JP5232482B2 - 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, 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 structural coloring chip in which specific spherical particles are regularly arranged in a binder on a colored base material 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. A color clear layer and a clear layer are laminated on the colored substrate layer.
The color clear layer is formed from at least a binding material 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 laminated body, wherein the clear layer is formed from at least a binder, and the light transmittance of the clear layer is 60% or more.
2. 1. The clear layer is formed of at least a binder and a crosslinkable compound . The laminated body as described in.
3. 1. The clear layer is formed of at least a binder and a light diffusing agent . The laminated body as described in.
4). 1. The binder for forming the clear layer is an acrylic resin containing 50% by weight or more of methyl methacrylate monomer and / or methyl methacrylate oligomer . To 3. The laminated body in any one of.
5. 1. The color clear layer contains 0.001 to 10 parts by weight of the structural coloring chip with respect to 100 parts by weight of the binder . To 4. The laminated body in any one of.
6). The structure coloring chip is obtained by rolling a solid product in which spherical particles having an average particle diameter of 5 nm to 800 nm and a standard deviation of the particle diameter distribution of 20% or less of the average particle diameter are dispersed in the chip forming resin. It is characterized by the following. To 5. The laminated body in any one of.
7). In the chip-forming resin having a structural coloring chip, a spherical particle having an average particle diameter of 5 nm to 800 nm, a standard deviation of the particle diameter distribution of 20% or less of the average particle diameter, and a softening point higher than that of the chip-forming resin. 7. The dispersed 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 . 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 obtained by laminating a binder and a color clear layer containing 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 on a colored substrate layer. It is.

The laminate of the present invention is characterized in that a sense of brightness is expressed using a structural coloring chip. Such a structural color developing chip can express a soft, deep, and calm brightness compared to 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 structural coloring chip in the color clear layer, and a laminate having excellent aesthetics. Can be obtained.

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 A mixed cement board, a calcium silicate board, a slag cement perlite board, an ALC board, a siding board, etc. are mentioned. Further, the surface of such a material may be the hue of the material itself, but may be colored by a generally known method such as colored coating or colored plating.

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, optical phenomenon (light interference, diffraction, scattering, etc.) generated by having a light wavelength in the visible region or a fine structure smaller than that. , Structural coloration generated by regularly arranging particles is used.

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 out of this range, it will be difficult to develop structural coloration, and if the standard deviation of the particle size distribution of the spherical particles is larger than 20% of the average particle size, it will be difficult to arrange the particles regularly. It is difficult to develop structural color.

  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 resin described above, or a reaction existing in the resin with a reactive functional group present in the newly added crosslinking agent. It may be a reaction of a reactive functional group, a reaction between reactive functional groups present in a crosslinking agent, or the like.

  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).
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-described spherical particles and non-spherical particles, other particles (for example, particles having a standard deviation of particle size distribution exceeding 20% of the average particle size, Particles having a particle diameter of more than 600 nm and less than 50 nm) may be included.

  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.

  Various manufacturing methods may be adopted as a method of manufacturing the structural color developing chip. 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.

The color clear layer of the present invention has a structural color chip immobilized by the above-mentioned binder. For example, the color clear layer composition containing the above-mentioned binder and structural color chip is used as the colored base layer. A method of laminating on top, a method of laminating a structural coloring chip after laminating a binder on a colored base material layer, a method of laminating a binding color on a colored base layer after spraying a structural coloring chip, and a binding material Can be formed by, for example, a method in which a structural coloring chip is sprayed and a binder is further laminated thereon.
The mixing ratio of the binder and the structural coloring chip in the color clear layer is not particularly limited. For example, it may 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 binder. preferable. When the structural coloring chip is less than 0.001 part by weight, it is difficult to confirm deep and calm aesthetics.

  The color clear layer may contain a coloring material to the 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 including such a coloring material, 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 above, the color clear layer has aggregates, extender pigments, fibers, matting agents, thickeners, film-forming aids, leveling agents, plasticizers, antifreezes, etc., as long as the effects of the present invention are not impaired. Agents, pH adjusters, antiseptics, antifungal agents, anti-algae agents, antibacterial agents, dispersants, antifoaming agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents, and the like may be included.

