Decorative sheet and decorative material using same

Abstract

The present invention provides: a decorative sheet which has good weather resistance, while being suppressed in decrease of the scratch resistance of a surface protection layer, and which exhibits high initial adhesion strength during a construction process, thereby having excellent construction adequacy, while exhibiting excellent long-term adhesion, thereby being free from separation even after a long period of use; and a decorative material.　A decorative sheet which has a surface protection layer on a base material, wherein: the surface protection layer is formed by crosslinking and curing a composition A that contains an ionizing radiation curable resin composition and a radical scavenger; the radical scavenger contains a radical scavenger i which is polymerizable with the ionizing radiation curable resin composition, while having an ethylenic double bond, and a radical scavenger ii which is polymerizable with the ionizing radiation curable resin composition, while having no ethylenic double bond; the content of the radical scavenger in the composition A is 0.5 part by mass or more but less than 10.0 parts by mass relative to 100 parts by mass of the ionizing radiation curable resin composition; and the water vapor transmission rate of this decorative sheet as determined in accordance with the testing methods for determination of the water vapor transmission rate of moisture-proof packaging materials (Dish Method) set forth in JIS Z0208 (1976) is from 0.75 g / m2∙24 h to 45 g / m2∙24 h.

Description

[Technical field]

[0001] The present invention relates to a decorative sheet and a decorative material using the same. [Background technology]

[0002] Decorative sheets have been used to decorate and protect the surfaces of interior and exterior components of buildings, interior and exterior components of vehicles such as automobiles, furniture, fixtures, home appliances, etc. Decorative sheets have a configuration having, for example, a surface protective layer on a substrate.

[0003] When these decorative sheets are used outdoors or indoors near windows or other locations exposed to sunlight, they are susceptible to changes in color and resin deterioration due to the effects of ultraviolet rays. For this reason, decorative sheets have been proposed that have radical scavengers or the like added to the surface protective layer in order to improve weather resistance.

[0004] However, there is a problem that the radical scavenger is prone to bleed out from the surface protective layer over time. "Bleed out" is also sometimes called "bleed out" or "migration." When the radical scavenger bleeds out, the aesthetic appearance of the decorative sheet surface is impaired, and the concentration of the radical scavenger in the surface protective layer decreases over time, resulting in insufficient weather resistance. In order to solve the problem caused by bleeding out of the radical scavenger, for example, a decorative sheet has been proposed in Patent Document 1.

[0005] In addition, as decorative materials used for components and the like for the above-mentioned applications, for example, plastic products using decorative sheets with a polyvinyl chloride sheet as a base material and, as necessary, a decorative layer, a surface protection layer, etc., as a decorative treatment are also used (for example, Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2012-206375 A [Patent Document 2] Special Publication No. 58-14312 DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0007] In the decorative sheet of Patent Document 1, the hindered amine light stabilizer (radical scavenger) in the surface protective layer has a reactive functional group, so that the hindered amine light stabilizer is fixed in the surface protective layer and bleed-out is suppressed. However, although the decorative sheet of Patent Document 1 can suppress the bleed-out of the hindered amine light stabilizer, it cannot adequately capture radicals generated by irradiation with ultraviolet light, so the decorative sheet deteriorates over time and its weather resistance is insufficient. In addition, the decorative sheet of Patent Document 1 has a problem in that the scratch resistance of the surface protective layer decreases due to a decrease in the crosslink density of the ionizing radiation curable resin composition.

[0008] Furthermore, when the decorative sheets and the like of Patent Documents 1 and 2 are attached to an adherend to produce a decorative material, there is a problem in that the end faces of the decorative sheets peel off due to insufficient initial adhesion strength, that is, so-called springback occurs. Decorative sheets that cause springback have insufficient workability. On the other hand, when using a decorative material in which the above-mentioned decorative sheet is attached to an adherend, there has been a problem in that the decorative sheet can peel off from the adherend due to factors such as deterioration of the base material constituting the decorative sheet provided on the outermost surface and deterioration of the adhesive that bonds the decorative sheet to the adherend, caused by the effects of moisture in the air, wind and rain, and even ultraviolet rays from sunlight.

[0009] The present invention aims to provide a decorative sheet and decorative material that has good weather resistance, can suppress a decrease in the scratch resistance of a surface protective layer, has high initial adhesion strength during the application process, is excellent in application suitability, and does not peel off even after long-term use, thereby exhibiting excellent long-term adhesion. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention provides the following [1] and [2]. [1] A decorative sheet having a surface protective layer on a substrate, the surface protective layer being a layer formed by crosslinking and curing a composition A containing an ionizing radiation curable resin composition and a radical scavenger, the radical scavenger comprising a radical scavenger i having an ethylenic double bond polymerizable with the ionizing radiation curable resin composition and a radical scavenger ii having no ethylenic double bond polymerizable with the ionizing radiation curable resin composition, the content of the radical scavenger in the composition A being 0.5 parts by mass or more and less than 10.0 parts by mass per 100 parts by mass of the ionizing radiation curable resin composition, the moisture permeability of the decorative sheet being 0.75 g / m or less as measured in accordance with the moisture permeability test method for moisture-proof packaging materials (cup method) specified in JIS Z0208:1976. 2 ·45g / m for 24 hours or more 2 · Decorative sheets that are less than 24 hours old. [2] A decorative material having an adherend and the decorative sheet described in [1] above. Effect of the Invention

[0011] According to the present invention, it is possible to provide a decorative sheet and a decorative material which have good weather resistance, can suppress a decrease in the scratch resistance of the surface protective layer, have high initial adhesion strength during the application process, are excellent in application suitability, and do not peel even with long-term use, thereby exhibiting excellent long-term adhesion. [Brief description of the drawings]

[0012] [Figure 1] 1 is a cross-sectional view showing one embodiment of a decorative sheet of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] [Decorative sheet] The decorative sheet of the present invention will be described below. In this specification, the numerical values ​​related to "greater than or equal to" and "less than or equal to" in the description of a numerical range are numerical values ​​that can be arbitrarily combined, and the numerical values ​​in the examples are numerical values ​​that can be used as the upper and lower limits of the numerical range.

[0014] The decorative sheet of the present invention is a decorative sheet having a surface protective layer on a substrate, the surface protective layer being a layer formed by crosslinking and curing a composition A containing an ionizing radiation curable resin composition and a radical scavenger, the radical scavenger comprising a radical scavenger i having an ethylenic double bond polymerizable with the ionizing radiation curable resin composition and a radical scavenger ii having no ethylenic double bond polymerizable with the ionizing radiation curable resin composition, the content of the radical scavenger in the composition A being 0.5 parts by mass or more and less than 10.0 parts by mass relative to 100 parts by mass of the ionizing radiation curable resin composition, the moisture permeability of the decorative sheet being 0.75 g / m or less as measured in accordance with the moisture permeability test method for moisture-proof packaging materials (cup method) specified in JIS Z0208:1976. 2 ·45g / m for 24 hours or more 2 -24 hours or less.

[0015] <Moisture permeability> The decorative sheet of the present invention has a moisture permeability of 0.75 g / m2 as measured in accordance with the moisture permeability test method for moisture-proof packaging materials (cup method) specified in JIS Z0208:1976. 2 ·45g / m for 24 hours or more 2 - It is characterized by being 24 hours or less. The decorative sheet of the present invention exhibits high initial adhesion strength during the application process by setting the moisture permeability within a specific range. Therefore, the decorative sheet of the present invention can suppress the occurrence of so-called springback, in which the end surface of the decorative sheet peels off due to insufficient initial adhesion strength during application, thereby improving application efficiency. On the other hand, when the decorative sheet and the adherend are used as decorative members via an adhesive layer, deterioration of the adhesive layer between the decorative sheet and the adherend can be suppressed. Therefore, peeling due to deterioration of the adhesive layer is suppressed, and excellent long-term adhesion is exhibited without peeling even after long-term use. In other words, by setting the moisture permeability of the decorative sheet of the present invention within a specific range, it is possible to achieve both excellent application suitability due to high initial adhesion strength during the application process and long-term adhesion without peeling even after long-term use.

