JP7415403B2 - Decorative sheets and decorative materials - Google Patents

Description

The present invention relates to a decorative sheet and a decorative material using the same.

In addition to interior and exterior materials for buildings such as walls, ceilings, floors, and entrance doors, fittings and fixtures such as window frames, doors, handrails, skirting boards, edges, and moldings, kitchens, furniture, and light electrical appliances, For surface decorative boards of cabinets such as OA equipment, interior materials or exterior members of vehicles, metal members such as steel plates, resin members, and wood members are generally used as adherends, and decorative sheets are applied to these adherends. A decorative material made by pasting together is used. In particular, when the decorative material to which the decorative sheet is attached is used outdoors, the weather resistance of the decorative sheet decreases if it is exposed to ultraviolet rays in sunlight or lighting rays for a long time, and as a result, the design quality There is a problem that the performance is impaired. For example, if you try to use it on parts that are used in environments exposed to direct sunlight, such as exterior parts such as entrance doors, window frames, door fittings, etc., cracking and peeling may occur and the product may not be able to withstand long-term use. there were.

In order to solve these problems, it has been proposed to improve weather resistance by incorporating an ultraviolet absorber and a light stabilizer into the surface protective layer and primer layer of the decorative sheet.
It is known that there are generally two types of ultraviolet absorbers: organic ultraviolet absorbers and inorganic ultraviolet absorbers (ultraviolet shielding agents). It is known that inorganic ultraviolet screening agents include titanium oxide, zinc oxide, iron oxide, cerium oxide, zirconium oxide, bismuth oxide, and the like (for example, Patent Document 1). Weather resistance can be improved by using an organic ultraviolet absorber and an inorganic ultraviolet shielding agent together.

Furthermore, in order to impart various functions to decorative materials, it is known that various additives are added to impart various functions. For example, by adding a matting agent, it is possible to control the surface gloss and obtain a decorative material with a matte effect (for example, Patent Document 2)

Japanese Patent Application Publication No. 2018-171839 Japanese Patent Application Publication No. 2009-255502

An object of the present invention is to provide a decorative sheet having a matte effect and excellent weather resistance, and a decorative material having the decorative sheet.

As the inorganic ultraviolet screening agent, zinc oxide is preferably used from the viewpoint of absorption wavelength range and weather resistance. However, the inventors of the present application faced the problem that sufficient weather resistance could not be obtained in a decorative sheet with a matte design, even when a surface protective layer containing zinc oxide was formed. As a result of intensive investigation into the cause of this problem, it was discovered that the combined use of a matting agent and zinc oxide to impart a matte design greatly affects the weather resistance of the decorative sheet. Therefore, in view of these circumstances, the present invention was developed in order to realize a decorative material that has high weather resistance and a matte effect.

In order to solve the above problems, the present invention provides the following [1] to [10].
[1] A decorative sheet having a surface protective layer on the outermost layer, the surface protective layer containing a cured product of a curable resin composition and an inorganic ultraviolet screening agent, and substantially containing a matting agent. wherein the inorganic ultraviolet shielding agent is zinc oxide, and the outermost surface of the surface protective layer has fine irregularities.
[2] The decorative sheet according to [1], wherein the maximum height (Sz) of the fine irregularities measured in accordance with ISO25178-6:2010 is 4.0 μm or more.
[3] The decorative sheet according to [1] or [2], wherein the arithmetic mean height (Sa) of the fine irregularities measured in accordance with ISO25178-6:2010 is 0.5 μm or more.
[4] The maximum height (Sz) of the fine irregularities measured in accordance with ISO25178-6:2010 relative to the arithmetic mean height (Sa) of the fine irregularities measured in accordance with ISO25178-6:2010. The decorative sheet according to any one of [1] to [3], wherein the ratio (Sz/Sa) is 40 or less.
[5] The decorative sheet according to any one of [1] to [4], wherein the zinc oxide is particles having an average particle size of 0.5 nm or more and 300 nm or less.
[6] The decorative sheet according to any one of [1] to [5], wherein the zinc oxide content is 1 part by mass or more and 50 parts by mass or less, based on 100 parts by mass of the curable resin composition.
[7] The decorative sheet according to any one of [1] to [6], wherein the surface protective layer further contains an organic ultraviolet absorber.
[8] The decorative sheet according to any one of [1] to [7], further comprising at least one of a primer layer and a transparent resin layer on the back side of the surface protective layer.
[9] The decorative sheet according to any one of [1] to [8], wherein the curable resin composition is an ionizing radiation curable resin.
[10] The decorative sheet according to [7], wherein the organic UV absorber is a triazine UV absorber.
[11] A decorative material comprising an adherend and the decorative sheet according to any one of [1] to [10].

According to the present invention, it is possible to obtain a decorative sheet that substantially does not contain a matting agent, has a matting effect, and has further improved weather resistance, and a decorative material including the same.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram explaining an example of the decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram explaining an example of the decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram explaining an example of the decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram explaining an example of the decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram explaining an example of the decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram explaining an example of the decorative material of this invention.

[Cosmetic sheet]
The decorative sheet of the present invention is a decorative sheet having a surface protective layer on the outermost layer, the surface protective layer containing a cured product of a curable resin composition, an inorganic ultraviolet shielding agent, and a matting agent. The inorganic ultraviolet screening agent is zinc oxide, and the outermost surface of the surface protective layer has fine irregularities.

As a result of the inventors' studies, a decorative sheet that forms a surface protective layer using both zinc oxide and a matting agent is superior to a decorative sheet that forms a surface protective layer containing only zinc oxide without adding a matting agent. It was found that the weather resistance was poor. Furthermore, it has been found that weather resistance is significantly inferior, especially when silica is used as a matting agent. It is thought that the interaction between zinc oxide and the matting agent (especially silica) affected weather resistance, but the mechanism has not been elucidated.
On the other hand, if the design of the decorative sheet requires a matte feel, it is easy to add a matting agent in terms of process. However, the decorative sheet of the present invention has a matte design by adding fine irregularities to the outermost surface of the surface protective layer (the surface opposite to the surface in contact with other layers) without adding a matting agent. , and has excellent weather resistance.

