Decorative materials and decorative components

Abstract

To provide a decorative material which has high initial adhesion strength in the application process, is excellent in application suitability, does not peel even after long-term use, and exhibits excellent long-term adhesion, and a decorative member having excellent long-term adhesion. The base material is decoratively treated, and 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 A decorative member having a decorative material with a shelf life of 24 hours or less, a decorative material, and a substrate, with an adhesive layer interposed between the substrate and the substrate so that the substrate faces the decorative material.

Description

[Technical field]

[0001] The present invention relates to a decorative material and a decorative member. [Background technology]

[0002] Decorative panels may be placed on the surfaces of interior building components such as walls, ceilings, and floors; window frames; various doors such as entrance doors; fixtures or fittings such as handrails, baseboards, moldings, window frames, door frames, and moldings; kitchens; furniture; low-electricity appliances; cabinets for office equipment, and the like. Examples of decorative panels include decorative members or materials formed by bonding a decorative material to various substrates such as resin members, wood members, and metal members. As such decorative materials, decorative materials having a configuration with a surface protective layer on a substrate, for example, sheet-shaped decorative materials (also called "decorative sheets"), are used.

[0003] As such decorative materials, for example, plastic products using decorative sheets having a polyvinyl chloride sheet as a base material and, as necessary, a decorative layer, a surface protective layer, etc. as a decorative treatment are used (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 58-14312 DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0005] However, when a decorative material such as the decorative sheet of Patent Document 1 is attached to a substrate to produce a decorative member, a problem may occur in that the end face of the decorative material peels off due to insufficient initial adhesion strength, i.e., the so-called springback occurs. A decorative material that causes springback has insufficient workability. On the other hand, when using a decorative component in which the above-mentioned decorative material is affixed to a base, problems may arise in which the decorative material peels off from the base due to factors such as deterioration of the base material that constitutes the decorative material provided on the outermost surface and deterioration of the adhesive that bonds the decorative material to the base, caused by the effects of moisture in the air, wind and rain, and even ultraviolet light from sunlight.

[0006] The present invention has been made under these circumstances, and aims to provide a decorative material that has high initial adhesion strength during the construction process, is excellent in construction suitability, does not peel off even after long-term use, and exhibits excellent long-term adhesion, and a decorative member having excellent long-term adhesion. [Means for solving the problem]

[0007] As a result of intensive research into solving the above problems, the present inventors have found that the above problems can be solved by an invention relating to a decorative material having the following configuration.

[0008] 1. The base material is decorated and has a moisture permeability of 0.75 g / m2, measured in accordance with the moisture permeability test method for moisture-proof packaging materials (cup method) specified in JIS Z0208:1976. 2 ·45g / m for 24 hours or more 2 Cosmetic materials that last less than 24 hours. 2. The decorative material according to the above item 1, wherein the base material is made of at least one resin selected from the group consisting of vinyl chloride resins and polyolefin resins. 3. The decorative material according to the above 1 or 2, further comprising a surface protective layer on the outermost surface. 4. The decorative material according to claim 3, wherein the surface protective layer is a layer composed of a cured product of a curable resin. 5. A decorative material described in any one of 1 to 4 above, in which the decorative treatment is by a decorative layer, and the decorative layer, adhesive layer, resin layer and primer layer are provided in the following order: base material, decorative layer, adhesive layer, resin layer and primer layer. 6. The decorative material according to any one of 1 to 5 above, having a tensile modulus at 60° C. of 80 MPa or more and 600 MPa or less. 7. A decorative member comprising the decorative material according to any one of the above 1 to 6 and a substrate, with an adhesive layer between the substrate and the base of the decorative material so that the substrate faces the base. 8. The decorative member according to claim 7, wherein the adhesive layer is made of a urethane resin-based adhesive. 9. The decorative member according to claim 8, wherein the urethane resin adhesive is a moisture-curing adhesive. 10. The decorative member according to any one of the above items 7 to 9, wherein the substrate is a resin substrate or a metal substrate. Effect of the Invention

[0009] According to the present invention, it is possible to provide a decorative material that has high initial adhesion strength during the application process, is excellent in application suitability, and does not peel even after long-term use, thereby exhibiting excellent long-term adhesion, and a decorative member having excellent long-term adhesion. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view showing one embodiment of a decorative material according to the present embodiment. [Diagram 2] FIG. 1 is a schematic cross-sectional view showing one embodiment of a decorative material according to the present embodiment. [Diagram 3] 1 is a schematic cross-sectional view showing one embodiment of a decorative member of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] [Decorative materials] Hereinafter, an embodiment of the present invention (hereinafter, sometimes referred to as "the present embodiment") will be described. In this specification, the numerical values ​​related to "not less than" and "not more than" in a numerical range are numerical values ​​that can be arbitrarily combined. In addition, in this specification, the numerical values ​​in the examples are numerical values ​​that can be used as the upper and lower limits of a numerical range.

