent particles include sulfides such as CaS: Bi, CaSr: Bi, ZnS: Cu, ZnCdS: Cu, and compounds represented by MAl ₂ O ₄ (M = Ca, Sr, Ba). Examples include those obtained by adding Eu as an activator and adding Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, Yb, and Lu as coactivators.
The average particle diameter of the particles having the luminous property is preferably 5 μm to 100 μm, more preferably 10 μm to 80 μm. By being in such a range, the above effect can be obtained more clearly. When the average particle size is too large, there is a risk of inhibiting the structural color development. When the average particle size is too small, the luminous properties are lowered, and it is difficult to obtain the effect due to the luminous properties at night.

The particles having phosphorescent properties are 0.5 wt% or more and 50 wt% or less (preferably 0.5 wt% or more and 30 wt% or less, more preferably 1.0 wt% or more and 20 wt% or less) of all particles. It is preferable that When the amount is more than 50% by weight, the arrangement of the spherical particles may be disturbed, and the color due to structural color development may be impaired. When the amount is less than 0.5% by weight, the phosphorescent property is lowered, and it is difficult to obtain the effect due to the luminous property at night.
Further, by including particles having fluorescence, light emitted from the particles having fluorescence passes through the structural color body and can be combined with the hue of the structural color to obtain excellent aesthetics.

The solid product (Q) in the present invention has an average particle size of 5 nm to 800 nm and a standard deviation of the particle size distribution of 20% or less of the average particle size in the color forming structure-forming resin (a) having thermoplasticity. Is characterized in that spherical particles (b) higher than the colored structure-forming resin are dispersed, and the mixing ratio of (a) and (b) is different from the solid (P) in weight ratio. It is.
In each solid material, since the mixing ratio of the coloring structure forming resin (a) and the spherical particles (b) is different, in the present invention, the structural color and the solid color of the coloring structure obtained from the solid material (P) are different. A structural color having excellent optical coherence, which is mixed with the structural color of the color forming structure obtained from the shaped product (Q), can be expressed.

As the color-forming structure-forming resin (a) having thermoplasticity used in the solid material (Q), the same one as the above-mentioned (a) can be used, and the color-forming structure used in the solid material (P) It may be the same as or different from the forming resin.
Similarly, the spherical particles (b) used in the solid material (Q) can be the same as the above-mentioned (b), and are the same as or different from the spherical particles used in the solid material (P). Also good.
As the solid (Q), in addition to the spherical particles (b), non-spherical particles having an average particle diameter of 600 nm or less and a softening point higher than that of the color forming structure-forming resin may be added. preferable.
In the present invention, in addition to the above-mentioned spherical particles and non-spherical particles, other particles (for example, particles having a standard deviation of the particle size distribution of more than 20% or an average particle size of 600 nm to the extent that the effects of the present invention are not impaired). Or particles less than 50 nm, etc.).

In the solid material (P) and the solid material (Q), in addition to the difference in the mixing ratio of the color forming structure forming resin (a) and the spherical particles (b), the difference in the average particle diameter of the spherical particles, Different structural colors may be developed due to differences in refractive index, differences in refractive index of the color forming structure forming resin, differences in refractive index between the spherical particles and the color forming structure forming resin, differences in the shape of the spherical particles, etc. it can. Moreover, as solid matter, solid matter other than solid matter (P) and solid matter (Q) can also be included, and 2 or 3 types obtained from 2 or 3 or more types of solid matter A more excellent structural color in which the above plurality of structural colors are mixed can also be expressed.
Moreover, it is preferable that the mixing ratio of solid matter (P) and solid matter (Q) is in the range of 100: 1 to 1: 100. When it is within this range, a more excellent structural color in which a plurality of structural colors are mixed can be expressed.
The sizes of the solid material (P) and the solid material (Q) are not particularly limited as long as each structural color can be recognized, but may be about 0.1 mm to 100 mm.

The method for producing a solid product (solid product (P), solid product (Q), etc.) in the present invention is not particularly limited.
In the present invention, spherical particles are regularly arranged by rolling, which will be described later, and it is not always necessary to arrange the spherical particles regularly at the time of manufacturing a solid product. Therefore, a solid product can be easily produced.
For example, as a method for obtaining a solid material, spherical particles are mixed with a resin solution composed of a color forming structure-forming resin and a solvent to prepare a mixed solution in which spherical particles are dispersed, and the solvent is removed from the mixed solution. By doing so, a solid substance can be obtained. The solvent may be removed usually at 30 to 200 ° C. for about 5 minutes to 24 hours. When non-spherical particles are used in addition to spherical particles, the solvent may be removed after preparing the above mixed solution with non-spherical particles added.

