JP7000699B2 - Decorative sheet and decorative material using it - Google Patents

Description

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

Conventionally, decorative sheets have been used to decorate or protect the surfaces of interior and exterior members of buildings, furniture, building members, home appliances, and the like. The decorative sheet has, for example, a structure having a surface protective layer on a base material.

These decorative sheets cause a change in color tone and deterioration of the resin due to the influence of ultraviolet rays in outdoor use and indoor use where they are exposed to sunlight near a window or the like. Therefore, for the purpose of improving the light resistance, an ultraviolet absorber is added to the surface protective layer of the decorative sheet.

However, there is a problem that the ultraviolet absorber tends to bleed out (also referred to as "bleed out" or "transition") from the surface protective layer over time. When the ultraviolet absorber bleeds out, there is a problem that the appearance of the surface of the decorative sheet is spoiled and the concentration of the ultraviolet absorber in the surface protective layer decreases with time, resulting in insufficient light resistance. For example, Patent Document 1 has been proposed in order to eliminate the bleeding of the ultraviolet absorber.

Japanese Unexamined Patent Publication No. 2000-117905

The decorative sheet of Patent Document 1 contains an electron beam reaction type ultraviolet absorber selected from a specific benzotriazole-based compound or the like in a cured layer of a resin containing an electron beam curable resin as a main component. The decorative sheet of Patent Document 1 can solve the problem of bleed-out of the ultraviolet absorber.

On the other hand, decorative sheets are often required to have processing aptitudes such as embossing, bending, and molding. In recent years, decorative sheets are laminated with a layer containing a polyolefin resin having excellent processing aptitude, and further laminated with a surface protective layer. Has been proposed. When the surface protective layer of Patent Document 1 is applied to a decorative sheet obtained by laminating layers containing such a polyolefin resin, even if the bleed-out of the ultraviolet absorber in the surface protective layer is suppressed, the decorative sheet In many cases, it was not possible to suppress the deterioration over time due to ultraviolet rays.

The present invention has been made under such circumstances, and an object of the present invention is to suppress deterioration over time due to ultraviolet rays in a decorative sheet formed by laminating layers containing a polyolefin resin and a decorative material using the same. Is.

In order to solve the above problems, the present invention provides the following [1] to [2].
[1] The surface protective layer has a surface protective layer, a transparent resin layer containing a polyolefin resin, and a base material layer containing a polyolefin resin in this order, and the wavelength of the surface protective layer is 310 nm, which is measured in accordance with JIS K0115: 2004. The absorbance A ₁ in the above is 0.8 or more, and the absorbance A ₂ of the surface protective layer and the transparent resin layer containing the polyolefin resin measured in accordance with JIS K0115: 2004 at a wavelength of 310 nm is 1.2 or more. Is a decorative sheet.
[2] A decorative material having the adherend and the decorative sheet according to the above [1].

According to the present invention, in a decorative sheet in which layers containing a polyolefin resin are laminated, deterioration over time due to ultraviolet rays can be suppressed.

It is sectional drawing which shows one Embodiment of the decorative sheet of this invention.

[Cosmetic sheet]
The decorative sheet of the present invention has a surface protective layer, a transparent resin layer containing a polyolefin resin, and a base material layer containing a polyolefin resin in this order, and the surface protection measured in accordance with JIS K0115: 2004. The absorbance A ₁ of the layer at a wavelength of 310 nm is 0.8 or more, and the absorbance A ₂ of the surface protective layer and the transparent resin layer containing the polyolefin resin measured in accordance with JIS K0115: 2004 at a wavelength of 310 nm is. It is 1.2 or more.
Hereinafter, "absorbance A _{1 of the surface protective layer measured in accordance with JIS K0115: 2004" at a wavelength of 310 nm is referred to as "absorbance A 1 "} , and the surface protective layer and surface protective layer measured in accordance with JIS K0115: 2004. The "absorbance A _{2" of the transparent resin layer containing the polyolefin resin at a wavelength of 310 nm may be referred to as "absorbance A 2 "} . Further, hereinafter, the "transparent resin layer containing a polyolefin-based resin" may be referred to as a "transparent resin layer", and the "base material layer containing a polyolefin-based resin" may be referred to as a "base material layer".

FIG. 1 is a cross-sectional view showing an embodiment of the decorative sheet 100 of the present invention.
The decorative sheet 100 of FIG. 1 has a surface protective layer 10, a transparent resin layer 20 containing a polyolefin-based resin, and a base material layer 40 containing a polyolefin-based resin in this order. Further, the surface protective layer 10 of the decorative sheet 100 of FIG. 1 is composed of a primer layer 12 and a top coat layer 11. Further, the decorative sheet 100 of FIG. 1 has a decorative layer 30 between the base material layer 40 and the transparent resin layer 20.