1 to 5 are schematic cross-sectional views illustrating an example of the decorative sheet of the present invention. However, the structure of the decorative sheet of the present invention is not limited to those shown in FIGS. 1 to 5.
The decorative sheet 10 shown in FIG. 1 has a surface protection layer 11 on one side of a sheet-like base material 12. The decorative sheet 10 shown in FIG. 2 has a decorative layer 13 between the base material 12 and the surface protection layer 11. In the decorative sheet 10 shown in FIG. 3, a decorative layer 13, a transparent resin layer 14, and a surface protection layer 15 are laminated in this order on a base material 12. An adhesive layer may be formed between the decorative layer 13 and the transparent resin layer 14. The decorative sheet 10 shown in FIG. 4 has a structure that further includes a primer layer 15 between the transparent resin layer 14 and the surface protection layer 11. In the configurations shown in FIGS. 1 to 4, a back primer layer may be formed on the other surface of the base material 12 (the surface opposite to the surface on which the surface protective layer 11 is formed).
The decorative sheet 10 in FIG. 5 has a surface protective layer 11 on one side of a transparent resin layer 14, and a decorative layer 13 on the other side. In this case, the transparent resin layer serves as the base material. In the decorative sheet of FIG. 5, a primer layer may be further formed between the transparent resin layer and the surface protection layer.
Each layer constituting the decorative sheet of the present invention will be explained below.

[Surface protective layer]
The surface protective layer is located at the outermost layer when the decorative sheet is adhered to the adherend. The surface protective layer of the decorative sheet of the present invention contains a cured product of a curable resin composition and zinc oxide as an inorganic ultraviolet shielding agent, and substantially does not contain a matting agent. The thickness of the surface protective layer is not particularly limited, but is preferably 1 μm or more and 25 μm or less, more preferably 1 μm or more and 20 μm or less.

A matting agent is an additive that imparts a matte effect to the surface. Examples of the matting agent include inorganic fine powder and organic filler. Examples of the inorganic fine powder include silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and fine silicate powder. Examples of organic fillers include fillers made of acrylic, urethane, nylon, polypropylene, urea resins, etc., styrene crosslinked fillers, and benzoguanamine crosslinked fillers. Note that the filler also contains beads.
In the present invention, "substantially free of" means that the amount of the matting agent is 0.1 part by mass or less, more preferably 0.01 part by mass or less, when the total mass of the surface protective layer is 100. means.

<Curable resin composition>
The surface protective layer of the decorative sheet of the present invention is required to contain a cured product of a curable resin composition. As the resin component of the curable resin composition, ionizing radiation curable resins, two-component curable resins, and thermosetting resins can be used. Among these resins, ionizing radiation-curable resins are preferably used from the viewpoint of heat resistance, scratch resistance, and suppression of bleed-out of inorganic UV-screening agents. A curable resin and a thermosetting resin can be used together. It may also be of a so-called hybrid type, in which a curable resin and a thermoplastic resin are used together.

<Ionizing radiation curable resin>
The ionizing radiation-curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation, and has an ionizing radiation-curable functional group. Here, the ionizing radiation-curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, and preferably includes functional groups having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. It will be done. In addition, in this specification, "(meth)acryloyl group" means "acryloyl group or methacryloyl group." In addition, ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quantum that can polymerize or crosslink molecules, and ultraviolet rays (UV) or electron beams (EB) are usually used, but other It also includes electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams.
The ionizing radiation-curable resin can be appropriately selected from conventionally used polymerizable monomers and polymerizable oligomers.

As the polymerizable monomer, (meth)acrylate monomers having a radically polymerizable unsaturated group in the molecule are preferred, and polyfunctional (meth)acrylate monomers are particularly preferred.
Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group.
From the viewpoint of improving processing properties, scratch resistance, and weather resistance, the number of functional groups is preferably 2 or more and 8 or less. These polyfunctional (meth)acrylate monomers may be used alone or in combination. Alternatively, a composition may be used in which one or more of these polyfunctional (meth)acrylate monomers and one or more of the below-mentioned polymerizable oligomers are mixed. By preparing a composition in which both are mixed, it is possible to adjust the crosslink density, molecular weight between crosslinks, etc. of the cured product, and adjust various physical properties of the cured product.

Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group. Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, and the like.
In addition, other polymerizable oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers that have (meth)acrylate groups in their side chains, and silicone (meth)acrylate oligomers that have polysiloxane bonds in their main chains. , aminoplast resin (meth)acrylate oligomer modified from aminoplast resin with many reactive groups in a small molecule, or molecules of novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having cationically polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination. From the viewpoint of improving processing properties, scratch resistance and weather resistance, urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, Acrylic (meth)acrylate oligomers are preferred, urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are more preferred, and urethane (meth)acrylate oligomers are even more preferred.

The number of functional groups in these polymerizable oligomers is preferably 2 or more and 8 or less from the viewpoint of improving processing characteristics, scratch resistance, and weather resistance.
Moreover, the weight average molecular weight of these polymerizable oligomers is preferably 700 or more and 7,500 or less, and more preferably 1,000 or more and 7,000 or less, from the viewpoint of improving processing characteristics, scratch resistance, and weather resistance. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted to standard polystyrene.

In the present invention, monofunctional (meth)acrylates can be appropriately used in combination with polyfunctional (meth)acrylates, etc., for the purpose of reducing the viscosity, etc., as long as the purpose of the present invention is not impaired. These monofunctional (meth)acrylates may be used alone or in combination.

In the present invention, the ionizing radiation-curable resin preferably contains a polymerizable oligomer from the viewpoint of improving processing characteristics, scratch resistance, and weather resistance. The content of the polymerizable oligomer in the ionizing radiation-curable resin is preferably 80% by mass or more.

<Two-component curing resin>
When using a two-component curable resin for the surface protective layer, the two-component curable resin may be a single polymer polyol such as vinyl chloride-vinyl acetate copolymer, polyester, urethane, or acrylic, or a mixture thereof. On the other hand, those to which a curing agent is added immediately before use are used. The curing agent is preferably a polyvalent isocyanate, such as aromatic isocyanates such as 2,4-tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, , 2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and other aliphatic (or cycloaliphatic) isocyanates, or adducts or large amounts of the above various isocyanates For example, adducts of tolylene diisocyanate, tolylene diisocyanate trimers, etc. can also be used. The polymer polyol is preferably a polyester polyol, such as poly(ethylene adipate), poly(butylene adipate), poly(neopentyl adipate), poly(hexamethylene adipate), poly(butylene azelaate), poly(butylene seba). (Kate), polycaprolactone, etc. are used. Furthermore, acrylic polymer polyols can also be preferably used.

<Thermosetting resin>
When a thermosetting resin is used for the surface protective layer, examples of the thermosetting resin include epoxy resin, unsaturated polyester resin, diallyl phthalate resin, urea resin, and melamine resin.

