Decorative sheet, decorative member, and fitting

Abstract

To provide a decorative sheet, a decorative member, and a fitting, having superior workability and recyclability, and formed using a polyvinyl chloride resin.SOLUTION: A decorative sheet 1 comprises at least a colored polyvinyl chloride resin layer 2, a pattern layer 4, a transparent polyvinyl chloride resin layer 6, and a surface protective layer 8, stacked in this order, wherein the decorative sheet 1 has a Martens hardness of 50 MPa or more and 150 MPa or less as measured in accordance with ISO14577-1:2002. This structure can achieve the decorative sheet 1 with superior workability and recyclability.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a cosmetic sheet, a cosmetic member, and a fitting.

Background Art

[0002] Conventionally, a vinyl chloride resin-based cosmetic sheet used for decorating interior materials for housing and the like is known (for example, Patent Document 1).

Prior Art Document

Patent Document

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, it has been pointed out that conventionally, polyvinyl chloride resin may contain dioxin, which is a harmful substance in the gas when burned. However, in recent years, due to the improvement of incineration facilities and exhaust gas treatment technologies, the generation of harmful substances has been suppressed. Therefore, the existence of polyvinyl chloride resin is being reexamined. In addition, more than half of the raw materials of polyvinyl chloride resin are made from salt, and the ethylene polymerization ratio derived from petrochemicals is also lower than that of olefin resins, so it is sometimes referred to as a resource-saving resin. Furthermore, due to the increasing awareness of zero-energy houses (ZEH) and the like, there is a high demand for highly heat-insulating window frames (resin sashes) using polyvinyl chloride resin, and it is also considered to decorate these base materials. When an olefin resin sheet is used as a decorative material for such window frames (resin sashes) and the like, there are problems such as difficulty in recycling.

[0005] On the other hand, polyvinyl chloride resin has the advantages of excellent processing suitability and easy recyclability. Therefore, by using polyvinyl chloride resin as a decorative material together with a base material such as a vinyl chloride window frame, it is expected to greatly contribute to reducing the environmental impact. However, when using conventional polyvinyl chloride resin as a decorative material, for example, when a polyvinyl chloride resin sheet is used by laminating it to a base material such as a window frame, the sheet is often bent and processed, and the polyvinyl chloride resin sheet is prone to cracking when processed. Therefore, it is important to design considering this characteristic.

[0006] The present invention has been made in view of the above points, and an object thereof is to provide a decorative sheet, a decorative member, and a fixture that are excellent in processing suitability and recyclability.

Means for Solving the Problems

[0007] As a result of intensive research, the present inventors have found that in a decorative sheet containing polyvinyl chloride resin, by adjusting the physical properties of this decorative sheet, specifically the Martens hardness and the complex elastic modulus, to appropriate values, the above object can be achieved. That is, the decorative sheet according to one aspect of the present invention is a decorative sheet in which at least a colored polyvinyl chloride resin layer, a pattern layer, a transparent polyvinyl chloride resin layer, and a surface protection layer are laminated in this order, and the Martens hardness of the decorative sheet measured according to ISO14577-1:2002 is in the range of 50 MPa or more and 150 MPa or less, and the complex elastic modulus of the decorative sheet measured according to ISO14577-1:2002 is in the range of 2000 MPa or more and 4500 MPa or less.

[0008] Further, the decorative member according to another aspect of the present invention is characterized by including the decorative sheet of the above aspect and a base material disposed on the side of the colored polyvinyl chloride resin layer opposite to the pattern layer. Furthermore, the fitting according to another aspect of the present invention includes the decorative sheet of the above aspect and a fitting member disposed on the side of the colored polyvinyl chloride resin layer opposite to the pattern layer.

Advantages of the Invention

[0009] According to one aspect of the present invention, it is possible to obtain a decorative sheet, a decorative member, and a fitting that are excellent in processing suitability and recyclability.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0011] Hereinafter, embodiments of the present technology will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thicknesses of the respective layers, etc. are different from the actual ones. As long as it is within the scope of the present disclosure, it is not necessarily stacked in the order shown in the drawings. Also, layers not described in these drawings may be added. Further, the following embodiments illustrate configurations for embodying the technical idea of the present disclosure, and the technical idea of the present disclosure is not limited to the materials, shapes, structures, etc. of the constituent parts being the following. The technical idea of the present disclosure can be variously modified within the technical scope defined by the claims described in the claims. In addition, the directions of "left and right" and "up and down" in the following description are merely definitions for convenience of explanation and do not limit the technical idea of the present disclosure. Therefore, for example, if the paper surface is rotated 90 degrees, "left and right" and "up and down" are read in exchange, and if the paper surface is rotated 180 degrees, it goes without saying that "left" becomes "right" and "right" becomes "left".

[0012] (Configuration of the Decorative Sheet) FIG. 1 is a cross-sectional view schematically showing an example of a cosmetic sheet 1 according to an embodiment of the present invention. As shown in FIG. 1, the cosmetic sheet 1 includes a colored polyvinyl chloride resin layer 2, a pattern layer 4, a transparent polyvinyl chloride resin layer 6, and a surface protective layer 8. An embossed portion 10 is formed on the surface protective layer 8, which is the outermost layer of the cosmetic sheet 1, from the surface side to the transparent polyvinyl chloride resin layer 6.

[0013] (Colored polyvinyl chloride resin layer) The colored polyvinyl chloride resin layer 2 functions as a support of the cosmetic sheet 1, is opaque and colored, and has concealability. Thereby, when the cosmetic sheet 1 is adhered to an adherend such as a window frame, the colored polyvinyl chloride resin layer 2 can conceal color variations, defects, etc. on the surface of the adherend. The colored polyvinyl chloride resin layer 2 is formed of a polyvinyl chloride resin, and is formed of, for example, a flexible, thermoplastic polyvinyl chloride (PVC) resin film having good moldability and processing suitability and further having printability. By forming the cosmetic sheet 1 using the colored polyvinyl chloride resin layer 2, the edge material of the cosmetic sheet 1 when the cosmetic sheet 1 is adhered to an adherend or the used cosmetic sheet 1 can be melted and extruded by an extruder or the like and reused as a recycled base material. In addition, since PVC is easier to reuse by melting than an olefin-based resin, that is, the cosmetic sheet 1 according to the present embodiment can improve processing suitability and recyclability.

[0014] In addition, the colored polyvinyl chloride resin layer 2 colored opaque can appropriately select a hue as an undercolor of the pattern layer 4. Further, when making use of the texture of the surface of the adherend, the colored polyvinyl chloride resin layer 2 preferably has transparency to such an extent that the surface of the adherend can be seen through when viewed from the surface protective layer 8 side. The colored polyvinyl chloride resin layer 2 can be obtained, for example, by mixing a colorant such as a pigment with the polyvinyl chloride resin or kneading it. As the colorant, organic and inorganic pigments can be used, but it is preferable to use inorganic pigments. That is, the colored polyvinyl chloride resin layer 2 preferably contains an inorganic substance as a colorant. For example, the colored polyvinyl chloride resin layer 2 preferably contains any one or more inorganic substances such as calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides. In addition, if necessary, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss modifiers may be added to the colored polyvinyl chloride resin layer 2.

