Decorative sheet and decorative member

Abstract

To provide a decorative sheet including a substrate layer composed of a vinyl chloride-based resin, which features superior weather resistance.SOLUTION: In the present disclosure, a decorative sheet is provided which includes a substrate layer, a weather resistance layer, and a surface protective layer in this order in a thickness direction, wherein the substrate layer contains a vinyl chloride-based resin, the weather resistance layer contains a (meth)acrylic resin and a triazine-type ultraviolet absorber and has a thickness of 30 μm or more, and the surface protective layer contains a triazine-type ultraviolet absorber.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present disclosure relates to a cosmetic sheet and a cosmetic member.

Background Art

[0002] For example, as an interior member or an exterior member used for building materials, a cosmetic member having a substrate and a cosmetic sheet is known. Various resins are used for the base material layer of the cosmetic sheet. Among them, a cosmetic sheet using a base material layer containing a vinyl chloride resin has good processability when disposed on a substrate. Conventionally, various cosmetic sheets using a base material layer containing a vinyl chloride resin have been proposed (for example, Patent Documents 1 to 3).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

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

[0005] The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a cosmetic sheet having excellent weather resistance.

Means for Solving the Problems

[0006] In the present disclosure, a decorative sheet is provided which has a base material layer, a design layer, a weather resistance layer, and a surface protection layer in this order in the thickness direction. The base material layer contains a vinyl chloride resin, the weather resistance layer contains a (meth)acrylic resin and a triazine-based ultraviolet absorber and has a thickness of 30 μm or more, and the surface protection layer contains a triazine-based ultraviolet absorber.

[0007] In the present disclosure, a decorative member is provided which has a substrate and the above-described decorative sheet.

Advantages of the Invention

[0008] In the present disclosure, there is an effect that a decorative sheet having excellent weather resistance can be provided.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0010] Embodiments will be described below with reference to the drawings and the like. However, the present disclosure can be implemented in many different modes and should not be limited to the description of the embodiments exemplified below. Also, for the purpose of making the description clearer, the drawings may schematically represent the widths, thicknesses, and shapes of each part compared to the actual forms, but this is merely an example and should not be construed as limiting.

[0011] In this specification, when expressing the manner of arranging another member on a certain member, if simply denoted as "on" or "under", unless otherwise specified, it includes both the case of arranging another member directly above or below in contact with a certain member, and the case of arranging another member above or below a certain member with yet another member interposed therebetween. Further, in this specification, when expressing the manner of arranging another member on the surface of a certain member, if simply denoted as "on the surface", unless otherwise specified, it includes both the case of arranging another member directly above or below in contact with a certain member, and the case of arranging another member above or below a certain member with yet another member interposed therebetween.

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

[0013] According to the present disclosure, by providing a specific weather-resistant layer and a specific surface protection layer, even when the base material layer contains a vinyl chloride-based resin, a decorative sheet having excellent weather resistance can be obtained. As described above, a decorative sheet using a base material layer containing a vinyl chloride-based resin has the advantage of good workability when disposed on a substrate. On the other hand, a decorative sheet using a base material layer containing a vinyl chloride-based resin requires good weather resistance to suppress discoloration over time. In particular, in the case of an exterior member (a decorative member for exterior use), a decorative sheet using a base material layer containing a vinyl chloride-based resin is required to have excellent weather resistance. Specifically, since the exterior member is exposed to an environment where it is easily irradiated with sunlight and an environment where the temperature change is large, discoloration is more likely to occur in the vinyl chloride-based resin compared to an interior member. In such a respect, a decorative sheet using a base material layer containing a vinyl chloride-based resin is required to have excellent weather resistance.

[0014] The inventors of the present invention considered providing a weather-resistant layer containing a triazine-based ultraviolet absorber having a high ultraviolet absorption ability between a base material layer containing a vinyl chloride-based resin and a surface protection layer. Here, as the resin used for the weather-resistant layer, by using a vinyl chloride-based resin as in the base material layer, there is an advantage that a decorative sheet having good workability when disposed on a substrate can be easily obtained. On the other hand, when a detailed study was conducted on a decorative sheet using a weather-resistant layer containing a vinyl chloride-based resin, it was found that there is room for further improvement in weather resistance. Therefore, as a result of intensive research on improving weather resistance by the inventors of the present invention, when a (meth)acrylic resin is adopted as the resin constituting the weather-resistant layer and the thickness of the weather-resistant layer is made equal to or greater than a predetermined range, the weather resistance of the decorative sheet can be improved. Further, by making the thickness of the weather-resistant layer within a predetermined range, even when a (meth)acrylic resin is used, a weather-resistant layer having good workability can be obtained in the same manner as when a vinyl chloride-based resin is used.