[0016] The decorative sheet of the present invention has a coating weight of 0.75 g / m 2 ·45g / m for 24 hours or more 2 - Moisture permeability of 0.75g / m2 or less for 24 hours. 2 If the time is less than 24 hours, when the decorative material is attached to an adherend via an adhesive layer, poor adhesion is likely to occur due to insufficient hardening of the adhesive used in the adhesive layer, and excellent initial adhesive strength and excellent workability cannot be obtained. 2 If it exceeds 24 hours, the decorative sheet and the adherend are likely to peel off during long-term use due to deterioration of the substrate caused by moisture in the air, wind and rain, and even ultraviolet rays from sunlight, as well as deterioration due to hydrolysis of the adhesive used in the adhesive layer, and long-term adhesion without peeling even with long-term use cannot be obtained. Therefore, as described above, by setting the moisture permeability within a specific range, the decorative sheet of the present invention can achieve both excellent application suitability due to high initial adhesion strength during the application process and long-term adhesion without peeling even with long-term use.

[0017] To improve workability and long-term adhesion, the moisture permeability is set at 1.2g / m 2 24 hours or more, preferably 1.5g / m 2 24 hours or more, preferably 2.5 g / m2 24h or more, even more preferably 4.5g / m 2 24h or more, with the upper limit preferably being 40g / m 2 24h or less, preferably 35g / m 2 24 hours or less, more preferably 30 g / m 2 24h or less, even more preferably 20g / m 2 Less than 24 hours. In the present invention, the moisture permeability can be adjusted mainly by the type of material constituting the substrate described below, and, if a transparent resin layer is provided, the type of material constituting the transparent resin layer.

[0018] FIG. 1 is a cross-sectional view showing a representative embodiment of a decorative sheet 100 of the present invention. The decorative sheet 100 in Fig. 1 has a surface protective layer 10 on a substrate 50. The decorative sheet 100 in Fig. 1 also has a primer layer 20 in contact with the surface of the surface protective layer 10 facing the substrate 50. Furthermore, the decorative sheet 100 in Fig. 1 has a transparent resin layer 30 and a decorative layer 40 between the substrate 50 and the surface protective layer 10. Each layer constituting the decorative sheet of the present invention will now be described in more detail.

[0019] <Base material> Examples of the substrate include films, sheets, and plates made of various types of paper, plastic, metal, woven or nonwoven fabric, wood, ceramic materials, and the like. Usually, flat substrates having a certain thickness are called films, sheets, and plates in the order of decreasing thickness, but since there is no particular need to distinguish between different thicknesses in the present invention, these names are treated as not being essentially different even if they are appropriately substituted for each other in this specification. Furthermore, the differences in names (differences in thickness) do not cause any difference in the interpretation of the claims of the present invention. Among these, plastics are preferred because, although they do not have sufficient weather resistance, the weather resistance of the entire decorative sheet can be improved by the surface protective layer described below.

[0020] Specific examples of resins constituting plastics include polyolefin resins such as polyethylene and polypropylene, vinyl resins such as vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol and ethylene-vinyl alcohol copolymer, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate, polymethyl acrylate and polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, polycarbonate, etc. Among these, polyolefin resins, vinyl chloride resins, polyester resins and acrylic resins are preferred from the viewpoints of various physical properties such as weather resistance and water resistance, printability, moldability, price, etc.

[0021] Among the above, polyolefin resins and vinyl chloride resins are more preferred in consideration of the moisture permeability of the decorative sheet of the present invention being easily within the above range, improving application suitability and long-term adhesion, and versatility and suitability for use as a decorative material, and polyolefin resins are even more preferred in consideration of environmental performance. In the present invention, the above resins can be used alone or in combination of multiple types. When multiple types are combined, substrates made of various individual resins may be combined, or multiple types of resins may be mixed and used as one substrate.

[0022] More specifically, examples of polyolefin resins include homopolymers of olefins such as ethylene, propylene, and butene; various copolymers such as ethylene-propylene block copolymers and random copolymers; copolymers of at least one of ethylene and propylene with at least one other olefin such as butene, pentene, and hexene; copolymers of at least one of ethylene and propylene with at least one other monomer such as vinyl acetate and vinyl alcohol; and the like. Of the above, polyethylene-based resins containing ethylene as a constituent unit and polypropylene-based resins containing propylene as a constituent unit are preferred, as they make it easier to achieve moisture permeability within the above range and also improve long-term adhesion as well as workability, with polypropylene-based resins being more preferred.

[0023] The moisture permeability is preferably adjusted by adjusting the thickness of the layer in which the resin can be used, such as the substrate and the transparent resin layer, because this is easy and more reliable. In order to make the moisture permeability of the decorative sheet of the present invention within the above-mentioned predetermined range, it is preferable to take into consideration the ratio of the thickness of the substrate and the transparent resin layer to the total thickness of the decorative sheet in the laminated structure of the decorative sheet, and to set the thickness of the substrate and the transparent resin layer within a predetermined range according to the material constituting these layers, preferably the type of resin. In order to make it easier to keep the moisture permeability of the decorative sheet within the above-mentioned specified range, the thickness of the base material, when using polyethylene-based resin, polypropylene-based resin, or vinyl chloride-based resin, should be selected, taking into consideration the laminate structure of the decorative sheet and the desired moisture permeability, preferably from the range of 40 μm or more and 200 μm or less.

[0024] More specifically, the polyethylene resin may be a homopolymer of ethylene, i.e., polyethylene, or a copolymer of ethylene and another comonomer copolymerizable with ethylene (e.g., α-olefins such as propylene, 1-butene, 1-hexene, and 1-octene, vinyl acetate, vinyl alcohol, etc.). Examples of polyethylene include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra-high molecular weight polyethylene (UHMWPE), cross-linked polyethylene (PEX), etc. These polyethylene resins may be used alone or in combination of two or more.

[0025] The polypropylene-based resin may be a homopolymer of propylene, i.e., polypropylene, or a copolymer of propylene and another comonomer copolymerizable with propylene (e.g., α-olefins such as ethylene, 1-butene, 1-hexene, and 1-octene; vinyl acetate, vinyl alcohol, etc.). These polypropylenes may be used alone or in combination of two or more.

[0026] When a propylene homopolymer (polypropylene) is used, the moisture permeability of the substrate can be adjusted by adjusting the crystallinity. In general, the higher the crystallinity, the lower the moisture permeability of the polypropylene resin. When the polypropylene resin having a thickness in the range of 40 μm to 200 μm is used as the substrate, the crystallinity is preferably 30% or more, more preferably 40% or more, and the upper limit is preferably 80% or less, more preferably 70% or less. In addition, when a propylene homopolymer (polypropylene) is used, the moisture permeability of the substrate can be adjusted by adjusting the mass ratio of isotactic polypropylene to atactic polypropylene. In general, the moisture permeability of the substrate can be reduced by adding isotactic polypropylene compared to when the proportion of atactic polypropylene in polypropylene is 100% by mass. In this case, the mass ratio of atactic polypropylene to isotactic polypropylene is preferably 0 / 100 to 20 / 80, taking into consideration the ease of adjusting the moisture permeability.

[0027] In addition, when a vinyl chloride-based resin is used, the vinyl chloride-based resin may be a homopolymer of a vinyl chloride monomer, i.e., polyvinyl chloride, or a copolymer obtained by copolymerizing a vinyl chloride monomer with a monomer copolymerizable with the vinyl chloride monomer. Examples of monomers copolymerizable with vinyl chloride monomer include vinyl esters such as vinyl acetate and vinyl propionate; acrylic esters such as methyl acrylate and butyl acrylate; methacrylic esters such as methyl methacrylate and ethyl methacrylate; maleic esters such as butyl maleate and diethyl maleate; fumaric esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; vinyl cyanides such as acrylonitrile and methacrylonitrile; olefins such as ethylene, propylene, butylene and styrene; dienes such as isoprene and butadiene; vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides; allyl phthalates such as diallyl phthalate, etc. These monomers may be used alone or in combination of two or more kinds.

[0028] The average degree of polymerization of the vinyl chloride resin is preferably 500 to 4000, more preferably 700 to 3900, and even more preferably 1000 to 3800, so that the moisture permeability is easily within the above range and long-term adhesion is improved along with application suitability. When the average degree of polymerization is within the above range, excellent mechanical strength and moldability are also obtained. In this specification, the average degree of polymerization is the average degree of polymerization measured in accordance with JIS K6721.