[0015] (Pattern layer) The pattern layer 4 is laminated on one surface (the upper surface in FIG. 1) of the colored polyvinyl chloride resin layer 2 and is a layer for adding a pattern for imparting design properties to the decorative sheet 1. In addition, the pattern layer 4 is formed using printing ink, paint, or the like. The printing ink, paint, or the like for forming the pattern layer 4 is formed, for example, by dissolving or dispersing a colorant such as a dye or a pigment in a suitable diluting solvent together with a suitable binder resin. Examples of the pigment include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica.

[0016] The printing ink, paint, or the like for forming the pattern layer 4 is applied using various printing methods such as the gravure printing method or the offset printing method, or various coating methods such as the gravure coating method or the roll coating method. The binder resin contained in the pattern layer 4 is not particularly limited, but it is preferable to use a resin having good adhesion. That is, a resin having heat fusion properties with the polyvinyl chloride resin, for example, a vinyl chloride-vinyl acetate copolymer, a single acrylic resin, or a mixture thereof is preferable. As the pattern formed by the pattern layer 4, any pattern can be used. For example, it is possible to use a wood grain pattern, a stone grain pattern, a cloth grain pattern, an abstract pattern, a geometric pattern, characters, symbols, a single-color plain surface, etc., or a combination thereof. Further, in order to improve the concealability of the decorative sheet 1, a concealment layer may be provided between the pattern layer 4 and the colored polyvinyl chloride resin layer 2. The concealment layer is formed, for example, using an opaque printing ink or paint containing a large amount of an opaque pigment such as titanium dioxide or iron oxide.

[0017] The thickness of the pattern layer 4 is preferably in the range of 1 μm or more and 10 μm or less. This is because when the thickness of the pattern layer 4 is 1 μm or more, printing can be made clear. Also, when the thickness of the pattern layer 4 is 10 μm or less, the printing workability when manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed. Further, to the pattern layer 4, for the purpose of imparting various functions, for example, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, curing agents, curing accelerators, and curing retarders may be added. Further, the pattern layer 4 may have a configuration having a solid-coated colored base layer for concealing the color and pattern of the adherend to which the decorative sheet 1 is adhered, and a pattern layer for adding a pattern for imparting design properties.

[0018] (Transparent polyvinyl chloride resin layer) The transparent polyvinyl chloride resin layer 6 is a layer for improving the weather resistance of the decorative sheet 1. The transparent polyvinyl chloride resin layer 6 is formed of a polyvinyl chloride resin, and is formed, for example, of a flexible, thermoplastic polyvinyl chloride (PVC) resin film having good moldability and processability and further having printability. As described above, PVC can be used as a recycled base material by melting and extruding it, and is easier to reuse by melting compared to olefin-based resins. That is, the cosmetic sheet 1 according to the present embodiment can surely improve processing suitability and recyclability by using the colored polyvinyl chloride resin layer 2 containing a polyvinyl chloride resin and the transparent polyvinyl chloride resin layer 6.

[0019] In addition, the transparent polyvinyl chloride resin layer 6 preferably has such transparency that a pattern layer 4 provided on, for example, the surface (the lower surface in FIG. 1) on the colored polyvinyl chloride resin layer 2 side can be seen through from the surface protection layer 8 side. The transparent polyvinyl chloride resin layer 6 is preferably any one of colorless transparent, colored transparent, and translucent, for example. Moreover, a plasticizer may be added to the transparent polyvinyl chloride resin layer 6. As the plasticizer, a high molecular weight polyester resin is preferable, and the content of the plasticizer is preferably 20 PHR or more and 30 PHR or less. Also, in terms of viscosity, it is preferable that the plasticizer is contained such that the viscosity of the transparent polyvinyl chloride resin layer 6 is 500 mPa·s or more and 3000 mPa·s or less.

[0020] Among polyester resins, high molecular weight polyesters are preferable as the plasticizer. Phthalic acid resins (such as dioctyl phthalate (DOP), diisononyl phthalate (DINP), dioctyl adipate (DOA), etc.) and epoxy resins have good plasticizing efficiency, but are more likely to bleed out compared to high molecular weight polyesters, and high molecular weight polyesters are superior in terms of solvent resistance, oil resistance, and weather resistance. Also, when the viscosity of the transparent polyvinyl chloride resin layer 6 to which a plasticizer is added is less than 500 MPa, it has a low molecular weight, is likely to bleed out, and has poor weather resistance. Also, when the viscosity is greater than 3000 MPa, it is too high in molecular weight, has a high viscosity, and it is difficult to produce the resin. Also, the cold resistance is poor.

[0021] Furthermore, when the plasticizer content is lower than 20 PHR, even if a phthalic acid resin is used, the cold resistance deteriorates. Therefore, when using a high molecular weight polyester resin as the plasticizer, the plasticizer content is preferably 20 or more. When the plasticizer content is more than 30 PHR, the decorative sheet 1 becomes too soft and loses its firmness, making it difficult to handle and resulting in poor productivity during processing. Also, the scratch resistance of the decorative sheet 1 is low. When the plasticizer content satisfies these conditions, the elongation at break at 0 °C is 10% or more and 400% or less, and the production stability during processing such as wrapping is good. If the elongation at break at 0 °C is lower than 10%, it is too hard and whitening or cracking occurs. If it is more than 400%, it is too soft and lacks firmness, making it difficult to handle and resulting in poor productivity, and the scratch resistance is also poor.

[0022] 〔Ultraviolet Absorbent〕 The transparent polyvinyl chloride resin layer 6 further contains an ultraviolet absorbent. That is, the transparent polyvinyl chloride resin layer 6 is formed of a transparent polyvinyl chloride resin and contains an ultraviolet absorbent. Thereby, excellent weather resistance can be imparted to the transparent polyvinyl chloride resin layer 6. More specifically, the transparent polyvinyl chloride resin layer 6 preferably contains at least one ultraviolet absorbent of a benzotriazole-based ultraviolet absorbent or a triazine-based ultraviolet absorbent as the ultraviolet absorbent. Thereby, excellent weather resistance can be imparted to the transparent vinyl chloride resin forming the transparent polyvinyl chloride resin layer 6, and the weather resistance of the decorative sheet 1 can be improved. The addition amount of the ultraviolet absorbent in the transparent polyvinyl chloride resin layer 6 may be added according to the desired weather resistance. For example, it is preferably 0.5 parts by mass or more of the ultraviolet absorbent with respect to 100 parts by mass of the transparent vinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6. Thereby, the weather resistance of the decorative sheet 1 can be surely improved.