[0015] Furthermore, since the surface protective layer in the present disclosure contains a triazine-based ultraviolet absorber, in this regard as well, the cosmetic sheet has excellent weather resistance. Also, since both the surface protective layer and the weather-resistant layer contain a triazine-based ultraviolet absorber, the proportion of the triazine-based ultraviolet absorber in the surface protective layer can be relatively reduced. As a result, while improving the weather resistance of the cosmetic sheet, it is possible to suppress a decrease in the surface properties (e.g., stain resistance) required for the surface protective layer. Also, for example, assume a case where a surface protective layer is formed on the weather-resistant layer using an ionizing radiation-curable resin. When the weather-resistant layer contains a vinyl chloride-based resin, a dechlorination reaction (discoloration) may occur in the vinyl chloride-based resin contained in the weather-resistant layer due to ionizing radiation (e.g., electron beam irradiation, ultraviolet irradiation). On the other hand, when the weather-resistant layer contains a (meth)acrylic-based resin, since no dechlorination reaction occurs in the (meth)acrylic-based resin, deterioration of the weather-resistant layer during the formation of the surface protective layer can be suppressed.

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

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

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

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

[0020] (2) Triazine-based ultraviolet absorber 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 characteristic in terms of molecular structure that it is difficult to bleed out from the surface protection layer and escape due to steric hindrance. Examples of the preferred hydroxyphenyltriazine-based ultraviolet absorber include compounds represented by the following general formula (I).

[0021] [Chemical formula]

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

[0023] R 11 Examples of the divalent hydrocarbon group in include aliphatic hydrocarbon groups such as an alkylene group and an alkenylene group. From the viewpoint of weather resistance, an alkylene group is more preferable.) 11 The number of carbon atoms of the aliphatic hydrocarbon group in is preferably 20 or less, more preferably 12 or less, still more preferably 8 or less, and even more preferably 4 or less as the upper limit. On the other hand, the lower limit is not particularly limited and may be 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 Examples of the monovalent hydrocarbon group in include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and an alkyl group is more preferable.) 12 The number of carbon atoms of the alkyl group in is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more as the lower limit. On the other hand, the upper limit is preferably 20 or less, more preferably 16 or less, still more preferably 12 or less.) 12 The alkyl group and alkenyl group in may be linear, branched, or cyclic, but are preferably linear or branched, and more preferably branched.)

[0025] R 13 and R 14Examples of the monovalent hydrocarbon group in [compound name] include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Among these, groups containing aromatic hydrocarbon groups such as an aryl group and 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 [compound name] is preferably 20 or less, more preferably 12 or less, still more preferably 4 or less, and even more preferably 2 or less. That is, for R 13 and R 14 the alkyl group is particularly preferably a methyl group or an ethyl group, and considering availability, a methyl group is particularly preferred.

[0027] R 13 and R 14 The number of carbon atoms in the aryl group in [compound name] is preferably at least 6 as the lower limit, while as the upper limit, it is preferably 20 or less, more preferably 12 or less, and still more preferably 10 or less. R 13 and R 14 The number of carbon atoms in the aralkyl group in [compound name] is preferably at least 7 as the lower limit, and as the upper limit, it is preferably 20 or less, more preferably 12 or less, and still more preferably 10 or less.

[0028] R 15 R 16 and R 17 Examples of the monovalent hydrocarbon group in [compound name] include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Among these, aliphatic hydrocarbon groups such as an alkyl group and an alkenyl group are preferred, and an alkyl group is more preferred. For R 15 R 16 and R 17 the number of carbon atoms in the alkyl group and alkenyl group is preferably at least 2, more preferably at least 4 as the lower limit, and as the upper limit, it is preferably 20 or less, more preferably 16 or less, and still more preferably 12 or less.

