JP4675262B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate having excellent aesthetics.

2. Description of the Related Art Conventionally, materials having a feeling of brightness have been widely used in building materials such as walls, floors, and ceilings, and other home appliances, furniture, vehicles, 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 brightness feeling include materials described in Patent Document 1 and the like.
In Patent Document 1, for example, aluminum flake pigment, vapor-deposited aluminum flake pigment, metal oxide-coated aluminum flake pigment, colored aluminum flake pigment, metal oxide-coated mica pigment (pearl mica), 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 iron oxide, graphite, stainless steel flake, metal titanium flake pigment, plate sulfide A material having a luminance feeling such as molybdenum and plate-like bismuth chloride is described.

JP 2005-137852 A

As a material having such a feeling of brightness, for example, as a typical material, so-called pearl mica (metal oxide coating) in which natural or synthetic mica (mica) is used as a base material and the surface thereof is coated with titanium oxide or iron oxide, etc. Mica pigment).
Pearl mica can exhibit a design with brightness (“glitter”, “pearly luster”) based on reflection of light. In other words, pearl mica reflects light on the pearl mica and the coating film, and the phase of the light shifts depending on the incident angle, causing the light to interfere with each other. , “Pearly luster”).

However, a film formed using the various pigments described above is likely to have a strong luminance feeling (“glitter feeling”), and tends to have an artificial design feeling.
Therefore, the use on the inner wall, floor, ceiling, or the entire surface of a house is often avoided.

  In order to solve the above-mentioned problems, the present invention has been intensively studied, and as a result, by using a chip having two types of structural color developability with different particle diameters, hue change due to structural color developability and hue change ( It has been found that a design with a variety of hues) and a calm brightness and naturalness can be obtained, and the present invention has been completed.

That is, the present invention has the following characteristics.
1. On the colored substrate layer,
Binding material (1);
A structural coloring chip (2) having a particle diameter of 3 mm to 50 mm and a thickness of 30 μm to 500 μm;
A structural color-forming chip (3) having a particle diameter of 0.1 mm or more and less than 3 mm and a thickness of 30 μm or more and 500 μm or less,
The total amount of the structural coloring chip (2) and the structural coloring chip (3) is 0.05 to 100 parts by weight with respect to 100 parts by weight of the solid content of the binder (1).
A laminate comprising a color clear layer in which the mixing ratio of the structural coloring chip (2) and the structural coloring chip (3) is 5:95 to 95: 5 by weight.
2. The structural coloring chip (2) and the structural coloring chip (3) are characterized in that spherical particles having an average particle diameter of 5 nm to 800 nm and a standard deviation of the particle diameter distribution of 20% or less are regularly arranged. 1. The laminated body as described in.

  In the present invention, in the color clear layer, by using two types of structural chips having different particle diameters, hue changes (various hue feelings) due to changes in hue and viewing angle due to structural color development are provided, and A laminate having a calm brightness and natural feeling and excellent aesthetics can be obtained.

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

  The laminate of the present invention comprises a binder (1), a structural color chip (2) having a particle diameter of 3 mm to 50 mm, a thickness of 30 μm to 500 μm, and a particle diameter of 0.1 mm or more on the colored substrate layer. The structural coloring chip (3) having a thickness of less than 3 mm and a thickness of 30 μm or more and 500 μm or less, and the total of the structural coloring chip (2) and the structural coloring chip (3) with respect to 100 parts by weight of the solid content of the binder (1) A color clear layer having an amount of 0.05 to 100 parts by weight and a mixing ratio of the structural coloring chip (2) and the structural coloring chip (3) of 5:95 to 95: 5 is laminated. It is characterized by becoming.

The coloring substrate layer is not particularly limited, and materials used for building materials such as walls, floors, ceilings, home appliances / furnitures, vehicles, and the like 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 in the CIE L ^* a ^* b ^* color space 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, By changing the viewing angle, the hue changes, a variety of hues are imparted, and a design with a calm brightness is obtained.

In the present invention, among such structural color chips,
A structural coloring chip (2) having a particle diameter of 3 mm to 50 mm (preferably 5 mm to 30 mm) and a thickness of 30 μm to 500 μm (preferably 50 μm to 300 μm);
A structural coloring chip (3) having a particle size of 0.1 mm or more and less than 3 mm (preferably 0.2 mm or more and 2 mm or less) and a thickness of 30 μm or more and 500 μm or less (preferably 50 μm or more and 300 μm or less);
The total amount of the structural coloring chip (2) and the structural coloring chip (3) is 0.05 to 100 parts by weight (preferably 0.05 to 50 parts by weight, based on 100 parts by weight of the solid content of the binder (1). Preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight)
5:95 to 95: 5 (preferably 10:90 to 90:10, more preferably 20:80 to 80:20) when the mixing ratio is a weight ratio of the structural coloring chip (2): structural coloring chip (3). ) In the range.
By using the structural coloring chip (2) and the structural coloring chip (3) in combination, a variety of hues can be imparted, and a design with a natural aesthetic appearance can be imparted in addition to a calm brightness. it can.
When there are too many structural coloring chips (2) among the structural coloring chips and when there are too many structural coloring chips (3), an artificial (non-natural) design feeling tends to occur.

