Decorative sheet and decorative material

Abstract

To provide a decorative sheet and a decorative material that exhibit superior weather resistance and enable reduction of an environmental burden.SOLUTION: A decorative sheet is provided with, in sequence, a surface protective layer, a transparent resin layer, an adhesive layer, a printing ink layer, and a colored resin layer, wherein at least one of the transparent resin layer and the colored resin layer comprises a polyolefin resin containing a chemically recycled polyolefin resin, and the surface protective layer comprises an ultraviolet absorber and a light stabilizer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to decorative sheets and decorative materials. [Background technology]

[0002] A laminate formed by providing an ink layer on a base sheet with a pattern or the like is used as a component constituting a decorative sheet, and it is common to further laminate a transparent resin layer made of a transparent resin material on the ink layer to improve the design. For example, Patent Document 1 listed below discloses an embossed decorative sheet in which a pattern layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer are laminated in this order on a thermoplastic resin base sheet, at least the transparent thermoplastic resin layer is embossed, the back surface of the thermoplastic resin base sheet is surface-activated, and a primer layer is provided on the surface-activated surface. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2018-062071 Summary of the Invention [Problem to be solved by the invention]

[0004] Conventionally, most of the resins used in decorative sheets have been petroleum-derived resins, but with increasing environmental concerns, recycled resins are increasingly being used to reduce the environmental burden.

[0005] However, even if the resin contained in the thermoplastic resin substrate sheet or transparent thermoplastic resin layer of the decorative sheet described in Patent Document 1 is a recycled resin, there is room for improvement in terms of weather resistance if the recycled resin is a so-called material recycled resin, which is a resin made by cleaning and crushing recovered resin products such as used packaging materials, and then heating and melting them to regenerate them into raw materials.

[0006] The present disclosure has been made in consideration of the above-mentioned problems, and aims to provide a decorative sheet and decorative material that have excellent weather resistance and can reduce the environmental impact. [Means for solving the problem]

[0007] In order to solve the above problems, the present disclosure provides the following decorative sheets and decorative materials.

[0008] [1] A decorative sheet comprising a surface protective layer, a transparent resin layer, an adhesive layer, a printing ink layer, and a colored resin layer in this order, wherein at least one of the transparent resin layer and the colored resin layer contains a polyolefin resin including a chemically recycled polyolefin resin, and the surface protective layer contains an ultraviolet absorber and a light stabilizer. [2] The decorative sheet according to [1], wherein the ultraviolet absorber is a triazine-based ultraviolet absorber, and the light stabilizer is a hindered amine-based light stabilizer. [3] The decorative sheet according to [1] or [2], wherein the printing ink layer contains a urethane resin, and the urethane resin is a resin obtained using a composition containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate. [4] The decorative sheet according to any one of [1] to [3], wherein the chemically recycled polyolefin resin includes a post-consumer recycled resin. [5] The decorative sheet according to any one of [1] to [4], wherein the chemically recycled polyolefin resin is at least one of chemically recycled polypropylene and chemically recycled polyethylene. [6] The decorative sheet according to any one of [1] to [5], wherein the content of the chemically recycled polyolefin resin in the transparent resin layer is 1 to 99% by mass, and the content of the chemically recycled polyolefin resin in the colored resin layer is 1 to 99% by mass. [7] The decorative sheet according to any one of [2] to [6], wherein the transparent resin layer contains a triazine-based ultraviolet absorber different from the triazine-based ultraviolet absorber contained in the surface protective layer, and a hindered amine-based light stabilizer different from the hindered amine-based light stabilizer contained in the surface protective layer. [8] The decorative sheet according to any one of [2] to [7], wherein the colored resin layer contains a triazine-based ultraviolet absorber different from the triazine-based ultraviolet absorber contained in the surface protective layer, and a hindered amine-based light stabilizer different from the hindered amine-based light stabilizer contained in the surface protective layer. [9] The decorative sheet according to any one of [1] to [8], wherein the adhesive layer is obtained using an adhesive composition containing a polyester resin and a bisphenol A type epoxy resin, the polyester resin being a resin obtained using a polyester resin forming composition containing phthalic acid, a linear dicarboxylic acid, and an alkylene diol, and the mass ratio of the polyester resin to the bisphenol A type epoxy resin in the polyester resin forming composition (the polyester resin / the bisphenol A type epoxy resin) is 50 / 50 to 90 / 10.

[10] The decorative sheet according to any one of [1] to [9], wherein at least one of the transparent resin layer and the colored resin layer is obtained using a resin composition containing a core and the polyolefin resin.

[11] The decorative sheet according to

[10] , wherein the cores are nano-sized cores, and the amount of the cores added is 0.05 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of the polyolefin resin.

[12] The decorative sheet according to any one of [1] to

[11] , wherein the colored resin layer has a thickness of 40 to 100 μm, and the transparent resin layer has a thickness of 30 to 150 μm.

[13] The colored resin layer has a density of 0.90 to 1.70 g / cm 3 The transparent resin layer has a density of 0.90 to 0.99 g / cm 3 The decorative sheet according to any one of [1] to

[12] , wherein

[14] A decorative material comprising a substrate and a decorative sheet bonded to at least one surface of the substrate, wherein the decorative sheet is the decorative sheet according to any one of [1] to

[13] .

[0009] The decorative sheet according to [1] above has excellent weather resistance and can reduce environmental impact because at least one of the transparent resin layer and the colored resin layer contains a polyolefin resin including chemically recycled polyolefin, and the surface protective layer contains an ultraviolet absorber and a light stabilizer.

[0010] The inventors of the present disclosure speculate that the reason for such effects is as follows: At least one of the transparent resin layer and the colored resin layer contains a polyolefin resin, including a chemically recycled polyolefin resin, which is a recycled resin. Therefore, the decorative sheet according to [1] above can reduce the environmental impact.

[0011] Furthermore, because the surface protective layer contains an ultraviolet absorber, it absorbs ultraviolet rays. Furthermore, because the surface protective layer contains a light stabilizer, it is less susceptible to ultraviolet rays. Therefore, the amount of ultraviolet rays incident on the transparent resin layer and the colored resin layer is reduced. However, this does not prevent ultraviolet rays from reaching the transparent resin layer and the colored resin layer. In contrast, in the decorative sheet of the present disclosure, at least one of the transparent resin layer and the colored resin layer contains a polyolefin resin, including a chemically recycled polyolefin resin. Here, chemically recycled polyolefin resin is a recycled resin produced by first depolymerizing waste resin through a process, depending on the material characteristics, such as a process for monomerization via gasification, oilification, and refined naphtha, or a process for monomerization by depolymerization, and then polymerizing the monomer. Therefore, unlike material recycled polyolefin, which is a resin made by cleaning and crushing used packaging and other resin products, and then melting them into a recycled raw material, chemically recycled polyolefin resin is not affected by heat treatment such as melting, and therefore is less susceptible to degradation by ultraviolet rays in its resin state. For this reason, it is believed that the decorative sheet of the present disclosure has excellent weather resistance.

[0012] According to the decorative sheet according to [2] above, the ultraviolet absorber is a triazine-based ultraviolet absorber, and the light stabilizer is a hindered amine-based light stabilizer, so that the ultraviolet absorption and light stability of these are suppressed for a long period of time, and therefore the decorative sheet according to [2] above is prevented from decreasing in weather resistance for a long period of time.

