JP2022133017A - Decorative sheet and decorative material using thereof - Google Patents

Abstract

To suppress time degradation of a decorative sheet having a substrate layer containing a polyolefin resin due to ultraviolet light to prevent an ultraviolet absorber and a radical scavenger from bleedout.SOLUTION: A decorative sheet 100 has a resin layer 30 on a substrate layer 10 containing polyolefin resin, the resin layer has a transparent resin layer 31 and a surface protective layer 33 in this order from the side of the substrate layer, the surface protective layer is a cross-linkage cured composite layer of a composite including an ionization radiation curable resin composition, an ultraviolet absorber, and a radical scavenger, and contains at least two types of ultraviolet absorbers as an ultraviolet absorber, and contains a reactive radical scavenger and a non-reactive radical as a radical scavenger, the amount of the radical scavenger is 0.5 pt.mass to 10.0 pts.mass for 100 pts.mass of the ionization radiation curable resin composition, the absorbance of the resin layer in a wavelength range between 270nm to 300nm is more than 2.7, and the absorbance of the resin layer in a wavelength range between 360nm to 380nm is more than 0.3.SELECTED DRAWING: Figure 1

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 or protect the surfaces of building interior members, building exterior members, furniture, fitting members, home electric appliances, and the like. The decorative sheet has, for example, a structure having a surface protective layer on a base material.

Decorative sheets are sometimes used outdoors and indoors in places exposed to sunlight, such as by windows. When the decorative sheet is used in a place exposed to sunlight, the decorative sheet changes color tone or deteriorates resin due to the influence of ultraviolet rays. For this reason, an ultraviolet absorber, a radical scavenger, etc. are added to the surface protective layer of the decorative sheet for the purpose of improving the weather resistance of the decorative sheet.

However, ultraviolet absorbers and radical scavengers have the problem that they tend to bleed out from the surface protective layer over time. When the UV absorber and radical scavenger bleed out from the surface protective layer, the aesthetic appearance of the surface of the decorative sheet is impaired, and the concentration of the UV absorber and radical scavenger in the surface protective layer decreases over time, resulting in poor weather resistance. There is a problem of inadequacy. Patent Documents 1 and 2, for example, propose to eliminate the bleeding out of ultraviolet absorbers and radical scavengers.

JP-A-2000-117905 JP 2012-206375 A

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.
In the decorative sheet of Patent Document 2, the hindered amine light stabilizer (radical scavenger) in the surface protective layer has a reactive functional group.
As described above, Patent Documents 1 and 2 are techniques aimed at eliminating the bleeding out of the ultraviolet absorber and the radical scavenger by using the reactive ultraviolet absorber and radical scavenger.

On the other hand, decorative sheets are often required to be suitable for processing such as embossing, bending, and molding. For this reason, a decorative sheet has been proposed in which a base layer containing a polyolefin-based resin having excellent workability is used as the base layer, and a surface protective layer is laminated on the base layer.
When a surface protective layer such as those disclosed in Patent Documents 1 and 2 is applied as a surface protective layer of a decorative sheet in which a surface protective layer is laminated on a base material layer containing a polyolefin resin, the UV absorber and radicals in the surface protective layer Even if the bleed-out of the scavenger was suppressed, there were many cases where deterioration of the decorative sheet due to UV rays over time could not be suppressed.
In addition, when a large amount of reactive ultraviolet absorber and radical scavenger is used, there is a problem that bleeding out of the ultraviolet absorber and radical scavenger is accelerated.

The present invention has been made under such circumstances, and provides a decorative sheet having a base material layer containing a polyolefin resin, in which deterioration of the decorative sheet over time due to ultraviolet rays is suppressed, and an ultraviolet absorber and a radical scavenger bleed out. The task is to suppress the out.

