Decorative sheets and decorative materials

Abstract

To provide a decorative sheet having an excellent weather resistance.SOLUTION: A decorative sheet includes a substrate layer 1, a weather resistance layer 2, and a surface protective layer 3 in this order in a thickness direction. The substrate layer contains a vinyl chloride resin. The weather resistance layer contains a (meth)acrylic resin and a triazine-type ultraviolet absorber, and has thickness of 30 μm or thicker. The surface protective layer contains a triazine-type ultraviolet absorber.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present disclosure relates to a decorative sheet and a decorative member. [Background technology]

[0002] For example, decorative members having a base and a decorative sheet are known as interior or exterior components used in building materials. Various resins are used for the base layer of the decorative sheet. Among them, decorative sheets using a base layer containing a vinyl chloride resin have good processability when placed on a base. Various decorative sheets using a base layer containing a vinyl chloride resin have been proposed in the past (for example, Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2021-154669 A [Patent Document 2] JP 2020-055290 A [Patent Document 3] JP 2020-163576 A Summary of the Invention [Problem to be solved by the invention]

[0004] A decorative sheet using a base layer containing a vinyl chloride resin is required to have good weather resistance in order to suppress discoloration over time. In particular, in the case of exterior components (decorative components for exterior use), a decorative sheet using a base layer containing a vinyl chloride resin is required to have excellent weather resistance.

[0005] The present disclosure has been made in consideration of the above-mentioned circumstances, and has an object to provide a decorative sheet having excellent weather resistance. [Means for solving the problem]

[0006] The present disclosure provides a decorative sheet having a base layer, a design layer, a weather-resistant layer, and a surface protective layer, in that order in the thickness direction, wherein the base layer contains a vinyl chloride-based resin, the weather-resistant layer contains a (meth)acrylic resin and a triazine-based ultraviolet absorber, and has a thickness of 30 μm or more, and the surface protective layer contains a triazine-based ultraviolet absorber.

[0007] The present disclosure provides a decorative member having a substrate and the decorative sheet described above. Effect of the Invention

[0008] The present disclosure has an effect of providing a decorative sheet having excellent weather resistance. [Brief description of the drawings]

[0009] [Figure 1] 1 is a schematic cross-sectional view illustrating a decorative sheet according to the present disclosure. [Diagram 2] 1 is a schematic cross-sectional view illustrating a decorative sheet according to the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The following describes the embodiments with reference to the drawings. However, the present disclosure can be implemented in many different forms and should not be limited to the description of the embodiments exemplified below. In addition, the drawings may show the width, thickness, and shape of each part in a schematic manner compared to the actual form in order to make the description clearer, but this is merely an example and should not be interpreted as being limiting.

[0011] In this specification, when describing an aspect in which another component is disposed on a certain component, the term "above" or "below" includes both cases in which another component is disposed directly above or below a certain component so as to be in contact with the component, and cases in which another component is disposed above or below a certain component with another component interposed therebetween, unless otherwise specified. Also, in this specification, when describing an aspect in which another component is disposed on the surface of a certain component, the term "on the surface" includes both cases in which another component is disposed directly above or below a certain component so as to be in contact with the component, and cases in which another component is disposed above or below a certain component with another component interposed therebetween, unless otherwise specified.

[0012] A. Decorative sheet 1 and 2 are schematic cross-sectional views illustrating decorative sheets according to the present disclosure. T 2 has a base layer 1, a weather-resistant layer 2, and a surface protective layer 3, in this order. The base layer 1 contains a vinyl chloride resin, the weather-resistant layer 2 contains a (meth)acrylic resin and a triazine-based ultraviolet absorber, and the surface protective layer 3 contains a triazine-based ultraviolet absorber. The weather-resistant layer 2 has a thickness of 30 μm or more. The decorative sheet 10 shown in FIG. 2 has a thickness of 100 μm or more in the thickness direction D T has a base layer 1, a design layer 4, a weather-resistant layer 2 and a surface protective layer 3, in this order.

[0013] According to the present disclosure, by providing a specific weather-resistant layer and a specific surface protective layer, even if the substrate layer contains a vinyl chloride resin, the decorative sheet has excellent weather resistance. As described above, a decorative sheet using a substrate layer containing a vinyl chloride resin has the advantage of being easily processable when placed on a substrate. On the other hand, a decorative sheet using a substrate layer containing a vinyl chloride resin is required to have good weather resistance in order to suppress discoloration over time. In particular, in the case of exterior members (decorative members for exterior use), a decorative sheet using a substrate layer containing a vinyl chloride resin is required to have excellent weather resistance. Specifically, since exterior members are exposed to an environment that is easily exposed to sunlight and an environment with large changes in temperature, vinyl chloride resins are more likely to discolor than interior members. In this respect, a decorative sheet using a substrate layer containing a vinyl chloride resin is required to have excellent weather resistance.

[0014] The present inventors have considered providing a weather-resistant layer containing a triazine-based ultraviolet absorber having high ultraviolet absorbing ability between a substrate layer containing a vinyl chloride resin and a surface protective layer. Here, by using a vinyl chloride-based resin as the resin used in the weather-resistant layer, like the substrate layer, there is an advantage that a decorative sheet having good processability when placed on a substrate can be obtained. On the other hand, detailed studies on decorative sheets using a weather-resistant layer containing a vinyl chloride resin have revealed that there is room for further improvement in weather resistance. Therefore, the present inventors have conducted intensive research into improving weather resistance, and have found that when a (meth)acrylic resin is used as the resin constituting the weather-resistant layer and the thickness of the weather-resistant layer is set to a predetermined range or more, the weather resistance of the decorative sheet can be improved. In addition, by setting the thickness of the weather-resistant layer within a predetermined range, a weather-resistant layer having good processability can be obtained, similar to the case of using a vinyl chloride resin, even when a (meth)acrylic resin is used.