[0013] According to the decorative sheet pertaining to [3] above, the printed ink layer contains a urethane resin, and the urethane resin is a resin obtained using a composition containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate. This means that, compared to a printed ink layer containing a polyester-based resin, the printed ink layer has sufficient adhesion to the colored resin layer, and embrittlement due to hydrolysis of the printed ink layer is suppressed, making the printed ink layer less likely to fall off and the transparent resin layer provided on the printed ink layer less likely to peel off. Furthermore, since the printed ink layer contains the urethane resin, hydrolysis is less likely to occur and sufficient moist heat resistance is possible. Therefore, the decorative sheet pertaining to [3] above has sufficient interlayer adhesion and moisture resistance.

[0014] According to the decorative sheet according to [4] above, post-consumer recycled resins are available in large quantities on the market and have stable quality compared to recycled materials extracted from ordinary industrial waste, so the decorative sheet according to [4] above can stabilize its quality.

[0015] According to the decorative sheet according to [5] above, since the chemically recycled polyolefin resin is at least one of chemically recycled polypropylene and chemically recycled polyethylene, the flexibility of the transparent resin layer or the colored resin layer is improved, and the bending processability of the decorative sheet according to [5] above can be improved.

[0016] According to the decorative sheet according to [6] above, the content of chemically recycled polyolefin resin in the transparent resin layer is 1 to 99 mass %, and the content of chemically recycled polyolefin resin in the colored resin layer is 1 to 99 mass %, thereby achieving better weather resistance while further reducing the environmental impact.

[0017] According to the decorative sheet according to [7] above, the transparent resin layer contains a triazine-based UV absorber different from the triazine-based UV absorber contained in the surface protective layer, and a hindered amine-based light stabilizer different from the hindered amine-based light stabilizer contained in the surface protective layer, so that the transparent resin layer has absorbency and stability for light of a different wavelength than the surface protective layer, and therefore the decorative sheet according to [7] above has better weather resistance.

[0018] According to the decorative sheet according to [8] above, the colored resin layer contains a triazine-based UV absorber different from the triazine-based UV absorber contained in the surface protective layer, and a hindered amine-based light stabilizer different from the hindered amine-based light stabilizer contained in the surface protective layer, so that the colored resin layer has absorbency and stability for light of a different wavelength than the surface protective layer, and therefore the decorative sheet according to [8] above has better weather resistance.

[0019] According to the decorative sheet according to [9] above, the adhesive layer is obtained using an adhesive composition containing a polyester resin and a bisphenol A type epoxy resin, and the polyester resin is a resin obtained using a polyester resin-forming composition containing phthalic acid, a linear dicarboxylic acid, and an alkylene diol, and the mass ratio of the polyester resin contained in the adhesive layer (polyester resin / bisphenol A type epoxy resin) is 50 / 50 to 90 / 10, so that the adhesive layer has better adhesion to the transparent resin layer and the printed layer and also has excellent moist heat resistance, and therefore the decorative sheet according to [9] above has better interlayer adhesion and moist heat resistance.

[0020] According to the decorative sheet according to the above item

[10] , at least one of the transparent resin layer and the colored resin layer is obtained using a resin composition containing a core and the polyolefin resin, which makes the layer containing the resin composition sufficiently hard, and therefore the decorative sheet according to the above item

[10] has sufficient scratch resistance.

[0021] According to the decorative sheet according to

[11] above, the cores are nano-sized cores, and the amount of cores added is 0.05 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of polyolefin resin, so that the layer containing the resin composition has sufficient hardness, and therefore the decorative sheet according to

[11] above has sufficient scratch resistance.

[0022] According to the decorative sheet according to

[12] above, the thickness of the colored resin layer is 100 μm or less, and the thickness of the transparent resin layer is 150 μm or less, thereby reducing the amount of resin material used in the decorative sheet. Therefore, the decorative sheet according to

[12] above can further reduce the environmental impact, is easier to bend, and has good processability. Furthermore, the thickness of the colored resin layer is 40 μm or more, and the thickness of the transparent resin layer is 30 μm or more, thereby providing better weather resistance.

[0023] According to the decorative sheet according to the above item

[13] , the density of the colored resin layer is 0.90 to 1.70 g / cm 3 and the density of the transparent resin layer is 0.90 to 0.99 g / cm 3 As a result, the decorative sheet has sufficient designability, printability, hiding power, and processability.

[0024] The decorative material according to

[14] above has the decorative sheet attached to at least one surface of the substrate, and therefore has excellent weather resistance and can reduce the environmental load. [Effects of the Invention]

[0025] According to the present disclosure, it is possible to provide decorative sheets and decorative materials that have excellent weather resistance and can reduce environmental impact. [Brief explanation of the drawings]

[0026] [Figure 1] 1 is a cross-sectional view showing one embodiment of a decorative sheet of the present disclosure. [Figure 2] 1 is a cross-sectional view showing one embodiment of a decorative material of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0027] Hereinafter, embodiments of the present disclosure will be described in detail.

[0028] <Decorative sheet> Fig. 1 is a cross-sectional view showing one embodiment of a decorative sheet of the present disclosure. The decorative sheet 1 shown in Fig. 1 comprises a surface protection layer 12, a transparent resin layer 11, an adhesive layer 13, a printing ink layer 15, and a colored resin layer 14, in this order. At least one of the transparent resin layer 11 and the colored resin layer 14 contains a chemically recycled polyolefin resin. The surface protection layer 12 contains an ultraviolet absorber and a light stabilizer.

[0029] The decorative sheet 1 may further have a primer layer 18 on the surface of the colored resin layer 14 opposite the printed ink layer 15 . The decorative sheet 1 has excellent weather resistance and reduces environmental impact because at least one of the transparent resin layer 11 and the colored resin layer 14 contains chemically recycled polyolefin resin, and the surface protective layer 12 contains an ultraviolet absorber and a light stabilizer.

[0030] From the standpoint of further reducing the environmental load, the content of chemically recycled polyolefin resin in the decorative sheet 1 is preferably 1% by mass or more, more preferably 30% by mass or more, and particularly preferably 60% by mass or more. The content of chemically recycled polyolefin resin in the decorative sheet 1 may be 99% by mass or less, 70% by mass or less, or 50% by mass or less.

[0031] The surface protection layer 12, the transparent resin layer 11, the adhesive layer 13, the printing ink layer 15, the colored resin layer 14, and the primer layer 18 will be described in detail below.

[0032] (Surface protective layer) The surface protection layer 12 is a transparent layer that protects the surface of the transparent resin layer 11, and is a layer that has enough light transmittance to allow the printed ink layer 15 to be visible. The surface protective layer 12 can be formed by coating a resin composition containing a hard resin, an ultraviolet absorber, and a light stabilizer. Examples of hard resins include urethane-based resins, acrylic-based resins, acrylic silicone-based resins, fluorine-based resins, and epoxy-based resins. When the hard resin is an acrylic-based resin, the decorative sheet 1 has better weather resistance. The resin composition may further contain various additives such as an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, as required.

[0033] Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a hydroxyphenyltriazine-based ultraviolet absorber. The ultraviolet absorber contained in the surface protective layer 12 is preferably a triazine-based ultraviolet absorber. The triazine-based ultraviolet absorber contained in the surface protective layer 12 can function as an ultraviolet absorber for a long period of time, thereby preventing a decrease in the light resistance of the surface protective layer 12 and a decrease in the adhesion between the surface protective layer 12 and the transparent resin layer 11 for a long period of time.