[0029] In this embodiment, when a vinyl chloride resin is used, it is preferable to add a plasticizer in order to easily adjust the moisture permeability within the above range, improve long-term adhesion as well as application suitability, and further improve processability. The plasticizer is not particularly limited as long as it is compatible with vinyl chloride resins, and examples thereof include phthalic acid plasticizers such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), etc.; adipic acid plasticizers such as dibutyl adipate; phosphate plasticizers such as tributyl phosphate, tricresyl phosphate, triphenyl phosphate, etc.; trimellitic acid plasticizers such as tributyl trimellitate, trioctyl trimellitate, etc.; various known polyester plasticizers such as adipic acid polyesters; and citric acid esters such as acetyl tributyl citrate, acetyl trioctyl citrate, etc. Among them, in order to easily set the moisture permeability within the above range, improve long-term adhesion as well as application suitability, and improve processability, phthalic acid plasticizers, adipic acid plasticizers, and polyester plasticizers are preferred, and phthalic acid plasticizers and polyester plasticizers are more preferred. These plasticizers may be used alone or in combination of two or more kinds.

[0030] The content of the plasticizer may be appropriately adjusted according to the desired moisture permeability, and although it cannot be said in general, the moisture permeability of the vinyl chloride resin tends to increase as the amount of the plasticizer additive is increased. In consideration of this point, the content of the plasticizer is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, with respect to 100 parts by mass of the vinyl chloride resin, and the upper limit is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 35 parts by mass or less. By setting the content of the plasticizer within the above range, it becomes easier to adjust the moisture permeability to a desired range, and it is possible to improve the long-term adhesion as well as the application suitability. In addition, by setting the content of the plasticizer to 20 parts by mass or more, it is possible to make the vinyl chloride resin flexible and improve the processability. On the other hand, if it is 50 parts by mass or less, the bleeding out of the plasticizer is suppressed, and it becomes easier to stably adjust the moisture permeability to a desired range, and it is possible to improve the long-term adhesion as well as the application suitability.

[0031] In particular, in order to easily adjust the moisture permeability to a desired range and improve long-term adhesion together with application suitability, for example, when a phthalate ester plasticizer is used, the content is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more, relative to 100 parts by mass of vinyl chloride resin, and the upper limit is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less. In addition, when a polyester plasticizer is used, the content is preferably 15 parts by mass or more, more preferably 18 parts by mass or more, and even more preferably 20 parts by mass or more, relative to 100 parts by mass of vinyl chloride resin, and the upper limit is preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less.

[0032] The substrate may be colorless and transparent, or may be colored to improve the design. When the substrate is colored, a coloring agent such as a dye or a pigment can be added to the substrate. Among these coloring agents, a pigment is preferred because it is easy to suppress fading. Examples of pigments include white pigments such as zinc oxide, white lead, lithopone, titanium dioxide (titanium white), precipitated barium sulfate, and baryte; black pigments such as carbon black, aomethine azo black pigments, and perylene black pigments; red pigments such as red lead, iron oxide red, quinacridone red, and polyazo red; yellow pigments such as yellow lead, zinc yellow (zinc yellow type 1, zinc yellow type 2), isoindolinone yellow, and nickel-azo complexes; and blue pigments such as ultramarine blue and Prussian blue (potassium ferrocyanide). Titanium dioxide is preferred as a pigment to be added to the substrate because it has a high hiding power and is less susceptible to the influence of the color of the adherend. However, titanium dioxide generates radicals when irradiated with light including the ultraviolet spectrum, which reduces the weather resistance of the decorative sheet. When rutile and brookite titanium oxides are used, the generation of radicals can be suppressed, but still more radicals are generated than when titanium dioxide is not included. However, in the present invention, even if a substrate containing titanium dioxide is used, the surface protective layer contains radical scavengers I and II, so that the weather resistance can be improved for a long period of time. In particular, when a substrate containing titanium dioxide is used, it is preferable that the substrate and the surface protective layer are in contact with each other (when a primer layer is included, it is preferable that the substrate and the primer layer are in contact with each other).

[0033] The thickness of the substrate is not particularly limited, but when the substrate is a plastic film or sheet, it is preferably 20 μm or more, and the upper limit is preferably 3200 μm or less. In consideration of making it easier to adjust the moisture permeability of the decorative sheet to within the above-mentioned specified range, it is more preferably 40 μm or more, and the upper limit is more preferably 200 μm or less, and even more preferably 100 μm or less. When the substrate is paper, the basis weight is usually 20 g / m 2 More than 150g / m 2 Less than 30 g / m is preferable. 2 More than 100g / m 2 The following is more preferred:

[0034] The shape of the substrate is not limited to a flat plate shape, but may be a special shape such as a three-dimensional shape. In order to improve adhesion to a layer provided on the substrate, one or both sides of the substrate may be subjected to an adhesion enhancing treatment such as a physical treatment or a chemical surface treatment.

[0035] In order to enhance adhesion to other layers of the decorative sheet or to the adherend, the substrate may be subjected to a surface treatment such as a physical surface treatment such as an oxidation method or a roughening method, or a chemical surface treatment, or a primer layer may be formed on one or both sides of the substrate.

[0036] <Surface protective layer> The surface protective layer of the decorative sheet of the present invention is a layer formed by crosslinking and curing composition A containing an ionizing radiation curable resin composition and a radical scavenger.

[0037] <<Ionizing radiation curable resin composition>> The surface protective layer contains a crosslinked and cured product of the ionizing radiation curable resin composition. By containing the crosslinked and cured product of the ionizing radiation curable resin composition in the surface protective layer, the scratch resistance of the decorative sheet can be improved. Note that a part of the crosslinked and cured product of the ionizing radiation curable resin composition is polymerized with a radical scavenger i described later. Examples of the ionizing radiation curable resin composition include an electron beam curable resin composition and an ultraviolet ray curable resin composition, and among these, an electron beam curable resin composition is preferred because it can be applied without a solvent, which reduces the environmental impact, and because a polymerization initiator is not required, etc. In addition, when composition A contains an ultraviolet ray absorber described later, an electron beam curable resin composition is also preferred in that it is easier to increase the crosslink density of the surface protective layer.

[0038] The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as "ionizing radiation curable compound"). The ionizing radiation curable functional group is a group that crosslinks and cures when irradiated with ionizing radiation, and preferred examples thereof include functional groups having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, and an allyl group. In this specification, the (meth)acryloyl group refers to an acryloyl group or a methcroyl group. In addition, in this specification, the (meth)acrylate refers to an acrylate or a methacrylate. In addition, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing and / or crosslinking molecules. Typically, ultraviolet rays (UV) or electron beams (EB) are used, but it also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams. Specifically, the ionizing radiation curable compound can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable resins.

[0039] As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate monomer is preferable. Here, "(meth)acrylate" means "acrylate or methacrylate". The polyfunctional (meth)acrylate monomer includes a (meth)acrylate monomer having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the functional group. In order to improve processing characteristics, scratch resistance and weather resistance, the number of functional groups in the polyfunctional (meth)acrylate monomer is preferably from 2 to 8, more preferably from 2 to 6, even more preferably from 2 to 4, and even more preferably from 2 to 3. These polyfunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0040] Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group, such as urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers. Further examples of the polymerizable oligomer include highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chains, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in a small molecule, and oligomers having cationically polymerizable functional groups in the molecules of novolac type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc.

[0041] These polymerizable oligomers may be used alone or in combination of two or more kinds. In order to improve processing characteristics, scratch resistance and weather resistance, urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer, acrylic (meth)acrylate oligomer are preferred, urethane (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer are more preferred, and urethane (meth)acrylate oligomer is even more preferred.

[0042] In order to improve processing characteristics, scratch resistance and weather resistance, the number of functional groups of these polymerizable oligomers is preferably 2 or more and 8 or less, with the upper limit being more preferably 6 or less, even more preferably 4 or less, and even more preferably 3 or less. In order to improve processing characteristics, scratch resistance and weather resistance, the weight average molecular weight of these polymerizable oligomers is preferably from 2,500 to 7,500, more preferably from 3,000 to 7,000, and even more preferably from 3,500 to 6,000. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0043] In the ionizing radiation curable resin composition, a monofunctional (meth)acrylate can be used in combination for the purpose of reducing the viscosity of the ionizing radiation curable resin composition, etc. These monofunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0044] When the ionizing radiation curable compound is an ultraviolet ray curable compound, composition A preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing speed, and examples of the accelerator include one or more types selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0045] <<Radical scavenger>> In the present invention, the radical scavenger includes a radical scavenger i having an ethylenic double bond polymerizable with the ionizing radiation curable resin composition, and a radical scavenger ii not having an ethylenic double bond polymerizable with the ionizing radiation curable resin composition.