[0015] Furthermore, since the surface protective layer in the present disclosure contains a triazine-based ultraviolet absorber, the decorative sheet has excellent weather resistance in this respect as well. In addition, since both the surface protective layer and the weather-resistant layer contain a triazine-based ultraviolet absorber, the ratio of the triazine-based ultraviolet absorber in the surface protective layer can be relatively reduced. As a result, the weather resistance of the decorative sheet can be improved while suppressing the deterioration of the surface properties (e.g., contamination resistance) required for the surface protective layer. Also, for example, assume a case where a surface protective layer is formed on a weather-resistant layer using an ionizing radiation curable resin. When the weather-resistant layer contains a vinyl chloride-based resin, there is a possibility that a dechlorination reaction (discoloration) will occur in the vinyl chloride-based resin contained in the weather-resistant layer due to ionizing radiation (e.g., electron beam irradiation, ultraviolet irradiation). In contrast, when the weather-resistant layer contains a (meth)acrylic resin, a dechlorination reaction will not occur in the (meth)acrylic resin, so that the deterioration of the weather-resistant layer during the formation of the surface protective layer can be suppressed.

[0016] 1. Weatherproof layer The weather-resistant layer in the present disclosure is disposed between the substrate layer and the surface protective layer, and contains a (meth)acrylic resin and a triazine-based ultraviolet absorber. (Meth)acrylic means acrylic or methacrylic.

[0017] (1) (Meth)acrylic resin The weather-resistant layer in the present disclosure contains a (meth)acrylic resin. Examples of the (meth)acrylic resin include polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, methyl(meth)acrylate-butyl(meth)acrylate copolymer, methyl(meth)acrylate-styrene copolymer, methyl(meth)acrylate-butyl(meth)acrylate-2-hydroxyethyl(meth)acrylate copolymer, and methyl(meth)acrylate-butyl(meth)acrylate-2-hydroxyethyl(meth)acrylate-styrene copolymer. Among them, polymethyl(meth)acrylate and polybutyl(meth)acrylate are preferred.

[0018] The weather-resistant layer may contain only a (meth)acrylic resin as a resin, or may further contain other resins different from the (meth)acrylic resin. Examples of other resins include olefin resins. The weather-resistant layer preferably contains a (meth)acrylic resin as a main resin component. In the weather-resistant layer, the ratio of the (meth)acrylic resin to all resins is, for example, 50% by mass or more, may be 70% by mass or more, or may be 90% by mass or more. In addition, the weather-resistant layer may not contain a vinyl chloride resin. Details of the vinyl chloride resin will be described later.

[0019] The proportion of the (meth)acrylic resin in the weather-resistant layer is, for example, 70% by mass or more, optionally 80% by mass or more, or optionally 90% by mass or more.

[0020] (2) Triazine-based UV absorbers The weather-resistant layer in the present disclosure contains a triazine-based ultraviolet absorber. The triazine-based ultraviolet absorber is preferably a hydroxyphenyltriazine-based ultraviolet absorber. The hydroxyphenyltriazine-based ultraviolet absorber is an ultraviolet absorber having a hydroxyphenyltriazine structure. The hydroxyphenyltriazine structure has a molecular structural characteristic that it is difficult to bleed out and escape from the surface protective layer from the viewpoint of steric hindrance. As a preferred hydroxyphenyltriazine-based ultraviolet absorber, for example, a compound represented by the following general formula (I) can be mentioned.

[0021] [ka]

[0022] (In general formula (I), R 11 is a divalent hydrocarbon group or a single bond, and R 12 is a monovalent hydrocarbon radical, -C(=O)OR 15 , -OC(=O)R 16 OR 17 and R 13 , R 14 , R15 , R 16 and R 17 are each independently a hydrogen atom or a monovalent hydrocarbon group, 11 and n 12 are each independently an integer of 1 to 5. 13 and R 14 If there are multiple, they may be the same or different.)

[0023] R 11 Preferred examples of the divalent hydrocarbon group in R include aliphatic hydrocarbon groups such as alkylene groups and alkenylene groups, and from the viewpoint of weather resistance, alkylene groups are more preferred. 11 The upper limit of the number of carbon atoms in the aliphatic hydrocarbon group in R is preferably 20 or less, more preferably 12 or less, even more preferably 8 or less, and still more preferably 4 or less, while the lower limit is not particularly limited as long as it is 1 or more. 11 The alkylene group and alkenylene group in may be linear, branched, or cyclic, but are preferably linear or branched.

[0024] R 12 Preferred examples of the monovalent hydrocarbon group in R include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and an alkyl group is more preferred. 12 The lower limit of the number of carbon atoms in the alkyl group in R is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more, while the upper limit is preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less. 12 The alkyl group and alkenyl group in may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably branched.

[0025] R 13 and R 14Preferred examples of the monovalent hydrocarbon group in include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Among these, groups containing an aromatic hydrocarbon group such as an aryl group or an aralkyl group are preferred, and an aryl group is more preferred.

[0026] R 13 and R 14 The number of carbon atoms in the alkyl group in R is preferably 20 or less, more preferably 12 or less, even more preferably 4 or less, and still more preferably 2 or less. 13 and R 14 As the alkyl group in the above formula, a methyl group or an ethyl group is particularly preferred, and in consideration of availability, a methyl group is particularly preferred.

[0027] R 13 and R 14 The lower limit of the number of carbon atoms in the aryl group in the formula (I) is preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and even more preferably 10 or less. R 13 and R 14 The lower limit of the number of carbon atoms in the aralkyl group in the formula (I) is preferably 7 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and even more preferably 10 or less.

