JP2016137693A - Decorative laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative laminate sufficiently excellent in a depth feeling and exquisite feeling of color.SOLUTION: There is provided a decorative laminate in which a transparent layer is formed on a colored substrate and the transparent layer has a regular reflection brightness of 10 to 60 and a haze value of 0.2 to 10%.SELECTED DRAWING: None

Description

  The present invention relates to a decorative laminate excellent in a sense of color depth, and particularly to a decorative laminate for a vehicle interior.

  In recent years, due to the spread of luxury, various colors are required to have a sense of depth. For example, many attempts have been made to obtain lacquer black in which a deep feeling is expressed in black.

  Conventionally, in order to obtain lacquer black, it is known that the higher the regular reflection brightness on the outermost surface and the lower the haze of the transparent layer formed on the surface, the more effective. However, the lacquer black member obtained by the conventional technique cannot provide a sufficient depth feeling in an environment where diffused light is incident from various directions, such as in an automobile. Moreover, in such an environment, since the contrast between the light and the shadow reflected on the lacquer black member is not clear, a sufficient sense of precision could not be obtained.

  Thus, for example, in Patent Document 1, a first base paint containing a specific amount of carbon black pigment is applied on a base material, a second base paint containing a black dye is applied on the obtained coating film, and A technique for obtaining a lacquer-like coating film having a texture like natural lacquer by coating a transparent paint containing a specific gloss adjusting agent on the obtained coating film is disclosed.

JP 2006-239519 A

  However, the lacquer black member obtained by such a technique also did not have a sufficient depth and precision.

  An object of the present invention is to provide a decorative laminate that is sufficiently excellent in color depth and precision.

In the present specification, the sense of depth of color is one of the visual characteristics that makes a color feel a sense of thickness, depth, or profoundness, unlike a planar solid sense of color.
Exquisiteness is one of the visual characteristics based on the sharpness of reflection and the contrast between light and shadow.

  The present invention relates to a decorative laminate, wherein a transparent layer is formed on a colored substrate, and the transparent layer has a regular reflection brightness of 10 to 60 and a haze value of 0.2 to 10%.

  The decorative laminate of the present invention is sufficiently excellent in color depth and precision.

[Decorative laminate]
The decorative laminate according to the present invention has a transparent layer formed on the surface of a colored substrate. The color of the colored substrate means that it is not transparent, and is used in a concept including all colors including white. Specific examples of the colors include black, red, orange, yellow, green, blue, indigo, purple, white, and mixed colors thereof. Preferred colors from the viewpoint of further improving the sense of depth and precision of colors are black, red, orange, yellow, green, blue, indigo, purple, and mixed colors thereof.

  The visible light transmittance of the colored substrate is usually 15% or less, preferably 10% or less, more preferably 1% or less. The visible light transmittance of the colored substrate means the visible light transmittance at the thickness of the colored substrate used. In the present specification, the visible light transmittance uses a value measured by UV-2400PC (manufactured by Shimadzu Corporation).

  As the colored base material, for example, a colored resin base material, a colored metal base material, a colored main base material and the like can be used based on the constituent materials.

  The colored resin substrate contains a polymer, and may further contain a colorant.

  The polymer constituting the colored resin substrate is not particularly limited. For example, poly (meth) acrylate such as polymethyl acrylate and polymethyl methacrylate (PMMA); polycarbonate (PC); acrylonitrile-butadiene-styrene (ABS) Copolymers; and mixtures thereof (especially PCABS).

  The colorant (pigment and / or dye) contained in the colored resin substrate and the content thereof and the thickness of the substrate are not particularly limited as long as the visible light transmittance is achieved.

  The shape of the colored resin base material is not particularly limited. For example, a colored resin molded product molded into a desired shape may be used, or a colored resin coating film formed on an arbitrary base material. There may be. When the colored resin substrate is a colored resin coating film, the coating film alone has the visible light transmittance defined for the colored substrate.

  The colored metal base material is a base material made of metal, and usually has a metal color such as achromatic or silver. Examples of the metal constituting the colored metal substrate include aluminum, magnesium, stainless steel, titanium, tin, zinc, nickel, chromium, silver, indium, and an alloy or metal oxide containing at least one of them. The colored metal substrate satisfies the visible light transmittance defined for the colored substrate. The thickness of the colored metal substrate is not particularly limited as long as the visible light transmittance is achieved.

  The shape of the colored metal substrate is not particularly limited, and may be a metal molded product processed and molded into a desired shape. The colored metal substrate may have a translucent or opaque resin coating on the entire surface or a part thereof. The translucent or opaque resin coating film is a resin coating film made of the same polymer as that constituting the colored resin substrate and having a visible light transmittance of less than 20%. When the colored metal base material has such a resin coating film, it is only necessary to have the visible light transmittance defined for the colored base material as the whole base material on which the resin coating film is laminated.

  The colored main base material is a base material made of wood. The colored main base material satisfies the visible light transmittance defined for the colored base material. The thickness of the colored main substrate is not particularly limited as long as the visible light transmittance is achieved.

  The shape of the colored main base material is not particularly limited, and may be a woodwork processed and formed into a desired shape. The colored main base may have a translucent or opaque resin coating on the entire surface or a part thereof. The translucent or opaque resin coating is the same as the translucent or opaque resin coating that the colored metal substrate may have. When the colored main base material has such a resin coating film, it is only necessary to have the visible light transmittance defined for the colored base material as the entire base material on which the resin coating film is laminated.

  The transparent layer formed on the colored substrate has a regular reflection brightness of 10 to 60, and is preferably 10 to 50, more preferably 35 to 50, from the viewpoint of further improving the sense of depth and precision of color. . If the regular reflection brightness is too large, a sufficient color depth cannot be obtained. If the regular reflection brightness is too small, a sufficient sense of precision cannot be obtained.