[0046] Examples of the radical scavenger include aromatic radical scavengers, amine radical scavengers, organic acid radical scavengers, catechin radical scavengers, and hindered amine radical scavengers, and among these, hindered amine radical scavengers are preferred. The hindered amine radical scavengers have a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.

[0047] When only the radical scavenger i is used, the radical scavenger in the surface protective layer is almost entirely immobilized, and there is almost no radical scavenger that can move freely within the surface protective layer, resulting in insufficient radical scavenging performance and failure to improve the weather resistance of the decorative sheet. In addition, since the radical scavenger i polymerizes with the ionizing radiation curable resin composition, when only the radical scavenger i is used, the crosslink density of the crosslinked product of the ionizing radiation curable resin composition decreases, resulting in reduced scratch resistance. On the other hand, if only radical scavenger II is used, radical scavenger II will bleed out from the surface protective layer over time, impairing the appearance of the decorative sheet surface, and the concentration of the radical scavenger in the surface protective layer will decrease over time, resulting in insufficient weather resistance.

[0048] In the present invention, the content of the radical scavenger in composition A is 0.5 parts by mass or more and less than 10.0 parts by mass based on 100 parts by mass of the ionizing radiation curable resin composition. When the content of the radical scavenger is less than 0.5 parts by mass relative to 100 parts by mass of the ionizing radiation curable resin composition, the absolute amount of the radical scavenger is insufficient, so that even if radical scavenger I and radical scavenger II are used in combination, the weather resistance of the decorative sheet cannot be improved. Also, when the content of the radical scavenger exceeds 10.0 parts by mass relative to 100 parts by mass of the ionizing radiation curable resin composition, the crosslink density of the crosslinked product of the ionizing radiation curable resin composition in the surface protective layer decreases, resulting in problems such as decreased scratch resistance and increased susceptibility to bleeding out of the radical scavenger.

[0049] The content of the radical scavenger in composition A is preferably 0.8 parts by mass or more and 5.0 parts by mass or less, and more preferably 1.0 parts by mass or more and 4.0 parts by mass or less, based on 100 parts by mass of the ionizing radiation curable resin composition.

[0050] <<Radical Scavenger i>> The radical scavenger i has an ethylenic double bond polymerizable with the ionizing radiation curable resin composition. Examples of the group having an ethylenic double bond include a (meth)acryloyl group, a crotonoyl group, a vinyl group, and an allyl group, and among these, a (meth)acryloyl group is preferred. That is, the radical scavenger i is preferably one having a (meth)acryloyl group. The number of ethylenic double bonds in the radical scavenger i is not particularly limited, and may be 1 or may be 2 or more. In addition, only one type of radical scavenger i may be used, or two or more types of radical scavenger i may be used.

[0051] Examples of the radical scavenger i having one ethylenic double bond include 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, pentamethylpiperidinyl (meth)acrylate, the compound having CAS number 1010692-24-6, and the compound having CAS number 1010692-21-3. Examples of the radical scavenger i having two or more ethylenic double bonds include 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine, the compound having CAS number 1954659-42-7, and the compound having CAS number 1010692-23-5.

[0052] << Radical Scavenger II >> The radical scavenger II does not have an ethylenic double bond polymerizable with the ionizing radiation curable resin composition. Only one type of radical scavenger II may be used, or two or more types may be used.

[0053] Radical scavengers II include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate. , 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxy-benzyl)-2-n-butylmalonate, and the like.

[0054] When the decorative sheet has a primer layer in contact with the substrate side surface of the surface protective layer, it is preferable that the radical scavenger ii has a functional group capable of reacting with a functional group of a component of the primer layer. By adopting such a configuration, the radical scavenger ii present near the interface between the surface protective layer and the primer layer is fixed at the interface, suppressing bleeding out, while the radical scavenger ii present at other locations can move freely in the surface protective layer, which is preferable in that it can maintain radical scavenging performance. In addition, the radical scavenger ii reacts with the component of the primer layer at the interface between the surface protective layer and the primer layer, thereby improving the adhesion of the surface protective layer. Examples of combinations of functional groups that satisfy the above conditions include those shown in A to D in the following Table 1. Among these, the following A (radical scavenger ii has a hydroxyl group, and a component of the primer layer has an isocyanate group) is preferred.

[0055] [Table 1]

[0056] Hindered amine radical scavengers suitable as the radical scavengers i and ii can be divided, for example, into amino ether type and non-amino ether type. The aminoether-type hindered amine radical scavenger is a radical scavenger in which the hydrogen atom bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton is OR 1 or O.C.O.R. 2 In addition, R 1 and R 2 represents an alkyl group and / or a cycloalkyl group, and is preferably an alkyl group and / or a cycloalkyl group having 5 to 12 carbon atoms. On the other hand, the non-amino ether type hindered amine radical scavenger refers to a compound in which the hydrogen atom bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton remains as a hydrogen atom or is substituted with an alkyl group.

[0057] The blending ratio of the radical scavenger i to the radical scavenger ii on a mass basis is preferably 8:2 to 2:8, more preferably 7:3 to 3:7, and further preferably 6:4 to 4:6. By making the radical scavenger i 8 and the radical scavenger ii 2 or more, it is possible to improve weather resistance and easily suppress a decrease in the crosslink density of the crosslinked cured product of the ionizing radiation curable resin composition. In addition, by making the radical scavenger i 2 and the radical scavenger ii 8 or less, it is possible to suppress bleeding out of the radical scavenger ii.

[0058] <<Ultraviolet absorbing agent>> The composition A that forms the surface protective layer preferably contains an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and triazine-based ultraviolet absorbers, and triazine-based ultraviolet absorbers are preferred.In addition, among the triazine-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers in which at least one organic group selected from hydroxyphenyl groups, alkoxyphenyl groups, and organic groups containing these groups are linked to a triazine ring are more preferred, and hydroxyphenyltriazine-based ultraviolet absorbers represented by the following general formula (1) are even more preferred.Since hydroxyphenyltriazine-based ultraviolet absorbers have a branched structure, they are expected to be less likely to bleed out from the surface protective layer, and can provide excellent weather resistance for a long period of time. Moreover, ultraviolet absorbents having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, or an allyl group, are preferred because they are easy to suppress bleed-out.

[0059] [ka]

[0060] In general formula (1), R 11 is a divalent organic group, and R 12 -C(=O)OR 15 R is an ester group represented by the formula: 13 , R 14 and R 15 are each independently a monovalent organic group; 11 and n 12 are each independently an integer of 1 or more and 5 or less.

[0061] R 11 Examples of the divalent organic group include aliphatic hydrocarbon groups such as an alkylene group and an alkenylene group, and in order to improve weather resistance, an alkylene group is preferred, and the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 12, even more preferably from 1 to 8, and particularly preferably from 1 to 4. The alkylene group and alkenylene group may be linear, branched, or cyclic, and is preferably linear or branched. Examples of alkylene groups having 1 to 20 carbon atoms include a methylene group, a 1,1-ethylene group, a 1,2-ethylene group, various propylene groups such as 1,3-propylene, 1,2-propylene and 2,2-propylene (hereinafter, "various" refers to linear, branched and isomeric groups thereof), various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups, various undecylene groups, various dodecylene groups, various tridecylene groups, various tetradecylene groups, various pentadecylene groups, various hexadecylene groups, various heptadecylene groups, various octadecylene groups, various nonadecylene groups and various icosylene groups.