[0034] The content of the ultraviolet absorber in the surface protective layer 12 is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less. When the content is 20% by mass or less, the original function of the surface protective layer 12, that is, protecting the surface of the transparent resin layer 11, can be sufficiently maintained. The content of the ultraviolet absorber in the surface protective layer 12 is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more. When the content of the ultraviolet absorber is 1% by mass or more, the surface protective layer 12 has sufficient ultraviolet absorption properties, and the decorative sheet 1 has better weather resistance.

[0035] The light stabilizer contained in the surface protective layer 12 is preferably a hindered amine light stabilizer. The hindered amine light stabilizer contained in the surface protective layer 12 can function as a light stabilizer for a long period of time. Therefore, deterioration in the weather resistance of the surface protective layer 12 can be suppressed for a long period of time, and deterioration in the adhesion between the surface protective layer 12 and the transparent resin layer 11 can be suppressed for a long period of time.

[0036] The content of the light stabilizer in the surface protective layer 12 is preferably 1% by mass or more. With this content being 1% by mass or more, the surface protective layer 12 has sufficient light stability, and the decorative sheet 1 has better weather resistance. Furthermore, the content of the light stabilizer in the surface protective layer 12 is preferably 30% by mass or less. By keeping the content at 30% by mass or less, the original function of the surface protective layer 12, that is, protecting the surface of the transparent resin layer 11, can be fully maintained, and the decorative sheet 1 has sufficient flexibility and processability.

[0037] The thickness of the surface protective layer 12 is not particularly limited, but is preferably 2 μm or more, more preferably 9 μm or more, and even more preferably 15 μm or more. When the thickness of the surface protective layer 12 is 2 μm or more, the decorative sheet 1 has sufficient scratch resistance. Furthermore, the thickness of the surface protective layer 12 is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 9 μm or less. When the thickness of the surface protective layer 12 is 20 μm or less, the decorative sheet 1 has sufficient flexibility.

[0038] (Transparent resin layer) The transparent resin layer 11 is a layer that improves the weather resistance and abrasion resistance of the decorative sheet 1 and protects the printed ink layer 15, and has enough light transparency to allow the printed ink layer 15 to be visible. The transparent resin layer 11 is a layer made of a resin composition that contains a thermoplastic resin.

[0039] The thermoplastic resin contained in the transparent resin layer 11 includes a polyolefin resin. Examples of polyolefin resins include polyethylene and polypropylene, which can be used either alone or in combination of two or more. When the polyolefin resin is made of at least one of polyethylene and polypropylene, the decorative sheet 1 has sufficient flexibility and bending processability.

[0040] The polyolefin resin may be a non-recycled polyolefin resin, a recycled polyolefin resin, or a mixture thereof. The recycled polyolefin resin may be a chemically recycled polyolefin resin, a mechanically recycled polyolefin resin, or a mixture thereof. The recycled polyolefin resin may be post-consumer recycled resin (PCR), post-industrial recycled resin (PIR), or a mixture thereof, but preferably contains PCR. PCR is available in large quantities on the market and has more stable quality than recycled materials collected from ordinary industrial waste, making it possible to stabilize the quality of the decorative sheet 1. The chemically recycled polyolefin resin may be composed of a single chemically recycled polyolefin resin, or may be composed of a mixture of multiple types of chemically recycled polyolefin resins. The mechanically recycled polyolefin resin may be composed of a single mechanically recycled polyolefin resin, or may be composed of a mixture of multiple types of mechanically recycled polyolefin resins.

[0041] The non-recycled polyolefin resin may be a petroleum-derived polyolefin resin obtained using petroleum-derived raw material monomers, a biomass-derived polyolefin resin obtained using biomass-derived raw material monomers, or a mixture thereof, but from the viewpoint of reducing the environmental load, a biomass-derived polyolefin resin is preferred.

[0042] The content of the chemically recycled polyolefin resin in the transparent resin layer 11 is not particularly limited, but may be 99% by mass or less, 80% by mass or less, or 50% by mass or less, based on the transparent resin layer 11. A content of 99% by mass or less enables cost reduction. The content of chemically recycled polyolefin resin in the transparent resin layer 11 may be 1% by mass or more, 5% by mass or more, 51% by mass or more, or 70% by mass or more, based on the transparent resin layer 11. When the content is 1% by mass or more, the decorative sheet 1 can have a lower environmental impact. It should be noted that the content of the chemically recycled polyolefin resin in the transparent resin layer 11 may be 0 mass % when the colored resin layer 14 contains the chemically recycled polyolefin resin.

[0043] The content of chemically recycled polyolefin resin in the polyolefin resin in the transparent resin layer 11 is not particularly limited, but may be 99% by mass or less, 80% by mass or less, or 50% by mass or less based on the total amount of polyolefin resin in the transparent resin layer 11. Having the content of 99% by mass or less enables cost reduction. The content of chemically recycled polyolefin resin in the polyolefin resin in the transparent resin layer 11 may be 1% by mass or more, 5% by mass or more, 51% by mass or more, or 70% by mass or more, based on the total amount of polyolefin resin in the transparent resin layer 11. When the content is 1% by mass or more, the decorative sheet 1 can have a lower environmental impact. The content of the chemically recycled polyolefin resin in the polyolefin resin in the transparent resin layer 11 may be 0 mass % when the colored resin layer 14 contains the chemically recycled polyolefin resin.

[0044] The transparent resin layer 11 may further contain additives such as ultraviolet absorbers, light stabilizers, cores, fillers, antioxidants, antistatic agents, plasticizers, lubricants, light-shielding pigments, antiblocking agents, catalyst scatterers, light-scattering agents, and gloss adjusters, as necessary.

[0045] The ultraviolet absorber may be the same as that contained in the surface protective layer 12. In particular, the ultraviolet absorber contained in the transparent resin layer 11 is preferably a triazine-based ultraviolet absorber. In particular, the triazine-based ultraviolet absorber is preferably a hydroxyphenyltriazine ultraviolet absorber.

[0046] The triazine-based UV absorber contained in the transparent resin layer 11 may be the same as or different from the triazine-based UV absorber contained in the surface protective layer 12, but it is more preferable that they are different. In this case, the transparent resin layer 11 has UV absorption properties different from those of the surface protective layer 12, so that UV rays that are not absorbed by the surface protective layer 12 can be absorbed by the transparent resin layer 11, and the decorative sheet 1 has better weather resistance. A preferred combination of triazine-based ultraviolet absorbers contained in the surface protective layer 12 and the transparent resin layer 11 is 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol.

[0047] The content of the ultraviolet absorber in the transparent resin layer 11 is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. When the content is 0.2% by mass or more, the transparent resin layer 11 has sufficient ultraviolet absorption properties, and the decorative sheet 1 has better weather resistance. Furthermore, the content of the ultraviolet absorber in the transparent resin layer 11 is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 1.0% by mass or less. By keeping the content at 5.0% by mass or less, the original properties of the transparent resin layer 11 can be sufficiently maintained.

[0048] The light stabilizer may be the same as that contained in the surface protective layer 12. In particular, the light stabilizer contained in the transparent resin layer 11 is preferably a hindered amine-based light stabilizer. The light stabilizer contained in the surface protective layer 12 may be the same as or different from the hindered amine light stabilizer contained in the surface protective layer 12, but is preferably different. By containing a light stabilizer in the transparent resin layer 11 that is different from that in the surface protective layer 12, the surface protective layer 12 and the transparent resin layer 11 have different light stability properties, and therefore the decorative sheet 1 has better weather resistance.

