JP7115615B2 - Decorative sheet and decorative material using the same - Google Patents

Description

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

Building interior or exterior materials such as walls, ceilings, floors, entrance doors, roofs, etc., window frames, doors, handrails, baseboards, curbs, malls, etc. fittings or fixtures, as well as kitchens, furniture or light electrical appliances. Products, surface decorative boards of cabinets such as OA equipment, interior materials or exterior members of vehicles are generally applied to metal members such as steel plates, resin members, and wooden members as adherends. A laminate of decorative sheets is used. When bonding the decorative sheet to an adherend such as a steel plate, or after bonding the decorative sheet to the adherend, it is common to perform bending such as V-cutting and lapping. If the workability of the steel sheet is low, cracks will form in the bent portion, resulting in whitening.

In order to solve such problems, the base material has a pattern printed layer, a transparent resin layer, a primer layer and a surface protective layer, and the base material and the primer layer are made of a predetermined resin material, A decorative sheet has been proposed in which the primer layer and the surface protective layer contain a predetermined ultraviolet absorber (for example, Patent Document 1).

JP 2008-238444 A

However, the decorative sheet described in Patent Document 1 is not suitable for use in particularly severe environments, such as environments exposed to direct sunlight, such as exterior members such as exterior walls, entrance doors, and roofs, and fittings or fixtures such as window frames and doors. If you try to use it for the members used in the decorative sheet, the degree of heat shrinkage of each layer that makes up the decorative sheet may reduce the gloss and cause cracks, etc., which may cause the appearance to change. It's getting tough.

By the way, decorative sheets used for members such as exterior members, fittings, fixtures, etc. are used in an environment where scratches such as dents are likely to occur. . In general, in order to improve scratch resistance, each layer constituting the decorative sheet can be made to have a higher hardness, and in order to improve weather resistance, a layer containing an ultraviolet absorber can be used. can be handled by making the hardness moderately high and holding the ultraviolet absorber more firmly. However, if each layer constituting the decorative sheet is made to have a higher hardness, the workability deteriorates, cracks appear in the bent portion, and whitening occurs, resulting in deterioration of the appearance. Thus, the processing characteristics of the decorative sheet, the weather resistance, and the scratch resistance are contradictory characteristics, and it is desired that these characteristics be compatible even under severer environments.

It is an object of the present invention to provide a decorative sheet having excellent processability, weather resistance and scratch resistance, and a decorative material using the same.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by an invention relating to a decorative sheet having the following configuration and a decorative material using the same.

[1] having a base material and a surface protective layer composed of a cured product of a curable resin composition having a Martens hardness of 10 N/mm ² or more and 30 N/mm ² or less and containing an ultraviolet absorber; A decorative sheet having a modulus of 400 MPa or more and 1,800 MPa or less.
[2] The decorative sheet according to [1] above, which further has a resin layer and a primer layer, and has, in order, a substrate, a resin layer, a primer layer, and a surface protective layer.
[3] The decorative sheet according to [1] or [2] above, further comprising a decorative layer between the substrate and the surface protective layer.
[4] A decorative material comprising an adherend and the decorative sheet according to any one of [1] to [3] above.

ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet which has the outstanding processability, weather resistance, and scratch resistance, and a decorative material using the same can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the cross section of an example of the decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the cross section of an example of the decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the layer structure of the decorative material of this invention.

[Cosmetic sheet]
The decorative sheet of the present invention comprises a base material and a surface protective layer composed of a cured product of a curable resin composition having a Martens hardness of 10 N/mm ² or more and 30 N/mm ² or less and containing an ultraviolet absorber. and has an elastic modulus of 400 MPa or more and 1,800 MPa or less. The configuration of the decorative sheet of the present invention will be described with reference to FIGS. 1 and 2. FIG. FIG. 1 is a schematic diagram showing a cross section of an example of the decorative sheet 10 of the present invention, which has a substrate 11 and a surface protective layer 16, and the surface protective layer 16 contains an ultraviolet absorber 18. . FIG. 2 is a schematic diagram showing a cross section of an example of a preferred embodiment of the decorative sheet 10 of the present invention. The decorative sheet 10 comprises a substrate 11, a decorative layer 12, an adhesive layer 13, a resin layer 14, a primer layer 15, and a surface protective layer 16 in this order, and a rear surface primer layer 17 on the surface of the substrate 11 opposite to the surface of the substrate 11 facing the surface protective layer 16 . Further, in FIG. 2, the surface (outermost surface) of the surface protective layer 16 opposite to the substrate 11 has a recess 19. 14, some to the substrate 11, and so on.

(Martens hardness and elastic modulus)
In the decorative sheet of the present invention, the surface protective layer must have a Martens hardness of 10 N/mm ² or more and 30 N/mm ² or less, and the elastic modulus of the decorative sheet must be 400 MPa or more and 1,800 MPa or less.
If the elastic modulus of the decorative sheet is less than 400 MPa, the decorative sheet is soft and thus excellent processing characteristics can be obtained. is not obtained. On the other hand, when the modulus of elasticity of the decorative sheet exceeds 1,800 MPa, the decorative sheet becomes hard, so resistance to scratches such as dents is improved according to the hardness of the surface protective layer, and scratch resistance is obtained. properties are not obtained.

Even if the elastic modulus of the decorative sheet is 400 MPa or more and 1,800 MPa or less, if the Martens hardness of the surface protective layer is less than 10 N/mm ² , processing characteristics can be obtained, but scratch resistance is poor due to insufficient hardness of the surface protective layer. is not obtained. In addition, the difference in heat shrinkage between the layers that make up the decorative sheet (especially the base material and the surface protective layer) increases, and with use in harsh environments, the difference in heat shrinkage causes a decrease in luster and the occurrence of cracks. Weather resistance is also not obtained because the appearance changes due to factors such as Conversely, if the Martens hardness of the surface protective layer exceeds 30 N/mm ² , scratch resistance can be obtained, but the surface protective layer becomes too hard to obtain processing properties, and use in severe environments Also, the difference in heat shrinkage causes a decrease in luster and changes in appearance due to the occurrence of cracks, and weather resistance cannot be obtained.
The decorative sheet of the present invention is intended to simultaneously achieve excellent processing properties, weather resistance, and scratch resistance, which are contradictory properties, by balancing the elastic modulus of the decorative sheet and the Martens hardness of the surface protective layer. It is possible.

In the present invention, the measurement of Martens hardness is specifically a value measured using an ultra-micro hardness tester. The surface area A (mm ² ) was calculated from the length of the diagonal of the pyramid-shaped recess formed on the sample (the surface of the surface protective layer), and the test load F ( N) divided by the surface area A. As the ultra-micro hardness tester, for example, a micro-hardness tester "Picodenter HM-500" (manufactured by Fisher Instruments) may be used.

The Martens hardness of the surface protective layer may be appropriately selected from the range of 10 N/mm ² or more and 30 N/mm ² or less in relation to the elastic modulus of the decorative sheet. 12 N/mm ² or more is preferable, 15 N/mm ² or more is more preferable, and 18 N/mm ² or more is still more preferable from the viewpoint of obtaining . The upper limit is preferably 28 N/mm ² or less, more preferably 27 N/mm ² or less, and even more preferably 25 N/mm ² or less. In addition, in this specification, numerical values related to “more than” and “less than” regarding the description of numerical ranges are numerical values that can be arbitrarily combined.

The Martens hardness of the surface protective layer is measured when the indentation depth reaches 2 μm. It can be adjusted by the material of the curable resin composition to be formed.