<Asorbance>
The decorative sheet of the present invention has an absorbance A ₁ of 0.8 or more and an absorbance A ₂ of 1.2 or more. A large absorbance A ₁ means that there is little light having a wavelength of 310 nm that reaches the layer containing the polyolefin resin (transparent resin layer) located on the side close to the surface protective layer, and a large absorbance A ₂ means that there is little light. This means that there is little light having a wavelength of 310 nm that reaches the layer (base material layer) containing the polyolefin resin located on the far side of the surface protective layer.
Conventional decorative sheets are usually designed to add an ultraviolet absorber only to the surface protective layer (top coat layer or primer layer). That is, the conventional decorative sheet was designed _only for the absorbance A1. However, the design with only the absorbance A ₁ has a limit in improving the light resistance of the decorative sheet. That is, although the degree of various ultraviolet absorbers varies depending on the material, all of them are lost over time due to bleeding out from the layer to the outside, and the concentration thereof decreases. Therefore, even if the deterioration of each layer below the transparent resin layer directly under the surface protective layer due to ultraviolet rays can be suppressed in the short term, the suppression of deterioration due to ultraviolet rays cannot be sustained for a long period of time. Usually, the light resistance is the time until the deterioration of each layer below the transparent resin layer (that is, the entire decorative sheet) due to ultraviolet rays in the state of being exposed to sunlight including ultraviolet rays reaches a predetermined degree assumed in advance. Be evaluated. Therefore, there is a limit to the improvement of light resistance in the design in which _only the absorbance A1 of the surface protective layer is increased. It is also conceivable to design to improve the light resistance (the number of hours until deterioration) by adding an extra amount of the ultraviolet absorber in the surface protective layer as much as it is lost due to migration over time. There are problems such as deterioration of the main physical properties such as scratch resistance and stain resistance of the surface protective layer due to excessive addition of the UV absorber, and deterioration of the appearance such as white turbidity of the surface due to the bleed-out UV absorber. The design was also virtually difficult to adopt.
Even if two types of absorbances (absorbance A ₁ and absorbance A ₂ ) are specified, if the absorbance A ₁ is less than 0.8 or the absorbance A ₂ is less than 1.2, the polyolefin. With respect to a decorative sheet in which layers containing a based resin are laminated, deterioration over time due to ultraviolet rays cannot be sufficiently suppressed.

The absorbance A ₁ and the absorbance A ₂ defined in the present invention are both absorbances of light having a wavelength of 310 nm, and are also characterized in that the wavelength of ultraviolet rays to be absorbed is specified in the present invention.
The polyolefin-based resin has an absorption wavelength, and is usually 300 nm and 310 to 340 nm for polyethylene, and 310 nm and 370 nm or 320 to 380 nm for polypropylene. It is considered that photons of these wavelengths contribute to the deterioration of the polyolefin resin.
In the present invention, attention is paid to two types of absorbances (absorbance A ₁ and absorbance A ₂ ) for light having a wavelength of 310 nm, which is common to various polyolefin resins and has a high energy (photon) among the absorption wavelengths of the polyolefin resin. By setting the two types of absorbances (absorbance A ₁ and absorbance A ₂ ) in a specific range, it is possible to suppress the deterioration of the decorative sheet formed by laminating layers containing a polyolefin resin over time due to ultraviolet rays. ..

The absorbance A ₁ is preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 2.5 or more.
The large absorbance A ₁ means that the content of the ultraviolet absorber in the surface protective layer is high, or that the film thickness of the surface protective layer is thick. When the content of the ultraviolet absorber in the surface protective layer is high, the scratch resistance of the bleed-out and the surface protective layer tends to decrease, and when the film thickness of the surface protective layer is thick, the processability of the decorative sheet decreases. Tend. Therefore, the absorbance A ₁ is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less.

The absorbance A ₂ is preferably 1.5 or more, more preferably 3.0 or more, and even more preferably 4.0 or more.
The upper limit of the absorbance A ₂ is not particularly limited, but in consideration of bleed-out, it is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.
Absorbance A ₁ and absorbance A ₂ can be adjusted by the content ratio of the ultraviolet absorber and the thickness of the layer containing the ultraviolet absorber.

Absorbance A ₂ is obtained by measuring the absorbance of a laminate having a surface protective layer formed on a transparent resin layer at a wavelength of 310 nm in accordance with JIS K0115: 2004. Absorbance A ₁ is obtained by measuring the absorbance A ₀ of the transparent resin layer at a wavelength of 310 nm and subtracting the absorbance A ₀ from the absorbance A ₂ in accordance with JIS K0115: 2004 (absorbance A ₁ = absorbance A ₂ ). -Absorbance A ₀ ).

<Surface protective layer>
The surface protective layer is a layer located on the surface opposite to the base material layer of the transparent resin layer. The surface protective layer may be formed of a single layer or may be formed of two or more layers as shown in FIG.
In the present specification, the layer of the surface protective layer farthest from the transparent resin layer is referred to as a "top coat layer". That is, when the surface protective layer is formed from a single layer, the surface protective layer has a single layer structure of the top coat layer. When the surface protective layer is formed of two or more layers, the layer located between the top coat layer and the transparent resin layer is a layer other than the top coat layer among the layers constituting the surface protective layer. It means that there is.

The surface protective layer is mainly composed of resin.
It is preferable that the resin constituting the surface protective layer does not substantially contain an olefin resin. In the present invention, the light having a wavelength of 310 nm reaching the transparent resin layer is sufficiently limited by defining the absorbance A ₁ , but the surface protective layer is reached by a larger amount of light having a wavelength of 310 nm than the transparent resin layer. is doing. Therefore, it is preferable that the resin constituting the surface protective layer does not substantially contain an olefin resin, so that the light resistance of the surface protective layer can be easily improved.
The fact that the olefin resin is substantially not contained means that the ratio of the olefin resin to the total resin components constituting the surface protective layer is 1% by mass or less, preferably 0.1% by mass or less. , More preferably 0.01% by mass or less, still more preferably 0% by mass.

(UV absorber)
It is preferable to contain an ultraviolet absorber in the surface protective layer and / or the transparent resin layer described later.
When the surface protective layer is formed from two or more layers, it is preferable that at least the top coat layer contains an ultraviolet absorber, and it is more preferable that all the layers constituting the surface protective layer contain an ultraviolet absorber.

Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, and the like, and a triazine-based ultraviolet absorber is preferable. Further, among the triazine-based ultraviolet absorbers, the hydroxyphenyltriazine-based ultraviolet absorber is preferable from the viewpoint of light resistance.
Further, an ultraviolet absorber having a reactive functional group such as a (meth) acryloyl group, a vinyl group or an allyl group is preferable because it is easy to suppress bleed-out.