[0049] Although there are no particular limitations on the content of the light stabilizer in the transparent resin layer 11, it is preferably 0.2% by mass or more. When the content is 0.2% by mass or more, the transparent resin layer 11 has sufficient light stability, and the decorative sheet 1 has better weather resistance. The content of the light stabilizer in the transparent resin layer 11 is preferably 1.0% by mass or less. When the content is 1.0% by mass or less, the inherent properties of the transparent resin layer 11 can be sufficiently maintained.

[0050] The core contains a nucleating agent. Examples of the nucleating agent include sodium 2,2'-methylenebis(4,6-di-tert-butylphenol)phosphonate. The core may be a nucleating agent vesicle in which the nucleating agent is encapsulated. The vesicle is composed of, for example, a monolayer membrane. By including cores in the transparent resin layer 11, the crystallinity of the transparent resin layer 11 can be increased, and the hardness can be increased, thereby improving the scratch resistance (scratch resistance) of the decorative sheet 1.

[0051] The nucleating agent is not particularly limited as long as it is a substance that serves as a starting point for crystallization when the polyolefin resin crystallizes. Examples of the nucleating agent include metal phosphate salts, metal benzoates, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, it is preferable to use metal phosphates, metal benzoates, metal pimelate or metal rosin salts, which are non-melting and expected to have good transparency. If the material itself can be made transparent by nano-processing, colored quinacridone, cyanine blue, talc, etc. may also be used. In addition, a non-melting nucleating agent may be appropriately mixed with melting benzylidene sorbitol.

[0052] Materials constituting the vesicles include, for example, substances containing biological substances such as phospholipids, and dispersants. These can be used either alone or in combination of two or more. Examples of phospholipids include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol. Examples of dispersants include nonionic surfactants and mixtures of nonionic surfactants with cholesterols or triacylglycerols.

[0053] The cores may be nano-sized cores (hereinafter also referred to as "nano-cores") or non-nano-sized cores. Here, "nano-sized" refers to an average particle size of less than 1 μm, and "non-nano-sized" refers to an average particle size of 1 μm or more. The average particle size of the cores is not particularly limited as long as it is less than 1 μm, but the average particle size is preferably 375 nm or less, more preferably 250 nm or less, and even more preferably 180 nm or less. By making the average particle size of the cores 375 nm or less, the transparent resin layer 11 can be made into a resin layer with high crystallinity and high hardness, and a transparent resin layer can be realized. The average particle size of the cores may be 50 nm or more, or 150 nm or more.

[0054] The amount of the core added per 100 parts by mass of the polyolefin resin is not particularly limited, but is preferably 0.05 to 0.5 parts by mass, more preferably 0.1 to 0.3 parts by mass. When the amount of the core added is 0.05 parts by mass or more relative to 100 parts by mass of the polyolefin resin, the hardness of the transparent resin layer 11 can be effectively improved. By adding 0.5 parts by mass or less of the core to 100 parts by mass of the polyolefin resin, the inherent properties of the transparent resin layer 11 can be prevented from being deteriorated.

[0055] The thickness of the transparent resin layer 11 is not particularly limited, but is preferably 10 to 150 μm, more preferably 40 to 120 μm, and even more preferably 50 to 90 μm. When the thickness of the transparent resin layer 11 is 10 μm or more, the decorative sheet has sufficient scratch resistance. Furthermore, when the thickness of the transparent resin layer 11 is 150 μm or less, the amount of resin material used can be further reduced, and the decorative sheet 1 can further reduce its environmental impact.

[0056] The density of the transparent resin layer 11 is not particularly limited, but is preferably 0.90 g / cm 3 It is preferable that the concentration is 0.91 g / cm or more. 3 It is more preferable that the density of the transparent resin layer 11 is 0.90 g / cm or more. 3 As a result of the above, the decorative sheet 1 has sufficient design properties. The density of the transparent resin layer 11 is 0.99 g / cm 3 Preferably, it is 0.96 g / cm or less. 3 It is more preferable that the density of the transparent resin layer 11 is 0.99 g / cm or less. 3 When the thickness is equal to or less than this, the decorative sheet has sufficient processability.

[0057] (Colored resin layer) The colored resin layer 14 is a layer made of a resin composition containing a thermoplastic resin and a colorant. The colored resin layer 14 only needs to be colored to an extent that it can conceal the pattern of the substrate when the decorative sheet 1 is attached to the substrate, and may be a plain layer made of a single color.

[0058] The thermoplastic resin contained in the colored resin layer 14 may be a polyolefin resin. Examples of polyolefin resins include polyethylene, polypropylene, etc. These may be used alone or in combination of two or more. When the polyolefin resin is composed of at least one of polyethylene and polypropylene, the flexibility of the decorative sheet 1 is improved, and bending workability can be improved.

[0059] The polyolefin resin may be a non-recycled polyolefin resin, a recycled polyolefin resin, or a mixture thereof. The recycled polyolefin resin may be post-consumer recycled resin (PCR), post-industrial recycled resin (PIR), or a mixture thereof, but preferably contains PCR. PCR is available in large quantities on the market and has more stable quality than recycled materials collected from ordinary industrial waste, making it possible to stabilize the quality of the decorative sheet 1. The chemically recycled polyolefin resin may be composed of a single chemically recycled polyolefin resin, or may be composed of a mixture of multiple types of chemically recycled polyolefin resins. The mechanically recycled polyolefin resin may be composed of a single mechanically recycled polyolefin resin, or may be composed of a mixture of multiple types of mechanically recycled polyolefin resins.

[0060] The non-recycled polyolefin resin may be a petroleum-derived polyolefin resin obtained using petroleum-derived raw material monomers, a biomass-derived polyolefin resin obtained using biomass-derived raw material monomers, or a mixture thereof, but from the viewpoint of reducing the environmental load, a biomass-derived polyolefin resin is preferred.

[0061] The content of chemically recycled polyolefin resin in the colored resin layer 14 may be less than 99% by mass, 80% by mass or less, or 50% by mass or less, based on the colored resin layer 14. When the content is less than 99% by mass, the colored resin layer 14 can contain a sufficient amount of colorant, and the colored resin layer has sufficient hiding power, so that the decorative material obtained using the decorative sheet 1 has excellent design properties. The content of chemically recycled polyolefin resin in the colored resin layer 14 may be 1% by mass or more, 5% by mass or more, 51% by mass or more, or 70% by mass or more based on the colored resin layer 14. When the content is 1% by mass or more, the environmental impact of the decorative sheet 1 can be further reduced. When the transparent resin layer 11 contains a chemically recycled polyolefin resin, the content of the chemically recycled polyolefin resin in the colored resin layer 14 may be 0 mass %.

[0062] The content of chemically recycled polyolefin resin in the polyolefin resin in the colored resin layer 14 may be less than 99 mass%, 80 mass% or less, or 50 mass% or less based on the polyolefin resin in the colored resin layer 14. A content of less than 99 mass% enables cost reduction. The content of chemically recycled polyolefin resin in the polyolefin resin in the colored resin layer 14 may be 1% by mass or more, 5% by mass or more, 51% by mass or more, or 70% by mass or more based on the polyolefin resin in the colored resin layer 14. When the content is 1% by mass or more, the environmental impact of the decorative sheet 1 can be further reduced. In addition, the content of the chemically recycled polyolefin resin in the polyolefin resin in the colored resin layer 14 may be 0 mass % when the transparent resin layer 11 contains the chemically recycled polyolefin resin.

