JP5086573B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate having structural color development.

Materials having structural coloring 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 a structural color developability and a high luminance 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, in building materials such as walls, floors, and ceilings, materials having a deep and calm brightness feeling are 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 problems, the present invention has been intensively studied. As a result, a color clear layer containing a structural coloring chip is laminated on a colored base material layer, and a clear layer having light diffusibility is further formed thereon. It has been found that the laminated body has a deep, deep, calm brightness, and excellent 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 formed from a binder and a structural coloring chip having an average particle diameter of 0.1 mm to 50 mm and a thickness of 30 μm to 500 μm;
A clear layer having light diffusibility,
Are stacked,
The structural coloring chip is obtained by rolling a solid material in which spherical particles having an average particle diameter of 5 nm to 800 nm and a standard deviation of particle diameter distribution of 20% or less are dispersed in a chip forming resin.
A laminate characterized by the above.
2. The clear layer having light diffusibility has a concavo-convex structure in the surface structure. The laminated body as described in.
3. The clear layer having light diffusibility is formed of two or more substances having different refractive indexes. Or 2. The laminated body as described in.
4). The clear layer having light diffusibility is formed of a binder and a light diffusing agent. To 3. The laminated body in any one of.
5. The light transmittance of the clear layer having light diffusibility is 60% or more. To 4. The laminated body in any one of.
6). The color clear layer contains 0.001 to 10 parts by weight of a structural coloring chip with respect to 100 parts by weight of a binder. To 5. The laminated body in any one of.
7). In the chip forming resin having the structural coloring chip, spherical particles having an average particle size of 5 nm to 800 nm, a standard deviation of the particle size distribution of 20% or less, and a softening point higher than that of the chip forming resin are dispersed. The solid product 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. To 6 . The laminated body in any one of.

  Since the laminated body of the present invention uses a specific material having structural color development, a laminated body having a deep, deep, calm brightness and excellent aesthetics can be obtained.

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

  In the laminate of the present invention, on the colored substrate layer, a binder and a color clear layer formed from a structural coloring chip having an average particle size of 0.1 mm to 50 mm and a thickness of 30 μm to 500 μm are laminated, Further, a clear layer having light diffusibility is laminated thereon.

The laminate of the present invention is characterized in that a sense of brightness is expressed using a structural coloring chip. Such a structural coloring chip can express a calm brightness feeling that is softer, deeper and deeper than a metallic color expressed by a bright pigment such as a metallic pigment.
Furthermore, in the present invention, by laminating a clear layer having light diffusibility, it is possible to express a deep and calm brightness feeling due to the transparency, light diffusion, etc. of the clear layer. .

The coloring substrate layer is not particularly limited, and materials used for building materials such as home appliances / furniture, vehicles, walls, floors, and ceilings can be used.
Such materials include aluminum steel plates, galvanized 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.

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 structural color developing chip, those colored in a dark hue are preferable. Specifically, the L ^* value is preferably 50 or less, more preferably 40 or less.

The color clear layer of the present invention contains a structural coloring chip and imparts color with the structural coloring chip.
The structural coloring chip used in the present invention is colored by structural coloring, that is, an optical phenomenon (light interference, diffraction, scattering) caused by having a light wavelength in the visible region or a fine structure smaller than that, It utilizes structural coloration generated by regularly arranging particles.

By using a structural coloring chip having an average particle size of 0.1 mm or more and 50 mm or less and a thickness of 30 μm or more and 500 μm or less, in addition to the structural coloring characteristics of the structural coloring chip, depth sensation due to chip variation, orientation, etc. It can emit excellent aesthetics.
When the average particle diameter is smaller than 0.1 mm, the presence of the structural color developing chip is lost, and the design property by polarized light is difficult to visually recognize. When larger than 50 mm, a natural feeling and a high-class feeling are impaired and a sense of incongruity arises in terms of design.
On the other hand, when the thickness is less than 30 μm, the light transmittance is high, the structural color developability is lowered, the hue of the back surface of the structural color development chip is easily visible, and the color developability due to polarized light is impaired. On the other hand, when the thickness is larger than 500 μm, the surface on which the light is applied to the structural color developing chip is not constant, and the light hits the surface in the thickness direction, making it difficult to obtain the color developing property due to polarization.