  The regular reflection lightness of the transparent layer is the lightness of reflected light under the condition that the light source incident angle to the outermost transparent layer is 10 ° and the light receiving angle is in the range of 10 ± 0.05 °. The measuring method is as described later in detail. The transparent layer may be composed of a plurality of transparent layers as will be described later. In this case, the regular reflection brightness is a value at an incident angle of 10 ° when all the transparent layers on the colored substrate are overlapped.

  The transparent layer formed on the colored substrate also has a haze value of 0.2 to 10%, and preferably 0.3 to 8.5% from the viewpoint of further improving the feeling of depth and precision of color. More preferably, it is 0.5-8.5, Most preferably, it is 1-5. If the haze value is too large or too small, a sufficient color depth cannot be obtained. In particular, if the haze value is too large, a sufficient sense of precision cannot be obtained.

  The haze value is a haze value that the transparent layer itself has, for example, using a value obtained by subtracting the haze value of the transparent glass plate based on a predetermined formula from the measured value of the transparent layer formed on the transparent glass plate. Yes. The measuring method is as described later in detail. When the transparent layer is composed of a plurality of transparent layers as described later, the haze value is a haze value in a state where all the transparent layers are stacked.

  The configuration of the transparent layer is not particularly limited as long as the transparent layer is a resin layer having both the antireflection property to achieve the above-described regular reflection brightness and the appropriate transparency to achieve the above-described haze value. Absent.

  The visible light transmittance of the transparent layer is usually 20% or more, preferably 50% or more, more preferably 70% or more. The upper limit of the visible light transmittance of the transparent layer is not particularly limited, and the visible light transmittance of the transparent layer is usually 100% or less, particularly 99% or less. Visible light transmittance means the visible light transmittance at the thickness of the transparent layer used. The visible light transmittance is a value measured by UV-2400PC (manufactured by Shimadzu Corporation). When the transparent layer is composed of a plurality of transparent layers as described later, the visible light transmittance in a state in which all the transparent layers are stacked may be within the above-described range.

  The thickness of the transparent layer is not particularly limited, and is preferably from 2 to 2000 μm, more preferably from 4 to 1000 μm, from the viewpoint of further improving the sense of color depth and precision. When the transparent layer is composed of a plurality of transparent layers as described later, the thickness of each transparent layer may be within the above range.

  The surface roughness (λc = 0.08 mm) of the transparent layer is usually 0.001 to 0.100 μm in Ra, preferably 0.001 to 0.05 μm, more preferably 0.001 to 0.020 μm. It is. When the transparent layer is composed of a plurality of transparent layers as described later, the surface roughness (λc = 0.08 mm) of the outermost transparent layer may be in the above range.

  The transparent layer usually contains a transparent resin, and if desired, inorganic fine particles, organic fine particles, UV absorber, light stabilizer, photopolymerization initiator, thermosetting catalyst, plasticizer, flame retardant, heat stabilizer, antioxidant, You may further contain additives, such as a lubricant, an antistatic agent, a mold release agent, a foaming agent, a nucleating agent, a toning agent, a crosslinking agent, and a dispersion aid.

  The transparent resin constituting the transparent layer is not particularly limited as long as the above-described regular reflection brightness, haze value, and visible light transmittance are achieved in the transparent layer. As the transparent resin, any polymer that is recognized to have so-called transparency in the field of plastic materials and coating materials can be used. Specific examples of such transparent resins are, for example, selected from the group consisting of polysiloxane compounds, polyurethane compounds, acrylic / vinyl polymer compounds, fluorine-containing resin compounds, epoxy resin compounds, and cured products thereof. And at least one compound. Polysiloxane compounds, polyurethane compounds, acrylic / vinyl polymer compounds, or fluorine-containing resin compounds are preferred.

  The polysiloxane compounds are siloxane compounds obtained by hydrolyzing and condensing alkoxysilane. The alkoxysilane is one or more alkoxysilanes selected from the group consisting of the following organoalkoxysilanes and tetraalkoxysilanes.

The organoalkoxysilane is an organoalkoxysilane represented by the following general formula (I).
R ¹ _a Si (OR ² ) _4-a (I)

In the formula (I), R ¹ represents an organic group having 1 to 10 carbon atoms (for example, an alkyl group or an aryl group), and part or all of the hydrogen atoms may be substituted with fluorine atoms; R ² Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms; a represents an integer of 1 to 3; R ¹ is preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of further improving the sense of color depth and elaboration, wherein some or all of the hydrogen atoms are substituted with fluorine atoms. Or a phenyl group, more preferably a methyl group or an ethyl group. R ² is preferably a methyl group or an ethyl group in terms of a high hydrolysis / condensation rate. a is 1 or 2 from the viewpoint of further improving the sense of depth and precision of color.

  Specific examples of organoalkoxysilanes include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, Diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmethoxysilane, triethylethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxy Siliconation of silane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, etc. Or the like can be mentioned things. These compounds can be used alone or in combination of two or more.

  Tetraalkoxysilanes are tetraalkoxysilanes represented by the following general formula (II) or general formula (III):

Si (OR ³ ) ₄ (II)
In formula (II), R ³ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. R ³ is preferably a methyl group or an ethyl group in terms of a high hydrolysis / condensation rate.

R ⁴ —O— [Si (OR ⁴ ) ₂ —O] _n —R ⁴ (III)
In formula (III), R ⁴ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 100. R ⁴ is preferably a methyl group or an ethyl group in terms of a high hydrolysis / condensation rate. n is preferably 2 to 10 from the viewpoint of further improving the sense of depth and precision of color.

  Specific examples of tetraalkoxysilane include silicon compounds such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxy silane, tetraisopropoxy silane, tetra n-butoxy silane, tetraisobutoxy silane, methyl silicate, Examples thereof include alkyl silicates such as ethyl silicate and propyl silicate. These compounds can be used alone or in combination of two or more.