The elastic modulus of the decorative sheet is required to be 400 MPa or more and 1,800 MPa or less. The elastic modulus of the decorative sheet may be appropriately selected from within the above range in relation to the Martens hardness of the surface protective layer. It is preferably 500 MPa or more, more preferably 550 MPa or more. Moreover, as an upper limit, 1,700 MPa or less is preferable, 1,600 MPa or less is more preferable, and 1,500 MPa or less is still more preferable. In the present invention, the elastic modulus of the decorative sheet means the tensile elastic modulus measured by the following measuring method.
(Method for measuring elastic modulus)
A test piece punched into a dumbbell shape conforming to JIS K7127 is prepared, and a tensile tester is used in a temperature environment of 25 ° C. under the conditions of a tensile speed of 50 mm / min, a distance between chucks of 80 mm, and a width of 10 mm. Obtained tensile stress - E (tensile modulus) calculated from the first direct part of the strain curve by the following formula.
Tensile modulus = Δρ/Δε
Δρ: Stress difference due to the original average cross-sectional area between two points on the straight line Δε: Strain difference between the same two points

The elastic modulus of the decorative sheet can be adjusted mainly by the thickness of the base material, the type of resin constituting the base material, and the like. Moreover, when providing a resin layer, it can also adjust with a resin layer.
Each layer constituting the decorative sheet of the present invention will be described below.

(Base material)
As the base material, those commonly used as base materials for decorative sheets can be employed without limitation, and resin base materials made of thermoplastic resins are typically used. Examples of thermoplastic resins include 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, and the like. be.
Among these resins, polyolefin resins, polyester resins, polycarbonate resins and ABS resins are preferred from the viewpoint of obtaining better processability, weather resistance, and scratch resistance. , and particularly polyolefin resins are preferred. In the present invention, these resins can be used singly or in combination.

The polyolefin resin is not particularly limited, and examples thereof include polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate. Copolymers, ethylene-acrylic acid copolymers, ethylene-propylene-butene copolymers, polyolefin thermoplastic elastomers, and the like can be mentioned. Among them, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, and propylene-butene copolymer are preferable from the viewpoint of obtaining better processability, weather resistance, and scratch resistance. Considering ease of adjusting the elastic modulus of the decorative sheet, polypropylene resins such as polypropylene, ethylene-propylene copolymer and propylene-butene copolymer are more preferable.

The substrate may be colored or may not be colored (it may be transparent), and when colored, the mode of coloring is not particularly limited, and may be transparently colored, Opaque coloring (concealing coloring) may be used, and these can be selected arbitrarily. For example, when the base color of the adherend such as a steel plate to which the decorative sheet is adhered is to be hidden by coloring, opaque coloring may be selected. On the other hand, when the background pattern of the adherend used for the decorative material is to be visually observed, transparent coloring may be selected.

When the substrate is colored, examples of coloring agents include white pigments such as titanium white, inorganic pigments such as iron black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; quinacridone red. , isoindolinone yellow, phthalocyanine blue and other organic pigments or dyes; metal pigments consisting of scale-like foils such as aluminum and brass; pearl luster consisting of scale-like foils such as titanium dioxide-coated mica and basic lead carbonate ) coloring agents such as pigments. In particular, when the surface hue of the adherend to which the decorative sheet is attached varies, the surface hue can be easily concealed, a more excellent design can be obtained, and the color tone of the decorative layer provided as desired can be improved. It is preferable that an inorganic pigment such as a white pigment is included because it can improve the stability.

When using an inorganic pigment such as a white pigment, the content thereof may be appropriately adjusted depending on whether the color is transparent or opaque (concealing). For example, 100 parts by mass of the resin constituting the base material is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less.

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 amount of the additive compounded is not particularly limited as long as it does not impair the processing characteristics, and can be appropriately set according to the required characteristics and the like.

From the viewpoint of improving the weather resistance of the decorative sheet of the present invention, it is preferable to use weather resistance agents such as ultraviolet absorbers and light stabilizers among the above additives.
Since the base material is a layer located between the surface protective layer and the adherend when used as a decorative material, the effect of bleed out of weathering agents such as UV absorbers and light stabilizers on deterioration of weather resistance. can be said to be small compared to other layers. The UV absorber used in the substrate is not particularly limited, and examples thereof include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, and the like. Further, for example, a specific hydroxyphenyltriazine-based ultraviolet absorber exemplified as one particularly preferably used for the surface resin layer described later can also be preferably used.

As the light stabilizer, hindered amine light stabilizers are preferred, and examples include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl (meth ) acrylate, 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, 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. Among these, 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, methyl (1,2,2,6,6-pentamethyl- Hindered amine light stabilizers derived from decanedioic acid (sebacic acid) such as 4-piperidinyl) sebacate are preferred.

These ultraviolet absorbers and light stabilizers can be used alone or in combination. In addition, the ultraviolet absorber and the light stabilizer are, as exemplified above as one of the light stabilizers, for example, a reactive functional group having an ethylenic double bond such as (meth)acryloyl group, vinyl group and allyl group. It may have a group.

The content of the ultraviolet absorber in the substrate is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and still more preferably 0.3 parts by mass with respect to 100 parts by mass of the resin constituting the substrate. The upper limit is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less. In addition, the content of the light stabilizer in the substrate is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass or more with respect to 100 parts by mass of the resin constituting the substrate. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less. When the content of the ultraviolet absorber and the light stabilizer in the base material is within the above range, bleed-out is less likely to occur, and excellent addition effects can be obtained.

The base material may be a single layer of the above resin, or may be a multilayer of the same or different resins.
The thickness of the substrate is preferably 20 μm or more, more preferably 30 μm or more, from the viewpoint of obtaining better processing characteristics, weather resistance, and scratch resistance, and considering the ease of adjusting the elastic modulus of the decorative sheet. 40 μm or more is more preferable. The upper limit is preferably 200 µm or less, more preferably 160 µm or less, and even more preferably 100 µm or less.

In order to improve the interlayer adhesion between the base material and other layers and strengthen the adhesion with various adherends, one or both sides of the base material may be subjected to a physical treatment such as an oxidation method or roughening method. Surface treatment such as surface treatment or chemical surface treatment can be applied.
Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, and the like. Examples of roughening methods include sandblasting and solvent treatment. These surface treatments are appropriately selected according to the type of substrate, but in general, the corona discharge treatment method is preferably used from the standpoints of surface treatment effects, operability, and the like.
In addition, in order to improve the interlayer adhesion between the base material and other layers and strengthen the adhesion to various adherends, the base material is treated with a primer layer and a back primer layer. good too. These primer layers will be described later.

(Surface protective layer)
The surface protective layer has a Martens hardness of 10 N/mm ² or more and 30 N/mm ² or less, and is a layer composed of a cured product of a curable resin, directly on the substrate, or another layer, such as a necessary It is a layer located on the outermost surface of the decorative sheet of the present invention, which is provided on a decorative layer provided according to the above, a primer layer or the like for improving interlayer adhesion between the substrate or the decorative layer and the surface protective layer . By having such a surface protective layer, the decorative sheet of the present invention has excellent processability, scratch resistance and weather resistance.

The surface protective layer is a layer composed of a cured product of a resin composition containing a curable resin.
As the curable resin used for forming the surface protective layer, in addition to thermosetting resins such as two-component curable resins, ionizing radiation curable resins and the like are preferably used. A so-called hybrid type, in which a radiation curable resin and a thermosetting resin are used in combination, or a curable resin and a thermoplastic resin are used in combination, may also be used.
As the curable resin, from the viewpoint of increasing the crosslink density of the resin constituting the surface protective layer to obtain better processing characteristics, scratch resistance and weather resistance, and considering the ease of adjusting the Martens hardness of the surface protective layer. , ionizing radiation-curable resins are preferred, and electron beam-curable resins are more preferred from the viewpoint of ease of handling.

(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 a functional group having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. be done. In addition, ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing or cross-linking molecules, usually ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.
As the ionizing radiation-curable resin, specifically, it is possible to appropriately select and use from polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation-curable resins.

As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth)acrylate monomer is particularly preferable. Here, "(meth)acrylate" means "acrylate or methacrylate".
Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group, Acrylate monomers having an acryloyl group are preferred from the standpoint of obtaining better processing properties, scratch resistance, and weather resistance, and the ease of adjusting the Martens hardness of the surface protective layer.
From the viewpoint of obtaining better processing properties, scratch resistance and weather resistance, and considering the ease of adjusting the Martens hardness of the surface protective layer, the number of functional groups is preferably 2 or more, and the upper limit is preferably 8 or less. It is more preferably 6 or less, still more preferably 4 or less, and particularly preferably 3 or less. These polyfunctional (meth)acrylates may be used alone or in combination.