[0023] (Benzotriazole-based Ultraviolet Absorbent) Examples of the benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and the like, as well as mixtures, modified products, polymers, and derivatives thereof.

[0024] (Triazine-based ultraviolet absorber) Examples of the triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, and the like, as well as mixtures, modified products, polymers, and derivatives thereof.

[0025] The transparent polyvinyl chloride resin layer 6 may further contain a hindered amine light stabilizer (HALS). Examples of the hindered amine light stabilizer (HALS) applicable to the transparent polyvinyl chloride resin layer 6 include the light stabilizers applied to the surface protective layer 8 described below. The thickness of the transparent polyvinyl chloride resin layer 6 is preferably in the range of 50 μm or more and 150 μm or less, more preferably in the range of 50 μm or more and 100 μm or less, and even more preferably in the range of 60 μm or more and 80 μm or less. When the thickness is 50 μm or more, the weather resistance of the decorative sheet 1 can be surely improved, and further, unevenness and the like of an adherend such as a window frame can be absorbed to improve the construction finish of the decorative sheet 1. Further, when the thickness of the transparent polyvinyl chloride resin layer 6 is 150 μm or less, the transparent polyvinyl chloride resin layer 6 is not formed thicker than necessary, the processing propriety (for example, bend processability) is improved, and the manufacturing cost of the decorative sheet 1 can be reduced.

[0026] (Surface protection layer) The surface protection layer 8 is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and designability to the decorative sheet 1. The material constituting the surface protection layer 8 is not particularly limited, and for example, it can be appropriately selected and used from resin materials such as urethane-based, acrylic-based, acrylic-silicone-based, fluorine-based, and epoxy-based. The surface protection layer 8 may be blended with various additives such as an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, if necessary.

[0027] Hereinafter, an example of the surface protection layer 8 according to the present embodiment will be described with specific examples. In the present embodiment, the surface protection layer 8 may mainly include an acrylic resin composition containing cyclohexyl (meth) acrylate as a monomer component. In the present embodiment, cyclohexyl (meth) acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. By containing cyclohexyl (meth) acrylate as a monomer component, the affinity for water can be reduced, and deterioration due to hydrolysis or the like can be suppressed.

[0028] As for the content of cyclohexyl (meth) acrylate, among the monomer components of all the acrylic resin compositions, that is, among the monomer components of the acrylic resin composition which is the main component of the surface protective layer 8, it is desirable that the content of cyclohexyl (meth) acrylate is in the range of 5% by mass or more and 50% by mass or less. By setting the content of cyclohexyl (meth) acrylate to 5% by mass or more, a sufficient deterioration suppressing effect can be obtained. Further, by setting the content of cyclohexyl (meth) acrylate to 50% by mass or less, it becomes possible to impart high weather resistance over time without significantly changing various performances of the surface protective layer 8 of the decorative sheet such as maintaining and improving surface hardness, improving stain resistance, and adjusting the gloss of the surface. Here, the above-mentioned "main component" means that the content of the acrylic resin composition constituting the surface protective layer 8 is 50% by mass or more with respect to the mass of the entire surface protective layer 8.

[0029] As monomer components of the acrylic resin composition that can be used for the surface protective layer 8 according to the present embodiment, in addition to cyclohexyl (meth) acrylate, for example, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, cyclohexylbutyl (meth) acrylate, dimethylcyclohexane mono (meth) acrylate, dimethylcyclohexane di (meth) acrylate, trimethylcyclohexane mono (meth) acrylate, trimethylcyclohexane di (meth) acrylate, trimethylcyclohexane tri (meth) acrylate, tetramethylcyclohexane mono (meth) acrylate, tetramethylcyclohexane di (meth) acrylate, tetramethylcyclohexane tri (meth) acrylate, tetramethylcyclohexane tetra (meth) acrylate, dicyclohexylmethyl (meth) acrylate, dicyclohexylmethyl (meth) acrylate, phenoxycyclohexylmethyl (meth) acrylate, methoxycyclohexylmethyl (meth) acrylate and the like can be mentioned. Among these, those containing isomers may be each isomer alone and / or a mixture of each isomer.

[0030] Also, in the present embodiment, the surface protective layer 8 may be formed by applying a coating liquid containing an acrylic resin composition containing the above-described cyclohexyl (meth) acrylate as a monomer component and a weathering agent such as an ultraviolet absorber described later to the outermost surface of the decorative sheet. Although details will be described later, for example, after applying a coating liquid containing the above-described acrylic resin composition and a weathering agent onto the transparent polyvinyl chloride resin layer 6 having the embossed portion 10, wiping may be performed to embed the coating liquid into the embossed portion 10 to form the surface protective layer 8. As a method for curing the coating liquid for forming the surface protective layer 8, for example, any of a one-component curing type, a two-component curing type using a curing agent, or an active energy ray curing type in which curing is performed by irradiating ultraviolet rays, ionizing radiation, or the like can be used. However, considering weather resistance, the two-component curing type or the active energy ray curing type is preferable. If the post-processability after being bonded to various base materials to form a decorative member is considered, the two-component curing type crosslinked by isocyanate curing is desirable.

[0031] As the two-component curing type acrylic resin composition, for example, a composition containing an acrylic resin having two or more functional groups selected from a hydroxyl group, an amino group, and a carboxyl group in one molecule and a polyisocyanate compound having two or more isocyanate groups capable of reacting with the functional group in one molecule is preferable. Particularly preferably, it is a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound.

[0032] As the acrylic polyol having two or more carboxyl groups in one molecule, in addition to the cyclohexyl (meth) acrylate described above, for example, a (meth) acrylic acid ester copolymer containing hydroxyethyl (meth) acrylate as a monomer component can be used. On the other hand, as the polyisocyanate compound having two or more isocyanate groups in one molecule, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and their hydrogenated compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer types, TMP adduct types, burette types, etc. synthesized from one or more of these compounds by known techniques can be mentioned. In addition, a composition in which one or more selected from these different types of polyisocyanates are mixed can be used. Among them, HDI, or the trimer type, TMP adduct type, burette type of HDI is preferable from the viewpoint of weather resistance. The content of the isocyanate compound with respect to the resin component described above can be arbitrarily set, but it is desirable to set it so that the equivalent ratio of hydroxyl group / isocyanate group is about 1 / 1 to 1 / 3. In particular, when the equivalent of the hydroxyl group is more than the equivalent of the isocyanate group, crosslinking does not proceed sufficiently and the desired performance is not added to the surface protective layer 8, which may not be preferable.