Further, the shape of the structural coloring chip is not particularly limited, such as a circle, an ellipse, a triangle, a quadrangle, or a polygon.
In addition, the particle diameter of the structural coloring chip is a value obtained by sieving using a metal mesh sieve defined in JIS Z8801-1: 2000.
In addition, the thickness of the structural coloring chip is a value obtained by calculating a value measured by a micrometer (manufactured by Mitutoyo Corporation).

Such a structural coloring chip is not particularly limited as long as it exhibits structural coloring, but a structural coloring chip in which particles are regularly arranged, a structural coloring chip in which thin films are superimposed, a hologram structural coloring chip, a cholesteric structure Examples include a coloring chip.
In the present invention, a structural coloring chip in which particles are regularly arranged is particularly preferably used.

  As the structural color developing chip, for example, the average particle size is 5 nm to 800 nm (preferably 10 nm to 790 nm, more preferably 30 nm to 780 nm), and the standard deviation of the particle size distribution is 20% or less (preferably 15% or less, More preferably, spherical particles that are 10% or less) are regularly arranged.

  By using the structural color developing chip in which such particles are regularly arranged, it is possible to express a deep and calm brightness and a natural aesthetic.

  If the average particle size of the spherical particles is outside this range, it will be difficult to develop structural coloration. If the standard deviation of the particle size distribution of the spherical particles is greater than 20%, the particles will be difficult to arrange regularly, and structural coloration will occur. It is difficult to express.

  The average particle size and particle size distribution can be measured by electron microscope observation, centrifugal sedimentation method, or the like. The average particle size in the present invention is a number average value obtained by observation with an electron microscope, and the particle size distribution is obtained by measurement by a centrifugal sedimentation method.

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. Since the inorganic particles are excellent in durability and the like, they can improve the durability of the obtained structural color body and can maintain an excellent color over a long period of time.

  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 are regularly arranged and can exhibit a more excellent structural color. The aspect ratio mentioned here is a value represented by b / a which is the ratio of the length b in the longitudinal direction of the particle to the length a in the lateral direction.

It is preferable that the structural color-developing chip is arranged regularly by fixing the above-described spherical particles using a chip-forming resin.
The chip forming resin is not particularly limited. For example, acrylic resin, polyester resin, polyether resin, vinyl resin, polyamide resin, phenol resin, urethane resin, epoxy resin, fluororesin, vinyl acetate resin, vinyl chloride resin, acrylic resin -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 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, it is preferable that chip forming resin contains what forms a crosslinked network. 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 forming the crosslinked network include compounds 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 content of the compound having a reactive functional group is 50% by weight or less, more preferably 0.5% by weight or more and 40% by weight or less, and further 1% by weight or more and 30% by weight with respect to the total amount of the resin forming the structural coloring chip. % Or less is preferable. When it is more than 50% by weight, it is difficult to obtain a chip in which spherical particles are uniformly arranged.

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 a structural color can be easily presented.
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 is usually about 0.8 to 1.8, and the refractive index of the spherical particles may be about 0.8 to 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 structural coloring chip can be freely set by appropriately setting the particle diameter of the spherical particles, the shape 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, etc. Can be set.
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 addition to the spherical particles and the chip-forming resin described above, it is preferable to contain 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 as components constituting the structural coloring chip.
The inclusion of such non-spherical particles is preferable because the color of the structural coloring chip finally obtained becomes clearer (coloring improvement effect). 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 that provides the effect of improving the color developability is not clear, it is thought that the disorder of the arrangement of the spherical particles is suppressed by the non-spherical particles entering the gaps of the spherical particles at regular intervals.
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.

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

  As the non-spherical particles, those having the same material as the spherical particles can be used, but in the present invention, for example, scaly silica, acicular titanium oxide, acicular zinc oxide, acicular iron oxide, iron hydroxide oxide, carbonic acid Zinc 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 And inorganic particles such as barium carbonate, clay, kaolin, porcelain clay, china clay, talc, carbon black, white carbon, diatomaceous earth, bentonite, hydrotalcite, etc. be able to.