<Thermoplastic resin>
When a thermoplastic resin is mixed and used in the surface protective layer, a thermoplastic resin that can be used for the base material described below can be used.

<Inorganic UV screening agent>
The surface protective layer is required to contain zinc oxide as an inorganic ultraviolet shielding agent. The inorganic ultraviolet shielding agent is a component that can improve the weather resistance of the decorative sheet because it is less susceptible to deterioration due to ultraviolet light than the organic ultraviolet absorbers described below.

Zinc oxide exists in the form of particles dispersed in the resin constituting the surface protective layer. In the present invention, zinc oxide particles having an average particle size of 0.5 nm or more and 300 nm or less can be suitably used. By setting the average particle size within the above range, transparency of the surface protective layer can be ensured, and good design of the decorative sheet can be ensured. The average particle size is more preferably 1 nm or more. Further, the average particle diameter is preferably 200 nm or less, more preferably 100 nm or less. Here, the "average particle size" can be determined as the number average value D50 in particle size distribution measurement by laser light diffraction method.
Further, the content of zinc oxide contained in the surface protective layer is preferably 1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the cured product of the curable resin composition. The transparency of the surface protective layer can be ensured, and the good design of the decorative sheet can be ensured. Considering the ultraviolet shielding effect, the content of zinc oxide is preferably 5 parts by mass or more, more preferably 10 parts by mass or more. Furthermore, in consideration of transparency, the content of zinc oxide is preferably 45 parts by mass or less, more preferably 40 parts by mass or less.

In addition, in the present invention, other inorganic ultraviolet shielding agents may be added to the surface protective layer in addition to zinc oxide. Examples of inorganic ultraviolet screening agents other than zinc oxide include titanium oxide, iron oxide, cerium oxide, zirconium oxide, and bismuth oxide. However, in consideration of photodeterioration due to photocatalytic action, it is preferable not to contain titanium oxide. When the surface protective layer contains an inorganic ultraviolet screening agent other than zinc oxide, in consideration of transparency, the total content of the inorganic ultraviolet screening agent is preferably 5 parts by mass or more and 40 parts by mass or less.

<Organic ultraviolet absorber>
The surface protective layer may further contain an organic ultraviolet absorber. Organic ultraviolet absorbers have superior transparency compared to the above-mentioned inorganic ultraviolet shielding agents.
Although the organic UV absorber is not particularly limited, preferred examples of the organic UV absorber include benzotriazole, triazine, benzophenone, salicylate, and acrylonitrile. Among these, triazine type materials are more preferable because they have high ultraviolet absorption ability and are resistant to deterioration even when exposed to high energy such as ultraviolet rays. Further, as the ultraviolet absorber, an ultraviolet absorber having an electron beam reactive group in the molecule can also be used. These ultraviolet absorbers can be used alone or in combination.

Among triazine-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers in which three at least one organic group selected from a hydroxyphenyl group, an alkoxyphenyl group, and an organic group containing these groups are linked to a triazine ring are more preferable. , hydroxyphenyltriazine ultraviolet absorbers represented by the following general formula (1) are more preferred. Since the surface protective layer is the layer located on the outermost surface of the decorative sheet, it is preferably one that does not easily bleed out from the layer, and since the hydroxyphenyltriazine ultraviolet absorber represented by the following general formula (1) has a branched structure. It is expected that it will be less likely to bleed out, and from the viewpoint of weather resistance, it is particularly preferred as an ultraviolet absorber used in the surface protective layer.

In general formula (1), R ¹¹ is a divalent organic group, and R ¹² is an ester group represented by -C(=O)OR ¹⁵ or an organyloxy group represented by -OR ¹⁶ . , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a monovalent organic group, and n ₁₁ and n ₁₂ are each independently an integer of 1 to 5.

Examples of the divalent organic group for ^R11 include aliphatic hydrocarbon groups such as alkylene groups and alkenylene groups, and from the viewpoint of weather resistance, alkylene groups are preferable, and the number of carbon atoms thereof is preferably 1 or more, with an upper limit of It is preferably 20 or less, more preferably 12 or less, even more preferably 8 or less, particularly preferably 4 or less. The alkylene group and alkenylene group may be linear, branched, or cyclic, but linear or branched are preferable.
Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,3-propylene, 1,2-propylene, 2,2-propylene, etc. Various propylene groups (hereinafter, "various" refers to those including linear, branched, and isomers 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, various icosylene groups Examples include groups.

Examples of monovalent organic groups for R ¹³ and R ¹⁴ include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and arylalkyl groups. A hydrogen group is preferred, and an alkyl group and an aryl group are preferred.
Examples of alkyl groups include alkyl groups preferably having 1 to 20 carbon atoms, such as methyl groups, ethyl groups, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various nonyl groups, Examples include 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 number of carbon atoms in the alkyl group of the monovalent organic group R ¹³ and R ¹⁴ is more preferably 16 or less, even more preferably 8 or less, even more preferably 4 or less, and particularly preferably 2 or less. That is, the monovalent alkyl group for R ¹³ and R ¹⁴ is particularly preferably a methyl group or an ethyl group. Furthermore, in consideration of availability, a methyl group is preferred.

The aryl group for R ¹³ and R ¹⁴ includes an aryl group having preferably 6 or more carbon atoms, preferably 20 or less carbon atoms, more preferably 12 or less carbon atoms, and even more preferably 10 or less carbon atoms, such as phenyl groups and various methylphenyl groups. , various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, and the like. As the arylalkyl group, the number of carbon atoms is preferably 7 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and even more preferably 10 or less, such as benzyl group, phenethyl group, various phenylpropyl groups, Examples include various phenylbutyl groups, various methylbenzyl groups, various ethylbenzyl groups, various propylbenzyl groups, various butylbenzyl groups, and various hexylbenzyl groups. Among these, phenyl group is preferred.

Examples of monovalent organic groups for R ¹⁵ and R ¹⁶ include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and arylalkyl groups, and aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups are preferable. , an alkyl group is more preferred. That is, R ¹² is preferably an alkyl ester group, an alkenyl ester group, an alkoxy group, or an alkenyloxy group, and more preferably an alkyl ester group or an alkoxy group.
Examples of the alkyl group include the alkyl groups exemplified as the monovalent organic groups for R ¹³ and R ¹⁴ above. The number of carbon atoms in the alkyl group of R ¹³ and R ¹⁴ is preferably 1 or more, more preferably 2 or more, even more preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, and even more preferably 14 or less. It is.