In order to solve the above problems, the present invention provides the following [1] to [9].
[1] A decorative sheet having a resin layer on a base material layer,
The resin layer has a transparent resin layer and a surface protective layer in this order from the substrate layer side,
The base material layer contains a polyolefin resin,
The surface protective layer is a crosslinked cured product layer of a surface protective layer composition containing an ionizing radiation curable resin composition, an ultraviolet absorber 1 and a radical scavenger,
As the ultraviolet absorber 1, at least two ultraviolet absorbers having different maximum absorption wavelengths are included,
The radical scavenger includes a reactive radical scavenger and a non-reactive radical scavenger,
The content of the radical scavenger is 0.5 parts by mass or more and less than 10.0 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition,
Absorbance A1 of the resin layer at a wavelength of 270 nm or more and 300 nm or less is 2.7 or more,
Absorbance A2 of the resin layer at a wavelength of 360 nm or more and 380 nm or less is 0.3 or more,
cosmetic sheet.
[2] The decorative sheet according to [1], wherein the resin layer has an absorbance A3 of 1.1 or more at a wavelength of 310 nm.
[3] The decorative sheet according to [1] or [2], wherein the UV absorber 1 is a triazine-based UV absorber.
[4] The content of the ultraviolet absorber 1 is more than 0.5 parts by mass and 10.0 parts by mass or less with respect to 100 parts by mass of the ionizing radiation curable resin composition of [1] to [3] A cosmetic sheet according to any one of the above.
[5] The decorative sheet according to any one of [1] to [4], wherein the resin layer has a primer layer between the transparent resin layer and the surface protective layer.
[6] The decorative sheet according to any one of [1] to [5], which contains an ultraviolet absorber 2 in the transparent resin layer.
[7] The makeup according to [6], wherein the content of the ultraviolet absorber 2 is 0.05 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 transparent resin layer. sheet.
[8] The decorative sheet according to any one of [1] to [7], which has a decorative layer between the base layer and the resin layer.
[9] A decorative material comprising an adherend and the decorative sheet according to any one of [1] to [8].

ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet which has a layer containing a polyolefin-type resin WHEREIN: While suppressing deterioration with time by an ultraviolet-ray, the bleed-out of an ultraviolet absorber and a radical scavenger can be suppressed.

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 disclosure has a resin layer on the base layer,
The resin layer has a transparent resin layer and a surface protective layer in this order from the substrate layer side,
The base material layer contains a polyolefin resin,
The surface protective layer is a crosslinked cured product layer of a surface protective layer composition containing an ionizing radiation curable resin composition, an ultraviolet absorber 1 and a radical scavenger,
As the ultraviolet absorber 1, at least two ultraviolet absorbers having different maximum absorption wavelengths are included,
The radical scavenger includes a reactive radical scavenger and a non-reactive radical scavenger,
The content of the radical scavenger is 0.5 parts by mass or more and less than 10.0 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition,
Absorbance A1 of the resin layer at a wavelength of 270 nm or more and 300 nm or less is 2.7 or more,
The absorbance A2 of the resin layer at a wavelength of 360 nm or more and 380 nm or less is 0.3 or more.

As used herein, absorbance A1, absorbance A2 and absorbance A3 are absorbances measured according to JIS K0115:2004.

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 the resin layer 30 on the base layer 10 . In the decorative sheet 100 of FIG. 1, the resin layer 30 has a transparent resin layer 31, a primer layer 32 and a surface protection layer 33 in this order from the base material layer 10 side. In addition, the decorative sheet 100 of FIG. 1 has the decorative layer 20 between the base layer 10 and the resin layer 30 .

<Base material layer>
The base material layer is a layer containing a polyolefin resin. The substrate layer is located on the opposite side of the transparent resin layer to the surface protective layer.
The content of the polyolefin resin in the substrate layer is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total resin components of the substrate layer in order to improve processability. It is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

Examples of polyolefin-based resins for the substrate layer include polypropylene-based resins such as polypropylene, ethylene-propylene copolymer, propylene-butene copolymer and ethylene-propylene-butene copolymer, low-density polyethylene, medium-density polyethylene, high-density Examples thereof include polyethylene resins such as polyethylene, ethylene-vinyl acetate copolymer and ethylene-acrylic acid copolymer, polymethylpentene, polybutene, and the like. Among these, polypropylene-based resins and polyethylene-based resins are preferable, and polypropylene-based resins are more preferable. Among polypropylene-based resins, polypropylene (propylene homopolymer), ethylene-propylene copolymer and propylene-butene copolymer are preferable, and propylene homopolymer is more preferable.

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 the colorants, pigments that easily 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 zinc yellow type 1 and zinc yellow type 2); 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, ultraviolet absorbers, and radical scavengers. The blending amount of the additive can be appropriately adjusted within a range that does not impair the effects of the present invention.
In the present disclosure, since the absorbances A1 and A2 are set within a predetermined range, the weather resistance of the base layer can be improved even if the base layer does not contain an ultraviolet absorber and a radical scavenger.

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 more preferably 40 μm or more and 90 μm or less, in order to achieve a good balance between designability and processability. More preferred.

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.