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

[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, more preferably 1 or 2. When n 11 and n 12 are integers of 2 or more, the plurality of R 13 and R 14 may be the same or different from each other, but from the viewpoint of availability, it is preferable that they are the same.

[0031] Examples of the compound represented by the 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 ("Adekastab 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]

Chemical formula

[0033]

Chemical formula

[0034]

Chemical formula

[0035] [Chemical formula]

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

[0037] The triazine-based ultraviolet absorber contained in the weather-resistant layer in the cosmetic sheet and the triazine-based ultraviolet absorber contained in the surface protection layer may be of the same type or different types.

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

[0039] The weather-resistant layer may be transparent, translucent, or opaque. Further, the weather-resistant layer may be colored or uncolored. When the cosmetic sheet has a design layer, the weather-resistant layer preferably has a transparency that can distinguish the design layer.

[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, the processability may decrease.

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

[0042] Examples of the method for forming the weather-resistant layer include extrusion film formation using an extruder such as a T-die extruder. Alternatively, the weather-resistant layer may be prepared in advance and thermally laminated with other layers. Further, the weather-resistant layer may be subjected to a surface treatment such as corona discharge treatment.

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

[0044] (1) Triazine-based ultraviolet absorber Since the triazine-based ultraviolet absorber is the same as the content described in the above "1. Weather-resistant layer", the description here is omitted.

[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 thermosetting resin composition. In the present disclosure, an ionizing radiation curable resin composition is preferred because of its 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 the resin component.

[0047] Specific examples of the ionizing radiation curable resin composition include an electron beam curable resin composition and an ultraviolet curable resin composition. Among them, the electron beam curable resin composition has advantages such as less odor because no polymerization initiator is required and less coloring occurs.

[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 an "ionizing radiation curable compound"). The ionizing radiation curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation. Specific examples thereof include functional groups having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. Further, other specific examples of the ionizing radiation curable functional group include an epoxy group and an oxetanyl group. In the present specification, the (meth)acryloyl group means an acryloyl group or a methacryloyl group. Also, in the present specification, (meth)acrylate means acrylate or methacrylate. Also, ionizing radiation means those having energy quanta capable of polymerizing or crosslinking molecules among electromagnetic waves or charged particle beams. 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 γ-rays, and charged particle beams such as α-rays and ion beams.

[0049] The ionizing radiation curable resin composition may contain only one kind of ionizing radiation curable compound, or may contain two or more kinds. The type of the ionizing radiation curable compound is not particularly limited, and known polymerizable monomers and known polymerizable oligomers (polymerizable prepolymers) can be used.

[0050] The ionizing radiation curable compound preferably includes a compound having two or more ethylenically unsaturated bond groups. Among them, the ionizing radiation curable compound preferably includes 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 difunctional (meth)acrylate monomer or a (meth)acrylate monomer having three or more functions. Examples of the difunctional (meth)acrylate monomer include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate. Examples of the (meth)acrylate monomer having three or more functions 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)acrylate is obtained, for example, by the reaction of a polyhydric alcohol and an organic diisocyanate with hydroxy (meth)acrylate. Also, epoxy (meth)acrylate is obtained, for example, by the reaction of an epoxy resin with (meth)acrylic acid. In this reaction, at least one of a polybasic acid and phenols may be further used. The epoxy resin may be bifunctional or may have three or more functional groups. Examples of the epoxy resin include aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

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

[0055] When the radiation curable compound is an ultraviolet curable compound, the 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, benzyldimethylketal, benzoyl benzoate, α-acyl oxime ester, and thioxanthone. Examples of the photopolymerization accelerator include isoamyl p-dimethylaminobenzoate and ethyl p-dimethylaminobenzoate.

[0056] On the one hand, a thermosetting resin composition is a composition containing at least a thermosetting resin. This resin composition cures upon heating. Examples of thermosetting resins 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 as required.

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

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

[0059] Examples of the method for forming the surface protection layer include a method of coating a mixture containing a resin component and an additive on the surface of the weather-resistant layer, drying, and curing. Also, the above mixture may be coated on the surface of a substrate having releasability, dried, and cured to form a surface protection layer, and then the surface protection layer may be transferred onto the weather-resistant layer.