In the method of laminating the color clear layer composition on the colored substrate layer to form the color clear layer, the color clear layer composition can be applied directly on the colored substrate layer. The color clear layer composition can be formed into a film (sheet) in advance, and the film (sheet) can be attached via an adhesive or 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 may be laminated on the color clear layer.
The clear layer is not particularly limited as long as the hue of the color clear layer and the colored base material layer can be visually recognized, but the light transmittance of the clear layer is 60% or more (more preferably 70% to 99%, more preferably 80%). About 99%). When the light transmittance is within such a range, a laminate can be obtained without losing the hue of the colored substrate, the hue of the color clear layer, and the brightness. 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

  Such a clear layer can be formed at least from a binder.

  The binder for forming the clear layer is not particularly limited, and known materials can be used. 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-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-silicone resin, silicone resin, alkyd resin, melamine resin, amino resin, vinyl chloride resin, vinyl resin, silane coupling agent, water glass, colloidal silica, phosphate-dispersed water dispersion type, water-soluble type, NAD type , Melt It can be used soluble, binder solventless type.

In the present invention, it is particularly preferable to use a binder containing an acrylic resin containing 50% by weight or more of a methyl methacrylate monomer and / or a methyl methacrylate oligomer as a binder for forming the clear layer.
A clear layer formed from such a binder containing an acrylic resin has characteristics that are particularly excellent in scratch resistance and wear resistance and excellent in transparency. Further, the clearness and the like of the clear layer can provide a deeper, deeper and more calm brightness.

As such an acrylic resin, those containing 50 wt% or more (preferably 50 wt% or more and 99 wt% or less, more preferably 70 wt% or more and 99 wt% or less) of methyl methacrylate monomer and / or methyl methacrylate oligomer If it is, it will not specifically limit, Other compounds, such as a well-known monomer and an oligomer, may be contained.
Examples of other compounds include methacrylic acid such as ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. Acid esters; acrylic acid esters such as ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, and benzyl acrylate; methacrylic acid Hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate; N, N-dimethylamino methacrylate And amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl acrylate; alkanediol compounds such as ethylene glycol dimethacrylate and ethylene glycol diacrylate; polyoxyalkylene glycol compounds such as diethylene glycol dimethacrylate and diethylene glycol diacrylate Carboxyl group-containing compounds such as methacrylic acid, acrylic acid, crotonic acid, maleic acid and itaconic acid; amide group-containing compounds such as methacrylamide and acrylamide; aromatic vinyl compounds such as styrene and vinyltoluene; vinyl chloride, vinylidene chloride and the like And halogenated vinyl compounds.

  In the clear layer, coloring materials, aggregates, extender pigments, fibers, thickeners, film-forming aids, leveling agents, plasticizers, antifreeze agents, anti-settling agents are added to the extent that the effects of the present invention are not impaired. , PH adjusters, antiseptics, antifungal agents, anti-algae agents, antibacterial agents, dispersants, antifoaming agents, ultraviolet absorbers, antioxidants, yellowing inhibitors, organic peroxides, organic dyes, inorganic fillers, Additives such as a catalyst, a solvent, a crosslinkable compound, and a light diffusing agent can also be mixed.

  Examples of the catalyst include benzoyl peroxide and methyl ethyl ketone peroxide.

  Examples of the solvent include paraffin wax and / or wax, paraffin wax, polyethylene wax, higher fatty acids such as stearic acid and 1,2-hydroxystearic acid, and the like.

Examples of the crosslinkable compound include compounds having two or more reactive functional groups in the molecule. As a reactive functional group, it can set suitably with the monomer and oligomer to be used.
For example, as a combination of reactive functional groups applicable to the crosslinking reaction, for example, in addition to vinyl groups, carboxyl group and epoxy group, carboxyl group and carbodiimide group, carboxyl group and aziridine group, carboxyl group and oxazoline group, hydroxyl group And an isocyanate group, a carbonyl group and a hydrazide group, an epoxy group and an amino group, a reactive silyl group, a carboxyl group and a metal ion.

