JP5325532B2 - Laminated body and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aesthetically excellent laminate that has a brilliant feel with a depth and a calm. <P>SOLUTION: The laminate includes: a colored substrate layer having an L<SP>*</SP>value of &le;60 in the L<SP>*</SP>a<SP>*</SP>b<SP>*</SP>color coordinate system of CIE (International Commission on Illumination) 1976 (JIS Z8729), a transparent layer in which the thickness is randomly varied; and a design layer which contains a glittering pigment and has randomly varied thicknesses. The transparent layer is present between the colored substrate layer and the design layer. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a laminate excellent in design and a method for producing the same.

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, a material such as Patent Document 1 has a too strong brightness and tends to be a monotonous design, and in some cases, it may be avoided.

  In order to solve the above-mentioned problems, the present invention has been intensively studied, and as a result, by laminating a transparent layer having a random thickness and a design layer containing a glitter pigment on the colored substrate layer, As a result, the present invention has been completed.

That is, the present invention has the following characteristics.
1. A laminate having excellent design properties,
A colored substrate layer having an L ^* value of 60 or less in the L ^* a ^* b ^* color system of CIE (International Commission on Illumination) 1976 (JIS Z8729);
A transparent layer whose thickness is randomly displaced,
A design layer containing a luster pigment, the thickness of which is randomly displaced,
Including
The transparent layer includes two or more kinds of scaly transparent granules having a particle diameter of 0.5 mm or more and 50 mm or less and a thickness of 50 μm or more and 1500 μm or less,
The thickness of the transparent layer is in the range of 5 mm or less, the difference in thickness between the recess and the protrusion is 50 μm or more, the thickness of the protrusion is 50 μm or more and 5 mm or less, and the thickness of the recess is 2 mm or less. ,
The thickness of the transparent layer is one that changes continuously, or one that changes intermittently,
The thickness of the design layer is in the range of 5 mm or less, the difference in thickness between the concave and convex portions is 50 μm or more,
The thickness of the design layer is continuously changing,
A transparent layer exists between the colored substrate layer and the design layer,
A laminate characterized by the above.
2. 1. The light transmittance of the transparent layer is 10% or more. The laminated body as described in.
3. A protective layer is laminated on the transparent layer,
1. The light transmittance of the protective layer is 60% or more. Or 2. The laminated body as described in.
4). 2. The protective layer contains a light diffusing agent having a size of 50 μm or more and 5 mm or less. The laminated body as described in.

  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 a colored substrate layer having an L ^* value of 60 or less in the L ^* a ^* b ^* color system of CIE (International Commission on Illumination) 1976 (JIS Z8729) (simply “colored substrate layer”). A transparent layer whose thickness is randomly changed (also simply referred to as “transparent layer”), and a design layer containing a bright pigment and whose thickness is randomly changed (simply simply “design layer”). And a transparent layer is present between the colored base material layer and the design layer.

  Such a laminate has a structure in which the thickness of the transparent layer and the thickness of the design layer are randomly changed. Therefore, the color by the design layer is emphasized at a location where the thickness of the design layer is large, and conversely, the color by the colored base material layer is emphasized at a location where the thickness of the design layer is small. In addition, the sense of depth is enhanced at locations where the transparent layer is thick, and the depth can be changed due to the random thickness of the transparent layer. Together with the design layer, the sense of depth and depth It is possible to obtain a laminate having an excellent design having a feeling of calmness and brightness.

The colored base layer is particularly limited as long as the L ^* value in the L ^* a ^* b ^* color system of CIE (International Commission on Illumination) 1976 (JIS Z8729) is 60 or less (preferably 50 or less). Alternatively, it may be a monochromatic surface composed of one kind of hue or a multicolored surface composed of two or more kinds of hues. Further, the surface of the colored base material layer is not particularly limited, such as an uneven surface, a curved surface, a flat surface and the like.
As the colored base material layer, for example, materials used for building materials such as home appliances / furniture, vehicles, walls, floors, ceilings, and the like can be suitably used.
Examples of such materials include metal steel plates such as aluminum steel plates, galvanized steel plates, stainless steel plates, copper steel plates, plastic plates, extruded plates, ceramics, glass, fired tiles, porcelain tiles, wood, concrete, mortar, and gypsum boards. , Fiber mixed cement board, calcium silicate board, slag cement pearlite board, ALC board, siding board and the like. 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 as long as the L ^* value is 60 or less, and may be selected according to the use, such as black, brown, purple, blue, green, yellow, orange, and red. By using the L ^* value having a value of 60 or less, it is possible to express the brightness feeling due to the bright pigment. When the L ^* value exceeds 60, it is difficult to visually recognize the brightness feeling due to the bright pigment.

The L ^* value (lightness) in the L ^* a ^* b ^* color specification of CIE (International Commission on Illumination) 1976 (JIS Z8729) is a value representing a brighter color as it is higher and a darker color as it is lower. Such L ^* values can be measured using a color difference meter.

The transparent layer is not particularly limited as long as the thickness is randomly changed.
The transparent layer used in the present invention has a thickness of 5 mm or less (preferably 4 mm or less, more preferably 3 mm or less), and the difference in thickness between the concave and convex portions is 50 μm or more (preferably 80 μm or more, A transparent layer having a thickness that is preferably randomly changed to 100 μm or more can be suitably used. A transparent layer having such a range is effective for imparting excellent aesthetics having a sense of depth and depth, and having a calm brightness, and is preferably used. If the difference in thickness between the convex part and the concave part is less than 50 μm, the depth sensation hardly changes and the design may be monotonous.
Furthermore, the thickness of the transparent layer may be continuously changed, may be changed intermittently, and may be changed gradually or abruptly. Moreover, there may be a partially discontinuous portion where the thickness is partially 0 mm. In the present invention, the thickness of the convex portion is about 50 μm to 5 mm (preferably 70 μm to 4 mm, more preferably 90 μm to 3 mm), and the thickness of the concave portion is 2 mm or less (preferably 1.5 mm or less, Preferably, it is preferably about 1 mm or less.

  The concave portion of the transparent layer refers to the thinnest portion of the transparent layer, and the convex portion of the transparent layer refers to the thickest portion of the transparent layer. The thickness of the transparent layer is a value obtained by observing and measuring a cross section of the transparent layer with an optical microscope.

  The transparent layer of the present invention comprises a component that forms a transparent layer (hereinafter also referred to as “transparent layer forming component”).

  Examples of the transparent layer forming component include glass, silica, acrylic resin, polyester resin, polyether resin, vinyl resin, polyamide resin, phenol resin, urethane resin, epoxy resin, fluorine resin, vinyl acetate resin, vinyl chloride resin, acrylic resin. -Styrene resin, vinyl acetate-vinyl versatic acid ester resin, polyvinylpyrrolidone resin, polyvinylcaprolactam resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, AS resin, cellulose resin, acrylic-silicon resin, silicone resin, alkyd resin, melamine resin Amino resin, vinyl chloride resin, vinyl resin and the like.

  In addition, the transparent layer forming component can be mixed with known additives to the extent that the effects of the present invention are not impaired. Examples of additives include commonly used known color pigments, extender pigments, aggregates, fibers, plasticizers, antiseptics, antifungal agents, antifoaming agents, viscosity modifiers, leveling agents, silane coupling agents, and pigments. Examples thereof include a dispersant, an anti-settling agent, an anti-sagging agent, a matting agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antibacterial agent, an adsorbent, a photocatalyst, a solvent, and water. In addition, it is better not to include a luster pigment.

  The transparent layer of the present invention is obtained by using such a transparent layer forming component, and may be obtained by curing a liquid material of the transparent layer forming component, or an existing layer comprising a transparent layer forming component. The transparent granular powder may be obtained, or may be obtained by curing a mixture containing a transparent layer forming component liquid (= transparent binder) and the transparent granular powder.

In particular, when transparent granular powder is included, there is a steep step (transition) in the thickness of the transparent layer depending on the thickness (particle diameter) of the transparent granular powder between where the transparent granular powder exists and where it does not exist. It is easy to generate. Therefore, the depth and depth change abruptly in the vicinity of this boundary, and the thickness and location of the design layer, which will be described later, also change abruptly. The color change is clearly visible. Accordingly, it is possible to impart excellent aesthetics having a brightness feeling with enhanced contrast even in the presence of depth and calmness.
Further, since the refractive index is different between the location where the transparent granular powder is present and the location where the transparent granular powder is not present, aesthetics due to a change in color due to light interference or the like can also be imparted at this boundary.