[0033] When the curing method of the coating liquid for forming the surface protective layer 8 is active energy ray curing, as the active energy ray curing type acrylic resin composition, known monomers, oligomers, etc. having a (meth) acryloyl group can be used. In addition to these monomers and oligomers, the cyclohexyl (meth) acrylate described above may be blended. In order to further improve the weather resistance of the decorative sheet 1, in the present embodiment, an ultraviolet absorber and a light stabilizer are added to the surface protective layer 8 as weathering agents.

[0034] (Ultraviolet absorber) As the ultraviolet absorber, for example, known ones such as benzotriazole-based, triazine-based (e.g., hydroxyphenyltriazine-based), benzophenone-based ones can be used. Among these, if a hydroxyphenyltriazine-based ultraviolet absorber is selected, the triazine skeleton suppresses bleed, and the triazine skeleton is chemically more stable compared to the skeletons of benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers, etc., so that it becomes possible to maintain long-term ultraviolet absorption performance. That is, it is preferable that the surface protective layer 8 contains a triazine-based ultraviolet absorber as the ultraviolet absorber.

[0035] Examples of hydroxyphenyltriazine-based ultraviolet absorbers include, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-ethyl-hexanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine and the like. In the present embodiment, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (hereinafter, referred to as "ultraviolet absorber A" for convenience) may be contained in the surface protective layer 8. Note that 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, which is used as the ultraviolet absorber A, is generally known as the main component of "Tinuvin 479: manufactured by BASF Japan Ltd."

[0036] In the surface protective layer 8 of the present embodiment, the addition amount of the above-described triazine-based (hydroxyphenyltriazine-based) ultraviolet absorber is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin composition (for example, an acrylic resin composition) forming the surface protective layer 8. By setting the addition amount of the above-described ultraviolet absorber to 1 part by mass or more, the effect of improving weather resistance is exhibited, and by setting it to 30 parts by mass or less, the influence on physical properties other than the weather resistance of the surface protective layer 8 can be suppressed to a level that causes no practical problems. In particular, when the above-described ultraviolet absorber A is used as the ultraviolet absorber added to the surface protective layer 8, its addition amount is preferably in the range of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition, more preferably in the range of 5 parts by mass or more and 15 parts by mass or less, and even more preferably in the range of 8 parts by mass or more and 12 parts by mass or less. By setting the addition amount of ultraviolet absorber A to 1 part by mass or more, the effect of improving weather resistance is exhibited, and by setting it to 20 parts by mass or less, the influence on physical properties other than the weather resistance of the surface protective layer 8 can be suppressed to a level that causes no practical problems.

[0037] Further, in the present embodiment, by using ultraviolet absorber A and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (hereinafter, conveniently referred to as "ultraviolet absorber B") in combination as the triazine-based (hydroxyphenyltriazine-based) ultraviolet absorber in the surface protective layer 8, even more excellent weather resistance performance is imparted. This is because ultraviolet absorber B has a high ultraviolet absorption ability in the short wavelength region, which is relatively high in energy among ultraviolet rays, and is chemically stable compared to other ultraviolet absorbers that absorb in almost the same wavelength region. Therefore, the wavelength region for absorbing ultraviolet rays becomes wider by the combined use. Note that 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, which is used as ultraviolet absorber B, is generally known as the main component of "ADEKA STAB LA-46: manufactured by ADEKA CORPORATION".

[0038] In this embodiment, it is preferable that the addition amount of the ultraviolet absorber A in the surface protective layer 8 is in the range of 10 parts by mass or more and 200 parts by mass or less, more preferably in the range of 20 parts by mass or more and 100 parts by mass or less, and even more preferably in the range of 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the ultraviolet absorber B. By setting the addition amount of the ultraviolet absorber A within the above numerical range, more excellent weather resistance can be imparted.

[0039] (Light stabilizer) As the light stabilizer added to the surface protective layer 8, for example, a radical scavenger can be used. By using the above-mentioned triazine-based ultraviolet absorber and the radical scavenger in combination, the weather resistance performance of the cosmetic sheet 1 can be further improved. Examples of the hindered amine-based radical scavenger that can be used in this embodiment include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1-(2-hydroxyethyl)-2,2,6,6 -tetramethyl-4-piperidinol / succinic acid diethyl polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tri-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis〔2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl〕-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis〔2,4-bis(N-butyl-N-(1,2,2,6,(6-Pentamethyl-4-piperidyl)amino)-s-triazin-6-yl)-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate cyclohexane and the reaction product of N-butyl 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro-1,3,5-triazine with 2-aminoethanol, etc. are mentioned, but it is not limited thereto.,

[0040] In this embodiment, the addition amount of the light stabilizer (for example, a hindered amine-based radical scavenger) in the surface protection layer 8 is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin composition (for example, an acrylic resin composition) for forming the surface protection layer 8. By adding 1 part by mass or more of the light stabilizer, desired weather resistance can be obtained, and by setting it to 30 parts by mass or less, bleeding out of the weathering agent can be suppressed, and the influence on other physical properties of the surface protection layer 8 can be suppressed. In this embodiment, the surface protection layer 8 is described as containing an ultraviolet absorber and a light stabilizer, but the present disclosure is not limited thereto. The surface protection layer 8 may be provided with desired weather resistance according to the application, and the surface protection layer 8 may be configured to contain at least one of an ultraviolet absorber and a light stabilizer.

[0041] (Coating amount) The coating amount of the surface protection layer 8, that is, the coating amount of the material of the surface protection layer 8 on the transparent polyvinyl chloride resin layer 6 is 3 g / m 2 or more and 10 g / m 2 less is preferred. If the coating amount is less than 3 g / m 2 less, good weather resistance cannot be obtained, and if it is 10 g / m2 If it is more than this, there is a risk of inhibiting recyclability. Therefore, by setting the coating amount within the above range, it is possible to achieve both good weather resistance and recyclability. Further, by setting the coating amount within the above range, productivity and processability (for example, bend processability) can be improved.

[0042] (Embossed part) As shown in FIG. 1, an embossed part 10 is provided on the outermost surface of the decorative sheet 1. By providing the embossed part 10 on the outermost surface, it is possible to improve fingerprint resistance while maintaining, for example, the matte feeling on the surface of the decorative sheet 1. Further, the embossed part 10 can be provided with various uneven shapes such as wood grain conduit grooves, unevenness on the surface of a stone slab (such as a granite split surface), fabric surface texture, satin finish, sandblasted finish, hairline, and multi-line grooves, so as to impart a given design property to the surface of the decorative sheet 1. The embossed part 10 can have various uneven shapes according to, for example, the design of the pattern layer 4 or the desired design property. The embossed part 10 is formed on the surface (outermost surface) side of the surface protection layer 8 which is the outermost layer of the decorative sheet 1, and constitutes an uneven pattern. In the present embodiment, the above-described surface protection layer 8 is embedded in the embossed part 10 that constitutes this uneven pattern. Hereinafter, this point will be described.