  In the present invention, it is particularly preferable to use a compound containing two or more vinyl groups in the molecule as the compound containing two or more reactive functional groups in the molecule. Examples of such compounds include ethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, divinylbenzene, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol. Examples include dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, trimethylolpropane methoxylated triacrylate, trimethylolpropane ethoxylated triacrylate, and the like.

  In the present invention, a clear layer having more excellent scratch resistance and abrasion resistance can be obtained particularly by containing a crosslinkable compound, which is preferable. The blending amount of the crosslinkable compound is not particularly limited, but is preferably 1% by weight or more and 20% by weight with respect to the total amount of the clear layer.

  In addition, the clear layer of the present invention preferably has a function of diffusing reflected light with respect to incident light. By laminating such a clear layer, it is possible to bring out an excellent aesthetic appearance by light diffusion, to give a sense of depth, and to give a deeper sense of brightness and aesthetic appearance.

  For example, examples of the clear layer having light diffusibility include (i) a clear layer having a concavo-convex surface structure, and (ii) 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 the 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 Due to the effects, etc., there is a three-dimensional effect, and it is possible to express a calm and beautiful appearance with depth and depth.
Furthermore, due to the difference in phase between the incident light and the reflected light due to the refractive index of the clear layer, it is possible to express a calm appearance with a three-dimensional feeling and depth and depth.
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. 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, there is a three-dimensional appearance, and it is possible to express a calm aesthetic with depth and depth. .
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.

Such a clear layer having light diffusibility can be given surface irregularities by, for example, surface treatment such as embossing, or surface irregularities by laminating particles such as a light diffusing agent on the surface. It can also be granted.
The clear layer composition can also be provided with unevenness on the surface of the coating film by applying and laminating the surface so that the surface is uneven, and the clear layer composition contains particles such as a light diffusing agent. The unevenness | corrugation of the coating-film surface can also be provided by.
In addition, a clear layer having a different refractive index can be obtained by laminating layers having different refractive indexes. In the clear layer composition, a method of blending binders having different refractive indexes, or a refractive index different from that of the binder. By including a substance having a refractive index (for example, a light diffusing agent), clear layers 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 the clear layer composition.

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 shape of such a light diffusing agent is not particularly limited, and a light diffusing agent such as a spherical shape, a scale shape, a needle shape, a polygonal column shape, or a columnar shape can be used, and one or two or more kinds are appropriately selected and used. be able to. The size of the light diffusing agent may be appropriately designed depending on the intended use and the like, but may be about 50 μm to 5 mm, and further about 100 μm to 3 mm.

The method for laminating such a clear layer on the color clear layer is not particularly limited.
As a method of laminating, a clear layer is prepared in advance by a conventional method using a composition for a clear layer containing a binder and, if necessary, other additives, etc., and an adhesive or the like is formed on the color clear layer. And a method of directly laminating a composition for a clear layer containing a binder and, if necessary, other additives on the color clear layer.
In the method of directly laminating the clear layer composition, it may be applied using a coating tool such as a brush, roller, spray, coater, or iron, and is not particularly limited.

  Further, the clear layer may be a single layer or a multilayer structure in which a plurality of clear layers are laminated. For example, it is possible to further improve the aesthetics of the color clear layer by laminating a plurality of clear layers having different refractive indexes, or laminating a clear layer having excellent durability after laminating a clear layer having excellent adhesion. Thus, a laminate having excellent adhesion and durability with the color clear layer can also be obtained.

  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).