  Inorganic particles are suitable as the non-spherical particles in the present invention. When the non-spherical particles are inorganic particles, the durability of the structural coloring chip is increased, and the initial coloring performance can be maintained for a long time.

  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.).

  In the present invention, in particular, other particles 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). preferable. By including such particles, the transmitted light of the structural coloring chip is suppressed, and the reflected light of the structural coloring chip is recognized more clearly, which is preferable.

Such 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 0.02% of all particles). % By weight to 10% by weight).
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 the non-spherical particles, the reflected light of the structural coloring chip becomes clearer and excellent structural coloring due to 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.

  Moreover, it is preferable that the particle | grains (spherical particle | grains, non-spherical particle | grains, other particle | grains) which have luminous property are included as another particle | grain. By including particles having phosphorescent properties, light emitted from the particles passes through the structural color developing chip, combined with the hue of the structural color development, and excellent aesthetics can be obtained. Further, by adjusting the content of the phosphorescent particles, it is possible to clearly confirm the color of the structural color during the daytime, and it is possible to exhibit the color derived from the phosphorescent particles at night.

Examples of the phosphorescent particles include sulfides such as CaS: Bi, CaSr: Bi, ZnS: Cu, ZnCdS: Cu, and compounds represented by MAl ₂ O ₄ (M = Ca, Sr, Ba). Examples include those obtained by adding Eu as an activator and adding Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, Yb, and Lu as coactivators.

  The average particle diameter of the particles having the luminous property is preferably 5 μm to 100 μm, more preferably 10 μm to 80 μm. By being in such a range, the above effect can be obtained more clearly. When the average particle size is too large, there is a risk of inhibiting the structural color development. When the average particle size is too small, the luminous properties are lowered, and it is difficult to obtain the effect due to the luminous properties at night.

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

  As a method for producing the structural color developing chip, a known production method may be employed. In the present invention, in particular, a solid material in which spherical particles (further, non-spherical particles and other particles as necessary) are dispersed in a chip-forming resin for forming a structural color-forming chip can be produced by rolling. preferable. In such a method, spherical particles can be arranged regularly and easily, and a structural coloring chip having excellent light interference can be easily produced.

  Specifically, a solid material in which spherical particles (non-spherical particles, other particles) having a softening point higher than that of the chip-forming resin are dispersed in a chip-forming resin having thermoplasticity is used. It can be produced by rolling at a temperature higher than the softening point and lower than the softening point of the spherical particles.

  In such a manufacturing method, during 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 (non-spherical particles and other particles) is relaxed to some extent. By rolling in such a state, it becomes easy to close-pack the spherical particles, and accordingly, the spherical particles are regularly arranged to obtain a structural coloring chip.

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.
When spherical particles and non-spherical particles and / or other particles are used in combination, the temperature is higher than the softening point of the chip-forming resin and lower than the softening points of the spherical particles and non-spherical particles and other particles. Rolling may be performed.

Moreover, in such a manufacturing method, since a solid substance is used as a starting material, it is easy to handle and can be easily manufactured by rolling. In particular, since there is almost no volatilizing substance during rolling and there is almost no volume change before and after rolling, turbulence of spherical particles due to volume change can be suppressed. In addition, spherical particles are regularly arranged by starting the solid material and rolling the solid material, and it is not always necessary to regularly arrange the spherical particles when manufacturing the solid material.
Therefore, it is possible to easily obtain a structure in which spherical particles are uniformly arranged, that is, a chip (structural color developing chip) exhibiting a structural color having excellent optical coherence.

  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 structural coloring chip 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.

  In such a solid material, 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. At this time, a structural color body can be obtained by sandwiching a solid material between two rolls and applying pressure in a direction perpendicular to the surface direction. It is also possible to carry out using a single roll, and it is also possible to obtain a structural coloring chip by applying pressure to a solid material, changing the direction of the roll 180 ° around the axis, and applying 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.

  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 structural color body becomes thin, the light transmittance is higher than the light diffraction, and it is difficult to recognize the structural color development.

  The chip-forming resin used in such a method is particularly preferably one having thermoplasticity, and one that softens during rolling is selected and used. Even if a crosslinked network is formed in the chip-forming resin, it can be used as long as it softens during rolling.