[0062] R 13 and R 14 Examples of the monovalent organic group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group. Among these, aromatic hydrocarbon groups such as an aryl group and an arylalkyl group are preferred, and an aryl group is more preferred. 13 and R 14 The monovalent organic group is preferably a phenyl group. The aryl group preferably has 6 to 20 carbon atoms, more preferably has 6 to 12 carbon atoms, and even more preferably has 6 to 10 carbon atoms, such as a phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, and various naphthyl groups. The arylalkyl group preferably has 7 to 20 carbon atoms, more preferably has 7 to 12 carbon atoms, and even more preferably has 7 to 10 carbon atoms, such as a benzyl group, a phenethyl group, various phenylpropyl groups, various phenylbutyl groups, various methylbenzyl groups, various ethylbenzyl groups, various propylbenzyl groups, various butylbenzyl groups, and various hexylbenzyl groups.

[0063] R 15Examples of the monovalent organic group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group. An aliphatic hydrocarbon group such as an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. That is, R 12 As the alkyl group, an alkyl ester group or an alkenyl ester group is preferable, and an alkyl ester group is more preferable. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and even more preferably 6 to 12 carbon atoms, such as a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, and various icosyl groups. The alkenyl group is preferably an alkenyl group having 2 or more and 20 or less carbon atoms, more preferably 3 or more and 16 or less, and even more preferably 6 or more and 12 or less carbon atoms, such as a vinyl group, various propenyl groups, various butenyl groups, various pentenyl groups, various hexenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, various hexadecenyl groups, various heptadecenyl groups, various octadecenyl groups, various nonadecenyl groups, and various icosenyl groups.

[0064] More specifically, the hydroxyphenyltriazine compound represented by the general formula (1) is 11 is an alkylene group having 1 to 20 carbon atoms, and R 12 and R 15 is an alkyl ester group having 1 to 20 carbon atoms; R 13 and R 14 is an aryl group having 6 to 20 carbon atoms, 11 and n 12 Hydroxyphenyltriazine compounds having a value of 1 are preferred, and R 11 is an alkylene group having 1 to 12 carbon atoms, and R 12 and R15 is an alkyl ester group having 2 to 16 carbon atoms; R 13 and R 14 is an aryl group having 6 to 12 carbon atoms, 11 and n 12 Hydroxyphenyltriazine compounds having a value of 1 are more preferred, 11 is an alkylene group having 1 to 8 carbon atoms, and R 12 R 15 and an alkyl ester group, which is an alkyl group having 6 to 12 carbon atoms, R 13 and R 14 is an aryl group having 6 to 10 carbon atoms, 11 and n 12 More preferred are hydroxyphenyltriazine compounds having a R 11 is an alkylene group having 1 to 4 carbon atoms, and R 12 and R 15 is an ester group which is an alkyl group having 8 carbon atoms, and R 13 and R 14 is a phenyl group, and n 11 and n 12 Hydroxyphenyltriazine compounds having a moiety of 1 are particularly preferred.

[0065] More specifically, the hydroxyphenyltriazine compound represented by the general formula (1) is represented by the following chemical formula (2): 11 is an ethylene group, and R 12 and R 15 is an ester group which is an isooctyl group, and R 13 and R 14 is a phenyl group, and n 11 and n 12 A hydroxyphenyltriazine compound having a molecular weight of 1, i.e., 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine is preferred, and this hydroxyphenyltriazine compound is available, for example, as a commercial product ("TINUVIN 479", manufactured by BASF).

[0066] [ka]

[0067] The content of the ultraviolet absorber in composition A is preferably from 0.2 to 10.0 parts by mass, more preferably from 0.5 to 5.0 parts by mass, and even more preferably from 1.0 to 4.0 parts by mass, relative to 100 parts by mass of the ionizing radiation curable resin composition. The type of ultraviolet absorber used may be one type alone or multiple types may be used in combination.

[0068] <<Antioxidants>> The composition A forming the surface protective layer preferably contains an antioxidant. By containing an antioxidant, it is possible to easily improve weather resistance. Examples of the antioxidant include phenol-based, amine-based, sulfur-based, and phosphorus-based antioxidants, etc. Among these, phenol-based antioxidants are preferred.

[0069] Examples of the phenol-based antioxidant include hindered phenol-based antioxidants, and specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3'',5,5',5''-hexa-tert-butyl- a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl)propionate, t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like can be mentioned.

[0070] The thickness of the surface protective layer is preferably from 1.5 μm to 20 μm, more preferably from 2 μm to 15 μm, and even more preferably from 3 μm to 10 μm, in view of the balance between processing characteristics, scratch resistance, and weather resistance.

[0071] <Primer layer> The decorative sheet preferably has a primer layer in contact with the substrate-side surface of the surface protective layer. The primer layer improves adhesion between the substrate and the surface protective layer, and can easily ensure long-term interlayer adhesion when exposed to the outdoors (so-called weather-resistant adhesion) and good scratch resistance.

[0072] The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary. Examples of the binder resin include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate bond in the polymer main chain and having two or more hydroxyl groups at the end and side chain), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin (nitrocellulose), and cellulose acetate resin. These can be used alone or in combination. The binder resin may be a resin obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to these resins and crosslinking and curing them. Among these, a polyol-based resin such as an acrylic polyol resin is preferably crosslinked and cured with an isocyanate-based curing agent, and an acrylic polyol resin is more preferably crosslinked and cured with an isocyanate-based curing agent. As described above, the binder resin preferably has a functional group capable of reacting with the functional group contained in the radical scavenger ii.

[0073] The thickness of the primer layer is preferably from 1 μm to 10 μm, more preferably from 2 μm to 8 μm, and further preferably from 3 μm to 6 μm.

[0074] The decorative sheet may have a back primer layer on the side of the substrate opposite the surface protective layer for the purpose of improving adhesion to an adherend, etc.

[0075] <Transparent resin layer> The decorative sheet may have a transparent resin layer between the substrate and the surface protective layer for the purpose of increasing strength, etc. When the decorative sheet has a primer layer, the transparent resin layer is preferably located between the substrate and the primer layer. When the decorative sheet has a decorative layer, the transparent resin layer is preferably located between the decorative layer and the surface protective layer to protect the decorative layer.

[0076] Resins constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, vinyl chloride resins, etc., among which polyolefin resins are preferred in order to improve processability, and polyolefin resins and vinyl chloride resins are preferred in consideration of ease of adjusting moisture permeability, with polyolefin resins being more preferred. Furthermore, two or more of these exemplified resins may be laminated or mixed for use. In order to improve processability, the content of the polyolefin resin in the transparent resin layer is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more, of the total resin components of the transparent resin layer.

[0077] Examples of the polyolefin resin of the transparent resin layer include polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, etc. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, propylene-butene copolymer are preferred, and polypropylene is more preferred. In addition, the polyolefin resin can be preferably used from the polyethylene resin and polypropylene resin described as specific examples of the resin constituting the plastic of the above-mentioned substrate. When vinyl chloride resin is used for the transparent resin layer, the vinyl chloride resins described above as specific examples of the resin constituting the plastic of the substrate can be preferably used.

[0078] The transparent resin layer may contain additives such as an ultraviolet absorbing agent, a light stabilizer, and a colorant. The thickness of the transparent resin layer is preferably from 20 to 150 μm, more preferably from 40 to 120 μm, and even more preferably from 60 to 100 μm, from the viewpoint of ease of adjusting moisture permeability and furthermore, balance of scratch resistance, processability and weather resistance.

[0079] <Decorative layer> In order to improve the design, the decorative sheet preferably has a decorative layer at any position of the decorative sheet. In order to improve the weather resistance of the decorative layer, the position where the decorative layer is formed is preferably on the side close to the substrate. For example, when the decorative sheet has a primer layer, the decorative layer is preferably located between the substrate and the primer layer. In addition, when the decorative sheet has a transparent resin layer, the decorative layer is preferably located between the substrate and the transparent resin layer.

[0080] The decorative layer may be, for example, a colored layer (so-called solid colored layer) that covers the entire surface, or a pattern layer formed by printing various patterns using ink and a printing machine, and the pattern (design) of the pattern layer may be a wood grain pattern such as tree rings or vessel grooves on the surface of a wooden board, a stone grain pattern on the surface of a stone slab such as marble or granite, a fabric grain pattern on a fabric surface, a leather grain pattern on a leather surface, a geometric pattern, letters, figures, or a combination of these.

