Cosmetic material and resin composition for forming surface protective layer thereof

Abstract

Provided are a decorative material having superior weather resistance and a resin composition for forming a surface protective layer. The decorative material includes at least a base material and a surface protective layer on an outermost surface. The surface protective layer contains an ultraviolet absorbing agent. The content of the ultraviolet absorbing agent relative to 100 parts by mass of resin that forms the surface protective layer is 1-10 parts by mass inclusive. The content of an ultraviolet absorbing agent having a melting point of 90℃ or higher relative to the total amount of the ultraviolet absorbing agent is greater than or equal to 45 mass%.

Description

[Technical field]

[0001] The present invention relates to a decorative material and a resin composition for forming a surface protective layer thereof. [Background technology]

[0002] In addition to interior components of buildings such as walls, ceilings, and floors, exterior components such as exterior walls, roofs, eaves ceilings, fences, and gates, various doors such as window frames and entrance doors, building fixtures or fittings such as handrails, baseboards, moldings, window frames, door frames, and moldings, surface decorative panels for general furniture such as chests of drawers, shelves, and desks, kitchen furniture such as dining tables and sinks, and cabinets for low-electricity appliances and office automation equipment are generally made by bonding a decorative material to various members such as resin members, wood members, and metal members as adherends, or by using the decorative material as it is. As such decorative materials, decorative materials having a configuration having a surface protective layer on a substrate, for example, sheet-shaped decorative materials (also called "decorative sheets"), etc. are used.

[0003] When a decorative material is used for outdoor purposes, problems related to weather resistance, such as color change and resin deterioration, occur due to the effects of wind, rain, and even ultraviolet rays from sunlight. Even for indoor use, when the material is exposed to sunlight near a window, problems similar to those for outdoor use occur. As a method for improving the weather resistance of decorative sheets used for such purposes, it is common to add an ultraviolet absorbing agent as a weather resistance agent to the surface protective layer of the decorative material.

[0004] However, there is a problem that the ultraviolet absorber is likely to bleed out from the surface protective layer over time. When the ultraviolet absorber bleeds out, the aesthetic appearance of the decorative material surface is impaired, for example by causing stickiness, and the bleed-out ultraviolet absorber is gradually lost due to runoff from rain, etc., and the concentration of the ultraviolet absorber in the surface protective layer decreases over time, resulting in problems such as a decrease in weather resistance. Under these circumstances, in order to eliminate the bleeding out of the ultraviolet absorber, a decorative sheet has been proposed having a cured layer of a resin mainly composed of an electron beam curable resin, which contains, for example, an electron beam reactive ultraviolet absorber selected from specific benzotriazole-based compounds (for example, Patent Document 1). The decorative sheet described in Patent Document 1 can solve the problem of bleeding out of the ultraviolet absorber. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2000-117905 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0006] In recent years, with the rise in average temperatures due to global warming, decorative materials for outdoor use have come to be used under more severe temperature conditions, with the surface temperature of the decorative materials reaching up to about 70°C, and conventional decorative materials are no longer able to cope with this, and the progression of their deterioration tends to accelerate year by year. Therefore, although the design concept for suppressing the bleeding out of UV absorbers is valid, it is necessary to reconsider the means of achieving this.

[0007] The present invention has been made under these circumstances, and an object of the present invention is to provide a decorative material having excellent weather resistance, and a resin composition for forming a surface protective layer. [Means for solving the problem]

[0008] As a result of intensive research into solving the above problems, the inventors have found that the above problems can be solved by an invention relating to a decorative material and a resin composition for forming a surface protective layer thereof having the following configuration.

[0009] 1. A decorative material having at least a substrate and a surface protective layer on the outermost surface, The surface protective layer contains an ultraviolet absorbing agent, the content of the ultraviolet absorber relative to 100 parts by mass of a resin forming the surface protective layer is 1 part by mass or more and 10 parts by mass or less; The content of the ultraviolet absorber having a melting point of 90°C or more relative to the total amount of the ultraviolet absorbers is 45% by mass or more. Cosmetic materials. 2. The cosmetic material according to 1 above, wherein the ultraviolet absorber having a melting point of 90° C. or higher has a hydroxyphenyltriazine structure. 3. The decorative material according to the above item 1 or 2, wherein all of the ultraviolet absorbing agents contained in the surface protective layer have a hydroxyphenyltriazine structure. 4. The decorative material according to any one of the above 1 to 3, wherein the surface protective layer is a cured product of a curable resin composition containing a curable resin and an ultraviolet absorber. 5. The decorative material according to any one of the above items 1 to 4, wherein the surface protective layer further contains a light stabilizer. 6. The decorative material according to any one of 1 to 5 above, further comprising, between the substrate and the surface protective layer, a decorative layer, an adhesive layer, a resin layer and a primer layer in this order from the substrate side. 7. The decorative material according to any one of the above 1 to 6, further comprising an adherend, via an adhesive layer, on the surface of the substrate opposite to the surface protective layer. 8. The moisture permeability measured in accordance with the moisture permeability test method for moisture-proof packaging materials (cup method) specified in JIS Z0208:1976 is 0.75g / m 2 ·45g / m for 24 hours or more 2 The decorative material according to any one of the above items 1 to 6, wherein the shelf life is 24 hours or less. 9. A resin composition for forming a surface protection layer, comprising a resin constituting a surface protection layer and an ultraviolet absorber including an ultraviolet absorber having a melting point of 90°C or higher, wherein the content of the ultraviolet absorber relative to 100 parts by mass of the resin is 1 part by mass or more and 10 parts by mass or less, and the content of the ultraviolet absorber having a melting point of 90°C or higher relative to the total amount of the ultraviolet absorber is 45% by mass or more. Effect of the Invention

[0010] According to the present invention, it is possible to provide a decorative material and a resin composition for forming a surface protective layer having excellent weather resistance. [Brief description of the drawings]

[0011] [Figure 1] 1 is a schematic cross-sectional view showing one embodiment of a decorative material of the present invention. [Diagram 2] FIG. 1 is a schematic cross-sectional view showing one embodiment of a decorative material of the present invention. [Diagram 3] FIG. 1 is a schematic cross-sectional view showing one embodiment of a decorative material of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] [Decorative materials] The decorative material of the present invention will be described below. In this specification, the numerical values ​​related to "greater than or equal to," "less than or equal to," and "to" in the description of a numerical range are numerical values ​​that can be arbitrarily combined, and the numerical values ​​in the examples are numerical values ​​that can be used as the upper and lower limits of the numerical range.

[0013] The decorative material of the present invention is a decorative material having at least a substrate and a surface protective layer on the outermost surface, the surface protective layer containing an ultraviolet absorber, the content of the ultraviolet absorber relative to 100 parts by mass of the resin forming the surface protective layer being 1 part by mass or more and 10 parts by mass or less, and the content of the ultraviolet absorber having a melting point of 90° C. or more relative to the total amount of the ultraviolet absorbers being 45% by mass or more. By making the surface protective layer constituting the decorative material of the present invention a layer containing an ultraviolet absorber having a melting point of 90° C. or more in the above-mentioned predetermined content, bleeding out of the ultraviolet absorber is suppressed and excellent weather resistance is obtained even when the decorative material is used in a harsh environment, particularly under harsh temperature conditions.

[0014] Although the mechanism by which the ultraviolet absorber is likely to bleed out under harsh temperature conditions is unclear, it is speculated that the ultraviolet absorber is liquefied due to the temperature rise of the decorative material and leaks out from the surface protective layer. When the ultraviolet absorber liquefies, it becomes more likely to bleed out from the surface protective layer, and as the bleed-out progresses, the amount of ultraviolet absorber held by the decorative material itself decreases, and weather resistance is thought to decrease. Furthermore, even if the liquefied ultraviolet absorber remains in the surface protective layer, when the temperature conditions under which the decorative material is used fall below the melting point of the ultraviolet absorber, the ultraviolet absorber will liquefy once and solidify in a state in which adjacent ultraviolet absorbers aggregate together, so that it will exist in the surface protective layer in the form of lumps, and the ultraviolet absorber will lose its good dispersion state in the surface protective layer, resulting in a decrease in weather resistance.

[0015] The temperature conditions to which the decorative material is exposed during use rise and fall repeatedly throughout the day, and the ultraviolet absorber therefore undergoes a cycle of liquefaction, bleeding out, partial aggregation, and solidification resulting in the formation of lumps. Furthermore, as a result of bleeding out, the ultraviolet absorber that has come out from inside the decorative material to the outermost surface of the decorative material is washed away by rain and gradually disappears from the surface of the decorative material, and the weather resistance decreases by the amount of the ultraviolet absorber that has disappeared, accelerating the progression of deterioration of the decorative material. The decorative material of the present invention further suppresses the bleeding out of the ultraviolet absorber and exhibits excellent weather resistance even under such a usage environment.

[0016] The structure of the decorative material of the present invention will be described with reference to Figs. FIG. 1 is a schematic cross-sectional view showing the layer structure of a decorative material of the present invention, and shows that a decorative material 10 of the present invention has a substrate 1 and a surface protective layer 2. FIG. 2 is a schematic cross-sectional view showing one embodiment of a preferred layer structure of the decorative material of the present invention, in which, between the substrate 1 and the surface protective layer 2 provided on the outermost surface, there is, in order from the substrate side, a decorative layer 3 consisting of an overall colored layer 31 and a pattern layer 32, an adhesive layer A4, a resin layer 5, and a primer layer 6. Each layer constituting the decorative material of the present invention will now be described in more detail.

[0017] (Base material 1) The substrate can be any substrate normally used for cosmetic materials without any restrictions, and representative examples include substrates made of paper, nonwoven or woven fabric, resin, wood, metal, nonmetallic inorganic materials, etc. The thickness of the substrate is also not particularly limited, and a substrate in the form of a film, sheet, or plate can be appropriately used as desired, but typically, a substrate having a thickness of about 20 to 200 μm for a film or sheet, and about 500 μm to 10 cm for a plate, is used.