[0028] R 15 , R 16 and R 17 Preferred examples of the monovalent hydrocarbon group in R include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Among these, an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred. 15 , R 16 and R 17 The lower limit of the number of carbon atoms in the alkyl group and alkenyl group in the formula is preferably 2 or more, more preferably 4 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less.

[0029] In addition, R in the above general formula (I) 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 may have a substituent such as a halogen atom, a hydroxyl group, an amino group, or an alkyl group having 1 to 4 carbon atoms.

[0030] n 11 and n 12 are each independently an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. 11 and n 12 If is an integer equal to or greater than 2, multiple R 13 and R 14 may be the same or different, but from the viewpoint of availability, it is preferable that they are the same.

[0031] Examples of the compound represented by general formula (I) include compounds represented by the following chemical formulas (1) to (4). The compound represented by the following chemical formula (1) is available as a commercially available product ("Tinuvin 479 (product number)", manufactured by BASF). The compound represented by the following chemical formula (2) is available as a commercially available product ("ADK STAB LA-46 (product number)", manufactured by ADEKA Corporation). The compound represented by the following chemical formula (3) is available as a commercially available product ("Tinuvin 1600 (product number)", manufactured by BASF). The compound represented by the following chemical formula (4) is available as a commercially available product ("Tinuvin 1577 (product number)", manufactured by BASF).

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] The content of the triazine-based ultraviolet absorber in the weather-resistant layer is not particularly limited, but may be, for example, 0.1 parts by mass or more, or 1 part by mass or more, relative to 100 parts by mass of the (meth)acrylic resin. On the other hand, the content of the triazine-based ultraviolet absorber may be, for example, 5 parts by mass or less, or 3 parts by mass or less, relative to 100 parts by mass of the (meth)acrylic resin.

[0037] The triazine-based ultraviolet absorber contained in the weather-resistant layer of the decorative sheet and the triazine-based ultraviolet absorber contained in the surface protective layer may be the same kind or different kinds.

[0038] (3) Weatherproof layer The weather-resistant layer in the present disclosure may contain additives. Examples of additives include light stabilizers, heat stabilizers, antioxidants, antistatic agents, and flame retardants. Examples of light stabilizers include hindered amine compounds. Hindered amine compounds usually have a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule. Examples of hindered amine compounds include NH-type hindered amine compounds, NR-type hindered amine compounds, and NOR-type hindered amine compounds. Examples of antioxidants include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. In addition, in order to impart flexibility to the weather-resistant layer (to reduce the elastic modulus), crosslinked rubber (crosslinked polymer) may be blended.

[0039] The weather-resistant layer may be transparent, translucent, or opaque. The weather-resistant layer may be colored or uncolored. When the decorative sheet has a design layer, it is preferable that the weather-resistant layer has a transparency that allows the design layer to be identified.

[0040] The thickness of the weather-resistant layer is usually 30 μm or more, preferably 40 μm or more, and particularly preferably 50 μm or more. If the thickness of the weather-resistant layer is too thin, sufficient weather resistance may not be obtained. On the other hand, the thickness of the weather-resistant layer is, for example, 100 μm or less, preferably 80 μm or less, and particularly preferably 70 μm or less. If the thickness of the weather-resistant layer is too thick, processability may decrease.

[0041] From the viewpoint of processability, the tensile modulus of the weather-resistant layer is preferably 3000 MPa or less, and more preferably 2500 MPa or less. The tensile modulus in the present invention is a value measured in accordance with JIS K 7127-1:2014.

[0042] The weather-resistant layer may be formed, for example, by extrusion film formation using an extruder such as a T-die extruder. Alternatively, the weather-resistant layer may be prepared in advance and then thermally laminated with other layers. Alternatively, the weather-resistant layer may be subjected to a surface treatment such as a corona discharge treatment.

[0043] 2.Surface protection layer As described above, the decorative sheet in the present disclosure has a weather-resistant layer that contains a (meth)acrylic resin. (Meth)acrylic resins tend to have lower stain resistance (e.g., chemical resistance) than vinyl chloride resins. In the present disclosure, stain resistance can be improved by disposing a surface protective layer on the side of the weather-resistant layer opposite the substrate layer side. Furthermore, the weather resistance of the decorative sheet is further improved by the surface protective layer containing a triazine-based ultraviolet absorber. Moreover, as shown in Figures 1 and 2, the decorative sheet 10 may have a surface protective layer 3 as the outermost layer.

[0044] (1) Triazine-based UV absorbers The triazine-based ultraviolet absorbing agent is the same as that described above in "1. Weather-resistant layer," and therefore will not be described here.

[0045] (2) Resin component The surface protective layer contains a resin component. The resin component mainly functions as a binder resin. The surface protective layer preferably contains at least one of a resin composition and a cured product thereof as the resin component. The cured product may be a cured product obtained by curing a curable resin composition with ionizing radiation, or a cured product obtained by curing a curable resin composition with heat.

[0046] Examples of the curable resin composition include an ionizing radiation curable resin composition and a heat curable resin composition. In the present disclosure, an ionizing radiation curable resin composition is preferred. This is because it has excellent scratch resistance and production efficiency. That is, the surface protective layer preferably contains a cured product of an ionizing radiation curable resin composition as a resin component.

[0047] Specific examples of the ionizing radiation curable resin composition include an electron beam curable resin composition and an ultraviolet ray curable resin composition. Among them, an electron beam curable resin composition has advantages such as less odor and less coloring because it does not require a polymerization initiator.