Moreover, in this invention, a color pattern can be simply provided by selecting suitably the magnitude | size and shape of transparent granular powder. In the present invention, as the shape of the transparent granular material, for example, a transparent granular material such as a spherical shape, a scaly shape, a needle shape, a polygonal column shape, or a cylindrical shape can be used, and one or more kinds are appropriately selected. Can be used.
In particular, when two or more kinds of transparent powder particles having different sizes, shapes, and refractive indexes of the transparent powder particles are used, deeper and more calm aesthetics can be imparted.

  When a spherical transparent granular material is used as the transparent granular material, it may be appropriately designed depending on the intended use and the like, but the particle diameter is 0.5 mm or more and 5 mm or less, and further 0.6 mm or more and 2 mm or less. Is preferred.

When a scaly transparent granular material is used as the transparent granular material, it may be appropriately designed depending on the intended use and the like, but the particle diameter (short diameter and long diameter) is 0.5 mm to 50 mm (preferably 0. 6 mm or more and 20 mm), and the thickness is preferably 50 μm or more and 1500 μm or less (more preferably 80 μm or more and 1000 μm or less). If the particle diameter (minor axis and major axis) is smaller than 0.5 mm, it may be difficult to visually recognize the color pattern due to the transparent granular material.
In addition, the scale-like transparent granular material is prone to a sharp step (transition) depending on the thickness of the transparent granular powder between the location where the transparent granular powder exists and the location where the transparent granular powder does not exist. Among them, it is preferably used because it is easy to impart excellent aesthetics having a brightness with enhanced contrast.
Such a scaly transparent granular material may be used alone or in combination of two or more different shapes, sizes, thicknesses, and the like. In particular, when two or more types of scaly transparent particles having different thicknesses are included, it is possible to impart excellent aesthetics with richer color changes.
In addition, the particle diameter of the transparent granular material is a value obtained by actual measurement or measurement using an optical microscope.

  Although it does not specifically limit as a transparent granular material, What is necessary is just that the light transmittance is 10% or more (preferably 20% or more).

In addition, when the transparent layer is composed of a composite of a cured body of transparent binder and transparent granular powder, the material of the transparent binder, the material of the transparent granular powder, the mixing ratio of both, etc. The transparent layer can be formed by appropriately selecting. For example, a deeper and more pleasing aesthetics can be imparted by selecting a cured body of a transparent binder having a refractive index different from that of the transparent granular powder.
The content ratio of the transparent binder and the transparent granular powder is not particularly limited, but the solid content of the transparent binder is 0.1 to 500 parts by weight with respect to 100 parts by weight of the transparent granular powder. Is preferably about 1 to 200 parts by weight.
Moreover, when a transparent layer consists of a composite body of the transparent body hardening body and transparent granular powder, it is preferable to add a silane coupling agent at the time of transparent layer formation. By adding the silane coupling agent, it is possible to efficiently disperse the transparent granular powder and to form a tough transparent layer after forming the transparent layer. Furthermore, there is an effect of preventing the generation of a gap at the interface between the cured cured transparent binder and the transparent granular powder, and the transparency can be improved. When a transparent granular powder containing glass or a silica component is used, a silane coupling agent having a mercapto group is particularly preferable as the silane coupling agent.

  Further, when the transparent layer is made of a cured body of a transparent binder, the transparent layer may be formed by appropriately selecting the material of the transparent binder, for example, a transparent binder having a different refractive index. By blending and molding, deeper and calmer aesthetics can be imparted.

The transparent layer of the present invention has transparency and is not particularly limited as long as the color of the colored base material layer can be visually recognized. Usually, the light transmittance is 10% or more, further 10% or more and 99%. In the following, it is further preferable to use those that are 20% or more and 98% or less. When the light transmittance is less than 10%, it is difficult to visually recognize the color of the colored base material layer, and it is difficult to obtain a sense of depth and depth.
The light transmittance is all measured using an integrating sphere light transmittance measuring device in accordance with measurement method A defined in JIS K 7105-1981 5.5 “Light transmittance and total light reflectance”. It is a value of light transmittance. The light transmittance is a value measured at a wavelength of 550 nm and a transparent layer thickness of 2 mm.

The design layer may be any layer that contains a luster pigment and whose thickness is randomly changed.
By containing the glitter pigment, it is possible to give a bright color to the laminate, and the color of the design layer is emphasized at the place where the thickness of the design layer is large, and conversely the thickness of the design layer is reduced. In a small place, it is possible to obtain a laminated body with high aesthetics, in which the color of the colored base material layer is emphasized.

  Examples of glitter pigments include aluminum flake pigments, vapor-deposited aluminum flake pigments, metal oxide-coated aluminum flake pigments, colored aluminum flake pigments, metal oxide-coated mica pigments, metal oxide-coated synthetic mica pigments, and 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 molybdenum sulfide, plate Bismuth chloride, holographic pigment, cholesteric liquid crystal polymer, crushed product of metal-deposited polymer film, etc., especially metal oxide-coated mica pigment, metal oxide-coated synthetic mica pigment, hologram pigment, metal-deposited polymer film Good for shredded products Used properly.

  Further, as a component for forming the design layer (hereinafter, also referred to as “design layer forming component”), in addition to the luster pigment, a binder and a known additive are added to such an extent that the effects of the present invention are not impaired. They can also be mixed, and the color of the design layer can be set by appropriately setting the type and mixing ratio of the glitter pigment.

  The binding material is not particularly limited. For example, acrylic resin, polyester resin, polyether resin, vinyl resin, polyamide resin, phenol resin, urethane resin, epoxy resin, fluorine resin, vinyl acetate resin, vinyl chloride resin, acrylic 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, silicon resin, silicone resin, alkyd resin, A melamine resin, an amino resin, a vinyl chloride resin, a vinyl resin, etc. are mentioned, Among these, 1 type (s) or 2 or more types can be used. Moreover, you may use the thing similar to the transparent layer formation component mentioned above.

  The mixing ratio of the binder and the luster pigment is 0.001 to 10 parts by weight (more preferably 0.005 to 5 parts by weight) with respect to 100 parts by weight of the solid content of the binder. Any degree is acceptable.

  Moreover, the transparent granular material may be included as a design layer formation component. Although it does not specifically limit as a transparent granular material, It is preferable that a particle diameter is 0.5 mm or more and 5 mm or less, Furthermore, it is preferable that it is 0.6 mm or more and 2 mm or less. Moreover, when using a scaly transparent granular material The particle diameter (minor axis and major axis) is in the range of 0.5 mm to 5 mm (preferably 0.6 mm to 2 mm), and the thickness is in the range of 50 μm to 1000 μm (more preferably 80 μm to 800 μm). preferable.

Examples of additives include commonly used known color pigments, extender pigments, aggregates, fibers, plasticizers, antiseptics, antifungal agents, antifoaming agents, viscosity modifiers, leveling agents, silane coupling agents, and pigments. Examples thereof include a dispersant, an anti-settling agent, an anti-sagging agent, a matting agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antibacterial agent, an adsorbent, a photocatalyst, a solvent, and water.
In the present invention, it is particularly preferable to add a silane coupling agent. By adding a silane coupling agent, it is possible to efficiently disperse the luster pigment, to obtain more excellent design properties, and to form a tough design layer after forming the design layer. . In particular, when a silane coupling agent having a mercapto group is used as the silane coupling agent, the above effect can be exhibited more preferably.

  The design layer used in the present invention has a thickness of 5 mm or less (preferably 4 mm or less, more preferably 3 mm or less), and the difference in thickness between the concave and convex portions is 50 μm or more (preferably 80 μm or more, A design layer having a thickness that is preferably randomly changed to 100 μm or more can be suitably used.

The design layer in such a range can give a more aesthetically pleasing luminance feeling, and in combination with the transparent layer and the colored substrate layer, has a deeper and more calm luminance feeling. Aesthetics can be imparted.
Furthermore, the design layer may have a thickness that changes gradually, a thickness that changes abruptly, a thickness that changes intermittently, or a thickness that changes intermittently. It may be a partly discontinuous transition as follows.
In the present invention, it is particularly preferable that the thickness changes continuously, and the thickness of the convex portion is about 50 μm or more and 5 mm or less (preferably 70 μm or more and 4 mm or less, more preferably 90 μm or more and 3 mm or less). The thickness is preferably about 30 μm to 2 mm (preferably 40 μm to 1.5 mm, more preferably 50 μm to 1 mm).
Thus, not only the transparent layer but also the thickness of the design layer is randomly changed, so that a design with more sense of depth and depth can be imparted.
Moreover, when the thickness of the design layer becomes too thick, it may be difficult to visually recognize the color and contrast of the colored base material layer. Further, if the difference in thickness between the concave and convex portions is less than 50 μm, there are cases where aesthetic aesthetics rich in color cannot be obtained.