  The softening point of the chip-forming resin is preferably about 50 ° C to 300 ° C (preferably 80 ° C to 200 ° C). When the softening point of the chip-forming resin is lower than 50 ° 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 softening point of the spherical particles is not particularly limited as long as it is higher than the softening point of the chip-forming resin, but 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).

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

  As the spherical particles used in the present invention, it is particularly preferable to use inorganic spherical particles. Since the inorganic spherical particles are excellent in durability and the like, they can improve the durability of the obtained structural coloring chip and can maintain an excellent color over a long period of time. In addition, inorganic spherical 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.

  Further, the softening point of the non-spherical particles and other particles is higher than the softening point of the chip-forming resin, and particularly preferably higher than the softening point of the chip-forming resin by 20 ° C. or more, more preferably 50 ° C. or more. Specifically, the softening point of non-spherical particles and other particles may be 80 ° C. or higher (more preferably 100 ° C. or higher). Although the upper limit of the softening point of non-spherical particles and other particles is not particularly limited, it is usually preferably 1500 ° C. or lower (preferably 1000 ° C. or lower).

  As the non-spherical particles and other particles used in the present invention, inorganic non-spherical particles and other inorganic particles are suitable. If the non-spherical particles and other particles are inorganic particles, the durability of the structural color body is enhanced, and the initial color development performance can be maintained over a long period of 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.

As a method for obtaining a solid material, for example, spherical particles (non-spherical particles and other particles as required) are mixed in a resin solution composed of a chip-forming resin and a solvent, and a mixed solution in which the spherical particles are dispersed is used. A solid product can be obtained by preparing and removing the solvent from the mixed solution. The solvent may be removed usually at 30 to 200 ° C. for about 5 minutes to 24 hours.
In such a method, it is easy to obtain a solid material in which spherical particles are uniform and highly dispersed, and by rolling such a solid material, a structure in which the spherical particles are easily arranged uniformly and has a structural color is obtained. It can be easily obtained.

In the method of obtaining a solid material, it is preferable to use a solvent-soluble thermoplastic resin that is 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 the method for obtaining such a solid material, it is preferable that the solvent-soluble chip-forming resin itself soluble in a solvent exhibits the 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 a solid material are dispersants, plasticizers, antifoaming agents, leveling agents, thickeners, film-forming aids, ultraviolet rays, as long as the effects of the present invention are not impaired. Additives such as an absorbent and a pigment may be mixed.

In the color clear layer of the present invention, the structural color chip is fixed by the above-described binder. For example, a color clear coating containing the above-mentioned binder and the structural color chip is laminated on the colored base layer. And a method of laminating a binding material on a colored base material layer, then spraying a structural coloring chip, and further laminating a binding material thereon.
The mixing ratio of the binding material and the structural coloring chip is not particularly limited. For example, it is preferable to contain 0.001 to 10 parts by weight of the structural coloring chip with respect to 100 parts by weight of the solid content of the binding material. When the structural coloring chip is less than 0.001 part by weight, it is difficult to confirm deep and calm aesthetics.

  In addition, a coloring material can be mixed with the color clear coating material to such an extent that the effects of the present invention are 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.

  By mixing such coloring materials, the color range of the color clear layer can be expanded. Of these, those containing aluminum pigments, pearl pigments, colored mica, mica and the like are preferable because they can widen the range of hue and brightness.

  In addition, to the extent that the effects of the present invention are not impaired, aggregate, extender pigment, fiber, matting agent, thickener, film-forming aid, leveling agent, plasticizer, antifreeze agent, pH adjuster, Preservatives, antifungal agents, algae inhibitors, antibacterial agents, dispersants, antifoaming agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents, and the like can also be mixed.

Such a color clear coating is laminated on the colored substrate layer to form a color clear layer.
As a method of laminating, the color clear paint can be applied directly on the colored substrate layer, or the color clear paint is formed into a film (sheet) in advance, and the film (sheet) is used as an adhesive. It can also be attached via the like.
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.
The thickness of the color clear layer is preferably about 100 μm to 5 mm (preferably 200 μm to 2 mm).