  In such a method, it is easy to obtain a solid material in which spherical particles are uniform and highly dispersed, and by rolling such a solid material, a structure in which the spherical particles are easily arranged uniformly and has a structural color is obtained. It can be easily obtained. Moreover, the obtained solid-state thing can also be rolled as it is, and can also be rolled, after pressurizing beforehand and making it into a film form. In the method of pre-pressing and rolling, not only the color development is facilitated during the rolling process, but also the solid material is not stretched during the rolling process.

The method for mixing the solid product (P) and the solid product (Q) is not particularly limited.
Examples of the mixing method include a method of uniformly mixing a solid material (P) of the same size and a solid material (Q) at a specific mixing ratio, and a solid material (P) of a different size and a solid material (P). A method of uniformly mixing the shaped product (Q) at a specific mixing ratio, a method of spraying and mixing a solid product (Q) having a specific size on a film-like solid product (P), and the like. It is done.
In the present invention, various colors can be expressed depending on the degree of mixing of the solid (P) and the solid (Q).

In the production of such a method, it is preferable to use a solvent-soluble thermoplastic resin soluble in a solvent, particularly a water-soluble thermoplastic resin, as the color forming structure-forming resin.
When such a resin is used, the spherical particles are likely to be uniformly and highly dispersed in the resin solution composed of the color-forming structure-forming resin and the solvent, and the color-forming structure-forming resin and the spherical particles are unevenly distributed in the resulting solid product. Is preferable. Furthermore, it is easy to obtain a solid material having excellent transparency, and good structural color development can be exhibited. In particular, by selecting a resin having excellent compatibility between the color forming structure-forming resin and the solvent, even more excellent structural color development can be exhibited.

Examples of the solvent used here include water, methanol, ethanol, propanol, isopropyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, benzyl alcohol, diacetone alcohol and other alcohols, ethylene glycol, diethylene glycol, Polyhydric alcohols such as propylene glycol, dipropylene glycol, trimethylol ethane, glycerin, cellosolve, butyl cellosolve, isobutyl cellosolve, carbitol, methyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, ethylene glycol t-butyl ether, diethylene glycol monoethyl ether, tri Ethers such as tylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, n-butane, n-hexane, Aliphatic hydrocarbons such as cyclohexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, aromatic hydrocarbons such as toluene, xylene, solvent naphtha, ethyl acetate, Examples include esters such as n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.
In the present invention, a solvent containing water is particularly preferable as the solvent. Therefore, it is preferable to use a water-soluble thermoplastic resin that is soluble in water as the color forming structure-forming resin.

In such a method, a solvent-soluble thermoplastic resin that is soluble in a solvent preferably exhibits an effect as a dispersant for spherical particles.
For example, if the spherical particle surface has a negative charge, a nonionic and / or anionic thermoplastic resin, and if the spherical particle surface has a positive charge, nonionic and / or It is preferable to select a resin having cationic thermoplasticity. Moreover, what has a steric hindrance effect, what has interaction (a hydrophobic hydrophilic interaction is included), and what has the effect which activates the interface of a spherical particle and a solvent may be used.
For example, when inorganic particles are used as the spherical particles, the surface of the inorganic particles often has a negative charge, and it is preferable to use a nonionic and / or anionic thermoplastic resin as the thermoplastic resin.

  In addition to the above-mentioned components, the components that form the solid material in the present invention are dispersants, plasticizers, antifoaming agents, leveling agents, thickeners, film-forming aids to the extent that the effects of the present invention are not impaired. Additives such as an agent, an ultraviolet absorber, and a pigment may be mixed.

The present invention is characterized in that the solid material thus obtained is rolled at a temperature higher than the softening point of the color forming structure-forming resin (a) and lower than the softening point of the spherical particles (b). To do.
By rolling in such a temperature range, the color forming structure forming resin is in a state close to a liquid, and the spherical particles are easy to move. As a result, the spherical particles can be filled in close-packed and regularly arranged. Therefore, it is possible to easily obtain a coloring structure having light coherence.
When the rolling temperature is lower than the softening point of the color forming structure forming resin, rolling cannot be performed and it becomes difficult to obtain the structure coloring property. On the other hand, when the temperature is higher than the softening point of the spherical particles, the spherical particles are melted, and a colored structure cannot be obtained.
When using both spherical particles and non-spherical particles in a solid material, rolling is performed in a temperature range that is higher than the softening point of the color forming structure-forming resin and lower than the softening point of the spherical particles and the softening point of the non-spherical particles. Good.