<Resin layer>
The decorative sheet of the present disclosure has a resin layer on the base layer. The resin layer is required to have a transparent resin layer and a surface protective layer in this order from the substrate layer side. The surface protective layer as a resin layer needs to contain the ultraviolet absorber 1 . Moreover, it is preferable that the transparent resin layer as a resin layer contains the ultraviolet absorber 2 .
Moreover, the resin layer preferably has a primer layer between the transparent resin layer and the surface protective layer.

《Absorbance》
In the decorative sheet of the present disclosure, the resin layer needs to have an absorbance A1 of 2.7 or more at a wavelength of 270 nm or more and 300 nm or less, and an absorbance A2 of 0.3 or more at a wavelength of 360 nm or more and 380 nm or less.
A polyolefin resin absorbs ultraviolet rays having a wavelength of 270 nm or more and 300 nm or less and is likely to deteriorate significantly. Among polyolefin-based resins, polypropylene-based resins are particularly susceptible to deterioration in the above wavelength range. Therefore, it is thought that if the cut rate of ultraviolet rays with a wavelength of 270 nm or more and 300 nm or less is increased, deterioration of the polyolefin resin of the base material layer can be suppressed, and the weather resistance of the decorative sheet can be improved. However, as a result of research conducted by the present inventors, cases frequently occurred in which the weather resistance of the decorative sheet was not satisfied even if the cut rate of ultraviolet rays having a wavelength of 270 nm or more and 300 nm or less was increased. The inventors of the present invention have found that the cause of the above cases is that the absorption wavelength range of ultraviolet rays is changed by some deteriorated polyolefin resins and the like. The present inventors have found that by considering the absorbance at a wavelength of 360 nm or more and 380 nm or less in addition to the absorbance at a wavelength of 270 nm or more and 300 nm or less, the weather resistance of the decorative sheet whose base layer contains a polyolefin resin can be improved. I found out.

If the absorbance A1 is less than 2.7 or the absorbance A2 is less than 0.3, the weather resistance of the decorative sheet cannot be improved.
Absorbance A1 is preferably 3.0 or more, more preferably 3.2 or more. In addition, when the absorbance A1 is too large, the ultraviolet absorber may bleed out. Therefore, the absorbance A1 is preferably 6.0 or less, more preferably 5.7 or less, and even more preferably 5.5 or less.
Absorbance A2 is preferably 0.4 or more, more preferably 0.5 or more. In addition, when the absorbance A2 is too large, the ultraviolet absorber may bleed out. Therefore, the absorbance A2 is preferably 1.5 or less, more preferably 1.0 or less, and even more preferably 0.8 or less.

Both the absorbance A1 and the absorbance A2 are the absorbances of the resin layers including the surface protective layer and the transparent resin layer. In other words, the absorbance A1 and the absorbance A2 are neither the absorbance of the surface protective layer alone nor the absorbance of the transparent resin layer alone. In the present disclosure, since the absorbance A1 and the absorbance A2 mean the absorbance of the resin layers including the surface protective layer and the transparent resin layer, either the surface protective layer or the transparent resin layer is added with an excessive amount of ultraviolet absorber. Containment can be suppressed. Therefore, in the present disclosure, it is possible to easily suppress the bleeding out of the ultraviolet absorber.

The absorbance A1 and the absorbance A2 can be adjusted, for example, by adjusting the content of the ultraviolet absorbent and the thickness of the layer containing the ultraviolet absorbent. Further, by including at least two kinds of ultraviolet absorbers having different maximum absorption wavelengths as the ultraviolet absorber 1 in the surface protective layer, the absorbance A1 is set to 2.7 or more, and the absorbance A2 is easily set to 0.3 or more. can.

The absorbance A1 can be measured, for example, as follows.
First, a laminate is produced by forming a surface protective layer on a transparent resin layer. Alternatively, a laminate is produced by forming a primer layer and a surface protective layer on a transparent resin layer. Next, based on JIS K0115:2004, the average value of absorbance measured at wavelengths of 270 nm or more and 300 nm or less of the laminate can be taken as absorbance A1. The average absorbance at wavelengths from 270 to 300 nm is the average of absorbances measured at intervals of 1 nm (total of 31 absorbances) at wavelengths from 270 nm to 300 nm.
Absorbance A2 can be calculated as an average value of absorbance measured at wavelengths of 360 nm or more and 380 nm or less of the laminate in accordance with JIS K0115:2004. The average value of the absorbance at wavelengths of 360 nm or more and 380 nm or less is the average value of the absorbances measured at intervals of 1 nm (total of 21 absorbances) at wavelengths of 360 nm or more and 380 nm or less.