As an alkenyl group, an alkenyl group having preferably 2 or more carbon atoms, more preferably 3 or more carbon atoms, still more preferably 6 or more carbon atoms, and an upper limit of preferably 20 or less carbon atoms, more preferably 16 carbon atoms or less, and even more preferably 12 carbon atoms or less, such as vinyl groups, 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, Examples include various hexadecenyl groups, various heptadecenyl groups, various octadecenyl groups, various nonadecenyl groups, and various icosenyl groups.
The above R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may have a substituent such as a halogen atom, a hydroxyl group, an amino group, or an alkyl group having 1 or more and 4 or less carbon atoms. good.

n ₁₁ and n ₁₂ are each independently an integer of 1 to 5, preferably an integer of 1 to 3, more preferably an integer of 1 to 2. When n ₁₁ and n ₁₂ are integers of 2 or more, a plurality of R ¹³ and R ¹⁴ may be the same or different, and from the viewpoint of availability, they are preferably the same.

More specifically, in the hydroxyphenyltriazine compound represented by the general formula (1), R ¹¹ is an alkylene group having 1 to 20 carbon atoms, R ¹² is R ¹⁵ and R ¹⁶ is 1 to 20 carbon atoms. An alkyl ester group or an alkoxy group which is the following alkyl group, R ¹³ and R ¹⁴ are an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, and n ₁₁ and n ₁₂ are 1 or 2 is preferable, and R ¹¹ is an alkylene group having 1 to 12 carbon atoms, and R ¹² is an alkyl ester group or alkoxy in which R ¹⁵ and R ¹⁶ are alkyl groups having 2 to 16 carbon atoms. A hydroxyphenyltriazine compound in which R ¹³ and R ¹⁴ are an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms, and n ₁₁ and n ₁₂ are 1 or 2 is more preferable; R ¹¹ is an alkylene group having 1 to 8 carbon atoms, R ¹² is an alkyl ester group or alkoxy group in which R ¹⁵ and R ¹⁶ are alkyl groups having 6 to 14 carbon atoms, and R ¹³ and R ¹⁴ are More preferably, the compound is an aryl group having 6 to 10 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and a hydroxyphenyltriazine compound in which n ₁₁ and n ₁₂ are 1 or 2. Among them, R ¹¹ is an alkylene group having a hydroxyl group having 1 or more and 4 or less carbon atoms, R ¹² is an alkoxy group where R ¹⁶ is an alkyl group having 1 or 2 carbon atoms, and R ¹³ and R ¹⁴ are methyl groups. , n ₁₁ and n ₁₂ are 2 hydroxyphenyltriazine compounds, R ¹¹ is an alkylene group having 1 to 4 carbon atoms, R ¹² is an ester group in which R ¹⁵ is an alkyl group having 8 carbon atoms, and R Hydroxyphenyltriazine compounds in which ¹³ and R ¹⁴ are phenyl groups and n ₁₁ and n ₁₂ are 1 are particularly preferred.

More specifically, the hydroxyphenyltriazine compound represented by the general formula (1) is represented by the following chemical formula (2), in which R ¹¹ is a propylene group having a hydroxyl group (hydroxypropylene group), and R ¹² is R A hydroxyphenyltriazine compound in which ¹⁶ is an alkyl group having 12 or 13 carbon atoms, R ¹³ and R ¹⁴ are methyl groups, and n ₁₁ and n ₁₂ are 2, that is, 2-(2-hydroxy-4 -(2-hydroxy-[3-dodecyloxypropoxy]phenyl)-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-( 2-Hydroxy-[3-tridesiloxypropoxy]phenyl)-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or a mixture thereof is preferred, and this hydroxyphenyltriazine compound is For example, it is available as a commercial product (TINUVIN400, manufactured by BASF).

Furthermore, as the hydroxyphenyltriazine compound represented by the general formula (1), more specifically, an ester represented by the following chemical formula (3) in which R ¹¹ is an ethylene group, R ¹² is an isooctyl group, and R ¹⁵ is an isooctyl group. A hydroxyphenyltriazine compound in which R ¹³ and R ¹⁴ are phenyl groups, and n ₁₁ and n ₁₂ are 1, that is, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4 ,6-bis(4-phenylphenyl)-1,3,5-triazine is also preferred, and this hydroxyphenyltriazine compound is available, for example, as a commercial product ("TINUVIN479", manufactured by BASF).

<Other additives>
The surface protective layer of the present invention may contain various additives as long as the object of the present invention is not impaired. Various additives include, for example, light stabilizers, abrasion resistance improvers, polymerization accelerators, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, Examples include coupling agents, plasticizers, antifoaming agents, solvents, colorants, antioxidants, and the like.

<Fine irregularities on the surface protective layer>
The surface protective layer is required to have fine irregularities on the outermost surface. The fine irregularities can scatter visible light and give a matte feel to the decorative sheet. It is particularly preferable that the fine irregularities are provided over the entire surface of the surface protective layer.

The maximum height (Sz) of the fine irregularities measured in accordance with ISO25178-6:2010 is preferably 0.5 μm or more, more preferably 1.0 μm or more, and 4.0 μm or more. It is even more preferable. By satisfying the above numerical values, a matte feel can be imparted to the decorative sheet. However, if Sz becomes large, the visibility of the decoration (for example, decorative layer or base material) lower than the surface protective layer may decrease, and the design may be inferior. Therefore, Sz is preferably 50 μm or less, It is more preferably 45 μm or less, and even more preferably 30 μm or less.

The arithmetic mean height (Sa) measured in accordance with ISO25178-6:2010 is preferably 0.5 μm or more, more preferably 0.7 μm or more, and preferably 1.0 μm or more. More preferred. By satisfying the above numerical values, a matte feel can be imparted to the decorative sheet. However, when Sa becomes large, the visibility of the decoration (for example, a decoration layer or a base material) lower than the surface protective layer decreases, and the design may be inferior. Considering the above circumstances, Sa is preferably 50 μm or less, more preferably 40 μm or less.

Note that Sz and Sa are average values of values measured at 10 or more measurement points within the surface of the decorative sheet within a measurement range of 300 μm x 300 μm to 800 μm x 800 μm.

Further, the Sz/Sa of the fine irregularities is preferably 40 or less, more preferably 20 or less. A small Sz/Sa means that the fine unevenness is uniform and does not have any unevenness that stands out from the average height difference of the unevenness. When Sz/Sa satisfies the above range, visibility becomes good. Furthermore, it is possible to suppress damage when peeling off the shaped sheet.