  The concave portion of the design layer refers to the thinnest portion of the design layer, and the convex portion of the design layer refers to the thickest portion of the design layer. The thickness of the design layer is a value obtained by observing and measuring a cross section of the design layer with an optical microscope.

The design layer of the present invention imparts color, and has a light transmittance lower than that of the transparent layer. The light transmittance of the design layer is preferably 1% or more and 80% or less, more preferably 2% or more and 70% or less, and further preferably 3% or more and 50% or less.
When the light transmittance is less than 1%, it is difficult to visually recognize the color of the colored base material layer, and it is difficult to obtain a sense of depth and depth. Moreover, if the light transmittance exceeds 80%, the color of the design layer is difficult to recognize.
The light transmittance is all measured using an integrating sphere light transmittance measuring device in accordance with measurement method A defined in JIS K 7105-1981 5.5 “Light transmittance and total light reflectance”. It is a value of light transmittance. The light transmittance is a value measured at a wavelength of 550 nm and a design layer thickness of 2 mm.

The laminated body of this invention will not be specifically limited if the said transparent layer exists between the said colored base material layer and the said design layer, For example, the laminated body shown in FIG.
Examples of the laminated structure of the laminate include a laminated structure of a colored substrate layer / transparent layer / design layer, a colored substrate layer / design layer / transparent layer / design layer, etc. In the present invention, in particular, a colored substrate. A layer having a laminated structure of a colored base material layer / transparent layer / design layer in which a layer, a transparent layer, and a design layer are sequentially laminated is preferable.
The surface of the laminate is not particularly limited, whether it is an uneven surface, a curved surface, or a flat surface, and may be appropriately set according to the application. Further, if necessary, a laminate having a later-described protective layer or the like may be laminated on the surface of the laminate. In this invention, the laminated body which has a flat surface is easy to use for uses, such as household appliances / furniture, a vehicle, and building materials, such as a wall, a floor, and a ceiling, and is used suitably.

  Specifically, the laminate of the present invention can be produced by the following method or the like. Note that the present invention is not limited to these manufacturing methods.

Examples of the method for laminating the transparent layer on the colored substrate layer include the following methods.
(1) A method of preparing a transparent plate / sheet whose thickness has been changed randomly using a transparent layer forming component in advance and sticking it to a colored substrate layer (2) A transparent granular material and a transparent binder A method of preparing a coating liquid containing, coating and laminating on a colored substrate layer, and drying and curing (3) Dispersing a transparent granular material on the colored substrate layer, and after spraying, coating including a transparent binder Method of applying and laminating liquid and drying and curing (4) Applying and laminating a coating liquid containing a transparent binder on the colored substrate layer, and before the coating liquid is dried and cured, Method of spraying and drying and curing

Moreover, the following methods etc. are mentioned as a method of laminating a design layer on a transparent layer.
(A) A method for preparing a design plate / sheet using a design layer forming component in advance and sticking it to the transparent layer (B) A coating solution comprising the design layer forming component is prepared, applied and laminated on the transparent layer, and dried. Method of curing (C) A method of preparing a design chip (design layer) composed of a design layer forming component in advance and then spraying and fixing the design chip on the transparent layer. A design chip (design layer) to be manufactured, a coating liquid containing the design chip and a binder is applied and laminated on a transparent layer, and then dried and cured.

Moreover, the following methods etc. are mentioned as another method of laminating | stacking a transparent layer and a design layer on a colored base material layer.
(I) A method in which a laminate in which a transparent layer and a design layer are laminated in advance is produced, and the laminate is laminated so that the colored substrate layer and the transparent layer are in contact with each other. (II) Bright pigment, transparent powder A method of preparing a coating liquid containing granules and a binder, applying and laminating to a colored substrate layer, and drying and curing (III) Dispersing transparent granules on the colored substrate layer, spreading, and then brightening A method of applying and laminating a coating liquid comprising a design layer forming component containing a functional pigment and a binder, and drying and curing (IV) A colored base material layer is laminated on one side of a previously produced transparent layer, and the other side Method of Laminating the Design Layer (V) A design chip (design layer) containing a glitter pigment and a binder is prepared in advance, and a transparent layer forming component containing the design chip is applied and laminated on the colored substrate layer, followed by drying and curing. Method,

  In the present invention, a laminate can be produced by appropriately combining the methods (1) to (4), (A) to (D), and (I) to (V).

The method (1) is a method for producing a transparent plate / sheet whose thickness has been randomly changed in advance using a transparent layer forming component.
For example, the thickness is determined by a method such as a mold manufacturing method in which a transparent layer forming component is poured into a mold having a concavo-convex surface and cured and a concavo-convex shape is provided using an embossing roller. What is necessary is just to produce the transparent board and sheet which changed at random.
By sticking the transparent plate / sheet thus produced using a known adhesive or pressure-sensitive adhesive, a transparent layer whose thickness is randomly changed can be laminated on the colored base material layer. Moreover, you may give the unevenness | corrugation to the coloring base material layer surface previously.

  The adhesive and the pressure-sensitive adhesive are not particularly limited as long as the effects of the present invention are not impaired, but it is preferable to use a transparent adhesive or pressure-sensitive adhesive. For example, an acrylic resin, a polyester resin, a polyether resin, a 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 A resin, ABS resin, AS resin, cellulose resin, acrylic-silicon resin, silicone resin, alkyd resin, melamine resin, amino resin, vinyl chloride resin, vinyl resin, or the like may be used.

  In the method (2), first, a coating liquid containing a transparent granular material and a transparent binder is prepared, and then this coating liquid is applied and laminated on the colored base material layer, followed by drying and curing. This is a method for obtaining a transparent layer whose thickness is randomly changed. In addition to the transparent granular material and the binder, additives that are usually used can be included to the extent that the effects of the present invention are not impaired.

  The method (2) is characterized by applying and laminating a coating liquid containing a transparent granular material and a transparent binder, and the transparent layer is formed by curing the transparent granular material and the transparent binder. It consists of the body.

  The randomly changing thickness of the transparent layer can be provided by appropriately setting the mixing ratio of the transparent granular material and the binder, the size and shape of the granular material, the viscosity of the coating liquid, and the like. A concavo-convex shape can be imparted to the surface using a concavo-convex pattern imparting tool.

  It is also possible to give irregularities on the surface of the colored base material layer to give a transparent layer whose thickness is randomly changed, the surface free energy of the surface of the colored base material layer, and the surface free energy and viscosity of the coating liquid. Can be appropriately set, and a transparent layer whose thickness is randomly changed can be provided by drying and curing in a state where the coating liquid is arranged in a mottled pattern.

The method (3) is a method in which a transparent granular material is first sprayed, and after spraying, a coating liquid containing a transparent binder is applied and laminated, and then dried and cured.
In such a method, it is particularly preferable to use a scaly transparent granular material. The scaly transparent granular material is preferable because it is easily arranged along the surface of the colored base material layer, and the thickness of the transparent layer is easily controlled by the thickness of the scaly transparent granular material.

  The method of spraying the transparent granular material is not particularly limited, but other than the method of spraying by hand, the method of spraying with a sieve, the method of spraying by spraying, the method of spraying using a known spraying device, etc. Can be adopted. The number of times of spraying may be one, or it may be sprayed in multiple times.

  When spraying the transparent granular material, an undercoat material may be used so that the transparent granular material can be fixed. When using the undercoat material, the transparency is required before the undercoat material is dried and solidified. What is necessary is just to spray a granular material.

  Further, when the transparent powder particles are excessively dispersed, they may be removed using a brush, broom, vacuum cleaner, air broker or the like. At this time, it is only necessary to remove the excessively dispersed transparent powder particles in a state where the undercoat material is completely or partially dried.

  After spraying the transparent granular material, a coating liquid composed of a transparent layer forming component containing a transparent binder is applied and laminated.

  The transparent layer thus obtained consists of a transparent granular material and a cured body of a transparent binder, and adjusts the size and thickness of the transparent granular material, the required amount of coating liquid, etc. By doing this, it is possible to obtain a transparent layer in which the thickness at which the transparent granular material portion becomes a convex portion is randomly changed. Further, by adjusting the required amount of the coating liquid, the surface free energy of the transparent granular material, etc., it is possible to obtain a transparent layer in which the thickness at which the transparent granular material portion becomes a concave portion is randomly changed. Moreover, the transparent layer from which the thickness changed at random can also be obtained by providing uneven | corrugated shape on the surface using an uneven | corrugated pattern provision tool.

  The method (4) is a method in which a coating liquid containing a transparent binder is first applied and laminated, and before the coating liquid is dried and cured, the transparent powder particles are sprayed.