The content of the ultraviolet absorber in the surface protective layer is not particularly limited as long as the absorbance A ₁ is 0.8 or more.
The content of the ultraviolet absorber in the top coat layer constituting the surface protective layer is preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the resin constituting the top coat layer, preferably 1.0. It is more preferably 2 parts by mass or more and 9.5 parts by mass or less, further preferably 2.0 parts by mass or more and 9.0 parts by mass or less, and further preferably 5.0 parts by mass or more and 8.5 parts by mass or less.
When the other layer constituting the surface protective layer contains an ultraviolet absorber, the content of the ultraviolet absorber in the other layer is 0.5 with respect to 100 parts by mass of the resin constituting the other layer. It is preferably 1.0 part by mass or more and 10.0 parts by mass or less, more preferably 1.0 part by mass or more and 9.5 parts by mass or less, further preferably 2.0 parts by mass or more and 9.0 parts by mass or less, and 5.0 parts by mass or more. It is even more preferably 8.5 mass or less.

(Light stabilizer)
The surface protective layer and / or the transparent resin layer described later preferably contain a light stabilizer. In particular, since the surface protective layer is the layer to which ultraviolet rays are first incident among the layers constituting the decorative sheet, it is preferable to contain a light stabilizer.

As the light stabilizer, a hindered amine-based light stabilizer is preferable.
Examples of the hindered amine-based light stabilizer include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl (meth) acrylate and bis (2,2). , 6,6-Tetramethyl-4-piperidyl) sevacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sevakate, bis (1-octyl oshiki-2,2,6,6-tetramethyl) -4-piperidinyl) sevacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sevakate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sevakate, 2,4 -Bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine) , Tetrakiss (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis- (1,2,2,6,6-pentamethyl-4-) Piperidil) -2- (3,5-di-t-butyl-4-hydroxy-benzyl) -2-n-butylmalonate and the like can be mentioned. Among these, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyl oshiki-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- A hindered amine-based photostabilizer derived from decanedioic acid (sebacic acid) such as 4-piperidinyl) sebacate is preferable.

The content of the light stabilizer in the top coat layer constituting the surface protective layer is preferably 0.1 part by mass or more and 10 parts by mass or less, preferably 0.5 part by mass with respect to 100 parts by mass of the resin constituting the top coat layer. 8 parts by mass or less is more preferable, 1 part by mass or more and 5 parts by mass or less is further preferable, and 1.5 parts by mass or more and 3 parts by mass or less is further preferable.
When the other layer constituting the surface protective layer contains a light stabilizer, the content of the light stabilizer in the other layer is 0.1 with respect to 100 parts by mass of the resin constituting the other layer. It is preferably 5 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 8 parts by mass or less, further preferably 1 part by mass or more and 5 parts by mass or less, and further preferably 1.5 parts by mass or more and 3 parts by mass or less. ..

(Nanoshelling of UV absorbers and / or light stabilizers)
The UV absorber and / or the light stabilizer may be encapsulated in nanoshells.
By using the UV absorber and / or the light stabilizer contained in the nanoshell, the dispersibility (compatibility) between the resin in the surface protective layer and the UV absorber and / or the light stabilizer is improved, and the inside of the layer is improved. The effect of light resistance can be homogenized and the mechanical strength can be improved. Further, it is expected that the bleed-out of the ultraviolet absorber and / or the light stabilizer is suppressed by the binding between the nanoshell and the resin of the surface protective layer.

A "nanoshell" is a "hollow endoplasmic reticulum having a nano-sized shell-like closed membrane structure".
The average primary particle size of the nanoshell containing the ultraviolet absorber and / or the light stabilizer is less than the wavelength region of visible light (380 to 780 nm) and about ½ or less of the wavelength of visible light, that is, It is less than 380 nm. More specifically, it is preferably 1 nm or more and less than 380 nm, more preferably 1 to 375 nm, further preferably 5 to 300 nm, still more preferably 10 to 250 nm, and particularly preferably 15 to 200 nm.

The average primary particle size is a value calculated by statistical processing from observation images measured by a transmission electron microscope (TEM) and a scanning transmission electron microscope (STEM). Specifically, the calculation by statistical processing is performed by the calculation using the following formula (A) when the diameter is measured for 1000 particles randomly selected from the SEM image and a histogram of the 3 nm division is created. It is a thing. The number average primary particle diameter _Dnp obtained by the formula (A) was taken as the average primary particle diameter of the present specification.

D _np = Σn _{i di / Σn i (} A)
D _np : Number average primary particle diameter di: Histogram _{i-th diameter n i :} Frequency

The nanoshell is not particularly limited as long as it can contain an ultraviolet absorber and / or a light stabilizer, and may be a single-layer film or a multilayer film, but the average primary particle size is higher. A single-layer film is preferable from the viewpoint of making it smaller and improving dispersibility (compatibility). Further, phospholipids are preferable as the material for forming the nanoshell. That is, the morphology of the nanoshell is more preferably a monolayer membrane made of phospholipids.

Phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yellow egg lecithin, hydrogenated yellow egg lecithin, soy lecithin, hydrogenated soy lecithin and other glycerophospholipids; Sphingophospholipids such as myerin, ceramide phosphoriethanolamine, ceramide phosphorylglycerol; and the like. These phospholipids can be used alone or in combination of two or more.

Examples of the method of encapsulating an ultraviolet absorber and / or a light stabilizer in a nanoshell include a Bangham method, an extrusion method, a hydration method, a surfactant dialysis method, a reverse phase evaporation method, a freeze-thaw method, and a supercritical reverse phase. Evaporation method and the like can be mentioned.
In the Bangham method, a phospholipid is added to a solvent such as chloroform or methanol to dissolve the phospholipid, and then the solvent is removed using an evaporator to form a thin film composed of the phospholipid, and an ultraviolet absorber and / or a light stabilizer is added. After that, it is a method of hydrating and dispersing by stirring at a high speed rotation of, for example, about 1000 to 2500 rpm using a mixer, and encapsulating an ultraviolet absorber and / or a light stabilizer in a nanoshell. The extrusion method is a method of passing a filter instead of the mixer used as an external perturbation. The hydration method is a method in the Bangham method in which a nanoshell is encapsulated with an ultraviolet absorber and / or a light stabilizer by gently stirring and dispersing without using a mixer. In the reverse phase evaporation method, a phospholipid is dissolved in a solvent such as diethyl ether or chloroform, and an ultraviolet absorber and / or a light stabilizer (which may be in the state of a dispersion) is added to prepare a W / O emulsion. , The solvent is removed from the emulsion under reduced pressure, water is added, and an ultraviolet absorber and / or a light stabilizer is encapsulated in a nanoshell. The freeze-thaw method is a method of performing at least one of cooling and heating as an external perturbation, and is a method of encapsulating an ultraviolet absorber and / or a light stabilizer in a nanoshell by repeating cooling and heating.