Since the decorative sheet of the present invention has the above-mentioned fine irregularities on the outermost surface of the surface protective layer, it is possible to impart a matte feel to the decorative sheet even without substantially containing a matting agent.
Specifically, in the decorative sheet of the present invention, the 60° gloss of the surface of the surface protective layer measured by a method based on JIS Z8741:1997 is preferably 20% or less, and preferably 15% or less. is more preferable.

In the present invention, the shape of the unevenness, the width (pitch) of the repeating unit, etc. are not particularly limited as long as the above-mentioned Sz, Sa and gloss are satisfied.

As a method for imparting fine irregularities to the outermost surface of the surface protective layer, known methods such as transfer using a shaped sheet and embossing can be applied. In particular, it is advantageous to employ transfer using a shaped sheet because it is possible to form fine irregularities of a desired shape with high precision.

In the transfer using a shaped sheet, first, a laminate is formed as a base material or a lower layer of the surface protective layer illustrated in FIGS. 1 to 5. A coating solution for forming a surface protective layer containing zinc oxide, a curable resin composition, and other additives is applied onto the base material or laminate. The coating method is preferably a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, or die coating, preferably die coating. Further, it is preferable to apply the coating so that the thickness after curing falls within the above-mentioned range.

The shaped sheet has, on its surface, an uneven shape complementary to the fine unevenness provided on the surface protective layer. The shaping sheet is placed on and brought into contact with the coating film so that the surface of the shaping sheet on which the uneven shape is formed faces the coating film. In this state, the resin of the coating film is cured. After curing, desired fine irregularities are formed on the surface of the surface protective layer by peeling off the shaped sheet.

Peeling discharge may occur on the surface of the surface protective layer when the shaped sheet is peeled off or when the decorative sheet is separated from the transport roll or drum during the manufacturing process. Since the decorative sheet of the present invention contains electrically conductive zinc oxide in the surface protective layer, peeling discharge is suppressed, and damage to fine irregularities during manufacturing can also be suppressed.

〔Base material〕
As the resin used for the base material, any resin that is normally used as a base material for decorative sheets can be used without limitation, and thermoplastic resins are typically used. As the thermoplastic resin, for example, polyolefin resins such as polypropylene and polyethylene, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, vinyl chloride resins, etc. are used. Ru. Among these, polyolefin resins, polyester resins, polycarbonate resins, and ABS resins are preferred, and polyolefin resins are particularly preferred, considering processing characteristics. In the present invention, these resins can be used alone or in combination.

Polyolefin resins are not particularly limited, and include, for example, polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate. Examples include copolymers, ethylene-acrylic acid copolymers, ethylene-propylene-butene copolymers, and polyolefin thermoplastic elastomers. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, and propylene-butene copolymer are preferred.

The base material may be colored. There is no particular restriction on the manner of coloring, and transparent coloring or opaque coloring (hidden coloring) may be used, and these can be arbitrarily selected.
Preferably, the base material contains a white pigment. By containing a white pigment, it is possible to hide the background color of the adherend to which the decorative sheet is attached, providing better design properties and improving the color stability of the resulting decorative sheet.

Examples of the white pigment include titanium oxide (titanium white), lead white, antimony white, titanium dioxide-coated mica, and the like, and these can be used alone or in combination. In the present invention, titanium oxide (titanium white) is preferred in consideration of concealing properties (color development), ease of handling, and the like.
There are anatase type, brookite type, and rutile type of titanium oxide, and any of them can be used, but the rutile type is preferable in consideration of excellent hiding power (color development) and weather resistance. Rutile-type titanium oxide has low photocatalytic activity, so even if it is used in an environment exposed to direct sunlight, it is difficult to cause a photocatalytic reaction, resulting in deterioration of the base material, decorative layer, and other optional layers due to the photocatalytic reaction. As a result, weather resistance is improved.

The white pigment is preferably surface-treated from the viewpoint of selecting one with low photocatalytic activity in consideration of weather resistance. Preferred examples of the surface-treated white pigment include those whose surface has been treated with an inorganic metal hydrated oxide and whose surface is covered with inorganic hydrated oxide fine particles. Preferred examples of the inorganic metal hydrate include alumina, silica, titania, zirconia, tin oxide, antimony oxide, zinc oxide, and the like. In addition, titanium oxide with an untreated surface or titanium oxide whose surface has been surface-treated with the above-mentioned inorganic metal hydrated oxide can be coated with a coupling agent such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, or a silicone oil. Preferred examples include those whose surfaces are made hydrophobic or lipophilic by surface treatment with fluorine-based oil or the like. In the present invention, a white pigment that has been subjected to the above surface treatment alone or a combination of a plurality of surface treatments can be used.
In the present invention, from the viewpoint of obtaining excellent hiding properties, surface treatment with alumina, silica, and zinc oxide is preferred, surface treatment with alumina and silica is more preferred, and surface treatment with alumina and silica is particularly preferred.

The average particle diameter of the white pigment is preferably 0.02 μm or more and 1.5 μm or less, more preferably 0.15 μm or more and 0.5 μm or less, and even more preferably 0.1 μm or more and 0.3 μm or less. When the average particle diameter of the white pigment is within the above range, excellent color development can be obtained, and high hiding power and designability can be obtained. Here, the average particle diameter is a value that can be determined as the mass average value D50 in particle size distribution measurement using laser light diffraction.

The content of the white pigment in the base material may be adjusted as appropriate depending on whether transparent coloring or opaque coloring (hidden coloring) is used. For example, with respect to 100 parts by mass of the resin constituting the base material, the amount is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 40 parts by mass or less, still more preferably 5 parts by mass or more and 30 parts by mass or less, and 5 parts by mass or more and 30 parts by mass or less. Parts by mass or more and 20 parts by mass or less are particularly preferred.

The substrate may contain colorants other than white pigments. For example, inorganic pigments such as iron black, yellow lead, titanium yellow, Bengara, cadmium red, ultramarine, and cobalt blue, organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue, and scaly materials such as aluminum and brass. Examples include colorants such as metal pigments made of foil flakes, mica coated with titanium dioxide, and pearlescent pigments made of scaly foil flakes such as basic lead carbonate.

Additives may be added to the base material, if necessary. Examples of additives include inorganic fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. The blending amount of the additive is not particularly limited as long as it does not impede the processing properties, and can be set as appropriate depending on the required properties.