As described above, the absorbance A1 and the absorbance A2 mean the absorbance of the resin layers including the surface protective layer and the transparent resin layer.
Of the absorbance A1, when the absorbance of the surface protective layer is defined as the absorbance A1I and the absorbance of the transparent resin layer is defined as the absorbance A1II, the absorbance A1I and the absorbance A1II are preferably within the following ranges.
The absorbance A1I is preferably 0.5 or more, more preferably 1.0 or more, and still more preferably 1.5 or more in order to suppress deterioration of the transparent resin layer. If the absorbance A1I is too high, the UV absorber may bleed out from the surface protective layer, or the hardness of the surface protective layer may decrease. Therefore, the absorbance A1I is preferably 5.0 or less, more preferably 4.5 or less, and even more preferably 4.0 or less.
Absorbance A1II is preferably 0.5 or more, more preferably 1.0 or more, and still more preferably 1.5 or more. If the absorbance A1II is too high, the ultraviolet absorber may bleed out from the transparent resin layer. Therefore, the absorbance A1II is preferably 5.5 or less, more preferably 5.0 or less, and even more preferably 4.5 or less.
The absorbance A1I is obtained by measuring the absorbance A1II at a wavelength of 270 nm or more and 300 nm or less of the transparent resin layer in accordance with JIS K0115: 2004 and subtracting the absorbance A1II from the absorbance A1 (absorbance A1I = absorbance A1 - absorbance A1II ). The absorbance A1II is an average value of absorbances measured at a wavelength of 270 nm or more and 300 nm or less of the transparent resin layer.

Of the absorbance A2, when the absorbance of the surface protective layer is defined as the absorbance A2I and the absorbance of the transparent resin layer is defined as the absorbance A2II, the absorbance A2I and the absorbance A2II are preferably within the following ranges.
The absorbance A2I is preferably 0.15 or more, more preferably 0.2 or more, and still more preferably 0.25 or more in order to suppress deterioration of the transparent resin layer. If the absorbance A2I is too large, the ultraviolet absorber may bleed out from the surface protective layer, or the hardness of the surface protective layer may decrease. Therefore, the absorbance A2I is preferably 1.2 or less, more preferably 0.9 or less, and still more preferably 0.7 or less.
Absorbance A2II is preferably 0.05 or more, more preferably 0.07 or more, and still more preferably 0.09 or more. If the absorbance A2II is too large, the ultraviolet absorber may bleed out from the transparent resin layer. Therefore, the absorbance A2II is preferably 1.3 or less, more preferably 1.0 or less, and still more preferably 0.8 or less.
The absorbance A2I is obtained by measuring the absorbance A2II at a wavelength of 360 nm or more and 380 nm or less of the transparent resin layer in accordance with JIS K0115: 2004 and subtracting the absorbance A2II from the absorbance A2 (absorbance A2I = absorbance A2 - absorbance A2II ). The absorbance A2II is an average value of absorbance measured at wavelengths of 360 nm or more and 380 nm or less of the transparent resin layer.

In order to improve the weather resistance of the decorative sheet of the present disclosure, the absorbance A3 of the resin layer at a wavelength of 310 nm is preferably 1.1 or more, more preferably 1.6 or more, and 2.0. It is more preferable that it is above. In addition, when the absorbance A3 is too large, the ultraviolet absorber may bleed out. Therefore, the absorbance A3 is preferably 3.0 or less, more preferably 2.8 or less, and even more preferably 2.6 or less.

Of the absorbance A3, when the absorbance of the surface protective layer is defined as the absorbance A3I and the absorbance of the transparent resin layer is defined as the absorbance A3II, the absorbance A3I and the absorbance A3II are preferably within the following ranges.
The absorbance A3I is preferably 0.3 or more, more preferably 0.5 or more, and still more preferably 0.7 or more to suppress deterioration of the transparent resin layer. If the absorbance A3I is too high, the ultraviolet absorber may bleed out from the surface protective layer, or the hardness of the surface protective layer may decrease. Therefore, the absorbance A3I is preferably 2.8 or less, more preferably 2.5 or less, and still more preferably 2.2 or less.
Absorbance A3II is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. If the absorbance A3II is too large, the ultraviolet absorber may bleed out from the transparent resin layer. Therefore, the absorbance A3II is preferably 2.7 or less, more preferably 2.5 or less, and still more preferably 2.3 or less.
The absorbance A3I is obtained by measuring the absorbance A3II of the transparent resin layer at a wavelength of 310 nm in accordance with JIS K0115:2004 and subtracting the absorbance A3II from the absorbance A3 (absorbance A3I = absorbance A3 - absorbance A3II).