The color clear layer has transparency enough to recognize the hue of the structural coloring chip and the hue of the colored base material 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 within such a range, a laminated structure can be obtained without losing the color and brightness of the structural color developing 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).

In the present invention, a clear layer having light diffusibility (hereinafter also simply referred to as “clear layer”) is laminated on the color clear layer.
A clear layer having light diffusivity is a layer having a function of diffusing reflected light with respect to incident light, and by laminating such a clear layer, it brings out an excellent aesthetics by light diffusion, In addition to providing a sense of depth, providing a deeper brightness and aesthetics, there is also an effect of protecting the color clear layer.
The clear layer is transparent so that the hues of the color clear layer and the colored substrate layer can be recognized.
As the transparency of the clear layer, the light transmittance is preferably about 60% or more (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 (b) a clear layer having a concavo-convex structure on the surface, and (b) a clear layer formed from two or more substances having different refractive indexes.

(Ii) The clear layer having a concavo-convex structure on the surface has an effect of diffusing and reflecting incident light due to the concavo-convex structure on the surface, and also diffuses and reflects light transmitted through the clear layer. Because the distance between the right eye and the left eye seems to be different due to the effect of the effect, etc., there is a three-dimensional effect, and it is possible to express a calm aesthetic with a depth and depth.
In addition, because the distance between the right eye and the left eye seems to be different due to the phase difference between the incident light and the reflected light due to the refractive index of the clear layer, there is a three-dimensional effect, deep and deep, calm Aesthetics can be expressed.
The degree of unevenness is preferably about 0.05 mm to 5 mm, more preferably about 0.1 mm to 3 mm, and further preferably about 0.1 mm to 1 mm.
(B) Clear layers made of two or more materials with different refractive indices are different in the incident angle and reflection angle at the boundary due to the difference in refractive index, and incident light and reflection due to the difference in refractive index. The reflected light appears to be diffused with respect to the incident light due to the phase difference of the light, etc., and as a result, the distance of what is confirmed between the right eye and the left eye looks different, so there is a stereoscopic effect, Yuki Yuki, deep and calm aesthetics can be expressed.
The degree of difference in refractive index is preferably 0.01 or more, and more preferably about 0.01 to 1.0. If the difference in refractive index is smaller than 0.01, it is difficult to confirm the depth and depth of the aesthetic appearance. If the difference in refractive index is too large, the transparency is lost and the lower layer design is visually recognized. It becomes impossible.

Examples of such a light diffusing 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, surface unevenness can be imparted by applying surface treatment such as embossing to a glass plate or acrylic resin plate, or surface irregularity can be imparted by laminating particles such as a light diffusing agent on the surface. it can. In addition, the coating surface can be made uneven by applying the clear coating so that the surface becomes uneven, and the surface of the coating can be made uneven by including particles such as a light diffusing agent in the clear coating. Can also be given. It is also possible to provide surface irregularities by laminating a clear coating containing particles such as a light diffusing agent on a clear layer such as a glass plate or an acrylic resin plate. The clear layers having different refractive indexes can be obtained by laminating different materials, and the clear coating material can be blended with a binder having a different refractive index, or a material having a refractive index different from that of the binder (for example, By containing a light diffusing agent or the like, clear coating films having different refractive indexes can be obtained.
The clear layer of the present invention is preferably formed of two or more kinds of substances having a concavo-convex structure in the surface structure and different refractive indexes, and is composed of, for example, a binder and a light diffusing agent. It is preferable to obtain a clear layer having light diffusibility by applying a clear paint.

  Examples of the light diffusing agent include calcium carbonate, barium sulfate, titanium oxide, aluminum hydroxide, clay, talc, kaolin, montmorillonite, bentonite, hectorite, silica, glass, mica, magnesium oxide, zinc oxide, zinc sulfide, phosphorus Titanium oxide, magnesium titanate, magnesium titanate, etc., and those subjected to surface treatment with fatty acid, silane coupling agent, titanate coupling agent, etc., styrene crosslinked particles, acrylic crosslinked particles, Examples include styrene-acrylic crosslinked particles, silicone crosslinked particles, urethane crosslinked particles, norbornene crosslinked particles, and the like.

