JP7306443B2 - 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.

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

When these decorative sheets are used outdoors, or when used indoors where they are exposed to sunlight near a window or the like, ultraviolet rays cause a change in color tone and deterioration of the resin. For this reason, an ultraviolet absorber is added to the surface protective layer of the decorative sheet for the purpose of improving the light resistance.

However, there is a problem that the ultraviolet absorber tends to bleed out (also referred to as "bleed out" or "migration") from the surface protective layer over time. When the UV absorber bleeds out, the appearance of the surface of the decorative sheet is impaired, and the concentration of the UV absorber in the surface protective layer decreases over time, resulting in insufficient light resistance. Patent document 1, for example, proposes to eliminate the bleeding of the ultraviolet absorber.

JP-A-2000-117905

The decorative sheet of Patent Document 1 contains an electron beam reactive ultraviolet absorber selected from specific benzotriazole compounds and 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 bleeding out of the ultraviolet absorber.

On the other hand, in many cases, decorative sheets are required to have processability such as embossing, bending, and molding. is proposed. When the surface protective layer of Patent Document 1 is applied to a decorative sheet formed 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, deterioration over time due to ultraviolet rays could not be suppressed.

The present invention has been made under such circumstances, and it is an object of the present invention 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] Having a surface protective layer, a transparent resin layer containing a polyolefin resin, and a substrate layer containing a polyolefin resin in this order, the wavelength of the surface protective layer of 310 nm measured according to JIS K0115:2004. is 0.8 or more, and the absorbance _A2 at a wavelength of 310 nm of the transparent resin layer containing the surface protective layer and the polyolefin resin, measured in accordance with JIS K0115:2004, is _1.2 or more. A cosmetic sheet.
[2] A decorative material comprising an adherend and the decorative sheet according to [1] above.

ADVANTAGE OF THE INVENTION According to this invention, the deterioration with time by an ultraviolet-ray can be suppressed in the decorative sheet which laminates the layer containing a polyolefin-type resin.

1 is a cross-sectional view showing an embodiment of the decorative sheet of the present invention; FIG.

[Decorative sheet]
The decorative sheet of the present invention has a surface protective layer, a transparent resin layer containing a polyolefin resin, and a substrate layer containing a polyolefin resin in this order, and the surface protection measured in accordance with JIS K0115:2004. The absorbance _A1 of the layer at a wavelength of 310 nm is 0.8 or more, and the absorbance _A2 of the transparent resin layer containing the surface protective layer and the polyolefin resin at a wavelength of 310 nm, measured in accordance with JIS K0115:2004, is 1.2 or more.
Hereinafter, "absorbance A ₁ at a wavelength of 310 nm of the surface protective layer measured in accordance with JIS K0115:2004" is referred to as "absorbance A ₁ ", and "surface protective layer and Absorbance A _{2 ″} at a wavelength of 310 nm of the transparent resin layer containing polyolefin resin may be referred to as “absorbance A ₂ ”. Further, hereinafter, the "transparent resin layer containing polyolefin resin" may be referred to as "transparent resin layer", and the "base material layer containing polyolefin resin" may be referred to as "base material layer".

FIG. 1 is a 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 polyolefin resin, and a substrate layer 40 containing polyolefin resin in this order. The surface protective layer 10 of the decorative sheet 100 shown in FIG. 1 is composed of a primer layer 12 and a topcoat layer 11. Further, the decorative sheet 100 of FIG. 1 has the decorative layer 30 between the base material layer 40 and the transparent resin layer 20 .