[0048] The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as "ionizing radiation curable compound"). The ionizing radiation curable functional group is a group that crosslinks and hardens by irradiation with ionizing radiation, and specific examples thereof include functional groups having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, and an allyl group. Other specific examples of the ionizing radiation curable functional group include an epoxy group and an oxetanyl group. In this specification, a (meth)acryloyl group refers to an acryloyl group or a methcroyl group. In this specification, a (meth)acrylate refers to an acrylate or a methacrylate. In addition, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Specific examples of ionizing radiation include ultraviolet rays (UV) and electron beams (EB). Other specific examples of ionizing radiation include electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0049] The ionizing radiation curable resin composition may contain only one type of ionizing radiation curable compound, or may contain two or more types. The type of ionizing radiation curable compound is not particularly limited, and a known polymerizable monomer or a known polymerizable oligomer (polymerizable prepolymer) can be used.

[0050] The ionizing radiation curable compound preferably contains a compound having two or more ethylenically unsaturated bond groups. In particular, the ionizing radiation curable compound preferably contains a polyfunctional (meth)acrylate compound having two or more ethylenically unsaturated bond groups. The polyfunctional (meth)acrylate compound may be a monomer or an oligomer.

[0051] The polyfunctional (meth)acrylate compound may be a bifunctional (meth)acrylate monomer, or may be a trifunctional or higher functional (meth)acrylate monomer. Examples of bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy diacrylate, bisphenol A tetrapropoxy diacrylate, and 1,6-hexanediol diacrylate. Examples of trifunctional or higher functional (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and isocyanuric acid modified tri(meth)acrylate.

[0052] Examples of the polyfunctional (meth)acrylate oligomer include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.

[0053] Urethane (meth)acrylates are obtained, for example, by the reaction of polyhydric alcohols and organic diisocyanates with hydroxy (meth)acrylates. Epoxy (meth)acrylates are obtained, for example, by the reaction of epoxy resins with (meth)acrylic acid. At least one of polybasic acids and phenols may be further used in this reaction. The epoxy resins may be bifunctional or trifunctional or higher. Examples of epoxy resins include aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

[0054] The ionizing radiation curable compound may contain silicone (meth)acrylate. The use of silicone (meth)acrylate improves the contamination resistance of the surface protective layer. Examples of silicone (meth)acrylate include silicone oils containing polysiloxane. The silicone (meth)acrylate may be modified silicone oils in which a (meth)acrylic group is introduced at the end of polysiloxane. The content of silicone (meth)acrylate may be, for example, 1 part by mass or more and 7 parts by mass or less, or 2 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the ionizing radiation curable compound (excluding silicone (meth)acrylate).

[0055] When the ionizing radiation curable compound is an ultraviolet ray curable compound, the ionizing radiation curable resin composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. Examples of the photopolymerization initiator include acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, and thioxanthone. Examples of the photopolymerization accelerator include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester.

[0056] On the other hand, a thermosetting resin composition is a composition that contains at least a thermosetting resin. This resin composition is cured by heating. Examples of the thermosetting resin include acrylic resins, urethane resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. The thermosetting resin composition may contain additives such as a curing agent and a curing catalyst, if necessary.

[0057] (3) Surface protective layer The surface protective layer may further contain at least one of an antioxidant, a light stabilizer, an antibacterial agent, an antiviral agent, and an antiallergen agent as an additive. Any known additive can be used as these additives. For the antioxidant and light stabilizer, for example, the materials described in "1. Weather-resistant layer" above can be used.

[0058] The thickness of the surface protective layer is not particularly limited, but is, for example, 1 μm or more and 50 μm or less. If the surface protective layer is thin, it may not be possible to provide sufficient durability, and if the surface protective layer is thick, the visibility of the design layer may be reduced. The thickness of the surface protective layer may be 3 μm or more and 40 μm or less, or 5 μm or more and 35 μm or less.

[0059] The method for forming the surface protective layer may be, for example, a method in which a mixture containing a resin component and an additive is applied to the surface of the weather-resistant layer, dried, and cured. Alternatively, the mixture may be applied to the surface of a substrate having releasability, dried, and cured to form a surface protective layer, and the surface protective layer may be transferred onto the weather-resistant layer.

[0060] 3.Base material layer The substrate layer in the present disclosure is a layer that supports the weather-resistant layer and the surface protective layer. The substrate layer contains a vinyl chloride resin. An example of the vinyl chloride resin is polyvinyl chloride, which is a homopolymer of vinyl chloride. Another example of the vinyl chloride resin is a copolymer of vinyl chloride and another monomer that can be copolymerized with vinyl chloride. Examples of other monomers copolymerizable with vinyl chloride 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 (excluding vinyl chloride) such as vinylidene chloride and vinyl bromide, vinyl halides; and allyl phthalates such as diallyl phthalate. These other monomers can be used alone or in combination of two or more.

[0061] The average degree of polymerization of the vinyl chloride resin is, for example, from 500 to 4000, or may be from 700 to 3900, or may be from 1000 to 3800. In the present disclosure, the average degree of polymerization is measured in accordance with JIS K 6721.

[0062] The base layer may contain only vinyl chloride resin as a resin, or may further contain other resins different from vinyl chloride resin. Examples of other resins include (meth)acrylic resin, chlorinated polyethylene, and ethylene-vinyl acetate copolymer. The base layer preferably contains vinyl chloride resin as a main resin component. In the base layer, the ratio of vinyl chloride resin to all resins is, for example, 50% by mass or more, may be 70% by mass or more, or may be 90% by mass or more.