  The alkoxysilane for obtaining polysiloxane compounds may contain a radical polymerizable group-containing silane. Examples of the radical polymerizable group-containing silane include methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, Examples include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

  The polysiloxane compounds are alkoxysilanes including at least one or more organoalkoxysilanes represented by the general formula (I), in particular, the general formula (I), from the viewpoint of further improving the sense of color depth. It is preferably a compound obtained by hydrolyzing and condensing one or more kinds of organoalkoxysilanes shown and an alkoxysilane containing one or more kinds of tetraalkoxysilanes represented by the general formula (II) or (III).

The hydrolysis / condensation reaction of alkoxysilane can be performed using a known method.
In the hydrolysis, for example, organoalkoxysilane and tetraalkoxysilane are mixed in an arbitrary ratio, and 10 to 1000 parts by mass of water and 0 to 1000 parts by mass of alcohol are added to 100 parts by mass of the solution and stirred. A method can be mentioned. Stirring may be performed by controlling the temperature to 0 to 100 ° C. Alternatively, acid such as hydrochloric acid or acetic acid may be added to make the solution acidic (pH 2 to 5). Alcohol generated upon hydrolysis can be distilled out of the reaction system.

  The condensation following the hydrolysis can be allowed to proceed, for example, by standing or stirring for 1 to 4 hours. At that time, for example, by controlling the pH to pH 6 to 7, the progress of the condensation can be accelerated. Further, the progress of the condensation can be accelerated by heating from about 40 ° C. to about 80 ° C. Water generated during the condensation can be distilled out of the reaction system.

  The polyurethane compounds are polyurethanes obtained by polyaddition reaction of isocyanate compounds and polyols.

  Isocyanate compounds are compounds having two or more isocyanate groups in one molecule. Specific examples of isocyanate compounds include, for example, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer Polyisocyanates such as acid diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate; adducts of polyisocyanates with polyhydric alcohols and / or low molecular weight polyester resins; polymers of polyisocyanates (dimers, three (Including polymer and cyclized polymer); Door can be. These compounds can be used alone or in combination of two or more. A polyisocyanate polymer is preferred, and a homopolymer of a polyisocyanate (especially hexamethylene diisocyanate) is more preferred.

  Polyols are compounds having two or more hydroxyl groups in one molecule. Specific examples of the polyols include branched alcohols such as trimethylolpropane, pentaerythritol, glycerin, polyglycerin, and xylitol; acrylic polyols such as hydroxy (meth) acrylate-containing acrylic copolymers. These compounds can be used alone or in combination of two or more. Acrylic polyol is preferred.

  Acrylic / vinyl polymer compounds are polymers obtained by addition reaction of one or more compounds selected from the group consisting of acrylic unsaturated compounds and vinyl unsaturated compounds.

  Acrylic unsaturated compounds are compounds having one or more acryloyl groups in one molecule. Specific examples of the acrylic unsaturated compounds include, for example, tricyclo [5.2.1.02,6] decane diacrylate, dicyclopentanyl diacrylate, tricyclo [5.2.1.02,6] de Candiacrylate, tricyclo [5.2.1.02,6] decanedimethacrylate, tricyclo [5.2.1.02,6] decanedimethacrylate, tricyclo [5.2.1.02,6] decaneacrylate methacrylate , Tricyclo [5.2.1.02,6] decane acrylate methacrylate, pentacyclo [6.5.1.13, 6.02, 7.09,13] pentadecane diacrylate, pentacyclo [6.5.1.13 , 6.02, 7.09, 13] pentadecane diacrylate, pentacyclo [6.5.1.13, 6.02, 7. 9,13] pentadecanedimethacrylate, pentacyclo [6.5.1.13,6.02,7.09,13] pentadecanedimethacrylate, pentacyclo [6.5.1.13,6.02,7.09, 13] Pentadecane acrylate methacrylate, pentacyclo [6.5.1.13, 6.02, 7.09, 13] pentadecane acrylate methacrylate, epoxy acrylate, epoxidized oil acrylate, urethane acrylate, polyester acrylate, polyether acrylate, vinyl acrylate , Silicone acrylate, polystyrylethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl Chryrate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, hydroxypivalin Acid neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexameta The Relates or other reactive monomers or oligomers can be mentioned. Preferred are trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate. These compounds can be used alone or in combination of two or more.

  Vinyl unsaturated compounds are compounds having one or more vinyl groups in one molecule. Specific examples of vinyl unsaturated compounds include, for example, ethylene, propylene, styrene, vinyl acetate, N-vinyl pyrrolidone, diallyl maleate, butadiene, polyene / thiol, unsaturated polyester, or other reactive monomers or oligomers. And so on. These compounds can be used alone or in combination of two or more.

  Acrylic / vinyl-based polymer compounds are polymers obtained by subjecting the above-mentioned acrylic unsaturated compounds and / or vinyl unsaturated compounds, particularly acrylic unsaturated compounds, to addition reaction of unsaturated compounds containing siloxane bonds. It is preferable that

  Siloxane bond-containing unsaturated compounds are siloxane compounds having one or more radically polymerizable double bonds in one molecule, and for example, silsesquioxane is preferably used.

Silsesquioxane is composed of Si—O bond in the main chain skeleton, and [(RSiO _1.5 ) _n ] (wherein R is an organic group containing a radical polymerizable double bond; n is 2 or more The upper limit of n is not particularly limited as long as silsesquioxane can be dissolved in an organic solvent; preferred n is a siloxane compound represented by a composition formula of 8 to 12, particularly 8, 10 or 12. is there. Examples of the silsesquioxane include those having a so-called cage type, ladder type, and random type structure. Preferred silsesquioxanes have a cage type structure.

  As a raw material compound that can constitute silsesquioxane, for example, acryloxymethyltrimethoxylane, methacryloxymethyltrimethoxylane, acryloxymethyltriethoxysilane, methacryloxymethyltriethoxysilane, 3-acryloxypropyltrichlorosilane, 3-methacryloxypropyltrichlorosilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyl Examples include triethoxysilane, vinyltriacetoxysilane, and γ-methacryloyloxypropyltrimethoxysilane. 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane are preferred.

  Fluorine-containing resin compounds are polymers formed by addition reaction of monomers containing one or more compounds selected from the group consisting of fluorine-containing olefins.