[0060] 3. Substrate layer In the present disclosure, the base material layer is a layer that supports a weather-resistant layer and a surface protection layer. The base material layer contains a vinyl chloride-based resin. An example of the vinyl chloride-based resin is polyvinyl chloride, which is a homopolymer of vinyl chloride. Other examples of the vinyl chloride-based resin include copolymers of vinyl chloride and other monomers copolymerizable 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-based resin is, for example, 500 or more and 4000 or less, may be 700 or more and 3900 or less, or may be 1000 or more and 3800 or less. In the present disclosure, the average degree of polymerization is measured in accordance with JIS K 6721.

[0062] The base material layer may contain only the vinyl chloride-based resin as the resin, or may further contain other resins different from the vinyl chloride-based resin. Examples of other resins include, for example, (meth)acrylic resins, chlorinated polyethylene, and ethylene-vinyl acetate copolymers. It is preferable that the base material layer contains the vinyl chloride-based resin as the main component of the resin. In the base material layer, the proportion of the vinyl chloride-based 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] In addition to the vinyl chloride resin, the base material layer preferably contains a plasticizer. By adding a plasticizer, a soft base material layer can be obtained. Examples of the plasticizer include phthalic acid-based plasticizers such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and diundecyl phthalate (DUP); adipic acid-based plasticizers such as dibutyl adipate; phosphoric acid-based plasticizers such as tributyl phosphate, tricresyl phosphate, and triphenyl phosphate; trimellitic acid-based plasticizers such as tributyl trimellitate, trioctyl trimellitate, and tri-2-ethylhexyl trimellitate (TOTM); ester-based plasticizers such as adipic acid-based polyesters; 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 for example, it is 5 parts by mass or more, and may be 8 parts by mass or more, based on 100 parts by mass of the vinyl chloride resin. On the other hand, the content of the plasticizer is, for example, 30 parts by mass or less based on 100 parts by mass of the vinyl chloride resin.

[0065] The base material layer may further contain additives such as a heat stabilizer, a flame retardant, a light stabilizer, an ultraviolet absorber, a filler, and a colorant, if necessary. In addition, the base material layer may be surface-treated, 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] Examples of the shape of the base material layer include a sheet shape. The thickness of the base material layer is not particularly limited, but for example, it is 10 μm or more and 300 μm or less. The basis weight of the base material layer is not particularly limited, but for example, it is 50 g / m 2 or more and 300 g / m 2 or less, and 60 g / m2 Above 160 g / m 2 It may also be below.

[0067] 4. Design layer The cosmetic sheet in the present disclosure may have a design layer on one surface side of the weather-resistant layer. Further, the cosmetic sheet may have a design layer between the base material layer and the weather-resistant layer. By providing the design layer, the design property of the cosmetic sheet is improved. On the other hand, the cosmetic sheet may not have a design layer. Further, when the cosmetic sheet is viewed in a plan view along the thickness direction, the design layer may be disposed on the entire surface of the cosmetic sheet, or may be disposed on a part of the cosmetic sheet.

[0068] Examples of the design layer include a solid layer (a layer coated with ink) and a pattern layer (a layer printed with ink). Examples of the pattern in the pattern layer include a wood grain pattern, a stone grain pattern, a sand grain pattern, a tile pasted pattern, a brick stacked pattern, a cloth pattern, a leather grain pattern, a geometric figure, a character, a symbol, an abstract pattern, and a floral pattern.

[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, lead yellow, titanium yellow, bengara, cadmium red, ultramarine blue, cobalt blue, etc., organic pigments (including dyes) such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, azomethine azo black, etc., metal pigments such as aluminum and brass, and pearl pigments such as titanium dioxide-coated mica and basic lead carbonate.

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

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

[0072] Examples of the method for forming the design layer include a method of coating ink containing a colorant, a binder resin, and a solvent and then drying it. As the coating method, a gravure printing method is preferable.

[0073] 5. Decorative sheet The decorative sheet in the present disclosure has at least a base material layer, a weather-resistant layer, and a surface protection layer. The decorative sheet may have only the base material layer, the weather-resistant layer, and the surface protection layer, or may have other layers in addition to the base material layer, the weather-resistant layer, and the surface protection layer. The decorative sheet may further include 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 following layer structures.