  The binder used in the clear paint includes 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-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, Examples of the resin include a vinyl chloride resin and a vinyl resin. 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.

  In addition, aggregates, extenders, fibers, thickeners, film-forming aids, leveling agents, plasticizers, antifreezing agents, pH adjusters, preservatives, A glaze, an anti-algae agent, 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 method of laminating such a light diffusing clear layer on the color clear layer is not particularly limited.
As a method of laminating, a clear plate with unevenness in advance, or a clear film (sheet) that has been made into a clear paint film (sheet) is pasted on the color clear layer via an adhesive or the like. do it.
Moreover, a clear paint can also be applied on the color clear layer.
In the method of applying the clear paint, it may be applied using a painting tool such as a brush, a roller, or a spray, and there is no particular limitation such as one-time application or multiple-time application.

  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).

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

<Preparation of structural coloring chip (A)>
Using the raw materials shown in Table 1, a resin solution was prepared by mixing the resin A with the solvent A at a temperature of 23 ° C. and a relative humidity of 50% (hereinafter also referred to as “standard state”) at the mixing ratio shown in Table 2. The resin solution was mixed with particles A to prepare a mixed solution.
50 g of 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 PET film after rolling showed interference by light and showed an excellent purple color structure.
The structural color-developing chip (A) was obtained by crushing and pulverizing the structural color-developing body by a conventional method.
-Blue structural coloring chip (A1) having a particle diameter of 0.5 to 5 mm and a thickness of 100 μm
-Blue structural coloring chip (A2) having a particle diameter of 5 to 50 mm and a thickness of 100 μm

<Preparation of structural coloring chip (B)>
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 object after rolling showed interference by light and showed an excellent purple color structure.
The structural color body was crushed and pulverized by a conventional method to obtain the following structural color chip (B).
A purple structural coloring chip (B1) having a particle diameter of 1 to 50 mm and a thickness of 100 μm

<Preparation of structural coloring chip (C)>
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 D 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 showed interference by light and showed a strong yellow structure.
The structural color-developing chip (C) was obtained by crushing and pulverizing the structural color-developing body by a conventional method.
-Yellow structural coloring chip (C1) having a particle diameter of 1 to 50 mm and a thickness of 100 μm

<Preparation of structural coloring chip (D)>
Using the raw materials shown in Table 1, a resin solution in which resin C was mixed with solvent A at a mixing ratio shown in Table 2 in a standard state was prepared, and particles A were mixed into the resin solution to prepare a mixed 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 showed interference by light and showed a strong green color. Furthermore, when the obtained structural color body was allowed to stand in a standard state for one week, excellent structural color was exhibited even after one week.
The structural color body was crushed and pulverized by a conventional method to obtain the following structural color chip (D).
A green structural color development chip (D1) having a particle diameter of 1 to 50 mm and a thickness of 100 μm

<Preparation of structural coloring chip (E)>
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 D and particles F were added at the mixing ratio shown in Table 2, and the resin A was replaced with the resin D. . 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 exhibited interference with light and an excellent structural color showing a clear blue system. Furthermore, when the obtained structural color body was allowed to stand in a standard state for one week, excellent structural color was exhibited even after one week.
The structural color body was crushed and pulverized by a conventional method to obtain the following structural color chip (E).
-Blue structural coloring chip (E1) having a particle diameter of 1 to 50 mm and a thickness of 100 μm

<Preparation of structural coloring chip (F)>
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 D, particles F, and particles G were added at the mixing ratio shown in Table 2, and the resin A was replaced with the resin D. 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 exhibited interference with light and an excellent structural color showing a clear blue system. Furthermore, when the obtained structural color body was allowed to stand in a standard state for one week, excellent structural color was exhibited even after one week.
The structural color body was crushed and pulverized by a conventional method to obtain the following structural color chip (F).
-Blue structural coloring chip (F1) having a particle diameter of 1 to 50 mm and a thickness of 100 μm