  The fluorine-containing olefin is an olefinic hydrocarbon having one or more fluorine atoms in one molecule. Specific examples of the fluorine-containing olefin include, for example, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, perfluoroalkoxy group-containing ethylene, perfluoroalkoxy group-containing propylene, tetrafluoroethylene, and hexafluoropropylene. Can be mentioned.

  Specific examples of the fluorine-containing resin compounds include, for example, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin), tetrafluoroethylene / hexafluoropropylene copolymer , Ethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, and the like. These compounds can be used alone or in combination of two or more.

  Epoxy resin compounds are resin compounds obtained by a ring-opening reaction of epoxy groups in epoxy-containing compounds. Examples of the curing agent that forms a crosslinked structure by a ring-opening reaction include polyamines and acid anhydrides.

  Epoxy-containing compounds are monomers or polymers having two or more epoxy groups in one molecule. Specific examples of the epoxy-containing compounds include, for example, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, trimethylolpropane polyglycidyl ether, diethylene glycol diglycidyl ether. And so on. These compounds can be used alone or in combination of two or more.

  Examples of the inorganic fine particles include fluoride fine particles and oxide fine particles.

Examples of the fine fluoride particles include cryolite (Na ₃ AlF ₆ ), sodium fluoride (NaF ₂ ), thiolite (Na ₅ Al ₃ F1 ₄ ), aluminum fluoride (AlF ₃ ), and barium fluoride (BaF _2). ), Calcium fluoride (CaF ₂ ), gadolinium fluoride (GdF ₃ ), lead fluoride (PbF ₂ ), lanthanum fluoride (LaF ₃ ), lithium fluoride (LiF), magnesium fluoride (MgF ₂ ), fluorine And neodymium iodide (NdF ₃ ), sodium fluoride (NaF), yttrium fluoride (YbF ₃ ), and yttrium fluoride (YF ₃ ).

  Examples of the oxide fine particles include fine particles composed of silicon oxide, aluminum oxide, titanium oxide, tin oxide, zircon oxide, cerium oxide, zinc oxide, antimony oxide, and double oxides thereof.

  The average primary particle size of the inorganic fine particles is usually 5 to 100 nm, and 15 to 80 nm is preferable from the viewpoint of further improving the sense of color depth.

  Content of an inorganic fine particle is 0-500 mass parts normally with respect to 100 mass parts of transparent resin, Preferably it is 10-400 mass parts. When the transparent resin is a polysiloxane compound, the content with respect to 100 parts by mass of the siloxane compound before curing may be within the above range. As the inorganic fine particles, two or more types of inorganic fine particles having different types or average primary particle diameters may be used, and in this case, the total amount thereof may be within the above range.

  The transparent layer may be a single layer or a multilayer composed of a plurality of transparent layers. The transparent layer is a multilayer having a multilayer structure composed of two or more transparent layers having different transparent resin structures (types), types of additives such as inorganic fine particles and / or their contents. It means to have. As embodiments in which the structure of the transparent resin is different, for example, the following embodiments (1) to (2) are included:

Embodiment (1):
As in the embodiment in which the first transparent layer formed on the colored substrate surface contains polyurethane compounds and the second transparent layer formed next contains fluorine-containing resin compounds, the type of transparent resin in each transparent layer is A completely different embodiment;

Embodiment (2):
In an embodiment in which both the first transparent layer and the second transparent layer contain polysiloxane compounds, the polysiloxane compounds contained in the first transparent layer and the polysiloxane compounds contained in the second transparent layer are configured. Embodiments having different compositions such as types, combinations and / or blending amounts of alkoxysilanes, presence or absence of additives

[Regular brightness control]
The regular reflection brightness in the transparent layer can be controlled by adjusting the refractive index and / or surface roughness of the transparent layer and / or by light interference of the transparent layer. Specifically, the regular reflection brightness of the transparent layer can be controlled by the following method.

(Method x1)
By making the refractive index of the transparent layer lower than the refractive index of the colored resin substrate, the regular reflection brightness of the transparent layer can be reduced. In order to make the refractive index of the transparent layer lower than the refractive index of the colored resin substrate, the resin constituting the transparent layer is a resin having a refractive index lower than the refractive index of the colored resin substrate, and / or is transparent. The layer can contain inorganic fine particles capable of lowering the refractive index. This method x1 can be adopted when the colored substrate is a colored resin substrate.

  Examples of the resin having a refractive index lower than that of the colored resin base material include polysiloxane compounds, polyurethane compounds, and acrylic / vinyl polymer compounds when the resin constituting the colored resin base material is polycarbonate. , Fluorine-containing resin compounds, epoxy resin compounds and cured products thereof. Thus, by making the resin constituting the transparent layer a resin having a refractive index lower than that of the colored resin substrate, the refractive index of the transparent layer can be made lower than that of the colored resin substrate. As a result, the regular reflection brightness in the transparent layer decreases.

Among the inorganic fine particles that can lower the refractive index, cryolite (Na ₃ AlF ₆ ), sodium fluoride (NaF ₂ ), thiolite (Na ₅ Al ₃ F 1 ₄ ), and hollow silica particles among the above-mentioned inorganic fine particles And inorganic oxide fine particles having a hollow or porous form. By including such inorganic fine particles in the transparent layer, the refractive index of the transparent layer can be made lower than the refractive index of the colored resin substrate, and as a result, the regular reflection brightness in the transparent layer is lowered.

  When the transparent layer has a multilayer structure, it is sufficient that the refractive index of the outermost transparent layer is lower than the refractive index of the colored resin substrate.

Refractive index of the transparent layer _{(n 1)} and the difference in refractive index of the colored resin substrate and _{(n 0) (n 0 -n} 1) is 0.0 Ultra 0.4, preferably 0.0 Ultra 0.2 The following. Thereby, the regular reflection brightness in a transparent layer can be reduced effectively.

