JP4895747B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate having optical coherence.

Materials having optical coherence and high brightness are widely used as building materials for home appliances, furniture, vehicles, walls, floors, ceilings and the like.
By using such a material for a part or all of a product, it is possible to express design with high chroma and impact.

  Examples of the material having such light coherence and high brightness feeling include materials described in Patent Document 1 and the like. In Patent Document 1, in order to express light interference and high brightness, aluminum flake pigment, vapor-deposited aluminum flake pigment, metal oxide-coated aluminum flake pigment, colored aluminum flake pigment, metal oxide are used as fine flake pigments. Coated mica pigment, metal oxide coated synthetic mica pigment, metal oxide coated alumina flake pigment, metal oxide coated silica flake pigment, metal coated glass flake pigment, metal oxide coated glass flake pigment, metal oxide coated plate oxidation Iron, graphite, stainless steel flakes, metallic titanium flake pigments, plate-like molybdenum sulfide, plate-like bismuth chloride, hologram pigments, cholesteric liquid crystal polymers, etc. are used.

JP 2005-137852 A

Recently, there is a growing demand for materials with a sense of brightness in a wide range of fields such as home appliances / furniture, vehicles, walls, floors, ceilings, and other building materials. Is often requested.
For example, for building materials such as walls, floors, and ceilings, a material having a deep and calm brightness has been desired.
However, the material as in Patent Document 1 tends to have a too strong brightness, and in some cases, the material may be avoided.

  In order to solve the above-mentioned problems, the present invention has been intensively studied. As a result, a color clear layer containing a light-interfering chip in which specific spherical particles are regularly arranged in a resin on a colored substrate layer. It has been found that a laminate obtained by laminating a layer has a deep and calm brightness and is excellent in aesthetics, and the present invention has been completed.

That is, the present invention has the following characteristics.
1. On the colored substrate layer, a color clear layer containing a light-interfering chip exhibiting structural coloring is laminated,
In the optical coherent chip, 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 are arranged in the chip forming resin .
Furthermore, a laminate comprising non-spherical particles having an average particle diameter of 600 nm or less and an aspect ratio of 1.2 or more and 600 or less .
2. A color clear layer containing a light-interfering chip exhibiting structural color development on the colored substrate layer, and a clear layer is laminated on the color clear layer;
In the optical coherent chip, 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 are arranged in the chip forming resin .
Furthermore, a laminate comprising non-spherical particles having an average particle diameter of 600 nm or less and an aspect ratio of 1.2 or more and 600 or less .
3. The optical coherent chip has a spherical particle having an average particle diameter of 5 nm to 800 nm and a standard deviation of the particle diameter distribution of 20% or less in the chip forming resin , and an average particle diameter of 600 nm or less, and an aspect ratio of 1.2 to 600. It is obtained by rolling a solid material in which non-spherical particles are dispersed. Or 2. The laminated body as described in.
4). Iridescent chip, the chip forming resin having thermal plasticity, the average particle diameter 5Nm～800nm, with a standard deviation of the particle size distribution than 20%, a high spherical particles softening point than the chip forming resin, and an average particle A solid material in which non-spherical particles having a diameter of 600 nm or less and an aspect ratio of 1.2 to 600 and having a softening point higher than that of the chip-forming resin is dispersed is higher than the softening point of the chip-forming resin, 1. Rolled at a temperature lower than the softening point of the spherical particles and the softening point of the non-spherical particles . To 3. The laminated body in any one of.
5). The ratio of the chip forming resin to the spherical particles is 1: 0.01 to 1:10 by weight, and the ratio of the chip forming resin to the non-spherical particles is 1: 0.0001 to 1: 0.01 by weight. It is characterized by the following. To 4. The laminated body in any one of.
6). From a mixed solution consisting of a chip-forming resin, spherical particles having an average particle size of 5 nm to 800 nm, non-spherical particles having an average particle size of 600 nm or less and an aspect ratio of 1.2 to 600, and a solvent, 2. It is obtained by removing the solvent. To 5. The laminated body in any one of.

  The laminate of the present invention has a deep and calm brightness, and has excellent aesthetics.

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

  The laminate of the present invention is formed by laminating a color clear layer containing a light coherent chip exhibiting structural coloring on a colored substrate layer, and the light coherent chip is averaged in the chip forming resin. Spherical particles having a particle diameter of 5 nm to 800 nm and a standard deviation of the particle diameter distribution of 20% or less are arranged.

The laminate of the present invention is characterized in that a brightness feeling is expressed using an optical coherent chip. Such a light interference chip is capable of expressing a soft, deep, and calm brightness as compared with a metal color expressed by a bright pigment such as a metal pigment.
In the present invention, it is possible to express a soft, deep and calm brightness by the hue of the colored base material layer and the brightness of the light interference chip in the color clear layer, and a laminate having excellent aesthetics. You can get a body.

The coloring base layer is not particularly limited, and materials used for building materials such as home appliances / furniture, vehicles, sheets, tiles, walls, floors, ceilings, and the like can be used.
Such materials include aluminum steel plates, zinc steel plates, stainless steel plates, copper steel plates and other metal steel plates, plastic plates, extruded plates, ceramics, glass, fired tiles, porcelain tiles, wood, concrete, mortar, gypsum boards, fibers Examples include a mixed cement board, a calcium silicate board, a slag cement pearlite board, an asbestos cement board, an ALC board, and a siding board. The surface of such a material may be the hue of the material itself, but may be colored by some method.

Examples of a method of coloring the surface of such a material include a method of coloring by coating with a coating material containing a coloring material and a binder.
Examples of the colorant include titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, molybdate orange, permanent red, permanent carmine, Anthraquinone red, perylene red, quinacridone red, ferric oxide, yellow iron oxide, titanium yellow, first yellow, chrome green, ocher, ultramarine, bitumen, cobalt green, cobalt blue and other inorganic color pigments, azo, naphthol , Pyrazolone, anthraquinone, perylene, quinacridone, benzimidazole, phthalocyanine, disazo, isoindolinone, quinophthalone and other organic color pigments, aluminum pigments, pearl pigments, fluorescent Fee, phosphorescent pigments, colored mica, mica, colored sand, aggregate, such as white marble, dyes and the like, may be used alone or two or more of them. In this invention, since it is excellent in the color effect by the combination with the optical interference chip | tip of a color clear layer, scale-like coloring materials, such as colored mica and mica, are used suitably.
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 Examples of the binder include solventless types such as vinyl resins, solvent-soluble types, NAD types, water-soluble types, and water-dispersed types, and one or more of these can be used.
By appropriately setting such a colorant and the like, the hue of the colored base material layer can be selected.