[0043] In the decorative sheet 1 according to the present embodiment, the embossed part 10 is provided in the transparent polyvinyl chloride resin layer 6. That is, the transparent polyvinyl chloride resin layer 6 is a layer in which the embossed part 10 is formed. The shape of the uneven pattern provided on the surface of the transparent polyvinyl chloride resin layer 6 is not particularly limited, but the shape of the embossed part 10 that constitutes the uneven pattern is preferably such that the opening diameter increases from the pattern layer 4 side of the transparent polyvinyl chloride resin layer 6 toward the surface protection layer 8. With such a shape, when the surface protection layer composition (coating liquid) is embedded in the embossed part 10 by wiping, the embedding becomes easy.

[0044] Also, the side surface forming the embossed portion 10 is preferably an inclined surface. If the side surface forming the embossed portion 10 is an inclined surface, when embedding the surface protective layer composition (coating liquid) into the embossed portion 10 by wiping, the embedding becomes easy. Also, all of the side surfaces forming the embossed portion 10 may be covered with the surface protective layer 8. Also, the depth of the embossed portion 10 is preferably in the range of 1 μm or more and 50 μm or less with respect to the thickness direction of the transparent polyvinyl chloride resin layer 6. If the depth of the embossed portion 10 is within the above numerical range, when embedding the surface protective layer composition (coating liquid) into the embossed portion 10 by wiping, the embedding becomes easy, and peeling of the surface protective layer can be prevented.

[0045] Also, the width of the embossed portion 10 in the cross section shown in FIG. 1 is preferably in the range of 1 μm or more and 20 μm or less. If the width of the embossed portion 10 is within the above numerical range, when embedding the surface protective layer composition (coating liquid) into the embossed portion 10 by wiping, the embedding becomes easy, and peeling of the surface protective layer embedded in the embossed portion 10 can be prevented.

[0046] Also, the embossed portion 10 is preferably entirely filled (packed) with the surface protective layer composition (coating liquid), but the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 is preferably 10% or more. If the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 is 10% or more, the weather resistance in the embossed portion 10 can be improved. That is, if the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 is 10% or more, for example, the occurrence of whitening and breakage in the conduit portion can be reduced. Also, as described above, the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 is preferably 100%, but more preferably 80% or less, and even more preferably 60% or less with respect to the volume of the embossed portion 10. If the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 is 80% or less, a sufficient tactile sensation can be obtained in the embossed portion 10.

[0047] Also, by setting the filling rate of the surface protection layer 8 with respect to the volume of the embossed portion 10 to 100%, the surface of the surface protection layer 8 filled in the embossed portion 10 and the surface of the transparent polyvinyl chloride resin layer 6 in the region without the embossed portion 10 may be flush, so to speak. Note that the embossed portion 10 does not necessarily have to be provided.

[0048] (Weather-resistant resin layer) As described above, the transparent polyvinyl chloride resin layer 6 contains an ultraviolet absorber, and further, the surface protection layer 8 contains at least one of an ultraviolet absorber and a light stabilizer. In the present embodiment, the laminate formed by combining the two layers of the transparent polyvinyl chloride resin layer 6 and the surface protection layer 8 is also referred to as a weather-resistant resin layer. The weather-resistant resin layer imparts excellent weather resistance to the decorative sheet 1. By providing the weather-resistant resin layer (transparent polyvinyl chloride resin layer 6 and surface protection layer 8), the decorative sheet 1 according to the present embodiment is imparted with excellent weather resistance, and for example, it can be expected to withstand long-term outdoor use as a decorative sheet for decorating the surface of fixtures such as window frames for exterior applications. Furthermore, in the decorative sheet 1, the transmittance of ultraviolet rays with a wavelength of 380 nm when the two layers of the transparent polyvinyl chloride resin layer 6 and the surface protection layer 8 are combined is preferably 20%T or less. That is, in the weather-resistant resin layer, the transmittance of ultraviolet rays with a wavelength of 380 nm is preferably 20%T or less. Thereby, the weather resistance of the decorative sheet 1 can be further improved.

[0049] (Total thickness of the decorative sheet) The total thickness of the decorative sheet 1, that is, the sum of the thickness of the colored polyvinyl chloride resin layer 2, the pattern layer 4, the transparent polyvinyl chloride resin layer 6, and the surface protective layer 8, is preferably in the range of 80 μm or more and 300 μm or less, and more preferably in the range of 120 μm or more and 200 μm or less. When the total thickness of the decorative sheet 1 is less than 80 μm, the concealability and scratch resistance decrease. Further, when processing the decorative sheet 1, the sheet has no stiffness and the productivity decreases. When the total thickness of the decorative sheet 1 is more than 300 μm, the processing suitability such as bending decreases. Thereby, for example, a decorative sheet 1 having concealability equivalent to that of a conventional decorative sheet formed using an olefin resin and having good processing suitability can be formed. Here, the total thickness of the decorative sheet 1 means, in the case of the decorative sheet 1 shown in FIG. 1, the sum of the thickness of the colored polyvinyl chloride resin layer 2, the pattern layer 4, the transparent polyvinyl chloride resin layer 6, and the surface protective layer 8, that is, the sum of the thicknesses of all the layers constituting the decorative sheet 1. For example, in the decorative sheet 1 shown in FIG. 1, when a concealment layer is provided between the pattern layer 4 and the colored polyvinyl chloride resin layer 2, it means the total thickness of the decorative sheet 1 obtained by adding the thickness of the colored polyvinyl chloride resin layer 2, the pattern layer 4, the transparent polyvinyl chloride resin layer 6, the surface protective layer 8, and the thickness of the concealment layer.

[0050] (Martens hardness of decorative sheet) The decorative sheet 1 preferably has a Martens hardness measured according to ISO14577-1:2002 in the range of 50 MPa or more and 150 MPa or less. When the Martens hardness of the decorative sheet 1 is less than 50 MPa, the productivity and scratch resistance decrease. When the Martens hardness is more than 150 MPa, the decorative sheet 1 is too hard and causes whitening cracks or the like when processing the decorative sheet 1. Here, the Martens hardness is a kind of index indicating the hardness of a substance. A load is applied to an indenter to press it into the surface of a sample, and the depth (indentation depth) of the depression (indentation) formed at that time is measured. It is defined as the quotient of the indentation force calculated from the load and the surface area of the depression calculated from the indentation depth.