When the transparent layer has a multilayer structure, the refractive index (n ₁ ) of the outermost transparent layer may have the above relationship with the refractive index (n ₀ ) of the colored resin substrate.

The refractive index (n ₁ ) of the transparent layer is usually 1.3 to 1.6, preferably 1.3 to 1.45.

When the transparent layer has a multilayer structure, the refractive index of the transparent layer on the outermost surface is preferably within the range of the refractive index (n ₁ ). The transparent layer other than the outermost surface may not be in the range of the refractive index (n ₁ ) (it may be higher than the refractive index of the colored resin substrate). From the viewpoint of further improving the sense of color depth, it is preferable that the refractive index of the transparent layer immediately below the outermost transparent layer is larger than the refractive index of the outermost transparent layer. The refractive index of the transparent layer directly below the outermost transparent layer is preferably 0.05 or more larger than the refractive index of the outermost transparent layer.

(Method x2)
By adjusting the surface roughness of the transparent layer and diffusing the regular reflection light in the vicinity of the regular reflection direction, the regular reflection brightness (regular reflection direction ± 0.05 °) of the transparent layer in appearance can be reduced. Specifically, while keeping the surface roughness Ra (λc = 0.08 mm) of the transparent layer within the above range, the root mean square slope RΔq is 0.005 to 0.100, and the absolute value of the skewness Rsk is 0.1 to 10. By doing so, the regular reflection brightness of the transparent layer can be reduced without impairing the sense of precision.

  Examples of the method for adjusting the surface roughness of the transparent layer include a method of polishing the surface of the transparent layer with abrasive grains having a particle size of 10 μm or less, a method of transferring a desired transfer surface to the surface of the transparent layer, and the like.

(Method x3)
The regular reflection brightness of the transparent layer can be reduced by light interference between the reflected light from the surface of the outermost transparent layer and the reflected light from the transparent layer directly below or the surface of the colored substrate. In this case, the average thickness of the outermost transparent layer is usually 10 to 1000 nm, preferably 20 to 500 nm. The refractive index (n ₁ ) of the outermost transparent layer is preferably 1.3 to 1.45, and the refractive index of the transparent layer or colored resin substrate immediately below is 0 than the refractive index of the outermost transparent layer. .05 or more is preferable.

(Method x4)
By forming a nano uneven structure on the surface of the outermost transparent layer and continuously changing the refractive index, the regular reflection brightness of the transparent layer can be lowered. In this case, in order to satisfactorily reduce the regular reflection brightness, the interval between adjacent convex portions or concave portions of the nano-concave structure is preferably 380 nm or less, which is a size of the wavelength of visible light (380 to 780 nm) or less, From the viewpoint of suppressing an increase in reflectance at a specific wavelength, the height of the convex portion or the depth of the concave portion is preferably 90 nm or more.

[Control of haze value]
The haze value in the transparent layer is adjusted by adjusting the thickness of the transparent layer, the content of fine particles such as inorganic fine particles, organic fine particles, emulsions and bubbles in the transparent layer, and the content of additives such as ultraviolet absorbers and toning agents. Can be controlled. Specifically, the haze value of the transparent layer can be controlled by the following method.

(Method y1)
The haze value of the transparent layer is controlled by adjusting the thickness of the transparent layer. Specifically, the haze value of the transparent layer can be increased by increasing the thickness of the transparent layer within the above range. On the other hand, the haze value of the transparent layer can be lowered by reducing the thickness of the transparent layer within the above range.

(Method y2)
The haze value of the transparent layer is controlled by adjusting the content of fine particles such as inorganic fine particles, organic fine particles, emulsion, and bubbles in the transparent layer. Specifically, the haze value of the transparent layer can be increased by increasing the content of the inorganic fine particles in the transparent layer within the above range. On the other hand, the haze value of the transparent layer can be reduced by reducing the content of the inorganic fine particles within the above range.

[Method for forming transparent layer]
The transparent layer, in particular the first transparent layer, is applied to a colored substrate with a coating for transparent layer containing at least a transparent resin or a raw material thereof, and additives such as inorganic fine particles added if desired, dried, and heated or heated as desired. It can be formed by light irradiation and curing (crosslinking). The transparent layers after the second transparent layer can be formed by the same method as the first transparent layer, except that the transparent layer coating is applied on the transparent layer immediately below. Examples of the coating method include bar coating, dip coating, spray coating, roll coating, gravure coating, flexo coating, screen coating, spin coating, and flow coating.

  The coating material for the transparent layer usually contains an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the transparent resin or its raw material, and examples thereof include organic solvents similar to those described later when the transparent resin is a polysiloxane compound.

  Hereinafter, a method for forming a transparent layer when the transparent resin is a polysiloxane compound will be described in detail.

  When the transparent resin is a polysiloxane compound, first, a siloxane compound obtained by hydrolyzing and condensing the alkoxysilane is obtained. Thereafter, a transparent layer coating containing at least an additive such as a siloxane compound and optionally added inorganic fine particles, an organic solvent, an ultraviolet absorber, a light stabilizer, a curing catalyst, and a leveling agent is colored in the same manner as described above. After applying to a substrate and drying, it can be cured by heating or light irradiation to form a transparent layer.

  The coating material for the transparent layer preferably contains a curing catalyst in addition to the inorganic fine particles and the organic solvent that are optionally added. As the curing catalyst, an active energy ray functional acid generator that generates acid upon irradiation with active energy rays such as visible light, ultraviolet rays, heat rays, and electron beams, or a pH adjuster such as an acid or an alkali can be used. In particular, a light-sensitive acid generator that generates an acid by visible light or ultraviolet light as an active energy ray is preferable.