[0074] (1) Base material layer / Weather-resistant layer / Surface protection layer (2) Base material layer / Weather-resistant layer / Primer layer / Surface protection layer (3) Base material layer / Design layer / Weather-resistant layer / Surface protection layer (4) Base material 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 material layer / Adhesive layer / Design layer / Weather-resistant layer / Surface protection layer (7) Base material layer / Design layer / Adhesive layer / Weather-resistant layer / Surface protection layer (8) Base material layer / Adhesive layer / Weather-resistant layer / Primer layer / Surface protection layer (9) Base material layer / Adhesive layer / Design layer / Weather-resistant layer / Primer layer / Surface protection layer (10) Base material layer / Design layer / Adhesive layer / Weather-resistant layer / Primer layer / Surface protection layer (11) Base material layer / Foamed resin layer / Weather-resistant layer / Surface protection layer (12) Base material layer / Foamed resin layer / Weather-resistant layer / Primer layer / Surface protection layer (13) Base material layer / Foamed resin layer / Design layer / Weather-resistant layer / Surface protection layer (14) Base material layer / Foamed resin layer / Design layer / Weather-resistant layer / Primer layer / Surface protection layer (15) Base material layer / Foamed resin layer / Adhesive layer / Weather-resistant layer / Surface protection layer (16) Base material layer / Foamed resin layer / Adhesive layer / Design layer / Weather-resistant layer / Surface protection layer (17) Base material layer / Foamed resin layer / Design layer / Adhesive layer / Weather-resistant layer / Surface protection layer (18) Base material layer / Foamed resin layer / Adhesive layer / Weather-resistant layer / Primer layer / Surface protection layer (19) Base material layer / Foamed resin layer / Adhesive layer / Design layer / Weather-resistant layer / Primer layer / Surface protection layer (20) Base material layer / Foamed resin layer / Design layer / Adhesive layer / Weather-resistant layer / Primer layer / Surface protection layer

[0075] The above “ / ” indicates the relative positional relationship between the layers. For example, “A / B / C” means that A, B, and C are arranged in this order along the thickness direction. Also, for example, when described as “A / B”, A and B may be arranged so as to be in direct contact, or may be arranged via other layers. Further, as exemplified in (11) to (20) above, when the decorative sheet includes a foamed resin layer, a non-foamed resin layer may be arranged on one or both surfaces of the foamed resin layer.

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

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

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

[0079] The primer layer may further contain at least one of an ultraviolet absorber and a light stabilizer. General ones can be used as the ultraviolet absorber and the light stabilizer. 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 may be 1 μm or more and 6 μm or less. Examples of the method for forming the primer layer include a method of coating a resin composition containing a binder resin and a solvent and then drying it. A curing treatment may be performed as necessary.

[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 base material layer and the weather-resistant layer. Further, when the decorative sheet has a design layer, the adhesive layer may be disposed between the design layer and the weather-resistant layer. Further, when the base material layer is a laminate of two or more layers, an adhesive layer may be disposed between the layers constituting the base material layer. Further, the decorative sheet may have an adhesive layer (back adhesive layer) on the surface opposite to the surface protection layer of the base material layer. In this case, the decorative sheet may have a separable separator layer on the surface opposite to the base material layer of the adhesive layer.

[0081] The adhesive layer contains a resin. Examples of the resin include 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, fluororesin, silicone resin fiber derivative, and rubber resin.

[0082] The thickness of the adhesive layer is, for example, 0.1 μm or more and 10 μm or less. Examples of the method for forming the adhesive layer include a method of coating a resin composition containing a resin and a solvent and then drying it.

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

[0084] The foamed resin layer contains a resin. The foamed resin layer may contain a cured product of the above resin. Examples of the above resin include thermoplastic resins. Examples of thermoplastic resins 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 air bubbles inside. The air bubbles may be closed cells or open cells. Also, in the foamed resin layer, closed cells and open cells may coexist. The air bubbles are formed by the foaming of the foaming agent contained in the foaming agent-containing resin layer, and their number, size, density, and shape are not particularly limited.