《Surface protective layer》
The surface protective layer is a layer located on the opposite side of the transparent resin layer to the substrate layer.
In the decorative sheet of the present disclosure, the surface protective layer is a crosslinked cured product layer of a surface protective layer composition containing an ionizing radiation-curable resin composition, an ultraviolet absorber 1 and a radical scavenger.

-Ionizing radiation curable resin composition-
The surface protective layer contains a crosslinked cured product of an ionizing radiation-curable resin composition. By including the crosslinked cured product of the ionizing radiation-curable resin composition in the surface protective layer, the scratch resistance of the decorative sheet can be improved. A part of the cross-linked cured product of the ionizing radiation-curable resin composition is polymerized with a reactive radical scavenger, which will be described later.

The ratio of the crosslinked cured product of the ionizing radiation-curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass, based on the total resin components constituting the surface protective layer. % or more is more preferable.
It is preferable that the resin constituting the surface protective layer does not substantially contain a polyolefin resin. By substantially not containing a polyolefin-based resin as a resin constituting the surface protective layer, it is preferable in terms of easily improving the weather resistance of the surface protective layer.
“Substantially free of polyolefin resin” means that the proportion of polyolefin 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.

The ionizing radiation curable resin composition includes an electron beam curable resin composition and an ultraviolet curable resin composition. Among these, the electron beam curable resin composition is preferred from the viewpoints of low environmental load because it can be applied without a solvent and no need for a polymerization initiator. In addition, since the surface protective layer composition contains the ultraviolet absorber 1, the electron beam curable resin composition is preferable to the ultraviolet curable resin composition in that the crosslink density can be easily increased.

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 a (meth)acryloyl group, a vinyl group, and an 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, usually ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.
Specifically, the ionizing radiation-curable compound can be appropriately selected and used from polymerizable monomers and polymerizable oligomers commonly 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 weather 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 novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having cationic polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination. Urethane (meth)acrylate 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 weather 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 weather 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 weather 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.

-Ultraviolet absorber 1-
The decorative sheet of the present disclosure is required to contain UV absorber 1 in the surface protective layer. Furthermore, the decorative sheet of the present disclosure is required to contain, as the UV absorber 1, at least two types of UV absorbers having different maximum absorption wavelengths. In this way, by including at least two kinds of ultraviolet absorbers having different maximum absorption wavelengths in the surface protective layer, it is possible to suppress the bleeding out of the ultraviolet absorber 1 and easily make the absorbance A1 and the absorbance A2 within the above-described ranges. .

Among at least two types of ultraviolet absorbers having different maximum absorption wavelengths, when defining an ultraviolet absorber with a short maximum absorption wavelength as an ultraviolet absorber A and an ultraviolet absorber with a large maximum absorption wavelength as an ultraviolet absorber B, the ultraviolet absorber The maximum absorption wavelengths of agent A and ultraviolet absorbent B are preferably within the following ranges.
The maximum absorption wavelength of the ultraviolet absorbent A is preferably 270 nm or more and 310 nm or less, more preferably 275 nm or more and 305 nm or less. The maximum absorption wavelength of the ultraviolet absorbent B is preferably 310 nm or more and 370 nm or less, more preferably 315 nm or more and 365 nm or less.

Examples of the ultraviolet absorbent 1 include benzotriazole-based ultraviolet absorbents, benzophenone-based ultraviolet absorbents, triazine-based ultraviolet absorbents, and the like, and among them, triazine-based ultraviolet absorbents are preferable. Among triazine-based UV absorbers, hydroxyphenyltriazine-based UV absorbers are preferred from the viewpoint of weather resistance.
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.

As the hydroxyphenyltriazine-based UV absorber, one represented by the following general formula (1) can be mentioned.

In general formula (1), R ¹¹ is a divalent organic group, R ¹² is an acyloxy group represented by —O—C(═O)R ¹⁵ , and R ¹³ , R ¹⁴ and R ¹⁵ are each independent is a hydrogen atom or a monovalent organic group, and n ₁₁ and n ₁₂ are each independently an integer of 0 to 5. Moreover, when there are multiple R ¹³ and R ¹⁴ , they may be the same or different.
Examples of the divalent organic group for R ¹¹ include aliphatic hydrocarbon groups such as an alkylene group and an alkenylene group, and from the viewpoint of weather resistance, an alkylene group is preferred, and the number of carbon atoms thereof is preferably 1 or more, more preferably It is 2 or more, and the upper limit is preferably 16 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 4 or less. These aliphatic hydrocarbon groups may be linear, branched or cyclic, preferably linear or branched, more preferably linear, from the viewpoint of weather resistance.