  Examples of the photosensitive acid generator include diphenyliodonium compounds, triphenylsulfonium compounds, diazodisulfone compounds, and the like. Specifically, Irgacure 250 manufactured by Ciba Japan Co., Ltd., Adekaoptomer SP-150 and SP-170 manufactured by ADEKA Co., Ltd., Syracure UVI-6992 manufactured by Dow Chemical Japan Co., Ltd., and Sanshin Chemical Industry Co., Ltd. Sun Aid SI-60L, SI-80L, SI-85L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L, SI-15H, SI-20H, manufactured by Corporation Commercial products such as SI-25H, SI-40H, SI-50H, CPI-100P, CPI-101A manufactured by San Apro Co., Ltd., MPI-103, MP-105, MP-109 manufactured by Midori Chemical Co., Ltd. Can be mentioned. These photosensitive acid generators can be used alone or in combination of two or more.

  As the pH adjuster, mineral acids or mineral acid salts can be used. Specifically, dilute aqueous solutions such as acetic acid, hydrochloric acid, and sulfuric acid, and alkali metals such as lithium salts, sodium salts, and potassium salts of aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, and succinic acid Salts, benzyltrimethylammonium salts of the above aliphatic carboxylic acids, choline salts, quaternary ammonium salts such as tetramethylammonium salts, tetraethylammonium salts, etc., and the like are not particularly limited as long as they are effective in promoting the condensation reaction. Absent.

  The content of the curing catalyst in the transparent layer coating is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the siloxane compound.

  Examples of the organic solvent contained in the transparent layer coating material include alcohols, ketones, ethers, esters, cellosolves, and aromatic compounds. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxy Methoxy) ethanol, 2-butoxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene Glycol monomethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol No ethyl ether, tripropylene glycol monomethyl ether, diacetone alcohol, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Acetophenone, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, anisole, phenetole, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, glycerin Ether, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, propionic acid Methyl, ethyl propionate, butyl propionate, γ-butyrolactone, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzene , Toluene, xylene and the like. These organic solvents can be used alone or in admixture of two or more.

  The content of the organic solvent is preferably in the range of 40 to 50000 parts by mass with respect to 100 parts by mass of the siloxane compound.

When the coating material for transparent layer contains a photosensitive acid generator, the active energy ray is irradiated after drying and before curing by heating. Examples of the active energy ray include vacuum ultraviolet rays, ultraviolet rays, and visible rays. Specific examples of active energy rays include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, and excimer laser. And light using sunlight as a light source. Among these, light using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp and a metal halide lamp as a light source is preferable. An active energy ray can be used individually by 1 type or in combination of 2 or more types. As the irradiation time and irradiation energy irradiation amount of the active energy ray, for example, in the case of irradiation with ultraviolet rays, the integrated light amount is preferably in the range of 100 to 5000 mJ / cm ² .

  Examples of the heating method for curing include a heating method using an infrared heater, a circulating heating method using hot air, and a direct heating method using a hot plate. As heating temperature, the temperature from which the temperature of a coating film becomes 50-120 degreeC is preferable, for example. The heating time is preferably 30 seconds to 60 hours. More preferably, it is 1 minute-6 hours, More preferably, it is 5 minutes-3 hours.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “part” means “part by mass”.

[Example 1]
(Formation of cured layer)
A transparent paint (KX-2250 made by Nippon Paint; containing hexamethylene diisocyanate homopolymer and acrylic polyol) is used to make a black polycarbonate plate (S3000 made by Mitsubishi Engineering Plastics; visible light transmittance 0) having a length of 10 cm, a width of 10 cm and a thickness of 3 mm. (Less than 1%) was applied by spraying (using W-100 made by Anest Iwata) so that the thickness after drying was 40 μm and dried at 70 ° C. for about 30 minutes to form a first transparent layer . Next, a low refractive transparent paint (FG-5040H manufactured by Fluoro Technology; including fluorine-containing resin compounds) is formed on the formed transparent layer so that the thickness after drying by a dip coating method is about 0.1 μm. It was applied and dried at room temperature for about 24 hours to form a second transparent layer.

[Example 2]
(Synthesis of silsesquioxane compound)
To a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 40 ml of 2-propanol (IPA) as a solvent and 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst were added. To the dropping funnel, 15 ml of IPA and 12.69 g of 3-methacryloxypropyltrimethoxysilane (SZ-6030 manufactured by Toray Dow Corning Silicone Co., Ltd.) were added. Subsequently, an IPA solution of 3-methacryloxypropyltrimethoxysilane was dropped over 30 minutes at room temperature while stirring the reaction vessel. After completion of dropping, the mixture was stirred for 2 hours in a non-heated environment. Subsequently, the solvent was removed under reduced pressure and dissolved in 50 ml of toluene. The reaction solution was washed with saturated brine until neutral, and dehydrated over anhydrous magnesium sulfate. Subsequently, anhydrous magnesium sulfate was filtered off and concentrated. As a result, 8.6 g of a hydrolysis product (silsesquioxane) was obtained. Such silsesquioxane was a colorless viscous liquid soluble in various organic solvents. Next, put 20.65 g of the obtained silsesquioxane, 82 ml of toluene and 3.0 g of 10% TMAH aqueous solution into a reaction vessel equipped with a stirrer, a Dinsterk and a cooling tube, and gradually heat to distill off the water. did. Subsequently, this was heated to 130 ° C., and toluene was recondensed at the reflux temperature. The temperature of the reaction solution at this time was 108 ° C. The mixture was stirred for 2 hours after refluxing toluene to complete the reaction. The reaction solution was washed with saturated brine until neutral, and dehydrated over anhydrous magnesium sulfate. Subsequently, anhydrous magnesium sulfate was filtered off and concentrated. As a result, 18.77 g of a cage-type silsesquioxane (mixture) S-1 as a target product was obtained. S-1 was a colorless viscous liquid soluble in various organic solvents. Moreover, the weight analysis after the liquid chromatography separation of the reaction material after a recondensation reaction was performed, and it confirmed that it was curable resin containing about 60% of cage | basket | type silsesquioxane.

(Preparation of composition)
0.25 g of S-1 above, 0.65 g of trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate TMP-A), dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE) -6A) 0.1 g, sodium fluoride slurry (manufactured by CI Kasei Co., Ltd., solid content 15% by mass, average particle size 75 nm) 20 g (solid content 3 g), 1-hydroxycyclohexyl phenyl ketone 0. 025 g and 25 ml of 2-propanol (IPA) as a solvent were mixed to obtain a composition P-1.