The hue is not particularly limited, such as black, brown, purple, blue, green, yellow, orange, red, and white. In the present invention, each hue can have a deep and calm brightness, and can have excellent aesthetics. In the present invention, in order to enhance the effect of the optical coherent chip, those colored in a dark hue are preferable. Specifically, the L ^* value is preferably 50 or less, more preferably 40 or less, and if the L ^* value is 50 or less, a luminance feeling due to structural color development can be clearly expressed.

As these coloring base material layers, the surface may have a concavo-convex structure. By having the concavo-convex structure, the optical coherent chip is fixed in an irregularly arranged state with a certain degree of inclination, so that the obtained laminate emits various colors depending on the viewing angle, the amount of light, etc. It is possible to express a soft, deep and calm brightness.
When unevenness is applied to the surface of the colored base material layer, the colored base material layer itself may be provided with unevenness by embossing or the like, or a mold with unevenness is used, and the sheet forming component is poured into the mold, A sheet material obtained by demolding after curing can also be used as a base material, and irregularities may be applied by coating a coating material containing pigments and aggregates on the above-described material. .
Such a colored base material layer is preferably a colored base material layer having irregularities in which the difference between the bottom and the top is 0.1 mm or more and 50 mm or less, and further 0.3 mm or more and 30 mm or less. By having such irregularities, it is possible to express a soft, deep, and calm color that emits various colors.

The color clear layer of the present invention contains a light coherent chip and imparts a color of structural coloring by the light coherent chip.
Structural coloration is a color developed by an optical phenomenon (light interference, diffraction, scattering) caused by having a fine structure with a wavelength of light in the visible region or less, and the structural coloration of the present invention is a chip. It is one that develops color due to the fine structure of spherical particles arranged in the forming resin.

Specifically, as an optical coherent chip, the average particle size is 5 nm or more and 800 nm or less (preferably 10 nm or more and 790 nm or less, more preferably 30 nm or more and 780 nm or less), and the standard deviation of the particle size distribution is 20% or less of the average particle size ( Spherical particles that are preferably 15% or less, more preferably 10% or less) are used in which the spherical particles are regularly arranged in the chip-forming resin.
By using such an optical coherent chip, it is possible to express a deep and calm brightness and a three-dimensional aesthetic.
If the average particle size is out of this range or the standard deviation of the particle size distribution is higher than 20% of the average particle size, the light coherence in the visible light region is impaired and the desired aesthetics are difficult to obtain. .
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 optical coherent chip used in the present invention is one in which spherical particles are arranged in a chip forming resin. A known manufacturing method may be employed as a method for manufacturing the optical coherent chip. In the present invention, in particular, it is preferable to manufacture by rolling a solid material in which spherical particles are dispersed in a chip-forming resin for forming an optical coherent chip. In such a method, spherical particles can be easily arranged regularly, and an optical coherent chip having excellent optical coherence can be easily manufactured.

  In particular, in a chip-forming resin, a solid material in which spherical particles having an average particle size of 5 nm to 800 nm and a standard deviation of particle size distribution of 20% or less and a softening point higher than that of the chip-forming resin are dispersed, It is preferably produced by rolling at a temperature higher than the softening point of the chip-forming resin and lower than the softening point of the spherical particles.

Such a method is characterized in that, during rolling, a solid material is used as a starting material, and the solid material is rolled at a temperature higher than the softening point of the chip-forming resin and lower than the softening point of the spherical particles. It is what. Therefore, at the time of rolling, the chip-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, and an optical coherent chip can be obtained.
When rolling at a temperature lower than the softening point of the chip-forming resin, the degree of freedom of the spherical particles is constrained and may not be regularly arranged. In addition, when rolling at a temperature higher than the softening point of the spherical particles, the spherical particles may be softened, and the shape may be lost and the color may not be developed.

Moreover, in such a method, since a solid substance is used as a starting material, handling is simple and it 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 chip that exhibits structural color development having excellent optical coherence.

The chip forming resin used in such a method has thermoplasticity and is not particularly limited as long as it softens during rolling, and various resins can be used.
Chip forming resins 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-silicon resin, silicone resin, alkyd resin, melamine resin, amino resin, vinyl chloride resin, Examples of the resin include solvent-free types, solvent-soluble types, NAD types, water-soluble types, water-dispersed types, and the like.

Further, the chip forming resin preferably includes 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 monomer having such a reactive functional group is 50% by weight or less, further 0.5% by weight, based on the total amount of the monomer components when polymerizing the resin forming the light interference chip. 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 chip in which spherical particles are uniformly arranged.

  The softening point of the chip-forming resin in the present invention is preferably about 20 ° C. or higher and 300 ° C. or lower (preferably 50 ° C. or higher and 200 ° C. or lower). When the softening point of the chip-forming resin is lower than 20 ° C., structural coloration can be exhibited by rolling, but softening occurs at room temperature, and the arrangement of spherical particles may be disturbed, resulting in no structural coloration.

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

  The spherical particles used in the present invention are not particularly limited as long as they finally exhibit structural coloration, but in order to exhibit structural coloration, the average particle diameter of spherical particles is 5 nm to 800 nm (preferably 10 nm to 500 nm). Or less).

In the present invention, structural coloration can be exhibited by further uniforming the size of the spherical particles. Specifically, the standard deviation of the particle size distribution of the spherical particles is 20% or less of the average particle size (moreover, 10 % Or less, and further 5% or less), the spherical particles can be regularly arranged and can exhibit excellent structural color development.
The aspect ratio of the spherical particles 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 can be arranged regularly and can exhibit better structural color development. 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 spherical particles 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, hafnium oxide, and oxide. Examples include inorganic particles such as magnesium, strontium oxide, calcium carbonate, zinc carbonate hydroxide, potassium titanate, iron hydroxide oxide, barium sulfate, barium carbonate, and carbon black, and organic particles such as polystyrene beads, acrylic beads, and polyolefin beads. 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.

Further, when an optical coherent chip is obtained by the above-described manufacturing method, the softening point of the spherical particles is higher than the softening point of the chip forming resin. For example, the softening point of the spherical particles is preferably 20 ° C. or higher, more preferably 50 ° C. or higher, than the softening point of the chip-forming resin.
Specifically, the softening point of the spherical particles may be 80 ° C. or higher (more preferably, 100 ° C. or higher). The upper limit of the softening point of the spherical particles is not particularly limited, but is preferably 1500 ° C. or lower (more preferably 1000 ° C. or lower).

In addition, the softening point of inorganic particles is a value calculated by measuring at a heating 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. 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 chip-forming resin. Therefore, the limitation of the heating temperature during rolling is relaxed, and the limitation of the chip forming resin that can be used is relaxed, which is preferable.