[0086] (4) Non-foamed resin layer The decorative sheet may have a non-foamed resin layer between the base material layer and the weather-resistant layer. The non-foamed resin layer is a layer that does not contain air bubbles caused by the foaming of a foaming agent. When the decorative sheet has a foamed resin layer, the non-foamed resin layer may be disposed on the surface of the foamed resin layer on the side of the base material layer, or may be disposed on the surface of the foamed resin layer on the side of the surface protection layer. On the other hand, the decorative sheet may not have a non-foamed resin layer. Since the resin used for the non-foamed resin layer is the same as the resin used for the foamed resin layer, the description here is omitted.

[0087] (5) Decorative sheet The decorative sheet in the present disclosure has at least a base material layer, a weather-resistant layer, and a surface protection 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 on the surface protection layer side with reference to the base material layer. Among them, it is preferable that the embossed pattern is arranged on the surface of the surface protection layer opposite to the base material layer. Examples of the embossed pattern include wood grain board conduit grooves, unevenness on the surface of slate, fabric surface texture, satin finish, grained finish, hairline, and myriad stripe grooves.

[0089] As a method for forming the embossed pattern, for example, a method of heating the decorative sheet and pressing an embossing plate can be mentioned. The heating temperature of the decorative sheet is, for example, 80°C or higher and 260°C or lower, and may be 85°C or higher and 200°C or lower, or may be 100°C or higher and 180°C or lower.

[0090] 6. Use The decorative sheet in the present disclosure is used, for example, for the decorative members described later. The decorative members are used, for example, for building materials, and may be interior members or exterior members. The decorative sheet is preferably used, for example, as a surface material for the outer walls, inner walls, roofs, eaves ceilings, door pockets, window frames, door frames, etc. of buildings such as houses, offices, stores, hospitals, and clinics.

[0091] 7. Manufacturing method The method for manufacturing the decorative sheet in the present disclosure is not particularly limited. As a method for manufacturing the decorative sheet, for example, a surface protection layer side sheet manufacturing step of forming the surface protection layer on one surface of the weather-resistant layer and manufacturing a surface protection layer side sheet, and an optional design layer is formed on one surface of the base material layer to manufacture a base material layer side sheet. A manufacturing method having a step of laminating and thermally laminating the surface of the surface protection layer side sheet on the weather-resistant layer side and the surface of the base material layer side sheet on the design layer side so as to face each other can be mentioned. The surface protection layer side sheet manufacturing step and the base material layer side sheet manufacturing step may be performed first or in parallel.

[0092] B. Decorative member In the present disclosure, a decorative member having a base and the above-described decorative sheet is provided. The base and the decorative sheet are arranged such that the base and the surface of the decorative sheet on the base material layer side face each other.

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

[0094] 1. Decorative sheet The decorative sheet in the present disclosure is the same as the content described in the above "A. Decorative sheet", so the description here is omitted.

[0095] 2. Substrate The substrate in the present disclosure is a member decorated with a decorative sheet. Examples of the substrate include resin members. Examples of the resin used for the resin member include, for example, vinyl chloride-based resins, acrylic resins, ester resins, styrene resins, olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), phenolic resins, cellulose resins, and rubbers. Among them, vinyl chloride-based resins are preferred. Regarding the details of each resin, the content described in the above "A. Decorative sheet" can be appropriately cited. Further, other examples of the substrate include wood members. Examples of the wood members include, for example, wood veneers, plywood, particle boards, and wood fiber boards. Examples of the wood used for the wood members include, for example, cedar, cypress, pine, and lauan.

[0096] Further, other examples of the substrate include metal members. Examples of the metal used for the metal members include, for example, iron and aluminum. Further, other examples of the substrate include ceramic members. The material of the ceramic member may be ceramics such as glass and porcelain, may be non-cement ceramic-based materials such as gypsum, or may be non-porcelain ceramic-based materials such as ALC (lightweight cellular concrete).

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

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

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

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

Example

[0101] [Example 1] (Production process of the sheet on the base material layer side) First, as a base material, a polyvinyl chloride film (thickness: 80 μm) containing 20 parts by mass of a polyester plasticizer with respect to 100 parts by mass of polyvinyl chloride was prepared. By applying a printing ink containing a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin as a binder to one surface of the base material, a design layer (pattern layer) was formed.