[0012] The decorative material of this embodiment is formed by applying a decorative treatment to a substrate, and has a moisture permeability of 0.75 g / m2 measured in accordance with the moisture permeability test method (cup method) for moisture-proof packaging materials specified in JIS Z0208:1976. 2·45g / m for 24 hours or more 2 The characteristic feature is that the period is 24 hours or less. The decorative material of the present embodiment exhibits high initial adhesion strength during the application process of the decorative material by setting the moisture permeability within a specific range. Therefore, the decorative material of the present embodiment can suppress the occurrence of so-called springback, in which the end surface of the decorative sheet peels off due to insufficient initial adhesion strength during application, and can improve application suitability. On the other hand, when the decorative material and the substrate are used as a decorative member via an adhesive layer, deterioration of the adhesive layer between the decorative material and the substrate can be suppressed, so that peeling due to the deterioration is suppressed, and excellent long-term adhesion is exhibited without peeling even after long-term use. In other words, by setting the moisture permeability of the decorative material of the present invention within a specific range, it is possible to achieve both excellent application suitability due to high initial adhesion strength during the application process and long-term adhesion without peeling even after long-term use.

[0013] The decorative material of this embodiment has a thickness of 0.75 g / m 2 ·45g / m for 24 hours or more 2 The moisture permeability is 0.75g / m2 or less. The effect obtained by the moisture permeability is explained in more detail. 2 If the time is less than 24 hours, when the decorative member is attached to a substrate via an adhesive layer, poor adhesion is likely to occur due to insufficient hardening of the adhesive used in the adhesive layer, and excellent initial adhesive strength and excellent workability cannot be obtained. 2 If it exceeds 24 hours, the decorative material and the substrate are likely to peel off during long-term use due to deterioration of the substrate caused by moisture in the air, wind and rain, and even ultraviolet rays from sunlight, and deterioration due to hydrolysis of the adhesive used in the adhesive layer, so that long-term adhesion without peeling even with long-term use cannot be obtained. Therefore, as described above, by setting the moisture permeability within a specific range, the decorative material of this embodiment can achieve both excellent application suitability due to high initial adhesion strength during the application process and long-term adhesion without peeling even with long-term use.

[0014] 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 this embodiment, the moisture permeability can be adjusted mainly by the type of material constituting the substrate, which will be described later, and the type of material constituting the resin layer, if any, that is included.

[0015] The configuration of the decorative material of this embodiment will be described with reference to FIGS. FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of a decorative material of the present embodiment, and shows that a decorative material 10 of the present embodiment has a substrate 1 and a decorative layer 2 as a representative embodiment of a decorative treatment. FIG. 2 is a schematic cross-sectional view showing one embodiment of a preferred layer configuration of the decorative material of this embodiment, which shows that it has a substrate 1, a decorative layer 2, an adhesive layer 3, a resin layer 4, a primer layer 5 and a surface protective layer 6. Each layer constituting the decorative material of the present embodiment will be described in more detail below.

[0016] (Base material 1) As the material of the substrate, any material that is usually used as a substrate for a decorative material can be used without any restrictions, so long as the moisture permeability in the state of the decorative material is within the above-mentioned specified range. Representative examples of the substrate material include substrates made of paper, nonwoven or woven fabric, resin, wood, metal, nonmetallic inorganic materials, etc., and substrates made of resin are preferred from the viewpoints of keeping the moisture permeability within the above-mentioned range and improving long-term adhesion as well as application suitability. The thickness of the substrate is not particularly limited as long as the moisture permeability in the state of being configured as a decorative material is within the above-mentioned specified range, and a film, sheet, or plate-like form can be appropriately used as desired. The thickness of the substrate is usually about 20 μm to 200 μm for a film or sheet, and about 500 μm to 10 cm for a plate, taking into consideration the moisture permeability of the decorative material.

[0017] Examples of resins include polyolefin resins such as polypropylene-based resins and polyethylene-based resins; 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; and resin substrates made of thermoplastic resins such as polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), and vinyl chloride-based 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.

[0018] Among the above, polyolefin resins and vinyl chloride resins are preferred in consideration of the moisture permeability being easily within the above range, improving long-term adhesion as well as application suitability, and versatility and suitability for use as a decorative material, and polyolefin resins are preferred in consideration of environmental performance. In this embodiment, the above resins can be used alone or in combination of multiple types. When multiple types are combined, substrates made of various individual resins may be combined, or multiple types of resins may be mixed and used as one substrate.

[0019] 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. From the viewpoint of easily achieving a moisture permeability within the above range and improving both application suitability and long-term adhesion, among 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.

[0020] The moisture permeability is preferably adjusted by adjusting the thickness of the layer in which the resin is used, such as the substrate and the resin layer, because this is easy and more reliable. In order to set the moisture permeability of the decorative material in this embodiment within the above-mentioned predetermined range, it is preferable to set the thickness of the substrate and the resin layer within a predetermined range according to the material constituting these layers, preferably the type of resin, taking into consideration the ratio of the thickness to the total thickness of the decorative material in the laminated structure of the decorative material. In order to make it easier to keep the moisture permeability of the decorative material within the above-mentioned specified range, the thickness of the base material, when using polyethylene-based resin, polypropylene-based resin, or polyvinyl chloride-based resin, may be selected, taking into consideration the layered structure of the decorative material and the desired moisture permeability, preferably from the range of 40 μm or more and 200 μm or less.