R ¹³ and R ¹⁴ are preferably hydrogen atoms from the viewpoint of weather resistance. In addition, when R ¹³ and R ¹⁴ are monovalent organic groups, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, arylalkyl groups and the like are preferable. An aromatic hydrocarbon group such as is preferred, and an aryl group, especially a phenyl group, is preferred.
R ¹⁵ is preferably a monovalent organic group from the viewpoint of weather resistance, and preferably includes an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group, and the like. is more preferred, and an alkyl group is even more preferred. When the monovalent organic group of R ¹⁵ is an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, it may be linear, branched or cyclic. The number of carbon atoms is preferably 2 or more, more preferably 4 or more, and the upper limit is preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less, from the viewpoint of weather resistance.

Further, as the hydroxyphenyltriazine-based ultraviolet absorber, one represented by the following general formula (2) can also be mentioned.
Since the hydroxyphenyltriazine compound represented by the general formula (2) does not contain an ester bond in its molecule, its molecular structure is not easily deformed. Therefore, the hydroxyphenyltriazine compound represented by the general formula (2) is preferable to the hydroxyphenyltriazine compound represented by the general formula (1) in terms of suppressing bleed out and maintaining long-term weather resistance.
The variation in molecular structure originating from the ester bond is considered to be caused by acidic conditions. Therefore, the hydroxyphenyltriazine compound represented by the general formula (2) can exhibit excellent effects when used outdoors where it is exposed to acid rain.

In general formula (2), R ²¹ is a hydrogen atom or a monovalent organic group, R ²² and R ²³ are each independently a hydroxyl group or a monovalent organic group, and n ₂₁ , n ₂₂ and n ₂₃ are Each is independently an integer from 1 to 5. Moreover, when there are a plurality of R ²¹ , R ²² and R ²³ , they may be the same or different.

Preferred examples of the monovalent organic groups for R ²¹ , R ²² and R ²³ include those exemplified as the monovalent organic groups for R ¹³ and R ¹⁴ in the general formula (1), and from the viewpoint of weather resistance. , an alkyl group and an alkenyl group are more preferred, and an alkyl group is even more preferred. In this case, the monovalent organic groups represented by R ²¹ , R ²² and R ²³ may be linear, branched or cyclic, preferably linear or branched from the viewpoint of weather resistance. A chain shape is more preferable. From the viewpoint of weather resistance, the number of carbon atoms is preferably 2 or more, more preferably 3 or more, and the upper limit is preferably 16 or less, more preferably 12 or less, and still more preferably 8 or less.
In addition, n ₂₁ , n ₂₂ and n ₂₃ are preferably 2 or more, the plurality of R ²¹ , R ²² and R ²³ may be the same or different, and from the viewpoint of weather resistance, the plurality of R ²¹ should be the same. is preferred and R ²² and R ²³ are preferably different. One of the different R ²² and R ²³ is preferably a hydrogen atom. Moreover, when R ²¹ , R ²² and R ²³ are monovalent organic groups, they are preferably the same organic group.

The content of the UV absorber 1 in the surface protective layer is not particularly limited as long as the absorbances A1 and A2 can be within the above ranges. By setting the content of the ultraviolet absorber 1 to a predetermined amount or more, the absorbances A1 and A2 can be easily made within the above ranges. Further, by setting the content of the ultraviolet absorber 1 to a predetermined amount or more, deterioration of the transparent resin layer can be easily suppressed. Further, by setting the content of the ultraviolet absorbent 1 to a predetermined amount or less, the bleeding out of the ultraviolet absorbent 1 can be easily suppressed.
The content of the ultraviolet absorber 1 is preferably more than 0.5 parts by mass and 10.0 parts by mass or less with respect to 100 parts by mass of the ionizing radiation curable resin composition, and 1.0 parts by mass or more and 8.0 parts by mass or less. It is more preferably 2.0 parts by mass or more and 7.0 parts by mass or less, and even more preferably 3.0 parts by mass or more and 6.5 parts by mass or less.

-Radical Scavenger-
The decorative sheet of the present disclosure is required to contain a radical scavenger in the surface protective layer. Furthermore, the decorative sheet of the present disclosure is required to contain a reactive radical scavenger and a non-reactive radical scavenger as the radical scavenger.
As used herein, the reactive radical scavenger means a radical scavenger having an ethylenic double bond polymerizable with the ionizing radiation-curable resin composition. Moreover, in this specification, the non-reactive radical scavenger means a radical scavenger that does not have a polymerizable ethylenic double bond in the ionizing radiation-curable resin composition.
Ethylenic double bonds are possessed by functional groups such as (meth)acryloyl groups, vinyl groups and allyl groups.