[0018] Examples of paper substrates include kraft paper, titanium paper, linter paper, parchment paper, glassine paper, parchment paper, resin-impregnated paper, tissue paper, Japanese paper, etc. Examples of nonwoven or woven substrates include nonwoven or woven substrates made of inorganic fibers such as glass fiber, alumina fiber, silica fiber, and carbon fiber, and organic fibers of various synthetic resins such as polyester resin, acrylic resin, polyethylene resin, and polypropylene resin, as well as composites thereof.

[0019] Examples of resins include resin substrates made of thermoplastic resins such as polypropylene, polyethylene, polyolefin-based thermoplastic elastomers, ionomers, etc.; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as polymethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyester resins; polycarbonate resins; acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"); and vinyl chloride resins. In addition, in the present specification, for example, the terms "(meth)acrylate" and "(meth)acrylic acid" are abbreviations meaning "acrylate or methacrylate (or methacrylate)" and "acrylic acid or methacrylic acid (or methacrylic acid)", respectively.

[0020] Examples of wood include wood substrates made of various kinds of wood such as cedar, cypress, pine, oak, lauan, teak, rubber tree, etc. The wood substrate can be in the form of a film or sheet called veneer, or in the form of a board such as a single board, plywood, laminated wood, particle board, fiberboard, etc. Examples of metals include metal substrates made of iron, aluminum, copper, tin, titanium, or alloys containing at least one of these metals (for example, carbon steel, stainless steel, duralumin, brass, bronze, etc.). Examples of non-metallic inorganic materials include cement, gypsum, calcium silicate, porcelain, and various ceramics.

[0021] The substrate may be colored or uncolored (it may be transparent). If the substrate is colored, the manner of coloring is not particularly limited, and the substrate may be transparently colored or opaquely colored (hiding colored), which can be selected as desired.

[0022] When the substrate is colored, examples of the coloring agent include inorganic pigments such as titanium white, antimony white, iron black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, nickel-azo complex, azomethine azo-based black pigment, and perylene-based black pigment; metal pigments made of scaly foil such as aluminum and brass; and pearlescent (pearl) pigments made of scaly foil such as titanium dioxide-coated mica and basic lead carbonate. For example, when the surface hue of the adherend to which the decorative sheet is attached varies, and it is desired to conceal the surface hue and improve the stability of the color tone of the decorative layer provided as desired, an inorganic pigment such as a white pigment may be used.

[0023] In the case of coloring a resin, any of the following methods can be used: addition to the resin (mixing, kneading), coating with a paint containing the resin and the colorant, etc. In the case of coloring paper, nonwoven fabric, or woven fabric, any of the following methods can be used: mixing with pulp or fiber materials, or coating with a paint, or a combination of these. Coloring of wood can be carried out by either dyeing with a dye or forming a coating film, or by a combination of these. Coloring of metals can be carried out by forming a coating film or by a decoloring method in which a metal oxide film is formed on the surface using anodizing. In the case of non-metallic inorganic materials, coloring can be carried out by either coating film formation or addition to the base material, or by a combination of these.

[0024] The base material may contain additives as necessary. Examples of additives include inorganic fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. The amount of additives to be added is not particularly limited as long as it does not impair processing characteristics, and can be appropriately set according to required characteristics.

[0025] From the viewpoint of improving the weather resistance of the decorative material of the present invention, among the above-mentioned additives, it is preferable to use weather resistance agents such as ultraviolet absorbers and light stabilizers. As the ultraviolet absorbent, any ultraviolet absorbent commonly used in cosmetic materials can be used without any particular limitation, and both organic and inorganic ultraviolet absorbents can be used. For example, organic ultraviolet absorbents include benzotriazole ultraviolet absorbents, benzophenone ultraviolet absorbents, triazine ultraviolet absorbents, and hydroxyphenyltriazine ultraviolet absorbents. As the light stabilizer, any ultraviolet stabilizer commonly used in cosmetic materials can be used without any particular limitation, and for example, hindered amine light stabilizers such as piperidinyl sebacate light stabilizers can be used. In addition, these ultraviolet absorbents and light stabilizers may have reactive functional groups having ethylenic double bonds such as (meth)acryloyl groups, vinyl groups, and allyl groups in the molecule. As inorganic ultraviolet absorbents, titanium dioxide, ferric oxide, zinc oxide, cerium oxide, zirconium oxide, and the like, each having an average particle size of 380 nm or less, which is the shortest wavelength of visible light, preferably 100 nm or less, can be used. These ultraviolet absorbents, weather resistance agents such as light stabilizers, and other various additives may be used alone or in combination of two or more kinds.

[0026] In the present invention, the above-mentioned substrates can be used alone or in combination. A combination of a plurality of paper substrates is also possible, or a combination of a paper substrate and a fiber substrate, a paper substrate and a resin substrate, a fiber substrate and a resin substrate, or a combination of a paper substrate, a fiber substrate and a resin substrate. The resin substrate may be a single layer of the above-mentioned resin, or a multi-layer structure of the same or different resins. In the present invention, from the viewpoint of making it easier to keep the moisture permeability of the decorative sheet described below within a specified range and improving long-term adhesion as well as application suitability, a resin substrate is preferred among the above-mentioned substrates, and preferred resins include polyolefin resins such as polypropylene, polyethylene, polyolefin-based thermoplastic elastomers, and ionomers, and vinyl chloride resins.

[0027] More specifically, examples of polyolefin resins include homopolymers of olefins such as ethylene, propylene, and butene; various copolymers such as ethylene-propylene block copolymers and random copolymers; copolymers of at least one of ethylene and propylene with at least one other olefin such as butene, pentene, and hexene; copolymers of at least one of ethylene and propylene with at least one other monomer such as vinyl acetate and vinyl alcohol; and the like. Of the above, polyethylene-based resins containing ethylene as a constituent unit and polypropylene-based resins containing propylene as a constituent unit are preferred, with polypropylene-based resins being more preferred, from the viewpoint of making it easier to keep the moisture permeability (described later) within a specified range and improving long-term adhesion as well as workability.

[0028] More specifically, the polyethylene resin may be a homopolymer of ethylene, i.e., polyethylene, or a copolymer of ethylene and another comonomer copolymerizable with ethylene (e.g., α-olefins such as propylene, 1-butene, 1-hexene, and 1-octene, vinyl acetate, vinyl alcohol, etc.). Examples of polyethylene include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra-high molecular weight polyethylene (UHMWPE), cross-linked polyethylene (PEX), etc. These polyethylene resins may be used alone or in combination of two or more.

[0029] The polypropylene-based resin may be a homopolymer of propylene, i.e., polypropylene, or a copolymer of propylene and another comonomer copolymerizable with propylene (e.g., α-olefins such as ethylene, 1-butene, 1-hexene, and 1-octene; vinyl acetate, vinyl alcohol, etc.). These polypropylenes may be used alone or in combination of two or more.

[0030] When a propylene homopolymer (polypropylene) is used, the moisture permeability of the substrate can be adjusted by adjusting the crystallinity. In general, the higher the crystallinity, the lower the moisture permeability of the polypropylene resin. When the polypropylene resin having a thickness in the range of 40 μm to 200 μm is used as the substrate, the crystallinity is preferably 30% or more, more preferably 40% or more, and the upper limit is preferably 80% or less, more preferably 70% or less. In addition, when a propylene homopolymer (polypropylene) is used, the moisture permeability of the substrate can be adjusted by adjusting the mass ratio of isotactic polypropylene to atactic polypropylene. In general, the moisture permeability of the substrate can be reduced by adding isotactic polypropylene compared to when the proportion of atactic polypropylene in polypropylene is 100% by mass. In this case, the mass ratio of atactic polypropylene to isotactic polypropylene is preferably 0 / 100 to 20 / 80, taking into consideration the ease of adjusting the moisture permeability.

[0031] As the vinyl chloride resin, a homopolymer of a vinyl chloride monomer, that is, polyvinyl chloride, or a copolymer obtained by copolymerizing a vinyl chloride monomer with a monomer copolymerizable with the vinyl chloride monomer can also be used. Examples of monomers copolymerizable with vinyl chloride monomer include vinyl esters such as vinyl acetate and vinyl propionate; acrylic esters such as methyl acrylate and butyl acrylate; methacrylic esters such as methyl methacrylate and ethyl methacrylate; maleic esters such as butyl maleate and diethyl maleate; fumaric esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; vinyl cyanides such as acrylonitrile and methacrylonitrile; olefins such as ethylene, propylene, butylene and styrene; dienes such as isoprene and butadiene; vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides; allyl phthalates such as diallyl phthalate, etc. These monomers may be used alone or in combination of two or more kinds.

[0032] The average degree of polymerization of the vinyl chloride resin is preferably 500 to 4000, more preferably 700 to 3900, and even more preferably 1000 to 3800, from the viewpoint of easily setting the moisture permeability described below within a predetermined range and improving long-term adhesion as well as application suitability. When the average degree of polymerization is within the above range, excellent mechanical strength and moldability are also obtained. In this specification, the average degree of polymerization is the average degree of polymerization measured in accordance with JIS K6721.

[0033] In this embodiment, when vinyl chloride resin is used, it is preferable to add a plasticizer from the viewpoints of easily adjusting the moisture permeability within the above range, improving long-term adhesion as well as application suitability, and improving processability. The plasticizer is not particularly limited as long as it is compatible with the vinyl chloride resin, and examples thereof include phthalic acid-based plasticizers such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), etc.; adipic acid-based plasticizers such as dibutyl adipate; phosphate-based plasticizers such as tributyl phosphate, tricresyl phosphate, triphenyl phosphate, etc.; trimellitic acid-based plasticizers such as tributyl trimellitate, trioctyl trimellitate, etc.; various known polyester-based plasticizers such as adipic acid-based polyesters; and citric acid esters such as acetyl tributyl citrate, acetyl trioctyl citrate, etc. Among them, from the viewpoints of easily achieving moisture permeability within the above range, improving long-term adhesion as well as application suitability, and improving processability, phthalic acid plasticizers, adipic acid plasticizers, and polyester plasticizers are preferred, and phthalic acid plasticizers and polyester plasticizers are more preferred. These plasticizers may be used alone or in combination.