Polymerizable oligomers include, for example, (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least (meth)acryloyl groups as the functional groups. For example, urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer, acrylic (meth)acrylate oligomer, polycaprolactone urethane (meth) ) acrylate oligomer, polycaprolactone diol urethane (meth)acrylate, and the like.
Furthermore, as polymerizable oligomers, there are also highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, and silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain. , Aminoplast resin modified aminoplast resin with many reactive groups in a small molecule (meth)acrylate oligomer, or novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having cationic polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination. Urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate from the viewpoint of obtaining better processing properties, scratch resistance and weather resistance. Acrylate oligomer, acrylic (meth)acrylate oligomer, polycaprolactone urethane (meth)acrylate oligomer, polycaprolactone diol urethane (meth)acrylate is preferred, urethane (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer, polycaprolactone urethane (meth) Acrylate oligomers and polycaprolactone diol urethane (meth)acrylate oligomers are more preferred, and urethane (meth)acrylate oligomers are preferred, and urethane acrylate oligomers are particularly preferred, in view of the ease of adjusting the Martens hardness of the surface protective layer. In addition, polycarbonate (meth)acrylate has high hydrolysis resistance and suppresses the bleeding out of weathering agents such as UV absorbers and light stabilizers from cracks in the surface protective layer, and from the viewpoint of obtaining better weather resistance. Oligomers are preferred, particularly polycarbonate acrylate oligomers.

From the viewpoint of obtaining better processing properties, scratch resistance and weather resistance, and considering the ease of adjusting the Martens hardness of the surface protective layer, the number of functional groups of these polymerizable oligomers is preferably 2 or more, The upper limit is preferably 8 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 3 or less.

The weight-average molecular weight of these polymerizable oligomers is preferably 2,500 or more from the viewpoint of obtaining better processing properties, scratch resistance, and weather resistance, and considering the ease of adjusting the Martens hardness of the surface protective layer. , is more preferably 2,750 or more, and even more preferably 2,900 or more. The upper limit is preferably 15,000 or less, more preferably 12,500 or less, even more preferably 10,000 or less, and particularly preferably 6,000 or less. Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

In particular, considering the ease of adjusting the Martens hardness of the surface protective layer, it is preferable to use two or more ionizing radiation-curable resins in combination. At least a meth)acrylate oligomer (hereinafter sometimes referred to as "(meth)acrylate oligomer 1") selected from urethane (meth)acrylate oligomers and polycarbonate urethane (meth)acrylate oligomers having a weight average molecular weight of 3,500 or more It is preferable to use together with a kind of (meth)acrylate oligomer having a weight average molecular weight of 3,500 or more (hereinafter sometimes referred to as "(meth)acrylate oligomer 2").
The weight average molecular weight of the (meth)acrylate oligomer 1 is preferably 2,750 or more, more preferably 2,900 or more, and the upper limit is preferably 3,400 or less, more preferably 3,300 or less, and 3,200. More preferred are: The weight average molecular weight of the (meth)acrylate oligomer 2 is preferably 3,600 or more, more preferably 3,800 or more, and even more preferably 4,100 or more. The upper limit is preferably 15,000 or less, more preferably 12,500 or less, still more preferably 10,000 or less, and particularly preferably 6,000 or less.
When these are used together, the compounding ratio (mass ratio) of (meth)acrylate oligomer 1 and (meth)acrylate oligomer 2 is preferably 1:99 to 90:10, more preferably 5:95 to 85:15. preferable.

In the present invention, a monofunctional (meth)acrylate can be used in combination with the polyfunctional (meth)acrylate or the like as long as the object of the present invention is not impaired, for the purpose of reducing the viscosity thereof. . 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 processability, scratch resistance, and weather resistance. The content of the polymerizable oligomer in the ionizing radiation-curable resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.

The curable resin composition that constitutes the surface protective layer contains an ultraviolet absorber. The UV absorber is stably retained in the surface protective layer because the surface protective layer contains the UV absorber, the surface protective layer has a predetermined Martens hardness, and the decorative sheet has a predetermined elastic modulus. Therefore, excellent weather resistance can be obtained even in harsh environments.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and triazine-based ultraviolet absorbers, which are exemplified as ultraviolet absorbers that can be contained in the base material. Triazine-based ultraviolet absorbers are preferred. More specifically, among triazine-based UV absorbers, hydroxyphenyltriazine-based compounds 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. A UV absorber is more preferable, and a hydroxyphenyltriazine-based UV absorber represented by the following general formula (1) is even more preferable. Since the surface protective layer is a layer located on the outermost surface of the decorative sheet, it is preferable that it is difficult to bleed out from the layer. , it is expected that bleeding out will be difficult, and from the viewpoint of weather resistance performance, it is particularly preferable as an ultraviolet absorber used in the surface protective layer.

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

Examples of the divalent organic group for R ¹¹ include aliphatic hydrocarbon groups such as an alkylene group and an alkenylene group, and from the viewpoint of weather resistance, an alkylene group is preferable, and the number of carbon atoms thereof is preferably 1 or more, and the upper limit is It is preferably 20 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 4 or less. The alkylene group and alkenylene group may be linear, branched, or cyclic, but preferably linear or branched.
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 and 2,2-propylene. various propylene groups (hereinafter, "various" refers to 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. groups.

Examples of monovalent organic groups for R ¹³ and R ¹⁴ include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and arylalkyl groups. Preferred are aryl groups. Among them, a phenyl group is preferable as the monovalent organic group for R ¹³ and R ¹⁴ .
The aryl group preferably has 6 or more carbon atoms, and the upper limit is preferably 20 or less, more preferably 12 or less, and still more preferably 10 or less, such as a phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, and the like. The arylalkyl group preferably has 7 or more carbon atoms, and the upper limit is preferably 20 or less, more preferably 12 or less, and still more preferably 10 or less, 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, various hexylbenzyl groups, and the like.

Examples of monovalent organic groups for R ¹⁵ include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and arylalkyl groups. Aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups are preferred. is more preferred. That is, R ¹² is preferably an alkyl ester group or an alkenyl ester group, more preferably an alkyl ester group.
The alkyl group preferably has 1 or more carbon atoms, more preferably 2 or more carbon atoms, more preferably 6 or more carbon atoms, and the upper limit is preferably 20 or less, more preferably 16 or less, and still more preferably 12 or less. groups, ethyl groups, 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 Examples include pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, and various icosyl groups.
The alkenyl group preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, more preferably 6 or more carbon atoms, and the upper limit is preferably 20 or less, more preferably 16 or less, and still more preferably 12 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.

More specifically, as the hydroxyphenyltriazine compound represented by the general formula (1), R ¹¹ is an alkylene group having 1 to 20 carbon atoms, and R ¹² and R ¹⁵ are alkyl having 1 to 20 carbon atoms. A hydroxyphenyl triazine compound in which R ¹³ and R ¹⁴ are aryl groups having 6 to 20 carbon atoms, n ₁₁ and n ₁₂ are 1, and R ¹¹ has 1 to 12 carbon atoms. the following alkylene groups, wherein R ¹² and R ¹⁵ are alkyl ester groups that are alkyl groups having 2 to 16 carbon atoms, R ¹³ and R ¹⁴ are aryl groups having 6 to 12 carbon atoms, and n ₁₁ and a hydroxyphenyltriazine compound in which n12 is ₁ is more preferable, R11 is an alkylene group having ¹ to ⁸ carbon atoms, and R12 and R15 are an alkyl ester group having 6 to ¹² carbon atoms. and more preferably a hydroxyphenyltriazine compound in which R ¹³ and R ¹⁴ are aryl groups having 6 to 10 carbon atoms, n ₁₁ and n ₁₂ are 1, and R ¹¹ is an alkylene group having 1 to 4 carbon atoms. , R ¹² and R ¹⁵ are C8 alkyl ester groups, R ¹³ and R ¹⁴ are phenyl groups, and n ₁₁ and n ₁₂ are 1.