  In the method (4), the timing of spraying the transparent granular material is not particularly limited as long as it is before the coating solution is dried and cured, and is usually about 1 to 15 minutes after coating and laminating the coating solution. That's fine.

  In addition, the method for spraying the transparent granular material is not particularly limited, but other than the method of spraying by hand, the method of spraying with a sieve, the method of spraying by spraying, the method of spraying using a known spraying device, etc. Can be adopted as appropriate. The number of times of spraying may be one, or it may be sprayed in multiple times. Moreover, when the transparent granular material is sprayed excessively, it may be removed using a brush, broom, vacuum cleaner or the like. At this time, it is only necessary to remove the excessively dispersed transparent granular material in a state where the coating liquid is completely or partially dried.

  In the method of (4), it is a transparent layer manufactured from the cured body of the transparent binder and the transparent granular material, and the thickness at which the dispersed transparent granular material portion becomes a convex portion randomly changes. A transparent layer is obtained.

  As a method of laminating a design layer on a transparent layer after laminating a transparent layer on a colored base material layer by methods (1)-(4) etc., the method of (A)-(D) mentioned above. Etc.

The method (A) is a method in which a design plate / sheet is prepared in advance using a design layer forming component, and the design plate / sheet is stuck on the transparent layer.
Examples of the design layer forming component include those containing a binder and other additives in addition to the glitter pigment, and the color of the design layer is set by appropriately setting the type and mixing ratio of the glitter pigment. can do.

  As a method for producing a design plate / sheet, for example, a design layer production method in which a design layer forming component is poured into a mold and cured to produce a method, or a roll coater method using a roller, etc. A sheet may be produced. Further, unevenness can be imparted to the design plate / sheet after curing.

Thus, the manufactured design board and sheet | seat can be stuck using a well-known adhesive agent or an adhesive.
At this time, the adhesive and the pressure-sensitive adhesive are not particularly limited as long as the effects of the present invention are not impaired, but the above-described transparent adhesive and pressure-sensitive adhesive are preferably used.

  In the method (B), a coating liquid containing a bright pigment and a binder is prepared, applied and laminated on a transparent layer, and then dried and cured.

In the method (B), the design layer is composed of a bright pigment and a cured body of a binder.
The randomly changing thickness of the design layer can be used to give an uneven shape to the surface using an uneven pattern imparting tool, or a design layer whose thickness is changed randomly using the unevenness on the surface of the transparent layer. The surface free energy on the surface of the transparent layer and the surface free energy and viscosity of the coating solution can be set as appropriate, and the coating solution can be dried and cured in a mottled pattern, resulting in a random thickness. It is also possible to provide a transparent layer transformed to.

The methods (C) and (D) are methods for producing a design chip (design layer) made of a design layer forming component in advance. The production method of the design chip is not particularly limited, and for example, a molded body produced by the method (A) can be obtained by adjusting it to a predetermined size by a known method. For example, a method for obtaining a mold layer having a predetermined size by pouring a design layer forming component including a glitter pigment and a binder into a predetermined size, and a molded body obtained with a normal mold shape having a predetermined size. The method obtained by crushing is mentioned.
The size of the design chip is not particularly limited, but it is preferable to use a design chip having a particle diameter of about 0.5 cm to 20 cm and a thickness of about 50 μm to 5 mm.
A method ((C)) in which the design chip thus obtained is dispersed and fixed on the transparent layer, and a coating solution containing the design chip and the binder is prepared, applied and laminated on the transparent layer, and dried. The design layer can be formed by the curing method ((D)). At this time, it is possible to form a design layer whose thickness is randomly changed depending on the thickness of the design chip and the degree of overlap of the design chip.
What is necessary is just to implement about the method to disperse | distribute in (C), and the method to fix by the method similar to the transparent granular material in the method of (3) and (4).
Moreover, what is necessary is just to implement about the method of (D) by the method similar to the transparent granular material in the method of (2).

  Other methods for laminating a transparent layer and a design layer on the colored substrate layer include the above-described methods (I), (II), (III), (IV), and (V).

In the method (I), first, a laminate in which a transparent layer and a design layer are laminated is manufactured.
Although it does not specifically limit as a manufacturing method, The method of sticking the design layer which consists of a pre-made design board and a sheet to the transparent layer which consists of a pre-made transparent board and a sheet, or produced beforehand. A method of applying and laminating a coating liquid comprising a design layer forming component including a glittering pigment and a binder to a transparent layer comprising a transparent plate / sheet, and a design layer comprising a design board / sheet prepared in advance. And a method of coating and laminating a coating liquid comprising a transparent layer forming component containing a binder.
The transparent plate / sheet, the design plate / sheet, various coating solutions, and the like are as described above.

  The laminate of the present invention can be produced by laminating the laminate composed of the transparent layer and the design layer thus obtained so that the colored base material layer and the transparent layer are in contact with each other. . Moreover, what is necessary is just to stick using the adhesive agent and adhesive which were mentioned above, when laminating | stacking.

The method (II) is a method in which a coating liquid containing a luster pigment, a transparent granular material, and a binder is first prepared, the coating liquid is applied and laminated on a colored substrate layer, and then dried and cured.
In the laminate obtained in this way, the transparent granular material becomes a transparent layer, and the cured body made of a bright pigment, a binder or the like becomes a design layer.

  In the method (II), at least a part of the transparent granular material that becomes the transparent layer is present between the colored base material layer and the cured material that is made of the glitter pigment that becomes the design layer, the binder, or the like. For example, by adjusting various specific gravities, mixing amounts, etc., by applying a plurality of times, and by appropriately selecting a coating method, between the colored base material layer and the design layer. In addition, a transparent layer can be present.

In the method (III), first, a transparent granular material is sprayed on a colored base material layer, and then a coating liquid containing a bright pigment and a binder is applied and laminated.
The laminated body thus obtained is a transparent layer in which the dispersed transparent granular material is a transparent layer, and a cured product of the coating liquid is a design layer. The size and thickness of the transparent granular material, the required coating liquid By appropriately setting the amount, the design of the laminate can be imparted.

The method (IV) is a method of laminating a colored base material layer on one surface of a previously produced transparent layer and laminating a design layer on the other surface.
As a method of laminating the colored base material layer, the above-mentioned colored base material layer can be adhered via an adhesive or an adhesive material, or a coating solution colored so that the L ^* value is 60 or less. You may laminate by applying and laminating.
The colored coating liquid is not particularly limited, and examples thereof include those having the above-mentioned binder and coloring pigment as essential components, and other additives may be mixed to such an extent that the effects of the present invention are not impaired. Good.

  The method (V) is a method in which a transparent layer forming component in which a design chip prepared in advance as described above is blended is applied and laminated on a colored substrate layer, followed by drying and curing. The method for applying and laminating is not particularly limited, and for example, it may be applied and laminated using a known applicator such as a roller, a brush, a trowel, a spatula, or a gun. At this time, it is possible to form a design layer whose thickness is randomly changed depending on the thickness of the design chip and the degree of overlap of the design chip.

A transparent layer and a design layer can be laminated | stacked by the method of such (1)-(4), (A)-(D), (I)-(V).
The thickness of the transparent plate / sheet and the design plate / sheet used here is 5 mm or less (preferably 4 mm or less, more preferably 3 mm or less), and there is a difference in thickness between the concave and convex portions. What is 50 μm or more (preferably 80 μm or more, more preferably 100 μm or more) may be used.
The method of applying and laminating the coating liquid is not particularly limited, and for example, the laminating may be performed using a known applicator such as a roller, a brush, a trowel, a spatula, or a gun. Further, the required amount of the coating solution may be appropriately set depending on the thickness of the transparent layer and the design layer, but is usually about 50 g / m ² or more and 5000 g / m ² or less (100 g / m ² or more and 3000 g / m ² or less). I just need it. In addition, before applying and laminating the coating liquid, the surface of the colored base layer can be surface-treated with an undercoat material (sealer, surfacer, primer, etc.) as necessary.

In particular, the present invention is a method in which the method (3) or (4) is combined with the method (B), or (III), since a transparent layer whose thickness is randomly changed can be easily produced. The method etc. are preferable and the method which combined the method of said (4) and the method of said (B) especially is preferable.
Moreover, in this invention, the laminated body which is more excellent in aesthetics can be obtained by performing a defoaming process at the time of mixing of various components, and / or after application | coating lamination.