(Formation of cured layer)
Thickness after drying composition P-1 on a black polycarbonate plate (S3000 manufactured by Mitsubishi Engineering Plastics; visible light transmittance of less than 0.1%) having a length of 10 cm, a width of 10 cm, and a thickness of 3 mm by a flow coating method Was applied to a thickness of 4 μm and heated at 80 ° C. for 3 minutes. Further, irradiation is performed using a mercury lamp under the condition that the illuminance in the wavelength region of 200 nm or more and 400 nm or less is 505 mW / cm ² and cured with an accumulated exposure amount of 8400 mJ / cm ² , and the first transparent layer is formed on the surface of the polycarbonate plate. Formed.

[Example 3]
Black PMMA / PCABS laminate (PMMA: Kaneka 24120A, PCABS: Mitsubishi Engineering Plastics 21-G10; visible light transmittance 0) with composition P-1 of Example 2 having a length of 10 cm, a width of 10 cm, and a thickness of 5 mm (Less than 1%) was applied by a flow coating method so that the thickness after drying was 4 μm, and heated at 80 ° C. for 3 minutes. Further, in the illumination of a wavelength band 400nm or 200nm is 505mW / cm ² conditions, irradiation using a mercury lamp, and cured at integrated exposure amount of 8400mJ / cm ^2, a on the surface of the PMMA / PCABS laminate 1 A transparent layer was formed.

[Example 4]
(Synthesis of siloxane compounds)
2 parts of distilled water and 20 parts of acetic acid are added to 100 parts of a water-dispersed colloidal silica dispersion (Snowtex 30, manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30% by weight) and stirred. Under cooling, 130 parts of methyltrimethoxysilane was added. This mixed solution was stirred at 25 ° C. for 1 hour to obtain a siloxane compound solution S-2.

(Preparation of composition)
To the total amount of the solution S-2, 2 parts of sodium acetate as a curing catalyst was mixed with cooling with ice water, and diluted with 200 parts of isopropanol to obtain a composition P-2.

(Formation of cured layer)
An appropriate amount of the composition P-2 was dropped onto a black polycarbonate plate (S3000 manufactured by Mitsubishi Engineering Plastics; visible light transmittance of less than 0.1%) having a length of 10 cm, a width of 10 cm, and a thickness of 3 mm, and a bar coating method (bar coater). No. 26) was applied so that the thickness after drying was 4 μm, and dried at room temperature for about 30 minutes. Furthermore, it heated at 120 degreeC with the hot air dryer for 2 hours, and formed the 1st transparent layer on the surface of a polycarbonate board.

[Example 5]
(Formation of cured layer)
30 g of transparent paint (KX-2250 manufactured by Nippon Paint; including hexamethylene diisocyanate homopolymer and acrylic polyol) (solid content 20 g) and hollow silica (Suriria 2320 manufactured by JGC Catalysts & Chemicals Co., Ltd., solid content 20 mass%, average particle 50 g of diameter (mixed with 1 g of solid content) was mixed on a black polycarbonate plate (S3000 made by Mitsubishi Engineering Plastics; visible light transmittance of less than 0.1%) having a length of 10 cm, a width of 10 cm, and a thickness of 3 mm. It apply | coated so that the thickness after drying might be set to 40 micrometers by the spray method (Anest Iwata use W-100), and it dried at 70 degreeC for about 30 minutes, and formed the 1st transparent layer on the surface of a polycarbonate plate.

[Example 6]
Example 5 except that the mixture was applied and allowed to stand at room temperature for 48 hours, dried at 70 ° C. for about 30 minutes to form the first transparent layer, and then buffed with alumina abrasive grains having an average particle diameter of 0.05 μm. A transparent layer was formed by the same method as described above.

[Example 7]
A red paint (R303 made by Nippon Paint) was dried on a black PCABS board (Mitsubishi Engineering Plastics 21-G10) having a length of 10 cm, a width of 10 cm, and a thickness of 3 mm by a spray method (using W-100 made by Anest Iwata). The coating was applied to a thickness of 40 μm and dried at 70 ° C. for about 30 minutes to form a colored resin layer. The colored resin layer having a visible light transmittance of 10% or less thus obtained was used as a base material. Except for this, a transparent layer was formed in the same manner as in Example 1.

[Example 8]
A blue paint (Nihon Paint R303) is dried on a black PCABS board (Mitsubishi Engineering Plastics 21-G10) having a length of 10 cm, a width of 10 cm, and a thickness of 3 mm by a spray method (using W-100 made by Anest Iwata). The coating was applied to a thickness of 40 μm and dried at 70 ° C. for about 30 minutes to form a colored resin layer. The colored resin layer having a visible light transmittance of 10% or less thus obtained was used as a base material. Except for this, a transparent layer was formed in the same manner as in Example 1.

[Example 9]
100 parts of water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30% by weight) and 100 parts of water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.) Example 4 except that 60 parts by weight and 30 parts by weight of a water-dispersed large particle size colloidal silica dispersion (Snowtex ZL manufactured by Nissan Chemical Industries, Ltd., solids concentration 40% by weight) were replaced with 20 parts. A transparent layer was formed by the same method.

[Comparative Example 1]
A black polycarbonate plate having a length of 10 cm, a width of 10 cm, and a thickness of 3 mm (S3000 manufactured by Mitsubishi Engineering Plastics; visible light transmittance of less than 0.1%) was evaluated as it was.

[Comparative Example 2]
100 parts of water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30% by weight) is added to water-dispersed large particle size colloidal silica dispersion (Snowtex manufactured by Nissan Chemical Industries, Ltd.). A transparent layer was formed in the same manner as in Example 4 except that 80 parts (ZL, solid concentration 40 wt%) were substituted.