Further, by adopting the supercritical reverse phase evaporation method, the nanoshell can be made into a monolayer film made of phospholipid more reliably and easily. In the supercritical reverse phase evaporation method, for example, as described in JP-A-2016-137585, a crystal nucleating agent is used by using carbon dioxide in a supercritical state, a temperature condition equal to or higher than a critical point, or a pressure condition. Is a method of encapsulating in a nanoshell. Here, carbon dioxide in a supercritical state means carbon dioxide in a supercritical state having a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, and a temperature condition above the critical point. Carbon dioxide under lower or pressure conditions means carbon dioxide under conditions where only one of the temperature and the critical condition exceeds the critical condition.

In the supercritical reverse phase evaporation method, specifically, water is added to a mixture of an ultraviolet absorber and / or a light stabilizer, supercritical carbon dioxide, and phospholipids, and the mixture is stirred to obtain supercritical carbon dioxide. By forming an aqueous phase emulsion and then depressurizing, carbon dioxide expands and evaporates to cause phase inversion, forming a nanoshell in which the surface of the ultraviolet absorber and / or light stabilizer is covered with a monolayer of phospholipid. It is to obtain an ultraviolet absorber and / or a light stabilizer that is formed and encapsulated in a nanoshell. In addition, when it is desired to form a multilayer film as in the prior art, supercritical carbon dioxide may be added to a mixture of an ultraviolet absorber and / or a light stabilizer, a phospholipid, and water in the above method.

(Nanoshelling of dispersant)
Further, by containing the dispersant contained in the nanoshell in the surface protective layer, the dispersibility (compatibility) between the resin in the surface protective layer and the ultraviolet absorber and / or the light stabilizer is improved, and the layer is formed. It is possible to homogenize the effect of light resistance inside and improve the mechanical strength.
The size of the dispersant contained in the nanoshell and the embodiment of the material of the nanoshell are the same as those of the ultraviolet absorber and / or the light stabilizer encapsulated in the nanoshell. Further, as the means for encapsulating the dispersant in the nanoshell, the same means as the means for encapsulating the ultraviolet absorber and / or the light stabilizer in the nanoshell can be adopted.

<Top coat layer>
The top coat layer preferably contains a cured product of the curable resin composition in order to enhance the scratch resistance of the decorative sheet.
Further, the ratio of the cured product of the curable resin composition to the total resin components constituting the top coat layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass. The above is more preferable, and 100% by mass is even more preferable.

Examples of the cured product of the curable resin include a cured product of a thermosetting resin, a cured product of an ionizing radiation curable resin, or a mixture thereof. Among these, a cured product of an ionizing radiation curable resin composition is preferable from the viewpoint of increasing the crosslink density of the top coat layer and improving scratch resistance and light resistance, and it can be applied without a solvent and can be handled. From the viewpoint of ease of use, a cured product of the electron beam curable resin composition is more preferable.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like. To the thermosetting resin composition, a curing agent is added to these curable resins as needed.

(Ionizing radiation curable resin)
The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as “ionizing radiation curable compound”). The ionizing radiation curable functional group is a group that 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.
Further, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, an ultraviolet ray (UV) or an electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays are also included.
Specifically, the ionizing radiation curable compound can be appropriately selected and used from the polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.

As the polymerizable monomer, a (meth) acrylate-based 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 the polyfunctional (meth) acrylate monomer include a (meth) acrylate monomer having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group.
From the viewpoint of improving processing characteristics, scratch resistance and light resistance, the number of functional groups of the polyfunctional (meth) acrylate monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, still more preferably 2 or more and 4 or less. More preferably 2 or more and 3 or less. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

Examples of the polymerizable oligomer include (meth) acrylate oligomers having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional groups. Examples thereof 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.
Further, as the polymerizable oligomer, a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group in the side chain of the polybutadiene oligomer, and a silicone (meth) acrylate-based oligomer having a polysiloxane bond in the main chain. In a molecule such as an aminoplast resin (meth) acrylate-based oligomer in which an aminoplast resin having many reactive groups in a small molecule is modified, or a novolak type epoxy resin, a bisphenol type epoxy resin, an aliphatic vinyl ether, an aromatic vinyl ether, etc. There are oligomers and the like having cationically polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination of two or more. Urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) acrylate oligomer from the viewpoint of improving processing characteristics, scratch resistance and light resistance. , Acrylic (meth) acrylate oligomers are preferable, urethane (meth) acrylate oligomers and polycarbonate (meth) acrylate oligomers are more preferable, and urethane (meth) acrylate oligomers are even more preferable.

The number of functional groups of these polymerizable oligomers is preferably 2 or more and 8 or less, more preferably 6 or less, still more preferably 4 or less, from the viewpoint of improving processing characteristics, scratch resistance and light resistance. 3 or less is even more preferable.
The weight average molecular weight of these polymerizable oligomers is preferably 2,500 or more and 7,500 or less, and more preferably 3,000 or more and 7,000 or less, from the viewpoint of improving processing characteristics, scratch resistance and light resistance. , 3,500 or more and 6,000 or less are more preferable. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

A monofunctional (meth) acrylate can be used in combination with the ionizing radiation curable resin composition for the purpose of reducing the viscosity of the ionizing radiation curable resin composition. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

The thickness of the top coat layer is preferably 1.5 μm or more and 20 μm or less, more preferably 2 μm or more and 15 μm or less, and further preferably 3 μm or more and 10 μm or less, from the viewpoint of the balance between processing characteristics, scratch resistance and light resistance.