[0081] The ink used for the decorative layer is a suitable mixture of a binder resin, a pigment, a colorant such as a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardener, an ultraviolet absorber, a light stabilizer, etc. The binder resin of the decorative layer is not particularly limited, and examples thereof include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, etc. In addition, various types of resins can be used, such as one-component curing resins and two-component curing resins accompanied by a curing agent such as an isocyanate compound.

[0082] As the colorant, a pigment having excellent hiding power and weather resistance is preferable. The pigment may be the same as those exemplified for the plastic substrate. The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and even more preferably 30 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the resin constituting the decorative layer.

[0083] The decorative layer may contain additives such as an ultraviolet absorbing agent, a light stabilizer, and a colorant. The thickness of the decorative layer may be appropriately selected according to the desired pattern, but in order to conceal the base color of the adherend and improve the design, the thickness is preferably 0.5 μm to 20 μm, more preferably 1 μm to 10 μm, and even more preferably 2 μm to 5 μm.

[0084] <Adhesive layer A> When the decorative sheet has a transparent resin layer, it is preferable to form an adhesive layer A between the substrate and the transparent resin layer in order to improve the adhesion between the two layers. When a decorative layer is further provided between the substrate and the transparent resin layer, the positional relationship between the adhesive layer A and the decorative layer is not particularly limited. Specifically, the decorative sheet of the present invention may have, in this order from the side closer to the substrate, a decorative layer, an adhesive layer A, and a transparent resin layer, or may have, in this order from the side closer to the substrate layer, an adhesive layer A, a decorative layer, and a transparent resin layer.

[0085] The adhesive layer A can be composed of, for example, an adhesive such as a urethane adhesive, an acrylic adhesive, an epoxy adhesive, a rubber adhesive, etc. Among these adhesives, a urethane adhesive is preferred in terms of adhesive strength. Examples of urethane-based adhesives include adhesives that utilize a two-liquid curing urethane resin that contains various polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol, and a curing agent such as an isocyanate compound.

[0086] The thickness of the adhesive layer A is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less.

[0087] The decorative layer, adhesive layer A, primer layer and topcoat layer described above can be formed by applying a coating liquid containing a composition for forming each layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating or comma coating, and drying and curing as necessary.

[0088] The decorative sheet may be given (also called shaping) a desired uneven shape (also called an uneven pattern) by embossing or the like. When embossing is performed, for example, the decorative sheet is heated to preferably from 80° C. to 260° C., more preferably from 85° C. to 160° C., and even more preferably from 100° C. to 140° C., and an embossing plate is pressed against the decorative sheet to perform the embossing. The area to be pressed with the embossing plate is preferably the surface protective layer side of the decorative sheet.

[0089] [Cosmetic materials] The decorative material of the present invention comprises an adherend and the decorative sheet of the present invention described above, and specifically, is laminated so that the surface of the adherend that requires decoration faces the substrate layer side of the decorative sheet.

[0090] <Adherent material> Examples of the adherend include various materials such as flat plates, curved plates, three-dimensional objects such as cylinders and polygonal columns, and sheets (or films). Examples of the adherend include wood members such as veneers, wood plywood, laminated lumber, particle boards, and MDF (medium density fiberboard) made of various wood materials such as cedar, cypress, pine, and lauan; metal members made of metals such as iron, aluminum, copper, and alloys containing one or more of these metals; ceramic members made of non-ceramic ceramic materials such as glass, ceramics, gypsum, cement, ALC (lightweight aerated concrete), and calcium silicate; and resin members made of resins such as acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, and rubber. These members can be used alone or in combination of multiple types.

[0091] The adherend may be appropriately selected from the above depending on the application, and when the application is for interior building components such as walls, ceilings, and floors, exterior building components such as exterior walls, roofs, eaves ceilings, fences, and gates, fittings or fixtures such as window frames, doors, handrails, baseboards, moldings, etc., it is preferable to use at least one member selected from wood members, metal members, and resin members. Also, when the application is for exterior components such as entrance doors, fittings such as window frames and doors, etc., it is preferable to use at least one member selected from metal members and resin members.

[0092] The thickness of the adherend may be appropriately selected depending on the application and material, and is preferably 0.1 mm to 100 mm, more preferably 0.3 mm to 5 mm, and even more preferably 0.5 mm to 3 mm.

[0093] <Adhesive layer B> In order to obtain excellent adhesion, the adherend and the decorative sheet are preferably attached via the adhesive layer B.

[0094] The adhesive used in the adhesive layer B is not particularly limited, and known adhesives can be used, and may be appropriately selected according to the application. Preferred examples of the adhesive used in the adhesive layer B include moisture-curing adhesives, anaerobic-curing adhesives, dry-curing adhesives, UV-curing adhesives, heat-sensitive adhesives (e.g., hot-melt adhesives), and pressure-sensitive adhesives. Considering compatibility with the decorative material of the present embodiment having a predetermined water vapor permeability, ease of handling, and the like, moisture-curing adhesives and heat-sensitive adhesives are preferred. Furthermore, moisture-curing and heat-sensitive adhesives are more preferred. A heat-sensitive adhesive is preferred because the adhesive strength of the molten liquid adhesive layer B increases to a saturated state as soon as it is cooled and solidified. The decorative material of this embodiment has a moisture permeability of 0.75 g / m 2 24 hours or more. Therefore, the moisture-curing adhesive can be exposed to moderate moisture during the application process, which makes it easier to increase the initial adhesive strength of the adhesive used in adhesive layer B. In addition, the decorative material of this embodiment has a moisture permeability of 45 g / m 2 24 hours or less. Therefore, moisture-curing adhesives do not come into contact with excessive moisture, so the decrease in adhesion caused by deterioration due to hydrolysis of the moisture-curing adhesive is suppressed, resulting in better application suitability and long-term adhesion. Moisture-curing adhesives are also preferable in terms of ease of handling.

[0095] Resins used in these adhesives include, for example, acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, polyester resins, amide resins, cyanoacrylate resins, epoxy resins, etc., which can be used alone or in combination. Two-liquid curing type urethane adhesives and ester adhesives using an isocyanate compound or the like as a curing agent can also be used. The adhesive layer may contain a pressure-sensitive adhesive, which may be appropriately selected from acrylic, urethane, silicone, rubber, or other pressure-sensitive adhesives.

[0096] One of the adhesives preferably used in this embodiment is a moisture-curing adhesive, the resin system of which is a urethane resin, which contains a prepolymer having an isocyanate group at the molecular end as an essential component. The prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at each of both molecular ends, and is in a solid thermoplastic resin state at room temperature. Examples of such polyisocyanate prepolymers include those using a polyester polyol that is crystalline and solid at room temperature as the polyol component, and a polyisocyanate consisting of 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, etc. as the polyisocyanate component.

[0097] The thickness of the adhesive layer B is not particularly limited, but in order to obtain excellent adhesiveness, it is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, and even more preferably from 10 μm to 30 μm.

[0098] <Manufacturing method of decorative materials> The decorative material can be manufactured through a process of laminating a decorative sheet and an adherend. This step is a step of laminating the adherend and the decorative sheet of the present invention, with the surface of the adherend that requires decoration facing the substrate side of the decorative sheet. Examples of a method for laminating the adherend and the decorative sheet include a lamination method in which the decorative sheet is pressed against the plate-shaped adherend via the adhesive layer B using a pressure roller.

[0099] When a hot melt adhesive (heat-sensitive adhesive) is used as the adhesive, the heating temperature is preferably 160° C. to 200° C., and for reactive hot melt adhesives, the heating temperature is preferably 100° C. to 130° C. In addition, in the case of vacuum forming, processing is generally performed while heating, and the heating temperature is preferably 80° C. to 130° C., and more preferably 90° C. to 120° C.

[0100] In the embodiment shown in Fig. 1, the decorative sheet 100 has the following layered structure (1), but as long as it has at least the specific surface protective layer of the present invention on the substrate, various layered structure configurations can be selected according to the application, required performance, etc. For example, other specific layered structures of the decorative sheet of the present invention include the following layered structures (2) to (7). (1) Substrate 50 / decorative layer 40 / transparent resin layer 30 / primer layer 20 / surface protective layer 10 (2) Base material 50 / Surface protection layer 10 (3) Substrate 50 / Primer layer 20 / Surface protective layer 10 (4) Base material 50 / transparent resin layer 30 / surface protection layer 10 (5) Base material 50 / decorative layer 40 / surface protective layer 10 (6) Substrate 50 / Transparent resin layer 30 / Decorative layer 40 / Surface protective layer 10 (7) Substrate 50 / transparent resin layer 30 / decorative layer 40 / primer layer 20 / surface protective layer 10 In the above (1) to (7), a known adhesive layer (the above-mentioned adhesive layer A) can be interposed between the substrate and the transparent resin layer and / or the decorative layer, and the surface of the substrate, the transparent resin layer, etc. can be given an uneven shape such as wood grain vessel grooves, sand grain, pear-skin, hairline, leather grain, etc. by using the above-mentioned embossing process or other various known techniques. In this paragraph, " / " indicates the interface between layers.