[0063] The base layer preferably contains a plasticizer in addition to the vinyl chloride resin. By adding a plasticizer, a soft base layer can be obtained. Examples of the plasticizer include phthalic acid plasticizers such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and diundecyl phthalate (DUP); adipic acid plasticizers such as dibutyl adipate; phosphoric acid plasticizers such as tributyl phosphate, tricresyl phosphate, and triphenyl phosphate; trimellitic acid plasticizers such as tributyl trimellitate, trioctyl trimellitate, and tri-2-ethylhexyl trimellitate (TOTM); ester plasticizers such as adipic acid polyester; and citrate esters such as acetyl tributyl citrate and acetyl trioctyl citrate. These plasticizers can be used alone or in combination of two or more.

[0064] The content of the plasticizer is not particularly limited, but may be, for example, 5 parts by mass or more, or 8 parts by mass or more, relative to 100 parts by mass of the vinyl chloride resin, while the content of the plasticizer is, for example, 30 parts by mass or less, relative to 100 parts by mass of the vinyl chloride resin.

[0065] The substrate layer may further contain additives such as a heat stabilizer, a flame retardant, a light stabilizer, an ultraviolet absorber, a filler, and a colorant, as necessary. The substrate layer may also be subjected to a surface treatment, for example, for the purpose of improving adhesion. Examples of the surface treatment include an oxidation method and a roughening method. Examples of the oxidation method include a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone-ultraviolet treatment method. Examples of the roughening method include a sandblasting method and a solvent treatment method.

[0066] The shape of the substrate layer may be, for example, a sheet. The thickness of the substrate layer is not particularly limited, but is, for example, 10 μm or more and 300 μm or less. The basis weight of the substrate layer is not particularly limited, but is, for example, 50 g / m 2 More than 300g / m 2 60 g / m2 More than 160g / m 2 It may be the following.

[0067] 4. Design layer The decorative sheet in the present disclosure may have a design layer on one side of the weather-resistant layer. The decorative sheet may also have a design layer between the substrate layer and the weather-resistant layer. Providing a design layer improves the design of the decorative sheet. On the other hand, the decorative sheet may not have a design layer. When the decorative sheet is viewed in a plan view along the thickness direction, the design layer may be disposed on the entire surface of the decorative sheet, or may be disposed on a part of the decorative sheet.

[0068] Examples of the design layer include a solid layer (a layer where ink is applied solidly) and a picture layer (a layer where ink is printed). Examples of the picture (pattern) in the picture layer include wood grain patterns, stone grain patterns, sand grain patterns, tile patterns, brickwork patterns, fabric patterns, leather-stained patterns, geometric figures, letters, symbols, abstract patterns, and floral patterns.

[0069] The design layer usually contains a colorant and a binder resin. Examples of the colorant include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue, organic pigments (including dyes) such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azo black, metal pigments such as aluminum and brass, and pearl pigments such as titanium dioxide-coated mica and basic lead carbonate.

[0070] Examples of binder resins include urethane-based resins, acrylic polyol-based resins, acrylic-based resins, ester-based resins, amide-based resins, butyral-based resins, styrene-based resins, urethane-acrylic copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-acrylic copolymers, chlorinated propylene-based resins, nitrocellulose-based resins, and cellulose acetate-based resins.

[0071] The design layer may contain additives such as ultraviolet absorbers, light stabilizers, curing agents, plasticizers, catalysts, etc., as necessary. The thickness of the design layer is, for example, 0.5 μm or more and 20 μm or less, or may be 1 μm or more and 10 μm or less, or may be 2 μm or more and 5 μm or less.

[0072] The design layer can be formed, for example, by coating an ink containing a colorant, a binder resin and a solvent, followed by drying. As the coating method, gravure printing is preferred.

[0073] 5. Decorative sheets The decorative sheet in the present disclosure has at least a substrate layer, a weather-resistant layer, and a surface protective layer. The decorative sheet may have only the substrate layer, the weather-resistant layer, and the surface protective layer, or may have other layers in addition to the substrate layer, the weather-resistant layer, and the surface protective layer. The decorative sheet may further have at least one layer of, for example, a design layer, an adhesive layer, a primer layer, a foamed resin layer, and a non-foamed resin layer. Examples of the layer structure of the decorative sheet include the layer structure shown below.

[0074] (1) Base material layer / weather resistant layer / surface protection layer (2) Base layer / weather-resistant layer / primer layer / surface protection layer (3) Base layer / design layer / weather-resistant layer / surface protection layer (4) Base layer / design layer / weather-resistant layer / primer layer / surface protection layer (5) Base material layer / adhesive layer / weather resistant layer / surface protection layer (6) Base layer / adhesive layer / design layer / weather-resistant layer / surface protection layer (7) Base layer / design layer / adhesive layer / weather-resistant layer / surface protection layer (8) Base layer / adhesive layer / weather-resistant layer / primer layer / surface protective layer (9) Base layer / adhesive layer / design layer / weather-resistant layer / primer layer / surface protection layer (10) Base layer / design layer / adhesive layer / weather-resistant layer / primer layer / surface protection layer (11) Base layer / foamed resin layer / weather-resistant layer / surface protective layer (12) Base layer / foamed resin layer / weather-resistant layer / primer layer / surface protective layer (13) Base layer / foamed resin layer / design layer / weather-resistant layer / surface protection layer (14) Base layer / foamed resin layer / design layer / weather-resistant layer / primer layer / surface protection layer (15) Base layer / foamed resin layer / adhesive layer / weather-resistant layer / surface protective layer (16) Base layer / foamed resin layer / adhesive layer / design layer / weather-resistant layer / surface protection layer (17) Base layer / foamed resin layer / design layer / adhesive layer / weather-resistant layer / surface protection layer (18) Base layer / foamed resin layer / adhesive layer / weather-resistant layer / primer layer / surface protective layer (19) Base layer / foamed resin layer / adhesive layer / design layer / weather-resistant layer / primer layer / surface protection layer (20) Base layer / foamed resin layer / design layer / adhesive layer / weather-resistant layer / primer layer / surface protection layer

[0075] The " / " indicates the relative positional relationship of each layer, for example, "A / B / C" means that A, B, and C are arranged in that order along the thickness direction. For example, when it is written as "A / B", A and B may be arranged so as to be in direct contact with each other, or may be arranged via another layer. Furthermore, as exemplified in the above (11) to (20), when the decorative sheet has a foamed resin layer, a non-foamed resin layer may be arranged on one or both sides of the foamed resin layer.