<Absorbance>
The decorative sheet of the present invention has an absorbance _A1 of 0.8 or more and an absorbance _A2 of 1.2 or more. A large absorbance _A1 means that _less light with a wavelength of 310 nm reaches the layer (transparent resin layer) containing a polyolefin resin located closer to the surface protective layer. , means that less light with a wavelength of 310 nm reaches the layer (substrate layer) containing the polyolefin resin located farther from the surface protective layer.
Conventional decorative sheets are usually designed to add an ultraviolet absorber only to the surface protective layer (topcoat layer or primer layer). In other words, the conventional decorative sheet was designed only for the absorbance _A1 . However, the design with only the absorbance _A1 has limitations in improving the light resistance of the decorative sheet. That is, all of the various ultraviolet absorbers are lost with time due to bleeding out from the layer to the outside, and the concentration of the ultraviolet absorbers decreases, although there are differences in degree depending on the material. For this reason, even if it is possible to suppress deterioration due to ultraviolet rays in each layer below the transparent resin layer immediately below the surface protective layer in the short term, it has not been possible to sustain the suppression of deterioration due to ultraviolet rays over a long period of time. Usually, the light resistance is the time required for each layer below the transparent resin layer (i.e., the entire decorative sheet) to reach a pre-determined degree of deterioration due to ultraviolet rays when exposed to sunlight containing ultraviolet rays. evaluated. Therefore, there is a limit to the improvement in light resistance with a design in which only the absorbance _A1 of the surface protective layer is increased. In addition, it is possible to improve the light resistance (the number of hours until deterioration occurs) by adding an excess amount of the ultraviolet absorber to the surface protective layer, which is lost due to migration over time. , 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 ultraviolet absorber, and appearance deterioration such as white turbidity of the surface due to the ultraviolet absorber bleeding out. The design was also practically difficult to adopt.
Also, even if two types of absorbance (absorbance A ₁ and absorbance A ₂ ) are defined, if the absorbance A ₁ is less than 0.8 or the absorbance A ₂ is less than 1.2, the polyolefin Deterioration over time due to ultraviolet rays cannot be sufficiently suppressed for a decorative sheet formed by laminating layers containing a base resin.

Both the absorbance _A1 and the absorbance _A2 defined in the present invention are absorbances of light having a wavelength of 310 nm, and the present invention is also characterized in that the wavelength of ultraviolet rays to be absorbed is specified.
Polyolefin resins have absorption wavelengths, typically 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 light quanta of these wavelengths contribute to deterioration of the polyolefin resin.
In the present invention, attention is focused on two types of absorbance (absorbance A ₁ and absorbance A ₂ ) for light with a wavelength of 310 nm, which has high energy (light quanta) among the absorption wavelengths of polyolefin resins and is common to various polyolefin resins, and By setting the two types of absorbance (absorbance A ₁ and absorbance A ₂ ) within specific ranges, it is possible to suppress deterioration over time of a decorative sheet formed by laminating a layer containing a polyolefin resin due to ultraviolet rays. .

The absorbance _A1 is preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 2.5 or more.
A large absorbance _A1 means that the content of the ultraviolet absorber in the surface protective layer is large, or that the film thickness of the surface protective layer is large. When the content of the ultraviolet absorber in the surface protective layer is high, bleed-out and scratch resistance of the surface protective layer tend to decrease. Tend. Therefore, the absorbance _A1 is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less.

The absorbance _A2 is preferably 1.5 or more, more preferably 3.0 or more, and even more preferably 4.0 or more.
Although the upper limit of the absorbance _A2 is not particularly limited, it is preferably 7.0 or less, more preferably 6.5 or less, further preferably 6.0 or less in consideration of bleeding out.
The absorbance _A1 and the absorbance _A2 can be adjusted by adjusting the content of the ultraviolet absorber and the thickness of the layer containing the ultraviolet absorber.

The absorbance _A2 is obtained by measuring the absorbance at a wavelength of 310 nm of a laminate in which a surface protective layer is formed on a transparent resin layer in accordance with JIS K0115:2004. The 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 (absorbance A ₁ = absorbance A ₂ - Absorbance A ₀ ).

<Surface protective layer>
The surface protective layer is a layer located on the opposite side of the transparent resin layer to the substrate 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 this specification, the layer farthest from the transparent resin layer among the surface protective layers is referred to as a "topcoat layer". That is, when the surface protective layer is formed of a single layer, the surface protective layer has a single layer structure of the topcoat layer. In addition, when the surface protective layer is formed of two or more layers, the layer positioned 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, light with a wavelength of 310 nm reaching the transparent resin layer is sufficiently limited by defining the absorbance _A1 , but a larger amount of light with a wavelength of 310 nm reaches the surface protective layer than the transparent resin layer. are doing. Therefore, substantially no olefin-based resin is contained as a resin constituting the surface protective layer, which is preferable in that the light resistance of the surface protective layer can be easily improved.
“Containing substantially no olefin resin” means that the proportion of the olefin resin is 1% by mass or less, preferably 0.1% by mass or less, relative to the total resin components constituting the surface protective layer. , more preferably 0.01% by mass or less, and still more preferably 0% by mass.