[0021] 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.

[0022] 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.

[0023] 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 or more and 20 / 80 or less, taking into consideration the ease of adjusting the moisture permeability.

[0024] In addition, when a vinyl chloride-based resin is used, the vinyl chloride-based resin may be a homopolymer of a vinyl chloride monomer, i.e., polyvinyl chloride, or a copolymer obtained by copolymerizing a vinyl chloride monomer with a monomer copolymerizable with the vinyl chloride monomer. 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.

[0025] 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 keeping the moisture permeability within the above 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.

[0026] In this embodiment, when a 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 vinyl chloride resins, and examples thereof include phthalic acid plasticizers such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), etc.; adipic acid plasticizers such as dibutyl adipate; phosphate plasticizers such as tributyl phosphate, tricresyl phosphate, triphenyl phosphate, etc.; trimellitic acid plasticizers such as tributyl trimellitate, trioctyl trimellitate, etc.; various known polyester plasticizers such as adipic acid 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.

[0027] 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 easy to adjust the moisture permeability to a 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 easy to stably adjust the moisture permeability to a desired range, and it is possible to improve the long-term adhesion as well as the application suitability.

[0028] In particular, from the viewpoint of easily adjusting 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.

[0029] 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.

[0030] 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, glass, and various ceramics.

[0031] 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.

[0032] When the substrate is colored, examples of the colorant 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 substrate to which the cosmetic material 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.

[0033] In the case of coloring a resin substrate, 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 a paper, nonwoven fabric, or woven fabric substrate, any of the following methods can be used: mixing with pulp or fiber material, coating, etc., or a combination of these.

[0034] 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.

[0035] 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.

[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 substrates, 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 substrates, 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] (Decorative treatment) The decorative material of the present embodiment is obtained by subjecting a base material to a decorative treatment. The decorative treatment imparts a design, such as a color, a pattern, or a textured pattern, to the decorative material of the present embodiment, thereby improving the design and enabling the decorative material of the present embodiment to be used as a decorative material. In this embodiment, the decorative treatment may be of various known forms, such as forming a decorative layer, such as a pattern layer and a colored layer by printing or the like, a metal processed layer by vacuum deposition or the like, adding a colorant to the base material or a resin layer described later, forming a concave-convex pattern (shape transfer) by embossing or the like, etc. Among these, the decorative treatment that is most commonly used is the formation of a decorative layer. The decorative treatment will be described below mainly focusing on the formation of the decorative layer.

[0039] In the decorative material of this embodiment, the decorative layer as a decorative treatment may be a layer composed only of a full-colored layer 2A (also called a "full-colored solid layer") that is provided on one side of the base material and covers the entire surface, or a layer composed only of a pattern layer 2B that is provided to cover a part of the base material and form a pattern, or a layer that combines the full-colored layer 2A and the pattern layer 2B. From the viewpoint of expressing a higher design, it is preferable that the decorative layer is a layer composed of a pattern layer and a full-colored layer. In this case, the decorative material of this embodiment preferably has the base material, the full-colored layer, and the pattern layer in this order, and the pattern layer may be one layer or two or more layers.

[0040] The pattern imparted by the decorative layer is not particularly limited and may be selected as desired, and examples thereof include wood grain patterns imitating the appearance of the board surface of various trees such as cedar, cypress, and pine, marble patterns (e.g., travertine marble patterns), stone grain patterns imitating the surface of rocks such as the cleavage plane of a granite board, fabric patterns imitating cloth 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 inlay, patchwork, block patterns, etc. Also, examples of patterns combining these include artificial stone patterns, so-called artificial marble, which is made by mixing crushed stone such as marble with white cement, hardening it, and polishing it to make it look like 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.

[0041] The decorative layer can be formed in the form of a picture layer or a full-color color layer formed by laminating ink or paint over the entire surface or in a desired pattern by various printing methods, or a metal layer formed by laminating various metal layers made of aluminum, chromium, gold, silver, copper, tin, etc. over the entire surface or in a desired pattern by vacuum deposition, sputtering, plating, etc. Below, a description will be given of the form of the decorative layer constituted by a picture layer and / or a full-color color layer that is particularly widely used. To form a decorative layer having the form of a picture layer or a full-colored layer, it is preferable to use a resin composition containing at least a binder resin and a colorant such as a pigment or dye, and it is also possible to use an appropriate 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 or dye, and can contain other components used as desired as described above.

[0042] 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, nitrocellulose (nitrocellulose), cellulose acetate, and other resins. In addition, curable resins such as two-liquid curing urethane resins, which use various polyols such as acrylic polyols as the main component and various isocyanates as the curing agent, may also be used. These may be used alone or in combination.