  In the present invention, in particular, since a solid material is used as a starting material, there are almost no volatile components, and there is almost no volume change before and after rolling. Therefore, the disturbance of the spherical particles accompanying the volume change can be suppressed, and a light-interfering color developing structure in which the spherical particles are uniformly arranged can be easily obtained.

  When a liquid or gel-like material is used as a starting material, the volatile component evaporates, resulting in a volume change before and after production. Therefore, the spherical particles are disturbed due to the volume change, and it is difficult to obtain a coloring structure having excellent light interference. Moreover, in order to suppress evaporation of a volatile component, it may be manufactured by sealing a liquid material or a gel-like material, but the manufacturing process becomes complicated and cannot be said to be a simple method.

  Moreover, the pressure at the time of heat rolling is not particularly limited, but the area of the solid material is preferably stretched about twice or more, and preferably 1 MPa to 100 MPa (more preferably 10 MPa to 50 MPa). If it is less than that, it is not preferred because the resin is not easily stretched, the spherical particles are difficult to arrange regularly, and the structural color development is difficult to occur. On the other hand, when the pressure is high, the resulting color developing structure becomes thin, the light transmittance is higher than the light diffraction, and the structural color developability is hardly recognized, which is not preferable.

  In the solid material of the present invention, by applying pressure in a direction perpendicular to and parallel to the surface direction by rolling, the arrangement of the spherical particles becomes regular, and structural coloring occurs. Here, as a specific method of applying pressure in a direction perpendicular to and parallel to the surface direction, a solid object is curved using two rolls, and the moving distance between the roll side and the other roll side is set. By causing the difference, pressure is applied in a direction parallel to the surface direction. Further, at this time, a colored structure can be obtained by sandwiching a solid material with two rolls and applying pressure in a direction perpendicular to the surface direction. It is also possible to use a single roll, and a colored structure can be obtained by applying pressure to a solid material, changing the direction of the roll 180 ° about the roll, and applying a shear stress. . At this time, the spherical particles are easily arranged by sandwiching the solid material with a flexible film having a higher softening point than the softening point of the color forming structure-forming resin.

The coloring structure obtained in this way can be used after adjusting to a predetermined size if necessary.
For example, a coloring structure adjusted to a predetermined size can be laminated on each substrate and used as a laminate. As the base material, for example, aluminum steel plate, zinc steel plate, stainless steel plate, copper steel plate, etc., metal steel plate, plastic sheet / board, extruded plate, ceramic, glass, fired tile, porcelain tile, wood, concrete, mortar, gypsum board , Fiber-mixed cement board, calcium silicate board, slag cement pearlite board, ALC board, siding board, and the like, and a coloring structure can be laminated on such a substrate via a known adhesive or the like.

Alternatively, the coloring structure may be crushed to obtain a coloring structure chip, and a composition for a color coating layer obtained by mixing the coloring structure chip in a binder may be applied and laminated on each substrate to be used as a laminate. it can. In such a case, the size of the color developing structure chip is not particularly limited, but is preferably 0.1 mm or more and 50 mm or less (more preferably 0.5 mm or more and 30 mm or less). The thickness of the coloring structure chip is preferably 1 μm or more and less than 500 μm (preferably 5 μm or more and less than 200 μm).
Examples of the binder include acrylic resin, polyester resin, polyether resin, vinyl resin, polyamide resin, phenol resin, urethane resin, epoxy resin, fluororesin, vinyl acetate resin, vinyl chloride resin, acrylic-styrene resin, vinyl acetate. -Versamic acid vinyl ester resin, polyvinyl pyrrolidone resin, polyvinyl caprolactam resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, AS resin, cellulose resin, acrylic-silicone resin, silicone resin, alkyd resin, melamine resin, amino resin, vinyl chloride resin Vinyl resins, and the like. Solvent-free, solvent-soluble, NAD, water-soluble, and water-dispersed types of such resins can be used.

  The mixing amount of the coloring structure chip and the binder is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the solid content of the binder.

  In addition, the color coating layer composition includes a colorant, an aggregate, a dye, an extender pigment, a fiber, a thickener, a film-forming aid, a leveling agent, and a plasticizer to the extent that the effects of the present invention are not impaired. Antifreezing agents, pH adjusting agents, antiseptics, antifungal agents, antialgae agents, antibacterial agents, dispersants, antifoaming agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents, and the like can also be mixed.