In the laminate used in the present invention, a top coat layer can be further laminated on the clear layer as necessary.
As the top coat layer, for example, acrylic resin, acrylic-silicon resin, silicone resin, alkyd resin, fluorine resin, phenol resin, urethane resin, epoxy resin, polyester resin, polyether resin, vinyl resin, polyamide resin, etc. Can be used.
For example, by using a binder containing an acrylic resin containing 50% by weight or more of a methyl methacrylate monomer and / or a methyl methacrylate oligomer as a binder for forming the topcoat layer, scratch resistance and wear resistance are improved. be able to. Further, by using a binder containing an acrylic-silicon resin or a silicone resin, the anti-contamination property can be improved.
In addition to this, coloring materials, aggregates, extender pigments, fibers, thickeners, film-forming aids, leveling agents, plasticizers, antifreeze agents, anti-settling agents, pH, to the extent that the effects of the present invention are not impaired. Conditioning agent, antiseptic, antifungal agent, algaeproofing agent, antibacterial agent, dispersant, antifoaming agent, ultraviolet absorber, antioxidant, anti-yellowing agent, organic peroxide, organic dye, inorganic filler, catalyst, Additives such as a solvent, a crosslinkable compound, and a light diffusing agent can also be mixed.
As the transparency of the topcoat layer, the light transmittance is preferably about 60% or more (preferably 70% to 99%).

As a method of laminating, a topcoat film (sheet) obtained by forming a topcoat layer composition containing each component into a film (sheeting) is pasted on the clear layer via an adhesive or the like. do it.
Moreover, the composition for topcoat layers can be directly applied and laminated on the clear layer. In the method of direct coating and lamination, coating may be performed on the clear layer using a coating tool such as a brush, a roller, a spray, a coater, or a trowel, and the coating is not particularly limited.

  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 (φ100 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 structural color of purple.
The structural color-developing chip (A) was obtained by crushing and pulverizing the structural color-developing body by a conventional method.
A purple structural coloring chip (A1) having a particle diameter of 0.5 to 5 mm and a thickness of 100 μm
・ Purple structural color development chip (A2) with particle diameter of 5-50mm and thickness of 100μm

<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.
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 E 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 light interference and 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 (φ100 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).
・ Purple structural color development chip (D1) with particle diameter of 1-50mm and thickness of 100μm

<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 (φ100 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 film was peeled from the rolled PET film to obtain a blue structural color body having a thickness of 100 μm.
The structural color body was crushed and pulverized by a conventional method to obtain the following structural color chip (G).
-Blue structural coloring chip (G1) having a particle diameter of 1 mm to 5 mm and a thickness of 100 μm
-Blue structural coloring chip (G2) having a particle diameter of 5-30 mm and a thickness of 100 μm

Example 1
<Production of laminate>
Mixing 100 parts by weight of epoxy resin (solid content: 100% by weight) and 5 parts by weight of structural color chip (A2) on a porcelain tile plate (100 mm x 100 mm x 6 mm, L ^* = 10) colored black The color clear layer composition was applied with a brush so that the dry film thickness was 0.3 mm, 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. Got. The color clear layer had a light transmittance of 71%.
The surface of the obtained laminate had a calm purple brightness in a black background and had a soft aesthetic appearance.