<Preparation of structural coloring chip (G)>
Using the raw materials shown in Table 1, a resin solution was prepared by mixing Resin D in 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 C 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. It peeled from the PET film after rolling, and obtained the 100-micrometer-thick blue-type structural color body.
The structural color body was crushed and pulverized by a conventional method to obtain the following structural color chip (G).
-Red structural coloring chip (G1) having a particle diameter of 1 mm to 5 mm and a thickness of 100 μm
-Red structural coloring chip (G2) having a particle diameter of 5-30 mm and a thickness of 100 μm

Example 1
<Production of laminate>
A color clear paint in which 100 parts by weight of an epoxy resin (solid content: 100% by weight) and 5 parts by weight of a structural coloring chip (A2) are mixed on a porcelain tile plate (100 mm × 100 mm × 6 mm) colored black. The film 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 formed from the color clear paint was 71%.
Next, on the color clear layer, epoxy resin (solid content: 100% by weight, refractive index: 1.6) 100 parts by weight, quartz powder (average particle size: 0.2 μm, refractive index: 1.45) 10 The clear paint A consisting of parts by weight is applied with a brush so that the average wet film thickness is 0.5 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours to obtain a clear layer. Got the body. The light transmittance of the clear layer was 85%, and the degree of unevenness was such that the difference between the bottom and the top was 0.2 mm to 0.5 mm.
The surface of the obtained laminate had a calm blue brightness in a black background and had a soft, deep and deep aesthetics.

(Example 2)
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the structural coloring chip (B1) was used. The light transmittance of the color clear layer formed from the color clear paint was 70%.
Next, the clear paint A is applied onto the color clear layer with a brush so that the average wet film thickness is 0.5 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. A layer was obtained to obtain a laminate. The light transmittance of the clear layer was 85%, and the degree of unevenness was such that the difference between the bottom and the top was 0.2 mm to 0.5 mm.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft, deep and deep aesthetic appearance.

(Example 3)
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the structural coloring chip (C1) was used. The light transmittance of the color clear layer formed from the color clear paint was 66%.
Next, the clear paint A is applied onto the color clear layer with a brush so that the average wet film thickness is 0.5 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. A layer was obtained to obtain a laminate. The light transmittance of the clear layer was 85%, and the degree of unevenness was such that the difference between the bottom and the top was 0.2 mm to 0.5 mm.
The surface of the obtained laminate had a calm yellow brightness in a black background, and had a soft, deep and deep aesthetics.

Example 4
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the structural coloring chip (D1) was used. The light transmittance of the color clear layer formed from the color clear paint was 74%.
Next, the clear paint A is applied onto the color clear layer with a brush so that the average wet film thickness is 0.5 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. A layer was obtained to obtain a laminate. The light transmittance of the clear layer was 85%, and the degree of unevenness was such that the difference between the bottom and the top was 0.2 mm to 0.5 mm.
The surface of the obtained laminate had a calm green brightness in a black background, and had a soft, deep and deep aesthetics.

(Example 5)
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the structural coloring chip (E1) was used. The light transmittance of the color clear layer formed from the color clear paint was 62%.
Next, the clear paint A is applied onto the color clear layer with a brush so that the average wet film thickness is 0.5 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. A layer was obtained to obtain a laminate. The light transmittance of the clear layer was 85%, and the degree of unevenness was such that the difference between the bottom and the top was 0.2 mm to 0.5 mm.
The surface of the obtained laminate had a calm and clear blue brightness in a black background, and had a soft, deep and deep aesthetics.

(Example 6)
<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the structural coloring chip (F1) was used. The light transmittance of the color clear layer formed from the color clear paint was 62%.
Next, the clear paint A is applied onto the color clear layer with a brush so that the average wet film thickness is 0.5 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. A layer was obtained to obtain a laminate. The light transmittance of the clear layer was 85%, and the degree of unevenness was such that the difference between the bottom and the top was 0.2 mm to 0.5 mm.
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 7)
<Production of laminate>
100 parts by weight of epoxy resin (solid content: 100% by weight) on a porcelain tile plate (100 mm × 100 mm × 6 mm, degree of unevenness: difference between bottom and top is 0.5 mm to 2 mm) colored black A color clear coating mixed with 5 parts by weight of the structural color developing chip A was applied with a brush at a coating amount of 400 g / m ² and 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 formed from the color clear paint was 71%.
Next, the clear paint A is applied onto the color clear layer with a brush so that the average wet film thickness is 0.5 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. A layer was obtained to obtain a laminate. The light transmittance of the clear layer was 85%, and the degree of unevenness was such that the difference between the bottom and the top was 0.2 mm to 0.5 mm.
The surface of the resulting laminate had a variety of colors depending on the viewing angle, had a calm blue brightness in a black background, and had a soft, deep and deep aesthetic appearance.