  Such a color clear layer contains the binder (1), the structural color chip (2), and the structural color chip (3). The binder (1), the structural color chip (2), It can be molded from a color clear paint containing the structural coloring chip (3).

Specifically, as the color clear coating, the total amount of the structural coloring chip (2) and the structural coloring chip (3) is 0.05 to 100 parts by weight (preferably with respect to 100 parts by weight of the solid content of the binder (1)). Is 0.05 to 50 parts by weight, more preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight.
By being in such a range, it is possible to express a variety of hues and a calm brightness. When the total amount of the structural coloring chip (2) and the structural coloring chip (3) is too small, it tends to lack hue and brightness. On the other hand, if it is too much, it tends to lack a calm brightness, and the color clear layer tends to be inferior in physical properties of the coating film.

  Examples of the binder (1) include acrylic resin, polyester resin, polyether resin, vinyl resin, polyamide resin, phenol resin, urethane resin, epoxy resin, fluororesin, vinyl acetate resin, vinyl chloride resin, and acrylic-styrene resin. , Vinyl acetate-versaic acid vinyl ester resin, polyvinyl pyrrolidone resin, polyvinyl caprolactam resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, AS resin, cellulose resin, acrylic-silicon resin, silicone resin, alkyd resin, melamine resin, amino resin PVC resin, vinyl resin, and the like. Solvent-free, solvent-soluble, NAD, water-soluble, and water-dispersed types of such resins can be used.

  The structural coloring chip (2) and the structural coloring chip (3) are not particularly limited as long as they exhibit structural coloring, but the structural coloring chip in which particles are regularly arranged, the structural coloring chip in which thin films are superimposed, Examples include a hologram structure coloring chip and a cholesteric structure 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 10). % Or less) is preferably used in which spherical particles 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 is out of this range or the standard deviation of the particle size distribution is higher than 20%, the light coherence in the visible light region is impaired, and it becomes difficult to obtain the desired structural color development.

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 coloring structure and can maintain an excellent color over a long period of time.

  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.

  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 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 colors 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. Further, at this time, a colored structure can be obtained by sandwiching a solid material with two rolls and applying pressure in a direction perpendicular to the surface direction. It is also possible to carry out using a single roll, and it is also possible to obtain a colored structure chip by applying pressure to a solid material, changing the direction of the roll by 180 ° about the roll, 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 color developing structure becomes thin, the light transmittance is higher than the light diffraction, and the structural color developability is hardly recognized, which is not preferable.

  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 coloring structure is increased, and the initial coloring performance can be maintained for a long time. Furthermore, since the inorganic particles have a very high softening point compared to the chip-forming resin, the restriction on the heating temperature during rolling is relaxed, and the range of applicable chip-forming resins is expanded.

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 structural coloring chip thus obtained can be adjusted to a predetermined size by crushing, pulverizing, or the like, if necessary.
In the present invention, the structural color development chip (2) is formed by setting the particle diameter to 3 mm to 50 mm and the thickness of 30 μm to 500 μm, and the structural color generation chip is set to the particle diameter of 0.1 mm to less than 3 mm and the thickness of 30 μm to 500 μm. A chip (3) can be obtained.
In particular, when a structural coloring chip is manufactured by the above-described manufacturing method, it can be easily adjusted to a predetermined size by crushing and pulverizing the chip forming resin below the softening point. The structural coloring chip (2) and the structural coloring chip (3) used in the present invention may be the same type or different types, but the same type is preferable.
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).

  The color clear layer of the present invention can be formed by laminating a color clear paint containing the binder (1), the structural color developing chip (2), and the structural color developing chip (3) on the colored substrate layer. .

  Moreover, a coloring material can also be mixed 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 Organic color pigments such as pyrazolone, anthraquinone, perylene, quinacridone, benzimidazole, phthalocyanine, disazo, isoindolinone, quinophthalone, aluminum pigment, pearl pigment, firefly 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, it is preferable to laminate a clear layer on the color clear layer. By laminating the clear layer, there is an effect of providing a sense of depth, giving a deeper brightness and aesthetics, and protecting the color clear layer.
The clear layer has transparency enough to recognize the hue of the color clear layer and the colored substrate layer.
As the transparency of the clear layer, the light transmittance is preferably about 60% to 100% (preferably 70% to 99%).
When the light transmittance is within such a range, a laminated structure can be obtained without losing the hue of the colored substrate and the hue, brightness, and variety of the color clear layer. Moreover, the structure which is excellent in aesthetics with a three-dimensional effect and depth can be obtained.