[0063] Examples of the colorant contained in the colored resin layer 14 include organic pigments such as isoindolinone, diketopyrrolopyrrole, phthalocyanine blue, and disazo pigments, and inorganic pigments such as carbon black.

[0064] The colored resin layer 14 may further contain additives such as ultraviolet absorbers, light stabilizers, cores, fillers, antioxidants, antistatic agents, plasticizers, lubricants, light-shielding pigments, antiblocking agents, catalyst scatterers, light-scattering agents, and gloss adjusters, as necessary.

[0065] The ultraviolet absorber may be the same as that contained in the surface protective layer 12. In particular, the ultraviolet absorber contained in the colored resin layer 14 is preferably a triazine-based ultraviolet absorber. In particular, the triazine-based ultraviolet absorber is preferably a hydroxyphenyltriazine ultraviolet absorber. The triazine-based UV absorber contained in the colored resin layer 14 may be the same as or different from the triazine-based UV absorber contained in the surface protective layer 12, but it is more preferable that they are different. In this case, the colored resin layer 14 has UV absorption properties different from those of the surface protective layer 12, so that UV rays that are not absorbed by the surface protective layer 12 can be absorbed by the colored resin layer 14, and the decorative sheet 1 has better weather resistance.

[0066] Furthermore, when the surface protective layer 12, the transparent resin layer 11, and the colored resin layer 14 all contain an ultraviolet absorber, it is preferable that the ultraviolet absorbers contained in these layers are different from one another. In this case, since each layer has different ultraviolet absorption characteristics, it becomes possible for the colored resin layer 14 to absorb ultraviolet light that is not absorbed by the transparent resin layer 11 and the surface protective layer 12, and the decorative sheet 1 has better weather resistance.

[0067] The content of the ultraviolet absorber in the colored resin layer 14 is preferably 0.2% by mass or more. With this content of 0.2% by mass or more, the colored resin layer 14 has sufficient ultraviolet absorption properties, and the decorative sheet 1 has better weather resistance. Furthermore, the content of the ultraviolet absorber in the colored resin layer 14 is preferably 1.0% by mass or less. With a content of the ultraviolet absorber of 1.0% by mass or less, the original properties of the colored resin layer 14 can be sufficiently maintained.

[0068] The light stabilizer may be the same as that contained in the surface protective layer 12. In particular, the light stabilizer contained in the colored resin layer 14 is preferably a hindered amine light stabilizer. The light stabilizer contained in the colored resin layer 14 may be the same as or different from the hindered amine light stabilizer contained in the surface protective layer 12, but it is more preferable that they are different. In this case, the surface protective layer 12 and the colored resin layer 14 have different light stabilities, and therefore the decorative sheet 1 has better weather resistance.

[0069] Furthermore, when the surface protective layer 12, the transparent resin layer 11, and the colored resin layer 14 all contain a light stabilizer, it is preferable that the light stabilizers contained in these layers are different from one another. In this case, each layer has a different light stability, and therefore the decorative sheet 1 has better weather resistance.

[0070] The content of the light stabilizer in the colored resin layer 14 is preferably 0.2% by mass or more. With this content of 0.2% by mass or more, the colored resin layer 14 has sufficient light stability, and the decorative sheet 1 has better weather resistance. Furthermore, the content of the light stabilizer in the colored resin layer 14 is preferably 1.0% by mass or less. With this content of 1.0% by mass or less, the original properties of the colored resin layer 14 can be fully maintained.

[0071] The core contains a nucleating agent. Examples of the nucleating agent include sodium 2,2'-methylenebis(4,6-di-tert-butylphenol)phosphonate. The core may be a nucleating agent vesicle in which the nucleating agent is encapsulated. The vesicle is composed of, for example, a monolayer membrane. By including nuclei in the colored resin layer 14, the crystallinity of the colored resin layer 14 can be increased, and the hardness can be increased, thereby improving the scratch resistance (scratch resistance) of the decorative sheet 1.

[0072] The nucleating agent is not particularly limited as long as it is a substance that serves as a starting point for crystallization when the polyolefin resin crystallizes. Examples of the nucleating agent include metal phosphate salts, metal benzoates, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, it is preferable to use metal phosphates, metal benzoates, metal pimelate or metal rosin salts, which are non-melting and expected to have good transparency. If the material itself can be made transparent by nano-processing, colored quinacridone, cyanine blue, talc, etc. may also be used. In addition, a non-melting nucleating agent may be appropriately mixed with melting benzylidene sorbitol.

[0073] Materials constituting the vesicles include, for example, substances containing biological substances such as phospholipids, and dispersants. These can be used either alone or in combination of two or more. Examples of phospholipids include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol. Examples of the dispersant include a nonionic surfactant, or a mixture of a nonionic surfactant with a cholesterol or triacylglycerol.

[0074] The cores may be nano-sized or non-nano-sized. The average particle size of the cores is not particularly limited as long as it is less than 1 μm, but the average particle size is preferably 375 nm or less, more preferably 250 nm or less, and even more preferably 180 nm or less. By making the average particle size of the cores 180 nm or less, the colored resin layer 14 can be made into a resin layer with high crystallinity and high hardness, and a resin layer that is suppressed from cracking or whitening during bending can be realized. The average particle size of the cores may be 50 nm or more, or 150 nm or more.

[0075] The amount of the core added per 100 parts by mass of the polyolefin resin is not particularly limited, but is preferably 0.05 to 0.5 parts by mass, more preferably 0.1 to 0.3 parts by mass. When the amount of the core added is 0.05 parts by mass or more relative to 100 parts by mass of the polyolefin resin, the hardness of the transparent resin layer 11 can be effectively improved. By adding 0.5 parts by mass or less of the core to 100 parts by mass of the polyolefin resin, the inherent properties of the transparent resin layer 11 can be prevented from being deteriorated.

[0076] The thickness of the colored resin layer 14 is not particularly limited, but is preferably 30 μm or more and 100 μm or less, more preferably 40 μm or more and 80 μm or less, and even more preferably 50 μm or more and 70 μm or less. When the thickness of the colored resin layer 14 is 30 μm or more, the decorative sheet 1 has sufficient scratch resistance. Furthermore, when the thickness of the colored resin layer 14 is 100 μm or less, the amount of resin material used can be reduced, and therefore the decorative sheet 1 can further reduce its environmental impact.

[0077] The density of the colored resin layer 14 is not particularly limited, but is preferably 0.90 g / cm 3 It is preferable that the concentration is 0.91 g / cm or more. 3 More preferably, it is 0.94 g / cm or more. 3It is more preferable that the density of the colored resin layer 14 is 0.90 g / cm or more. 3 As a result of the above, the decorative sheet 1 has sufficient printability. The density of the colored resin layer 14 is 1.70 g / cm 3 Preferably, it is 1.30 g / cm or less. 3 More preferably, it is 1.50 g / cm or less. 3 It is more preferable that the density of the colored resin layer 14 is 1.70 g / cm or less. 3 If the thickness is below this, the decorative sheet 1 will have sufficient hiding power.

[0078] (printing ink layer) The printed ink layer 15 is a layer formed by printing ink. The printed ink layer 15 may be a layer on which a pattern is formed using inks of multiple colors, or may be a plain layer made of ink of a single color. Examples of patterns include wood grain patterns, stone patterns, fabric patterns, leather patterns, geometric patterns, abstract patterns, letters, symbols, and line drawings.