[0051] (Composite Elastic Modulus of Cosmetic Sheet) The composite elastic modulus of the cosmetic sheet 1, measured in accordance with ISO14577-1:2002, is preferably in the range of 2000 MPa or more and 4500 MPa or less. When the composite elastic modulus of the cosmetic sheet 1 is less than 2000 MPa, the cosmetic sheet 1 is too soft, resulting in a decrease in productivity when printing a pattern layer or the like. When it is greater than 4500 MPa, sheet springing, cracking, etc. occur when processing the cosmetic sheet 1. Here, the composite elastic modulus refers to the elastic modulus including the elastic deformation of the sample and the elastic deformation of the indenter. Here, the indenter is a hard substance that is pressed into the test material in a hardness test. Also, elastic deformation refers to deformation that returns to its original shape when the force is removed. After the indenter is pressed into the sample until the maximum load (Fmax) is reached, the maximum load is held for a certain period of time. Then, the load is unloaded to zero to return to the original state to obtain a load-displacement curve. The composite elastic modulus Er is calculated from the following formula using the contact projected area Ap of the indenter and the slope S of the tangent line at the maximum load of the unloading curve in the load-displacement curve. Er = ((π 1 / 2 ) / 2) × (S / Ap)

[0052] (Cosmetic Member) The cosmetic sheet 1 shown in Fig. 1 may be bonded to the base material 20 as shown in Fig. 2 to form a cosmetic member 100.

[0053] (Base Material) As the base material 20, a wood base material or a metal base material can be used. As the wood base material, for example, a wood veneer, a plywood, a laminated wood, a particle board, a medium density fiberboard, or a hard fiberboard can be adopted. Further, as the metal base material, a steel plate, an aluminum plate, etc. can be adopted. Further, the base material 20 may be a resin such as plastic or a composite material thereof. When the base material 20 is a resin base material, for example, a vinyl chloride resin can be adopted. The base material 20 made of a vinyl chloride resin has high heat insulation properties and the demand as a window frame fixture (sash) is increasing. Further, the decorative member 100 obtained by decorating the base material 20 made of a vinyl chloride resin with the decorative sheet 1 can dissolve both the base material 20 and the decorative sheet 1 and can be reused, and the recyclability can be made better.

[0054] Further, the base material 20 may be composed of, for example, a non-combustible steel plate or a non-combustible material defined in the Ministry of Construction Notification No. 1400. Further, the base material 20 may have a structure subjected to bending processing or a three-dimensional structure. By bonding the decorative sheet 1 according to the present embodiment to the base material 20, even when the base material 20 is formed using a polyvinyl chloride resin, a decorative member having excellent weather resistance, further excellent processing suitability and recyclability can be obtained. Note that the configuration of the decorative member 100 is not limited to the example shown in FIG. 2. That is, the configuration of the decorative member 100 may be a configuration including a decorative sheet 1 laminated on the other surface (the lower surface in FIG. 1) of the base material 20 in addition to one surface of the base material 20.

[0055] When laminating the decorative sheet 1 on the base material 20, it may be laminated via an appropriately selected adhesive as necessary, or may be directly laminated without using an adhesive or the like. The adhesive may be selected according to the material of the base material 20, and may be a two-component curing type or a hot melt type adhesive. As a method of laminating and adhering the decorative sheet 1 to the base material 20, it is possible to use a method of pressing flat by contacting a metal plate or a rotary laminating method. In particular, when using a continuous laminating method using an endless metal belt, there are no warps or undulations on the surface, and furthermore, the adhesion between layers is good, and it is possible to continuously manufacture high-quality decorative members 100 that are densely cured and integrated at high speed.

[0056] Applying it to a fitting member such as a window frame, particularly an exterior fitting member, as the base material 20 is effective. That is, exterior fittings are particularly required to have weather resistance. In addition, due to the increasing awareness of zero-energy houses (ZEH), etc., there is a high demand for fittings such as highly heat-insulating window frames using polyvinyl chloride resin. Since the decorative sheet 1 is formed using polyvinyl chloride, by particularly attaching it to a fitting member such as a window frame using polyvinyl chloride resin and making the base material 20 and the decorative sheet 1 monomaterial, it is possible to obtain a fitting, particularly an exterior fitting, having higher recyclability compared to the case of using an olefin-based resin sheet or the like. In addition, it is also possible to apply a fitting member made of other materials, such as an aluminum material, as the base material 20. In this case, although the recyclability decreases somewhat compared to the case of making it monomaterial, by bonding the decorative sheet 1 using polyvinyl chloride resin, it is possible to obtain a fitting with high weather resistance and good processing suitability.

[0057] (Method for manufacturing decorative sheet and decorative member) Hereinafter, an example of the manufacturing method of the decorative sheet 1 according to the present embodiment will be briefly described. For example, a pattern layer 4 is printed on a colored polyvinyl chloride resin layer 2 made of a colored polyvinyl chloride resin sheet. Next, a transparent polyvinyl chloride resin layer 6 is formed by thermal lamination on the colored polyvinyl chloride resin layer 2 on which the pattern layer 4 is formed. At the same time, an embossed pattern is provided on the surface of the transparent polyvinyl chloride resin layer 6 opposite to the colored polyvinyl chloride resin layer 2 by embossing to form an embossed portion 10. Next, a coating liquid for forming the surface protective layer 8 is applied to the surface of the transparent polyvinyl chloride resin layer 6 having the concavo-convex pattern (embossed portion 10). Finally, the coating liquid is wiped so as to be embedded in the embossed portion 10 constituting the concavo-convex pattern, and the coating liquid is cured to form the surface protective layer 8 on the transparent polyvinyl chloride resin layer 6. Thus, the decorative sheet 1 according to the present embodiment is formed.

[0058] An adhesive is applied to the surface of the decorative sheet 1 formed in this way on the colored polyvinyl chloride resin layer 2 side, and the base material 20 is attached, whereby the decorative sheet 1 and the base material 20 are bonded via the adhesive layer 12 to form a decorative member 100. Note that the above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment, and various modifications can be made according to the design and the like as long as they do not deviate from the technical idea of the present invention even in forms other than this embodiment.

[0059] (Effect) (1) In the decorative sheet 1 according to the present embodiment, at least the colored polyvinyl chloride resin layer 2, the pattern layer 4, the transparent polyvinyl chloride resin layer 6, and the surface protective layer 8 are laminated in this order, and the Martens hardness of the decorative sheet 1 is in the range of 50 MPa or more and 150 MPa or less, and the complex elastic modulus is in the range of 2000 MPa or more and 4500 MPa or less. Therefore, it is possible to suppress a decrease in productivity and scratch resistance, and also to suppress the occurrence of whitening cracks and the like during processing, and to obtain a decorative sheet excellent in processing suitability and recyclability. Further, it is possible to suppress the occurrence of sheet flaking and cracking during processing.

[0060] (2) The colored polyvinyl chloride resin layer 2 contains an inorganic substance. Therefore, when the decorative sheet 1 is bonded to an adherend, it is possible to conceal variations in the color of the surface of the base material or the like, and to improve the thermal stability of the entire decorative sheet 1. (3) Since the total thickness of the cosmetic sheet 1 is 80 μm or more and 300 μm or less, concealment and scratch resistance can be exhibited, and since it has an appropriate stiffness, it is possible to suppress improper processing and a decrease in productivity during processing. (4) Since the outermost surface on the surface protection layer side is embossed, the design property can be improved.