[0043] 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 can be selected appropriately from among these depending on the desired pattern.

[0044] 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, kaolinite, 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, and urea resin.

[0045] 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, the wood grain pattern exemplified as a preferred 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 addition, by not including a matting agent in the full color layer, or by making the content of the matting agent in the full color layer less than the content of the matting agent in the pattern layer, it is also possible to increase the gloss difference between the full color layer and the pattern layer and improve the design.

[0046] The volume average particle size of these matting agents is preferably 0.5 μm or more and 25 μm or less, more preferably 1 μm or more and 15 μm or less, and further preferably 3 μm or more and 10 μm or less. 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.

[0047] 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 they may be appropriately selected from among them depending on the desired performance.

[0048] 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.

[0049] (Surface protective layer 6) The decorative material of this embodiment may have a surface protective layer in addition to the above-mentioned substrate and decorative layer. The surface protective layer is a layer provided on the outermost surface when the decorative material is laminated on various substrates and used for various applications (for example, interior materials for buildings, etc.), that is, on the outermost surface side when used. The surface protective layer is a layer capable of protecting the decorative material of this embodiment, that is, a layer capable of imparting surface properties such as stain resistance and abrasion resistance to the decorative material of this embodiment. From this viewpoint, it is preferable that the surface protective layer is a layer provided over the entire outermost surface of the decorative material of this embodiment.

[0050] 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 embodiment 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 a curable resin. It may also be a layer composed of a combination of a thermoplastic resin and a curable resin, and in this specification, the cured product of a curable resin also includes a cured product of a resin composition containing a curable resin.

[0051] Examples of the thermoplastic resin include acrylic resin, polyester resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyester urethane resin, and thermoplastic (non-crosslinked) urethane resin.

[0052] As the curable resin, curable resins such as thermosetting resins, two-component curable resins, and ionizing radiation curable resins can be used, and from the viewpoint of improving the surface properties of the decorative material of this embodiment, such as contamination resistance and abrasion resistance, ionizing radiation curable resins are preferred.

[0053] 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 two-component curing resins include two-component curing urethane resins that use a polyol compound as a base and an isocyanate compound as a curing agent, two-component curing epoxy resins that use an amine or the like as a curing agent, two-component curing urethane-modified acrylic resins, and two-component curing polyester resins.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] To the surface protective layer, as desired, for example, weather resistance agents such as ultraviolet absorbers and light stabilizers, ultraviolet screening 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. may be added within the scope of the present invention. Among these, it is preferable that the surface protective layer contains weather resistance agents such as ultraviolet absorbers and light stabilizers. The ultraviolet absorbent and light stabilizer can be appropriately selected from those listed as the ultraviolet absorbent and light stabilizer that can be used in the substrate.

[0060] From the viewpoint of protecting the decorative material of the present embodiment 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.

[0061] The decorative material of this embodiment may further have at least one layer selected from an adhesive layer, a resin layer, and a primer layer depending on the desired performance, and preferably has an adhesive layer, a resin layer, and a primer layer. The order of lamination of these layers is not particularly limited, and they may be provided in an appropriate order depending on the desired performance, etc., but in this embodiment, they are usually provided in order on the side opposite to the side on which the base material is provided of the decorative layer, and it is preferable that the order is the base material, the decorative layer, the adhesive layer, the resin layer, and the primer layer, as shown in Figure 2. In addition, when a surface protective layer is provided, it is preferable that the order is the base material, the decorative layer, the adhesive layer, the resin layer, the primer layer, and the surface protective layer, as shown in Figure 2. These layers will now be described.

[0062] (Resin layer 4) The resin layer is provided to improve the surface properties of the decorative material of this embodiment, such as stain resistance and abrasion resistance, and to protect the decorative layer. Therefore, in the decorative material of this embodiment, the resin layer is preferably provided on the side of the decorative layer opposite to the side on which the substrate is provided.

[0063] Examples of resins constituting the resin layer include resins exemplified as materials constituting the above-mentioned base material, polyolefin resins such as polypropylene and polyethylene, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymer, and polyester-based thermoplastic elastomers, acrylic resins such as polymethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymer, polyester resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin (hereinafter also referred to as "ABS resin"), and vinyl chloride-based resins, and other thermoplastic resins are examples of resin base materials.

[0064] As the resin constituting the resin layer, from the viewpoint of easily making the moisture permeability within the above range, improving the long-term adhesion as well as the application suitability, improving the surface characteristics, and protecting the decorative layer, polyolefin resins and vinyl chloride resins are preferred, and polyolefin resins are more preferred. These polyolefin resins and vinyl chloride resins can be selected from the polyolefin resins and vinyl chloride resins described as being usable in the above substrate.