The mixing ratio of the chip-forming resin and the spherical particles is 1: 0.01 to 1:10 (more 1: 0.05 to 1: 8, more preferably 1: 0.1 to 1: 5) by weight. It is preferable. With such a ratio, light in the visible light region is efficiently diffracted, and can be recognized as a color for human vision, and can easily exhibit structural color development.
If the number of spherical particles is too small, the distance between the arranged spherical particles becomes too long, exceeding the wavelength of visible light, and the color cannot be recognized by human vision, resulting in structural color development. It's hard to be done. Moreover, when there are too many spherical particles, aggregation of spherical particles will occur easily and fixation of spherical particles will become difficult.

  The refractive index of the chip-forming resin and the spherical particles in the optical interference chip of the present invention is not particularly limited, but the refractive index of the chip-forming resin is usually about 0.8 to 1.8, and the refractive index of the spherical particles is 0.8. It should just be about -4.5. Further, the difference in refractive index between the chip-forming resin and the spherical particles is preferably about 0.01 to 2.7, and more preferably about 0.02 to 1.8. Can be expressed.

The color of the optical coherent chip of the present invention is appropriately set such as the particle diameter of the spherical particles, the form of the spherical particles, the distance between the spherical particles, the regular arrangement, the difference in refractive index between the spherical particles and the chip-forming resin. Thus, it can be set freely.
For example, if the spherical particles are arranged at intervals of about 160 nm to 170 nm, they are purple, if they are about 180 nm to 190 nm, blue, if they are about 200 nm to 230 nm, green, and 240 nm to 260 nm. If it is present, it can be set to yellow, if it is an interval of about 270 nm to 290 nm, etc.

In the present invention, it is also possible to easily obtain a laminate exhibiting a plurality of structural colors.
For example, as an optical coherent chip, an optical coherent chip (A) made of a chip-forming resin and spherical particles (a), and a chip-forming resin and spherical particles (a) are made of spherical particles (b) having different particle diameters. By mixing the optical coherent chip (B), it is possible to obtain a laminate exhibiting a plurality of structural colors.
Such a laminate exhibiting a plurality of colors of color structure has, for example, an average particle size of 5 nm to 800 nm, a standard deviation of particle size distribution of 20% or less in the chip forming resin, and a softening point higher than that of the chip forming resin. A solid (A ′) in which high spherical particles (a) are dispersed;
In the chip-forming resin, spherical particles having an average particle size of 5 nm to 800 nm, a standard deviation of particle size distribution of 20% or less, a softening point higher than that of the chip-forming resin, and having a different average particle size from the spherical particles (a) ( a solid material containing a solid material (B ′) in which b) is dispersed,
It can be obtained by rolling at a temperature higher than the softening point of the chip-forming resin and lower than the softening points of the spherical particles (a) and spherical particles (b).

In addition, as a method for obtaining a laminate exhibiting a plurality of structural colors, an optical coherent chip comprising a chip-forming resin and spherical particles in a weight ratio of 1: 0.01 to 1:10 as an optical coherent chip. (C) and optical coherent chip (C) may be obtained by mixing optical coherent chips (D) having different ratios of chip-forming resin and spherical particles to obtain a laminate exhibiting a plurality of structural colors. it can.
Such a laminate exhibiting a plurality of colors of color structure has, for example, an average particle size of 5 nm to 800 nm, a standard deviation of particle size distribution of 20% or less in the chip forming resin, and a softening point higher than that of the chip forming resin. High spherical particles are dispersed, and a solid material (C ′) in which the mixing ratio of the chip-forming resin and the spherical particles is 1: 0.01 to 1:10 by weight ratio;
In the chip forming resin, spherical particles having an average particle size of 5 nm to 800 nm and a standard deviation of the particle size distribution of 20% or less and having a softening point higher than that of the chip forming resin are dispersed. The mixing ratio is from 1: 0.01 to 1:10 by weight, and the solid (C ′) and the solid (D ′) having a different mixing ratio are mixed,
A mixture of the solid material (C ′) and the solid material (D ′) can be obtained by rolling at a temperature higher than the softening point of the chip-forming resin and lower than the softening point of the spherical particles.

In addition to the spherical particles and the chip-forming resin, the components constituting the optical interference chip are non-spherical particles having an average particle diameter of 600 nm or less, an aspect ratio of 1.2 to 600, and a softening point higher than that of the chip-forming resin. It is preferable to add particles. By adding such non-spherical particles, the color of the finally obtained light interference chip 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 nm or more and 600 nm or less are more preferable. When the average particle diameter is larger than 600 nm, the transparency and glossiness of the optical coherent chip may be impaired.
Furthermore, as the non-spherical particles, acicular or scaly particles having an aspect ratio of 1.2 or more and 600 or less (1.5 or more and 500 or less) are preferable. 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 aspect ratio of the above-mentioned spherical particles is usually about 1.0 or more and less than 1.2 (preferably 1.0 or more and 1.15 or less, more preferably 1.0 or more and 1.1 or less).

  As the non-spherical particles, those having a softening point higher than the softening point of the chip-forming resin, particularly higher than the softening point of the chip-forming resin by 20 ° C. or more, preferably 50 ° C. or higher are preferable. 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 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 compared to the chip-forming resin, the restriction on the heating temperature during rolling is relaxed, and the range of applicable chip-forming resins is expanded.

  Examples of such non-spherical particles include scaly silica, acicular titanium oxide, acicular zinc oxide, acicular iron oxide, iron hydroxide oxide, zinc carbonate hydroxide, aluminum oxide, zirconium oxide, tantalum pentoxide, Gadolinium oxide, Yttrium oxide, Barium oxide, Cobalt oxide, Chromium oxide, Vanadium oxide, Hafnium oxide, Magnesium oxide, Strontium oxide, Calcium carbonate, Potassium titanate, Barium sulfate, Barium carbonate, Clay, Kaolin, Porcelain clay, China clay, Talc Inorganic particles such as carbon black, white carbon, diatomaceous earth, bentonite, hydrotalcite and the like can be used, and among these, one kind or a combination of two or more kinds can be used.

  The mixing ratio of the chip-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.).
Other particles also preferably have a softening point higher than the softening point of the chip-forming resin, particularly 20 ° C. or higher, more preferably 50 ° C. or higher than the softening point of the chip-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 optical coherent chip, and combined 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, and 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 light coherent chip and can be combined with the hue of the structural color to obtain excellent aesthetics.

  In the method of manufacturing the optical interference chip as described above, a solid material containing a chip-forming resin, spherical particles, etc. is used as a starting material, and the spherical particles are regularly arranged by rolling the solid material. The spherical particles do not necessarily have to be regularly arranged at the time of producing the solid product. Therefore, an optical coherent chip can be easily manufactured.