[0061] (5) Since the decorative member 100 includes the base material 20 and the cosmetic sheet 1 bonded to the base material 20, even when the cosmetic sheet 1 is formed using a polyvinyl chloride resin, it has excellent weather resistance, and furthermore, a decorative member 100 excellent in processing suitability and recyclability can be provided. (6) Since the cosmetic sheet 1 is bonded to the fixture member as the base material 20 to form a fixture, even when the cosmetic sheet 1 is formed using a polyvinyl chloride resin, it has excellent weather resistance, and furthermore, a fixture excellent in processing suitability and recyclability can be provided. In particular, by bonding the cosmetic sheet 1 to the exterior fixture member (base material 20) made of a vinyl chloride-based material, both the cosmetic sheet 1 and the fixture member are made of a vinyl chloride-based material to be a single material, so that the recyclability can be further enhanced.

Example

[0062] Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to the following examples.

[0063] (Example 1) A colored polyvinyl chloride resin sheet as the colored polyvinyl chloride resin layer 2 was used, and a printing ink for vinyl chloride was gravure-printed on one surface of the colored polyvinyl chloride resin layer 2 to form a pattern layer 4. Then, a transparent polyvinyl chloride sheet having high weather resistance was thermally laminated on the colored polyvinyl chloride resin layer 2 including the pattern layer 4. Then, as the surface protection layer 8, a resin composition mainly composed of an acrylic resin composition was laminated on the transparent polyvinyl chloride sheet. Then, the decorative member 100 of Example 1 was obtained by bonding the base material 20 using a urethane-based adhesive to the surface of the colored polyvinyl chloride resin sheet opposite to the pattern layer 4. The composition of each layer is as follows.

[0064] (Colored polyvinyl chloride resin layer 2) Material: Polyvinyl chloride resin (PVC) Thickness: 80 μm Colorant: Inorganic substance

[0065] (Pattern layer 4) Material: Ink using a mixture of vinyl chloride resin-vinyl acetate resin copolymer resin and acrylic resin as a binder resin Thickness: 1 μm

[0066] (Transparent polyvinyl chloride resin layer 6) Material: Polyvinyl chloride resin (PVC) Thickness: 20 μm UV absorber: Triazine-based UV absorber 0.5 parts by mass Plasticizer: Polyester-based resin (PN-7160, manufactured by ADEKA Corporation) 25 PHR

[0067] (Surface protection layer 8) Main agent: Methyl methacrylate / 2-hydroxyethyl methacrylate = 95 / 5 copolymer) 90 parts by mass UV absorber: Tinuvin 479 manufactured by BASF Japan Ltd. 9 parts by mass Light stabilizer: Tinuvin 123 manufactured by BASF Japan Ltd. 1 part by mass Hardening agent: Takenate D170 manufactured by Mitsui Chemicals, Inc. 10 parts by mass Solvent: Ethyl acetate 240 parts by mass Coating amount 3 g / m 2 Thickness: 1 μm

[0068] (Example 2) A decorative member of Example 2 was obtained in the same manner as in Example 1 above, except that the thickness of the transparent polyvinyl chloride resin layer 6 was changed to 170 μm. (Example 3) A decorative member of Example 3 was obtained in the same manner as in Example 1, except that the thickness of the transparent polyvinyl chloride resin layer 6 was 80 μm.

[0069] (Example 4) A decorative member of Example 4 was obtained in the same manner as in Example 3, except that the plasticizer content in the transparent polyvinyl chloride resin layer 6 was 20 PHR. (Example 5) A decorative member of Example 5 was obtained in the same manner as in Example 3, except that the plasticizer content in the transparent polyvinyl chloride resin layer 6 was 30 PHR.

[0070] (Example 6) A decorative member of Example 6 was obtained in the same manner as in Example 3, except that the plasticizer content in the transparent polyvinyl chloride resin layer 6 was 35 PHR. (Example 7) A decorative member of Example 7 was obtained in the same manner as in Example 4, except that the plasticizer in the transparent polyvinyl chloride resin layer 6 was a phthalic acid resin.

[0071] (Example 8) A decorative member of Example 8 was obtained in the same manner as in Example 7, except that the plasticizer content in the transparent polyvinyl chloride resin layer 6 was 30 PHR. (Example 9) A decorative member of Example 9 was obtained in the same manner as in Example 3, except that an organic substance was used as the colorant for the colored polyvinyl chloride resin layer 2.

[0072] (Comparative Example 1) A decorative member of Comparative Example 1 was obtained in the same manner as in Example 1, except that the thickness of the colored polyvinyl chloride resin layer 2 was 40 μm and the thickness of the transparent polyvinyl chloride resin layer 6 was 10 μm. (Comparative Example 2) A decorative member of Comparative Example 2 was obtained in the same manner as in Example 1, except that the thickness of the transparent polyvinyl chloride resin layer 6 was 270 μm.

[0073] (Comparative Example 3) A decorative member of Comparative Example 3 was obtained in the same manner as in Example 3 above, except that the plasticizer content in the transparent polyvinyl chloride resin layer 6 was set to 10 PHR. (Comparative Example 4) A decorative member of Comparative Example 4 was obtained in the same manner as in Example 3 above, except that the plasticizer content in the transparent polyvinyl chloride resin layer 6 was set to 15 PHR.

[0074] (Comparative Example 5) A decorative member of Comparative Example 5 was obtained in the same manner as in Example 3 above, except that the plasticizer content in the transparent polyvinyl chloride resin layer 6 was set to 40 PHR. (Comparative Example 6) A decorative member of Comparative Example 6 was obtained in the same manner as in Example 7 above, except that the plasticizer content in the transparent polyvinyl chloride resin layer 6 was set to 10 PHR.

[0075] (Comparative Example 7) A decorative member of Comparative Example 7 was obtained in the same manner as in Example 7 above, except that the plasticizer content in the transparent polyvinyl chloride resin layer 6 was set to 40 PHR. (Comparative Example 8) A decorative member of Comparative Example 8 was obtained in the same manner as in Example 3 above, except that an olefin resin was used as the colored polyvinyl chloride resin layer 2.

[0076] [Evaluation] For each of the decorative members of the examples and comparative examples, evaluation was performed on Martens hardness, complex elastic modulus, pencil hardness, productivity, processability, weather resistance, recyclability, and hiding power. The evaluation criteria are as follows.

[0077] (Martens hardness and complex elastic modulus) For each of the decorative sheets, in accordance with ISO 14577-1:2002, using a nanoindenter (manufactured by BRUKER), Martens hardness and complex elastic modulus were measured at a penetration speed of 10.0 mm / s and a load of 2.0 mN.