[0065] Like the substrate, the resin layer can also be a layer that affects the moisture permeability of the decorative material, so the thickness of the resin layer is preferably determined depending on the type of resin that constitutes the resin layer. In order to make it easier to keep the moisture permeability of the decorative material within the above-mentioned specified range, the thickness of the resin layer, when using polyethylene-based resin, polypropylene-based resin, or vinyl chloride-based resin, may be selected, taking into consideration the layered structure of the decorative material and the desired moisture permeability, preferably from the range of 40 μm or more and 200 μm or less. When a polypropylene-based resin is used for the resin layer, it is also preferable to appropriately adjust the crystallinity of the polypropylene-based resin and the mass ratio of isotactic polypropylene to atactic polypropylene, as in the case of the substrate.

[0066] 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.

[0067] 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. The ultraviolet absorbent and light stabilizer can be appropriately selected from those listed as the ultraviolet absorbent and light stabilizer that can be used in the substrate.

[0068] 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.

[0069] 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.

[0070] (adhesive layer 3) The adhesive layer is preferably provided from the viewpoint of improving the adhesion between the resin layer and the decorative layer when the resin layer is provided.

[0071] Examples of adhesives used in the adhesive layer 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.

[0072] 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 is preferably from 0.1 μm to 30 μm, more preferably from 1 μm to 15 μm, and even more preferably from 2 μm to 10 μm.

[0073] (Primer layer 5) The primer layer is a layer provided mainly to improve the interlayer adhesion of each layer constituting the decorative material of this embodiment, and is also called an easy-adhesion layer. For example, by providing the primer layer between the resin layer and the surface protective layer, the interlayer adhesion of these layers can be improved as shown in Fig. 2. Fig. 2 shows an embodiment in which the primer layer is provided between the decorative layer and the surface protective layer, but the present invention is not limited thereto, and the primer layer can also be provided between the substrate and the decorative layer, for example. For example, when the decorative material of this embodiment is used as a decorative component, a primer layer (also referred to as a "rear primer layer") can be provided on the surface opposite to the surface on which the decorative layer of the base material is provided, facing the base body that constitutes the decorative component, in order to improve adhesion.

[0074] 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.

[0075] As the binder resin used for forming the primer layer, those exemplified as the binder resin used in the resin composition capable of forming the above-mentioned decorative layer, and those exemplified as the curable resin capable of forming the above-mentioned surface protective layer, among which thermosetting resins and two-component curable resins can be preferably used. In addition, for example, a mixture of these curable resins and a thermoplastic resin such as nitrocellulose exemplified above may be used. In this embodiment, an appropriate resin may be selected from these resins as desired.

[0076] 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.

[0077] (Method of manufacturing decorative materials) The method for producing the decorative material of this embodiment will be described using as an example a decorative material having, in order, a base material, a decorative layer composed of an overall colored layer and a picture layer, an adhesive layer, a resin layer, a primer layer, and a surface protective layer, as shown in Figure 2, which is one of the preferred embodiments of the decorative material of this embodiment.

[0078] The decorative material of this embodiment can be manufactured, for example, by providing a full-surface color layer and a pattern layer on a substrate, and sequentially going through the steps of forming a decorative layer, forming an adhesive layer, forming a resin layer, forming a primer layer, and forming a surface protective layer to cover the primer layer.

[0079] 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.

[0080] 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.

[0081] In the step of providing the adhesive layer, the decorative layer is formed, and then an adhesive is applied onto the decorative layer to form the adhesive layer. The application method is not particularly limited, and may be appropriately selected from application methods that can be used to form the decorative layer, for example.

[0082] The process of forming the resin layer can be carried out by forming the adhesive layer, 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.

[0083] 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.

[0084] The surface protective layer is formed by applying a curable resin composition, which is preferably a liquid uncured product of a curable resin used in forming the surface protective layer, to the entire surface of the decorative material, and curing the composition 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.

[0085] When using an uncured resin composition containing a liquid uncured product of an ionizing radiation resin, 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 using electron beams 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 kV 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 kGy to 300 kGy (0.5 Mrad to 30 Mrad), preferably 10 kGy to 50 kGy (1 Mrad to 5 Mrad). The electron beam source is not particularly limited, and various electron beam accelerators such as Cockcroft-Walton type, Van de Graft 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 nm or more and 380 nm or less is emitted. There are no particular limitations on the source of ultraviolet light, and examples of the source that can be used include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps.

[0086] 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.

[0087] The conditions for the hot and pressure molding can be appropriately adjusted depending on the type of curable resin used, and are not particularly limited, but are usually a temperature of 100°C to 200°C, a pressure of 0.1 MPa to 9.8 MPa, and a time of 10 seconds to 120 minutes.

[0088] (Characteristics of decorative materials) As described above, the properties of the decorative material of this embodiment are moisture permeability of 0.75 g / m 2 ·45g / m for 24 hours or more 2 ·24h or less. By having such properties, the decorative material of the present embodiment achieves both excellent application suitability due to high initial adhesion strength during application, and long-term adhesion without peeling even after long-term use. The preferred range is also as described above.