The base material may have a single layer of the above resin or a multilayer structure of the same or different resins.
The thickness of the base material is preferably 20 μm or more and 150 μm or less, more preferably 25 μm or more and 120 μm or less, even more preferably 30 μm or more and 100 μm or less, particularly preferably 40 μm or more and 80 μm or less, especially when processing characteristics are considered.

In addition, in order to improve interlayer adhesion between the base material and other layers, strengthen adhesion to various adherends, etc., the base material may be coated with oxidation methods, roughening methods, etc. on one or both sides of the base material. Surface treatments such as physical or chemical surface treatments can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, etc., and examples of the roughening method include sandblasting, solvent treatment, and the like. These surface treatments are appropriately selected depending on the type of substrate, but corona discharge treatment is generally preferably used in terms of surface treatment effects and operability.
In addition, in order to improve interlayer adhesion between the base material and other layers, and to strengthen adhesion with various adherends, treatments such as forming a base primer layer and a back primer layer are applied to the base material. Good too.

[Decorative layer]
The decorative sheet of the present invention preferably has a decorative layer from the viewpoint of improving design. The decorative layer may be, for example, a colored layer covering the entire surface (so-called solid colored layer), or a pattern layer formed by printing various patterns using ink and a printing machine. It may also be a combination of these. For example, when hiding the ground color of the adherend by using a solid colored layer, it is possible to improve the design while hiding the color. The layer and the pattern layer may be combined, or, on the other hand, if the background pattern of the adherend is to be utilized, it is sufficient to provide only the pattern layer without using a solid colored layer.

The ink used for the decorative layer is a mixture of a binder, colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, ultraviolet absorbers, light stabilizers, etc. be done.
There are no particular restrictions on the binder, and examples include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers (polymer-based Polymers with carbonate bonds in the chain and two or more hydroxyl groups in the terminal and side chains (urethane-acrylic copolymer derived from polycarbonate polyol), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acetic acid Preferred examples include vinyl-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin, and these resins can be used alone or in combination. In addition to the one-component curing type, we also cure isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID), and xylylene diisocyanate (XDI). Various types of resins can be used, such as a two-component curing type with an agent.

As the coloring agent, a white pigment is preferably used from the viewpoint of hiding the ground color of the adherend and improving the design. The content of the white pigment in the decorative layer 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 30 parts by mass based on 100 parts by mass of the resin constituting the decorative layer. The amount is more preferably 70 parts by mass or less.

The decorative layer also contains colorants other than white pigments, such as iron black, yellow lead, titanium yellow, Bengara, cadmium red, ultramarine, cobalt blue, and other inorganic pigments, quinacridone red, isoindolinone yellow, and phthalocyanine blue. , organic pigments or dyes such as azomethine, azo compounds, and perylene compounds; metallic pigments made of flaky foils such as aluminum and brass; pearlescent pigments made of scaly foils such as titanium dioxide-coated mica, and basic lead carbonate; ) Coloring agents such as pigments can also be used.

From the viewpoint of improving weather resistance, the decorative layer preferably contains a weathering agent such as an ultraviolet absorber and a light stabilizer, and more preferably contains a light stabilizer. As the ultraviolet absorber and light stabilizer, those that can be included in the surface protective layer can be used.

When a pattern layer is included as a decorative layer, the pattern may include a wood grain pattern, a stone grain pattern imitating a rock surface such as a marble pattern (for example, a travertine marble pattern), a fabric pattern imitating a cloth grain or cloth-like pattern, or a tile. There are pasting patterns, brickwork patterns, etc., and there are also patterns that combine these, such as marquetry and patchwork. These patterns are formed by multicolor printing using the usual process colors of yellow, red, blue, and black, but also by multicolor printing using spot colors, which is performed by preparing plates for the individual colors that make up the pattern. be done.

The thickness of the decorative layer may be appropriately selected depending on the desired pattern, but from the viewpoint of concealing the ground color of the adherend and improving the design, it is preferably 0.5 μm or more and 20 μm or less, and 1 μm or less. The thickness is more preferably 10 μm or more, and even more preferably 2 μm or more and 5 μm or less.

When the decorative sheet of the present invention has a base material and a decorative layer, it is preferable that at least one of the base material and the decorative layer contains a white pigment. By using a base material and a decorative layer colored with a white pigment, when the surface hue of the adherend to which the decorative sheet is attached varies, the surface hue can be easily concealed well. As a result, more excellent design properties can be obtained, and the color stability of the decorative sheet can be improved.

[Transparent resin layer]
The decorative sheet of the present invention may have a transparent resin layer. By providing the transparent resin layer on the decorative layer, various properties such as scratch resistance and stain resistance can be improved. Furthermore, as shown in FIG. 5, a surface protective layer or the like may be formed using a transparent resin layer as a base material.
The transparent resin layer is not particularly limited as long as it is transparent, and includes any of colorless transparent, colored transparent, translucent, etc. Examples of resin components forming the transparent resin layer include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylic acid. Examples include ester copolymers, ionomers, polymethylpentene, acrylic esters, methacrylic esters, polycarbonates, and cellulose triacetate. Among the above, polyolefin resins such as polypropylene are preferred. More preferably, it is a polyolefin resin having stereoregularity. When using a polyolefin resin, it is desirable to form a transparent resin layer by extruding the molten polyolefin resin.

The transparent resin layer may contain fillers, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, radical scavengers, soft components (e.g. rubber), etc., as necessary. Various additives may be included.
Examples of the method for forming the transparent resin layer include a method of laminating a resin composition containing the above-mentioned resin components on the decorative layer by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.
The thickness of the transparent resin layer is not particularly limited, but it is generally preferably about 20 to 250 μm, particularly about 30 to 200 μm.

The surface of the transparent resin layer on which the surface protective layer is to be formed may be subjected to surface treatments such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., if necessary. good. The surface treatment may be performed according to a conventional method for each treatment.

[Primer layer]
The decorative sheet of the present invention may be provided with a primer layer. When a primer layer is provided, it is preferably provided between the decorative layer and the surface protective layer. When a decorative layer and a transparent resin layer are provided, they are preferably provided between the transparent resin layer and the surface protection layer. By providing a primer layer, the adhesion between the decorative layer and the surface protection layer or the adhesion between the transparent resin layer and the surface protection layer can be improved, and the stress on the surface protection layer is alleviated, thereby improving the surface protection. It becomes possible to suppress cracking due to weather resistance deterioration of the layer, and durability can be significantly improved.