(Ultraviolet absorber)
It is preferable that the surface protective layer and/or the transparent resin layer described later contains an ultraviolet absorber.
When the surface protective layer is formed of two or more layers, it is preferable that at least the topcoat layer contains the ultraviolet absorber, and it is more preferable that all layers constituting the surface protective layer contain the ultraviolet absorber.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and the like, with triazine-based ultraviolet absorbers being preferred. Among triazine-based UV absorbers, hydroxyphenyltriazine-based UV absorbers are preferred from the viewpoint of light fastness.
Moreover, an ultraviolet absorber having a reactive functional group such as a (meth)acryloyl group, vinyl group, or allyl group is preferable in terms of easily suppressing bleeding out.

The content of the ultraviolet absorber in the surface protective layer is not particularly limited as long as the absorbance _A1 can be 0.8 or more.
The content of the ultraviolet absorber in the topcoat 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 topcoat layer, and 1.0 It is more preferably 9.5 parts by mass or less, more preferably 2.0 parts by mass or more and 9.0 parts by mass or less, and even more preferably 5.0 parts by mass or more and 8.5 parts by mass or less.
Further, 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 parts per 100 parts by mass of the resin constituting the other layer. 10.0 parts by mass or less is preferable, 1.0 parts by mass or more and 9.5 parts by mass or less is more preferable, 2.0 parts by mass or more and 9.0 parts by mass or less is more preferable, and 5.0 parts by mass or more 8.5 mass or less is even more preferable.

(light stabilizer)
The surface protective layer and/or the transparent resin layer described below preferably contains a light stabilizer. In particular, the surface protective layer preferably contains a light stabilizer because it is the first layer to which ultraviolet light is incident among the layers constituting the decorative sheet.

As the light stabilizer, a hindered amine light stabilizer is preferred.
Hindered amine light stabilizers 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.

The content of the light stabilizer in the top coat layer constituting the surface protective layer is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts 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 even more preferable, and 1.5 parts by mass or more and 3 parts by mass or less is even more preferable.
Further, 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 per 100 parts by mass of the resin constituting the other layer. 10 parts by mass or less is preferable, 0.5 parts by mass or more and 8 parts by mass or less is more preferable, 1 part by mass or more and 5 parts by mass or less is more preferable, and 1.5 parts by mass or more and 3 parts by mass or less is even more preferable. .

(Nanoshell formation of ultraviolet absorber and/or light stabilizer)
UV absorbers and/or light stabilizers may be encapsulated in nanoshells.
By using the ultraviolet absorber and/or light stabilizer encapsulated in the nanoshell, the dispersibility (compatibility) between the resin in the surface protective layer and the ultraviolet absorber and/or light stabilizer is improved. It is possible to homogenize the effect of light resistance and improve the mechanical strength. In addition, it is expected that the bleed-out of the ultraviolet absorber and/or the light stabilizer is suppressed due to the bonding 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 nanoshells encapsulating the ultraviolet absorber and/or light stabilizer is less than the wavelength region of visible light (380 to 780 nm) and is about 1/2 or less of the wavelength of visible light, that 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, even more preferably 5 to 300 nm, even 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 calculating using the following formula (A) when measuring the diameter of 1000 particles randomly selected from the SEM image and creating a histogram of 3 nm sections. It is a thing. The number average primary particle diameter _Dnp obtained by the formula (A) was defined as the average primary particle diameter in the present specification.

D _np =Σn _i d _i /Σn _i (A)
D _np : number average primary particle diameter d _i : i-th diameter of the histogram 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. A single-layer film is preferable from the viewpoint of reducing the size and improving the dispersibility (compatibility). Phospholipids are preferred as materials for forming nanoshells. That is, the form of the nanoshell is more preferably a monolayer membrane made of phospholipids.

Phospholipids include glycerophospholipids such as phosphatidylcholine, phosphatidiethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, and hydrogenated soybean lecithin; sphingophospholipids such as myelin, ceramide phosphoriethanolamine, ceramide phosphorylglycerol; and the like. These phospholipids can be used alone or in combination of two or more.