For example, as a method for obtaining a solid material, spherical particles are mixed with a resin solution composed of a chip-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. Thus, a solid product can be obtained. The solvent may be removed usually at 30 ° C. 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, spherical particles are easily arranged uniformly, and a structure exhibiting a structural color development is obtained. It can be easily obtained.

In the method of obtaining such a solid material, it is preferable to use a solvent-soluble thermoplastic resin soluble in a solvent, particularly a water-soluble thermoplastic resin, as the chip-forming resin.
When such a resin is used, spherical particles are easily and uniformly dispersed in a resin solution composed of a chip-forming resin and a solvent, and unevenness of the chip-forming resin and spherical particles can be suppressed in the obtained solid product. 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 that is excellent in compatibility between the chip-forming resin and the solvent, it is possible to show even better structural color development.

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, those containing water are particularly preferable as the solvent. Therefore, it is preferable to use a water-soluble resin having water-soluble thermoplasticity as the chip-forming resin.

In such a method, a solvent-soluble chip-forming resin itself 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.

In the present invention, the solid material thus obtained is rolled at a temperature higher than the softening point of the chip-forming resin and lower than the softening point of the spherical particles.
By rolling in such a temperature range, the chip-forming resin is in a state close to a liquid, and the spherical particles can move easily. As a result, the spherical particles can be packed closely and arranged regularly. Thus, a chip having optical coherence can be easily obtained.
When the rolling temperature is lower than the softening point of the chip-forming resin, rolling cannot be performed and it becomes difficult to obtain structural color development. 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 spherical particles and non-spherical particles and / or other particles are used together in a solid material, the softening point is higher than the softening point of the chip-forming resin, and is higher than the softening point of the spherical particles and the non-spherical particles and other particles. Rolling may be performed in a low temperature region.

  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 structural color body having a light interference property 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, volatile components may evaporate, resulting in a volume change before and after production. Therefore, the spherical particles are disturbed due to the volume change, and it may be difficult to obtain a color developing structure having excellent optical coherence. 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 softening point higher than that of the chip-forming resin.

  The size of the optical coherent chip thus obtained is preferably such that the particle diameter is 0.1 mm or more and 50 mm or less (more preferably 0.5 mm or more and 30 mm or less). If necessary, the optical coherent chip can be crushed into a predetermined size. The shape of the optical coherent chip is not particularly limited. The size and shape of the optical coherent chip may be uniform or irregular. The thickness of the optical coherent chip is preferably 30 μm or more and 500 μm or less.

  As an optical coherent chip used in the present invention, in particular, an optical coherent chip (E) having a particle diameter of 3 mm to 50 mm (preferably 5 mm to 30 mm) and a thickness of 30 μm to 500 μm (preferably 50 μm to 300 μm). And an optical coherent chip (F) having a particle diameter of 0.1 mm to less than 3 mm (preferably 0.2 mm to 2 mm) and a thickness of 30 μm to 500 μm (preferably 50 μm to 300 μm). It is preferable. By using such optical coherent chips with different sizes, hue changes (various hue feelings) due to changes in hue and viewing angle due to structural color development are provided, and there is a calm brightness and natural feeling. A laminate having excellent aesthetics can be obtained. The mixing ratio of the optical coherent chip (E) and the optical coherent chip (F) is 5:95 to 95: 5 (preferably 10:90 to 90:10, more preferably 20:80 to 80) by weight. : 20) What is necessary is just about.

  The size of the optical coherent chip is a value obtained by sieving using a metal net sieve defined in JIS Z8801-1: 2000.

  The color clear layer of the present invention can be formed by laminating a color clear paint containing the above-described light-interfering chip and binder on the colored substrate layer.

  Examples of the binder used here include acrylic resin, polyester resin, polyether resin, vinyl resin, polyamide resin, phenol resin, urethane resin, epoxy resin, fluororesin, vinyl acetate resin, vinyl chloride resin, and acrylic-styrene resin. , Vinyl acetate-versaic acid vinyl ester resin, polyvinyl pyrrolidone resin, polyvinyl caprolactam resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, AS resin, cellulose resin, acrylic-silicon resin, silicone resin, alkyd resin, melamine resin, amino resin PVC resin, vinyl resin, and the like. Solvent-free, solvent-soluble, NAD, water-soluble, and water-dispersed types of such resins can be used.

  Moreover, a coloring material can also be mixed to such an extent that the effect of this invention is not impaired. By mixing the coloring material, the color range of the color clear layer can be expanded.

  Examples of coloring materials include titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, molybdate orange, permanent red, permanent carmine, Anthraquinone red, perylene red, quinacridone red, ferric oxide, yellow iron oxide, titanium yellow, first yellow, chrome green, ocher, ultramarine, bitumen, cobalt green, cobalt blue and other inorganic color pigments, azo, naphthol , Pyrazolone, anthraquinone, perylene, quinacridone, benzimidazole, phthalocyanine, disazo, isoindolinone, quinophthalone and other organic color pigments, aluminum pigments, pearl pigments, fireflies Pigments, phosphorescent pigments, colored mica, mica, colored sand, aggregate, such as white marble, dyes and the like, may be used alone or two or more of them.

  In addition, to the extent that the effects of the present invention are not impaired, aggregates, dyes, extender pigments, fibers, thickeners, film-forming aids, leveling agents, plasticizers, antifreeze agents, pH adjusters, preservatives An antifungal agent, an algal inhibitor, an antibacterial agent, a dispersant, an antifoaming agent, an ultraviolet absorber, an antioxidant, a catalyst, a crosslinking agent, and the like can also be mixed.

The content of the light interference chip, the color clear layer, 0.05 g / ^{m 2} or more 100 g / ^{m 2} (preferably 0.1 g / ^{m 2} or more 80 g / ^{m 2} or less, more preferably 0.5 g / m ^{2 to} 50 g / m ² or less) is preferable.

Such a color clear coating can be laminated on the colored substrate layer to form a color clear layer.
As a method of laminating, a color clear paint can be applied directly on the colored substrate layer, or a light-interfering chip is sprayed on the colored substrate layer, and a binder or the like is applied thereon. It can also be laminated by doing. In the latter case, a color clear layer is formed by the scattered optical coherent chips and the bonding material thereon.
In addition, the color clear paint can be formed into a film (sheet) in advance, and the film (sheet) can be attached via an adhesive or the like.
The method for forming the color clear paint in advance (film formation) is not particularly limited, but it may be formed into a film (sheet formation) by a known method such as extrusion molding or roll coater.
In the case of a colored substrate layer using a thermoplastic resin, it is possible to mold a color clear layer simultaneously with the production of the colored substrate layer by an extrusion molding method or a roll coater method. What is necessary is just to manufacture at the temperature below the softening point of chip formation resin, when forming into a film (sheet formation) by such a method.