[0034] The content of the plasticizer may be appropriately adjusted according to the desired moisture permeability, and it cannot be said in general, but usually, as the amount of the plasticizer additive is increased, the moisture permeability of the vinyl chloride resin tends to increase. In consideration of this point, it is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, and the upper limit is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 35 parts by mass or less, relative to 100 parts by mass of the vinyl chloride resin. By setting the content of the plasticizer within the above range, it becomes easier to adjust the moisture permeability to the desired range, and it is possible to improve the long-term adhesion as well as the application suitability. In addition, by setting the content of the plasticizer to 20 parts by mass or more, it is possible to make the vinyl chloride resin flexible and improve the processability, while if it is 50 parts by mass or less, it is possible to suppress the bleeding out of the plasticizer, and it becomes easier to stably adjust the moisture permeability to the desired range, and it is possible to improve the long-term adhesion as well as the application suitability.

[0035] In particular, from the viewpoint of making it easier to adjust the moisture permeability to a desired range and improving long-term adhesion together with application suitability, for example, when a phthalate ester plasticizer is used, the content is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more, relative to 100 parts by mass of vinyl chloride resin, and the upper limit is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less. In addition, when a polyester plasticizer is used, the content is preferably 15 parts by mass or more, more preferably 18 parts by mass or more, and even more preferably 20 parts by mass or more, relative to 100 parts by mass of vinyl chloride resin, and the upper limit is preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less.

[0036] The shape of the substrate is not particularly limited and may be appropriately selected as desired. For example, the substrate may be flat, curved, or non-flat, such as having corners. Although a flat (or "sheet-like") decorative material is shown in Figures 1 and 2, the shape of the decorative material of the present invention is not limited to this. Considering the ease of manufacturing the decorative material, applications, ease of processing, etc., a flat shape is preferable. The thickness of the substrate is preferably 20 μm or more, more preferably 30 μm or more, and even more preferably 40 μm or more, in consideration of surface properties such as abrasion resistance, weather resistance, and scratch resistance, processing properties, ease of handling, etc. The upper limit is preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 150 μm or less.

[0037] The substrate may be subjected to a surface treatment, such as a physical surface treatment such as an oxidation method or a roughening method, or a chemical surface treatment, on one or both sides thereof in order to improve interlayer adhesion between the substrate and other layers, strengthen adhesion to various adherends, etc. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet light treatment, etc., and examples of the roughening method include sandblasting, solvent treatment, etc. These surface treatments are appropriately selected depending on the type of substrate, but generally, corona discharge treatment is preferably used in terms of the effect of the surface treatment, operability, etc. In addition, in order to improve the interlayer adhesion between the substrate and other layers, and to strengthen the adhesion to various adherends, at least one surface of the substrate may be subjected to a treatment such as forming a primer layer (also referred to as an "easy adhesion layer") described below.

[0038] (Surface protective layer 2) The surface protective layer is a layer provided over the entire outermost surface of the decorative material of the present invention so as to cover the substrate, and is a layer that protects the decorative material of the present invention. The surface protective layer must contain an ultraviolet absorber in an amount of 1 to 10 parts by mass relative to 100 mass of the resin constituting the surface protective layer, and the content of the ultraviolet absorber having a melting point of 90° C. or higher relative to the total amount of the ultraviolet absorbers must be 45 mass% or more. In the present invention, unless a specific ultraviolet absorber having a melting point of 90° C. or higher is contained in the above amount, excellent weather resistance cannot be obtained.

[0039] The ultraviolet absorbing agent used in the surface protective layer is not particularly limited as long as it has a melting point of 90° C. or higher, and either an organic or inorganic ultraviolet absorbing agent can be used. For example, preferred examples of organic ultraviolet absorbents include the ultraviolet absorbents exemplified as those that can be used in the above-mentioned substrate, benzotriazole-based ultraviolet absorbents, benzophenone-based ultraviolet absorbents, triazine-based ultraviolet absorbents, and hydroxyphenyltriazine-based ultraviolet absorbents, and among these, hydroxyphenyltriazine-based ultraviolet absorbents are preferred. Examples of inorganic ultraviolet absorbents include the ultraviolet absorbents exemplified as those that can be used in the above-mentioned base material, i.e., titanium dioxide, ferric oxide, zinc oxide, cerium oxide, zirconium oxide, etc., each having an average particle size of 380 nm or less, preferably 100 nm or less, and more preferably 50 nm or less. However, from the standpoint of the transparency of the surface protective layer, dispersibility in the transparent protective layer, and processability of the decorative sheet, organic ultraviolet absorbents are more preferred.

[0040] The hydroxyphenyltriazine-based ultraviolet absorber is an ultraviolet absorber having a hydroxyphenyltriazine structure. The hydroxyphenyltriazine structure has a molecular structural characteristic that it is difficult to bleed out from the surface protective layer from the viewpoint of steric hindrance, and since it has a melting point of 90°C or higher, it is difficult to bleed out due to liquefaction, and it remains in a good dispersed state in the surface protective layer, so that excellent weather resistance can be obtained. In the present invention, by using a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of 90° C. or higher, it is possible to suppress the occurrence of bleed-out due to liquefaction that may occur during use of the cosmetic material, and to maintain excellent weather resistance.

[0041] The melting point of the ultraviolet absorber used in the surface protective layer is preferably 95° C. or higher, more preferably 100° C. or higher, and even more preferably 105° C. or higher, from the viewpoint of further suppressing the occurrence of bleed-out due to liquefaction and improving weather resistance. There is no particular upper limit, but from the viewpoint of solubility in the coating liquid, it is preferably 200° C. or lower, and more preferably 150° C. or lower. In this specification, the melting point of an ultraviolet absorber is the "temperature at which liquefaction begins." Specifically, the ultraviolet absorber is placed in a glass container and placed in an oven. If liquefaction begins when the oven is heated to a specified temperature for one hour, the specified temperature is regarded as the melting point.

[0042] More specifically, preferred examples of hydroxyphenyltriazine-based ultraviolet absorbents include those represented by the following general formula (1).

[0043] [ka]

[0044] In general formula (1), R 11 is a divalent organic group or a single bond, R 12 is a monovalent organic group, -C(=O)OR 15 An ester group represented by -OC(=O)R 16 or an acyloxy group represented by -OR 17 R is an organyloxy group represented by the formula 13 , R 14 , R 15 , R 16 and R 17 are each independently a hydrogen atom or a monovalent organic group, X is an oxygen atom or a single bond, and n 11 and n 12 are each independently an integer of 1 to 5. 13 and R 14 When there are multiple, they may be the same or different.

[0045] R 11 Preferred examples of the divalent organic group include aliphatic hydrocarbon groups such as alkylene groups and alkenylene groups, and from the viewpoint of weather resistance, alkylene groups are more preferred. The number of carbon atoms in these aliphatic hydrocarbon groups is preferably 1 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 4 or less. The alkylene group and alkenylene group may be linear, branched, or cyclic, but linear or branched is preferred.

[0046] R 12Preferred examples of the monovalent organic group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group, with an alkyl group being more preferred. The number of carbon atoms in the alkyl group is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more, with the upper limit being preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less. The alkyl group and the alkenyl group may be linear, branched, or cyclic, with linear or branched being preferred, and branched being more preferred.

[0047] R 13 and R 14 Examples of the monovalent organic group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group. An aromatic hydrocarbon group such as an aryl group or an arylalkyl group is preferred, and an aryl group is preferred.

[0048] R 13 and R 14 The number of carbon atoms in the alkyl group of the monovalent organic group is preferably 20 or less, more preferably 12 or less, even more preferably 4 or less, and particularly preferably 2 or less. That is, R 13 and R 14 As the monovalent alkyl group, a methyl group or an ethyl group is particularly preferred, and in consideration of availability, a methyl group is more preferred.

[0049] R 13 and R 14 The number of carbon atoms in the aryl group is preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and even more preferably 10 or less. The number of carbon atoms in the arylalkyl group is preferably 7 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and even more preferably 10 or less.

[0050] R 15 , R 16 and R 17Examples of the monovalent organic group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group. Among these, an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. 15 , R 16 and R 17 When is an alkyl group or an alkenyl group, the number of carbon atoms is preferably 2 or more, more preferably 4 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less.

[0051] The above R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 The group may have a substituent such as a halogen atom, a hydroxyl group, an amino group, or an alkyl group having 1 to 4 carbon atoms.

[0052] Also, n 11 and n 12 are each independently an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. 11 and n 12 If is an integer equal to or greater than 2, multiple R 13 and R 14 may be the same or different, and from the viewpoint of availability, it is preferable that they are the same.

[0053] Representative examples of hydroxyphenyltriazine-based ultraviolet absorbents having a melting point of 90° C. or higher include those represented by the following chemical formula (2), that is, those represented by the general formula (1) above, R 11 is an ethylene group, R 12 -OC(=O)R 16 An acyloxy group represented by the formula (R 16 is a 3-heptyl group), R 13 and R 14is a hydrogen atom. This hydroxyphenyltriazine-based ultraviolet absorber is available as a commercial product ("ADEKA STAB LA-46 (product number)", melting point: 106° C., manufactured by ADEKA Corporation).

[0054] [ka]

[0055] Representative examples of hydroxyphenyltriazine-based ultraviolet absorbents having a melting point of 90° C. or higher include those represented by the following chemical formula (3), that is, those represented by the general formula (1) above, 11 is a single bond, R 12 isooctyl group, R 13 and R 14 is a phenyl group, and n 11 and n 12 A preferred example is one in which the value is 1. This hydroxyphenyltriazine-based ultraviolet absorber is available as a commercial product ("Tinuvin 1600 (product number)", melting point: 120° C., manufactured by BASF).

[0056] [ka]

[0057] Representative examples of hydroxyphenyltriazine-based ultraviolet absorbents having a melting point of 90° C. or higher include those represented by the following chemical formula (4), that is, those represented by the general formula (1) above, R 11 is a single bond, R 12 is a hexyl group, R 13 and R 14 is a hydrogen atom. This hydroxyphenyltriazine-based ultraviolet absorber is available as a commercial product ("Tinuvin 1577 (product number)", melting point: 148° C., manufactured by BASF).