In the method of applying and laminating the composition for the color coating layer, it may be applied on the base material using a coating tool such as a brush, a roller, or a spray, and is not particularly limited, such as a single application or a multiple application. The required amount of color coating layer composition is not particularly ^{limited, 30g / m 2 ~5000g / m} 2, it is preferable that further, ^{100g / m 2 ~4000g / m 2} .
As the color coating layer obtained by applying and laminating the composition for the color coating layer, a layer having transparency enough to recognize the hue of the color developing structure chip and the hue of the substrate is preferable. The transparency of the color coating layer is not particularly limited, but the light transmittance is preferably about 20% to 95% (preferably 40% to 90%, more preferably 50% to 88%). When the light transmittance is in such a range, a laminate can be obtained without losing the color and brightness of the coloring structure chip. Moreover, when the base material is colored, the hue of the base material can be expressed, and a multicolored and various laminate can be obtained.

  The light transmittance is based on the measuring method A defined in JIS K 7105-1981 5.5 “Light transmittance and total light reflectance”, and an integrating sphere light transmittance measuring device (for example, Shimadzu Corporation). (Total thickness 0.4 mm).

  The thickness (dry film thickness) of the color coating layer is preferably about 0.1 mm to 5 mm (more preferably 0.2 mm to 2 mm). Furthermore, when the thickness of the color coating layer is 0.5 mm or more, it is possible to obtain a laminate having a deep feeling and a deep aesthetic appearance.

Furthermore, a topcoat layer can be laminated on the color coating layer.
For example, acrylic resin, acrylic-silicon resin, silicone resin, alkyd resin, fluorine resin, phenol resin, urethane resin, epoxy resin, polyester resin, polyether resin, vinyl resin, polyamide resin, etc. as a binder It can obtain from the composition for topcoat layers.
In the present invention, it is particularly preferable to use an acrylic resin containing 50% by weight or more of methyl methacrylate monomer and / or methyl methacrylate oligomer as the binder. By using such an acrylic resin, it is possible to form a topcoat layer having excellent scratch resistance and abrasion resistance. Moreover, the topcoat layer excellent in antifouling property can also be formed by using the binder containing acrylic-silicon resin and silicone resin.
In addition to this, coloring materials, aggregates, extender pigments, fibers, thickeners, film-forming aids, leveling agents, plasticizers, antifreezing agents, pH adjusters, antiseptics, etc. Agents, fungicides, anti-algae agents, antibacterial agents, dispersants, antifoaming agents, ultraviolet absorbers, antioxidants, catalysts, crosslinkable compounds, and the like can also be mixed.

In the present invention, it is particularly preferable to mix a crosslinkable compound because the scratch resistance and wear resistance can be improved. Examples of the crosslinkable compound include a compound having a reactive functional group, particularly a compound having two or more reactive functional groups in the molecule.
Examples of combinations of reactive functional groups include, in addition to vinyl groups, carboxyl groups and epoxy groups, carboxyl groups and carbodiimide groups, carboxyl groups and aziridines, carboxyl groups and oxazoline groups, hydroxyl groups and isocyanate groups, and carbonyl groups. Examples include hydrazide groups, epoxy groups and amino groups, reactive silyl groups, carboxyl groups and metal ions.

  Examples of the crosslinkable compound include ethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, divinylbenzene, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol diester. Examples include methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, trimethylolpropane methoxylated triacrylate, and trimethylolpropane ethoxylated triacrylate.

  The mixing amount of the crosslinkable compound is not particularly limited, but is preferably 1% by weight or more and 20% by weight with respect to the total amount of the composition for the topcoat layer.

As the transparency of the topcoat layer, the light transmittance is preferably about 60% or more (preferably 70% to 99%).
As a method of laminating, a topcoat film (sheet) obtained by forming a composition for a topcoat layer containing each component into a film (sheeting) is pasted on the color coating layer via an adhesive or the like. Just wear it.
Moreover, the composition for topcoat layers can also be directly apply | coated and laminated | stacked on a color coating layer. In the method of direct coating and lamination, coating may be performed on the color coating layer using a coating tool such as a brush, roller, spray, coater, or iron, and there is no particular limitation such as single coating or multiple coating.