  In the direct application method, it may be applied on the colored substrate layer using a coating tool such as a brush, a roller, or a spray, and is not particularly limited.

Such a color clear layer has transparency enough to recognize the hue of the light interference chip and the hue of the colored substrate layer.
As the transparency of the color clear layer, 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 laminated structure can be obtained without losing the color and brightness of the optical coherent chip. In addition, the hue of the colored substrate can be expressed, and a multicolored and multi-layered structure 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 0.1 mm).

  The thickness of the color clear layer is preferably about 100 μm to 2 mm (200 μm to 1 mm).

In the present invention, a clear layer may be laminated on the color clear layer. By laminating the clear layer, a depth feeling and a three-dimensional feeling are given, and a deeper brightness feeling and aesthetics are imparted, and the color clear layer is also protected.
The clear layer has transparency enough to recognize the hue of the color clear layer and the colored substrate layer.
As the transparency of the clear layer, the light transmittance is preferably about 60% to 100% (preferably 70% to 99%).
When the light transmittance is within such a range, a laminated structure can be obtained without losing the hue of the colored substrate and the hue, brightness, and variety of the color clear layer. Moreover, the structure which is excellent in aesthetics with a three-dimensional effect and depth 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). It is the value of total light transmittance measured using

  Examples of such a clear layer include a clear plate such as a glass plate and an acrylic resin plate, or a clear coating film formed from a clear paint containing a binder.

  For example, binders used in clear paints include acrylic resin, polyester resin, polyether resin, vinyl resin, polyamide resin, phenol resin, urethane resin, epoxy resin, fluorine resin, vinyl acetate resin, vinyl chloride resin, acrylic-styrene Resin, vinyl acetate-vinyl versatic acid ester resin, polyvinyl pyrrolidone resin, polyvinyl caprolactam resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, AS resin, cellulose resin, acrylic-silicon resin, silicone resin, alkyd resin, melamine resin, amino Examples thereof include resins, vinyl chloride resins, vinyl resins, and the like. Solvent-free, solvent-soluble, NAD, water-soluble, and water-dispersed types of such resins can be used.

Moreover, a coloring material can also be mixed with a clear coating material to such an extent that the effect of this invention is not impaired.
Examples of coloring materials include titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, molybdate orange, permanent red, permanent carmine, Anthraquinone red, perylene red, quinacridone red, ferric oxide, yellow iron oxide, titanium yellow, first yellow, chrome green, ocher, ultramarine, bitumen, cobalt green, cobalt blue and other inorganic color pigments, azo, naphthol , Pyrazolone, anthraquinone, perylene, quinacridone, benzimidazole, phthalocyanine, disazo, isoindolinone, quinophthalone and other organic color pigments, aluminum pigments, pearl pigments, fireflies Pigments, phosphorescent pigments, colored mica, mica, colored sand, aggregate, such as white marble, dyes and the like, may be used alone or two or more of them.

  Moreover, an optical coherent chip can be mixed to such an extent that the effects of the present invention are not impaired. By mixing a light-interfering chip with the clear layer, it is possible to obtain a laminate having a more versatile hue, a calm brightness, and a natural appearance and excellent in aesthetics. The optical coherent chip used for the clear layer may be the above-described optical coherent chip. However, by using an optical coherent chip that is larger than the size of the optical coherent chip used in the color clear layer, various hue feelings can be obtained. Thus, it is possible to obtain a laminate having a calm brightness feeling and a natural feeling and excellent in aesthetics.

  In addition, fibers, thickeners, film-forming aids, leveling agents, plasticizers, antifreezing agents, pH adjusting agents, preservatives, antifungal agents, and algaeproofing agents are added to the extent that the effects of the present invention are not impaired. , Antibacterial agents, dispersants, antifoaming agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents, and the like can also be mixed.

The method for laminating such a clear layer on the color clear layer is not particularly limited.
As a method of laminating, the clear coating can be directly applied on the color clear layer. In the direct application method, the color clear layer may be applied using a brush, roller, spray or the like, and there is no particular limitation such as one-time application or multiple-time application.
In addition, a clear plate or a clear film (sheet) in which a clear paint has been formed (sheeted) in advance may be attached to the color clear layer via an adhesive or the like.
The method for forming the clear coating in advance (sheeting) is not particularly limited, but it may be formed into a film (sheeting) by a known method such as extrusion molding or roll coater.
In addition, the clear layer can be formed simultaneously with the production of the colored base layer and the formation of the color clear layer by an extrusion molding method or a roll coater method.

The film thickness of such a clear layer is not particularly limited, but is preferably about 0.5 μm to 5 mm (10 μm to 2 mm).
Further, the surface of the clear layer may have an uneven structure.
By having a concavo-convex structure, a deeper color can be expressed. In addition, it can be expected to have an anti-slip effect when applied to home appliances and furniture, and an anti-slip effect when applied to tiles and floors. The degree of unevenness is not particularly limited, but the difference between the bottom and the top may be 0.1 mm or more and 50 mm or less, and further 0.3 mm or more and 30 mm or less.
Examples of the method for forming the unevenness include a method of applying a clear paint containing a pigment and an aggregate to the surface of the color clear layer.

  The laminate thus obtained can be applied in a wide range of fields such as home appliances / furniture, vehicles, sheets, tiles, walls, floors, ceilings and other building materials.