Techniques for encapsulating an ultraviolet absorber and/or a light stabilizer in a nanoshell include, for example, Bangham method, extrusion method, hydration method, surfactant dialysis method, reverse phase evaporation method, freeze-thaw method, supercritical reverse phase Evaporation method etc. are mentioned.
In the Bangham method, after adding and dissolving phospholipids in a solvent such as chloroform or methanol, the solvent is removed using an evaporator to form a thin film made of phospholipids, and an ultraviolet absorber and / or light stabilizer is added. After that, using a mixer, for example, by stirring at high speed rotation of about 1000 to 2500 rpm, it is hydrated and dispersed, and the ultraviolet absorber and / or light stabilizer is included in the nanoshell. The extrusion method is a method of passing through a filter instead of a mixer used as an external perturbation. The hydration method is a method in the Bangham method in which the UV absorber and/or the light stabilizer are encapsulated in the nanoshell by gently stirring and dispersing without using a mixer. In the reverse phase evaporation method, the phospholipid is dissolved in a solvent such as diethyl ether or chloroform, and an ultraviolet absorber and/or light stabilizer (which may be in the form of a dispersion) is added to make a W/O emulsion. 2) removing the solvent from the emulsion under reduced pressure, adding water, and encapsulating the ultraviolet absorber and/or light stabilizer in nanoshells. In addition, the freeze-thaw method is a method of performing at least one of cooling and heating as external perturbation, and is a method of encapsulating an ultraviolet absorber and/or a light stabilizer in nanoshells by repeating cooling and heating.

Moreover, by adopting the supercritical reversed-phase evaporation method, the nanoshell can be more reliably and easily formed into a monolayer membrane composed of phospholipids. In the supercritical reverse phase evaporation method, for example, as described in JP-A-2016-137585, using carbon dioxide in a supercritical state, a temperature condition above the critical point, or a pressure condition, a crystal nucleating agent is included in the nanoshell. Here, the carbon dioxide in a supercritical state means carbon dioxide in a supercritical state with a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, and temperature conditions above the critical point Carbon dioxide under sub- or pressure conditions means carbon dioxide under conditions where only one of temperature or critical is above critical conditions.

Specifically, the supercritical reverse phase evaporation method is performed by adding water to a mixture of an ultraviolet absorber and / or a light stabilizer, supercritical carbon dioxide, and phospholipids, and stirring to obtain supercritical carbon dioxide and An aqueous phase emulsion is formed, and then carbon dioxide expands and evaporates under reduced pressure to cause a phase inversion, forming nanoshells in which the surface of the UV absorber and/or light stabilizer is covered with a monolayer of phospholipids. forming and obtaining UV absorbers and/or light stabilizers encapsulated in nanoshells. In addition, when it is desired to form a multilayer film as in the conventional method, supercritical carbon dioxide may be added to the mixture of the ultraviolet absorber and/or light stabilizer, phospholipid, and water in the above method.

(Nanoshell formation of dispersant)
In addition, by containing a dispersant encapsulated in nanoshells in the surface protective layer, the dispersibility (compatibility) between the resin in the surface protective layer and the ultraviolet absorber and / or light stabilizer is improved, and the layer It can homogenize the effect of lightfastness inside and improve the mechanical strength.
Embodiments of the nanoshell-encapsulated dispersant size and nanoshell material are the same as those of the nanoshell-encapsulated UV absorber and/or light stabilizer. Moreover, the means for encapsulating the dispersant in the nanoshells can employ the same means as the means for encapsulating the ultraviolet absorber and/or the light stabilizer in the nanoshells.

<Top coat layer>
The topcoat layer preferably contains a cured product of a curable resin composition in order to improve the scratch resistance of the decorative sheet.
In addition, the ratio of the cured product of the curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 90% by mass, based on the total resin components constituting the topcoat layer. It is more preferably 100% by mass or more, and even more preferably 100% by mass.

A cured product of a curable resin includes a cured product of a thermosetting resin, a cured product of an ionizing radiation-curable resin, or a mixture thereof. Among these, the cured product of the ionizing radiation-curable resin composition is preferable from the viewpoint of increasing the cross-linking density of the topcoat layer and improving the scratch resistance and light resistance. A cured product of an electron beam-curable resin composition is more preferable from the viewpoint of ease of curing.

A thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Thermosetting resins include acrylic resins, urethane resins, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, and the like. If necessary, a curing agent is added to these curable resins in the thermosetting resin composition.

(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 an "ionizing radiation-curable compound"). The ionizing radiation-curable functional group is a group that is cross-linked and cured by irradiation with ionizing radiation, and preferably includes a functional group having an ethylenic double bond such as (meth)acryloyl group, vinyl group, and allyl group.
In addition, ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.
Specifically, the ionizing radiation-curable compound can be appropriately selected and used 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".
Polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group.
From the viewpoint of improving processability, 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, and further preferably 2 or more and 4 or less. 2 or more and 3 or less are even more preferable. 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. Examples thereof include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.
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 novolac 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 oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and polycarbonate (meth)acrylate oligomers from the viewpoint of improving processability, scratch resistance, and light resistance. , acrylic (meth)acrylate oligomers are preferred, urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are more preferred, and urethane (meth)acrylate oligomers are even more preferred.

The number of functional groups of these polymerizable oligomers is preferably 2 or more and 8 or less from the viewpoint of improving processability, scratch resistance, and light resistance, and the upper limit is more preferably 6 or less, and further preferably 4 or less. 3 or less is even more preferable.
In addition, the weight average molecular weight of these polymerizable oligomers is preferably 2,500 or more and 7,500 or less, more preferably 3,000 or more and 7,000 or less, from the viewpoint of improving processability, scratch resistance, and light resistance. , 3,500 or more and 6,000 or less. Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

A monofunctional (meth)acrylate may 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.

The thickness of the topcoat 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 even more preferably 3 μm or more and 10 μm or less, from the viewpoint of the balance between processability, scratch resistance, and light resistance.

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

The primer layer is mainly composed of a binder resin, and may contain additives such as ultraviolet absorbers and light stabilizers, if necessary.
Binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, and polycarbonate-based urethane-acrylic copolymers (carbonate bonds in the main chain of the polymer). urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having two or more hydroxyl groups at the end and side chain), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer Resins such as coalescent resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins are preferred, and these can be used alone or in combination. 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 even more preferably 3 μm or more and 6 μm or less.

<Transparent resin layer>
The transparent resin layer is a layer containing a polyolefin-based resin and positioned between the surface protective layer and the substrate layer.
From the viewpoint of processability, the content of the polyolefin 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. Preferably, it is 90% by mass or more, and even more preferably 100% by mass.

Polyolefin resins for the transparent resin layer include polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer. polymers, ethylene-acrylic acid copolymers, ethylene-propylene-butene copolymers, and the like. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer and propylene-butene copolymer are preferred, and polypropylene is more preferred.

When the transparent resin layer contains a resin other than polyolefin resin, for example, polyester resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin (hereinafter also referred to as "ABS resin"), acrylic resin, vinyl chloride resin, etc. 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 _A2 can be 1.2 or more. When the thickness of the transparent resin layer is within the range described later, the content of the ultraviolet absorber in the transparent resin layer is 0.05 parts 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, still more preferably 0.10 parts by mass or more and 3 parts by mass or less, and even more 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 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 8 parts by mass, based on 100 parts by mass of the resin constituting the transparent resin layer. It is more preferably 1 part by mass or less and 5 parts by mass or less, and even more 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 substrate layer side can be visually recognized from the transparent resin layer, and may be colorless and transparent, 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 even more preferably 60 μm or more and 100 μm or less, from the viewpoint of a balance between scratch resistance, processing suitability and light resistance.
Moreover, from the viewpoint of protecting the decorative layer and obtaining excellent scratch resistance, it is preferably 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, a crystal nucleating agent is added to the resin composition forming the transparent resin layer, melted, and then cooled. In this case, the cooling method includes, for example, cooling by a chill roll method in which the material extruded from the die is brought into contact with a cooling roll (chill roll) through which cooling water is passed during extrusion molding.
Examples of crystal nucleating agents include metal salt crystal nucleating agents such as fatty acid metal salts, phosphonic acid metal salts, phosphate metal salts, benzoic acid metal salts, pimelic acid metal salts, and rosin metal salts; fatty acid esters, aliphatic amides; , benzylidene sorbitol, quinacridone and cyanine blue; inorganic crystal nucleating agents such as talc; and the like.