Examples of radical scavengers include aromatic radical scavengers, amine radical scavengers, organic acid radical scavengers, catechin radical scavengers, and hindered amine radical scavengers. Among these, hindered amine radical scavengers are preferred. preferable. Hindered amine-based radical scavengers have a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.

When only a reactive radical scavenger is used, almost all of the radical scavenger in the surface protective layer is immobilized, and almost no free radical scavenger exists in the surface protective layer, so radicals are scavenged. It becomes difficult to demonstrate the performance to do. On the other hand, since the reactive radical scavenger polymerizes with the resin constituting the surface protective layer, the reactive radical scavenger reduces the crosslink density of the crosslinked cured product of the ionizing radiation curable resin composition. Then, the decrease in the crosslink density of the crosslinked cured product of the ionizing radiation curable resin composition makes it easier for the ultraviolet absorber 1 to bleed out.
On the other hand, when only the non-reactive radical scavenger is used, the non-reactive radical scavenger bleeds out from the surface protective layer over time, impairing the aesthetic appearance of the surface of the decorative sheet, and the surface protective layer over time. The concentration of the radical scavenger is lowered, resulting in insufficient weather resistance.

In addition, the content of the radical scavenger in the decorative sheet of the present disclosure is 0.5 parts by mass or more and less than 10.0 parts by mass with respect to 100 parts by mass of the ionizing radiation-curable resin composition.
When the content of the radical scavenger is less than 0.5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition, the absolute amount of the radical scavenger is insufficient, so the reactive radical scavenger and the non-reactive radical Even if a scavenging agent is used in combination, the weather resistance of the decorative sheet cannot be improved. Further, when the content of the radical scavenger is 10.0 parts by mass or more with respect to 100 parts by mass of the ionizing radiation-curable resin composition, the crosslink density of the crosslinked product of the ionizing radiation-curable resin composition in the surface protective layer is will decline.

The weight ratio of the reactive radical scavenger and the non-reactive radical scavenger is preferably 8:2 to 2:8, more preferably 7:3 to 3:7.
By setting the number of reactive radical scavengers to 8 and the number of non-reactive radical scavengers to 2 or more, it is possible to easily suppress a decrease in the crosslink density of the crosslinked cured product of the ionizing radiation-curable resin composition. In addition, by setting the number of reactive radical scavengers to 2 and the number of non-reactive radical scavengers to 8 or less, the bleeding out of the non-reactive radical scavengers can be suppressed.

The reactive radical scavenger has an ethylenic double bond polymerizable with the ionizing radiation-curable resin composition. The group having an ethylenic double bond includes a (meth)acryloyl group, a crotonoyl group, a vinyl group and an allyl group, and among these, a (meth)acryloyl group is preferred. That is, the reactive radical scavenger preferably has a (meth)acryloyl group.
The number of ethylenic double bonds in the reactive radical scavenger is not particularly limited, and may be one or two or more. Moreover, only one reactive radical scavenger may be used, or two or more thereof may be used.

Examples of reactive radical scavengers having one ethylenic double bond include 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6 ,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine , 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and 4-crotonoylamino-2 , 2,6,6-tetramethylpiperidine, pentamethylpiperidinyl (meth)acrylate, compounds of CAS No. 1010692-24-6 and compounds of CAS No. 1010692-21-3.
Reactive radical scavengers having two or more ethylenic double bonds include 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl -4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine, CAS number 1954659 -42-7 and CAS number 1010692-23-5.

A non-reactive radical scavenger does not have an ethylenic double bond polymerizable with the ionizing radiation-curable resin composition. Only one type of non-reactive radical scavenger may be used, or two or more types may be used.

Non-reactive radical scavengers include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6- pentamethyl-4-piperidinyl) sebacate, 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-butane tetracarboxylate, bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxy -benzyl)-2-n-butylmalonate and the like.

The thickness of the surface protective 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 weather resistance.

《Transparent resin layer》
The transparent resin layer is a layer located closer to the substrate layer than the surface protective layer.
Examples of the resin constituting the transparent resin layer include polyethylene resins, polypropylene resins, polyolefin resins such as polymethylpentene and polybutene, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"). ), acrylic resins, vinyl chloride resins, and the like. Among these, polyolefin-based resins are preferred, and polypropylene-based resins are more preferred, from the viewpoint of workability.