[0058] [ka]

[0059] In the present invention, the content of the ultraviolet absorber having a melting point of 90° C. or more relative to the total amount of the ultraviolet absorber used in the surface protective layer is 45% by mass or more. If the content of the ultraviolet absorber having a melting point of 90° C. or more is less than 45% by mass, excellent weather resistance cannot be obtained. From the viewpoint of improving weather resistance, the content is preferably 55% by mass or more, more preferably 65% ​​by mass or more, even more preferably 75% by mass or more, and even more preferably 80% by mass or more. There is no particular limit to the upper limit, and the content may be 100% by mass, that is, the total amount may be ultraviolet absorbers having a melting point of 90° C. or more. The ultraviolet absorbing agents having a melting point of 90° C. or higher may be used alone or in combination of two or more kinds.

[0060] In the present invention, as the ultraviolet absorber that can be used in the surface protective layer, it is possible to use the ultraviolet absorber having a melting point of 90°C or more as well as the ultraviolet absorber having a melting point of less than 90°C. In this case, ultraviolet absorbers that have been widely used in conventional cosmetic materials can be used without any particular restrictions, and can be appropriately selected from ultraviolet absorbers such as benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, and hydroxyphenyltriazine ultraviolet absorbers. In this case, the other ultraviolet absorber is preferably a hydroxyphenyltriazine ultraviolet absorber. That is, when an ultraviolet absorber other than an ultraviolet absorber having a melting point of 90°C or more is used in combination, it is preferable to use a hydroxyphenyltriazine ultraviolet absorber having a melting point of less than 90°C as the other ultraviolet absorber, and among them, it is preferable to use a hydroxyphenyltriazine ultraviolet absorber having a melting point of 90°C or more in combination with a hydroxyphenyltriazine ultraviolet absorber having a melting point of less than 90°C. The melting point of the hydroxyphenyltriazine ultraviolet absorber having a melting point of less than 90°C is preferably 60°C or more, more preferably 65°C or more.

[0061] The content of the ultraviolet absorber contained in the surface protective layer is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin constituting the surface protective layer. If it is less than 1 part by mass, the performance as an ultraviolet absorber is not sufficiently obtained, while if it is more than 10 parts by mass, bleeding out is likely to occur, and the strength of the surface protective layer may be reduced. From the viewpoint of improving weather resistance, the content of the ultraviolet absorber contained in the surface protective layer is preferably 2 parts by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the resin constituting the surface protective layer, and the upper limit is preferably 8 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 6 parts by mass or less. Thus, in the present invention, since the loss due to bleeding out of the ultraviolet absorber can be suppressed, excellent weather resistance can be obtained even if the amount is smaller than the amount usually mixed.

[0062] The surface protective layer may be composed of either a thermoplastic resin or a curable resin, and from the viewpoint of protecting the decorative material of the present invention and obtaining better surface properties such as stain resistance and abrasion resistance, it is preferable that the surface protective layer is composed of a curable resin, more specifically, a layer composed of a cured product of the curable resin. Alternatively, the surface protective layer may be composed of a combination of a thermoplastic resin and a curable resin.

[0063] Examples of the thermoplastic resin include acrylic resin, polyester resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer resin, polyester urethane resin, and thermoplastic (non-crosslinked) urethane resin.

[0064] As the curable resin, curable resins such as thermosetting resins, two-component curable resins, and ionizing radiation curable resins can be used. From the viewpoint of easily improving the tactile feel and design by the physical uneven shape and visual unevenness, and further from the viewpoint of improving the stain resistance and abrasion resistance of the decorative material of the present invention, ionizing radiation curable resins are preferred. The curable resin preferably does not contain cyclohexyl (meth)acrylate as a monomer component. In other words, the surface protective layer preferably does not contain a cured product of cyclohexyl (meth)acrylate. If the curable resin contains cyclohexyl (meth)acrylate as a monomer component, the surface protective layer may become hard and the processability of the decorative material may decrease, which may cause inconvenience in using the decorative material having the decorative material.

[0065] Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. A curing agent is added to the thermosetting resin as required. Examples of the two-component curing resin include a two-component curing urethane resin having a polyol compound as a base and an isocyanate compound as a curing agent, a two-component curing epoxy resin, a two-component curing urethane-modified acrylic resin, and a two-component curing polyester resin.

[0066] The ionizing radiation curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation, and has an ionizing radiation curable functional group. Here, the ionizing radiation curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, and preferred examples include functional groups having an ethylenic double bond such as (meth)acryloyl group, vinyl group, and allyl group. In addition, the ionizing radiation means electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules, and generally includes ultraviolet rays (UV) or electron beams (EB), but also includes electromagnetic waves such as X-rays and gamma rays, charged particle beams such as alpha rays, and ion beams. Specifically, the ionizing radiation curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable resins.

[0067] As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate monomer is preferable. Here, "(meth)acrylate" means "acrylate or methacrylate". Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the functional group. From the viewpoints of protecting the decorative material and further improving surface properties such as stain resistance and abrasion resistance, acrylate monomers having an acryloyl group are preferred. From the same viewpoint, the number of functional groups is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and particularly preferably 3 or less. These polyfunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0068] Preferred examples of such polymerizable monomers include bifunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy diacrylate, bisphenol A tetrapropoxy diacrylate, and 1,6-hexanediol diacrylate; and trifunctional or higher (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and isocyanuric acid-modified tri(meth)acrylate.

[0069] Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group. Examples of the polymerizable oligomer include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, polycaprolactone urethane (meth)acrylate oligomers, polycaprolactone diol urethane (meth)acrylates, etc. The polymerizable oligomer is preferably a urethane (meth)acrylate oligomer. That is, the surface protective layer preferably contains a cured product of the urethane (meth)acrylate oligomer. The ratio of the cured product of the urethane (meth)acrylate oligomer to the total amount of the resin components contained in the surface protective layer is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 100% by mass. The urethane (meth)acrylate oligomer can be obtained, for example, by reacting a polyol and an organic diisocyanate with a hydroxy (meth)acrylate. In terms of toughness and flexibility, the urethane (meth)acrylate oligomer preferably has an alkylene group derived from the polyol raw material having 1 to 6 carbon atoms, and more preferably has 2 to 4 carbon atoms.

[0070] From the viewpoint of protecting the decorative material and further improving surface properties such as stain resistance and abrasion resistance, the number of functional groups of these polymerizable oligomers is preferably 2 or more, with the upper limit being preferably 8 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 3 or less. From the same viewpoint, the weight average molecular weight is preferably 500 or more, more preferably 1,000 or more, and the upper limit is preferably 80,000 or less, more preferably 50,000 or less. In this specification, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0071] The surface protective layer may contain additives other than the ultraviolet absorber as desired, within the scope of the present invention, such as weather resistance agents such as light stabilizers, ultraviolet shielding agents, abrasion resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropy imparting agents, coupling agents, plasticizers, defoamers, fillers, antiblocking agents, lubricants, solvents, etc. Among these, it is preferable that the surface protective layer contains a weather resistance agent such as a light stabilizer.

[0072] The light stabilizer may be appropriately selected from the light stabilizers exemplified as those usable for the substrate, and examples of the hindered amine light stabilizers that can be preferably used include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate. , methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxy-benzyl) -2-n-butyl malonate, and the like. Among these, preferred are hindered amine light stabilizers derived from decanedioic acid (sebacic acid), such as bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and hindered amine light stabilizers having a reactive functional group, such as 1,2,2,6,6-pentamethyl-4-piperidinyl (meth)acrylate. Among the above, hindered amine-based light stabilizers having a (meth)acryloyl group, and light stabilizers having a reactive functional group other than a (meth)acryloyl group, such as a vinyl group or an allyl group, are more preferred in that they are easy to suppress bleed-out.

[0073] From the viewpoint of protecting the decorative material of the present invention and obtaining better weather resistance, the thickness of the surface protective layer is preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more, and the upper limit is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

[0074] The decorative material of the present invention may further have at least one layer selected from a decorative layer, an adhesive layer A, a resin layer, and a primer layer, depending on the desired performance. These layers are usually provided between the substrate and the surface protective layer, and in consideration of improving weather resistance and design, it is preferable to have all of the above layers. From the same viewpoint, the decorative material of the present invention preferably further has a decorative layer, an adhesive layer A, a resin layer, and a primer layer in this order from the substrate side between the substrate and the surface protective layer, as shown in FIG. 2, that is, the decorative material of the present invention preferably has a substrate, a decorative layer, an adhesive layer A, a resin layer, a primer layer, and a surface protective layer in this order. These layers are described below.

[0075] (Decorative layer 3) The decorative material of the present invention may have a decorative layer. The decorative layer is a layer that imparts a design such as color or pattern to the decorative material of the present invention and improves its design. In the decorative material of the present invention, the decorative layer may be a layer provided between the substrate and the surface protective layer and composed only of a full-colored layer 31 provided to cover the entire surface of the substrate, a layer composed only of a pattern layer 32 provided to cover a portion of the substrate and form a pattern, or a layer combining the full-colored layer 31 and the pattern layer 32 as shown in Fig. 2. From the viewpoint of expressing a higher level of design, the decorative layer is preferably a layer composed of a pattern layer and a full-colored layer. In this case, the decorative material of the present invention preferably has the substrate, the full-colored layer, and the pattern layer in this order, and the pattern layer may be one layer or two or more layers.

[0076] The pattern imparted by the decorative layer is not particularly limited and may be selected as desired, and examples thereof include wood grain patterns, marble patterns (e.g., travertine marble patterns), stone grain patterns imitating the surface of rocks such as the cleavage plane of a granite slab, fabric patterns imitating fabric grain or cloth-like patterns, leather (leather grain) patterns expressing leather grain, tile patterns, brick masonry patterns, hairlines, linear grooves, matte finish, sand grain, letters, symbols, geometric patterns, and patterns combining these, such as marquetry and patchwork. In addition, examples of patterns combining these include artificial stone patterns made by mixing crushed stone such as marble with white cement, hardening it, and polishing it to a marble-like finish, i.e., so-called artificial marble. Although the design demands of consumers change with fashion and the like, wood grain patterns remain popular, and therefore wood grain patterns are preferred for the pattern of the decorative material of the present invention. Wood grain patterns include straight grain patterns, cross grain patterns, figured grain patterns, end grain patterns, etc., and any of these may be used.