Furthermore, the laminate of the present invention may be one in which a protective layer is laminated on the design layer.
The protective layer is not particularly limited as long as the hue of the design layer and the colored base material layer can be visually recognized, but the light transmittance of the protective layer is 60% or more (more 70% to 99%, more preferably 80% to 80%). 99%) is preferable. 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 design layer, and the brightness. In addition, a structure with excellent three-dimensionality and depth and excellent aesthetics can be obtained.
The light transmittance is all measured using an integrating sphere light transmittance measuring device in accordance with measurement method A defined in JIS K 7105-1981 5.5 “Light transmittance and total light reflectance”. It is a value of light transmittance. The light transmittance is a value measured at a wavelength of 550 nm and a protective layer thickness of 2 mm.

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

  The binding material for forming the protective 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 , Solvent acceptable Type, can be used binder solventless type.

In this invention, it is preferable to use especially the binder containing the acrylic resin which contains 50 weight% or more of a methyl methacrylate monomer and / or a methyl methacrylate oligomer as a binder which forms a protective layer.
The protective 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. In addition, the sense of transparency of the protective layer makes it possible to express a more relaxed and deeper 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.

  Moreover, as a binding material for forming the protective layer, a binding material containing an epoxy resin can also be suitably used. By using an epoxy resin, it is possible to obtain a protective layer having excellent scratch resistance and abrasion resistance and excellent transparency.

  In addition, a binder containing water glass can be suitably used as the binder for forming the protective layer. Water glass is a component that forms glass, and it is possible to obtain a protective layer that is excellent in scratch resistance and abrasion resistance, and also excellent in transparency. Moreover, heat resistance and intensity | strength can also be improved using heat resistant glass and tempered glass.

  In addition, the protective layer has a coloring material, an aggregate, an extender pigment, a fiber, a thickener, a film-forming aid, a leveling agent, a plasticizer, an antifreezing agent, and an anti-settling agent 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, a light diffusing agent, and a silane coupling agent can also be mixed.

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

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

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 protective layer having more excellent scratch resistance and abrasion resistance can be obtained particularly by containing a crosslinkable compound, which is preferable. Although the compounding quantity of a crosslinkable compound is not specifically limited, It is preferable that they are 1 weight% or more and 20 weight% with respect to the whole quantity of the binder which forms a protective layer.

Examples of silane coupling agents include amino group-containing silane coupling agents, mercapto group-containing silane coupling agents, epoxy group-containing silane coupling agents, carboxy-containing silane coupling agents, and vinyl type unsaturated group-containing silane coupling agents. , Halogen-containing silane coupling agents, isocyanurate group-containing silane coupling agents, isocyanate group-containing silane coupling agents, and the like.
As a silane coupling agent, in particular, when a mercapto group-containing silane coupling agent is used, it is possible to obtain a better design, and to improve wear resistance and to form a tougher protective layer. preferable.

A method for laminating such a protective layer on the design layer is not particularly limited.
As a method of laminating, a protective layer (protective sheet, etc.) is prepared in advance by a conventional method using a composition for a protective layer containing a binder and, if necessary, other additives, etc., and then bonded onto the design layer. Examples thereof include a method of attaching via an agent, a pressure-sensitive adhesive, and the like, and a method of directly laminating a composition for a protective layer containing a binder and, if necessary, other additives on the design layer.
In the method of directly laminating the protective layer composition, it may be applied using a coating tool such as a brush, roller, spray, coater, or iron, and is not particularly limited.
Moreover, the method of sticking a glass plate, a plastic plate, etc. is also mentioned as a method of obtaining a protective layer.

  The film thickness of such a protective layer is not particularly limited, but is preferably about 0.5 μm to 5 mm (preferably 10 μm to 2 mm).

  The protective layer of the present invention preferably has a function of diffusing reflected light with respect to incident light. By laminating such a protective 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 luminance sense and aesthetic appearance.

  For example, examples of the protective layer having light diffusibility include (ii) a protective layer having a concavo-convex surface structure, and (ii) a protective layer formed from two or more substances having different refractive indexes.

(Ii) The protective 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 diffusing and reflecting the light transmitted through the protective 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 protective layer, it is possible to express a calm aesthetic that has a three-dimensional effect and has depth and depth.
The unevenness difference 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) The protective layer formed of two or more substances having different refractive indexes is different in the incident angle and reflection angle of light at the boundary surface 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 protective 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.
Moreover, the coating layer surface irregularities can be imparted by applying and laminating the protective layer composition so that the surface is irregular, and the protective layer composition contains particles such as a light diffusing agent. It is also possible to impart unevenness on the surface of the coating film.
In addition, a protective layer having a different refractive index can be obtained by laminating layers having different refractive indexes. In the protective layer composition, a method of blending a binder having a different refractive index, or a refractive index different from that of the binder. By containing a substance having a refractive index (for example, a light diffusing agent), protective layers having different refractive indexes can be obtained.
The protective 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 protective layer having light diffusibility by applying the protective 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.

A method for laminating such a protective layer on the design layer is not particularly limited.
As a method of laminating, a protective layer is prepared in advance by a conventional method using a composition for a protective layer containing a binder, and, if necessary, other additives, etc., and an adhesive or the like is formed on the design layer. The method of sticking, the method of laminating | stacking directly the composition for protective layers containing a binder and other additives etc. as needed on the design layer, etc. are mentioned.
In the method of directly laminating the protective layer composition, it may be applied using a coating tool such as a brush, roller, spray, coater, or iron, and is not particularly limited.

  The protective layer may be a single layer or a multi-layer structure in which a plurality of protective layers are stacked. For example, it is possible to further improve the aesthetics of the laminate of the present invention by laminating a plurality of protective layers having different refractive indexes, and laminating a protective layer having excellent durability after laminating a protective layer having excellent adhesion. Thus, a laminate having excellent adhesion to the design layer and durability can be obtained.

The thickness of the protective layer is not particularly limited, but is preferably about 0.5 μm to 5 mm (preferably 10 μm to 2 mm).
Furthermore, it is preferable that the thickness of the protective layer of the present invention is randomly changed.
The thickness of the protective layer is preferably one in which the thickness difference between the concave and convex portions is 50 μm or more (preferably 80 μm or more, more preferably 100 μm or more) and is randomly changed.
When the thickness of the protective layer is also changed randomly, a sense of depth and depth can be obtained, and excellent aesthetics with a calm brightness can be imparted.
Furthermore, the thickness of the protective layer may be continuously changed, may be changed intermittently, and may be changed slowly or rapidly, and is not particularly limited.

The laminated body used by this invention can also laminate | stack a topcoat layer further on a protective layer as needed.
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 methyl methacrylate monomer and / or methyl methacrylate oligomer as a binder for forming the topcoat layer, the 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%).
The light transmittance is all measured using an integrating sphere light transmittance measuring device in accordance with measurement method A defined in JIS K 7105-1981 5.5 “Light transmittance and total light reflectance”. It is a value of light transmittance. The light transmittance is a value measured at a wavelength of 550 nm and a top coat layer thickness of 2 mm.

As a method of laminating, a topcoat film (sheet) obtained by forming a composition for a topcoat layer containing each component into a film (sheeting) is pasted on a protective layer via an adhesive or the like. do it.
Moreover, the composition for topcoat layers can also be directly apply | coated and laminated | stacked on a protective layer. In the method of direct coating and lamination, coating may be performed on the protective 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.

Example 1
On the porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 24) whose surface is colored,
A coating solution containing an epoxy resin (solid content: 75% by weight, light transmittance of cured product: 85%) was applied with a brush at a required amount of 0.75 kg / m ² .
Three minutes after application, before the coating solution hardens, scaly glass granules A (particle diameter: major axis 10 mm, minor axis 8 mm, thickness 500 μm to 700 μm, light transmittance: 70%) is 0.3 kg / m. ² and sprayed at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a transparent layer.
The transparent layer has a concave portion of 0.5 mm and a convex portion having a thickness of 1.2 mm, and the transparent layer surface has a concave-convex pattern in which the scaly glass particles become convex portions. Met.
Next, on the transparent layer, 100 parts by weight of epoxy resin (solid content: 75% by weight, light transmittance of cured product: 85%), glitter pigment A: 0.1 parts by weight, glitter pigment B: 0.2 parts by weight A coating solution containing a coating solution was applied with a brush at a required amount of 0.5 kg / m ² and dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a design layer to obtain a laminate. The thickness of the design layer at which the concave portion was 0.1 mm and the convex portion was 0.8 mm was randomly changed, and the light transmittance of the design layer was 17.0%.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.

Moreover, about the obtained laminated body, it observed visually and evaluated the designability (a feeling of depth, versatility). The evaluation criteria are as follows. The results are shown in Table 1.
As for the sense of depth, “10” indicates that there is a sense of depth with a sense of depth from any angle, and “1” indicates that there is no sense of depth and lacks depth. Rated by stage.
In addition, with regard to a variety of colors, the color pattern shades are clear from any angle, and “10” is an excellent variety. What was missing was set to “1” and evaluated in 10 stages.