(Example 2)
<Production of laminate>
Mixing 100 parts by weight of epoxy resin (solid content: 100% by weight) and 5 parts by weight of structural color chip (A2) on a porcelain tile plate (100 mm x 100 mm x 6 mm, L ^* = 10) colored black The color clear layer composition 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 color clear layer had a light transmittance of 71%.
Next, a clear layer composition 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 becomes 0.1 mm, and the temperature is 80 ° C. It was dried and cured for 24 hours at a relative humidity of 50% to obtain a clear layer to obtain a laminate. The light transmittance of the clear layer was 85%.
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 laminate>
A laminate was obtained in the same manner as in Example 2 except that the structural color development chip (B1) was used. The light transmittance of the color clear layer 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 4
<Production of laminate>
A laminate was obtained in the same manner as in Example 2 except that the structural coloring chip (C1) was used. The light transmittance of the color clear layer 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 5)
<Production of laminate>
A laminate was obtained in the same manner as in Example 2 except that the structural coloring chip (D1) was used. The color clear layer had a light transmittance of 74%.
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 laminate>
A laminate was obtained in the same manner as in Example 2 except that the structural coloring chip (E1) was used. The color clear layer had a light transmittance of 62%.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 7 )
<Production of laminate>
A laminate was obtained in the same manner as in Example 2 except that the structural coloring chip (F1) was used. The color clear layer had a light transmittance of 62%.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 8 )
<Production of laminate>
A laminate was obtained in the same manner as in Example 2 except that the structural coloring chip (G2) was used. The color clear layer had a light transmittance of 71%.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 9 )
<Production of laminate>
On a porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* = 10) colored black on the surface, 100 parts by weight of epoxy resin (solid content: 100% by weight), 0.2 part by weight of structural color chip (A1) The composition for color clear layer mixed with 0.5 part by weight of the structural coloring chip (G2) 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 50%. A color clear layer was obtained by drying and curing for 24 hours. The color clear layer had a light transmittance of 71%.
Next, a clear layer composition 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 becomes 0.1 mm, and the temperature is 80 ° C. It was dried and cured for 24 hours at a relative humidity of 50% to obtain a clear layer to obtain a laminate. The light transmittance of the clear layer was 85%.
The surface of the obtained laminate had a calm blue and purple brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 10 )
<Production of laminate>
Mixing 100 parts by weight of epoxy resin (solid content: 100% by weight) and 5 parts by weight of structural color chip (C1) on a porcelain tile plate (100 mm x 100 mm x 6 mm, L ^* = 10) colored black The color clear layer composition thus obtained was applied with a brush so that the dry film thickness was 0.3 mm, 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 1. The light transmittance of the color clear layer 1 was 66%.
Next, a color clear layer composition 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 (D1) are mixed on the color clear layer has a dry film thickness of 0.00. The color clear layer 2 was obtained by applying with a brush so as to be 3 mm, and drying and curing for 24 hours at a temperature of 80 ° C. and a relative humidity of 50%. The light transmittance of the color clear layer 2 was 74%.
Next, a clear layer composition composed of an epoxy resin (solid content: 100% by weight) is applied onto the color clear layer 2 with a brush so that the wet film thickness is 0.1 mm, and the temperature is 80 ° C. The film was dried and cured at a relative humidity of 50% for 24 hours to obtain a clear layer to obtain a laminate. The light transmittance of the clear layer was 85%.
The surface of the obtained laminate had a calm yellow and purple brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 11 )
<Production of laminate>
A method similar to that in Example 2 except that a porcelain tile plate (100 mm × 100 mm × 6 mm, degree of unevenness: the difference between the bottom and the top is 0.5 mm to 2 mm, L ^* = 10) whose surface is colored black is used. Thus, a laminate was obtained. The color clear layer had a light transmittance of 71%.
The surface of the obtained laminate had various colors depending on the viewing angle, and had a calm and purple brightness in a black background, and had a soft and deep aesthetic appearance.

(Example 12 )
<Production of laminate>
Mixing 100 parts by weight of epoxy resin (solid content: 100% by weight) and 5 parts by weight of structural color chip (A2) on a porcelain tile plate (100 mm x 100 mm x 6 mm, L ^* = 10) colored black The color clear layer composition 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 color clear layer had a light transmittance of 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 A clear layer composition consisting of parts by weight was applied with a brush so that the wet film thickness was 0.5 mm, and was 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 purple brightness in a black background, and had a soft, deep and deep aesthetic appearance.

(Example 13 )
<Production of laminate>
Mixing 100 parts by weight of epoxy resin (solid content: 100% by weight) and 5 parts by weight of structural color chip (A2) on a porcelain tile plate (100 mm x 100 mm x 6 mm, L ^* = 10) colored black The color clear layer composition 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 color clear layer had a light transmittance of 71%.
Next, on the color clear layer, 75 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of quartz powder (average particle size: 30 μm, refractive index: 1.45), 2 parts by weight of benzoyl peroxide The clear layer composition A is applied so that the film thickness is 1.0 mm, dried and cured for 2 hours at a temperature of 25 ° C. and a relative humidity of 50% to obtain a clear layer, and a laminate is obtained. It was. The clear layer had a light transmittance of 85% and a refractive index of 1.49.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft, deep and deep aesthetic appearance.