Example 1
<Production of optical coherent chip>
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 the mixed solution was put into an aluminum container (φ1000 mm), and the solvent A was volatilized at 120 ° C. for 3 hours to obtain a solid product. The obtained solid was transparent and the particles were uniformly dispersed.
The obtained solid material was sandwiched between PET films, and rolled and curved at 130 ° C. and 30 MPa using a heated rolling roller. The object peeled off from the rolled PET film had a thickness of 100 μm, showed interference by light, and exhibited an excellent blue-based structural color.
The object was crushed to a size of about 1 to 30 mm to obtain a light coherent chip exhibiting a blue interference color.
<Production of laminate>
Optical coherent chip obtained in Example 1 on a porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* : 25) colored with black on the surface, 100 parts by weight of epoxy resin (solid content: 100% by weight) The color clear coating mixed with 5 parts by weight is applied with a brush so that the dry film thickness is 0.3 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. The chip content: 15 g / m ² ) was obtained. The light transmittance of the color clear layer formed from the color clear paint was 71%.
Next, a clear paint composed of an epoxy resin (solid content: 100% by weight) is applied onto the color clear layer with a brush so that the wet film thickness is 0.1 mm, and the temperature is 80 ° C. and the relative humidity is 50. %, And dried and cured for 24 hours to obtain a clear layer to obtain a laminate. The light transmittance of the clear layer formed from the clear paint was 85%.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 2)
<Production of optical coherent chip>
In the same manner as in Example 1, except that the raw materials shown in Table 1 were used, and the mixing ratio shown in Table 2 was changed from resin A to resin B, solvent A to solvent B, and particle A to particle B. A solid was obtained. The obtained solid was transparent and the particles were uniformly dispersed.
The obtained solid was sandwiched between PEN films, rolled at 170 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The rolled object had a thickness of 100 μm, showed interference by light, and exhibited an excellent purple structure color.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 2 was used. The light transmittance of the color clear layer formed from the color clear paint was 70%.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 3)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used and the particles A were replaced with the particles C at the mixing ratio shown in Table 2. The obtained solid was transparent and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The object after rolling had a thickness of 100 μm, showed interference by light, and exhibited an excellent red structure color.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 3 was used. The light transmittance of the color clear layer formed from the color clear paint was 71%.
The surface of the obtained laminate had a calm red brightness in a black background, and had a soft and deep aesthetic appearance.

Example 4
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used and the particles A were replaced with the particles D at the mixing ratio shown in Table 2. The obtained solid was transparent and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 80 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The object after rolling had a thickness of 100 μm, showed interference by light, and exhibited an excellent red structure color.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 4 was used. The light transmittance of the color clear layer formed from the color clear paint was 71%.
The surface of the obtained laminate had a calm red brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 5)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used and the resin A was replaced with the resin C at the mixing ratio shown in Table 2. The obtained solid was transparent and the particles were uniformly dispersed.
The obtained solid material was sandwiched between PET films, and rolled and curved at 130 ° C. and 30 MPa using a heated rolling roller. The rolled object had a thickness of 100 μm, showed interference by light, and showed a purple structure color.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 5 was used. The light transmittance of the color clear layer formed from the color clear paint was 70%.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 6)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used and the resin A was replaced with the resin D at the mixing ratio shown in Table 2. The obtained solid was transparent and the particles were uniformly dispersed.
The obtained solid material was sandwiched between PET films, and rolled and curved at 130 ° C. and 30 MPa using a heated rolling roller. The rolled object had a thickness of 100 μm, showed interference by light, and showed a purple structure color.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 6 was used. The light transmittance of the color clear layer formed from the color clear paint was 69%.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 7)
<Production of optical coherent chip>
The solid material obtained in Example 1 was sandwiched between PET films, and was bent using a non-heated rolling roller immediately after pressing at 130 ° C. and 30 MPa using a heating press. The rolled object had a thickness of 100 μm, showed interference by light, and exhibited an excellent purple structure color.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 7 was used. The light transmittance of the color clear layer formed from the color clear paint was 70%.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 8)
<Production of optical coherent chip>
Using the raw materials shown in Table 1, solid materials were obtained in the same manner as in Example 1 with the mixing ratios shown in Table 2. The obtained solid was transparent and the particles were uniformly dispersed.
The obtained solid material was sandwiched between PET films, and rolled and curved at 130 ° C. and 30 MPa using a heated rolling roller. The object after rolling had a thickness of 100 μm, showed interference by light, and exhibited an excellent red structure color.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 8 was used. The light transmittance of the color clear layer formed from the color clear paint was 72%.
The surface of the obtained laminate had a calm red brightness in a black background, and had a soft and deep aesthetic appearance.

Example 9
<Production of optical coherent chip>
Using the raw materials shown in Table 1, solid materials were obtained in the same manner as in Example 1 with the mixing ratios shown in Table 2.
The obtained solid material was sandwiched between PET films, and rolled and curved at 130 ° C. and 30 MPa using a heated rolling roller. The rolled object had a thickness of 100 μm, showed interference by light, and exhibited an excellent purple structure color.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 9 was used. The light transmittance of the color clear layer formed from the color clear paint was 68%.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 10)
<Production of optical coherent chip>
Using the raw materials shown in Table 1, solid materials were obtained in the same manner as in Example 1 with the mixing ratios shown in Table 2. The obtained solid was transparent and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The rolled object had a thickness of 100 μm, showed interference by light, and exhibited an excellent blue-green structural color. In addition, FIG. 1 shows a difference spectrum (hereinafter simply referred to as “difference spectrum”) calculated from ultraviolet-visible absorption spectra before and after rolling.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 10 was used. The light transmittance of the color clear layer formed from the color clear paint was 64%.
The surface of the obtained laminate had a calm blue-green luminance in a black background, and had a soft and deep aesthetic appearance.

(Example 11)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used and the particles G were added at the mixing ratio shown in Table 2. The obtained solid was transparent in red, and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The object after rolling had a thickness of 100 μm, showed interference by light, and showed a strong yellowish structural color. Further, it was confirmed that the difference spectrum calculated from the UV-visible absorption spectrum before and after rolling (hereinafter simply referred to as “difference spectrum”) was sharper than that in Example 10 (FIG. 2).
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 11 was used. The light transmittance of the color clear layer formed from the color clear paint was 67%.
The surface of the obtained laminate had a calm yellow brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 12)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used and the particles H were added at the mixing ratio shown in Table 2. The obtained solid was colorless and transparent, and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The object after rolling had a thickness of 100 μm, showed interference by light, and showed a strong yellowish structural color. Moreover, it has confirmed that a difference spectrum became sharper compared with Example 10 (FIG. 3).
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 12 was used. The light transmittance of the color clear layer formed from the color clear paint was 66%.
The surface of the obtained laminate had a calm yellow brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 13)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1, except that the raw materials shown in Table 1 were used and the resin A was replaced with the resin E at the mixing ratio shown in Table 2. The obtained solid was colorless and transparent, and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The object after rolling had a thickness of 100 μm, showed interference by light, and showed a strong blue-based structural color. 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.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 13 was used. The light transmittance of the color clear layer formed from the color clear paint was 75%.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 14)
<Production of optical coherent chip>
Using the raw materials shown in Table 1, a resin solution in which the resin D was mixed with the solvent A at a mixing ratio shown in Table 2 in a standard state was prepared, and the mixed solution was prepared by mixing the particles A with the resin solution.
Next, the mixed solution and the crosslinking agent A were mixed, put in an aluminum container (φ1000 mm), and the solvent A was volatilized at 120 ° C. for 3 hours to obtain a solid material. The obtained solid was colorless and transparent, and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The object after rolling had a thickness of 100 μm, showed interference by light, and showed a strong green structure color. 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.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
Example 14 A laminate was obtained in the same manner as in Example 1 except that the obtained optical coherent chip was used. The light transmittance of the color clear layer formed from the color clear paint was 74%.
The surface of the obtained laminate had a calm green brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 15)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used, the particles I were added at the mixing ratio shown in Table 2, and the resin A was replaced with the resin E. The obtained solid was black and transparent, and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The object after rolling had a thickness of 100 μm, showed interference by light, and exhibited an excellent structural color showing a clear blue system. 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.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 15 was used. The light transmittance of the color clear layer formed from the color clear paint was 62%.
The surface of the obtained laminate had a calm and clear blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 16)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used, the particles J were added at the mixing ratio shown in Table 2, and the resin A was changed to the resin E. The obtained solid was yellow and transparent, and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The object after rolling had a thickness of 100 μm, showed interference by light, and exhibited an excellent structural color showing a clear blue system. 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.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 16 was used. The light transmittance of the color clear layer formed from the color clear paint was 62%.
The surface of the obtained laminate had a calm and clear blue brightness in a black background, and had a soft, deep, and high-class aesthetic appearance.