The glitter pigment A was a crushed aluminum vapor deposited polymer film (average particle size: 150 μm, hue blue), and the glitter pigment B was a titanium oxide-coated mica pigment (average particle diameter: 30 μm, hue: blue). .
The L ^* value is a value measured with a color difference meter (CM-3700d, manufactured by Konica Minolta Holdings, Inc.).
The light transmittance is a scale-like glass powder adjusted with an integrating sphere light transmittance measuring device (manufactured by Shimadzu Corporation) to a thickness of 2 mm, a cured epoxy resin having a thickness of 2 mm. It is the value which measured the design layer adjusted so that a granule and thickness might be 2 mm. (Wavelength: 550 nm)
The thickness of a transparent layer and a design layer is the value which observed and measured the laminated body cross section using the optical microscope (BHT-364M, Olympus optical industry company make).

(Example 2)
On the porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 43) colored on the surface,
The required amount of coating solution containing 100 parts by weight of an epoxy resin (solid content 75% by weight, light transmittance of a cured product: 85%) and 0.5 parts by weight of a silane coupling agent (γ-mercaptopropyltrimethoxysilane) is 0. It was applied with a brush at 75 kg / m ² .
Three minutes after application, before the coating solution hardens, scaly glass granules A (particle diameter: major axis 10 mm, minor axis 8 mm, thickness 500 μm to 700 μm, light transmittance: 70%) is 0.3 kg / m. ² and sprayed at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a transparent layer.
The transparent layer has a concave portion of 0.5 mm and a convex portion having a thickness of 1.2 mm, and the transparent layer surface has a concave-convex pattern in which the scaly glass particles become convex portions. Met.
Next, on the transparent layer, 100 parts by weight of epoxy resin (solid content: 75% by weight, light transmittance of cured product: 85%), glitter pigment A: 0.1 parts by weight, glitter pigment B: 0.2 parts by weight A coating solution containing a coating solution was applied with a brush at a required amount of 0.5 kg / m ² and dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a design layer to obtain a laminate. The thickness of the design layer at which the concave portion was 0.1 mm and the convex portion was 0.8 mm was randomly changed, and the light transmittance of the design layer was 17.0%.
The obtained laminate has a color pattern in which the pattern randomly changes while having a blue hue as a whole, and also has a deep and calm brightness feeling that varies in color depending on the viewing angle. It had excellent aesthetics.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Example 3)
On the porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 36) whose surface is colored,
The required amount of coating solution containing 100 parts by weight of an epoxy resin (solid content 75% by weight, light transmittance of a cured product: 85%) and 0.5 parts by weight of a silane coupling agent (γ-mercaptopropyltrimethoxysilane) is 0. It was applied with a brush at 75 kg / m ² .
Three minutes after application, before the coating solution hardens, scaly glass granules A (particle diameter: major axis 10 mm, minor axis 8 mm, thickness 500 μm to 700 μm, light transmittance: 70%) is 0.3 kg / m. ² and sprayed at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a transparent layer.
The transparent layer has a concave portion of 0.5 mm and a convex portion having a thickness of 1.2 mm, and the transparent layer surface has a concave-convex pattern in which the scaly glass particles become convex portions. Met.
Next, on the transparent layer, 100 parts by weight of epoxy resin (solid content: 75% by weight, light transmittance of cured product: 85%), glitter pigment A: 0.1 parts by weight, glitter pigment B: 0.2 parts by weight A coating solution containing 0.5 part by weight of a silane coupling agent (γ-mercaptopropyltrimethoxysilane) was applied with a brush at a required amount of 0.5 kg / m ² , at a temperature of 50 ° C. and a relative humidity of 60%. It dried for 5 hours, the design layer was obtained, and the laminated body was obtained. The thickness of the design layer at which the concave portion was 0.1 mm and the convex portion was 0.8 mm was randomly changed, and the light transmittance of the design layer was 17.0%.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

Example 4
On the design layer of the laminate obtained in Example 3, 75 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 25 parts by weight of granular glass particles (particle diameter: 250 μm), 1 part by weight of benzoyl peroxide The coating solution consisting of was applied with a brush at a required amount of 1.0 kg / m ² and dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a protective layer, thereby obtaining a laminate. The light transmittance of the protective layer was 92.0%.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The light transmittance of the protective layer is a value obtained by measuring the protective layer having a thickness of 1 mm with an integrating sphere light transmittance measuring device (manufactured by Shimadzu Corporation). (Wavelength: 550 nm)

(Example 5)
On the design layer of the laminate obtained in Example 3, 75 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 30 parts by weight of granular glass particles (particle diameter: 250 μm), silane coupling agent A ( A coating solution comprising 5 parts by weight of γ-methacryloxypropyltrimethoxysilane), 2 parts by weight of silane coupling agent B (γ-mercaptopropylmethyldimethoxysilane), and 1 part by weight of benzoyl peroxide is 1.0 kg / m. ^The coating was applied with a brush at ² and dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a protective layer, thereby obtaining a laminate. The light transmittance of the protective layer was 92.0%.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The light transmittance of the protective layer is a value obtained by measuring the protective layer having a thickness of 1 mm with an integrating sphere light transmittance measuring device (manufactured by Shimadzu Corporation). (Wavelength: 550 nm)

(Example 6)
A coating liquid containing an epoxy resin (solid content: 75% by weight, light transmittance of cured body: 85%) on a silicon mold having an uneven surface so that the dry film thickness is 0.7 mm to 0.8 mm. Poured, dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours and demolded to obtain a transparent layer. One surface of the transparent layer was a flat surface, and the other surface was an uneven surface with an unevenness difference of 0.1 mm.
Next, a porcelain tile plate with a colored surface (100 mm × 100 mm × 6 mm, L ^* value: 23) and a flat surface of the transparent layer are made of epoxy resin (solid content: 75% by weight, light transmittance of cured body: 85%) ) Was used to attach.
Next, on the transparent layer, 100 parts by weight of an epoxy resin (solid content: 75% by weight, light transmittance of cured body: 85%), glitter pigment A: 0.1 parts by weight, glitter pigment B: 0.2 parts by weight The coating liquid containing was applied with a brush at a required amount of 0.5 kg / m ² and dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a design layer to obtain a laminate. The design layer was such that the thickness of the concave portion was 0.4 mm and the convex portion was 0.5 mm was randomly changed, and the light transmittance of the design layer was 17.0%.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Example 7)
On the surface of a transparent acrylic plate having an uneven shape (thickness of convex part: 0.8 mm, thickness of concave part: 0.7 mm, unevenness of convex part and concave part: 0.1 mm, light transmittance: 95.0%) A coating solution containing 100 parts by weight of epoxy resin (solid content 75% by weight), 0.1 part by weight of glitter pigment A and 0.2 part by weight of glitter pigment B is applied with a brush at a required amount of 0.5 kg / m ² . And dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a laminate of a transparent layer and a design layer. The design layer was such that the thickness of the concave portion was 0.4 mm and the convex portion was 0.5 mm was randomly changed, and the light transmittance of the design layer was 17.0%.
Next, the transparent layer surface of the laminate of the porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 22), the transparent layer, and the design layer, the surface of which is colored, 75 parts by weight of methyl methacrylate, 2-ethylhexyl acrylate 25 The laminate was bonded with an adhesive containing 2 parts by weight of benzoyl peroxide and 2 parts by weight of benzoyl peroxide.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Example 8)
On a porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 38) with a colored surface,
A coating solution containing an epoxy resin (solid content: 75% by weight, light transmittance of cured product: 85%) was applied with a brush at a required amount of 0.75 kg / m ² .
Five minutes after application, before the coating solution is cured, scaly glass granules A and scaly glass granules B (particle diameter: major axis 20 mm, minor axis 12 mm, thickness 700 μm to 900 μm, light transmittance: 70 %) Was sprayed at a mixing ratio (weight ratio) of 1: 1 at a total of 0.3 kg / m ² and dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a transparent layer.
The thickness of the transparent layer is 0.5 mm and the thickness of the convex portion is 1.2 mm. The surface of the transparent layer has a concavo-convex pattern in which the scaly glass powder particles are convex. It was.
Next, on the transparent layer, 100 parts by weight of epoxy resin (solid content: 75% by weight, light transmittance of cured product: 85%), glitter pigment A: 0.1 parts by weight, glitter pigment B: 0.2 parts by weight A coating solution containing a coating was applied with a brush at a required amount of 0.6 kg / m ² and dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a design layer to obtain a laminate. The design layer was such that the thickness of the concave portion was 0.1 mm and the convex portion was 1.0 mm randomly changed, and the light transmittance of the design layer was 17.0%.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