[0077] The decorative layer is preferably formed using a resin composition containing at least a binder resin and a colorant such as a pigment and a dye, and can be a suitable mixture of other components used as desired, such as a matting agent, an extender pigment, a stabilizer, an ultraviolet absorber, a light stabilizer, a solvent, etc. In other words, the decorative layer is a layer that contains at least a binder resin and a colorant such as a pigment and a dye, and can contain other components used as desired as described above.

[0078] The binder resin is not particularly limited, and examples thereof include urethane resin, acrylic polyol resin, acrylic resin, polyester resin, alkyd resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, nitrocellulose resin (nitrocellulose), cellulose acetate resin, and other resins. In addition, curable resins such as two-component curable resins that use various polyols such as acrylic polyols as the main component and various isocyanates as the curing agent may be used. These may be used alone or in combination.

[0079] Examples of colorants such as pigments and dyes that can be used in the decorative layer include the same colorants as those that can be used in the base material described above, and they may be selected appropriately from among these depending on the desired pattern.

[0080] In the present invention, from the viewpoint of further improving the design, it is preferable that the decorative layer contains a matting agent among the other components that are used as desired. Examples of the matting agent include inorganic fillers such as silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and silicic acid fine powder; and organic fillers such as acrylic resin, urethane resin, nylon resin, polypropylene resin, and urea resin.

[0081] By including a matte agent in the decorative layer, the decorative layer has a lower gloss, making it possible to achieve a design expression having a visual uneven feel due to differences in gloss. For example, in the wood grain pattern exemplified as a preferred pattern, the wood grain pattern has a lower gloss (matte or low gloss) vascular part, a higher gloss (glossy or high gloss) spring wood part, and an even higher gloss autumn wood part (shiny part). In the decorative layer, by combining multiple pattern layers such as a pattern layer forming a lower gloss vascular part, a pattern layer forming a higher gloss spring wood part, and a pattern layer forming an even higher gloss autumn wood part, it is possible to form a highly designed pattern. In this case, for example, by not containing a matting agent in the full color layer or by containing less of the matting agent than in the pattern layer, it is also possible to increase the gloss difference with the pattern layer and improve the design.

[0082] The volume average particle size of these matting agents is preferably from 0.5 to 25 μm, more preferably from 1 to 15 μm, and further preferably from 3 to 10 μm. The content of the matting agent relative to 100 parts by mass of the binder resin in the decorative layer is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, and the upper limit is usually 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. When the content of the matting agent is within the above range, the decorative layer can be visually recognized as a layer with a lower gloss, so that it is possible to improve the visual unevenness due to the gloss difference, and the coating performance is improved without the thixotropy of the resin composition becoming extremely high, resulting in improved design.

[0083] From the viewpoint of improving weather resistance, the decorative layer may contain weather resistance agents such as an ultraviolet absorber, a light stabilizer, etc. Examples of the ultraviolet absorber and the light stabilizer include the same ones that can be contained in the base material and the surface protective layer, and they may be appropriately selected from these depending on the desired performance.

[0084] The thickness of the decorative layer may be appropriately selected depending on the desired pattern, and is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, with the upper limit being preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

[0085] (Resin layer) The resin layer is a layer provided between the surface protective layer and the substrate layer, and by providing the resin layer, it is expected that the surface properties of the decorative material of the present invention, such as stain resistance and abrasion resistance, can be improved. In addition, when the decorative material of the present invention has a decorative layer, by providing the resin layer between the decorative layer and the surface protective layer, the layer also has the function of protecting the decorative layer.

[0086] Examples of the resin constituting the resin layer include polyolefin resin, polyester resin, acrylic resin, polycarbonate resin, polyurethane resin, polystyrene resin, vinyl chloride resin, vinyl acetate resin, etc. Among them, from the viewpoint of improving surface properties, polyolefin resin and polyester resin are preferred, and polyolefin resin is more preferred. Examples of the polyolefin resin include the resins exemplified as those that can constitute the base sheet, and among them, polypropylene resin is preferred. In addition to improving the surface characteristics, the moisture permeability described below is easily within a predetermined range, and from the viewpoint of improving the long-term adhesion as well as the application suitability, among the above, polyolefin resins and vinyl chloride resins are preferred, polyolefin resins are more preferred, polyethylene resins containing ethylene as a constituent unit, polypropylene resins containing propylene as a constituent unit are preferred, and polypropylene resins are preferred. These polyolefin resins and vinyl chloride resins are the same as those described as the resin of the resin substrate.

[0087] The resin layer is preferably transparent from the viewpoint of making the decorative layer more clearly visible. Here, the term "transparent" includes not only colorless transparency, but also colored transparency and translucency. In addition, when the resin layer is colored, the colorants exemplified as the colorants that can be used in the decorative layer above are preferably used as the colorant, and it is preferable to use a colorant of the same color as the decorative layer.

[0088] The resin layer may contain additives as necessary, and for example, it is preferable to use weathering agents such as ultraviolet absorbers, light stabilizers, etc., among which, those exemplified as additives that can be added to the above-mentioned base material and surface protective layer are used. The amount of additives added is not particularly limited, and can be appropriately set depending on the required properties, etc.

[0089] From the viewpoints of protecting the decorative layer and improving surface properties, the thickness of the resin layer is preferably from 10 μm to 150 μm, more preferably from 30 μm to 120 μm, and even more preferably from 50 μm to 100 μm. Moreover, from the viewpoints of protecting the decorative layer and obtaining excellent surface properties, it is preferable that the thickness of the resin layer is thicker than that of the substrate.

[0090] Like the substrate, the resin layer may be subjected to a surface treatment such as a physical surface treatment or a chemical surface treatment on one or both sides thereof in order to improve interlayer adhesion with other layers. In order to improve the interlayer adhesion between the resin layer and other layers, a primer layer may be formed on one or both sides of the resin layer. The primer layer will be described later.

[0091] (Adhesive layer A) The adhesive layer A is a layer provided between the surface protective layer and the substrate layer, and is preferably provided when the above-mentioned resin layer is provided from the viewpoint of improving adhesion between the resin layer and the substrate or decorative layer.

[0092] Examples of adhesives used in the adhesive layer A include urethane adhesives, acrylic adhesives, epoxy adhesives, and rubber adhesives, among which urethane adhesives are preferred in terms of adhesive strength. Examples of urethane adhesives include adhesives that utilize two-liquid curing urethane resins containing various polyol compounds such as polyether polyols, polyester polyols, and acrylic polyols, and curing agents such as the above-mentioned various isocyanate compounds. In addition, acrylic-polyester-vinyl chloride-vinyl acetate resins and the like are also suitable adhesives that easily exhibit adhesiveness by heating and can maintain adhesive strength even when used at high temperatures.

[0093] From the viewpoint of efficiently improving the adhesion between the resin layer and the substrate or the decorative layer, the thickness of the adhesive layer A is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less.

[0094] (Primer layer 6) The primer layer is a layer provided mainly to improve the interlayer adhesion of each layer constituting the decorative material of the present invention, and is also called an easy-adhesion layer. For example, by providing the primer layer between a resin layer and a surface protective layer as shown in FIG. 2, the interlayer adhesion of these layers can be improved. FIG. 2 shows an embodiment in which the primer layer is provided between a decorative layer and a surface protective layer, but the present invention is not limited to this, and the primer layer can also be provided between a substrate and a decorative layer, and when an adherend to be described later is further provided, a primer layer (also called a "back primer layer") can be provided on the surface of the substrate opposite to the surface on which the surface protective layer is provided, from the viewpoint of improving adhesion.

[0095] To form the primer layer, it is preferable to use a resin composition containing at least a binder resin, and it is also possible to use a suitable mixture of other components used as desired, such as an extender pigment, a stabilizer, an ultraviolet absorber, a light stabilizer, a solvent, etc. In other words, the primer layer is a layer that contains at least a binder resin, and can contain other components used as desired as described above.

[0096] Examples of the binder resin used in forming the primer layer include the same binder resins as those that can be used in forming the decorative layer, and any one of these may be appropriately selected as desired.

[0097] From the viewpoint of efficiently improving interlayer adhesion, the thickness of the primer layer is preferably 0.1 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, and the upper limit is preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 5 μm or less.

[0098] (Characteristics of decorative materials) The decorative material of the present invention has a moisture permeability of 0.75 g / m 2 ·45g / m for 24 hours or more 2 ·24h or less is preferable. Here, the moisture permeability is the moisture permeability of a decorative material consisting of layers other than the adhesive layer B and the adherend described below, i.e., a decorative material having at least a substrate and a surface protective layer, and preferably having other layers such as a decorative layer, an adhesive layer A, a resin layer, and a primer layer. By having such moisture permeability, the application suitability, long-term adhesion, processability, and weather resistance (particularly, suppression of appearance change when exposed to ultraviolet rays in sunlight) become even more excellent. Specifically, by setting the moisture permeability of the decorative material within the above range, the initial adhesion strength during the application process is improved, and the occurrence of so-called springback, in which the end surface of the decorative material peels off due to insufficient initial adhesion strength during application, can be suppressed, improving application efficiency. On the other hand, in the case of a decorative material in which an adherend is provided via an adhesive layer B, deterioration of the adhesive layer B, which is mainly used to provide the adherend, can be suppressed, and peeling due to the deterioration is suppressed, and peeling does not occur even after long-term use, improving long-term adhesion. In other words, by setting the moisture permeability of the decorative material of the present invention within a specific range, it is possible to improve application suitability by improving the initial adhesion strength during the application process, and to improve long-term adhesion that does not peel off even after long-term use. The effect of long-term adhesion by setting the moisture permeability in the above range is obtained when the content of all ultraviolet absorbents in the surface protective layer is 1 part by mass or more and 10 parts by mass or less relative to 100 parts by mass of resin, and the content of ultraviolet absorbents with a melting point of 90° C. or more relative to the total amount of ultraviolet absorbents is 45% by mass or more. In other words, if the surface protective layer does not have the above-mentioned configuration, even if the moisture permeability is within the above range, the substrate and adhesive layer will deteriorate due to the action of ultraviolet rays, such as scission of molecular chains of the resin and photochemical reactions, which will not only reduce the mechanical strength near the adhesive interface, but also increase the moisture permeability of the decorative material, making it impossible to achieve good long-term adhesion. On the other hand, even if the total content of the ultraviolet absorbers contained in the surface protective layer and the content ratio of the ultraviolet absorbers with a melting point of 90°C or higher to the total amount of the ultraviolet absorbers are optimized within the above-mentioned ranges, the moisture permeability of the decorative material is 45 g / m 2 If it exceeds 24 hours, not only will long-term adhesion decrease, but weather resistance in terms of appearance will also decrease. This is thought to be due to the fact that "as the moisture permeability of the cosmetic material increases, the permeability of the UV absorber contained in the cosmetic material also increases, making the UV absorber more likely to bleed out" and "with long-term outdoor exposure, the amount of UV absorber in the cosmetic material decreases more, gradually decreasing the UV resistance of the cosmetic material."