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

Examples of such a clear layer include a clear plate such as a glass plate and an acrylic resin plate, or a clear coating film formed from a clear paint containing a binder.
For example, the binder used in the clear coating can be selected from the binders (1) described above.

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.
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 for laminating such a clear layer on the color clear layer is not particularly limited.
As a method of laminating, a clear plate or a clear film (sheet) in which a clear paint is formed (sheeted) in advance may be attached to the color clear layer via an adhesive or the like.
Further, a clear paint can be applied directly on the color clear layer. In the direct application method, the color clear layer may be applied using a brush, roller, spray or the like, and there is no particular limitation such as one-time application or multiple-time application.

  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 3 mm).

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

<Manufacture of structural coloring chip>
<Production Example 1 (Structural Coloring Chips A to D)>
Using the raw materials shown in Table 1, a resin solution was prepared by mixing resin C with solvent A at a mixing ratio shown in Table 2 at a temperature of 23 ° C. and a relative humidity of 50% (hereinafter also referred to as “standard state”). 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. It peeled from the PET film after rolling, and obtained the 100-micrometer-thick blue-type structural color body.
The structural color development body was crushed and pulverized by a conventional method to obtain the following structural color development chip.
-Blue structural coloring chip (A) having a particle diameter of 0.5 mm to 1 mm and a thickness of 100 μm
-Blue structural coloring chip (B) having a particle diameter of 1 to 2 mm and a thickness of 100 μm
-Blue structural coloring chip (C) having a particle diameter of 15 mm to 20 mm and a thickness of 100 μm
-Blue structural coloring chip (D) having a particle diameter of 60 mm to 80 mm and a thickness of 100 μm

<Production Example 2 (Structural Coloring Chips E to F)>
Using the raw materials shown in Table 1, except for the mixing ratio shown in Table 2, a red structural color body having a thickness of 100 μm was obtained in the same manner as in Production Example 1.
The structural color development body was crushed and pulverized by a conventional method to obtain the following structural color development chip.
-Red structural coloring chip (E) with a particle diameter of 1 mm to 2 mm and a thickness of 100 μm
-Red structural coloring chip (F) having a particle diameter of 15 mm to 20 mm and a thickness of 100 μm

<Production Example 3 (Structural Coloring Chips G to H)>
Using the raw materials shown in Table 1, except for the mixing ratio shown in Table 2, a yellow-green structural color body having a thickness of 100 μm was obtained in the same manner as in Production Example 1.
The structural color development body was crushed and pulverized by a conventional method to obtain the following structural color development chip.
・ Yellow green structural coloring chip (G) having a particle diameter of 0.5 mm to 1.5 mm and a thickness of 100 μm
-Yellow-green structural coloring chip (H) having a particle diameter of 10 to 15 mm and a thickness of 100 μm

<Production Example 4 (Structural Coloring Chips I to J)>
Using the raw materials shown in Table 1, except for the mixing ratio shown in Table 2, a blue structural color body having a thickness of 100 μm was obtained in the same manner as in Production Example 1.
The structural color development body was crushed and pulverized by a conventional method to obtain the following structural color development chip.
-Blue structural coloring chip (I) having a particle diameter of 0.5 mm to 1.5 mm and a thickness of 100 μm
-Blue structural coloring chip (J) having a particle diameter of 12-16 mm and a thickness of 100 μm

<Production Example 5 (Structural Coloring Chips K to L)>
Using the raw materials shown in Table 1, except for the mixing ratio shown in Table 2, a blue structural color body having a thickness of 100 μm was obtained in the same manner as in Production Example 1.
The structural color development body was crushed and pulverized by a conventional method to obtain the following structural color development chip.
-Blue structural coloring chip (K) having a particle diameter of 0.5 mm to 1.5 mm and a thickness of 100 μm
-Blue structural coloring chip (L) having a particle diameter of 12-16 mm and a thickness of 100 μm

<Production Example 6 (Structural Coloring Chips M to N)>
Using the raw materials shown in Table 1, except for the mixing ratio shown in Table 2, a blue structural color body having a thickness of 100 μm was obtained in the same manner as in Production Example 1.
The structural color development body was crushed and pulverized by a conventional method to obtain the following structural color development chip.
-Blue structural coloring chip (M) having a particle diameter of 0.5 mm to 1.5 mm and a thickness of 100 μm
-Blue structural coloring chip (N) having a particle diameter of 12-16 mm and a thickness of 100 μm