[0079] The ink contains a resin and a colorant. Examples of the resin include urethane resin, acrylic resin, vinyl chloride-vinyl acetate copolymer, and epoxy resin. When the ink contains a urethane-based resin, the urethane-based resin may be a urethane resin obtained using a composition containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate. The composition preferably further contains neopentyl glycol. When the composition further contains neopentyl glycol, hydrolysis of the resin contained in the printing ink layer 15 is more effectively suppressed, and the moist heat resistance of the decorative sheet 1 is improved.

[0080] The colorants contained in the ink include pigments and dyes. Examples of pigments include inorganic pigments such as carbon black, iron black, titanium white (titanium oxide), antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue, and organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue. Dyes include dyes such as methylene blue, rhodamine, and indigo.

[0081] The thickness of the printed ink layer 15 is not particularly limited and can be set appropriately depending on the properties of the decorative sheet 1, and may be, for example, 0.1 μm or more, 3 μm or more, or 10 μm or more. The thickness of the printed ink layer 15 may be 20 μm or less, 15 μm or less, 10 μm or less, or 8 μm or less.

[0082] (Adhesive layer) The adhesive layer 13 is provided between the transparent resin layer 11 and the printed ink layer 15, and is a layer that bonds the transparent resin layer 11 and the printed ink layer 15 together. The adhesive layer 13 is a layer obtained using an adhesive composition containing a resin. Examples of resins that can be used include urethane resins, acrylic resins, ethylene-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers, polyester resins, and polyolefin resins. In particular, from the viewpoint of improving the adhesion between the transparent resin layer 11 and the printing ink layer 15, it is preferable that the resin contains a polyester resin and a bisphenol A epoxy resin. Here, it is preferable that the polyester resin is obtained using a composition containing phthalic acid, a linear dicarboxylic acid, and an alkylene diol.

[0083] In the adhesive layer 13, the mass ratio R of the polyester resin to the bisphenol A epoxy resin (polyester resin / bisphenol A epoxy resin) is preferably 50 / 50 to 90 / 10. With the mass ratio R within the above range, the adhesive layer 13 has better adhesion to the transparent resin layer 11 and the printing ink layer 15 and also has excellent moist heat resistance, so the decorative sheet 1 has better interlayer adhesion and moist heat resistance.

[0084] The method for forming the adhesive layer 13 is not particularly limited, and various lamination methods such as thermal lamination, extrusion lamination, dry lamination, and sand lamination can be used as this method.

[0085] (primer layer) The primer layer 18 is a layer for improving the adhesion between the decorative sheet 1 and a substrate (not shown) to which the decorative sheet 1 is attached. The primer layer 18 contains a resin and may further contain an inorganic substance. Examples of the resin include urethane resin, acrylic resin, vinyl chloride vinyl acetate copolymer, epoxy resin, and nitrocellulose. Examples of inorganic substances include silica and calcium carbonate. When the inorganic substance is silica, the primer layer 18 has sufficient adhesive stability, allowing stable adhesion between the colored resin layer 14 and the substrate to which the decorative sheet 1 is attached. There are no particular limitations on the thickness of the primer layer 18, and it may be 10 μm or less, 5 μm or less, or 1 μm or less. When the thickness of the primer layer 18 is 5 μm or less, the flexibility of the decorative sheet 1 can be further improved.

[0086] The thickness of the primer layer 18 may be 1 μm or more, 3 μm or more, or 5 μm or more. If the thickness of the primer layer 18 is 1 μm or more, the adhesion between the colored resin layer 14 and the substrate to which the decorative sheet 1 is to be attached can be improved. The primer layer 18 can be formed by applying a resin composition containing the above-mentioned resin and an organic solvent to the surface of the colored resin layer 14 and drying it.

[0087] <Decorative materials> Figure 2 is a cross-sectional view showing one embodiment of a decorative material of the present disclosure. The decorative material 10 shown in Figure 2 comprises a substrate 17 and a decorative sheet 1 bonded to the substrate 17. The decorative material 10 may further comprise an adhesive layer 16 between the decorative sheet 1 and the substrate 17 to bond them together. The decorative material 10 has excellent weather resistance and reduces environmental impact because the decorative sheet 1 is attached to the substrate 17.

[0088] The substrate 17, which is the adherend of the decorative sheet 1, can be selected appropriately depending on the use and type of the decorative material 10, and examples include substrates made of materials such as inorganic (non-metallic) substrates, metallic substrates, wood-based substrates, and plastic substrates.

[0089] Examples of inorganic substrates include tiles and gypsum boards. Examples of metal substrates include steel plates and aluminum plates. Examples of wood substrates include MDF (medium density fiberboard) and plywood. Examples of plastic substrates include polypropylene boards, PVC boards, polyester boards, acrylic boards, and styrene boards.

[0090] The adhesive layer 16 is obtained using an adhesive. Examples of the adhesive include a hot melt adhesive, an organic solvent adhesive, and a water-based adhesive. The resin contained in the adhesive may be a urethane resin, an ester resin, an acrylic resin, a vinyl acetate resin, or the like. [Example]

[0091] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples.

[0092] <Ink preparation> Polycaprolactone diol, polytetramethylene glycol, and neopentyl glycol were used as polyols, and isophorone diisocyanate was used as polyisocyanate. These were polymerized by a known addition polymerization method to obtain a polyisocyanate having a number average molecular weight of 2×10 4 Thus, a urethane resin having a terminal hydroxyl group was obtained. A copper phthalocyanine pigment was dispersed in the obtained urethane resin so that the mass ratio of pigment / urethane resin was 20 / 80, and an isocyanate curing agent was further added so that the mass ratio of curing agent / urethane resin was 5 / 100 to prepare an ink.

[0093] <Preparation of Adhesive Composition> First, isophthalic acid (IP) and adipic acid (AD) were used as dicarboxylic acids, and ethylene glycol and hexanediol were used as diols. These were polymerized by a known addition polymerization method to obtain a polymer having a number average molecular weight of 1×10 4 A polyester resin P having a hydroxyl value of 10 mgKOH / g of solid content was obtained. At this time, the IP / AD ratio was 90 / 10 (molar ratio). An adhesive composition was prepared by blending the polyester resin P obtained as described above and a bisphenol A-type epoxy resin EP (model number: jER1004AF, manufactured by Mitsubishi Chemical Corporation) so that the solid content mass ratio was P / EP = 70 / 30.

[0094] <Making decorative sheets> Example 1 A colored resin film A1 (thickness 55 μm) consisting of a resin composition for forming a colored resin layer containing chemically recycled polyethylene (CRPE) and colorants (isoindolinone, diketopyrrolopyrrole, carbon black, phthalocyanine blue, and disazo pigments), and having a CRPE content of 90% by mass, was prepared and used as the colored resin layer. Furthermore, a transparent resin film B1 (70 μm thick) was prepared from a resin composition for forming a transparent resin layer, containing chemically recycled polypropylene (CRPP), a light stabilizer, and a UV absorber. The CRPP content was 90% by mass. The light stabilizer and UV absorber were each added in amounts of 0.5 parts by mass per 100 parts by mass of CRPP. The light stabilizer used was a hindered amine-based light stabilizer (product name: Tinuvin 479, manufactured by BASF Japan Ltd.) containing 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine as the main component. The UV absorber used was a hydroxyphenyltriazine-based UV absorber (product name: Tinosorb S, manufactured by BASF Japan Ltd.) containing the compound shown in formula (1): [ka] One side of the colored resin layer was then subjected to a corona discharge treatment, and a wood grain pattern printing ink layer was then formed to a thickness of approximately 3 μm so as to cover the entire surface. The printing ink layer was formed by printing the ink using a gravure printing method. Next, a primer layer was formed on the other surface of the colored resin layer to a thickness of 3 μm or less by applying and drying a resin composition for forming a primer layer, which contains a urethane resin and an inorganic substance (silica). Next, the above adhesive composition was applied to the surface of the printed ink layer, and then the above transparent resin film B1 was superimposed thereon, and the adhesive composition was dried to form an adhesive layer, thereby attaching the transparent resin layer to the printed ink layer. Finally, a surface protective layer was formed on the surface of the transparent resin layer to a thickness of 8 μm. The surface protective layer was formed by applying and drying a resin composition for forming a surface protective layer obtained by mixing solids and an organic solvent. The solids were prepared by adding 5 parts by weight of a triazine-based ultraviolet absorber (Triazine UVA1, product name: Tinuvin 479, manufactured by BASF Japan Ltd.) and 5 parts by weight of a hindered amine-based light stabilizer (HALS), bis[2,2,6,6-tetramethyl-1(octyloxy)piperidin-4-yl] decanedioate (product name: Tinuvin 123, manufactured by BASF Japan Ltd.), to 100 parts by weight of an acrylic resin (hydrophobic-modified acrylic polyol). A decorative sheet was produced in this manner.