(Example 8)
<Production of laminate>
Color clear which mixed 100 parts by weight of epoxy resin (solid content: 100% by weight) and 0.2 parts by weight of structural coloring chip (G1) on a porcelain tile plate (100 mm × 100 mm × 6 mm) colored black. The paint was applied with a brush so that the dry film thickness was 0.2 mm, and was dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours to obtain a first color clear layer. The light transmittance of the first color clear layer was 75%.
Next, a color clear coating obtained by mixing 100 parts by weight of an epoxy resin (solid content: 100% by weight) and 0.3 parts by weight of a structural coloring chip (G2) on the first color clear layer has a dry film thickness of 0. A second color clear layer was obtained by applying with a brush to a thickness of 2 mm and drying and curing at 80 ° C. and 50% relative humidity for 24 hours. The light transmittance of the second color clear layer was 71%.
Next, the clear paint A is applied onto the second color clear layer with a brush so that the average wet film thickness is 0.5 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. A clear layer was obtained to obtain a laminate. The light transmittance of the clear layer was 85%, and the degree of unevenness was such that the difference between the bottom and the top was 0.2 mm to 0.5 mm.
The surface of the obtained laminate had a calm red brightness in a black background, and had a variety of sensations, a natural sensation, and a soft, deep and deep aesthetics.

Example 9
<Production of laminate>
On a porcelain tile plate (100 mm × 100 mm × 6 mm) colored black in surface, 100 parts by weight of epoxy resin (solid content: 100% by weight), 0.2 part by weight of structural color chip (A1), structural color chip ( G2) A color clear paint mixed with 0.5 parts by weight was applied with a brush so that the dry film thickness was 0.2 mm, and dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. A layer was obtained. The color clear layer had a light transmittance of 71%.
Next, the clear paint A is applied onto the color clear layer with a brush so that the average wet film thickness is 0.5 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. A layer was obtained to obtain a laminate. The light transmittance of the clear layer was 85%, and the degree of unevenness was such that the difference between the bottom and the top was 0.2 mm to 0.5 mm.
The surface of the obtained laminate had a calm blue and red brightness in a black background, and had a variety of sensations, a natural feeling, and a soft, profound and deep aesthetics.

Claims (7)

On the colored substrate layer,
A color clear layer formed from a binder and a structural coloring chip having an average particle diameter of 0.1 mm to 50 mm and a thickness of 30 μm to 500 μm;
A clear layer having light diffusibility,
Are stacked,
The structural coloring chip is obtained by rolling a solid material in which spherical particles having an average particle diameter of 5 nm to 800 nm and a standard deviation of particle diameter distribution of 20% or less are dispersed in a chip forming resin.
A laminate characterized by the above.   The laminate according to claim 1, wherein the clear layer having light diffusibility has an uneven structure in a surface structure.   The laminate according to claim 1 or 2, wherein the clear layer having light diffusibility is formed of two or more kinds of substances having different refractive indexes.   The laminate according to any one of claims 1 to 3, wherein the clear layer having light diffusibility is formed from a binder and a light diffusing agent.   The laminate according to any one of claims 1 to 4, wherein a light transmittance of the clear layer having light diffusibility is 60% or more.   The laminated layer according to any one of claims 1 to 5, wherein the color clear layer contains 0.001 to 10 parts by weight of a structural coloring chip with respect to 100 parts by weight of the binder. body. In the chip forming resin having the structural coloring chip, spherical particles having an average particle size of 5 nm to 800 nm, a standard deviation of the particle size distribution of 20% or less, and a softening point higher than that of the chip forming resin are dispersed. the become solid-like material, higher than the softening point of the chip forming resin, any of claims 1 to 6, characterized in that it is made by rolling at a temperature lower than the softening point of the spherical particles The laminated body as described in.