The obtained laminate was subjected to the following test.
<Abrasion resistance test>
A JIS K 5400 8.9 wear resistance test was performed using the obtained laminate. CS17 was used as the tapered wear wheel. The evaluation is represented by wear loss, and the results are shown in Table 3.
The laminate obtained in Example 2 was also subjected to the same abrasion resistance test. The results are shown in Table 3.
<Abrasion resistance test>
Using the obtained laminate, steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was used to repeatedly rub the surface of the laminate 10 times under the condition of a load of 500 g. The presence or absence of scratches was evaluated. The evaluation is as follows. The results are shown in Table 3.
5: No peeling or scratches are observed.
4: Occurrence of peeling and scratches is hardly observed.
3: Slightly thin scratches are observed.
2: A streak is recognized on the entire surface.
1: Peeling occurs.

(Example 14 )
<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 composition for color clear layer was 70%.
Next, the clear layer composition A was applied onto the color clear layer so as to have a film thickness of 1.0 mm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours. To obtain a laminate.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft, deep and deep aesthetic appearance.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

(Example 15 )
<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 composition for color clear layer was 66%.
Next, the clear layer composition A was applied onto the color clear layer so as to have a film thickness of 1.0 mm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours. To obtain a laminate.
The surface of the obtained laminate had a calm yellow brightness in a black background, and had a soft, deep and deep aesthetics.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

(Example 16 )
<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 composition for color clear layer was 74%.
Next, the clear layer composition A was applied onto the color clear layer so as to have a film thickness of 1.0 mm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours. To obtain a laminate.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft, profound and deep aesthetics.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

(Example 17 )
<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 composition for color clear layer was 62%.
Next, the clear layer composition A was applied onto the color clear layer so as to have a film thickness of 1.0 mm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours. To obtain a laminate.
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.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

(Example 18 )
<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 composition for color clear layer was 62%.
Next, the clear layer composition A was applied onto the color clear layer so as to have a film thickness of 1.0 mm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours. To obtain a laminate.
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.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

(Example 19 )
<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 The composition for color clear layer mixed with 5 parts by weight of the structural coloring chip (A1) was applied with a brush at a coating amount of 400 g / m 2 and dried and cured for 24 hours at a temperature of 80 ° C. and a relative humidity of 50%. A clear layer was obtained. The light transmittance of the color clear layer formed from the composition for color clear layer was 71%.
Next, the clear layer composition A was applied onto the color clear layer so as to have a film thickness of 1.0 mm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours. To obtain a laminate.
The surface of the resulting laminate had a variety of colors depending on the viewing angle, had a purple brightness with a calmness in a black background, and had a soft, deep and deep aesthetic appearance.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

(Example 20 )
<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 layer composition was applied with a brush so that the dry film thickness was 0.2 mm, and dried and cured for 24 hours at a temperature of 80 ° C. and a relative humidity of 50% to obtain a first color clear layer. The light transmittance of the first color clear layer was 75%.
Next, a color clear layer composition in which 100 parts by weight of an epoxy resin (solid content: 100% by weight) and 0.3 parts by weight of a structural color developing chip (G2) are mixed on the first color clear layer is dried. A thickness of 0.2 mm was applied with a brush and dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours to obtain a second color clear layer. The light transmittance of the second color clear layer was 71%.
Next, on the second color clear layer, 75 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 6 parts by weight of dipentaerythritol hexaacrylate, quartz powder (average particle size: 30 μm, refractive index: 1. 45) A clear layer composition B comprising 3 parts by weight and 2 parts by weight of benzoyl peroxide was applied so that the film thickness was 1.0 mm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours. To obtain a clear layer to obtain a laminate. The clear layer had a light transmittance of 85% and a refractive index of 1.49.
The surface of the obtained laminate had a calm blue brightness in a black background, and had a variety of sensations, a natural sensation, and a soft, deep and deep aesthetics.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

(Example 21 )
<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) The composition for color clear layer mixed with 0.5 part by weight is applied with a brush so that the dry film thickness is 0.2 mm, and is dried and cured at a temperature of 80 ° C. and a relative humidity of 50% for 24 hours. A color clear layer was obtained. The color clear layer had a light transmittance of 71%.
Next, the clear layer composition A was applied onto the color clear layer so as to have a film thickness of 1.0 mm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours. To obtain a laminate.
The surface of the resulting laminate had a calm blue and violet brightness in a black background, and had a colorful, natural, soft, deep and deep aesthetics.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