[0095] Example 2 A decorative sheet was produced in the same manner as in Example 1, except that in the resin composition for forming a colored resin layer, CRPE was changed to petroleum-derived PE.

[0096] Example 3 A decorative sheet was produced in the same manner as in Example 1, except that in the resin composition for forming a transparent resin layer, CRPP was changed to petroleum-derived PP.

[0097] Example 4 A decorative sheet was produced in the same manner as in Example 1, except that in the resin composition for forming the surface protective layer, the triazine-based ultraviolet absorber was changed from triazine-based UVA1 to triazine-based UVA2 (ADEKA STAB LA-F70 (manufactured by ADEKA Corporation) containing 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol as the main component).

[0098] Example 5 A decorative sheet was produced in the same manner as in Example 1, except that the ink used was changed to a general ink for building materials (two-component urethane ink, product name: V180, manufactured by Toyo Ink Co., Ltd.).

[0099] Example 6 A decorative sheet was produced in the same manner as in Example 1, except that in the resin composition for forming the surface protective layer, the triazine-based ultraviolet absorber was changed from triazine-based UVA1 to triazine-based UVA2 (ADEKA STAB LA-F70, manufactured by ADEKA Corporation), and the ink was changed to a general building material ink (two-component urethane ink, product name: V180, manufactured by Toyo Ink Co., Ltd.).

[0100] Example 7 In the resin composition for forming the colored resin layer, nano-sized cores are added in a ratio of 0.1 parts by mass to 100 parts by mass of CRPP, and the density is 1.1 g / cm 3 In the resin composition for forming a transparent resin layer, nano-sized cores were added at a ratio of 0.05 parts by mass to 100 parts by mass of CRPP, so that the density of the colored resin layer was 0.90 g / cm 3 A decorative sheet was manufactured in the same manner as in Example 1, except that a transparent resin layer was prepared. Note that the nanocores used were nucleating agent vesicles (average particle size: 300 nm) in which sodium 2,2'-methylenebis(4,6-di-tert-butylphenol)phosphonate was encapsulated as a nucleating agent.

[0101] Example 8 A non-nano core material (product name: Rikemaster CN-002, manufactured by Riken Vitamin Co., Ltd.) was added to the resin composition for forming the colored resin layer to make the density 1.1 g / cm 3 A non-nano-core material (product name: Rikemaster CN-002, manufactured by Riken Vitamin Co., Ltd.) was added to the resin composition for forming the transparent resin layer to make the density 0.95 g / cm 3 A decorative sheet was produced in the same manner as in Example 1, except that the transparent resin layer was prepared.

[0102] Example 9 In the resin composition for forming a colored resin layer, nano-sized cores are added at a ratio of 0.1 parts by mass to 100 parts by mass of CRPE, and the density is 1.1 g / cm 3In the resin composition for forming a transparent resin layer, nano-sized cores were added at a ratio of 0.05 parts by mass to 100 parts by mass of CRPP, so that the density of the colored resin layer was 0.90 g / cm 3 A decorative sheet was manufactured in the same manner as in Example 1, except that a transparent resin layer was prepared. Note that the nanocores used were nucleating agent vesicles (average particle size: 300 nm) in which sodium 2,2'-methylenebis(4,6-di-tert-butylphenol)phosphonate was encapsulated as a nucleating agent.

[0103] (Comparative Example 1) A decorative sheet was produced in the same manner as in Example 1, except that in the resin composition for forming the colored resin layer, CRPE was changed to petroleum-derived PE, and in the resin composition for forming the transparent resin layer, CRPP was changed to petroleum-derived PP.

[0104] (Comparative Example 2) A decorative sheet was produced in the same manner as in Example 1, except that in the resin composition for forming the colored resin layer, CRPE was changed to mechanically recycled polyethylene (MRPE), and in the resin composition for forming the transparent resin layer, CRPP was changed to mechanically recycled polypropylene (MRPP).

[0105] <Manufacturing of decorative materials> Decorative materials were produced by bonding the decorative sheets of Examples 1 to 9 and Comparative Examples 1 and 2 to a substrate. Specifically, a vinyl acetate resin adhesive was applied to an aluminum plate measuring 30 cm in length, 11 cm in width, and 1 mm in thickness as the substrate, and the decorative sheet was then placed on the vinyl acetate resin adhesive and allowed to cure for 72 hours or more to produce the decorative materials.

[0106] (1) Transparency The decorative sheets of the Examples and Comparative Examples were evaluated for design when the printed ink layer was visually observed from the surface protective layer side, based on the following criteria. The results are shown in Table 1. (standard) High transparency and clear images △ Transparency is neither high nor low, and the image is cloudy but not very noticeable ×...Low transparency and cloudy image

[0107] (2) Printability For the decorative sheets produced in the Examples and Comparative Examples, the number of printing voids (points formed by light leakage) in the printed ink layer per 1000 m was visually counted from a position 50 cm away from the primer layer side of the decorative sheet under a light source of 1000 lux or more, and evaluation was performed based on the following criteria. The number of printing voids in Comparative Example 1 was designated N1, the number of printing voids in Examples 1 to 9 and Comparative Example 2 was designated N2, and |N1-N2| was designated ΔN. The results are shown in Table 1. (standard) ○ΔN≦2 △···2<ΔN<5 × 5≦ΔN

[0108] (3) Scratch resistance For the decorative sheets of the examples and comparative examples, pencil hardness was measured by the pencil method under conditions in accordance with "JIS K5600-5-4 Scratch hardness (pencil method)." Specifically, for the decorative sheets of the examples and comparative examples, pencils of different hardness were placed on the surface protective layer, and slid under load to check whether any indentations (scratches) were formed in the surface protective layer, thereby measuring the pencil hardness of the surface. The scratch resistance was evaluated based on the pencil hardness and the following criteria. The results are shown in Table 1. (standard) ◎ Pencil hardness is 2B or higher ○ Pencil hardness is 4B or more but less than 2B × Pencil hardness is less than 4B