[0101] The decorative material obtained as described above can be cut as desired, and the surface or end of the wood can be decorated as desired, such as by groove processing or chamfering, using a cutting machine such as a router or cutter. It can be used for various purposes, such as interior components of buildings, such as walls, ceilings, and floors; exterior components, such as exterior walls, eaves ceilings, roofs, walls, and fences; fittings or fixtures, such as window frames, doors, door frames, handrails, baseboards, moldings, and other building materials; general furniture, such as chests of drawers, shelves, and desks; kitchen furniture, such as dining tables and sinks; surface decorative panels for cabinets, etc., for home appliances and office automation equipment; interior and exterior components for vehicles; etc. EXAMPLES

[0102] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples in any way. 1. Evaluation and Measurement 1-1. Weather resistance The decorative sheets obtained in the examples and comparative examples were subjected to an accelerated weathering test using a metal halide lamp (MWOM) for 1000 hours, after which their appearances were visually observed from the surface protective layer side. Twenty subjects rated the sheets, giving 3 points for a level at which no change in appearance was observed, 2 points for a slight decrease in gloss, and 1 point for a significant decrease in gloss or cracks. The average score of the 20 subjects was calculated and ranked according to the following criteria. The results are shown in Table 2. The test equipment and test conditions were as follows: <Weather resistance evaluation criteria> AA: Average score of 2.7 or higher A: Average score is between 2.5 and 2.7 B: Average score is 2.0 or more but less than 2.5 C: Average score is 1.5 or more but less than 2.0 D: Average score is less than 1.5

[0103] <Test Equipment> Product name "Daipla Metal Weather" manufactured by Daipla Wintes Co., Ltd. <Irradiation conditions> Illuminance: 65mW / m 2 , Black panel temperature: 63℃, chamber humidity: 50%RH, time: 20 hours <Condensation conditions> Illuminance: 0mW / m 2 , Humidity inside the tank: 98%RH, Time: 4 hours

[0104] 1-2. Scratch resistance 300 g / m2 on the surface of the decorative sheets obtained in the examples and comparative examples 2A rubbing test was carried out by moving steel wool ("Bonstar #0000", manufactured by Japan Steel Wool Co., Ltd.) back and forth five times at a load of 100000. After the rubbing test, the surface condition of the decorative sheet was visually observed. Twenty subjects gave the sheets a rating of 3 points for a level where no scratches and no noticeable change in gloss were observed, 2 points for minor scratches and a minor noticeable change in gloss, and 1 point for scratches and a significant change in gloss. The average score of the 20 subjects' ratings was calculated and ranked according to the following criteria. The results are shown in Table 2. <Scratch resistance evaluation criteria> A: Average score of 2.5 or higher B: Average score is 2.0 or more but less than 2.5 C: Average score is 1.5 or more but less than 2.0 D: Average score is less than 1.5

[0105] 1-3. Bleed out The decorative sheets obtained in the examples and comparative examples were immersed in 40°C warm water for one week. After the immersion, the decorative sheets were removed from the warm water and dried, and the appearance of the decorative sheets after immersion was visually observed from the surface protective layer side. Twenty subjects rated the sheets according to the following criteria: 3 points for a level where no change in appearance was observed, 2 points for a slight amount of bleeding observed but not problematic in practical use, and 1 point for a significant amount of bleeding observed. The average score of the 20 subjects was calculated and ranked according to the following criteria. The results are shown in Table 2. <Bleed-out evaluation criteria> AA: Average score of 2.7 or higher A: Average score is between 2.5 and 2.7 B: Average score is 2.0 or more but less than 2.5 C: Average score is 1.5 or more but less than 2.0 D: Average score is less than 1.5

[0106] 1-4. Measurement of moisture permeability The moisture permeability of the decorative sheets obtained in the examples and comparative examples was measured in accordance with the moisture permeability test method (cup method) for moisture-proof packaging materials specified in JIS Z0208:1976. 1-5.Evaluation of suitability for construction The decorative sheet obtained in the examples and comparative examples was attached to a 25 mm wide flat plate-shaped adherend (material: polyvinyl chloride (PVC)) via a 50 μm thick adhesive layer formed by melting a moisture-curing, hot-melt type urethane resin adhesive (a polyurethane prepolymer having an isocyanate group in the molecule, "1308.20 (product name)", manufactured by TAKA Corporation) at 120 ° C., and then the adhesive layer was cooled to room temperature of 23 ° C. to solidify. Next, the above-mentioned decorative sheet and adherend were left in an environment of 90 ° C. for 1 hour to prepare a sample. A peeling test was performed on the sample in a temperature environment of 25 ° C. using a Tensilon universal material testing machine ("Tensilon RTC-1250A (product name)", manufactured by Orientec Co., Ltd.) under the conditions of a tensile speed of 10 mm / min, a peeling direction of 90 °, and a chuck distance of 30 mm, and the peeling strength was measured as the initial adhesive strength. The measurement results were evaluated according to the following criteria. A rating of B or higher was deemed to be acceptable for construction suitability. <Evaluation criteria for construction suitability> A: The peeling strength was 1.0 N / mm or more. B: The peeling strength was 0.5 N / mm or more and less than 1.0 N / mm. C: The peeling strength was less than 0.5 N / mm. 1-6. Evaluation of long-term adhesion The samples prepared in "1-5. Evaluation of application suitability" above were left in a 70°C 90% RH humid heat environment for 6 weeks, and then a peeling test was carried out in a 25°C temperature environment using a Tensilon universal material testing machine ("Tensilon RTC-1250A (product name)", manufactured by Orientec Co., Ltd.) at a tensile speed of 50 mm / min and a peeling direction of 90° to measure the peeling strength. The measurement results were evaluated according to the following criteria. A rating of B or higher indicates that the long-term adhesion is acceptable. <Evaluation criteria for long-term adhesion> A: The peeling strength was 2.0 N / mm or more. B: The peeling strength was 1.0 N / mm or more and less than 2.0 N / mm. C: The peeling strength was less than 1.0 N / mm. 1-7. Processing suitability When preparing the samples in the above "1-5. Evaluation of workability," the lifting of the decorative material at the bent portion (bending angle: 1 mmR) during lamination was visually confirmed and evaluated according to the following criteria. If the evaluation was B or higher, the workability was acceptable. <Evaluation criteria for processing suitability> A: No floating was observed at all. B: Almost no floating was observed. C: Lifting was observed and peeling occurred.

[0107] 2. Preparation of decorative sheet [Example 1] A decorative layer ink containing a two-component curing acrylic-urethane resin and a colorant was applied by gravure printing to one side of a substrate (a titanium oxide-containing polypropylene resin sheet having a thickness of 80 μm (also referred to as "polypropylene-based resin sheet PO-1")) that had been subjected to corona discharge treatment on both sides, and then dried to form a 3 μm-thick wood grain pattern decorative layer. Next, a back primer layer ink containing a two-component curing type urethane-nitrocellulose mixed resin was applied to the other surface of the substrate and dried to form a back primer layer having a thickness of 3 μm. Next, a 3 μm-thick adhesive layer made of a urethane resin-based adhesive was formed on the decorative layer, and then a polypropylene-based resin was hot-melt extruded onto the adhesive layer using a T-die extruder to form an 80 μm-thick transparent resin layer. Next, the surface of the transparent resin layer was subjected to a corona discharge treatment, and then a primer layer ink having the following composition was applied onto the transparent resin layer by gravure printing and dried to form a primer layer having a thickness of 4 μm. Next, an ink for a surface protective layer (composition A) having the following composition was applied onto the primer layer by roll coating to form an uncured surface protective layer, and then the ink was irradiated with an electron beam (applied voltage: 175 KeV, 5 Mrad (5 kGy)) to crosslink and cure composition A, thereby forming a surface protective layer with a thickness of 5 μm. Next, embossing was performed from above the surface protective layer to form an uneven pattern of wood grain vessel grooves with recesses up to a maximum depth of 50 μm, thereby obtaining the decorative sheet of Example 1. The obtained decorative sheet was evaluated and measured according to the above-mentioned methods. The evaluation and measurement results are shown in Table 2.