[0089] The decorative material of this embodiment preferably has a tensile modulus at 60°C in the following range, in relation to the problem of the decorative material floating, which is detrimental to workability and the quality of the decorative material during bending, which is often used when laminating the decorative material on a base to make a decorative component. That is, the decorative material of this embodiment has a tensile modulus at 60°C of preferably 80 MPa or more, more preferably 90 MPa or more, even more preferably 100 MPa or more, and even more preferably 110 MPa or more, with the upper limit being preferably 600 MPa or less, more preferably 500 MPa or less, even more preferably 420 MPa or less, and even more preferably 375 MPa or less. By having the above tensile modulus, the decorative material of this embodiment can easily keep the moisture permeability within the above range, and can easily improve long-term adhesion as well as application suitability. In this specification, the tensile modulus is measured by the method implemented in the following examples.

[0090] (Use as cosmetic material) The decorative material of the present embodiment can be used for various applications as it is, or laminated to a substrate via an adhesive layer, or subjected to a predetermined molding process, etc. The decorative material of the present embodiment has excellent application suitability, and is therefore suitable for use in decorative members obtained by laminating to a substrate via an adhesive layer. The decorative components obtained in this manner are laminated onto substrates such as flat plates, curved plates, and other plate materials, sheets (or films), and are 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, building materials or fixtures such as window frames, various doors such as front doors, handrails, baseboards, moldings, window frames, door frames, and moldings, as well as surface decorative panels for cabinets in kitchens, furniture, low-electrical appliances, and office equipment, as well as interior and exterior components for vehicles, etc.

[0091] [Decorative materials] The decorative member of the present embodiment has the above-mentioned decorative material and substrate of the present embodiment via an adhesive such that the base material of the decorative material faces the substrate. That is, the decorative member of the present embodiment has a substrate, an adhesive layer, and a decorative material in that order. Fig. 3 shows, as a decorative member 20 of this embodiment, a decorative member in which a base 21 and the decorative material 10 shown in Fig. 1 are laminated together with an adhesive layer 22 interposed therebetween, specifically, a decorative member having a base 21 interposed between the adhesive layer 22 and the side of the base material 1 of the decorative material 10 opposite to the side having the decorative layer 2. That is, Fig. 3 shows a decorative member 20 having a base 21, adhesive layer 22, base material 1, and decorative layer 2 in that order. A preferred embodiment of the decorative member 20 of this embodiment is, for example, a decorative member in which a base 21 and a decorative material 10 shown in Fig. 2 are laminated via an adhesive layer 22. That is, a preferred embodiment of the decorative member 20 of this embodiment is a decorative member having, in order, a base 21, an adhesive layer 22, a base material 1, a decorative layer 2, an adhesive layer 3, a resin layer 4, a primer layer 5, and a surface protective layer 6. When the base material of the decorative material of this embodiment is in the form of a sheet (or film), that is, when the decorative material of this embodiment is in the form of a sheet (or film), it is easy to laminate to the base via an adhesive layer, and the decorative member of this embodiment can be easily obtained.

[0092] The substrate may be appropriately selected according to the desired member, and is not particularly limited. Examples of the substrate include wood substrates such as veneers, wood plywood, particle boards, and MDF (medium density fiberboard) made of various wood materials such as cedar, cypress, pine, and lauan; metal substrates such as iron and aluminum; ceramics such as glass and porcelain, non-cement ceramic materials such as gypsum, and ceramic substrates such as ALC (aerated lightweight concrete) boards; and resin substrates such as acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, and rubber. These substrates may be used alone or in combination. The shape of the substrate may be flat or three-dimensional. In this embodiment, the substrate may be appropriately selected depending on the application, but the above-mentioned resin substrate and metal substrate are preferred.

[0093] The adhesive used in the adhesive layer is not particularly limited, and known adhesives can be used, and may be appropriately selected according to the application. Preferred examples of adhesives used in the adhesive layer 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 the present embodiment having a predetermined water vapor permeability, ease of handling, and the like, moisture-curing adhesives and heat-sensitive adhesives are preferred. Furthermore, moisture-curing and heat-sensitive adhesives are more preferred. A heat-sensitive adhesive is preferred because the adhesive strength rises to a saturated state as soon as the molten liquid adhesive layer cools and solidifies. The decorative material of this embodiment has a moisture permeability of 0.75 g / m 2 24 hours or more. Therefore, the moisture-curing adhesive can be exposed to moderate moisture during the application process, which makes it easier to increase the initial adhesive strength of the adhesive used in the adhesive layer. In addition, the decorative material of this embodiment has a moisture permeability of 45 g / m 2 -24 hours or less. This means that the moisture-curing adhesive will not come into contact with excessive moisture, and the decrease in adhesion caused by deterioration associated with hydrolysis of the moisture-curing adhesive is suppressed, resulting in better application suitability and long-term adhesion. Moisture-curing adhesives are also preferable in terms of ease of handling.

[0094] Resins used in these adhesives include, for example, acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, polyester resins, amide resins, cyanoacrylate resins, epoxy resins, etc., which can be used alone or in combination. Two-liquid curing type urethane adhesives and ester adhesives using an isocyanate compound or the like as a curing agent can also be used. The adhesive layer may contain a pressure-sensitive adhesive, which may be appropriately selected from acrylic, urethane, silicone, rubber, or other pressure-sensitive adhesives.