(Experimental example 1)
<Preparation of solid material A>
Using the raw materials shown in Table 1, a resin solution was prepared by mixing the resin A with the solvent A at a temperature of 23 ° C. and a relative humidity of 50% (hereinafter also referred to as “standard state”) at the mixing ratio shown in Table 2. The resin solution was mixed with particles A to prepare a mixed solution. 50 g of this mixed solution was put into an aluminum container (φ100 mm), and the solvent A was volatilized at 120 ° C. for 3 hours to obtain a solid A. The obtained solid A was transparent and the particles were uniformly dispersed.
<Preparation of solid product B>
Using the raw materials shown in Table 1, a solid B was obtained in the same manner as the solid A with the mixing ratio shown in Table 2. The obtained solid B was transparent and particles were uniformly dispersed.
The obtained solid product A and solid product B were each pulverized to a size of 2 mm, and 50 parts by weight of solid product A and 50 parts by weight of solid product B were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color indicating purple and a structural color indicating blue were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 2)
<Preparation of solid product C>
Using the raw materials shown in Table 1, a solid product C was obtained in the same manner as the solid product A at the mixing ratio shown in Table 2. The obtained solid C was transparent and the particles were uniformly dispersed.
The obtained solid B and solid C were each pulverized to a size of φ2 mm, and 40 parts by weight of solid B and 60 parts by weight of solid C were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing a blue color and a structural color showing a green color were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 3)
<Preparation of solid product D>
Using the raw materials shown in Table 1, a solid material D was obtained in the same manner as the solid material A at the mixing ratio shown in Table 2. The obtained solid D was transparent and the particles were uniformly dispersed.
The obtained solid B was pulverized to a size of φ3 mm and the solid D was φ2 mm, and 50 parts by weight of the solid B and 50 parts by weight of the solid D were uniformly mixed. The mixed solid was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 80 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing a blue color and a structural color showing a red color were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 4)
The obtained solid A was pulverized to a size of 4 mm and the solid B was pulverized to a diameter of 2 mm, and 30 parts by weight of the solid A and 70 parts by weight of the solid B were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), rolled at 80 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent.
The object after rolling had excellent aesthetics in which a structural color indicating purple and a structural color indicating blue were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 5)
The obtained solid product A and solid product B were each pulverized to a size of 2 mm, and 50 parts by weight of solid product A and 50 parts by weight of solid product B were uniformly mixed. The mixed solid material was sandwiched between PEN films (100 mm × 100 mm), rolled and repeatedly curved at 170 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color indicating purple and a structural color indicating blue were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 6)
The obtained solid A is pressed and formed into a film, and then pulverized to a size of φ7 mm. The obtained solid B is pulverized to a size of φ2 mm, and the solid A is 30 wt. Parts and 70 parts by weight of solid B were mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent.
The object after rolling had excellent aesthetics in which the purple-based structural color derived from the solid material A was depicted in the form of spots in the blue-based structural color derived from the solid material B. . Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 7)
The obtained solid B was press-pressed and formed into a film and then pulverized to a size of φ8 mm. The obtained solid D was pulverized to a size of φ3 mm to obtain a solid B 20 weight. Part and solid part D80 weight part were mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), rolled at 80 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent.
The object after rolling had excellent aesthetics in which the blue structural color derived from the solid B was depicted in the form of spots in the red structural color derived from the solid D. . Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 8)
<Preparation of solid material E>
Using the raw materials shown in Table 1, a solid material E was obtained in the same manner as the solid material A at the mixing ratio shown in Table 2. The obtained solid E was transparent and the particles were uniformly dispersed.
<Preparation of solid material F>
Using the raw materials shown in Table 1, a solid product F was obtained in the same manner as the solid product A at the mixing ratio shown in Table 2. The obtained solid F was transparent and the particles were uniformly dispersed.
The obtained solid product E and solid product F were each pulverized to a size of 2 mm, and 50 parts by weight of solid product E and 50 parts by weight of solid product F were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color indicating green and a structural color indicating blue were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 9)
<Preparation of solid product G>
Using the raw materials shown in Table 1, a solid product G was obtained in the same manner as the solid product A at the mixing ratio shown in Table 2. The obtained solid G was transparent and the particles were uniformly dispersed.
<Preparation of solid product H>
Using the raw materials shown in Table 1, a solid material H was obtained in the same manner as the solid material A at the mixing ratio shown in Table 2. The obtained solid H was transparent and the particles were uniformly dispersed.
The obtained solid G was pulverized to a size of φ10 mm and the solid H was φ2 mm, and 30 parts by weight of the solid G and 70 parts by weight of the solid H were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color indicating green and a structural color indicating blue were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 10)
<Preparation of solid material I>
Using the raw materials shown in Table 1, the solid material I was obtained in the same manner as the solid material A at the mixing ratio shown in Table 2. The obtained solid I was transparent and the particles were uniformly dispersed.
<Preparation of solid J>
Using the raw materials shown in Table 1, a solid J was obtained in the same manner as the solid A with the mixing ratio shown in Table 2. The obtained solid J was transparent and the particles were uniformly dispersed.
The obtained solid I and solid J were each pulverized to a size of φ2 mm, and 50 parts by weight of solid I and 50 parts by weight of solid J were uniformly mixed. The mixed solid was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 80 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color indicating green and a structural color indicating red were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 11)
<Preparation of solid material K>
Using the raw materials shown in Table 1, the solid material K was obtained in the same manner as the solid material A at the mixing ratio shown in Table 2. The obtained solid K was transparent and particles were uniformly dispersed.
<Preparation of solid material L>
Using the raw materials shown in Table 1, a solid L was obtained in the same manner as the solid A with the mixing ratio shown in Table 2. The obtained solid L was transparent and particles were uniformly dispersed.
The obtained solid material K was pulverized to a size of φ1 mm and the solid material L was pulverized to a size of φ3 mm, and 90 parts by weight of the solid material K and 10 parts by weight of the solid material L were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color indicating red and a structural color indicating green were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week. Further, when the resulting color-developing structure was allowed to stand in water, it showed excellent structural color development even after 24 hours.