(Example 17)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used, the particles G and I were added at the mixing ratio shown in Table 2, and the resin A was replaced with the resin E. . The obtained solid was yellow and transparent, and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The object after rolling had a thickness of 100 μm, showed interference by light, and exhibited an excellent structural color showing a clear blue system. 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.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 17 was used. The light transmittance of the color clear layer formed from the color clear paint was 62%.
The surface of the obtained laminate had a calm and clear blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 18)
<Production of optical coherent chip>
Solid materials were used in the same manner as in Example 1 except that the raw materials shown in Table 1 were used, the particles G, I and J were added at the mixing ratio shown in Table 2, and the resin A was replaced with the resin E. Got. The obtained solid was yellow and transparent, and the particles were uniformly dispersed.
The obtained solid was sandwiched between PET films, rolled at 130 ° C. and 30 MPa using a heated rolling roller, and repeatedly bent. The object after rolling had a thickness of 100 μm, showed interference by light, and exhibited an excellent structural color showing a clear blue system. 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.
The object was crushed to a size of about 1 to 50 mm to obtain an optical coherent chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the optical coherent chip obtained in Example 18 was used. The light transmittance of the color clear layer formed from the color clear paint was 62%.
The surface of the obtained laminate had a calm and clear blue brightness in a black background, and had a soft, deep, and high-class aesthetic appearance.

(Example 19)
<Production of optical coherent chip>
In the same manner as in Example 1, the size was crushed to a size of about 1 to 30 mm, and an optical coherent chip showing a blue interference color was obtained.
<Production of laminate>
On a porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* : 25) whose surface is colored black, an optical coherent chip is sprayed at 10 g / m ² , and further an epoxy resin (solid content: 100) % By weight) was applied with a brush so that the dry film thickness was 0.3 mm, and was dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours to obtain a color clear layer. The light transmittance of the color clear layer was 71%.
Next, a clear paint composed of an epoxy resin (solid content: 100% by weight) is applied onto the color clear layer with a brush so that the wet film thickness is 0.1 mm, and the temperature is 80 ° C. and the relative humidity is 50. %, And dried and cured for 24 hours to obtain a clear layer to obtain a laminate. The light transmittance of the clear layer formed from the clear paint was 85%.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 20)
<Production of optical coherent chip>
In the same manner as in Example 1, the size was crushed to a size of about 1 to 30 mm, and an optical coherent chip showing a blue interference color was obtained.
<Production of laminate>
10 parts by weight of vinyl-toluene acrylic resin (softening point: 90 ° C.), 5 parts by weight of titanium oxide, 10 parts by weight of carbon black and 65 parts by weight of heavy calcium carbonate were mixed in a kneader (temperature 130 ° C.). Before the temperature of the take-out mixture returned to room temperature, a sheet (colored base material layer, L ^* : 30) having a thickness of 2 mm was produced using a rolling roller.
After leaving the obtained sheet in a thermostat at 100 ° C., the light-interfering chips are spread on the sheet at 10 g / m ² and dispersed, and then the light-interfering chips are fixed on the sheet surface with a rolling roller, Then, an epoxy resin (solid content: 100% by weight) was applied with a brush so that the dry film thickness was 0.3 mm, dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours, and a color clear layer Got. The light transmittance of the color clear layer was 71%.
Next, a clear paint composed of an epoxy resin (solid content: 100% by weight) is applied onto the color clear layer with a brush so that the wet film thickness is 0.1 mm, and the temperature is 80 ° C. and the relative humidity is 50. %, And dried and cured for 24 hours to obtain a clear layer to obtain a laminate. The light transmittance of the color clear layer was 71%, and the light transmittance of the clear layer formed from the clear paint was 85%.
The surface of the obtained laminate had a calm and clear blue brightness in a black background, and had a soft, deep, and high-class aesthetic appearance.

(Example 21)
<Production of optical coherent chip>
In the same manner as in Example 1, the size was crushed to a size of about 1 to 30 mm, and an optical coherent chip showing a blue interference color was obtained.
<Production of laminate>
10 parts by weight of vinyl-toluene acrylic resin (softening point: 90 ° C.), 5 parts by weight of titanium oxide, 10 parts by weight of carbon black and 65 parts by weight of heavy calcium carbonate were mixed in a kneader (temperature 130 ° C.). Before the temperature of the take-out mixture returned to room temperature, a sheet (colored base material layer, L ^* : 30) having a thickness of 2 mm was produced using a rolling roller.
After leaving the obtained sheet in a thermostat at 100 ° C., the light-interfering chips are spread on the sheet at 10 g / m ² and dispersed, and then the light-interfering chips are fixed on the sheet surface with a rolling roller, Then, an epoxy resin (solid content: 100% by weight) was applied with a brush so that the dry film thickness was 0.3 mm, dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours, and a color clear layer Got. The light transmittance of the color clear layer was 71%.
The surface of the obtained laminate had a calm and clear blue brightness in a black background, and had a soft, deep, and high-class aesthetic appearance.