<Primer layer>
The decorative sheet of the present embodiment preferably has, as the surface protective layer, a primer layer formed on the transparent resin layer side of the top coat layer in addition to the top coat layer. The primer layer can improve the adhesion between the top coat layer and the transparent resin layer.

The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary.
As the binder resin, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (carbonate bond to the polymer main chain). Urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having two or more hydroxyl groups at the terminal and side chains), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic co-weight Resins such as a coalesced resin, a chlorinated propylene resin, a nitrocellulose resin (nitrated cotton), and a cellulose acetate resin are preferably mentioned, and these can be used alone or in combination of two or more. For example, a mixture of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol resin can be used as the binder resin.

The thickness of the primer layer is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 8 μm or less, and further preferably 3 μm or more and 6 μm or less.

<Transparent resin layer>
The transparent resin layer is a layer containing a polyolefin resin, and is located between the surface protective layer and the base material layer.
The content of the polyolefin-based resin in the transparent resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total resin components of the transparent resin layer, from the viewpoint of processability. It is more preferably 90% by mass or more, and even more preferably 100% by mass.

The polyolefin resin of the transparent resin layer includes polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-vinyl acetate. Examples thereof include polymers, ethylene-acrylic acid copolymers, and ethylene-propylene-butene copolymers. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, propylene-butene copolymer are preferable, and polypropylene is more preferable.

When the transparent resin layer contains a resin other than the polyolefin resin, for example, heat from a polyester resin, a polycarbonate resin, an acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as “ABS resin”), an acrylic resin, a vinyl chloride resin, or the like. A plastic resin can be used.

As described above, the transparent resin layer preferably contains an ultraviolet absorber and a light stabilizer.
The content of the ultraviolet absorber in the transparent resin layer is not particularly limited as long as the absorbance A ₂ is 1.2 or more. When the thickness of the transparent resin layer is in the range described later, the content of the ultraviolet absorber in the transparent resin layer is 0.05 part by mass or more with respect to 100 parts by mass of the resin constituting the transparent resin layer. It is preferably 10 parts by mass or less, more preferably 0.07 parts by mass or more and 5 parts by mass or less, further preferably 0.10 parts by mass or more and 3 parts by mass or less, and further preferably 0.30 parts by mass or more and 1 part by mass or less.
The content of the light stabilizer in the transparent resin layer is preferably 0.1 part by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 8 parts by mass with respect to 100 parts by mass of the resin constituting the transparent resin layer. More preferably, it is more preferably 1 part by mass or more and 5 parts by mass or less, and further preferably 1.5 parts by mass or more and 3 parts by mass or less.

The transparent resin layer may be transparent to the extent that the base material layer side can be visually recognized from the transparent resin layer, and may be colorless and transparent, as well as colored transparent and translucent.

The thickness of the transparent resin layer is preferably 20 μm or more and 150 μm or less, more preferably 40 μm or more and 120 μm or less, and further preferably 60 μm or more and 100 μm or less, from the viewpoint of the balance between scratch resistance, processing suitability and light resistance.
Further, from the viewpoint of protecting the decorative layer and obtaining excellent scratch resistance, it is preferable to make the decorative layer thicker than the base sheet.

(Microcrystallization of transparent resin layer)
The transparent resin layer may be microcrystallized. By microcrystallizing the transparent resin layer, the strength of the transparent resin layer can be increased and the scratch resistance of the decorative sheet can be improved.

In order to microcrystallize the transparent resin layer, for example, the resin composition forming the transparent resin layer may be contained with a crystal nucleating agent, melted, and then cooled. In this case, examples of the cooling method include cooling by a chill roll method in which a material extruded from a die is brought into contact with a cooling roll (chill roll) through which cooling water has passed during extrusion molding to cool the material.
Examples of the crystal nucleating agent include fatty acid metal salts, phosphonic acid metal salts, phosphate ester metal salts, benzoic acid metal salts, pimelic acid metal salts, rosin metal salts and other metal salt-based crystal nucleating agents; fatty acid esters and aliphatic amides. , Benzilidene sorbitol, quinacridone, cyanine blue and other organic crystal nucleating agents; and talc and other inorganic crystal nucleating agents; and the like.

Further, as the crystal nucleating agent, for example, a crystal nucleating agent contained in a nanoshell as described in International Publication No. WO2016-07636A1 or the like can be used. By using the crystal nucleating agent contained in the nanoshell, the crystal nucleating agent is more uniformly dispersed in the transparent resin layer, so that the crystal nucleating agent can be easily and stably dispersed regardless of various conditions such as melting conditions and cooling conditions. The strength of the transparent resin layer can be increased.
The nanoshell phospholipid basically has a structure in which the hydrophilic group is directed outward. Therefore, when the transparent resin layer contains the crystal nucleating agent contained in the nanoshell, there is a concern that the durability of the decorative sheet when used outdoors is deteriorated due to water. In particular, since the material of the decorative sheet used outdoors is deteriorated by ultraviolet rays, there is a concern that the deterioration of the decorative sheet is promoted by the synergistic action of water and ultraviolet rays. However, since the decorative sheet of the present invention has excellent light resistance, even if the transparent resin layer or the base material layer described later contains a crystal nucleating agent contained in a nanoshell, the decrease in durability during outdoor use is suppressed. It is preferable in that it can be done.