[0095] 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.

[0096] The adhesive layer can be formed by applying and drying an adhesive in a coatable form such as a solution or emulsion of the above-mentioned resin by means of gravure printing, screen printing, or reverse coating using a gravure plate. The thickness of the adhesive layer 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.

[0097] The decorative member of this embodiment can be cut as desired, and the surface or end grain can be decorated as desired, such as by groove processing or chamfering, using a cutting machine such as a router or cutter. The decorative member of this embodiment can be used, for example, as a surface decorative panel for interior or exterior walls of buildings, such as walls, ceilings, and floors; exterior components, such as roofs, eaves ceilings, fences, and gates; window frames; various doors, such as entrance doors; fixtures or fittings, such as handrails, baseboards, moldings, window frames, door frames, and moldings; kitchens; furniture; low-electricity products; and cabinets for office automation equipment; or as interior or exterior components for vehicles. EXAMPLES

[0098] 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.

[0099] 1. Measurement 1-1. 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. 1-2. Measurement of tensile modulus For the decorative materials obtained in the examples and comparative examples, sheets were punched out into dumbbell-shaped test pieces conforming to JIS K6732: 2006 to prepare samples. In a temperature environment of 60°C, the samples were pulled to an arbitrary elongation using a Tensilon universal material testing machine ("Tensilon RTC-1250A (product name)", manufactured by Orientec Co., Ltd.) under conditions of a pulling speed of 50 mm / min, a chuck distance of 80 mm, and a width of 25 mm, to obtain the tensile modulus of the decorative material.

[0100] 2. Evaluation 2-1.Evaluation of suitability for construction The decorative materials obtained in the examples and comparative examples and a 25 mm wide flat substrate (material: polyvinyl chloride (PVC)) were attached via a 50 μm thick adhesive layer formed by melting a moisture-curing, 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 on the sample at a temperature 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 it is rated B or higher, the evaluation of the suitability for application is passed. A: The peeling strength was 1.0 N / mm or more. B: The peeling strength was 0.5 N / mm or more and less than 1.0 N / mm. C: The peeling strength was less than 0.5 N / mm. 2-2. Evaluation of long-term adhesion The samples prepared in "2-1. 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 B or higher indicates that the long-term adhesion has been evaluated as acceptable. A: The peeling strength was 2.0 N / mm or more. B: The peeling strength was 1.0 N / mm or more and less than 2.0 N / mm. C: The peeling strength was less than 1.0 N / mm. 2-3. Processing suitability When laminating the samples in the above "2-1. 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 it was rated B or higher, the workability was acceptable. A: No floating was observed at all. B: Almost no floating was observed. C: Lifting was observed and peeling occurred.

[0101] [Example 1] A decorative layer (thickness: 3 μm) was formed on one side of a substrate (thickness: 80 μm, polypropylene sheet, polyolefin 1) that had been subjected to corona discharge treatment on both sides by gravure printing using a printing ink with a two-component curing acrylic-urethane resin as a binder resin, and a resin composition containing a two-component curing urethane-nitrocellulose mixed resin (hardener: hexamethylene diisocyanate is contained in an amount of 5 parts by mass per 100 parts by mass of the mixed resin) was applied to the other side of the substrate to form a back primer layer (thickness: 3 μm). Next, a transparent urethane resin adhesive was applied on the decorative layer to form an adhesive layer (thickness: 3 μm), and a polypropylene resin was hot-melt extruded on the adhesive by a T-die extruder to form a transparent resin layer (thickness: 80 μm).

[0102] 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 (thickness: 4 μm). Next, the following ionizing radiation curable resin composition was applied onto the primer layer to form an uncured resin layer, and then the uncured resin layer was irradiated with an electron beam (165 keV, 5 Mrad (50 kGy)) to cure it, thereby forming a surface protective layer (thickness: 5 μm) and producing a decorative material. (Ionizing radiation curable resin composition) Ionizing radiation curable resin: urethane acrylate UV absorber 1 (product name: Adeka STAB LA-46, hydroxyphenyl triazine UV absorber, manufactured by ADEKA Corporation): 2 parts by weight per 100 parts by weight of the above resin UV absorber 2 (product name: Tinuvin 1600, hydroxyphenyltriazine-based UV absorber, manufactured by BASF): 2 parts by mass per 100 parts by mass of the above resin Hindered amine light stabilizer (product name: Tinuvin 123, manufactured by BASF): 3 parts by weight per 100 parts by weight of the above resin

[0103] A moisture-curing, hot-melt urethane resin adhesive was applied to the substrate to form a 5 μm thick adhesive layer, which was then attached to the resulting decorative material and left in an environment at 90° C. for 1 hour to obtain a decorative member. Separately, samples were prepared from the obtained decorative material according to the above method and evaluated. The results are shown in Table 1.