[0108] <Ink for primer layer> 100 parts by weight of a mixture of polycarbonate-based urethane-acrylic copolymer and acrylic polyol Hexamethylene diisocyanate 5 parts by weight - 3 parts by weight of ultraviolet absorber (hydroxyphenyltriazine, BASF's product name "TUNUVIN479") Ultraviolet absorber (hydroxyphenyltriazine, BASF's product name "TUNUVIN400") 12 parts by weight

[0109] <Ink for surface protective layer (Composition A)> Ionizing radiation curable resin composition (trifunctional urethane acrylate oligomer having a weight average molecular weight of 4000) 100 parts by mass 1 part by mass of a radical scavenger having an ethylenic double bond polymerizable with the ionizing radiation curable resin composition (pentamethylpiperidinyl methacrylate) (non-amino ether type, number of ethylenic double bonds: 1) 1 part by mass of radical scavenger ii-a (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate) (amino ether type, having no functional groups reactive with functional groups of the components of the primer layer) that does not have an ethylenic double bond polymerizable in the ionizing radiation curable resin composition -UV absorber (hydroxyphenyltriazine, TUNUVIN 479, manufactured by BASF) 2 parts by weight Hindered phenol antioxidant 1 part by weight

[0110] [Examples 2 to 7], [Comparative Examples 1 to 5] Decorative sheets of Examples 2 to 7 and Comparative Examples 1 to 5 were obtained in the same manner as in Example 1, except that the blending amounts of radical scavenger i and radical scavenger ii-a relative to the ionizing radiation curable resin composition in composition A were changed as shown in Table 1. The decorative sheets obtained were evaluated and measured according to the methods described above. The evaluation and measurement results are shown in Table 2.

[0111] [Example 8] A decorative sheet of Example 8 was obtained in the same manner as in Example 1, except that the radical scavenger ii-a in composition A was changed to the following radical scavenger ii-b. The decorative sheet obtained was evaluated and measured according to the above-mentioned methods. The evaluation and measurement results are shown in Table 2. <Radical scavenger ii-b of Example 8> 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine (amino ether type, has a functional group (hydroxyl group) that can react with the functional group (isocyanate group) of the components of the primer layer)

[0112] [Examples 9 to 11], [Comparative Examples 6 to 7] Decorative sheets of Examples 9 to 11 and Comparative Examples 6 to 7 were produced in the same manner as in Example 1, except that the substrate and transparent resin layer in Example 1 were replaced with those shown in Table 3. The decorative sheets obtained were evaluated and measured according to the above-mentioned methods. The evaluation and measurement results are shown in Table 3.

[0113] [Table 2]

[0114] [Table 3]

[0115] The materials and thicknesses of the substrates and transparent resin layers used in the respective Examples and Comparative Examples in Tables 2 and 3 above are as follows. PO-1: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 80 μm, crystallinity: 70%) PO-2: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 60 μm, crystallinity: 50%) PO-3: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 60 μm, crystallinity: 40%) PO-4: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 100 μm, crystallinity: 70%) PVC1: Polyvinyl chloride resin sheet (thickness: 120 μm) It was produced by extrusion molding a resin composition in which 38 parts by mass of a phthalate ester plasticizer (undecyl phthalate (DUP)) was added as a plasticizer to 100 parts by mass of polyvinyl chloride resin. PVC2: Polyvinyl chloride resin sheet (thickness: 120 μm) PVC1 was prepared in the same manner as PVC1, except that the plasticizer in PVC1 was a polyester-based plasticizer (adipic acid-based polyester) and its content was 33 parts by mass per 100 parts by mass of polyvinyl chloride resin. PO-A: Polypropylene resin (thickness: 80μm) PO-B: Polypropylene resin (thickness: 40μm) PO-C: Polypropylene resin (thickness: 100μm)

[0116] From the results in Table 2, it can be confirmed that the decorative sheets of Examples 1 to 8 are excellent in weather resistance and can suppress the deterioration of the scratch resistance of the surface protective layer. 2 ·45g / m for 24 hours or more 2 -Because the durability is less than 24 hours, it has been confirmed that the coating has excellent workability, long-term adhesion and processing characteristics. In addition, the results in Table 3 show that the decorative sheets of Examples 9 to 11 use a predetermined radical scavenger and have a moisture permeability of 0.75 g / m 2 ·45g / m for 24 hours or more 2 24h or less, it was confirmed that the decorative sheet of Comparative Example 6 has excellent weather resistance, scratch resistance, and bleed-out suppression effects, as well as excellent application suitability, long-term adhesion, and processing characteristics. On the other hand, the decorative sheet of Comparative Example 6 has a moisture permeability of 45g / m 2 The decorative sheet of Comparative Example 7 has a moisture permeability of 0.75 g / m 2 -Because it was less than 24 hours, it was confirmed that excellent long-term adhesion could not be obtained. [Industrial Applicability]

[0117] The decorative sheet of the present invention has excellent weather resistance and can suppress a decrease in the scratch resistance of the surface protective layer, and also has high initial adhesion strength during the construction process, making it suitable for construction, and does not peel even after long-term use, demonstrating excellent long-term adhesion. Therefore, it is suitable for use as a decorative sheet for components that are used in environments exposed to direct sunlight, such as exterior components such as entrance doors, and building materials such as window frames and doors. [Explanation of symbols]

[0118] 100: Decorative sheet 10: Surface protection 20: Primer layer 30: Transparent resin layer 40:Decorative layer 50: Base material

Claims

1. A decorative sheet having a surface protective layer on a substrate, the surface protective layer being a layer obtained by crosslinking and curing a composition A containing an ionizing radiation curable resin composition and a radical scavenger, the radical scavenger comprising a radical scavenger i having an ethylenic double bond polymerizable with the ionizing radiation curable resin composition and a radical scavenger ii having no ethylenic double bond polymerizable with the ionizing radiation curable resin composition, the content of the radical scavenger in the composition A being 0.5 parts by mass or more and less than 10.0 parts by mass relative to 100 parts by mass of the ionizing radiation curable resin composition, the moisture permeability of the decorative sheet being 0.75 g / m or less as measured in accordance with a moisture permeability test method for moisture-proof packaging materials (cup method) as specified in JIS Z0208:1976. ２ ・45g / m for 24 hours or more ２ - Decorative sheet lasting less than 24 hours.

2. 2. The decorative sheet according to claim 1, wherein the blending ratio of said radical scavenger i to said radical scavenger ii is from 8:2 to 2:8 by mass.

3. 3. The decorative sheet according to claim 1, wherein the radical scavenger is a hindered amine radical scavenger.

4. The decorative sheet according to any one of claims 1 to 3, wherein said composition A further comprises an ultraviolet absorbing agent.

5. The decorative sheet according to any one of claims 1 to 4, further comprising a primer layer in contact with the surface of the surface protective layer facing the substrate.

6. 6. The decorative sheet according to claim 5, wherein said radical scavenger ii has a functional group capable of reacting with a functional group possessed by a component of said primer layer.

7. The decorative sheet according to claim 6 , wherein said radical scavenger ii has a hydroxyl group, and a component of said primer layer has an isocyanate group.

8. The decorative sheet according to any one of claims 1 to 7, further comprising a decorative layer between the substrate and the surface protective layer.

9. The decorative sheet according to any one of claims 1 to 8, wherein the substrate comprises titanium dioxide.

10. A decorative material comprising an adherend and the decorative sheet according to any one of claims 1 to 9.

11. The decorative material according to claim 10, further comprising an adhesive layer made of a urethane adhesive between the decorative sheet and the adherend.

12. The decorative material according to claim 11, wherein the urethane adhesive is a moisture-curing adhesive.

13. The decorative material according to any one of claims 10 to 12, wherein the adherend is a metal member or a resin member.

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