As the crystal nucleating agent, for example, a crystal nucleating agent encapsulated in nanoshells as described in International Publication No. WO2016-076360A1 can also be used. By using the crystal nucleating agent encapsulated in the nanoshell, the crystal nucleating agent is more uniformly dispersed in the transparent resin layer, so that it can be easily and stably obtained 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 groups face outward. Therefore, when the transparent resin layer contains a crystal nucleating agent encapsulated in nanoshells, there is concern that the durability of the decorative sheet during outdoor use may deteriorate due to water. In particular, decorative sheets used outdoors are subject to material deterioration due to ultraviolet rays, so there is concern that the synergistic action of water and ultraviolet rays will accelerate the deterioration of decorative sheets. 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 encapsulated in nanoshells, deterioration in durability during outdoor use is suppressed. It is preferable in that it can be done.

Embodiments of the size of the crystal nucleating agent encapsulated in the nanoshells and the material of the nanoshells are the same as those of the ultraviolet absorber and/or light stabilizer encapsulated in the nanoshells. Moreover, the means for encapsulating the crystal nucleating agent in the nanoshell can employ the same means as the means for encapsulating the ultraviolet absorber and/or the light stabilizer in the nanoshell.

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

Polyolefin resins for the base layer include polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer. coalescence, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer and the like. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer and propylene-butene copolymer are preferred, and polypropylene is more preferred.

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

The substrate layer may be colorless and transparent, but is preferably colored from the viewpoint of design.
When coloring the substrate layer, a coloring agent such as a dye or a pigment can be added to the substrate layer. Among these colorants, pigments that tend to suppress fading are preferred.
Pigments include white pigments such as zinc white, white lead, lithopone, titanium dioxide, precipitated barium sulfate and barite; black pigments such as carbon black; red pigments such as red lead and iron oxide red;
yellow pigments such as chrome and zinc yellow (type 1 zinc yellow, type 2 zinc yellow); blue pigments such as ultramarine blue and Prussian blue (potassium iron ferrocyanide);

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 layer. It is more preferably 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 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.
In the present invention, since the absorbance _A2 is set to 1.2 or more, it is preferable in that the light resistance of the base layer can be improved even if the base layer does not contain an ultraviolet absorber and a light stabilizer. be.

The thickness of the substrate layer is preferably 20 μm or more and 150 μm or less, more preferably 25 μm or more and 120 μm or less, even more preferably 30 μm or more and 100 μm or less, and even more preferably 40 μm or more and 80 μm or less, from the viewpoint of a balance between designability and workability.

In order to improve adhesion with other layers of the decorative sheet and adherends, the base layer may be subjected to physical surface treatment such as an oxidation method or roughening method, or a chemical surface treatment on one or both sides of the base layer. A surface treatment such as treatment may be applied, or a primer layer may be formed.

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

<Decoration layer>
From the viewpoint of improving designability, the decorative sheet of the present invention preferably has a decorative layer at an arbitrary portion of the decorative sheet. From the viewpoint of enhancing the light resistance of the decoration layer, the location where the decoration layer is formed is preferably between the substrate layer and the transparent resin layer.

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.

The ink used for the decorative layer is a mixture of a binder resin and a coloring agent such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. used.
The binder resin for the decorative layer is not particularly limited, and examples include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, and vinyl chloride-vinyl acetate copolymers. Resins such as coalesced resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins, and cellulose acetate resins can be used. Moreover, various types of resins can be used, such as a one-pack curable resin and a two-pack curable resin with a curing agent such as an isocyanate compound.

As the coloring agent, pigments having excellent hiding properties and light resistance are preferred. Pigments similar to those exemplified for the base material layer can be used.
The content of the coloring agent 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 decoration layer. Part or more and 70 parts by mass or less 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 background color of the adherend and improving the design, the thickness is preferably 0.5 μm or more and 20 μm or less, and 1 μm or more and 10 μm. The following are more preferable, and 2 μm or more and 5 μm or less are even more preferable.