Example 9
A silicon mold having a flat surface, 100 parts by weight of an epoxy resin (solid content 75% by weight, light transmittance of a cured product: 85%), scaly glass powder A (particle size: major axis 2 mm, minor axis 0 0.5 mm, thickness 700 μm to 900 μm, light transmittance: 70%) A coating solution containing 55 parts by weight is poured at a required amount of 2.0 kg / m ² and dried at a temperature of 100 ° C. for 20 minutes to obtain a protective layer. It was.
The thickness of the protective layer at which the concave portion is 1.0 mm and the convex portion is 2.0 mm is randomly changed.
Next, 100 parts by weight of epoxy resin (solid content: 75% by weight, light transmittance of cured product: 85%), glitter pigment A: 0.1 parts by weight, glitter pigment B: 0.2% by weight on the uneven surface of the protective layer. The coating liquid containing the part was applied with a brush at a required amount of 0.5 kg / m ² and dried at a temperature of 100 ° C. for 20 minutes to obtain a design layer.
In the design layer, the thickness at which the concave portion was 0.1 mm and the convex portion was 0.5 mm was randomly changed.
Next, 100 parts by weight of epoxy resin (solid content 75% by weight, light transmittance of cured product: 85%), scaly glass powder A (particle size: major axis 15 mm minor axis) on the uneven surface of the design layer 4. A coating solution containing 80 parts by weight (4.75 mm, thickness 700 μm to 900 μm, light transmittance: 70%) is applied with a brush at a required amount of 1.5 kg / m ² , dried at a temperature of 100 ° C. for 20 minutes, and removed. And a laminate comprising a protective layer, a design layer, and a transparent layer was obtained.
The thickness of the transparent layer randomly changed to 0.5 mm for the concave portion and 2.0 mm for the convex portion, and the light transmittance of the transparent layer was 20.4%.
Next, a porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 35) having a colored surface and a transparent layer surface were adhered using an adhesive containing an epoxy resin to obtain a laminate.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Example 10)
A silicon mold having a flat surface, 100 parts by weight of an epoxy resin (solid content 75% by weight, light transmittance of a cured product: 85%), scaly glass powder A (particle size: major axis 2 mm, minor axis 0 0.5 mm, thickness 700 μm to 900 μm, light transmittance: 70%) and 55 parts by weight of a silane coupling agent (γ-mercaptopropyltrimethoxysilane) 0.5 part by weight, a required amount of 2.0 kg / m ² and then dried at a temperature of 100 ° C. for 20 minutes to obtain a protective layer.
The thickness of the protective layer at which the concave portion is 1.0 mm and the convex portion is 2.0 mm is randomly changed.
Next, 100 parts by weight of epoxy resin (solid content: 75% by weight, light transmittance of cured product: 85%), glitter pigment A: 0.1 parts by weight, glitter pigment B: 0.2% by weight on the uneven surface of the protective layer. A coating solution containing 0.5 parts by weight of a silane coupling agent (γ-mercaptopropyltrimethoxysilane) with a brush at a required amount of 0.5 kg / m ² and dried at a temperature of 100 ° C. for 20 minutes. The design layer was obtained.
In the design layer, the thickness at which the concave portion was 0.1 mm and the convex portion was 0.5 mm was randomly changed.
Next, 100 parts by weight of epoxy resin (solid content 75% by weight, light transmittance of cured product: 85%), scaly glass powder A (particle size: major axis 15 mm minor axis) on the uneven surface of the design layer 4.75 mm, thickness 700 μm to 900 μm, light transmittance: 70%) 80 parts by weight, coating liquid containing silane coupling agent (γ-mercaptopropyltrimethoxysilane) 0.5 part by weight A required amount of 1.5 kg / m ² was applied with a brush, dried at a temperature of 100 ° C. for 20 minutes, and demolded to obtain a laminate comprising a protective layer, a design layer, and a transparent layer.
The thickness of the transparent layer at which the concave portion was 0.5 mm and the convex portion was 2.0 mm was randomly changed, and the light transmittance of the transparent layer was 25.4%.
Next, the porcelain tile board (100 mm x 100 mm x 6 mm, L ^* value: 37) with which the surface was colored, and the transparent layer surface were stuck using the adhesive agent containing an epoxy resin, and the laminated body was obtained.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Example 11)
A transparent acrylic plate having a flat surface (light transmittance: 95.0%), 100 parts by weight of epoxy resin (solid content 75% by weight, light transmittance of cured body: 85%), scaly glass granules A (Particle size: major axis 20 mm, minor axis 0.5 mm, thickness 700 μm to 900 μm, light transmittance: 70%) A coating solution containing 55 parts by weight was applied at a required amount of 2.0 kg / m ² , at a temperature of 100 ° C. The protective layer was obtained by drying for 20 minutes.
In the protective layer, the thickness at which the concave portion was 1.5 mm and the convex portion was 2.0 mm was randomly changed.
Next, on the uneven surface of the protective layer, 100 parts by weight of an epoxy resin (solid content 75% by weight, light transmittance of a cured product: 85%), glitter pigment A0.1 parts by weight, glitter pigment B0.2. A coating solution containing parts by weight was applied with a brush at a required amount of 0.5 kg / m ² and dried at a temperature of 100 ° C. for 20 minutes to obtain a design layer.
In the design layer, the thickness at which the concave portion was 0.1 mm and the convex portion was 0.5 mm was randomly changed.
Next, 100 parts by weight of epoxy resin (solid content 75% by weight, light transmittance of cured product: 85%), scaly glass powder A (particle size: major axis 15 mm minor axis) on the uneven surface of the design layer 4. A coating solution containing 80 parts by weight (4.75 mm, thickness 700 μm to 900 μm, light transmittance: 70%) is applied with a brush at a required amount of 1.5 kg / m ² , dried at a temperature of 100 ° C. for 20 minutes, and transparent A layer was obtained.
The thickness of the transparent layer randomly changed to 0.5 mm for the concave portion and 2.0 mm for the convex portion, and the light transmittance of the transparent layer was 20.4%.
Next, the uneven surface of the transparent layer was colored (L ^* value: 21) to obtain a laminate.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Example 12)
A transparent acrylic plate having a flat surface (light transmittance: 95.0%), 100 parts by weight of epoxy resin (solid content 75% by weight, light transmittance of cured body: 85%), scaly glass granules A (Particle diameter: major axis 20 mm, minor axis 0.5 mm, thickness 700 μm to 900 μm, light transmittance: 70%) 55 parts by weight, silane coupling agent (γ-mercaptopropyltrimethoxysilane) 0.5 part by weight Was applied at a required amount of 2.0 kg / m ² and dried at a temperature of 100 ° C. for 20 minutes to obtain a protective layer.
In the protective layer, the thickness at which the concave portion was 1.5 mm and the convex portion was 2.0 mm was randomly changed.
Next, on the uneven surface of the protective layer, 100 parts by weight of an epoxy resin (solid content 75% by weight, light transmittance of a cured product: 85%), glitter pigment A0.1 parts by weight, glitter pigment B0.2. A coating solution containing parts by weight and 0.5 parts by weight of a silane coupling agent (γ-mercaptopropyltrimethoxysilane) is applied with a brush at a required amount of 0.5 kg / m ² and dried at a temperature of 100 ° C. for 20 minutes. The design layer was obtained.
In the design layer, the thickness at which the concave portion was 0.1 mm and the convex portion was 0.5 mm was randomly changed.
Next, 100 parts by weight of epoxy resin (solid content 75% by weight, light transmittance of cured product: 85%), scaly glass powder A (particle size: major axis 15 mm minor axis) on the uneven surface of the design layer 4.75 mm, thickness 700 μm to 900 μm, light transmittance: 70%) 80 parts by weight, coating liquid containing silane coupling agent (γ-mercaptopropyltrimethoxysilane) 0.5 part by weight A required amount of 1.5 kg / m ² was applied with a brush and dried at a temperature of 100 ° C. for 20 minutes to obtain a transparent layer.
The thickness of the transparent layer at which the concave portion was 0.5 mm and the convex portion was 2.0 mm was randomly changed, and the light transmittance of the transparent layer was 25.4%.
Next, the uneven surface of the transparent layer was colored (L ^* value: 23) to obtain a laminate.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Example 13)
A silicon mold having a flat surface, 100 parts by weight of an epoxy resin (solid content 75% by weight, light transmittance of a cured product: 85%), 0.1 parts by weight of a bright pigment A, 0.2 parts by weight of a bright pigment B A coating solution containing a coating material is applied with a brush at a required amount of 0.5 kg / m ² , dried at a temperature of 100 ° C. for 20 minutes, and the molded product is crushed, and the size is 2 cm to 7 cm and the thickness is 500 μm. A design chip was obtained.
Next, a required amount of a coating liquid containing 100 parts by weight of an epoxy resin (solid content: 75% by weight, light transmittance of a cured product: 85%) and 80 parts by weight of a design chip is applied to a silicon mold having a flat surface. It was applied at 5 kg / m ² , dried at a temperature of 100 ° C. for 20 minutes, and demolded to obtain a laminate composed of a design layer and a transparent layer. The laminate has a structure in which design chips (design layers) randomly overlap in a transparent layer made of an epoxy resin, and the thickness of the design layer changes randomly.
Next, the surface of the porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 37) and the transparent layer surface of the laminate are attached using an adhesive containing an epoxy resin to obtain a laminate. It was.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Example 14)
A transparent acrylic plate having a flat surface (light transmittance: 95.0%), 100 parts by weight of epoxy resin (solid content 75% by weight, light transmittance of cured body: 85%), scaly glass granules A (Particle diameter: major axis 20 mm, minor axis 0.5 mm, thickness 700 μm to 900 μm, light transmittance: 70%) 55 parts by weight, silane coupling agent (γ-mercaptopropyltrimethoxysilane) 0.5 part by weight Was applied at a required amount of 2.0 kg / m ² and dried at a temperature of 100 ° C. for 20 minutes to obtain a protective layer.
In the protective layer, the thickness at which the concave portion was 1.5 mm and the convex portion was 2.0 mm was randomly changed.
Next, on the uneven surface of the protective layer, 100 parts by weight of epoxy resin (solid content 75% by weight, light transmittance of cured body: 85%), design chip (size: 2 cm to 7 cm, thickness 500 μm) 80 weights The coating liquid containing the part was applied at a required amount of 1.5 kg / m ² and dried at a temperature of 100 ° C. for 20 minutes to obtain a design layer and a transparent layer. The design layer and the transparent layer have a structure in which design chips (design layers) overlap at random in a transparent layer made of an epoxy resin, and the thickness of the design layer changes randomly.
The design chip was obtained by the same method as in Example 13.
Next, the surface of the porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 37) and the design layer surface of the laminate are attached using an adhesive containing an epoxy resin to obtain a laminate. It was.
The obtained laminate had a blue hue as a whole, the pattern randomly changed, and had a color pattern with different colors depending on the viewing angle.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Comparative Example 1)
On the porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 75) whose surface is colored,
A coating solution containing an epoxy resin (solid content: 75% by weight, light transmittance of cured product: 85%) was applied with a brush at a required amount of 0.75 kg / m ² .
Three minutes after application, before the coating solution hardens, scaly glass granules A (particle diameter: major axis 10 mm, minor axis 8 mm, thickness 500 μm to 700 μm, light transmittance: 70%) is 0.3 kg / m. ² and sprayed at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a transparent layer.
The transparent layer has a concave portion of 0.5 mm and a convex portion having a thickness of 1.2 mm, and the transparent layer surface has a concave-convex pattern in which the scaly glass particles become convex portions. Met.
Next, on the transparent layer, 100 parts by weight of epoxy resin (solid content: 75% by weight, light transmittance of cured product: 85%), glitter pigment A: 0.1 parts by weight, glitter pigment B: 0.2 parts by weight A coating solution containing a coating solution was applied with a brush at a required amount of 0.5 kg / m ² and dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a design layer to obtain a laminate. The thickness of the design layer at which the concave portion was 0.1 mm and the convex portion was 0.8 mm was randomly changed, and the light transmittance of the design layer was 17.0%.
The obtained laminate had a uniform color with no pattern and lacked a sense of depth.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Comparative Example 2)
On a porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 27) having a colored surface, a coating liquid containing an epoxy resin (solid content: 75% by weight, light transmittance of cured body: 85%), A required amount of 0.75 kg / m ² was applied with a brush and dried at a temperature of 100 ° C. for 20 minutes to obtain a transparent layer.
The transparent layer had a uniform thickness of 0.7 mm, and the light transmittance of the transparent layer was 72.7%.
Next, on the transparent layer, 100 parts by weight of an epoxy resin (solid content: 75% by weight, light transmittance of cured body: 85%), glitter pigment A: 0.1 parts by weight, glitter pigment B: 0.2 parts by weight The coating liquid containing was applied with a brush at a required amount of 0.5 kg / m ² and dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a design layer to obtain a laminate.
The design layer had a uniform thickness of 0.5 mm, and the light transmittance of the design layer was 17.2%.
The resulting laminate had a uniform color with almost no pattern.
Moreover, about the obtained laminated body, the same designability evaluation as Example 1 was performed. The results are shown in Table 1.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Comparative Example 3)
100 parts by weight of epoxy resin (solid content 75% by weight, light transmittance of cured product: 85%), glitter pigment A 0.1 parts by weight, glitter pigment B 0.2 parts by weight on a silicon mold having an uneven surface A coating solution containing the composition was applied with a brush at a required amount of 0.5 kg / m ² , dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours, and demolded to obtain a design layer.
The design layer is flat on one side, the thickness of the concave portion is 0.4 mm, and the convex portion is 0.5 mm, and the light transmittance of the design layer is 17.0%. It was.
Next, the surface of the porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 25) and the flat surface of the design layer are epoxy resin (solid content 75% by weight, light transmittance of the cured product: 85%) ) Was used to obtain a laminate composed of a design layer and a colored substrate layer.
The adhesive layer had a uniform thickness of 0.1 mm.
The resulting laminate had a uniform color with almost no pattern.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