[0076] (1) Primer layer The decorative sheet may have a primer layer on the surface of the surface protective layer on the weather-resistant layer side. By providing the primer layer, the adhesion between the surface protective layer and the weather-resistant layer is improved, and for example, the decrease in interlayer adhesion when exposed to ultraviolet light can be suppressed. In addition, by providing the primer layer, the scratch resistance of the surface protective layer is improved.

[0077] The primer layer contains at least a binder resin. Examples of the binder resin include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-acrylic copolymer, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin. The primer layer may contain only one type of resin, or may contain two or more types of resin.

[0078] The primer layer may contain a cured product of a binder resin. Examples of the curing agent include an isocyanate-based curing agent and an epoxy-based curing agent. The cured product of the binder resin is preferably a cured product obtained by crosslinking and curing a polyol-based resin such as an acrylic polyol-based resin with an isocyanate-based curing agent.

[0079] The primer layer may further contain at least one of an ultraviolet absorber and a light stabilizer. The ultraviolet absorber and the light stabilizer may be general ones. The thickness of the primer layer is, for example, 0.01 μm or more and 10 μm or less, and may be 0.7 μm or more and 8 μm or less, or 1 μm or more and 6 μm or less. In addition, as a method for forming the primer layer, for example, a method of applying a resin composition containing a binder resin and a solvent and then drying it can be mentioned. If necessary, a curing treatment may be performed.

[0080] (2) Adhesive layer The decorative sheet may have an adhesive layer. The position of the adhesive layer is not particularly limited. The adhesive layer may be disposed between the substrate layer and the weather-resistant layer. In addition, when the decorative sheet has a design layer, the adhesive layer may be disposed between the design layer and the weather-resistant layer. In addition, when the substrate layer is a laminate of two or more layers, the adhesive layer may be disposed between each layer constituting the substrate layer. In addition, the decorative sheet may have an adhesive layer (back adhesive layer) on the surface of the substrate layer opposite to the surface protective layer. In this case, the decorative sheet may have a peelable separator layer on the surface of the adhesive layer opposite to the substrate layer.

[0081] The adhesive layer contains a resin, such as ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-(meth)acrylic acid copolymer (EMAA), acrylic resin, styrene resin, ester resin, urethane resin, chlorinated olefin resin, vinyl chloride-vinyl acetate copolymer resin, vinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, cellulose derivative, and rubber resin.

[0082] The thickness of the adhesive layer is, for example, 0.1 μm or more and 10 μm or less. In addition, examples of a method for forming the adhesive layer include a method in which a resin composition containing a resin and a solvent is applied and then dried.

[0083] (3) Foamed resin layer The decorative sheet may have a foamed resin layer between the substrate layer and the weather-resistant layer. When the decorative sheet has a design layer, the foamed resin layer may be disposed on the substrate layer side of the design layer, or on the weather-resistant layer side of the design layer. By providing a foamed resin layer, the design and texture of the decorative sheet are improved. On the other hand, the decorative sheet does not have to have a foamed resin layer.

[0084] The foamed resin layer contains a resin. The foamed resin layer may contain a cured product of the resin. Examples of the resin include thermoplastic resins. Examples of the thermoplastic resin include vinyl chloride resins, olefin resins, styrene resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), acrylonitrile-styrene copolymers, nylon, acetal resins, acrylic resins, carbonate resins, ester resins, vinyl acetate resins, vinyl alcohol resins, and urethane resins.

[0085] The foamed resin layer has bubbles inside. The bubbles may be closed or open. In addition, the foamed resin layer may contain both closed and open bubbles. The bubbles are formed by foaming the foaming agent contained in the foaming agent-containing resin layer, and the number, size, density, and shape of the bubbles are not particularly limited.

[0086] (4) Non-foamed resin layer The decorative sheet may have a non-foamed resin layer between the substrate layer and the weather-resistant layer. The non-foamed resin layer is a layer that does not contain bubbles due to foaming of a foaming agent. When the decorative sheet has a foamed resin layer, the non-foamed resin layer may be disposed on the substrate layer side of the foamed resin layer, or on the surface protective layer side of the foamed resin layer. On the other hand, the decorative sheet may not have a non-foamed resin layer. The resin used in the non-foamed resin layer is the same as the resin used in the foamed resin layer, so the description here is omitted.

[0087] (5) Decorative sheets The decorative sheet in the present disclosure has at least a substrate layer, a weather-resistant layer, and a surface protective layer. As described above, the decorative sheet may further have other layers such as a design layer, a primer layer, an adhesive layer, a foamed resin layer, and a non-foamed resin layer.

[0088] The decorative sheet may have an embossed pattern on the outermost surface of the surface protective layer side with respect to the base layer. In particular, it is preferable that the embossed pattern is disposed on the surface of the surface protective layer opposite the base layer. Examples of the embossed pattern include wood grain duct grooves, stone slab surface irregularities, cloth surface texture, matte finish, sand grain, hairline, and stripe grooves.

[0089] The embossed pattern can be formed, for example, by heating the decorative sheet and pressing an embossing plate against it. The heating temperature of the decorative sheet is, for example, 80° C. or more and 260° C. or less, or may be 85° C. or more and 200° C. or less, or may be 100° C. or more and 180° C. or less.