The size of the crystal nucleating agent contained in the nanoshell and the embodiment of the material of the nanoshell are the same as those of the ultraviolet absorber and / or the light stabilizer encapsulated in the nanoshell. Further, as the means for encapsulating the crystal nucleating agent in the nanoshell, the same means as the means for encapsulating the ultraviolet absorber and / or the light stabilizer in the nanoshell can be adopted.

<Base layer>
The base material layer is a layer containing a polyolefin-based resin, and is located on the side opposite to the surface protective layer of the transparent resin layer.
The content of the polyolefin-based resin in the base material layer is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total resin components of the base material layer, from the viewpoint of processability. It is more preferably 90% by mass or more, and even more preferably 100% by mass.

As the polyolefin resin of the base material layer, polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer weight Examples thereof include coalescing, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer and the like. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, propylene-butene copolymer are preferable, and polypropylene is more preferable.

When the base material layer contains a resin other than the polyolefin resin, for example, thermoplasticity such as polyester resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as "ABS resin"), acrylic resin, vinyl chloride resin and the like. Resin can be used.

The base material layer may be colorless and transparent, but is preferably colored from the viewpoint of designability.
When coloring the base material layer, a colorant such as a dye or a pigment can be added to the base material layer. Among these colorants, a pigment that easily suppresses fading is preferable.
Pigments include white pigments such as zinc flower, white lead, lithopone, titanium dioxide, precipitated barium sulfate and barite; black pigments such as carbon black; red pigments such as lead tan and iron oxide red;
Yellow pigments such as chrome yellow and zinc yellow (1 type of zinc yellow and 2 types of zinc yellow); blue pigments such as ultramarine blue and prussian blue (ferrocyanic iron potassium); and the like can be mentioned.

The content of the colorant is, for example, 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, and 5 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the resin constituting the base material layer. More preferably, it is 5 parts by mass or less and 20 parts by mass or less.

Additives may be added to the base material layer, if necessary. Examples of the additive include an inorganic filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, an antioxidant, an ultraviolet absorber, a light stabilizer and the like. The blending amount of the additive 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.
In addition, since the absorbance A ₂ is 1.2 or more in the present invention, it is suitable in that the light resistance of the base material layer can be improved without containing an ultraviolet absorber and a light stabilizer. be.

The thickness of the base material layer is preferably 20 μm or more and 150 μm or less, more preferably 25 μm or more and 120 μm or less, further preferably 30 μm or more and 100 μm or less, still more preferably 40 μm or more and 80 μm or less, from the viewpoint of the balance between designability and processability.

In order to improve the adhesion to the other layers of the decorative sheet and the adherend, the base material layer has a physical surface treatment such as an oxidation method or an unevenness method, or a chemical surface on one or both sides of the base material layer. Surface treatment such as treatment may be performed, or a primer layer may be formed.

(Microcrystallization of substrate layer)
The substrate layer may be microcrystallized to increase its strength. As the means for microcrystallization of the base material layer, the same means as for microcrystallization of the transparent resin layer can be adopted.

<Decorative layer>
From the viewpoint of improving the design, the decorative sheet of the present invention preferably has a decorative layer at any position on the decorative sheet. The portion where the decorative layer is formed is preferably between the base material layer and the transparent resin layer from the viewpoint of enhancing the light resistance of the decorative layer.

The decorative layer may be, for example, a colored layer that covers the entire surface (so-called solid colored layer), or may be a pattern layer formed by printing various patterns using ink and a printing machine. It may be good, or it may be a combination of these.

The ink used for the decorative layer is a binder resin mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, or the like. used.
The binder resin of the decorative layer is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate co-weight. Examples thereof include a coalesced resin, a vinyl chloride-vinyl acetate-acrylic copolymer resin, a chlorinated propylene resin, a nitrocellulose resin, and a cellulose acetate resin. Further, various types of resins such as a one-component curable resin and a two-component curable resin with a curing agent such as an isocyanate compound can be used.

As the colorant, a pigment having excellent hiding power and light resistance is preferable. As the pigment, the same pigment as those exemplified for the substrate layer can be used.
The content of the colorant in the base material 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 with respect to 100 parts by mass of the resin constituting the decorative layer. More than 70 parts by mass is more preferable.

From the viewpoint of improving light resistance, the decorative layer preferably contains a weather resistant agent such as an ultraviolet absorber and a light stabilizer.

The thickness of the decorative layer may be appropriately selected according to 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 more and 10 μm. The following is more preferable, and 2 μm or more and 5 μm or less is further preferable.

<Adhesive layer A>
It is preferable to form an adhesive layer A between the base material layer and the transparent resin layer in order to improve the adhesion between the two layers.
When the above-mentioned decorative layer is further provided between the base material layer and the transparent resin layer, the positional relationship between the adhesive layer A and the decorative layer is not particularly limited. Specifically, the decorative layer and the adhesive layer A may be provided in this order from the side closer to the base material layer, or the adhesive layer A and the adhesive layer A may be provided in order from the side closer to the base material layer. good.

The adhesive layer A can be composed of, for example, an adhesive such as a urethane-based adhesive, an acrylic-based adhesive, an epoxy-based adhesive, or a rubber-based adhesive. Among these adhesives, urethane-based adhesives are preferable in terms of adhesive strength.
Examples of the urethane-based adhesive include adhesives using a two-component curable urethane resin containing various polyol compounds such as polyether polyols, polyester polyols, and acrylic polyols and curing agents such as the above-mentioned various isocyanate compounds. Be done.

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

The decorative layer, the adhesive layer A, the primer layer and the top coat layer described above are coated with a coating liquid containing the composition forming each layer by a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method. It can be formed by applying it by a known method such as, and if necessary, drying and curing it.

The decorative sheet of the present invention may be embossed or the like to provide unevenness.
When embossing, for example, the decorative sheet is heated to preferably 80 ° C. or higher and 260 ° C. or lower, more preferably 85 ° C. or higher and 160 ° C. or lower, and further preferably 100 ° C. or higher and 140 ° C. or lower, and the embossed plate is pressed against the decorative sheet. Then, embossing can be performed. The portion where the embossed plate is pressed is preferably on the surface protective layer side of the decorative sheet.