[0099] The effect of keeping the moisture permeability within the above range will be described in more detail below. 2 If the adhesive layer is applied to an adherend via an adhesive layer for 24 hours or more, the occurrence of poor adhesion due to poor curing of the adhesive used in the adhesive layer is suppressed when the decorative material is applied to the adherend, improving the initial adhesive strength and improving application suitability. This effect of improving initial adhesion strength is particularly noticeable when the decorative sheet is applied to the adherend via an adhesive layer formed of a urethane resin adhesive, such as a moisture-curing and hot-melt urethane resin adhesive, which requires moisture for initial adhesion. On the other hand, if the moisture permeability is 45 g / m 2If the moisture permeability is 24 hours or less, deterioration of the substrate due to moisture in the air, wind and rain, and even ultraviolet rays from sunlight, as well as deterioration due to hydrolysis of the adhesive used in the adhesive layer, can be suppressed during long-term use, so that peeling between the decorative sheet and the adherend is less likely to occur, improving long-term adhesion without peeling even after long-term use. Such an effect of improving long-term adhesion strength is particularly evident when the decorative sheet is attached to the adherend via an adhesive layer formed of a urethane resin-based adhesive such as a moisture-curing and hot-melt urethane resin, which has the property of being deteriorated by hydrolysis due to moisture. Therefore, by setting the moisture permeability within the above range, the decorative sheet of the present invention can simultaneously improve the application suitability due to high initial adhesion strength during the application process and the long-term adhesion without peeling even after long-term use.

[0100] In order to improve long-term adhesion as well as application suitability, the moisture permeability is set at 1.2 g / m 2 24 hours or more, preferably 1.5g / m 2 24h, more preferably 2.5g / m 2 24h or more, even more preferably 4.5g / m 2 24h or more, with the upper limit preferably being 40g / m 2 24h or less, preferably 35g / m 2 24 hours or less, more preferably 30 g / m 2 24h or less, even more preferably 20g / m 2 Less than 24 hours. In the present invention, the moisture permeability can be adjusted, as described above, mainly by the type of material constituting the substrate, and, if a resin layer is provided, the type of material constituting the resin layer.

[0101] In the present invention, by having the moisture permeability in the above-mentioned predetermined range, the initial adhesive strength of the adhesive layer B that bonds the decorative material having at least a substrate and a surface protective layer on the outermost surface, and preferably having a decorative layer, an adhesive layer A, a resin layer, and a primer layer in this order between the substrate and the surface protective layer, to the adherend is improved, and deterioration due to moisture in the air, wind and rain, etc. from the surface protective layer side of the decorative material is suppressed. Therefore, when the decorative material of the present invention has the adherend 11 and the adhesive layer B12, it goes without saying that taking into account the effect obtained by having the moisture permeability in the above-mentioned predetermined range, the moisture permeability in the above-mentioned predetermined range means the moisture permeability of the decorative material having a layer structure excluding the adherend 11 and the adhesive layer B12.

[0102] (Method of manufacturing decorative materials) The manufacturing method of the decorative material of the present invention will be described using as an example a decorative material shown in FIG. 2, which is one of the preferred embodiments of the decorative material of the present invention, and which has, in that order, a base material, a decorative layer composed of an overall colored layer and a picture layer, an adhesive layer A, a resin layer, a primer layer, and a surface protective layer.

[0103] The decorative material of the present invention can be produced, for example, by providing a full-surface colored layer and a pattern layer on a substrate, and then sequentially going through the steps of forming a decorative layer, forming a resin layer, forming a primer layer, and forming a surface protective layer so as to cover the primer layer.

[0104] In the process of forming the decorative layer, the resin composition used for forming the overall colored layer is first applied to the substrate to form the desired overall colored layer, and then the resin composition used for forming the design layer is applied to form the design layer. The resin composition is applied by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating, preferably by gravure printing.

[0105] When the substrate is subjected to a surface treatment, it may be performed before forming the overall colored layer, and when a primer layer is provided, it may be performed before forming the overall colored layer. When a back primer layer is provided on the surface (back surface) of the substrate opposite to the surface on which the decorative layer is provided, it may be provided either before or after forming the decorative layer.

[0106] The process of providing the resin layer can be carried out by forming the decorative layer, applying an adhesive to the decorative layer as necessary to form adhesive layer A, and then laminating the resin composition constituting the resin layer by bonding and pressing using a method such as extrusion lamination, dry lamination, wet lamination, or thermal lamination.

[0107] Next, in the process of forming a primer layer so as to cover the resin layer, the resin composition used to form the primer layer can be applied to the surface of the resin layer, and the application method can be appropriately selected from the application methods of the resin composition that forms the decorative layer.

[0108] The surface protective layer is formed by applying a curable resin composition, which is used to form the surface protective layer and which preferably contains a liquid uncured product of a curable resin, to the entire surface of the decorative material, and curing it as necessary. As a method for applying the uncured resin composition containing a liquid uncured material, any of the known methods exemplified as the method for applying the resin composition for the decorative layer may be used. In addition, the method for curing the uncured resin composition containing the liquid uncured product of the curable resin may be selected according to the type of the curable resin contained in the uncured resin composition. For example, when the uncured resin composition is a resin composition containing the liquid uncured product of the thermosetting resin, the uncured resin composition may be cured by carrying out a heat treatment according to the thermosetting resin used.

[0109] When an uncured resin composition containing a liquid uncured product of an ionizing radiation resin is used, the uncured resin layer formed by coating the uncured resin composition may be irradiated with ionizing radiation such as electron beams or ultraviolet rays to form a cured product. When an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected depending on the resin used and the thickness of the layer, but it is usually preferable to cure the uncured resin layer at an acceleration voltage of about 70 to 300 kV. The exposure dose is preferably an amount at which the crosslink density of the ionizing radiation curable resin is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). The electron beam source is not particularly limited, and various electron beam accelerators such as Cockcroft-Walton type, Van de Graff type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. can be used. When ultraviolet light is used as the ionizing radiation, ultraviolet light having a wavelength of 190 to 380 nm is emitted. There are no particular limitations on the source of ultraviolet light, and examples of the source include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps.

[0110] After forming the surface protective layer, if necessary, an uneven shape can be imparted by hot pressing with an embossing plate. By forming an uneven shape, a tactile sensation is imparted and the design of the decorative material of the present invention is improved. In addition, for example, when a wood grain pattern is formed in the decorative layer, it is possible to express a high texture and an excellent design by harmonizing the duct parts in the wood grain pattern with the recesses of the uneven shape.

[0111] The conditions for the hot and pressure molding may be appropriately adjusted depending on the type of curable resin used, and are not particularly limited, but are usually a temperature of 100 to 200° C., a pressure of 0.1 to 9.8 MPa, and a time of 10 seconds to 120 minutes.

[0112] (Use as cosmetic material) The decorative material of the present invention is a decorative material having excellent weather resistance, and can be used for various purposes as it is, or by laminating it to an adherend via adhesive layer B, or by subjecting it to a predetermined molding process or the like. For example, it is laminated on adherends such as flat plates, curved plates, and other plate materials, sheets (or films), and the like, and is suitably used, for example, as interior components for buildings such as walls, ceilings, and floors, or exterior components such as exterior walls, roofs, eaves ceilings, fences, and gates, as fittings or fixtures such as various doors such as window frames and entrance doors, handrails, baseboards, moldings, window frames, door frames, and moldings, as well as general furniture such as chests of drawers, shelves, and desks, kitchen furniture such as dining tables and sinks, or surface decorative panels for cabinets for low-electricity products and office automation equipment, interior or exterior components for vehicles, etc. The decorative material of the present invention is also suitably used for the above-mentioned various components, and especially for components used in environments exposed to direct sunlight.

[0113] 3, the decorative material of the present invention can have an adherend 11 via an adhesive layer B 12 on the side of the substrate 1 opposite to the side having the surface protective layer 2. In this case, if the substrate is in the form of a sheet (or film), that is, if the decorative material having the substrate, the surface protective layer, the decorative layer which is provided as necessary, the adhesive layer A, the resin layer, and the primer layer is in the form of a sheet (or film), it is easy to laminate with the adherend via the adhesive layer B. As described above, when the decorative material of the present invention has an adhesive layer B and an adherend, the moisture permeability of the decorative material of the present invention is the moisture permeability of the layered structure of the decorative material excluding the adhesive layer B and the adherend. Therefore, the moisture permeability of a decorative material (also called a "decorative sheet") having a substrate, a surface protective layer, a decorative layer that is provided as necessary, an adhesive layer A, a resin layer, and a primer layer, in which the substrate is a sheet (or film), falls within the above-mentioned specified range. In addition, with regard to the "decorative sheet", the decorative material having the decorative sheet, the adhesive layer B, and the adherend is also called a decorative member.