More specifically, the hydroxyphenyltriazine compound represented by the general formula (1) includes an ester group represented by the following chemical formula (2), wherein R ¹¹ is an ethylene group and R ¹² and R ¹⁵ are an isooctyl group. and R ¹³ and R ¹⁴ are phenyl groups, and n ₁₁ and n ₁₂ are 1, namely 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 (“TINUVIN479”, manufactured by BASF).

The curable resin composition constituting the surface protective layer preferably contains a light stabilizer from the viewpoint of improving weather resistance. As the light stabilizer, a hindered amine light stabilizer is preferable, and the hindered amine light stabilizer exemplified as the light stabilizer that can be used in the base material can be used. and a light stabilizer having a reactive functional group having an ethylenic double bond, such as 1,2,2,6,6-pentamethyl-4-piperidinyl (meth)acrylate, are preferred.

In the surface protective layer, these ultraviolet absorbers and light stabilizers can be used alone or in combination. Moreover, the ultraviolet absorber and the light stabilizer may have a reactive functional group having an ethylenic double bond, such as a (meth)acryloyl group, vinyl group, or allyl group. Due to the interaction with the curable resin that constitutes the surface protective layer, it is difficult to bleed out.

The content of the ultraviolet absorber in the surface protective layer is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass with respect to 100 parts by mass of the curable resin constituting the surface protective layer. It is more preferably at least 0.5 part by mass, and particularly preferably 0.5 part by mass. Moreover, as an upper limit, 10 mass parts or less are preferable, and 5 mass parts or less are more preferable.
The content of the light stabilizer in the surface protective layer is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and 1 part by mass with respect to 100 parts by mass of the curable resin constituting the surface protective layer. The above is more preferable, and 1.5 parts by mass or more is particularly preferable. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. When the content of the ultraviolet absorber and the light stabilizer in the surface protective layer is within the above ranges, bleeding out does not occur, excellent processability can be obtained, and excellent addition effects can be obtained.

In addition to the above ultraviolet absorbers and light stabilizers, the surface protective layer may contain, as additives, ultraviolet shielding agents, wear resistance improvers, polymerization inhibitors, cross-linking agents, infrared Absorbents, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, antiblocking agents, lubricants, solvents and the like can be added.

In addition, from the viewpoint of improving design, the surface protective layer may contain a white pigment such as titanium white, and other coloring agents such as inorganic pigments exemplified as coloring agents that can be contained in the substrate. When an inorganic pigment such as a white pigment is contained in the surface protective layer, the content of the inorganic pigment is preferably 1 part by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass of the resin constituting the surface protective layer. It is more preferably 5 parts by mass or more, and the upper limit is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. When the content of the inorganic pigment is within the above range, excellent processing characteristics can be obtained, and the use of the inorganic pigment can also provide excellent design properties.

The thickness of the surface protective layer is preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more, from the viewpoint of improving processability, scratch resistance, and weather resistance. Moreover, as an upper limit, 15 micrometers or less are preferable, 10 micrometers or less are more preferable, and 8 micrometers or less are still more preferable.

(decorative layer)
The decorative sheet of the present invention preferably has a decorative layer between the substrate and the surface protective layer from the viewpoint of improving the 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. or a combination thereof. For example, when the base color of the adherend is to be colored and concealed, a solid colored layer can be used to conceal the color and improve the design, and from the viewpoint of further improving the design, solid coloring A layer and a pattern layer may be combined. On the other hand, when making the best use of the background pattern of the adherend, only the pattern layer may be provided without forming a solid colored layer.

The ink used for the decorative layer is a mixture of a binder and coloring agents 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. Polyurethane-acrylic copolymer derived from a polymer having a carbonate bond in the chain and two or more hydroxyl groups in the terminals and side chains (polycarbonate polyol), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acetic acid Resins such as vinyl-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins and cellulose acetate resins are preferred, and these can be used alone or in combination. In addition to the one-liquid curing type, curing of isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID), xylylene diisocyanate (XDI), etc. Various types of resins can be used, such as two-part curable types with agents.

In the decorative layer, for example, white pigments such as titanium white; inorganic pigments such as iron black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; Organic pigments or dyes; metal pigments made of scale-like foils such as aluminum and brass; coloring agents such as pearlescent (pearl) pigments made of scale-like foils such as titanium dioxide-coated mica and basic lead carbonate. can.

From the viewpoint of improving weather resistance, the decorative layer may contain weather resistance agents such as ultraviolet absorbers and light stabilizers.
Examples of the ultraviolet absorber and light stabilizer include the ultraviolet absorber and light stabilizer exemplified as those that can be contained in the base material. From the viewpoint of improving weather resistance, the content of the ultraviolet absorber and the light stabilizer can be exemplified in the same range as the content in the surface protective layer.

When a decorative layer has a pattern layer, the pattern may be a wood grain pattern, a marble pattern (e.g., travertine marble pattern) that imitates the surface of a rock, a fabric pattern that imitates a texture or cloth-like pattern, or a tile. There are pasted patterns, brickwork patterns, etc., and there are patterns such as marquetry and patchwork that combine these. These patterns are formed by multi-color printing using the usual yellow, red, blue, and black process colors, as well as multi-color printing using special colors, which is performed by preparing individual color plates that make up the pattern. be done.

The thickness of the decorative layer may be appropriately selected according to the desired pattern, but from the viewpoint of coloring and concealing the ground color of the adherend and improving the design property, the thickness is preferably 0.5 μm or more, and 1 μm or more. It is more preferably 2 µm or more, and the upper limit is preferably 20 µm or less, more preferably 10 µm or less, and even more preferably 5 µm or less.

(resin layer)
The resin layer is a layer that is preferably provided as desired from the viewpoints of protecting the decorative layer, processing properties, and improving scratch resistance and weather resistance.

Examples of resins constituting the resin layer preferably include polyolefin resins, polyester resins, acrylic resins, polycarbonate resins, polyurethane resins, polystyrene resins, vinyl chloride resins, and vinyl acetate resins. Among these resins, polyolefin resins and polyester resins are preferred, and polyolefin resins are more preferred, from the viewpoints of improving processability, scratch resistance and weather resistance. Examples of the polyolefin resin include the resins exemplified as those capable of constituting the base material, among which the polypropylene resin is preferable.

The resin layer may be provided between the base sheet and the surface protective layer, and when the decorative layer is provided, it should be provided between the decorative layer and the surface protective layer from the viewpoint of protecting the decorative layer. is preferred.
The resin layer may be transparent or opaque, and when provided between the decorative layer and the surface protective layer, it is preferably transparent from the viewpoint of making the decorative layer more clearly visible. Here, the term "transparent" includes not only colorless transparency, but also colored transparency and semi-transparency. In addition, in the case of being colored, the coloring agent used is preferably the same as the coloring agent used for the base material.

If necessary, the resin layer may contain additives. For example, the additives exemplified as additives that can be contained in the base material can be used. From the viewpoint of improving the weather resistance of the decorative sheet of the present invention, it is preferable to use weather resistance agents such as ultraviolet absorbers and light stabilizers among the above additives.
Examples of the ultraviolet absorber and light stabilizer include the ultraviolet absorber and light stabilizer exemplified as those that can be used in the substrate and the surface protective layer. From the viewpoint of improving weather resistance, the content of these weathering agents can be exemplified in the same range as the content in the substrate.

The thickness of the resin layer is preferably 10 µm or more, more preferably 30 µm or more, and even more preferably 50 µm or more, from the viewpoints of protection of the decorative layer, processing properties, and improvement of scratch resistance and weather resistance. The upper limit is preferably 150 µm or less, more preferably 120 µm or less, and even more preferably 100 µm or less. Moreover, from the viewpoint of protecting the decorative layer and obtaining excellent scratch resistance, the thickness is preferably equal to or greater than that of the substrate.