(Experimental example 12)
<Preparation of solid material M>
Using the raw materials shown in Table 1, a solid product M was obtained in the same manner as the solid product A at the mixing ratio shown in Table 2. The obtained solid M was red and transparent, and the particles were uniformly dispersed.
<Preparation of solid material N>
Using the raw materials shown in Table 1, a solid material N was obtained in the same manner as the solid material A at the mixing ratio shown in Table 2. The obtained solid N was transparent in red and the particles were uniformly dispersed.
The obtained solid M was pulverized to a size of 2 mm and the solid N was pulverized to 5 mm, and 50 parts by weight of the solid M and 50 parts by weight of the solid N were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing a clear blue-green color and a structural color showing a clear yellow color were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 13)
<Preparation of solid material O>
Using the raw materials shown in Table 1, solid materials O were obtained in the same manner as the solid materials A at the mixing ratios shown in Table 2. The obtained solid O was transparent and particles were uniformly dispersed.
<Preparation of solid material P>
Using the raw materials shown in Table 1, a solid P was obtained in the same manner as the solid A with the mixing ratio shown in Table 2. The obtained solid P was transparent and particles were uniformly dispersed.
The obtained solid product O and solid product P were each pulverized to a size of φ2 mm, and 50 parts by weight of solid product O and 50 parts by weight of solid product P were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing a clear blue system and a structural color showing a clear green system were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 14)
<Preparation of solid product Q>
Using the raw materials shown in Table 1, the solid material Q was obtained in the same manner as the solid material A at the mixing ratio shown in Table 2. The obtained solid Q was transparent and black, and the particles were uniformly dispersed.
<Preparation of solid material R>
Using the raw materials shown in Table 1, a solid material R was obtained in the same manner as the solid material A at the mixing ratio shown in Table 2. The obtained solid R was black and transparent, and the particles were uniformly dispersed.
The obtained solid product Q was pulverized to a size of φ2 mm and the solid product R was pulverized to a size of φ2 mm, and 20 parts by weight of the solid product Q and 80 parts by weight of the solid product R were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing a clear blue system and a structural color showing a clear green system were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 15)
<Preparation of solid material S>
Using the raw materials shown in Table 1, the solid material S was obtained in the same manner as the solid material A at the mixing ratio shown in Table 2. The obtained solid S was yellow and transparent, and the particles were uniformly dispersed.
<Preparation of solid product T>
Using the raw materials shown in Table 1, a solid product T was obtained in the same manner as the solid product A at the mixing ratio shown in Table 2. The obtained solid T was yellow and transparent, and the particles were uniformly dispersed.
The obtained solid product S and solid product T were each pulverized to a size of φ2 mm, and 40 parts by weight of solid product S and 60 parts by weight of solid product T were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing a blue color and a structural color showing a green color were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week. Moreover, when it was left to stand under a fluorescent lamp for 20 minutes and the phosphorescent property was confirmed in a dark place, the luminous property of 2 hours was confirmed visually.