(Example 22)
<Production of optical coherent chip>
In the same manner as in Example 1, the size was crushed to a size of about 1 to 30 mm to obtain a light coherent chip showing a blue interference color.
<Production of laminate>
Optical coherent chip obtained in Example 1 on a porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* : 25) colored with black on the surface, 100 parts by weight of epoxy resin (solid content: 100% by weight) The color clear coating mixed with 5 parts by weight is applied with a brush so that the dry film thickness is 0.3 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. Chip content: 15 g / m ² ) to obtain a laminate.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 23)
<Production of optical coherent chip>
In the same manner as in Example 1, the size was crushed to a size of about 1 to 30 mm, and an optical coherent chip showing a blue interference color was obtained.
<Production of laminate>
Porcelain tile plate colored in black (100 mm x 100 mm x 6 mm, degree of unevenness: difference between bottom and top 0.5 mm to 2 mm, L ^* : 25), epoxy resin (solid content: 100% by weight) ) 100 parts by weight of a color clear paint mixed with 5 parts by weight of the optical coherent chip obtained in Example 1 was applied with a brush so that the dry film thickness was 0.3 mm, and the temperature was 80 ° C. and the relative humidity was It was dried and cured at 50% for 24 hours to obtain a color clear layer (light interference chip content: 15 g / m ² ) to obtain a laminate.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance. The light transmittance of the color clear layer formed from the color clear paint was 71%.
Next, a clear paint composed of an epoxy resin (solid content: 100% by weight) is applied onto the color clear layer with a brush so that the wet film thickness is 0.1 mm, and the temperature is 80 ° C. and the relative humidity is 50. %, And dried and cured for 24 hours to obtain a clear layer to obtain a laminate. The light transmittance of the clear layer formed from the clear paint was 85%.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 24)
<Production of optical coherent chip>
In the same manner as in Example 1, the size was crushed to a size of about 1 to 30 mm to obtain a light coherent chip showing a blue interference color.
<Production of laminate>
A coating material containing 100 parts by weight of an epoxy resin (solid content: 100% by weight) and 15 parts by weight of mica (average particle diameter: 1.5 mm, thickness: 1 μm) on a porcelain tile plate colored black in surface, It is applied at a coating amount of 0.7 kg / m ² , dried in a standard state for 24 hours, and a colored substrate layer (100 mm × 100 mm × 7 mm, degree of unevenness: the difference between the bottom and the top is 0.5 mm to 1 mm, L ^* : 21) was obtained.
Next, a color clear coating material in which 100 parts by weight of an epoxy resin (solid content: 100% by weight) and 5 parts by weight of the light-interfering chip obtained in Example 1 were mixed on the colored base material layer was dried. Is applied with a brush so that the thickness becomes 0.3 mm, and is dried and cured for 24 hours at a temperature of 80 ° C. and a relative humidity of 50% to obtain a color clear layer (light interference chip content: 15 g / m ² ). Got the body.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance. The light transmittance of the color clear layer formed from the color clear paint was 71%.
Next, a clear paint composed of an epoxy resin (solid content: 100% by weight) is applied onto the color clear layer with a brush so that the wet film thickness is 0.1 mm, and the temperature is 80 ° C. and the relative humidity is 50. %, And dried and cured for 24 hours to obtain a clear layer to obtain a laminate. The light transmittance of the clear layer formed from the clear paint was 85%.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Comparative Example 1)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used and the particles A were replaced with the particles E at the mixing ratio shown in Table 2. The obtained solid was transparent and the particles were uniformly dispersed.
The obtained solid material was sandwiched between PET films, and rolled and curved at 130 ° C. and 30 MPa using a heated rolling roller. The object after rolling had a thickness of 100 μm and showed no interference by light.
The object was crushed to a size of about 1 to 50 mm to obtain a chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the chip obtained in Comparative Example 2 was used.
The surface of the obtained laminate was a simple gray color.

(Comparative Example 2)
<Production of optical coherent chip>
A solid material was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used and the particles A were replaced with the particles F at the mixing ratio shown in Table 2.
The obtained solid material was sandwiched between PET films, and rolled and curved at 130 ° C. and 30 MPa using a heated rolling roller. The object after rolling had a thickness of 100 μm and showed no interference by light.
The object was crushed to a size of about 1 to 50 mm to obtain a chip.
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the chip obtained in Comparative Example 7 was used.
The surface of the obtained laminate was a simple gray color.

(Comparative Example 3)
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that metal particles (aluminum powder: average particle diameter of 0.5 mm) were used instead of the optical coherent chip.
The surface of the obtained laminate had a metallic brightness.

It is a figure which shows the difference spectrum of the optical coherence chip | tip obtained in Example 10. FIG. It is a figure which shows the difference spectrum of the optical coherence chip | tip obtained in Example 11. FIG. It is a figure which shows the difference spectrum of the optical coherence chip | tip obtained in Example 12. FIG.

Claims (6)

On the colored substrate layer, a color clear layer containing a light-interfering chip exhibiting structural coloring is laminated,
In the optical coherent chip, 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 are arranged in the chip forming resin .
Furthermore, a laminate comprising non-spherical particles having an average particle diameter of 600 nm or less and an aspect ratio of 1.2 or more and 600 or less . A color clear layer containing a light-interfering chip exhibiting structural color development on the colored substrate layer, and a clear layer is laminated on the color clear layer;
In the optical coherent chip, 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 are arranged in the chip forming resin .
Furthermore, a laminate comprising non-spherical particles having an average particle diameter of 600 nm or less and an aspect ratio of 1.2 or more and 600 or less . The optical coherent chip has a spherical particle having an average particle diameter of 5 nm to 800 nm and a standard deviation of the particle diameter distribution of 20% or less in the chip forming resin , and an average particle diameter of 600 nm or less, and an aspect ratio of 1.2 to 600. The laminate according to claim 1 or 2, wherein the laminate is obtained by rolling a solid material in which non-spherical particles are dispersed. Iridescent chip, the chip forming resin having thermal plasticity, the average particle diameter 5Nm～800nm, with a standard deviation of the particle size distribution than 20%, a high spherical particles softening point than the chip forming resin, and an average particle A solid material in which non-spherical particles having a diameter of 600 nm or less and an aspect ratio of 1.2 to 600 and having a softening point higher than that of the chip-forming resin is dispersed is higher than the softening point of the chip-forming resin, The laminate according to any one of claims 1 to 3, wherein the laminate is rolled at a temperature lower than the softening point of the spherical particles and the softening point of the non-spherical particles . The ratio of the chip forming resin to the spherical particles is 1: 0.01 to 1:10 by weight, and the ratio of the chip forming resin to the non-spherical particles is 1: 0.0001 to 1: 0.01 by weight. The laminate according to any one of claims 1 to 4, wherein the laminate is any one of the above. From a mixed solution consisting of a chip-forming resin, spherical particles having an average particle size of 5 nm to 800 nm, non-spherical particles having an average particle size of 600 nm or less and an aspect ratio of 1.2 to 600, and a solvent, The laminate according to any one of claims 3 to 5, wherein the laminate is obtained by removing the solvent.

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