[0104] [Examples 2 to 4, Comparative Examples 1 and 2] The decorative materials and decorative members of Examples 2 to 4 were prepared 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 1. Samples were prepared and evaluated using the obtained decorative materials according to the above-mentioned method. The results are shown in Table 1.

[0105] [Table 1]

[0106] The substrates used in the examples and comparative examples in the above table 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) PVC1 was prepared in the same manner as PVC1, except that the plasticizer in PVC1 was a polyester-based plasticizer (adipic acid-based polyester) and its content was 33 parts by mass per 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)

[0107] From the results in Table 1, it was confirmed that the decorative material of this embodiment has a specified moisture permeability, and therefore has excellent coating suitability, and that the decorative components of this embodiment using this decorative material have excellent long-term adhesion. On the other hand, Comparative Example 1 confirmed that if the moisture permeability is too high, deterioration occurs due to a hydrolysis reaction between the moisture in the air and the adhesive that forms the adhesive layer, and excellent long-term adhesion cannot be obtained, and Comparative Example 2 confirmed that if the moisture permeability is too low, the adhesive that forms the adhesive layer does not harden well, the initial adhesion strength becomes small, and excellent workability cannot be obtained. [Industrial Applicability]

[0108] The decorative material and decorative member of the present embodiment have excellent workability and long-term adhesion, and therefore are suitable for use as interior components of buildings such as walls, ceilings, and floors, or exterior components such as exterior walls, roofs, eaves ceilings, fences, and gates, building materials or fixtures such as window frames, various doors such as front doors, handrails, baseboards, moldings, window frames, door frames, and moldings, as well as surface decorative panels for cabinets in kitchens, furniture, or low-electrical appliances, and office equipment, and interior or exterior components for vehicles. [Explanation of symbols]

[0109] 10: Cosmetic materials 1: Base material 2: Decorative layer 2A: Full colored layer 2B: Picture layer 3: Adhesive layer 4: Resin layer 5: Primer layer 6: Surface protective layer 20: Decorative materials 21: Base 22: Adhesive layer

Claims

1. A cosmetic material comprising: The decorative material is formed by subjecting a base material to a decorative treatment, the substrate is a resin substrate containing at least one resin selected from vinyl chloride resin, polyolefin resin, polyester resin, acrylic resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin; The decorative treatment is performed by a decorative layer, The decorative material further has an adhesive layer, a resin layer, a primer layer, and a surface protective layer, and the decorative material has the base material, the decorative layer, the adhesive layer, the resin layer, the primer layer, and the surface protective layer in this order, the resin layer contains a polyolefin resin, The decorative material has a moisture permeability of 0.75 g / m2 as measured in accordance with the moisture permeability test method for moisture-proof packaging materials (cup method) specified in JIS Z0208:1976. ２ ・45g / m for 24 hours or more ２ - Cosmetic materials lasting less than 24 hours.

2. The decorative material described in claim 1, wherein the substrate is a resin substrate containing at least one type of resin selected from polyvinyl chloride-based resins, polyethylene-based resins, and polypropylene-based resins.

3. A cosmetic material as described in claim 2, wherein the thickness of the substrate is 40 μm or more and 200 μm or less.

4. The cosmetic material described in claim 3, wherein the base material is a resin base material containing polypropylene resin, which is a homopolymer of propylene, and the crystallinity of the polypropylene resin is 30% or more and 80% or less.

5. The cosmetic material described in claim 3, wherein the substrate is a resin substrate containing a polyvinyl chloride resin, and the degree of polymerization of the polyvinyl chloride resin is 500 or more and 4,000 or less.

6. A decorative material described in any one of claims 1 to 5, wherein the surface protective layer comprises a cured product of a curable resin.

7. A decorative material described in any one of claims 1 to 6, wherein the thickness of the surface protective layer is 2 μm or more and 15 μm or less.

8. A decorative material described in any of claims 1 to 7, wherein the resin layer contains at least one type of resin selected from polyethylene-based resins and polypropylene-based resins, and has a thickness of 40 μm or more and 200 μm or less.

9. A decorative material described in any one of claims 1 to 8, wherein the thickness of the resin layer is greater than the thickness of the substrate.

10. The decorative material according to any one of claims 1 to 9, wherein the moisture permeability is 0.75 g / m 2 ·24 h or more and 10 g / m 2 ·24 h or less.

11. The decorative material according to any one of claims 1 to 9, wherein the moisture permeability is 2.5 g / m 2 ·24 h or more and 10 g / m 2 ·24 h or less.

12. A decorative member comprising a decorative material according to any one of claims 1 to 11 and a base, with a moisture-curing adhesive layer between the base material of the decorative material and the base facing each other.

13. The decorative material described in claim 12, wherein the moisture-curing adhesive layer is a moisture-curing urethane-based adhesive layer.

14. A decorative material as described in claim 12 or 13, wherein the thickness of the moisture-curing adhesive layer is 1 μm or more and 100 μm or less.

15. The decorative material according to claim 12, wherein the substrate is a resin substrate or a metal substrate.

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