(Experimental example 16)
<Preparation of solid U>
Using the raw materials shown in Table 1, solid materials U were obtained in the same manner as the solid materials A at the mixing ratios shown in Table 2. The obtained solid U was black and transparent, and the particles were uniformly dispersed.
<Preparation of Solid V>
Using the raw materials shown in Table 1, a solid V was obtained in the same manner as the solid A with the mixing ratio shown in Table 2. The obtained solid V was transparent and black, and the particles were uniformly dispersed.
The obtained solid substance U and solid substance V were each pulverized to a size of φ2 mm, and 50 parts by weight of solid substance U and 50 parts by weight of solid substance V were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing a clear blue system and a structural color showing a clear green system were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week. Moreover, when it was left to stand under a fluorescent lamp for 20 minutes and the phosphorescent property was confirmed in a dark place, the luminous property of 2 hours was confirmed visually.

(Experimental example 17)
The obtained solid A and solid N were each pulverized to a size of 2 mm, and 50 parts by weight of solid A and 50 parts by weight of solid N were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing a purple color and a structural color showing a clear yellow color were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experiment 18)
The obtained solid A and solid T were each pulverized to a size of φ2 mm, and 30 parts by weight of solid A and 70 parts by weight of solid T were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing purple and a structural color showing clear green were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week. Moreover, when it was left to stand under a fluorescent lamp for 20 minutes and the phosphorescent property was confirmed in a dark place, the luminous property of 2 hours was confirmed visually.

(Experimental example 19)
The obtained solid product A, solid product B, and solid product C were each pulverized to a size of φ2 mm, and the solid product A, 30 parts by weight, the solid product B, 40 parts by weight, and the solid product C, 30 parts by weight were evenly mixed. Mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing purple, a structural color showing blue, and a structural color showing green were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experiment 20)
<Preparation of solid material W>
Using the raw materials shown in Table 1, a solid product W was obtained in the same manner as the solid product A at the mixing ratio shown in Table 2. The obtained solid W was white and the particles were uniformly dispersed.
The obtained solid product A, solid product B, and solid product W were each pulverized to a size of φ2 mm, and 50 parts by weight of solid product A, 40 parts by weight of solid product B, and 10 parts by weight of solid product W were uniformly distributed. Mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a white portion and a structural color indicating purple and a structural color indicating blue were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 21)
The obtained solid A and solid W were each pulverized to a size of φ2 mm, and 50 parts by weight of solid A and 50 parts by weight of solid W were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling was a film composed of a portion showing a purple structure color and a white portion without showing the structure color.

(Experimental example 22)
<Preparation of solid X>
Using the raw materials shown in Table 1, the solid material X was obtained in the same manner as the solid material A at the mixing ratio shown in Table 2. The obtained solid X was transparent and the particles were uniformly dispersed.
The obtained solid product W and solid product X were each pulverized to a size of 2 mm, and 50 parts by weight of solid product W and 50 parts by weight of solid product X were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller. The object after rolling did not show structural coloring, and the obtained film was white.

(Experimental example 23)
The obtained solid product A and solid product D were each pulverized to a size of 2 mm, and 50 parts by weight of solid product A and 50 parts by weight of solid product D were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller. The object after rolling was a film composed of a portion showing a purple structure color and a white portion without showing the structure color.

(Experimental example 24)
The obtained solid substance D and solid substance J were each pulverized to a size of φ2 mm, and 50 parts by weight of the solid substance W and 50 parts by weight of the solid substance X were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller. The object after rolling did not show structural coloring, and the obtained film was white.

(Experimental example 25)
<Preparation of solid material Y>
Using the raw materials shown in Table 1, a solid product Y was obtained in the same manner as the solid product A at the mixing ratio shown in Table 2. The obtained solid Y was transparent and the particles were uniformly dispersed.
The obtained solid A and solid Y were each pulverized to a size of φ2 mm, and 50 parts by weight of solid A and 50 parts by weight of solid Y were uniformly mixed. The mixed solid material was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 130 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color indicating purple and a structural color indicating red were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experimental example 26)
<Preparation of solid product Z>
Using the raw materials shown in Table 1, a solid product Z was obtained in the same manner as the solid product A at the mixing ratio shown in Table 2. The obtained solid Z was transparent and the particles were uniformly dispersed.
The obtained solid I and solid Z were each pulverized to a size of φ2 mm, and 50 parts by weight of solid I and 50 parts by weight of solid Z were uniformly mixed. The mixed solid was sandwiched between PET films (100 mm × 100 mm), and rolled and bent at 80 ° C. and 30 MPa using a heated rolling roller.
The object after rolling had excellent aesthetics in which a structural color showing green and a structural color showing purple were expressed in a striped pattern. Furthermore, when the obtained color-developing structure was allowed to stand for one week in a standard state, excellent color development was exhibited even after one week.