The primer layer may be formed, for example, from a resin composition prepared by appropriately mixing the binder exemplified as the binder used in the decorative layer with a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. I can do it.
The thickness of the primer layer is preferably 0.1 to 10 μm, more preferably 0.5 μm to 8 μm, and even more preferably 1 to 6 μm, from the viewpoint of improving adhesion.

[Decorative materials]
The decorative material of the present invention comprises an adherend and the above decorative sheet. Specifically, the adherend and the surface of the decorative sheet opposite to the surface protective layer are laminated so as to face each other. FIG. 6 is a schematic cross-sectional view illustrating an example of the decorative material of the present invention. The decorative material 20 includes an adherend 21 and the decorative sheet 10 of the present invention (the decorative sheet shown in FIG. 1 as an example) in this order.

<Adherent material>
Examples of the adherend include plate materials such as flat plates and curved plates made of various materials, three-dimensional articles, sheets (or films), and the like. for example,
(1) Wood used for board materials such as wood veneers made of various woods such as cedar, cypress, pine, and lauan, wood plywood, particle boards, wood fiberboards such as MDF (medium density fiberboard), and three-dimensional shaped articles. Element,
(2) Metal members used as iron, aluminum plates, steel plates, three-dimensional articles, sheets, etc. (3) Glass, ceramics such as ceramics, non-cement ceramic materials such as plaster, ALC (lightweight cellular concrete) plates Ceramic components used as plate materials and three-dimensional shaped articles such as non-ceramic ceramic materials, etc.
(4) Plate materials and three-dimensional shaped articles made of acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, rubber, etc. Or a resin member used as a sheet etc.
etc. Further, these members can be used alone or in combination.

The adherend material may be selected from the above according to the intended use, and can be used for interior or exterior building materials such as walls, ceilings, and floors, window frames, doors, handrails, baseboards, surrounding edges, and moldings. When using fittings or fixtures such as, etc., it is preferable to use at least one type of member selected from wooden members, metal members, and resin members, and fittings such as exterior members such as entrance doors, window frames, doors, etc. In this case, it is preferable to use at least one member selected from metal members and resin members.

The thickness of the adherend may be appropriately selected depending on the application and material, and is preferably 0.1 mm or more and 10 mm or less, more preferably 0.3 mm or more and 5 mm, and even more preferably 0.5 mm or more and 3 mm or less.

The adherend and the decorative sheet are preferably bonded together using an adhesive in order to obtain excellent adhesion.
The adhesive used when bonding the adherend and the decorative sheet is not particularly limited, and any known adhesive can be used. For example, adhesives such as heat-sensitive adhesives and pressure-sensitive adhesives are preferred. Can be mentioned. Examples of resins used for the adhesive constituting this adhesive layer include acrylic resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acrylic copolymer resin, and polyester resin. , polyamide resin, etc., and these can be used alone or in combination. Furthermore, a two-component curing type polyurethane adhesive or polyester adhesive using an isocyanate compound or the like as a curing agent may also be used.
Furthermore, when using an adhesive, a pressure-sensitive adhesive can also be used in combination. As the adhesive, an acrylic adhesive, a urethane adhesive, a silicone adhesive, a rubber adhesive, or the like can be appropriately selected and used.
The thickness of the adhesive layer is not particularly limited, but from the viewpoint of obtaining excellent adhesiveness, it is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less, and even more preferably 10 μm or more and 30 μm or less.

<Method for manufacturing decorative materials>
A decorative material can be manufactured through a process of laminating a decorative sheet and an adherend.
The surface of the adherend that requires decoration and the surface of the decorative sheet opposite to the surface protective layer are stacked facing each other. Examples of the method for laminating the adherend and the decorative sheet include a lamination method in which the decorative sheet is laminated by pressing the adherend with a pressure roller or the like via the adhesive layer described above. If the decorative sheet is in the form of a sheet, the decorative material can be efficiently manufactured by applying pressure to the adherend using a pressure roller or the like and laminating the decorative sheet.

When using a hot melt adhesive (heat-sensitive adhesive) as an adhesive, the heating temperature is preferably 160°C or more and 200°C or less, although it depends on the type of resin constituting the adhesive. The temperature is preferably 130°C or higher. Further, in the case of vacuum forming processing, it is generally performed while heating, and the temperature is preferably 80°C or more and 130°C or less, more preferably 90°C or more and 120°C or less.

The decorative material obtained as described above can be arbitrarily cut, and arbitrary decorations such as grooving and chamfering can be applied to the surface and end portion using a cutting machine such as a router or a cutter. And various uses, for example, interior and exterior parts of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, surrounding edges, moldings and other fittings, as well as kitchens, furniture or home appliances, OA equipment, etc. It can be used for the decorative surface of cabinets, the interior and exterior of vehicles, etc.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.
<Evaluation>
(1) Weather resistance test A weather resistance test was conducted on the decorative sheets of Examples and Comparative Examples according to the following procedure.
Using a super accelerated weathering test device (trade name: Eye Super UV Tester SUV-W261) as a test device, irradiation under the following irradiation conditions and dew condensation under the dew condensation conditions were repeated.
(irradiation conditions)
Illuminance: 100mW/ ^cm2
Black panel temperature: 63℃
Humidity: 50%RH
Irradiation time: 20 hours Condensation time: 4 hours The appearance of the decorative sheet before the weather resistance test and after a predetermined period of time was visually observed and evaluated. The evaluation criteria are as follows.
A: No change in appearance was observed.
B: Minor changes in appearance (changes in gloss, color tone, cracks, etc.) were observed.
C: Significant changes in gloss, color tone, and cracks were observed.

(2) Design evaluation The design characteristics (matte properties and visibility of the decorative layer) were visually evaluated for each sample before the weather resistance test and after a predetermined period of time had elapsed in the weather resistance test. The evaluation criteria are as follows.
A: Matteness was felt. The decorative layer was visible.
B: Matteness was felt, but the surface protective layer became cloudy and the visibility of the decorative layer decreased.
C: The decorative layer was visible, but no matte appearance was felt.
D: The surface protective layer became cloudy, and the visibility of the decorative layer decreased. It didn't feel matte either.