<Production Example 7 (Structural Coloring Chips OP)>
Using the raw materials shown in Table 1, except for the mixing ratio shown in Table 2, a blue structural color body having a thickness of 100 μm was obtained in the same manner as in Production Example 1.
The structural color development body was crushed and pulverized by a conventional method to obtain the following structural color development chip.
-Blue structural coloring chip (O) having a particle diameter of 0.5 mm to 1.5 mm and a thickness of 100 μm
-Blue structural coloring chip (P) having a particle diameter of 12-16 mm and a thickness of 100 μm

Example 1
On the porcelain tile plate (100 mm x 100 mm x 6 mm) whose surface is colored black,
A color clear coating (Table 3) obtained by mixing 100 parts by weight of the resin D shown in Table 1, 0.16 parts by weight of the structural coloring chip (B) and 0.04 part by weight of the structural coloring chip (C) has a dry film thickness of 0. The color clear layer was obtained by applying with a brush so as to be 3 mm, and drying and curing at 80 ° C. and 50% relative humidity for 24 hours. The light transmittance of the color clear layer formed from the color clear paint was 71%.
Next, a clear paint made of an epoxy resin (solid content: 100% by weight) is applied onto the color clear layer with a brush so that the wet film thickness is 0.1 mm, and the temperature is 80 ° C. and the relative humidity is It was dried and cured at 50% for 24 hours to obtain a clear layer to obtain a laminate. The light transmittance of the clear layer formed from the clear paint was 85%.
The obtained laminate had a calm blue luminance feeling in a black background, and had good aesthetics with a variety of feelings and a natural feeling.

(Example 2)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm blue brightness in a black background, and had excellent aesthetics with a variety and naturalness.

(Example 3)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm blue brightness in a black background, and had excellent aesthetics with a variety and naturalness.

Example 4
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm blue brightness in a black background, and had a variety of aesthetics with a natural feeling.

(Example 5)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm blue brightness in a black background, and had a variety of aesthetics with a natural feeling.

(Example 6)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had an excellent aesthetics with a dark red luminance, a variety of colors and a natural feeling in a black background.

(Example 7)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm yellow-green luminance in a black background, and had excellent aesthetics with a variety of feelings and a natural feeling.

(Example 8)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm blue brightness in a black background, and had excellent aesthetics with a variety and naturalness.

Example 9
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The resulting laminate had a calm blue and yellow-green brightness in a black background, and had an excellent aesthetics with a variety of feelings and a natural feeling.

(Example 10)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm blue brightness in a black background, and had excellent aesthetics with a variety and naturalness.

(Example 11)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm blue luminance feeling in a black background, and had good aesthetics with a variety of feelings and a natural feeling.

(Example 12)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm blue brightness in a black background, and had a variety of aesthetics with a natural feeling.

(Example 13)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm blue brightness in a black background, and had excellent aesthetics with a variety and naturalness.

(Example 14)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate had a calm blue brightness in a black background, and had excellent aesthetics with a variety and naturalness.

(Example 15)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The resulting laminate had a calm blue brightness in a black background, and had excellent aesthetics with a variety of feelings, naturalness and luxury.

(Example 16)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The resulting laminate had a calm blue brightness in a black background, and had excellent aesthetics with a variety of feelings, naturalness and luxury.

(Example 17)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The resulting laminate had a calm blue brightness in a black background, and had excellent aesthetics with a variety of feelings, naturalness and luxury.

(Example 18)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The resulting laminate had a calm blue brightness in a black background, and had excellent aesthetics with a variety of feelings, naturalness and luxury.

(Comparative Example 1)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate was a blue monotonous design.

(Comparative Example 2)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate was a blue monotonous design.

(Comparative Example 3)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate was a blue artificial design.

(Comparative Example 4)
A laminate was obtained in the same manner as in Example 1 except for the mixing ratio shown in Table 3.
The obtained laminate was a blue artificial design.

Claims (2)

On the colored substrate layer,
Binding material (1);
A structural coloring chip (2) having a particle diameter of 3 mm to 50 mm and a thickness of 30 μm to 500 μm;
A structural color-forming chip (3) having a particle diameter of 0.1 mm or more and less than 3 mm and a thickness of 30 μm or more and 500 μm or less,
The total amount of the structural coloring chip (2) and the structural coloring chip (3) is 0.05 to 100 parts by weight with respect to 100 parts by weight of the solid content of the binder (1).
A laminate comprising a color clear layer in which the mixing ratio of the structural coloring chip (2) and the structural coloring chip (3) is 5:95 to 95: 5 by weight. The structural coloring chip (2) and the structural coloring chip (3) are characterized in that spherical particles having an average particle diameter of 5 nm to 800 nm and a standard deviation of the particle diameter distribution of 20% or less are regularly arranged. 2. The laminate according to claim 1.