(Experiment 27)
Using the raw materials shown in Table 1, 100 parts by weight of solvent A and 10 parts by weight of particles A were mixed in a standard state, and applied to an aluminum substrate by a dip coating method to produce a film having structural color development. The obtained film showed interference by light, but was not self-supporting, and particles were peeled off when rubbed with a finger.

(Experimental example 28)
The coloring structure obtained in Experimental Example 1 was crushed to a size of about 1 to 30 mm to obtain a coloring structure chip (thickness: 100 μm).
Color coating in which 100 parts by weight of epoxy resin (solid content: 100% by weight) and 5 parts by weight of colored structure chip are mixed on a porcelain tile plate (100 mm x 100 mm x 6 mm, L ^* = 10) colored black The layer composition was applied with a brush so that the thickness (dry film thickness) was 0.4 mm, and dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours to obtain a color coating layer, and a laminate. Got. The light transmittance of the color coating layer formed from the composition for color coating layer was 71%.
The surface of the obtained laminate had a calm purple and blue luminance feeling in a black background, and had a soft and deep aesthetic appearance.

(Experimental example 29)
On the laminate obtained in Experimental Example 28, 75 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of quartz powder (average particle size: 30 μm, refractive index: 1.45), peroxide The topcoat layer composition A consisting of 2 parts by weight of benzoyl was applied so that the thickness (dry film thickness) was 1.0 mm, dried and cured for 2 hours at a temperature of 25 ° C. and a relative humidity of 50%, and the top A coat layer was obtained to obtain a laminate. The light transmittance of the topcoat layer formed from the composition A for topcoat layer was 85%, and the refractive index was 1.49.
The surface of the obtained laminate had a calm purple and blue luminance feeling in a black background, and had a soft and deep aesthetic appearance.
Further, a JIS K 5400 8.9 wear resistance test was conducted. CS17 was used as the tapered wear wheel. As a result, the wear loss was 18 g / 100 cm ² .

(Experimental example 30)
On the laminate obtained in Experimental Example 28, 75 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 6 parts by weight of dipentaerythritol hexaacrylate, quartz powder (average particle size: 30 μm, refractive index: 1) .45) Topcoat layer composition B comprising 3 parts by weight and 2 parts by weight of benzoyl peroxide was applied so that the thickness (dry film thickness) was 1.0 mm, and the temperature was 25 ° C. and the relative humidity was 50%. Then, it was dried and cured for 2 hours to obtain a topcoat layer to obtain a laminate. The light transmittance of the topcoat layer formed from the composition B for topcoat layer was 85%, and the refractive index was 1.49.
The surface of the obtained laminate had a calm purple and blue luminance feeling in a black background, and had a soft and deep aesthetic appearance.
Further, a JIS K 5400 8.9 wear resistance test was conducted. CS17 was used as the tapered wear wheel. As a result, the wear loss was 13 g / 100 cm ² .

Claims (2)

In the coloring structure forming resin (a) having thermoplasticity, the average particle diameter is 5 nm to 800 nm, the standard deviation of the particle diameter distribution is 20% or less of the average particle diameter, and the softening point is higher than that of the coloring structure forming resin. Particles (b) are dispersed, and the solid (P) in which the mixing ratio of (a) and (b) is 1: 0.01 to 1:10 by weight,
In the coloring structure forming resin (a) having thermoplasticity, the average particle diameter is 5 nm to 800 nm, the standard deviation of the particle diameter distribution is 20% or less of the average particle diameter, and the softening point is higher than that of the coloring structure forming resin. Solid particles having a mixing ratio different from that of the solid material (P), wherein the particles (b) are dispersed, and the mixing ratio of (a) and (b) is 1: 0.01 to 1:10 by weight ratio. Thing (Q) is mixed,
Rolling a mixture of the solid material (P) and the solid material (Q) at a temperature higher than the softening point of the colored structure-forming resin (a) and lower than the softening point of the spherical particles (b). A method for producing a color developing structure having optical coherence characterized by 2. The method for producing a color developing structure having optical coherence according to claim 1, wherein the spherical particles (b) are inorganic particles.