(3) Surface roughness measurement Using a non-contact shape analysis laser microscope (Keyence: VK-X1000), measure Sz (maximum height) and Sa (arithmetic mean height) at the following 10 points within the surface of the decorative sheet. Measured under the following conditions. The average value of each measured value was defined as Sz and Sa of the decorative sheets of Examples and Comparative Examples. The results are shown in Table 1.
[Measurement conditions of surface roughness measuring instrument]
・S-filter: None
・L-filter: None ・Magnification: 400x ・Measurement range: 400μm x 500μm

<Example 1>
Using a polypropylene resin sheet (thickness 60 μm, corona discharge treatment on both sides) as a base material, a brown ink containing a two-component curable acrylic-urethane resin as a binder is applied to one side of the base material using a gravure printing method to create a wood grain pattern. A decorative layer (thickness after drying: 3 μm) was provided.
A resin composition containing a two-component curable urethane-nitrified cotton mixed resin (curing agent: 5 parts by mass of hexamethylene diisocyanate per 100 parts by mass of resin) is applied to the other surface of the base material, and a back primer is applied. A layer (thickness: 3 μm) was formed.
A transparent polyurethane resin adhesive was applied onto the decorative layer to form an adhesive layer (thickness after drying: 3 μm). A transparent polypropylene resin was heated and melted using a T-die extruder and extruded onto the adhesive layer to form a transparent resin layer (thickness: 80 μm).
Next, after subjecting the surface of the transparent resin layer to corona treatment, a resin composition containing a two-component curable urethane-nitrified cotton mixed resin (containing 5 parts by mass of hexamethylene diisocyanate as a curing agent per 100 parts by mass of resin) was prepared. was applied onto the transparent resin layer to form a primer layer (thickness after drying: 4 μm).

A coating liquid for forming a surface protective layer having the following formulation was applied onto the primer layer so that the thickness after curing was approximately 5 μm.
(Coating liquid for surface protective layer formation)
Urethane acrylate oligomer (weight average molecular weight: 1000, number of functional groups: 2) 100 parts by mass Zinc oxide particles (average particle size: 10 nm) 25 parts by mass Triazine-based ultraviolet absorber (trade name "Tinuvin479") 1 part by mass Hindered amine light stabilizer 5 parts by mass

The shaping sheet A was placed on the uncured coating film so that the uneven surface faced the coating film side, and the coating film and the shaping sheet A were brought into close contact with each other by dry laminating. In this state, the coating film was crosslinked and cured by irradiation with an electron beam under the conditions of 165 KeV and 5 Mrad (50 kGy).
After curing, the shaped sheet A was peeled off to obtain the decorative sheet of Example 1 (matte shaped decorative sheet). The evaluation results are shown in Table 1.

<Example 2>
The decorative sheet of Example 2 (a decorative sheet with matte shaping) was obtained in the same process as in Example 1, except that shaped sheet B was used which had a different size of surface unevenness from shaped sheet A. Ta. The evaluation results are shown in Table 1.

<Comparative example 1>
The same laminate as in Example 1 was produced except for the surface protective layer.
Silica (average particle size: 8 μm) was further added as a matting agent to the coating solution for forming a surface protective layer of Example 1 at a ratio of 25 parts by mass. After applying this coating liquid on the primer layer, it was directly cured under the same conditions as in Example 1 to form a surface protective layer (thickness: 5 μm). Decorative sheet of Comparative Example 1 (decorative sheet containing a matting agent) I got it. The evaluation results are shown in Table 1.

<Comparative example 2>
The same laminate as in Example 1 was produced except for the surface protective layer. Cosmetics of Comparative Example 2, in which the same coating solution for forming a surface protective layer as in Example 1 was applied on the primer layer and then cured under the same conditions as in Example 1 to form a surface protective layer (thickness: 5 μm). A sheet (clear decorative sheet) was obtained. The evaluation results are shown in Table 1.

Both of the decorative sheets of Examples 1 and 2 had excellent weather resistance, and there was no change in design properties (matte properties and visibility of the decorative layer) even during long-term tests.
On the other hand, as shown in Table 1, the decorative sheet of Comparative Example 1 containing a matting agent (silica) in the surface protective layer has less luster and color than Examples 1 and 2 and Comparative Example 2, which do not contain a matting agent. Changes were observed, and cracks were observed. The result was that the weather resistance was significantly inferior. Further, although the decorative sheet of Comparative Example 1 had excellent initial design, clouding (whitening) of the surface protective layer occurred in the above weather resistance test, and the visibility of the decorative layer decreased.
In Comparative Example 2, neither excipient nor addition of a matting agent was performed, so the decorative sheet before the test did not have a matte feel. Further, in the decorative sheet of Comparative Example 2, no change in color tone or gloss or occurrence of cracks was observed in the weather resistance test, but clouding (whitening) of the surface protective layer was observed.

10 Decorative sheet 11 Surface protection layer 12 Base material 13 Decorative layer 14 Transparent resin layer 15 Primer layer 20 Decorative material 21 Adherent material

Claims (10)

A decorative sheet having a surface protective layer on the outermost layer,
The surface protective layer contains a cured product of a curable resin composition and an inorganic ultraviolet shielding agent, and substantially does not contain a matting agent,
The inorganic ultraviolet screening agent is zinc oxide,
The outermost surface of the surface protective layer has fine irregularities,
A decorative sheet in which the maximum height (Sz) of the fine irregularities measured in accordance with ISO25178-6:2010 is 4.0 μm or more and 30 μm or less . The decorative sheet according to claim 1 , wherein the arithmetic mean height (Sa) of the fine irregularities measured in accordance with ISO25178-6:2010 is 0.5 μm or more. The ratio of the maximum height (Sz) of the fine irregularities measured in accordance with ISO25178-6:2010 to the arithmetic mean height (Sa) of the fine irregularities measured in accordance with ISO25178-6:2010 ( The decorative sheet according to claim 1 or 2 , wherein Sz/Sa) is 40 or less. The decorative sheet according to any one of claims 1 to 3 , wherein the zinc oxide is a particle having an average particle size of 0.5 nm or more and 300 nm or less. The decorative sheet according to any one of claims 1 to 4 , wherein the content of the zinc oxide is 1 part by mass or more and 50 parts by mass or less, based on 100 parts by mass of the curable resin composition. The decorative sheet according to any one of claims 1 to 5 , wherein the surface protective layer further contains an organic ultraviolet absorber. The decorative sheet according to any one of claims 1 to 6 , further comprising at least one of a primer layer and a transparent resin layer on the back side of the surface protective layer. The decorative sheet according to any one of claims 1 to 7 , wherein the curable resin composition is an ionizing radiation curable resin. The decorative sheet according to claim 6 , wherein the organic ultraviolet absorber is a triazine ultraviolet absorber. A decorative material comprising an adherend and the decorative sheet according to any one of claims 1 to 9 .