In order to improve interlayer adhesion between the resin layer and other layers, one or both sides of the resin layer may be subjected to physical surface treatment such as an oxidation method or roughening method, or surface treatment such as a chemical surface treatment. can be applied. These physical or chemical surface treatments are preferably exemplified by the same methods as the surface treatment of the substrate.
Further, in order to improve interlayer adhesion between the resin layer and other layers, a treatment such as forming a primer layer on one side or both sides of the resin layer may be performed. This primer layer will be described later.

(primer layer)
The decorative sheet of the present invention can be provided with a primer layer as desired. The primer layer is a layer provided mainly to obtain the effect of improving the adhesion between layers, but in the present invention, since the effect of alleviating the heat shrinkage of each layer is also obtained, the decrease in gloss due to the degree of heat shrinkage of each layer , suppresses changes in appearance due to cracks, etc., and provides excellent weather resistance. In addition, when the primer layer is provided on the surface of the substrate opposite to the surface protective layer side (the primer layer in such a case is also referred to as a “back primer layer”), the substrate and the substrate A blocking effect can be obtained in addition to the effect of improving the interlayer adhesion with the adhesive.
The primer layer is preferably provided between the base material and the surface protective layer, between the resin layer and the surface protective layer when the resin layer is provided, and on the surface of the base material opposite to the surface protective layer side. .

For forming the primer layer, a resin composition is used in which a binder is appropriately mixed with a curing agent, a weather resistance agent such as an ultraviolet absorber and a light stabilizer, and an additive such as an antiblocking agent.
Examples of binders include those exemplified as binders that can be used in the decorative layer, namely, urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, Polycarbonate-based urethane-acrylic copolymer (urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate bond in the polymer main chain and two or more hydroxyl groups in the terminals and side chains), vinyl chloride- Resins such as vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins are preferred. A combination of species can be used. For example, a mixture of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol resin can be used as the binder.

In addition to the one-liquid curing type, curing of isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID), xylylene diisocyanate (XDI), etc. Various types of resins can be used, such as two-part curable types with agents.

From the viewpoint of improving weather resistance, the primer layer preferably contains a weather resistance agent such as an ultraviolet absorber and a light stabilizer. Examples of ultraviolet absorbers and light stabilizers include the ultraviolet absorbers and light stabilizers exemplified as those that can be contained in the substrate and the surface protective layer.
The content of the UV absorber in the primer layer is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more with respect to 100 parts by mass of the resin constituting the primer layer, and the upper limit is is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less.
In addition, the content of the light stabilizer in the primer layer is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 1.5 parts by mass with respect to 100 parts by mass of the resin constituting the primer layer. As described above, the amount is particularly preferably 2 parts by mass or more, and the upper limit is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less. When the content of the ultraviolet absorber and the light stabilizer in the primer layer is within the above range, excellent performance as a primer layer and excellent weather resistance can be obtained.

In addition, the primer layer preferably contains an antiblocking agent from the viewpoint of preventing blocking between decorative sheets during production and storage. Antiblocking agents include, for example, oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide and zinc oxide; hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide; magnesium carbonate and carbonate. carbonates such as calcium; sulfates such as calcium sulfate and barium sulfate; silicates such as magnesium silicate, aluminum silicate, calcium silicate and aluminosilicate; inhibitor; and the like, and these can be used alone or in combination. are mentioned.

In the inorganic compound-based antiblocking agent, the average particle size is preferably 1 μm or more, more preferably 3 μm or more. Moreover, as an upper limit, 8 micrometers or less are preferable and 7 micrometers or less are more preferable. When the average particle size of the antiblocking agent is within the above range, an antiblocking effect can be obtained, and the decorative sheets are less likely to be scratched when rubbed against each other.
The content of the antiblocking agent is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and still more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the resin constituting the primer layer. Moreover, as an upper limit, 5 mass parts or less are preferable, 3 mass parts or less are more preferable, and 2 mass parts or less are still more preferable.

The thickness of the primer layer is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more, from the viewpoint of obtaining an effect of improving interlayer adhesion and an effect of alleviating thermal contraction of each layer. Moreover, as an upper limit, 10 micrometers or less are preferable, 8 micrometers or less are more preferable, and 6 micrometers or less are still more preferable.

(adhesion layer)
The decorative sheet of the present invention can have an adhesive layer as required. In particular, when the decorative sheet of the present invention has a resin layer, providing an adhesive layer is effective in improving the interlayer adhesion between the resin layer and the decorative layer. As the adhesive constituting the adhesive layer, any adhesive commonly used in decorative sheets can be used without limitation.

Examples of adhesives include urethane-based adhesives, acrylic adhesives, epoxy-based adhesives, rubber-based adhesives, etc. Among them, urethane-based adhesives are preferable in terms of adhesive strength. As the urethane-based adhesive, for example, a two-component curable urethane resin containing various polyol compounds such as polyether polyol, polyester polyol, acrylic polyol, and polycarbonate diol and a curing agent such as the above-mentioned various isocyanate compounds is used. adhesives. In addition, acrylic-polyester-vinyl chloride resins and the like are suitable adhesives that easily exhibit adhesiveness when heated and can maintain adhesive strength even when used at high temperatures.

The thickness of the adhesive layer is preferably 0.1 μm or more, more preferably 1 μm or more, and still more preferably 2 μm or more, from the viewpoint of obtaining sufficient adhesion, and the upper limit is preferably 20 μm or less, more preferably 10 μm or less. is.

(recess)
The decorative sheet of the present invention preferably has recesses on the surface of the surface protective layer opposite to the substrate side (also referred to as "front surface"). Since the decorative sheet of the present invention has the concave portions, the texture (tactile sensation) is improved, resulting in a high-class feeling and an improved design.

As shown in FIG. 2, the recesses may be present on the surface of the surface protective layer opposite to the substrate side, and the depth of the recesses may remain within the surface protective layer. , or even the base material. From the viewpoint of obtaining an excellent texture (tactile sensation), it is preferable to combine not only the material remaining in the surface protective layer, but also the resin layer, the decorative layer, and the base material.

From the viewpoint of improving designability, the maximum depth D of the recess and the total thickness T of the decorative sheet preferably have a relationship of 0.15×T≦D≦T. The ratio D/T to the total thickness T of the decorative sheet is preferably 0.15 or more and 1 or less. From the same point of view, the relationship between the depth D of the concave portion and the total thickness T of the decorative sheet is more preferably 0.2×T≦D≦0.9×T, and more preferably 0.25×T≦ More preferably, D≦0.8×T. That is, the ratio D/T between the depth D of the recess and the total thickness T of the decorative sheet is preferably 0.2 or more, more preferably 0.25 or more, preferably 0.9 or less, and further preferably 0.8 or less. preferable.
In addition, the maximum depth of the concave portion may change relatively depending on the total thickness T of the decorative sheet. The upper limit is preferably 120 µm or less, more preferably 110 µm or less, and even more preferably 100 µm or less. By having such a maximum depth, the decorative sheet does not break during processing of the recessed portions, for example, embossing, and the recessed portions are not finished as if they were crushed, and the texture (touch) is improved. A sense of quality is obtained as a result of the improvement, and designability is improved.

Here, for the measurement of the maximum depth D of the concave portion, the height from the lowest point of the concave portion to the surface of the surface protective layer for any 30 points of the concave shape is measured using a surface roughness profile measuring machine. Cut-off value: 2.50 mm, type of cut-off filter: 2RC, tilt correction method: measured under linear measurement conditions, and the deepest was defined as the maximum depth.

Examples of the pattern of the recesses include wood grain board conduit grooves, slate surface irregularities, cloth surface textures, satin finish, grain, hairline, parallel line grooves, and the like. From the viewpoint of improving designability, it is preferable that the pattern of the concave portion is a pattern that is synchronized with the pattern of the decorative layer. For example, when the picture layer has a wood grain pattern, selecting a wood grain plate duct groove as the pattern of the recess and synchronizing the wood grain of the picture layer with the wood grain of the recess creates a more realistic, textured and luxurious feeling. A decorative sheet and a decorative material are obtained.