<Adhesive Layer A>
An adhesive layer A is preferably formed between the substrate layer and the transparent resin layer in order to improve adhesion between the two layers.
In addition, when the decorative layer described above is further provided between the substrate 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 order from the side closer to the base layer, or the adhesive layer A and the decorative layer may be provided in order from the side closer to the base layer. good.

The adhesive layer A can be composed of, for example, an adhesive such as a urethane-based adhesive, an acrylic 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 urethane-based adhesives include adhesives using two-component curable urethane resins containing various polyol compounds such as polyether polyols, polyester polyols, and acrylic polyols, and curing agents such as the above-described 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 even more preferably 2 μm or more and 10 μm or less.

The decorative layer, the adhesive layer A, the primer layer and the topcoat layer described above can be obtained by applying 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 coating with a known method such as the above, and drying and curing as necessary.

The decorative sheet of the present invention may be provided with unevenness by embossing or the like.
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. The portion where the embossing plate is pressed is preferably on the side of the surface protective layer of the decorative sheet.

[Cosmetic material]
The decorative material of the present invention comprises an adherend and the decorative sheet of the present invention. Specifically, the surface of the adherend requiring decoration and the surface of the decorative sheet on the base layer side are are laminated facing each other.

<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 veneers made of various types of wood such as cedar, cypress, pine, lauan, etc., wood plywood, particle board, wood fiber boards such as MDF (medium density fiber board), and wood members used as three-dimensional articles. Plates and steel plates such as iron and aluminum, 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 interior or exterior members of buildings such as walls, ceilings, and floors, window frames, doors, handrails, baseboards, peripheral edges, moldings, etc. When it is used as fittings or fixtures, it is preferably made of at least one member selected from wooden members, metal members and resin members. In that case, it is preferable to use at least one member selected from metal members and resin members.

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

Although the thickness of the adhesive layer B 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 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, although it depends on the type of resin that constitutes the adhesive. °C or higher and 130 °C or lower. In the case of vacuum forming, it is generally carried 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. And various uses, for example, interior and exterior members of buildings such as walls, ceilings and floors, window frames, doors, handrails, baseboards, surrounding edges, fittings such as malls, kitchens, furniture or home appliances, OA equipment, etc. It can be used for the surface decorative plate of a cabinet, the interior and exterior of a vehicle, 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.
1. Evaluation and measurement 1-1. Absorbance Using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by Hitachi, Ltd., trade name: U-4000), in accordance with JIS K0115: 2004, a laminate having a surface protective layer formed on a transparent resin layer. Absorbance _A2 at a wavelength of 310 nm was measured. Also, the absorbance _A0 of the transparent resin layer at a wavelength of 310 nm was measured by the same means, and the absorbance _A1 of the surface protective layer at a wavelength of 310 nm was calculated by subtracting the absorbance _A0 from the absorbance _A2 .

1-2. Light resistance After irradiating the decorative sheets obtained in Examples and Comparative Examples with UV rays for 20 hours under the conditions of a black panel temperature of 63°C and an illuminance of 100 mW/ ^cm2 using the ultra-accelerated weather resistance tester described below. , and 4 hours of condensation were repeated. After 800 hours had elapsed, the appearance of the decorative sheet was visually evaluated according to the following criteria.
<Ultra-accelerated weather resistance test equipment>
A UV lamp (trade name: M04-L21WB/SUV, manufactured by Iwasaki Electric Co., Ltd.), a lamp jacket (trade name: WJ50-SUV, manufactured by Iwasaki Electric Co., Ltd.), and an illuminometer (trade name: UVD-365PD, manufactured by Iwasaki Electric Co., Ltd.) were used. Equipped with a 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 observed in the entire decorative sheet.
B: Slight whitening was observed in the appearance of the decorative sheet, but no change in color tone was observed in the transparent resin layer and/or the substrate layer.
C: A slight whitening was observed in the appearance of the decorative sheet, and a slight change in color tone was observed in the transparent resin layer and/or the substrate layer.
D: Remarkable whitening of the appearance of the decorative sheet and a large change in color tone of the transparent resin layer and/or base material layer were confirmed.