[0109] (4) Weather resistance The decorative sheets of the Examples and Comparative Examples were subjected to an accelerated weather resistance test using an Eye Super UV Tester (manufactured by Iwasaki Electric Co., Ltd., SUV-W161). Specifically, the decorative sheet was placed inside the tester, and the black panel temperature was 63°C and the illuminance was 65mW / cm. 2After UV irradiation for 20 hours under the above conditions, condensation was allowed to occur for 4 hours without UV irradiation, and this cycle was repeated 30 times. The changes in the appearance of the decorative sheet before and after the test were visually confirmed, and the weather resistance was evaluated based on the following criteria. The results are shown in Table 1. (standard) ◎ No change in the appearance of the decorative sheet ○: Very slight changes are observed in the appearance of the decorative sheet. × Cracks are observed in the decorative sheet

[0110] (5) Odor generation (safety during manufacturing) The decorative sheets of the Examples and Comparative Examples were analyzed using purge-and-trap gas chromatography-mass spectrometry. Specifically, a 1.0 g sample was cut from the decorative sheet, placed in a 20 mL vial along with an odor component collector, and heated at 60°C for 1 hour to adsorb the volatile components from the sample onto the collector. The volatile components in the collector were then analyzed using a purge-and-trap gas chromatography-mass spectrometry device, and a total ion chromatogram was obtained. Next, in the total ion chromatogram obtained as described above, the ratio R1 of the peak area of nonanal to the sum of the peak area values of all aliphatic hydrocarbon components, and the ratio R2 of the peak area of decanal to the sum of the peak area values of all aliphatic hydrocarbon components, were calculated as indicators of odor components. The degree of odorous component generation was evaluated based on the following criteria. The results are shown in Table 1. (standard) ○ R1 is less than 1.5% and R2 is less than 0.35% △ R1 is less than 1.5% and R2 is 0.35% or more, or R1 is 1.5% or more and R2 is less than 0.35% × R1 is 1.5% or more and R2 is 0.35% or more

[0111] (6) Extrusion suitability Pellets having the same composition as the transparent resin film used in the decorative sheets of the Examples and Comparative Examples were prepared, and films were extruded using these pellets. The rate of decrease ΔS in the production speed S2 of Examples 1 to 9 or Comparative Example 2 relative to the production speed S1 of Comparative Example 1 was calculated based on the following formula. Decrease rate ΔS=100×(S1-S2) / S1 The extrusion suitability was evaluated based on the thus determined reduction rate and the following criteria. The results are shown in Table 1. (standard) ○ ΔS is less than 1% △ ΔS is 1% or more and less than 3% × ΔS is 3% or more

[0112] (7) Post machinability The decorative material obtained as described above was evaluated for post-cutting properties. Specifically, the decorative material was cut using a panel saw, and the decorative sheet was observed for burrs and chips, and the post-cutting properties were evaluated based on the following criteria. The results are shown in Table 1. (standard) ○ No burrs or chips are visible on the decorative sheet × Burrs or chips are found on the decorative sheet

[0113] (8) Post-bending suitability The decorative materials obtained as described above were evaluated for their suitability for post-bending. Specifically, a post-bending process was performed in which a portion of the decorative material was bent at a 90-degree angle relative to the remaining portion. The post-bending suitability was evaluated by visually inspecting the surface of the decorative sheet after the post-bending process for any abnormalities such as whitening or cracks (fissures or crevices) in the bent portion. The results are shown in Table 1. (standard) ○ No whitening or cracks were observed on the decorative sheet. × Whitening or cracks were observed on the decorative sheet

[0114] (9) Environmental impact reduction (independent of fossil fuels) The decorative sheets according to the examples and comparative examples were evaluated for their ability to reduce environmental impact based on the following criteria. The results are shown in Table 1. (standard) ○ Low reliance on fossil fuel-derived materials △ Medium reliance on fossil fuel-derived materials × High reliance on fossil fuel-derived materials

[0115] [Table 1]

[0116] From the results shown in Table 1, the decorative sheets of Examples 1 to 9 and Comparative Example 1 were rated as "A" or "B" for weather resistance, whereas Comparative Example 2 was rated as "B". Furthermore, the reduction in environmental load was rated as "good" or "fair" for the decorative sheets of Examples 1 to 9 and Comparative Example 2, while Comparative Example 1 was rated as "poor." From the above, it has been confirmed that the decorative sheet of the present disclosure has excellent weather resistance and can reduce the environmental load. [Explanation of symbols]

[0117] 1...decorative sheet, 12...surface protection layer, 11...transparent resin layer, 13...adhesive layer, 15...printing ink layer, 14...colored resin layer, 10...decorative material, 17...base material.

Claims

1. A surface protective layer, a transparent resin layer, an adhesive layer, a printing ink layer, and a colored resin layer are provided in this order; At least one of the transparent resin layer and the colored resin layer contains a polyolefin resin including a chemically recycled polyolefin resin, The decorative sheet, wherein the surface protective layer contains an ultraviolet absorber and a light stabilizer.

2. the ultraviolet absorber is a triazine-based ultraviolet absorber, 2. The decorative sheet according to claim 1, wherein the light stabilizer is a hindered amine light stabilizer.

3. the printing ink layer contains a urethane resin, 3. The decorative sheet according to claim 1, wherein the urethane resin is a resin obtained using a composition containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate.

4. The decorative sheet according to claim 1 or 2, wherein the chemically recycled polyolefin resin comprises a post-consumer recycled resin.

5. 3. The decorative sheet according to claim 1, wherein the chemically recycled polyolefin resin is at least one of chemically recycled polypropylene and chemically recycled polyethylene.

6. the content of the chemically recycled polyolefin resin in the transparent resin layer is 1 to 99% by mass, The decorative sheet according to claim 1 or 2, wherein the content of the chemically recycled polyolefin resin in the colored resin layer is 1 to 99% by mass.

7. The transparent resin layer is a triazine-based ultraviolet absorber different from the triazine-based ultraviolet absorber contained in the surface protective layer; a hindered amine-based light stabilizer different from the hindered amine-based light stabilizer contained in the surface protective layer; The decorative sheet according to claim 2, comprising:

8. The colored resin layer is a triazine-based ultraviolet absorber different from the triazine-based ultraviolet absorber contained in the surface protective layer; a hindered amine-based light stabilizer different from the hindered amine-based light stabilizer contained in the surface protective layer; The decorative sheet according to claim 2 or 7, comprising:

9. the adhesive layer is obtained using an adhesive composition containing a polyester resin and a bisphenol A type epoxy resin; The polyester resin is a resin obtained using a polyester resin-forming composition containing phthalic acid, a linear dicarboxylic acid, and an alkylene diol, The decorative sheet according to claim 1 or 2, wherein the mass ratio of the polyester resin to the bisphenol A type epoxy resin in the polyester resin forming composition (the polyester resin / the bisphenol A type epoxy resin) is 50 / 50 to 90 / 10.

10. 3. The decorative sheet according to claim 1, wherein at least one of the transparent resin layer and the colored resin layer is obtained using a resin composition containing a core and the polyolefin resin.

11. The core is a nano-sized core, The decorative sheet according to claim 10, wherein the amount of the core added is 0.05 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of the polyolefin resin.

12. The thickness of the colored resin layer is 40 to 100 μm, 3. The decorative sheet according to claim 1, wherein the transparent resin layer has a thickness of 30 to 150 μm.

13. The colored resin layer has a density of 0.90 to 1.70 g / cm ３ and The transparent resin layer has a density of 0.90 to 0.99 g / cm ３ The decorative sheet according to claim 1 or 2, wherein

14. A substrate and a decorative sheet attached to at least one surface of the substrate, A decorative material, wherein the decorative sheet is the decorative sheet according to claim 1 or 2.

Images