(Comparative Example 4)
In a metal mold, 75 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 50 parts by weight of granular glass particles (particle diameter: 250 μm), silane coupling agent (γ-methacryloxypropyltrimethoxysilane) 5 A coating solution consisting of parts by weight and 1 part by weight of benzoyl peroxide was applied with a brush at a required amount of 1.0 kg / m ² and dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a protective layer. .
The protective layer had a uniform thickness of 0.5 mm and had a flat surface. The light transmittance of the transparent layer was 92.0%.
Next, on the flat surface of the protective layer, 100 parts by weight of an epoxy resin (solid content: 75% by weight, light transmittance of a cured product: 85%), glitter pigment A: 0.1 parts by weight, glitter pigment B: 0.2% by weight A coating liquid containing a coating part is applied with a brush at a required amount of 0.6 kg / m ² , dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours, and a laminate in which the cured body of the coating liquid becomes a design layer Obtained.
The design layer had a uniform thickness of 0.5 mm with no irregularities, and the light transmittance of the design layer was 16.9%.
Next, a porcelain tile plate (100 mm × 100 mm × 6 mm, L ^* value: 31) with a colored surface and an epoxy resin (solid content 75% by weight, light transmittance of the cured body: 85%) to be a transparent layer are included. The coating solution was stuck as an adhesive to obtain a laminate.
The resulting laminate had a uniform color with almost no pattern.
The L ^* value and the light transmittance are values measured by the same method as in Example 1.

It is sectional drawing of this invention laminated body. (1) to ( 13 ) are examples of the laminate of the present invention.

Claims (4)

A laminate having excellent design properties,
A colored substrate layer having an L ^* value of 60 or less in the L ^* a ^* b ^* color system of CIE (International Commission on Illumination) 1976 (JIS Z8729);
A transparent layer whose thickness is randomly displaced,
A design layer containing a luster pigment, the thickness of which is randomly displaced,
Including
The transparent layer includes two or more kinds of scaly transparent granules having a particle diameter of 0.5 mm or more and 50 mm or less and a thickness of 50 μm or more and 1500 μm or less,
The thickness of the transparent layer is in the range of 5 mm or less, the difference in thickness between the recess and the protrusion is 50 μm or more, the thickness of the protrusion is 50 μm or more and 5 mm or less, and the thickness of the recess is 2 mm or less. ,
The thickness of the transparent layer is one that changes continuously, or one that changes intermittently,
The thickness of the design layer is in the range of 5 mm or less, the difference in thickness between the concave and convex portions is 50 μm or more,
The thickness of the design layer is continuously changing,
A transparent layer exists between the colored substrate layer and the design layer,
A laminate characterized by the above.   The laminate according to claim 1, wherein the light transmittance of the transparent layer is 10% or more. A protective layer is laminated on the transparent layer,
  The laminate according to claim 1 or 2, wherein the light transmittance of the protective layer is 60% or more.   The laminate according to claim 3, wherein the protective layer contains a light diffusing agent having a size of 50 μm or more and 5 mm or less.