[0114] Examples of the adherend include wood members used as plate materials and three-dimensional articles, such as wood veneers made of various wood materials such as cedar, cypress, pine, and lauan, wood plywood, particle boards, and wood fiberboards such as MDF (medium density fiberboard); metal members used as plate materials and steel plates, three-dimensional articles, and sheets, such as iron and aluminum; ceramic members used as plate materials and three-dimensional articles, such as glass, ceramics such as porcelain, non-cement ceramic materials such as gypsum, and non-ceramic ceramic materials such as ALC (aerated lightweight concrete) boards; resin members used as plate materials, three-dimensional articles, and sheets, such as acrylic resins, polyester resins, polystyrene resins, polypropylene and other polyolefin resins, ABS (acrylonitrile-butadiene-styrene copolymer) resins, phenolic resins, vinyl chloride resins, cellulose resins, and rubber. These members can be used alone or in combination of two or more.

[0115] The adhesive used in the adhesive layer B is not particularly limited, and known adhesives can be used. For example, preferred adhesives include moisture-curing adhesives, anaerobic-curing adhesives, dry-curing adhesives, UV-curing adhesives, heat-sensitive adhesives (e.g., hot-melt adhesives), and pressure-sensitive adhesives. Considering compatibility with the decorative material of this embodiment having a predetermined water vapor permeability, ease of handling, and the like, moisture-curing adhesives and heat-sensitive adhesives are preferred. In particular, heat-sensitive adhesives are preferred in that the adhesive strength rises to a saturated state at the same time as the molten liquid adhesive layer is cooled and solidified. In addition, by using a moisture-curing adhesive in combination with the decorative material of this embodiment, it is possible to come into contact with moderate moisture during the construction process, making it easier to obtain the initial adhesion strength of the adhesive used in the adhesive layer, and on the other hand, since there is no contact with excessive moisture, the decrease in adhesion due to deterioration associated with hydrolysis is suppressed, and as a result, it is easier to obtain long-term adhesion as well as excellent construction suitability. It is also preferred in terms of ease of handling, etc.

[0116] Examples of the resin used in the adhesive constituting the adhesive layer B include acrylic resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acrylic copolymer resin, polyester resin, polyamide resin, etc., which can be used alone or in combination of two or more kinds. In addition, two-component curing type polyurethane adhesives and polyester adhesives using an isocyanate compound or the like as a curing agent can also be used. A pressure-sensitive adhesive may also be used for the adhesive layer B. The pressure-sensitive adhesive may be appropriately selected from acrylic, urethane, silicone, rubber, and other pressure-sensitive adhesives.

[0117] One of the adhesives preferably used in this embodiment is a moisture-curing adhesive, the resin system of which is a urethane resin, and which contains a prepolymer having an isocyanate group at the molecular end as an essential component. The prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at each of both molecular ends, and is in a solid thermoplastic resin state at room temperature. Examples of such polyisocyanate prepolymers include those using a polyester polyol that is crystalline and solid at room temperature as the polyol component, and a polyisocyanate made of 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, or the like as the polyisocyanate component.

[0118] The adhesive layer B can be formed by coating and drying the above-mentioned resin in a coatable form such as a solution or emulsion by means of gravure printing, screen printing, or reverse coating using a gravure plate. The thickness of the adhesive layer B is not particularly limited, but from the viewpoint of obtaining excellent adhesiveness, it is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, and even more preferably from 10 μm to 30 μm.

[0119] The decorative material having the adherend can be cut as desired, and the surface or end of the wood can be decorated as desired, such as by groove processing or chamfering, using a cutting machine such as a router or cutter. It can be suitably used for various applications, such as interior components for buildings, such as walls, ceilings, and floors, exterior components for exterior walls, roofs, eaves ceilings, fences, and gates, fittings or fixtures, such as various doors, such as window frames and entrance doors, handrails, baseboards, moldings, window frames, door frames, and moldings, general furniture, such as chests, shelves, and desks, kitchen furniture, such as dining tables and sinks, surface decorative panels for cabinets for low-electricity products and office automation equipment, interior and exterior components for vehicles, and the like.

[0120] [Resin composition for forming surface protective layer] The resin composition for forming a surface protective layer of this embodiment is a resin composition characterized in that it contains a resin constituting a surface protective layer and an ultraviolet absorber including an ultraviolet absorber having a melting point of 90° C. or higher, the content of the ultraviolet absorber relative to 100 parts by mass of the resin is 1 part by mass or more and 10 parts by mass or less, and the content of the ultraviolet absorber having a melting point of 90° C. or higher relative to the total amount of the ultraviolet absorber is 45 mass% or more. The resin constituting the surface protective layer, the ultraviolet absorber including an ultraviolet absorber having a melting point of 90° C. or higher, and other components that may be contained, the contents, etc., contained in the resin composition for forming a surface protective layer of this embodiment are the same as those described for the resin composition that can be used to form the surface protective layer of the above-mentioned decorative material.

[0121] The resin composition for forming a surface protective layer according to the present embodiment can suppress bleeding out of the ultraviolet absorber and exhibit excellent weather resistance even when the decorative material is used under severe environments, particularly under severe temperature conditions. In addition, the resin composition for forming a surface protective layer according to the present embodiment can exhibit excellent performance in terms of surface properties such as contamination resistance and abrasion resistance, which are required for the surface protective layer. EXAMPLES

[0122] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples in any way.

[0123] (Measurement method) Regarding the melting point of the ultraviolet absorbent used in the examples and comparative examples, the ultraviolet absorbent was placed in a glass container and placed in an oven. When the ultraviolet absorbent started to liquefy after the oven was heated to a specified temperature for one hour, the specified temperature was regarded as the melting point.

[0124] (Evaluation method) 1-1. Weather resistance evaluation The decorative materials obtained in the examples and comparative examples were subjected to an accelerated weathering test using a metal halide lamp (MWOM) for 1,200 hours, after which the appearance was visually observed from the surface protective layer side, and the appearance of the decorative materials was visually evaluated according to the following criteria. (Evaluation Criteria) 1: No change in appearance was observed. 2: A slight change in appearance was observed, but it was not significant enough for practical use. 3: A significant change in appearance was observed. 4: Significant changes in appearance were observed. 1-2. Measurement of moisture permeability The moisture permeability of the decorative materials obtained in the Examples and Comparative Examples was measured in accordance with the moisture permeability test method (cup method) for moisture-proof packaging materials specified in JIS Z0208:1976. 1-3.Evaluation of suitability for construction The decorative materials obtained in the examples and comparative examples and the adherend on a flat plate with a width of 25 mm (material: polyvinyl chloride (PVC)) were attached via a 50 μm thick adhesive layer formed by melting a moisture-curing and hot-melt type urethane resin adhesive (a polyurethane prepolymer having an isocyanate group in the molecule, "1308.20 (product name)", manufactured by TAKA Co., Ltd.) at 120 ° C., and the adhesive layer was cooled and solidified at room temperature of 23 ° C., and left in an environment of 90 ° C. for 1 hour to prepare a sample. A peeling test was performed in a temperature environment of 25 ° C. using a Tensilon universal material testing machine ("Tensilon RTC-1250A (product name)", manufactured by Orientec Co., Ltd.) under the conditions of a tensile speed of 10 mm / min, a peeling direction of 90 °, and a chuck distance of 30 mm, and the peeling strength was measured as the initial adhesive strength and evaluated according to the following criteria. If the evaluation is 2 or higher, the evaluation of the suitability for application is passed. 1: Peeling strength was 1.0 N / mm or more. 2: The peeling strength was 0.5 N / mm or more and less than 1.0 N / mm. 3: The peeling strength was less than 0.5 N / mm. 1-4. Evaluation of long-term adhesion The samples prepared in "1-3. Evaluation of application suitability" above were left in a 70°C 90% RH humid heat environment for 6 weeks, and then a peeling test was carried out in a 25°C temperature environment using a Tensilon universal material testing machine ("Tensilon RTC-1250A (product name)", manufactured by Orientec Co., Ltd.) at a tensile speed of 50 mm / min and a peeling direction of 90°. The peeling strength was measured and evaluated according to the following criteria. A rating of 2 or higher was deemed to be acceptable for the evaluation of long-term adhesion. 1: Peeling strength was 2.0 N / mm or more. 2: The peeling strength was 1.0 N / mm or more and less than 2.0 N / mm. 3: The peeling strength was less than 1.0 N / mm. 1-5. Processing suitability When laminating the samples in the above "1-3. Evaluation of workability," the decorative material was visually checked for lifting at the bent portion (bending angle: 1 mmR) and evaluated according to the following criteria. If the evaluation was 2 or higher, the workability was acceptable. 1: No floating was observed at all. 2: Floating was barely observed. 3: Lifting was observed and peeling occurred.

[0125] [Example 1] A decorative layer was formed on one side of a substrate (a 60 μm-thick colored polypropylene resin sheet) that had been subjected to corona discharge treatment on both sides, using a printing ink made of a two-component curing acrylic-urethane resin, and then an adhesive layer A made of a 3 μm-thick urethane resin-based adhesive was formed on the decorative layer. Next, a polypropylene-based resin was hot-melt extruded onto the adhesive layer A using a T-die extruder to form a transparent resin layer having a thickness of 80 μm.

[0126] After subjecting the surface of the resin layer to a corona discharge treatment, a resin composition obtained by mixing a composition consisting of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol with hexamethylene diisocyanate in a mass ratio of 100:5 was applied onto the resin layer and dried to form a primer layer having a thickness of 4 μm. Next, a resin composition containing 2 parts by mass of ultraviolet absorber 1 (trade name: Adeka STAB LA-46, hydroxyphenyl triazine-based ultraviolet absorber, manufactured by ADEKA Corporation), 2 parts by mass of ultraviolet absorber 2 (trade name: Tinuvin 1600, hydroxyphenyl triazine-based ultraviolet absorber, manufactured by BASF), and 3 parts by mass of hindered amine light stabilizer (trade name: Tinuvin 123, manufactured by BASF) was applied onto the primer layer, and the ionizing radiation curable resin composition was cured by irradiating with an electron beam to form a surface protective layer having a thickness of 5 μm. The weather resistance of the obtained decorative material was evaluated by the above method. The evaluation results are shown in Table 1.