[0102] (Surface protection layer side sheet production process) As a weather-resistant layer, an acrylic film (thickness: 50 μm) containing polymethyl methacrylate (PMMA) and a triazine-based ultraviolet absorber (UVA Tinuvin479) was prepared. The content of UVA with respect to 100 parts by mass of PMMA was 1 part by mass. An electron beam curable resin coating agent was applied to one surface of the acrylic film by a gravure coating method to form a coated layer. By irradiating the coated layer with an electron beam under the conditions of an acceleration voltage of 125 KeV and 5 Mrad, a surface protection layer with a thickness of 5 μm was formed. As the electron beam curable resin coating agent, a urethane acrylate as an ionizing radiation curable resin was used, to which 2 parts by mass of a triazine-based ultraviolet absorber (UVA Tinuvin479) and 2 parts by mass of a light stabilizer (HALS Tinuvin123) were added.

[0103] The sheet produced in the surface protection layer side sheet production process was overlapped with the sheet produced in the base material layer side sheet production process on the design layer side of the sheet such that the surface protection layer was on the outermost surface, and heat laminated at 150 °C. Thereby, a decorative sheet having a base material layer (polyvinyl chloride), a design layer, a weather-resistant layer (acrylic resin), and a surface protection layer in this order in the thickness direction was obtained.

[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 a plasticizer with respect to 100 parts by mass of a vinyl chloride-based resin (PVC)) containing a benzophenone-based ultraviolet absorber. The content of the ultraviolet absorber with respect to 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 the surface protective layer was not 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, after conducting an accelerated weathering test using a metal halide lamp (MWOM) (irradiating ultraviolet rays for 20 hours under the following irradiation conditions and then performing condensation for 4 hours under the following condensation conditions, with one cycle being the process of repeating this cycle), the appearance after 800 hours was visually observed from the surface protective layer side. <Test apparatus> Product name "Dipla Metal Weather" manufactured by Dipla Winters Co., Ltd. <Irradiation conditions> Illuminance: 65 mW / cm 2 , Black panel temperature: 63 °C, humidity inside the tank: 50% RH, time: 20 hours <Condensation conditions> Illuminance: 0 mW / cm 2 , Humidity inside the tank: 98% RH, time: 4 hours

[0109] Those with a level where no appearance change was confirmed were evaluated as ◎, those with a slight appearance change were evaluated as 〇, and those with significant discoloration were evaluated as ×.

[0110] (Processability) The processability of the cosmetic sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was evaluated. Specifically, a substrate having a bent portion (R = 1 mm) and the cosmetic sheet were pressure-bonded and laminated via an adhesive layer (hot melt) with a thickness of 50 μm, and the lifting of the cosmetic sheet at the bent portion was visually confirmed. Those with no lifting confirmed were evaluated as ◎, and those with almost no lifting confirmed were evaluated as 〇.

[0111] (Stain resistance) With respect to the outermost surface of the cosmetic sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2 (the surface on the side opposite to the base material layer with reference to the weather-resistant layer), ethanol rubbing (300 g / cm 2 load, 20 reciprocations) was carried out, and the appearance of the test portion was visually evaluated. Those with no appearance change were evaluated as 〇, and those with significant appearance change were evaluated as ×.

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

[0113] [Table 1]

[0114] It was confirmed that the cosmetic sheets obtained in Examples 1 to 3 had excellent weather resistance. Furthermore, the cosmetic sheets obtained in Examples 1 to 3 were also excellent in processability and stain resistance. On the other hand, the cosmetic sheet of Comparative Example 1 could not obtain excellent weather resistance. This is presumably because since the weather-resistant layer contains a vinyl chloride-based resin, discoloration over time due to a dechlorination reaction could not be suppressed. Also, it was confirmed that the cosmetic sheet of Comparative Example 2 having no surface protection layer was excellent in weather resistance itself but had low stain resistance. [Explanation of symbols]

[0115] 1... Base material layer 2... Weather-resistant layer 3... Surface protection layer 4... Design layer 10... Cosmetic sheet

Claims

[Claim 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.

Images