[0090] 6.Applications The decorative sheet in the present disclosure is used, for example, as a decorative member described below. The decorative member is used, for example, as a building material, and may be an interior member or an exterior member. The decorative sheet is preferably used, for example, as a surface material for the exterior walls, interior walls, roofs, eaves ceilings, door pockets, window frames, door frames, and the like of buildings such as houses, offices, stores, hospitals, and clinics.

[0091] 7. Manufacturing method The method for producing the decorative sheet in the present disclosure is not particularly limited. For example, the method for producing the decorative sheet includes a surface protection layer side sheet production step of forming the surface protection layer on one side of the weather-resistant layer to produce a surface protection layer side sheet, a base layer side sheet production step of forming a design layer on one side of the base layer as necessary to produce a base layer side sheet, and a step of laminating the weather-resistant layer side surface of the surface protection layer side sheet and the design layer side surface of the base layer side sheet so as to face each other, and thermally laminating the surface protection layer side sheet and the base layer side sheet. Either the surface protection layer side sheet production step or the base layer side sheet production step may be performed first, or may be performed in parallel.

[0092] B. Decorative materials The present disclosure provides a decorative member having a substrate and the decorative sheet described above. The substrate and the decorative sheet are arranged such that the substrate faces the surface of the decorative sheet facing the base layer.

[0093] According to the present disclosure, since it has the decorative sheet described above, it becomes a decorative member having excellent weather resistance.

[0094] 1. Decorative sheet The decorative sheet in this disclosure is similar to that described above in "A. Decorative sheet," and therefore will not be described here.

[0095] 2.Base The substrate in the present disclosure is a member decorated with a decorative sheet. An example of the substrate is a resin member. Examples of resins used in the resin member include vinyl chloride resins, acrylic resins, ester resins, styrene resins, olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), phenolic resins, cellulose resins, and rubber, among which vinyl chloride resins are preferred. For details of each resin, the contents described in "A. Decorative Sheet" above can be cited as appropriate. Another example of the substrate is a wood member. Examples of wood members include wood veneer, wood plywood, particle board, and wood fiberboard. Examples of wood used in the wood members include cedar, cypress, pine, and lauan.

[0096] Other examples of the substrate include metal members. Metals used for the metal members include, for example, iron and aluminum. Other examples of the substrate include ceramic members. The material of the ceramic member may be ceramics such as glass or porcelain, a non-cement ceramic material such as gypsum, or a non-ceramic ceramic material such as ALC (aerated lightweight concrete).

[0097] The shape of the substrate is not particularly limited, and may be, for example, a plate, a sheet, or a three-dimensional shape. The substrate may have a flat surface, a curved surface, or both a flat surface and a curved surface. The substrate may have at least one of a convex portion, a concave portion, a convex streak portion, a concave streak portion, and a through portion.

[0098] 3. Decorative materials The decorative member in the present disclosure has the decorative sheet and the substrate described above. The decorative member in the present disclosure may be an interior member or an exterior member, but the latter is preferred. This is because the decorative member in the present disclosure has excellent weather resistance. In addition, the uses of the decorative member are the same as those described in "A. Decorative sheet" above, so the description here is omitted.

[0099] The decorative member in the present disclosure can be obtained, for example, by laminating a decorative sheet and a base body. Specifically, the surface of the base body (the surface requiring decoration) and the surface of the decorative sheet on the base material layer side are laminated so as to face each other. Examples of methods for laminating the base body and the decorative sheet include lamination, wrapping, and vacuum forming. In the lamination method, for example, the decorative sheet is pressed onto a plate-shaped base body with a pressure roller. At this time, an adhesive layer may be disposed between the decorative sheet and the base body. In the wrapping method, for example, while supplying the decorative sheet, the decorative sheet is pressure-bonded sequentially to multiple side surfaces constituting the base body by multiple rollers with different orientations. At this time, an adhesive layer may be disposed between the decorative sheet and the base body. When a hot melt adhesive (heat-sensitive adhesive) is used when laminating the decorative sheet and the base body, the heating temperature is, for example, 160°C or more and 200°C or less. Also, when a reactive hot melt adhesive is used, the heating temperature is, for example, 100°C or more and 130°C or less.

[0100] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included in the technical scope of the present disclosure. EXAMPLES

[0101] [Example 1] (Base layer side sheet manufacturing process) First, a polyvinyl chloride film (thickness 80 μm) containing 100 parts by weight of polyvinyl chloride and 20 parts by weight of polyester plasticizer was prepared as a substrate. A design layer (picture pattern layer) was formed by applying a printing ink containing a mixture of vinyl chloride-vinyl acetate copolymer and acrylic resin as a binder to one side of the substrate.

[0102] (Surface protection layer side sheet manufacturing process) An acrylic film (50 μm thick) containing polymethylmethacrylate (PMMA) and a triazine-based ultraviolet absorber (UVA Tinuvin 479) was prepared as a weather-resistant layer. The content of UVA was 1 part by mass per 100 parts by mass of PMMA. An electron beam curable resin coating agent was applied to one side of the acrylic film by gravure coating to form a coating layer. An electron beam was irradiated to the coating layer under conditions of an acceleration voltage of 125 KeV and 5 Mrad to form a surface protection layer with a thickness of 5 μm. The electron beam curable resin coating agent was prepared by adding 2 parts by mass of a triazine-based ultraviolet absorber (UVA Tinuvin 479) and 2 parts by mass of a light stabilizer (HALS Tinuvin 123) to 100 parts by mass of urethane acrylate as an ionizing radiation curable resin.