1-3. Scratch resistance A rubbing test was performed by reciprocating steel wool (“Bonstar #0000”, manufactured by Nippon Steel Wool Co., Ltd.) five times at a load of 300 g/m ² on the surfaces of the decorative sheets obtained in Examples and Comparative Examples. did The state of the surface after the test was visually observed and evaluated according to the following criteria.
A: No scratches and no change in gloss was observed.
B: A very slight scratch and a very slight change in luster were confirmed.
C: A slight scratch and a slight change in luster were confirmed.
D: Scratching was confirmed, and significant gloss change was confirmed.

[Example 1]
A decoration layer was formed on one side of a substrate layer (a colored polypropylene resin sheet with a thickness of 60 μm) which had been subjected to corona discharge treatment on both sides, using a printing ink composed of a two-liquid curing type acrylic-urethane resin. Next, an adhesive layer made of a urethane resin-based adhesive and 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) is applied to 100 parts by mass of a polypropylene resin using a T-die extruder. A transparent resin layer having a thickness of 80 μm was formed by hot melt extrusion.
After the surface of the transparent resin layer was subjected to corona discharge treatment, the following composition B was applied on 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 comprising a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol and hexamethylene diisocyanate at a mass ratio of 100:5.

Next, on the primer layer, 100 parts by mass of an ionizing radiation-curable resin composition comprising a trifunctional urethane acrylate oligomer having a weight average molecular weight of 4000 is added to a hydroxyphenyltriazine-based ultraviolet absorber (trade name: TINUVIN460, manufactured by BASF). 2 parts by mass and 3 parts by mass of a hindered amine light stabilizer (trade name: TINUVIN123, manufactured by BASF) is applied, and an electron beam is irradiated to cure the ionizing radiation curable resin composition. A topcoat layer having a thickness of 5 μm was formed.
Next, the top coat layer was embossed to form a 50 μm-deep wood-grain vessel-like concave-convex pattern to obtain a decorative sheet of Example 1.

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

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

[Comparative Example 2]
A comparative example was prepared in the same manner as in Example 1, except that the content of the hydroxyphenyltriazine-based ultraviolet absorber in composition C was changed to 1.0 parts by mass with respect to 100 parts by mass of the ionizing radiation-curable resin composition. 2 cosmetic sheets were obtained.

[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 composition A was changed to 0 parts by mass.

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

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 has extremely excellent 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 protective layer 20: Transparent resin layer 30: Decorative layer 40: Base material layer

Claims (8)

Absorbance A at a wavelength of 310 nm of the surface protective layer, which has a surface protective layer, a transparent resin layer containing a polyolefin resin, and a substrate layer containing a polyolefin resin in this order, and was measured in accordance with JIS K0115:2004. ₁ is 1.5 or more and 4.0 or less, and the absorbance _A2 at a wavelength of 310 nm of the surface protective layer and the transparent resin layer containing the polyolefin resin measured in accordance with JIS K0115:2004 is 3.0 . 6.5 or more , and the thickness of the transparent resin layer is thicker than the thickness of the base material layer . Absorbance A at a wavelength of 310 nm of the surface protective layer, which has a surface protective layer, a transparent resin layer containing a polyolefin resin, and a substrate layer containing a polyolefin resin in this order, and was measured in accordance with JIS K0115:2004. ₁ is 1.5 or more and 4.0 or less, and the absorbance A2 at a wavelength of 310 nm of the surface protective layer and the transparent resin layer containing the polyolefin resin measured in accordance with JIS K0115:2004 is _3.0 . 6.5 or less, wherein the surface protective layer and the transparent resin layer contain an ultraviolet absorber. 3. The decorative sheet according to claim 1, wherein the surface protective layer comprises a topcoat layer containing a cured product of a curable resin composition. 4. The decorative sheet according to claim 3, further comprising a primer layer formed closer to said transparent resin layer than said top coat layer as said surface protective layer. The decorative sheet according to any one of claims 1 to 4, further comprising a decorative layer between the base layer and the transparent resin layer. The decorative sheet according to claim 2 , wherein the thickness of the transparent resin layer is thicker than the thickness of the base material layer. The decorative sheet according to any one of claims 1 to 6, wherein the base layer is a colored base layer. A decorative material comprising an adherend and the decorative sheet according to any one of claims 1 to 7.

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