[Cosmetic material]
The decorative material of the present invention has an adherend and the above-mentioned decorative sheet of the present invention, and specifically, a surface of the adherend that requires decoration and a surface of the decorative sheet on the base material layer side. Are laminated so as to face each other.

<Applied material>
Examples of the adherend include flat plates of various materials, plate materials such as curved plates, three-dimensional shaped articles, sheets (or films), and the like. For example, wood single boards made of various kinds of wood such as cedar, cypress, pine, and lauan, wood plywood, particle boards, wood fiber boards such as MDF (medium density fiber board), and wood members used as three-dimensional shaped articles. ; Plate materials such as iron and aluminum, steel plates, three-dimensional shaped articles, or metal members used as sheets; ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, and non-ceramic materials such as ALC (lightweight bubble concrete) plates. Ceramic members used as plate materials such as ceramic materials and three-dimensional shaped articles; polyolefin resins such as acrylic resin, polyester resin, polystyrene resin, polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride Examples thereof include resin, cellulose resin, plate materials such as rubber, three-dimensional shaped articles, resin members used as sheets and the like. In addition, these members can be used alone or in combination of a plurality of types.

The adherend may be appropriately selected from the above depending on the application, and is used for interior or exterior members of buildings such as walls, ceilings, and floors, window frames, doors, handrails, skirting boards, surrounding edges, moldings, and the like. When the fittings or building members of the above are used, those made of at least one member selected from wood members, metal members and resin members are preferable, and exterior members such as entrance doors, window frames, doors and other fittings are used. In this case, it is preferable that the member is composed of at least one member selected from a metal member and a resin member.

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

<Adhesive layer B>
It is preferable that the adherend and the decorative sheet are bonded to each other via the adhesive layer B in order to obtain excellent adhesiveness.

The adhesive used for the adhesive layer B is not particularly limited, and known adhesives can be used. For example, adhesives such as heat-sensitive adhesives and pressure-sensitive adhesives are preferable. Examples of the resin 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 and the like, and these can be used alone or in combination of two or more. Further, a two-component curable polyurethane-based adhesive or a polyester-based adhesive using an isocyanate compound or the like as a curing agent can also be applied.
Further, an adhesive may be used for the adhesive layer. As the pressure-sensitive adhesive, acrylic-based, urethane-based, silicone-based, rubber-based and other pressure-sensitive adhesives can be appropriately selected and used.

The thickness of the adhesive layer B 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 further preferably 10 μm or more and 30 μm or less.

<Manufacturing method of 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 the adherend and the decorative sheet of the present invention, in which the surface of the adherend that requires decoration and the surface of the decorative sheet on the substrate side face each other. Examples of the method of laminating the adherend and the decorative sheet include a laminating method in which the decorative sheet is pressurized and laminated on the plate-shaped adherend with a pressure roller via the adhesive layer B.

When a hot melt adhesive (heat sensitive adhesive) is used as the adhesive, the heating temperature is preferably 160 ° C or higher and 200 ° C or lower, and 100 for the reactive hot melt adhesive, although it depends on the type of resin constituting the adhesive. It is preferably ℃ or more and 130 ℃ or less. Further, in the case of vacuum forming, it is generally performed while heating, and it is preferably 80 ° C. or higher and 130 ° C. or lower, and 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 end of the wood can be arbitrarily decorated by grooving, chamfering, etc. using a cutting machine such as a router or a cutter. And various uses, for example, interior / exterior members of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, surrounding edges, fittings such as malls, kitchens, furniture or home appliances, OA equipment, etc. It can be used for the surface veneer of the cabinet, the interior of the vehicle, the exterior, etc.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.
1. 1. Evaluation and measurement 1-1. Absorbance A laminated body in which a surface protective layer is formed on a transparent resin layer in accordance with JIS K0115: 2004 using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Hitachi, Ltd., trade name: U-4000). The absorbance A ₂ at a wavelength of 310 nm was measured. Further, the absorbance A ₀ at a wavelength of 310 nm of the transparent resin layer was measured by the same means, and the absorbance A ₀ was subtracted from the absorbance A ₂ to calculate the absorbance A ₁ at a wavelength of 310 nm of the surface protective layer.

1-2. Light resistance After irradiating the decorative sheets obtained in Examples and Comparative Examples with ultraviolet rays for 20 hours under the conditions of a black panel temperature of 63 ° C. and an illuminance of 100 mW / cm ² , using the following ultra-accelerated weather resistance test apparatus. The cycle of dew condensation was repeated for 4 hours. After 800 hours, the appearance of the decorative sheet was visually evaluated according to the following criteria.
<Ultra-accelerated weather resistance test equipment>
UV lamp (trade name: M04-L21WB / SUV, manufactured by Iwasaki Electric Co., Ltd.), lamp jacket (trade name: WJ50-SUV, manufactured by Iwasaki Electric Co., Ltd.) and illuminance meter (trade name: UVD-365PD, manufactured by Iwasaki Electric Co., Ltd.) Super accelerated weather resistance test device (trade name: Eye Super UV Tester SUV-W161 ", manufactured by Iwasaki Electric Co., Ltd.)
<Evaluation criteria>
A: No change in appearance was confirmed on the entire decorative sheet.
B: A slight whitening was confirmed on the appearance of the decorative sheet, but a change in the color tone of the transparent resin layer and / or the base material layer could not be confirmed.
C: A slight whitening was confirmed on the appearance of the decorative sheet, and a slight change in color tone of the transparent resin layer and / or the base material layer was confirmed.
D: Remarkable whitening of the appearance of the decorative sheet and a large change in color tone of the transparent resin layer and / or the base material layer were confirmed.