[Comparative Example 3]
On a transparent PMMA / PC / PMMA film (no-clean manufactured by RP Topura) having a length of 10 cm, a width of 10 cm, and a thickness of 250 μm, the thickness after drying a black paint (Lake Cure UIM6292 manufactured by Jujo Chemical) by screen printing is used. The coating was applied to a thickness of 20 μm and photocured to a total light amount of about 350 mJ / cm ² with a metal halide lamp 120 W / cm ² to form a colored resin layer having a visible light transmittance of 10% or less.

[Evaluation]
(Evaluation of color depth)
In the evening of a sunny day, a test sample plate was fixed to the shoulder portion of the installation panel of the vehicle parked westward, and the color depth of the sample plate was visually evaluated. At this time, the illumination intensity of the shoulder portion was about 40 W / m ² . Next, the vehicle was stopped in the north direction, and the same evaluation was performed. At this time, the illumination intensity of the shoulder portion was about 90 W / m ² .
A: The color depth was remarkably excellent;
○: The color depth was good;
Δ: Although the color depth was not good, it was within a practically acceptable range;
X: A feeling of deep color was not recognized.

(Evaluation of elaborate feeling)
The evaluation was performed by the same method as the color depth feeling, except that the fineness was evaluated based on the sharpness of contrast between light and shadow reflected on the sample plate.
(Double-circle): The sharpness of contrast of light and shadow was remarkably excellent;
○: The contrast of light and shadow was clear.
Δ: The sharpness of the contrast between light and shadow is not good, but is within a range where there is no practical problem;
X: The contrast between light and shadow was not clear.

[Measurement]
(Specular brightness)
The sample plate obtained in each example / comparative example has a light source incident angle on the surface of the transparent layer of 10 ° and a light receiving angle in the range of 10 ± 0.05 ° (regular reflection direction in the range of ± 0.05 °). The brightness of the specularly reflected light was measured under the following conditions. Measurements were made at any 15 points, and the average value was shown. As a measuring device, HyperSpec-VNIR-C (manufactured by HeadWall Photonics) was used. Other measurement conditions are as follows:
Camera to sample distance; 16cm
Light source to sample distance; 5.2 cm
X-direction visual field resolution: 114 μm
Light source type: halogen Light source illuminance: 2 W / m ²
Light source spread angle: 33.7 °
Lens aperture; F2.8
Exposure time: 3400 seconds Imaging interval: 50 μm.

(Haze value)
A transparent layer was formed on a transparent glass plate (thickness 1 mm) having a visible light transmittance of 92% and a haze value of 0.25 by the same method as in each example / comparative example. When the first and second transparent layers were formed in each example / comparative example, one or both of these transparent layers were formed. The haze value was measured with UV-2400PC (manufactured by Shimadzu Corporation). From the haze value H ₁ of the transparent layer formed on the transparent glass plate (including the haze value of the transparent glass plate and the transparent layer) and the haze value H ₀ of the transparent glass plate, based on the following formula, the haze of only the transparent layer The value was determined. H ₁ and H ₀ were measured at arbitrary 15 points, and the average value thereof was used.

(Refractive index)
Formation of a transparent layer on the transparent glass plate and measurement of the refractive index were performed in the same manner as the haze value measurement method. The refractive index was measured using a plasma coupling method in a TE mode, a measurement wavelength of 632.8 nm, and a measurement temperature of 25 ° C.

(Visible light transmittance)
Formation of a transparent layer on a transparent glass plate and measurement of visible light transmittance were performed in the same manner as the haze value measurement method. The visible light transmittance was measured with UV-2400PC (manufactured by Shimadzu Corporation). From the visible light transmittance T ₁ (including the visible light transmittance of the transparent glass plate and the transparent layer) of the transparent layer formed on the transparent glass plate and the visible light transmittance T _{0 of the} transparent glass plate, based on the following formula: The visible light transmittance of only the transparent layer was determined. T ₁ and T ₀ were measured at arbitrary 15 points, and the average value thereof was used.

(Surface roughness Ra)
The surface of the sample plate obtained in each example / comparative example was measured using a laser microscope VK-X200 (manufactured by Keyence Corporation). The measurement was performed based on JIS B 0601: 2001 (ISO 4287: 1997). The measurement conditions were cut-off without λs and λc 0.08 mm, correction processing without light amount smoothing, height smoothing ± 2 simple average, and no inclination correction. Measurements were made at any 15 points, and the average value was shown.

(Root mean square slope RΔq)
It measured simultaneously by the method similar to surface roughness Ra.

(Absolute value of skewness Rsk)
It measured simultaneously by the method similar to surface roughness Ra.

  The decorative laminate of the present invention is useful as a member used in a vehicle such as an automobile and as a surface member constituting the surface of the member.

Claims (8)

  A decorative laminate, wherein a transparent layer is formed on a colored substrate, and the transparent layer has a regular reflection brightness of 10 to 60 or less and a haze value of 0.2 to 10%.   The decorative laminate according to claim 1, wherein the colored substrate has a visible light transmittance of 15% or less.   The decorative laminate according to claim 1 or 2, wherein the colored substrate is a colored resin substrate, a colored metal substrate, or a colored main substrate.   The additive according to claim 1 or 2, wherein the colored substrate is a colored resin substrate comprising a polymer selected from the group consisting of poly (meth) acrylates, polycarbonates, acrylonitrile-butadiene-styrene copolymers, and mixtures thereof. Decorated laminate.   The decorative laminate according to claim 4, wherein the colored resin substrate is a colored resin molded product or a colored resin coating film.   The decorative laminate according to claim 4 or 5, wherein the colored resin substrate is a black resin substrate.   The transparent layer is one or more transparent resins selected from the group consisting of polysiloxane compounds, polyurethane compounds, acrylic / vinyl-based polymer compounds, fluorine-containing resin compounds, epoxy resin compounds, and cured products thereof. The decoration laminated body in any one of Claims 1-6 containing.   The decorative laminated body according to any one of claims 1 to 7, wherein the regular reflection brightness is 10 to 50, and the haze value is 0.3 to 8.5%.