(Manufacturing method of decorative sheet)
Regarding the method for manufacturing the decorative sheet of the present invention, a decorative sheet having in order a substrate, a decorative layer, an adhesive layer, a resin layer, a primer layer and a surface protective layer, which is one of the preferred embodiments of the decorative sheet of the present invention, is used as an example. For, the manufacturing method thereof will be described.
For example, the decorative sheet of the present invention is prepared by applying a step (1) of providing a decorative layer to a base material, a step (2) of providing a resin layer on the decorative layer, and applying a curable resin composition on the resin layer, It can be produced by successively carrying out the step (3) of curing to form a surface protective layer.

Step (1) is a step of providing a decorative layer on the substrate. The decorative layer is formed by applying the ink used for forming the decorative layer on the base material to provide desired colored layers and pattern layers. The ink is applied by known methods such as gravure printing, bar coating, roll coating, reverse roll coating and comma coating, preferably gravure printing.

In the case of applying a surface treatment to the base material, in the case of forming the decoration layer, when providing the primer layer between the base material and the decoration layer, it may be provided before the formation of the decoration layer. When the back surface primer layer is provided on the surface (back surface) of the material opposite to the decoration layer side, it may be provided either before or after forming the decoration layer. The primer layer is formed by applying a resin composition constituting the primer layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, comma coating, and the like. can be done.

Step (2) is a step of providing a resin layer on the decoration layer. The resin layer is formed by applying an adhesive as necessary to the base material having the decorative layer to form an adhesive layer, and then using a resin composition that constitutes the resin layer to subject the resin layer to extrusion lamination or dry lamination. , wet lamination, thermal lamination, or the like.

When the resin layer is subjected to the surface treatment, the surface treatment may be performed after providing the resin layer.
Moreover, when providing a primer layer between a resin layer and a surface protective layer, after providing a resin layer, a primer layer may be provided using the resin composition which comprises a primer layer.

Step (3) is a step of applying a curable resin composition onto the resin layer and curing it to form a surface protective layer.
The surface protective layer is obtained by applying an ionizing radiation-curable resin composition containing the above-described ionizing radiation-curable resin onto a resin layer or a primer layer optionally provided on the resin layer, followed by curing. be done. In the case where the resin layer is not provided, the surface protective layer may be formed by applying a curable resin composition after providing the decorative layer on the base sheet and curing the composition.

Coating of the resin composition for forming the surface protective layer is preferably carried out by known methods such as gravure coating, bar coating, roll coating, reverse roll coating and comma coating so that the thickness after curing is a predetermined thickness. method, more preferably by gravure coating.

When an ionizing radiation resin composition is used to form the surface protective layer, the uncured resin layer formed by applying the resin composition is irradiated with ionizing radiation such as electron beams and ultraviolet rays to form a cured product, thereby improving the surface. It becomes a protective layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but usually the uncured resin layer can be cured at an acceleration voltage of about 70 to 300 kV. preferable.

The irradiation dose is preferably an amount that saturates the crosslink density of the ionizing radiation curable resin, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
The electron beam source is not particularly limited, and various electron beam accelerators such as Cockroft-Walton type, Vandegraft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type are used. be able to.
When ultraviolet rays are used as the ionizing radiation, radiation containing ultraviolet rays having a wavelength of 190 to 380 nm is emitted. There are no particular restrictions on the ultraviolet light source, and for example, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, carbon arc lamps and the like are used.

When a thermosetting resin composition is used to form the surface protective layer, the surface protective layer may be formed by performing heat treatment according to the resin composition to be used for curing.

When forming recesses in the surface protective layer, it is preferable to employ embossing, for example, in consideration of ease of work. Embossing may be performed by a conventional method using a known sheet-fed or rotary embossing machine.
When embossing is performed, for example, the decorative sheet is preferably heated to 80° C. or higher and 260° C. or lower, more preferably 85° C. or higher and 160° C. or lower, still more preferably 100° C. or higher and 140° C. or lower, and an embossing plate is pressed onto the decorative sheet. embossing can be performed.

[Cosmetic material]
The decorative material of the present invention comprises an adherend and the above-described decorative sheet of the present invention. They are laminated facing each other. That is, the decorative material of the present invention has at least an adherend, a substrate, and a surface protective layer in this order. FIG. 3 shows a schematic diagram showing a cross section of an example of a preferred embodiment of the decorative material of the present invention. The decorative material 20 of the present invention shown in FIG. 3 has an adherend 21, an adhesive layer 22, and the decorative sheet 10 of the present invention in this order.

(Substrate)
Examples of the adherend include flat plates of various materials, plate materials such as curved plates, three-dimensional articles, sheets (or films), and the like. For example, wood veneer made of various woods such as cedar, cypress, pine, lauan, etc., wood plywood, particle board, wood fiber board such as MDF (medium density fiber board), etc. Wood members used as three-dimensional articles, etc. ; Plate materials such as iron and aluminum, steel plates, three-dimensional articles, metal members used as sheets, etc.; Glass, ceramics such as ceramics, non-cement ceramic materials such as gypsum, non-ceramics such as ALC (lightweight cellular concrete) plates Plate materials such as ceramic materials and ceramic members used as three-dimensional articles; acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, vinyl chloride Plate materials such as resins, cellulose resins, and rubbers, three-dimensional articles, resin members used as sheets, and the like can be used. Moreover, these members can be used individually or in combination of multiple types.

The material to be adhered may be appropriately selected from the above according to the application, and may be interior or exterior materials for buildings such as walls, ceilings, floors, entrance doors, roofs, window frames, doors, handrails, baseboards. When used as fittings or fixtures such as rims, moldings, etc., it is preferably made of at least one member selected from wooden members, metal members and resin members, and exterior members such as outer walls, entrance doors, roofs, etc. In the case of use as fittings such as window frames, doors, etc., or fixtures, 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 according to the application and material, preferably 0.1 mm or more and 10 mm or less, more preferably 0.3 mm or more and 5 mm or less, and even more preferably 0.5 mm or more and 3 mm or less.

(adhesive layer)
The adherend and the decorative sheet are preferably bonded together via an adhesive layer in order to obtain excellent adhesiveness. That is, the decorative material of the present invention is preferably a member having at least an adherend, an adhesive layer, a substrate, and a surface protective layer in this order.

The adhesive used in the adhesive layer is not particularly limited, and known adhesives can be used. Preferred examples include adhesives such as heat-sensitive adhesives and pressure-sensitive adhesives. Examples of resins used for the adhesive constituting this adhesive layer include acrylic resins, polyurethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, and polyester resins. , polyamide resins, etc., and these can be used alone or in combination. In addition, a two-liquid curing type polyurethane-based adhesive or polyester-based adhesive using an isocyanate compound or the like as a curing agent can also be applied.
A pressure-sensitive adhesive can also be used for the adhesive layer. As the adhesive, acrylic-based, urethane-based, silicone-based, rubber-based, or other adhesives can be appropriately selected and used.

The adhesive layer is formed by coating the above resin in a form that can be applied, such as a solution or emulsion, by means of gravure printing, screen printing, reverse coating using a gravure plate, or the like, and drying. can do.
Although the thickness of the adhesive layer is not particularly limited, it is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, even more preferably 10 μm to 30 μm, from the viewpoint of obtaining excellent adhesiveness.

(Method for manufacturing decorative material)
The decorative material can be manufactured through a process of laminating a decorative sheet and an adherend.
This step is a step of laminating an adherend and the decorative sheet of the present invention, in which the surface of the adherend to be decorated faces the base-side surface of the decorative sheet. As a method for laminating the adherend and the decorative sheet, for example, there is a lamination method in which the decorative sheet is laminated on the plate-shaped adherend by pressing with a pressure roller with an adhesive interposed therebetween, and an adhesive is interposed. While the decorative sheet is supplied through the rollers, the decorative sheet is sequentially pressed and adhered to the multiple side surfaces of the adherend by a plurality of rollers in different directions. The decorative sheet is heated with a heater via a silicone rubber sheet until it reaches a predetermined temperature at which it softens, and a vacuum forming mold is pressed against the heated and softened decorative sheet. A preferred example is a vacuum forming process in which the decorative sheet is brought into close contact with a vacuum forming mold.