[0103] The sheet prepared in the surface protection layer side sheet preparation step was superimposed on the design layer side of the sheet prepared in the base layer side sheet preparation step, with the surface protection layer being the outermost surface, and heat laminated at 150° C. This produced a decorative sheet having a base layer (polyvinyl chloride), design layer, weather-resistant layer (acrylic resin), and surface protection layer in that order in the thickness direction.

[0104] [Example 2] A decorative sheet was produced in the same manner as in Example 1, except that the thickness of the acrylic film was 100 μm.

[0105] [Example 3] A decorative sheet was produced in the same manner as in Example 1, except that the thickness of the acrylic film was 30 μm.

[0106] [Comparative Example 1] A decorative sheet was produced in the same manner as in Example 1, except that the weather-resistant layer (transparent resin layer) was changed from an acrylic film containing a triazine-based ultraviolet absorber to a polyvinyl chloride film (thickness 90 μm, containing 25 parts by mass of plasticizer per 100 parts by mass of vinyl chloride resin (PVC)) containing a benzophenone-based ultraviolet absorber. The content of the ultraviolet absorber per 100 parts by mass of PVC was 1 part by mass.

[0107] [Comparative Example 2] A decorative sheet was produced in the same manner as in Example 1, except that no surface protective layer was formed.

[0108] [evaluation] (weather resistance) The weather resistance of the decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was evaluated. Specifically, an accelerated weather resistance test using a metal halide lamp (MWOM) was performed for 800 hours (a test in which one cycle was repeated, consisting of 20 hours of ultraviolet irradiation under the irradiation conditions described below, followed by 4 hours of condensation under the condensation conditions described below), and the appearance was then visually observed from the surface protective layer side. <Test Equipment> Product name "Daipla Metal Weather" manufactured by Daipla Wintes Co., Ltd. <Irradiation conditions> Illuminance: 65mW / cm 2 , Black panel temperature: 63℃, chamber humidity: 50%RH, time: 20 hours <Condensation conditions> Illuminance: 0mW / cm 2 , Humidity inside the tank: 98%RH, Time: 4 hours

[0109] Those for which no change in appearance was observed were rated as ⊚, those for which only a slight change in appearance was observed were rated as ◯, and those for which significant discoloration was observed were rated as x.

[0110] (processability) The processability of the decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was evaluated. Specifically, a base having a bent portion (R=1 mm) and a decorative sheet were laminated by pressure bonding via a 50 μm thick adhesive layer (hot melt), and the decorative sheet was visually inspected for lifting at the bent portion. Those in which no lifting was observed were rated as ⊚, and those in which almost no lifting was observed were rated as ◯.

[0111] (Stain resistance) The outermost surfaces (the surface opposite the substrate layer, with respect to the weather-resistant layer) of the decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were subjected to ethanol rubbing (300 g / cm 2 The test piece was subjected to a visual inspection of its appearance. Those that showed no change in appearance were rated as ◯, and those that showed a significant change in appearance were rated as ×.

[0112] The evaluation results are shown in Table 1.

[0113] [Table 1]

[0114] It was confirmed that the decorative sheets obtained in Examples 1 to 3 had excellent weather resistance. Furthermore, the decorative sheets obtained in Examples 1 to 3 also had excellent processability and stain resistance. On the other hand, the decorative sheet of Comparative Example 1 was unable to obtain excellent weather resistance. This is presumably because the weather-resistant layer contained a vinyl chloride resin and therefore was unable to suppress discoloration over time due to the dechlorination reaction. In addition, it was confirmed that the decorative sheet of Comparative Example 2, which did not have a surface protective layer, had excellent weather resistance itself but poor stain resistance. [Explanation of symbols]

[0115] 1 … Base material layer 2 … Weatherproof layer 3 … Surface protective layer 4 … Design layer 10... Decorative sheet

Claims

1. The laminate has a base layer, a weather-resistant layer, and a surface protective layer in this order in a thickness direction, The base layer contains a vinyl chloride resin, the weather-resistant layer contains a (meth)acrylic resin and a triazine-based ultraviolet absorber and has a thickness of 30 μm or more; The decorative sheet, wherein the surface protective layer contains a triazine-based ultraviolet absorber.

2. The decorative sheet is used as a decorative member, The decorative member has a base and the decorative sheet, The decorative sheet according to claim 1 , wherein the decorative member is an exterior member.

3. The decorative sheet according to claim 2 , wherein the substrate contains a vinyl chloride resin.

4. The decorative sheet according to claim 1 , wherein the weather-resistant layer contains the (meth)acrylic resin as a main resin component.

5. The decorative sheet according to any one of claims 1 to 4, wherein the weather-resistant layer contains, as the (meth)acrylic resin, at least one of polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, a methyl(meth)acrylate-butyl(meth)acrylate copolymer, a methyl(meth)acrylate-styrene copolymer, a methyl(meth)acrylate-butyl(meth)acrylate-2-hydroxyethyl(meth)acrylate copolymer, or a methyl(meth)acrylate-butyl(meth)acrylate-2-hydroxyethyl(meth)acrylate-styrene copolymer.

6. 6. The decorative sheet according to claim 1, wherein the weather-resistant layer has a thickness of 100 μm or less.

7. The decorative sheet according to claim 1 , further comprising a design layer between the base layer and the weather-resistant layer.

8. The decorative sheet according to any one of claims 1 to 7, wherein the surface protective layer contains a cured product of an ionizing radiation curable resin composition.

9. The decorative sheet according to claim 8 , wherein the ionizing radiation curable resin composition is an electron beam curable resin composition.

10. A substrate; A decorative sheet according to any one of claims 1 to 9, A decorative member having the above structure.

11. The decorative member according to claim 10 , wherein the decorative member is an exterior member.

12. The decorative member according to claim 10 or 11, wherein the substrate contains a vinyl chloride resin.

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