(Example 22 )
<Production of laminate>
A top coat layer composition comprising 20 parts by weight of polyalkylsiloxane and 80 parts by weight of isopropyl alcohol was applied to the clear layer surface of the laminate obtained in Example 13 so that the film thickness was 20 μm. Drying and curing at 1 ° C. for 1 hour to obtain a topcoat layer, a laminate was obtained. The refractive index of the top coat layer was 1.4.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft, deep and deep aesthetic appearance.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

(Example 23 )
<Production of laminate>
Mixing 100 parts by weight of epoxy resin (solid content: 100% by weight) and 5 parts by weight of structural color chip (A2) on a porcelain tile plate (100 mm x 100 mm x 6 mm, L ^* = 10) colored black The color clear layer composition 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 color clear layer had a light transmittance of 71%.
Next, on the color clear layer, 75 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of glass powder (average particle size: 0.2 mm, refractive index: 1.43), benzoyl peroxide A clear layer composition C consisting of 2 parts by weight was applied so that the film thickness was 0.5 mm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours to obtain a clear layer. Got. The clear layer had a light transmittance of 84% and a refractive index of 1.49.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft, deep and deep aesthetic appearance.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

(Example 24 )
<Production of laminate>
Mixing 100 parts by weight of epoxy resin (solid content: 100% by weight) and 5 parts by weight of structural color chip (A2) on a porcelain tile plate (100 mm x 100 mm x 6 mm, L ^* = 10) colored black The color clear layer composition 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 color clear layer had a light transmittance of 71%.
Next, on the color clear layer, 75 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 2 parts by weight of glass powder (average particle diameter: 0.2 mm, refractive index: 1.43), benzoyl peroxide 2 parts by weight of the clear layer composition D was applied so that the film thickness was 0.5 mm, and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours.
Furthermore, 75 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of glass powder (average particle diameter: 0.2 mm, refractive index: 1.43), and 2 parts by weight of benzoyl peroxide are included. The clear layer composition C was applied to a film thickness of 0.5 mm and dried and cured at a temperature of 25 ° C. and a relative humidity of 50% for 2 hours to obtain a clear layer to obtain a laminate. The clear layer had a light transmittance of 84% and a refractive index of 1.49.
The surface of the obtained laminate had a calm purple brightness in a black background, and had a soft, deep and deep aesthetic appearance.
Moreover, the same test as Example 13 was done about the obtained laminated body. The results are shown in Table 3.

Claims (7)

A color clear layer and a clear layer are laminated on the colored substrate layer.
  The color clear layer is formed from at least a binding material 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 laminated body, wherein the clear layer is formed from at least a binder, and the light transmittance of the clear layer is 60% or more. The laminate according to claim 1 , wherein the clear layer is formed of at least a binder and a crosslinkable compound. The laminate according to claim 1 , wherein the clear layer is formed of at least a binder and a light diffusing agent. Binder to form a clear layer, the laminate according to claims 1, characterized in that an acrylic resin comprising a methyl methacrylate monomer and / or methyl methacrylate oligomer 50 wt% or more to any one of claims 3 . Color clear layer, relative to the binder 100 parts by weight, the laminated body according to claims 1 to structural color chip is characterized in that which is contained 0.001 to 10 parts by weight to one of claims 4 . The structure coloring chip is obtained by rolling a solid product in which spherical particles having an average particle diameter of 5 nm to 800 nm and a standard deviation of the particle diameter distribution of 20% or less of the average particle diameter are dispersed in the chip forming resin. The laminate according to any one of claims 1 to 5 , wherein: In the chip-forming resin having a structural coloring chip, a spherical particle having an average particle diameter of 5 nm to 800 nm, a standard deviation of the particle diameter distribution of 20% or less of the average particle diameter, and a softening point higher than that of the chip-forming resin. the solid product obtained dispersed, the chip formed higher than the softening point of the resin, 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 in any one of.