[0078] (Pencil hardness) A Hi-uni pencil manufactured by Mitsubishi Pencil Co., Ltd. with its tip flattened using sandpaper was used to apply a load of 750 g and push the sample surface at a speed of 0.8 mm / s for a distance of 7 mm. The hardness (pencil hardness) of the hardest pencil that did not cause scratches on the surface was obtained. When the obtained pencil hardness was 4B or higher, it was considered qualified.

[0079] (Productivity) The production status during printing on the PVC sheet was evaluated. ◎: Can be produced under a wide range of production conditions 〇: Can be produced with limited printing conditions ×: Difficult to produce.

[0080] (Processing suitability) Lapping processing was performed on the PVC substrate using each decorative sheet. Visual observation was carried out to check if there were any abnormalities such as whitening or cracks (cracks / fissures) in the bent parts of the surface of the decorative sheet after lapping processing, and an evaluation was made on the state of processing suitability. Note that this lapping processability corresponds to what is commonly referred to as bending processability among processing suitability. ◎: No abnormalities were confirmed, and it has lapping processability equivalent to that of decorative sheets made of olefin-based resins 〇: Abnormalities were confirmed, but lapping processing is possible although it is inferior to that of decorative sheets made of olefin-based resins ×: Abnormalities were confirmed throughout, and lapping processing is impossible In this example, "〇" or above was considered qualified.

[0081] (Weather resistance) The appearance of each decorative member after the weathering acceleration test was visually evaluated according to the following criteria. The weathering acceleration test was carried out using a Metal Weather Tester (KU-R5DCI-A) manufactured by Daipra Winters Co., Ltd. at a black panel temperature of 63°C and an illuminance of 65 mW / cm 2 With (UV irradiation for 20 hours + dew condensation for 4 hours) as one cycle, 21 cycles (504 hours) were carried out. The color difference ΔE before and after the weathering acceleration test was evaluated. ◎: ΔE < 2.0 〇: ΔE = 2.0 or more and 4.0 or less ×: ΔE > 4.0 Those with "○" or above passed.

[0082] (Recyclability) The ease of decomposition of the cosmetic member, which is a laminated product of a cosmetic sheet and a base material, into a single material was evaluated. Specifically, each cosmetic member was melted, and the state when it was extruded by an extruder as a recycled base material after melting was evaluated. The evaluation criteria are shown below. ◎: No unmelted cosmetic sheet remains in the recycled base material, and it is in the same state as a normal PVC (non-recycled PVC) base material, and can be easily decomposed. 〇: Although the extrudability is inferior to that of a normal PVC base material, it can be decomposed. ×: Extrusion is very difficult and decomposition is difficult.

[0083] (Concealability) A white and a black plate were placed under the colored polyvinyl chloride resin layer 2, and when the color of the plate could be distinguished in that state, it was evaluated as "×", and when it could not be distinguished, it was evaluated as "○". The above evaluation results are shown in Table 1. In Table 1, the sum of the transparent polyvinyl chloride resin layer 6 and the colored polyvinyl chloride resin layer 2 is described as "thickness (transparent resin / colored resin)".

[0084]

Table 1

[0085] As shown in Table 1, in a cosmetic sheet in which a colored polyvinyl chloride resin layer, a pattern layer, a transparent polyvinyl chloride resin layer, and a surface protective layer are laminated in this order, the Martens hardness measured in accordance with ISO14577-1:2002 is in the range of 50 MPa or more and 150 MPa or less, and also, if the complex elastic modulus is in the range of 2000 MPa or more and 4500 MPa or less, a cosmetic sheet having high processing suitability and recyclability can be obtained. Furthermore, it was confirmed that the recyclability of the cosmetic member 100 can be further improved as compared with the case where an olefin-based resin is used as the cosmetic sheet.

[0086] Incidentally, the present invention can be configured as follows, for example. (1) A decorative sheet in which at least a colored polyvinyl chloride resin layer, a pattern layer, a transparent polyvinyl chloride resin layer, and a surface protection layer are laminated in this order, wherein the Martens hardness of the decorative sheet measured according to ISO14577-1:2002 is in the range of 50 MPa or more and 150 MPa or less, and the complex elastic modulus of the decorative sheet measured according to ISO14577-1:2002 is in the range of 2000 MPa or more and 4500 MPa or less. The decorative sheet according to (1) above. (2) The colored polyvinyl chloride resin layer contains any one or more inorganic substances of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, and titanium composite. The decorative sheet according to (1) above. (3) The total thickness of the decorative sheet is in the range of 80 μm or more and 300 μm or less. The decorative sheet according to (1) or (2) above. (4) The decorative sheet according to any one of (1) to (3) above, wherein embossing is applied to the outermost surface on the surface protection layer side. (5) A decorative sheet according to any one of (1) to (4) above, and a base material disposed on the side of the colored polyvinyl chloride resin layer opposite to the pattern layer side. A decorative member characterized by comprising. (6) A decorative sheet according to any one of (1) to (4) above, and a fitting member disposed on the side of the colored polyvinyl chloride resin layer opposite to the pattern layer side. A fitting characterized by comprising. (7) The fitting member is an exterior fitting member made of a vinyl chloride-based material. The fitting according to (6) above.

Explanation of symbols

[0087] 1 Cosmetic sheet 2 Colored polyvinyl chloride resin layer 4 Pattern layer 6 Transparent polyvinyl chloride resin layer 8 Surface protection layer 10 Embossed part 20 Base material 100 Cosmetic member

Claims

1. A decorative sheet in which at least a colored polyvinyl chloride resin layer, a pattern layer, a transparent polyvinyl chloride resin layer, and a surface protective layer are laminated in this order, wherein the Martens hardness of the decorative sheet measured according to ISO 14577-1:2002 is in the range of 50 MPa or more and 150 MPa or less, and the complex elastic modulus of the decorative sheet measured according to ISO 14577-1:2002 is in the range of 2000 MPa or more and 4500 MPa or less. A decorative sheet characterized by this.

2. The colored polyvinyl chloride resin layer according to claim 1, characterized in that it contains any one or more inorganic substances among calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, and titanium composites. Decorative sheet.

3. The total thickness of the decorative sheet is in the range of 80 μm or more and 300 μm or less. The decorative sheet according to claim 1, characterized by this.

4. The decorative sheet according to claim 1, characterized in that embossing is applied to the outermost surface on the surface protective layer side.

5. A decorative sheet according to any one of claims 1 to 4, and a base material disposed on the side of the colored polyvinyl chloride resin layer opposite to the pattern layer side. A decorative member characterized by this.

6. A decorative sheet according to any one of claims 1 to 4, and a fitting member disposed on the side of the colored polyvinyl chloride resin layer opposite to the pattern layer side. A fitting characterized by this.

7. The fitting according to claim 6, characterized in that the fitting member is an exterior fitting member made of a vinyl chloride-based material.

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