[0127] [Examples 2 to 6] The decorative materials of Examples 2 to 6 were prepared in the same manner as in Example 1, except that the type and amount of the ultraviolet absorbing agent in the surface protective layer were as shown in Table 1. The weather resistance of the obtained decorative materials was evaluated by the above-mentioned method. The evaluation results are shown in Table 1.

[0128] [Comparative Examples 1 to 5] The decorative materials of Comparative Examples 1 to 5 were prepared in the same manner as in Example 1, except that the type and amount of the ultraviolet absorbing agent in the surface protective layer were as shown in Table 1. The weather resistance of the obtained decorative materials was evaluated by the above-mentioned method. The evaluation results are shown in Table 1.

[0129] [Table 1]

[0130] The ultraviolet absorbents in the above table are as follows. LA-46: Trade name: Adeka STAB LA-46, manufactured by ADEKA Corporation, hydroxyphenyltriazine-based ultraviolet absorber (a compound represented by the above general formula (2)), melting point: 106°C. Tinuvin 1600: BASF, hydroxyphenyltriazine-based ultraviolet absorber (a compound represented by the above general formula (3)), melting point: 120°C Tinuvin 479: BASF, hydroxyphenyltriazine UV absorber, melting point: 70°C

[0131] From the results in Table 1, it was confirmed that the decorative material of the present invention has excellent weather resistance even under extremely severe conditions such as 1200 hours of accelerated weather resistance testing using a metal halide lamp (MWOM). On the other hand, the decorative materials of Comparative Examples 1 to 4, in which the content of ultraviolet absorbers with a melting point of 90°C or more is low relative to the total amount of ultraviolet absorbers used in the surface protective layer, were not excellent in terms of weather resistance even though they used a hydroxyphenyltriazine ultraviolet absorber (Tinuvin 479). Also, the decorative material of Comparative Example 5, in which the content of ultraviolet absorbers in the surface protective layer is too high, was not excellent in terms of weather resistance even though it used an ultraviolet absorber with a melting point of 90°C or more, because the amount of ultraviolet absorbers that could be held in the surface protective layer was too large, the crosslink density of the surface protective layer was not sufficient and sufficient durability could not be ensured, and bleedout occurred, causing deterioration of the appearance, which could be the starting point of deterioration. From the above results, it was confirmed that the decorative material of the present invention has extremely excellent weather resistance even when used in a relatively small amount of ultraviolet absorber, even under the extremely harsh conditions of an accelerated weathering test using a metal halide lamp (MWOM) for 1,200 hours.

[0132] [Examples 7 to 10] Decorative materials of Examples 7 to 10 were produced in the same manner as in Example 1, except that the substrate and resin layer in Example 1 were replaced with those shown in Table 2. Note that Example 10 does not have adhesive layer A and resin layer. The decorative materials of Examples 7 to 10 and Reference Examples 1 and 2 described later were evaluated for weather resistance, application suitability, long-term adhesion, and processing suitability by the above-mentioned methods. In addition, the moisture permeability of the obtained decorative materials was measured. The evaluation results and measurement results are shown in Table 2.

[0133] [Reference examples 1~2] Decorative materials of Reference Examples 1 and 2 were produced in the same manner as in Example 1, except that the substrate and resin layer in Example 1 were changed to those shown in Table 2. Note that Reference Example 2 does not have adhesive layer A and a resin layer.

[0134] [Table 2]

[0135] The materials and thicknesses of the substrates and resin layers in Table 2 above are as follows: Polyolefin 1: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 80 μm, crystallinity: 70%) Polyolefin 2: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 60 μm, crystallinity: 50%) Polyolefin 3: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 60 μm, crystallinity: 40%) Polyolefin 4: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 100 μm, crystallinity: 70%) PVC1: Polyvinyl chloride resin sheet (thickness: 120 μm) It was produced by extrusion molding a resin composition in which 38 parts by mass of a phthalate ester plasticizer (undecyl phthalate (DUP)) was added as a plasticizer to 100 parts by mass of polyvinyl chloride resin. PVC2: Polyvinyl chloride resin sheet (thickness: 120 μm) It was produced by extrusion molding a resin composition in which 33 parts by mass of a phthalate ester plasticizer (undecyl phthalate (DUP)) was added as a plasticizer to 100 parts by mass of polyvinyl chloride resin. Polyolefin A: Polypropylene resin (thickness: 80 μm) Polyolefin B: Polypropylene resin (thickness: 40 μm) Polyolefin C: Polypropylene resin (thickness: 100 μm)

[0136] From the results in Table 2, it was confirmed that the decorative material of the present invention has a specified moisture permeability, and therefore has excellent weather resistance as well as excellent coating suitability, and that the decorative component of this embodiment using this decorative material has excellent long-term adhesion. [Industrial Applicability]

[0137] The decorative material of the present invention has excellent weather resistance, and therefore can be suitably used as interior components of buildings such as walls, ceilings, and floors, or exterior components such as exterior walls, roofs, eaves ceilings, fences, and gates, as fittings or fixtures such as various doors such as window frames and entrance doors, handrails, baseboards, moldings, window frames, door frames, and moldings, as well as general furniture such as chests of drawers, shelves, and desks, kitchen furniture such as dining tables and sinks, or surface decorative panels for cabinets of low-electricity products and office automation equipment, interior or exterior components of vehicles, etc. The decorative material of the present invention can also be suitably used for the above-mentioned various components, and particularly for components used in environments exposed to direct sunlight. [Explanation of symbols]

[0138] 10: Cosmetic materials 1: Base material 2: Surface protective layer 3: Decorative layer 31: Full colored layer 32: Picture layer 4: Adhesive layer A 5: Resin layer 6: Primer layer 11: Adherent 12: Adhesive layer B

Claims

1. A decorative material having at least a substrate and a surface protective layer on the outermost surface, The surface protective layer contains an ultraviolet absorbing agent, the content of the ultraviolet absorber relative to 100 parts by mass of a resin forming the surface protective layer is 1 part by mass or more and 10 parts by mass or less; the content of an ultraviolet absorber represented by the following general formula (1) having a melting point of 90° C. or more, as measured by the following method, relative to the total amount of the ultraviolet absorbers is 45 mass% or more, and the resin composition containing a resin that forms the surface protective layer contains a (meth)acrylate oligomer having two or more (meth)acryloyl groups and having a weight average molecular weight of 500 or more and 80,000 or less; Cosmetic materials. 【Chemistry 1】 In general formula (1), R １１ is a divalent organic group or a single bond, R １２ is a monovalent organic group, -C(=O)OR １５ an ester group represented by the formula: -O-C(=O)R １６ or an acyloxy group represented by -O-R １７ R is an organyloxy group represented by the formula １３ , R １４ , R １５ , R １６ and R １７ are each independently a hydrogen atom or a monovalent organic group, １１ and n １２ are each independently an integer of 1 to 5. １３ and R １４ When there are multiple, they may be the same or different. (Method of measuring melting point) The ultraviolet absorbent was placed in a glass container and allowed to stand in an oven. The oven was heated to a predetermined temperature for 1 hour, and the predetermined temperature at which the ultraviolet absorbent began to liquefy was recorded as the melting point.

2. 2. The decorative material according to claim 1, wherein all of the ultraviolet absorbing agents contained in the surface protective layer have a hydroxyphenyltriazine structure.

3. 3. The decorative material according to claim 1, wherein the surface protective layer is a cured product of a curable resin composition containing a curable resin and an ultraviolet absorber.

4. The decorative material according to any one of claims 1 to 3, wherein the surface protective layer further comprises a light stabilizer.

5. The decorative material according to any one of claims 1 to 4, further comprising, between the substrate and the surface protective layer, a decorative layer, an adhesive layer A, a resin layer and a primer layer, in that order from the substrate side.

6. The moisture permeability measured in accordance with the moisture permeability test method for moisture-proof packaging materials (cup method) specified in JIS Z0208:1976 is 0.75 g / m ２ ・45g / m for 24 hours or more ２ The decorative material according to any one of claims 1 to 5, which has a shelf life of 24 hours or less.

7. The decorative material according to any one of claims 1 to 6, further comprising an adherend via an adhesive layer B on the surface of the substrate opposite to the surface protective layer.

8. 8. The decorative material according to claim 7, wherein the adhesive layer B is made of a urethane-based adhesive.

9. 9. The decorative material according to claim 8, wherein the urethane adhesive is a moisture-curing adhesive.

10. The decorative material according to any one of claims 7 to 9, wherein the adherend is a metal member or a resin member.

11. A resin composition for forming a surface protective layer, comprising: a resin constituting a surface protective layer; and an ultraviolet absorber including an ultraviolet absorber represented by the following general formula (1) having a melting point of 90°C or higher measured by the following method, wherein the content of the ultraviolet absorber relative to 100 parts by mass of the resin is 1 part by mass or more and 10 parts by mass or less, and the content of the ultraviolet absorber having a melting point of 90°C or higher relative to the total amount of the ultraviolet absorbers is 45 mass% or more, and the resin composition including the resin forming the surface protective layer includes a (meth)acrylate oligomer having two or more (meth)acryloyl groups and having a weight average molecular weight of 500 or more and 80,000 or less. 【Chemistry 2】 In general formula (1), R １１ is a divalent organic group or a single bond, R １２ is a monovalent organic group, -C(=O)OR １５ an ester group represented by the formula: -O-C(=O)R １６ or an acyloxy group represented by -O-R １７ R is an organyloxy group represented by the formula １３ , R １４ , R １５ , R １６ and R １７ are each independently a hydrogen atom or a monovalent organic group, １１ and n １２ are each independently an integer of 1 to 5. １３ and R １４ When there are multiple, they may be the same or different. (Method of measuring melting point) The ultraviolet absorbent was placed in a glass container and allowed to stand in an oven. The oven was heated to a predetermined temperature for 1 hour, and the predetermined temperature at which the ultraviolet absorbent began to liquefy was recorded as the melting point.

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