When using a hot-melt adhesive (heat-sensitive adhesive) in lamination or lapping, the heating temperature is preferably 160°C or higher and 200°C or lower, depending on the type of resin that constitutes the adhesive. For adhesives, the temperature is preferably 100° C. or higher and 130° C. or lower. Moreover, in the case of vacuum forming, it is common to carry out while heating, and the temperature is preferably 80° C. or higher and 130° C. or lower, more preferably 90° C. or higher and 120° C. or lower.

The decorative material obtained as described above can be arbitrarily cut, and the surface and the butt end portion can be arbitrarily decorated such as grooving and chamfering using a cutting machine such as a router and a cutter. Also, after the decorative sheet is adhered to a steel plate or the like, bending such as V-cutting or lapping may be applied. And various uses, for example, interior materials or exterior materials of buildings such as walls, ceilings, floors, entrance doors and roofs, window frames, doors, handrails, baseboards, surrounding edges, malls and other fittings or fixtures In addition, it can be used for kitchens, furniture or light electrical appliances, surface decorative boards of cabinets such as OA equipment, interior materials or exterior members of vehicles, and the like.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.
(Evaluation and measurement method)
(1) Measurement of Martens hardness The Martens hardness of the decorative sheet obtained in each example and comparative example was measured by the following method.
Using an ultra-micro hardness tester (micro-hardness tester, "Picodenter HM-500", manufactured by Fisher Instruments), at room temperature (23 ° C.), while continuously increasing the load, a pyramid-shaped diamond The indenter is pushed into the sample (the surface of the surface protective layer), the test load F (N) is measured when the indentation depth reaches 2 μm, and the surface area A (mm ² ) and dividing the test load F(N) by the surface area A, the Martens hardness was calculated.
(2) Evaluation of weather resistance The decorative material obtained in each example and comparative example was subjected to a weather resistance test in which it was left for 500 hours under the following test conditions. The appearance of the decorative material after the weather resistance test was visually observed and evaluated according to the following criteria. In addition, in the evaluation of this example, if it is superior to the “A” evaluation, it is “A ⁺ ”, and if it is superior to the “B” evaluation but does not reach the “A” evaluation, it is “B ⁺ ”. In some cases, a "+" is added.
A: No change in appearance was observed.
B: A slight gloss change was confirmed.
C: At least one of conspicuous gloss change and cracks was observed.
(Weatherability test test conditions)
During the test time of 500 hours, the following order of irradiation condition, shower, dew condensation condition, and shower was repeated.
Test equipment: Ultra-accelerated weather resistance tester (Isubar UV tester SUV-W261, manufactured by Iwasaki Electric Co., Ltd.)
Irradiation conditions Illuminance: 100 mW/cm ²
Black panel temperature: 63°C
Humidity: 50%
Time: 20 hours Dew condensation condition Illuminance: 0 mW/cm ²
Humidity: 98%
Time: 4 hours Shower: 30 seconds (3) Evaluation of scratch resistance (pencil hardness) The decorative sheets obtained in each example and comparative example were measured using a pencil-type scratch hardness tester ("Model 318", manufactured by Erichsen). , a scratch test was performed. The appearance after the test was evaluated according to the following criteria.
A: The test was performed with a hardness of 5N, and there was almost no change in appearance.
B: The test was performed at a hardness of 5N, and slight dents occurred on the surface of the coating film, but there were almost no scratches.
C: The test was performed at a hardness of 5N, and at least one of slight dents and scratches occurred on the surface of the coating film, but it was not noticeable.
D: The test was performed at a hardness of 5N, and significant scratches were generated on the surface of the coating film.
(4) Evaluation of processing characteristics (90-degree bending) For the decorative materials obtained in each example and comparative example, 90-degree bending at a test temperature of 25 ± 5 ° C. and an outer radius of 2.0 mm conforms to JIS K6744. After conducting the test, the processed portion was visually observed and evaluated according to the following criteria.
A: No change in appearance was observed at the corner (bent portion).
B: Slight whitening was confirmed at the corner (bend).
C: At least one of conspicuous whitening and cracks was observed at the corner (bent portion).
(5) Evaluation by hot water resistance test For the decorative material obtained in each example and comparative example, put the decorative material and water in a bottle with a lid and leave it in an oven (60 ° C.) for 200 hours. The appearance of the decorative material was visually observed and evaluated according to the following criteria.
A: No change in appearance was observed.
B: A slight gloss change was confirmed.
C: Appearance change was observed, but not noticeable.
D: Remarkable change in appearance was confirmed.

Example 1
A polypropylene resin sheet (thickness: 60 μm) subjected to double-sided corona discharge treatment was used as a base material, and printing ink containing a two-liquid curing type acrylic-urethane resin as a binder was applied to one side of the base material by gravure printing. A decorative layer with a wood grain pattern (thickness: 3 μm) is provided on the other side, and a two-liquid curing type urethane-nitrocellulose mixed resin (curing agent: 5 parts by weight of hexamethylene diisocyanate per 100 parts by weight of the resin) is applied. was applied to form a back primer layer (thickness: 3 μm).
A transparent polyurethane resin-based adhesive is applied on the decorative layer to form an adhesive layer (thickness after drying: 3 μm), and a transparent polypropylene resin is heat-melted and extruded using a T-die extruder to form a transparent adhesive. A resin layer (thickness: 80 μm) was formed.
Next, after subjecting the surface of the resin layer to corona discharge treatment, a composition obtained by mixing 100 parts by mass of the following resin composition for forming a primer layer and 5 parts by mass of hexamethylene diisocyanate (curing agent) was applied by gravure printing. to form a primer layer (thickness after drying: 4 μm).
Further, the following ionizing radiation-curable resin composition was applied onto the primer layer by a roll coating method to form an uncured resin layer, and an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) was applied. The uncured resin layer was cured to obtain a surface protective layer (thickness: 5 μm). Thereafter, embossing was applied from the surface protective layer side to form a wood grain vessel pattern having recesses with a maximum depth of 50 μm, thereby obtaining a decorative sheet.

A polyurethane heat-sensitive adhesive was applied to the base material of the obtained decorative sheet to form an adhesive layer (thickness: 20 μm), and before the adhesive layer was solidified, a galvanized steel sheet with a thickness of 0.4 mm was applied. to prepare a cosmetic material. The obtained decorative sheet and decorative member were evaluated as described above, and the evaluation results are shown in Table 1.

(Resin composition for primer layer formation)
Binder: mixture of polycarbonate urethane-acrylic copolymer and acrylic polyol resin UV absorber A: hydroxyphenyltriazine compound represented by the above general formula (2) ("TINUVIN479", manufactured by BASF) per 100 parts by mass of binder 3 parts by mass UV absorber B: Hydroxyphenyltriazine compound represented by the following general formula (3) ("TINUVIN400", manufactured by BASF) 12 parts by mass with respect to 100 parts by mass of the binder

Light stabilizer a: hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, "TINUVIN123", manufactured by BASF) 3 parts by weight per 100 parts by weight of the binder Department

(Ionizing radiation curable resin composition)
Ionizing radiation curable resin (oligomer 1): urethane acrylate oligomer (weight average molecular weight: 3,000, number of functional groups: 3) 70 parts by mass Ionizing radiation curable resin (oligomer 2): urethane acrylate oligomer (weight average molecular weight: 10, 000, number of functional groups: 2) 30 parts by mass Ultraviolet absorber A: Hydroxyphenyltriazine compound represented by the above general formula (2) ("TINUVIN479", manufactured by BASF) 2 parts by mass per 100 parts by mass of ionizing radiation curable resin Part light stabilizer a: Hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, "TINUVIN123", manufactured by BASF) ionizing radiation curable resin 100 parts by mass 2 parts by mass for

Examples 2-5, Comparative Examples 1-5
In Example 1, the amounts of the ionizing radiation-curable resins (oligomer 1) and (oligomer 2) in the ionizing radiation-curable resin composition forming the surface protective layer were set as shown in Table 1, and the decorative sheet was prepared. Decorative sheets and decorative materials of Examples 2 to 5 and Comparative Examples 1 to 5 were produced in the same manner as in Example 1, except that the elastic modulus of was set to that shown in Table 1.