1-3. Scratch resistance A rubbing test was performed by reciprocating steel wool (“Bonster # 0000”, manufactured by Nippon Steel Wool Co., Ltd.) 5 times with a load of 300 g / m ² on the surface of the decorative sheet obtained in Examples and Comparative Examples. Was done. The state of the surface after the test was visually observed and evaluated according to the following criteria.
A: There were no scratches and no change in gloss was confirmed.
B: Very slight scratches and slight changes in luster were confirmed.
C: A slight scratch and a slight change in gloss were confirmed.
D: Scratches were confirmed, and a marked change in gloss was confirmed.

[Example 1]
A decorative layer was formed on one surface of a base material layer (colored polypropylene resin sheet having a thickness of 60 μm) subjected to double-sided corona discharge treatment by using a printing ink made of a two-component curable acrylic-urethane resin. Next, an adhesive layer made of a urethane resin-based adhesive having a thickness of 3 μm was formed on the decorative layer.
Next, on the adhesive layer, a composition A containing 0.12 parts by mass of a hydroxyphenyltriazine-based ultraviolet absorber (trade name: TINUVIN460, manufactured by BASF) with respect to 100 parts by mass of a polypropylene-based resin is subjected to a T-die extruder. A transparent resin layer having a thickness of 80 μm was formed by heating, melting and extruding.
After the surface of the transparent resin layer was subjected to a corona discharge treatment, the following composition B was applied onto the transparent resin layer and dried to form a primer layer having a thickness of 4 μm.
<Composition B>
A composition obtained by mixing a composition composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol and hexamethylene diisocyanate in a mass ratio of 100: 5.

Next, a hydroxyphenyltriazine-based ultraviolet absorber (trade name: TINUVIN460, manufactured by BASF) was applied to 100 parts by mass of an ionized radiation curable resin composition composed of a trifunctional urethane acrylate oligomer having a weight average molecular weight of 4000 on the primer layer. By applying the composition C containing 2 parts by mass and 3 parts by mass of a hindered amine light stabilizer (trade name: TINUVIN123, manufactured by BASF) and irradiating with an electron beam to cure the ionized radiation curable resin composition. A top coat layer having a thickness of 5 μm was formed.
Next, a wood grain conduit-like uneven pattern having a depth of 50 μm was formed from above the top coat layer by embossing to obtain a decorative sheet of Example 1.

[Example 2]
The content of the hydroxyphenyltriazine-based ultraviolet absorber in the composition A was changed to 0.5 parts by mass with respect to 100 parts by mass of the polypropylene-based resin, and the content of the hydroxyphenyltriazine-based ultraviolet absorber in the composition C was changed. A decorative sheet of Example 2 was obtained in the same manner as in Example 1 except that the amount was changed to 8 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition.

[Comparative Example 1]
Comparative Example in the same manner as in Example 1 except that the content of the hydroxyphenyltriazine-based ultraviolet absorber in the composition C was changed to 1.5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition. Obtained 1 cosmetic sheet.

[Comparative Example 2]
Comparative Example in the same manner as in Example 1 except that the content of the hydroxyphenyltriazine-based ultraviolet absorber in the composition C was changed to 1.0 part by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition. I got 2 cosmetic sheets.

[Comparative Example 3]
A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that the content of the hydroxyphenyltriazine-based ultraviolet absorber in the composition A was changed to 0 parts by mass.

[Comparative Example 4]
The content of the hydroxyphenyltriazine ultraviolet absorber in the composition A was changed to 0.18 part by mass with respect to 100 parts by mass of the polypropylene resin, and the content of the hydroxyphenyltriazine ultraviolet absorber in the composition C was changed. A decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the ionizing radiation curable resin composition was changed to 1.5 parts by mass with respect to 100 parts by mass.

From the results in Table ₁ , it can be confirmed that the decorative sheet having an absorbance A1 of 0.8 or more and an absorbance _A2 of 1.2 or more is extremely excellent in weather resistance.

Since the decorative sheet of the present invention has excellent light resistance, it is suitably used as a decorative sheet for members used in an environment exposed to direct sunlight, such as exterior members such as entrance doors, window frames, and fittings such as doors.

100: Decorative sheet 11: Top coat layer 12: Primer layer 10: Surface protection layer 20: Transparent resin layer 30: Decorative layer 40: Base material layer

Claims (10)

The surface protective layer, the transparent resin layer containing the polyolefin resin, and the base material layer containing the polyolefin resin are provided in this order, and the absorbance A of the surface protective layer at a wavelength of 310 nm measured in accordance with JIS K0115: 2004. ₁ is 0.8 or more and 3.0 or less , and the absorbance A ₂ of the surface protective layer and the transparent resin layer containing the polyolefin resin measured in accordance with JIS K0115: 2004 at a wavelength of 310 nm is 1.2. A decorative sheet that is 4.5 or less . The decorative sheet according to claim 1, wherein the surface protective layer and / or the transparent resin layer contains a triazine-based ultraviolet absorber. The decorative sheet according to claim 1 or 2, wherein the surface protective layer and / or the transparent resin layer contains a light stabilizer. The decorative sheet according to any one of claims 1 to 3, which does not substantially contain an olefin resin as the resin constituting the surface protective layer. The decorative sheet according to any one of claims 1 to 4, which has a top coat layer containing a cured product of a curable resin composition as the surface protective layer. The decorative sheet according to claim 5, wherein the curable resin composition is an ionizing radiation curable resin composition. The decorative sheet according to claim 5 or 6, further comprising a primer layer formed on the transparent resin layer side of the top coat layer as the surface protective layer. The decorative sheet according to any one of claims 1 to 7, wherein the polyolefin-based resin of the base material layer and / or the polyolefin-based resin of the transparent resin layer is a polypropylene-based resin. The decorative sheet according to any one of claims 1 to 8, which has a decorative layer between the base material layer and the transparent resin layer. A decorative material having an adherend and a decorative sheet according to any one of claims 1 to 9.

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