Example 6
In Example 1, the light stabilizer a in the ionizing radiation curable resin composition forming the surface protective layer was the following reactive functional group having an ethylenic double bond in the molecule (methacryloyl group) A decorative sheet and a decorative material of Example 6 were produced in the same manner as in Example 1, except that the light stabilizer b was used.
Light stabilizer b: 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (“Sanol LS-3410 (trade name)”, manufactured by Nippon Nyukazai Co., Ltd.)

Example 7
In Example 1, the ionizing radiation-curable resins (oligomer 1) and (oligomer 2) in the ionizing radiation-curable resin composition forming the surface protective layer were replaced with the following ionizing radiation-curable resins (oligomer 3) and (oligomer 4), and in the same manner as in Example 1, except that the following reactive light stabilizer b having a reactive functional group (methacryloyl group) having an ethylenic double bond in the molecule is used as the light stabilizer a. , the decorative sheet and decorative material of Example 6 were produced.
Ionizing radiation curable resin (oligomer 3): urethane acrylate oligomer (weight average molecular weight: 3,000, number of functional groups: 2)
Ionizing radiation curable resin (oligomer 4): Polycarbonate urethane acrylate oligomer (weight average molecular weight: 4,200, number of functional groups: 2)
Light stabilizer b: 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (“Sanol LS-3410 (trade name)”, manufactured by Nippon Nyukazai Co., Ltd.)

The decorative sheets and decorative members obtained in the above Examples and Comparative Examples were evaluated as described above, and the evaluation results are shown in Table 1.

From the results of Examples 1 to 5, it was confirmed that the decorative sheet of the present invention has excellent processability, weather resistance and scratch resistance.
Moreover, in Example 6 using a light stabilizer having a methacryloyl group, an improvement effect was confirmed in comparison with Example 1 in the evaluation of weather resistance (ultra-accelerated weather resistance test) and hot water resistance test. This improvement effect is considered to be due to the fact that the light stabilizer is more strongly retained by the reaction between the methacryloyl group of the light stabilizer and the acryloyl group of the ionizing radiation-curable resin. Further, in Example 7, in which polycarbonate urethane acrylate was used as the ionizing radiation curable resin, an even more excellent effect of improving weather resistance (ultra-accelerated weather resistance test and hot water resistance test) was confirmed. This improvement effect is considered to be due to the fact that weather resistance agents such as ultraviolet absorbers and light stabilizers are more strongly retained due to the excellent hydrolysis resistance effect of polycarbonate urethane acrylate.
On the other hand, the decorative sheet of Comparative Example 1, in which the modulus of elasticity of the decorative sheet is as small as 300 MPa, cannot obtain scratch resistance even if the surface protective layer has a Martens hardness of 21 N/mm ² , which is the specified range of the present invention. The decorative sheet of Comparative Example 4, in which the surface protective layer had a Martens hardness as low as 8 N/mm ² , did not have scratch resistance even though the elastic modulus of the decorative sheet was 700 MPa, which was within the specified range of the present invention. The decorative sheet of Comparative Example 2, in which the elastic modulus of the decorative sheet was as high as 1,900 MPa, did not exhibit processability even when the Martens hardness of the surface protective layer was 21 N/mm ² , which is the specified range of the present invention. In the decorative sheet of Comparative Example 3, the surface protective layer had a Martens hardness as high as 32 N/mm ² , and even though the elastic modulus of the decorative sheet was 700 MPa, which was within the specified range of the present invention, the surface protective layer was too hard and processing characteristics were not obtained. In addition, since the surface protective layer had fine cracks, significant changes in luster and cracks occurred during use due to differences in heat shrinkage of each layer. Moreover, in Comparative Example 5 in which no ultraviolet absorber was used, weather resistance was not obtained.

The decorative sheet of the present invention has excellent processability, weather resistance and scratch resistance, and the decorative material using it has excellent weather resistance and scratch resistance. Therefore, in addition to building interior or exterior materials such as walls, ceilings, floors, entrance doors, roofs, window frames, doors, handrails, baseboards, surrounds, malls, etc., fittings or fixtures, kitchens, furniture Alternatively, it can be suitably used as a surface decorative board for cabinets of light electrical appliances, OA equipment, etc., or as an interior or exterior member for vehicles. Taking advantage of its excellent scratch resistance and weather resistance, it is especially suitable for members used in environments exposed to direct sunlight, such as exterior members such as exterior walls, entrance doors, and roofs, and fittings and fixtures such as window frames and doors. Used.

10. Cosmetic sheet 11 . base material 12 . decoration layer 13 . adhesive layer 14 . resin layer 15 . Primer layer 16 . surface protective layer 17 . back primer layer 18 . UV absorber 19. recess 20 . Cosmetic material 21 . adherend 22 . adhesive layer

Claims (13)

It has a base material and a surface protective layer composed of a cured product of a curable resin composition having a Martens hardness of 12 N/mm ² or more and 30 N/mm ² or less and containing an ultraviolet absorber, and has an elastic modulus of 400 MPa. A decorative sheet having a pressure of 1,800 MPa or more. 2. The decorative sheet according to claim 1, further comprising a transparent resin layer and a primer layer, and further comprising a substrate, a transparent resin layer, a primer layer and a surface protective layer in this order. 3. The decorative sheet according to claim 1, further comprising a decorative layer between the substrate and the surface protective layer. The decorative sheet according to any one of claims 1 to 3, wherein the curable resin composition is an ionizing radiation curable resin composition. The decorative sheet according to claim 4, wherein the ionizing radiation-curable resin contained in the ionizing radiation-curable resin composition contains a urethane (meth)acrylate oligomer having a weight average molecular weight of 2,500 or more. The ionizing radiation curable resin is at least one weight average selected from urethane (meth)acrylate oligomers having a weight average molecular weight of 2,500 or more and less than 3,500, urethane (meth)acrylate oligomers, and polycarbonate urethane (meth)acrylate oligomers. The decorative sheet according to claim 5, comprising a (meth)acrylate oligomer having a molecular weight of 3,500 or more. The compounding ratio (mass ratio) of the urethane (meth)acrylate oligomer having a weight average molecular weight of 2,500 or more and less than 3,500 and the (meth)acrylate oligomer having a weight average molecular weight of 3,500 or more is 1:99 to 90. :10. The decorative sheet according to any one of claims 1 to 7, wherein the ultraviolet absorber contains a hydroxyphenyltriazine compound represented by the following general formula (1).

(In general formula (1), R ¹¹ is a divalent organic group, R ¹² is an ester group represented by -C(=O)OR ¹⁵ , R ¹³ , R ¹⁴ and R ¹⁵ are each independently is a monovalent organic group, and _n11 and _n12 are each independently an integer of 1 to 5.) The hydroxyphenyltriazine compound is an alkyl ester group in which, in general formula (1), R ¹¹ is an alkylene group having 1 to 20 carbon atoms, and R ¹² and R ¹⁵ are alkyl groups having 1 to 20 carbon atoms. _9. The decorative sheet according to claim ⁸ , wherein R13 and R14 are aryl groups having 6 to 20 carbon atoms, and ⁿ¹¹ and _n12 are 1 compounds. The decorative sheet according to any one of claims 1 to 9, wherein the surface protective layer has a thickness of 3 µm or more and 10 µm or less. The decorative sheet according to any one of claims 1 to 10, wherein the substrate is an olefin resin substrate. A decorative material comprising an adherend and the decorative sheet according to any one of claims 1 to 11. 13. The decorative material according to claim 12, wherein the adherend comprises at least one member selected from metal members and resin members.

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