The content of the polypropylene-based resin in the transparent resin layer is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total resin components of the transparent resin layer, from the viewpoint of processability. It is preferably 70% by mass or more, and more preferably 70% by mass or more.

Examples of polypropylene-based resins for the transparent resin layer include propylene homopolymers, ethylene-propylene copolymers, propylene-butene copolymers, and ethylene-propylene-butene copolymers. Among these, propylene homopolymers, ethylene-propylene copolymers and propylene-butene copolymers are preferred, and propylene homopolymers are more preferred.

The transparent resin layer preferably contains an ultraviolet absorber 2 .
Examples of the ultraviolet absorbent 2 include the ultraviolet absorbents exemplified as the ultraviolet absorbent 1 of the surface protective layer. The number of ultraviolet absorbers 2 may be one, or two or more.
The maximum absorption wavelength of the ultraviolet absorbent 2 is preferably 270 nm or more and 310 nm or less, more preferably 280 nm or more and 300 nm or less.

The content of the ultraviolet absorbent 2 in the transparent resin layer is not particularly limited as long as the absorbances A1 and A2 can be within the above ranges.
The content of the ultraviolet absorber in the transparent resin layer is preferably 0.05 parts by mass or more and 10.0 parts by mass or less, and 0.07 parts by mass or more5 based on 100 parts by mass of the resin constituting the transparent resin layer. 0.0 mass parts or less is more preferable, 0.09 mass parts or more and 3.0 mass parts or less is still more preferable, and 0.10 mass parts or more and 1.0 mass parts or less is even more preferable. In particular, when the thickness of the transparent resin layer is within the range described later, it is preferable to set the content of the ultraviolet absorber within the above range.

The transparent resin layer may contain a radical scavenger.
The content of the radical scavenger in the transparent resin layer is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, preferably 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. 0 parts by mass or less, more preferably 1 part by mass or more and 5.0 parts by mass or less, and even more preferably 1.5 parts by mass or more and 3.0 parts by mass or less. In particular, when the thickness of the transparent resin layer is within the range described below, the content of the radical scavenger is preferably within the above range.

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 more preferably 50 μm or more and 90 μm or less, from the viewpoint of the balance between scratch resistance, workability and weather resistance.
Moreover, the thickness of the transparent resin layer is preferably thicker than that of the substrate layer from the viewpoint of protecting the decorative layer and obtaining excellent scratch resistance.

《Primer layer》
In the decorative sheet of the present disclosure, the resin layer preferably has a primer layer between the transparent resin layer and the surface protective layer. The primer layer can improve the adhesion between the surface protective 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 radical scavengers, 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 polymer main chain). 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 primer layer may contain additives such as ultraviolet absorbers and radical scavengers.
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.

<Decoration layer>
The decorative sheet of the present disclosure preferably has a decorative layer at any location on the decorative sheet in order to improve designability. From the viewpoint of enhancing the weather resistance of the decoration layer, the location where the decoration layer is formed is preferably between the base material layer and the 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 decoration layer is obtained by appropriately mixing a binder resin with coloring agents such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, ultraviolet absorbers, radical scavengers, and the like. 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 colorant, a pigment having excellent hiding properties and weather resistance is 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 weather resistance, the decorative layer preferably contains a weather resistance agent such as an ultraviolet absorber and a radical scavenger.

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 may be provided between the substrate layer and the resin layer in order to improve adhesion between the two layers.
When the decorative layer is provided between the substrate layer and the 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 surface protective layer described above can be obtained, for example, by applying a coating liquid containing the composition constituting each layer to a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, a comma It can be formed by coating by a known method such as a coating method and, if necessary, drying and curing. Also, the transparent resin layer can be formed, for example, by melt extruding a composition that constitutes the transparent resin layer.

The decorative sheet of the present disclosure 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 100° C. or higher and 220° C. or lower, still more preferably 120° C. or higher and 200° 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 disclosure includes an adherend and the above-described decorative sheet of the present disclosure. The decorative material of the present disclosure is, for example, laminated with the surface of the adherend requiring decoration facing the base layer side surface of the decorative sheet.

<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. Materials for the adherend include wood members, metal members, ceramic members, resin members, and the like.
Various types of wood such as cedar, Japanese cypress, pine, and lauan can be used as raw materials for the wooden member. Examples of the shape of the wooden member include wood veneer, wood plywood, particle board, wood fiberboard such as MDF (medium density fiberboard), and three-dimensional articles.
Raw materials for the metal member include iron, aluminum, and the like. Examples of the shape of the metal member include a plate material, a steel plate, a three-dimensional article, a sheet, and the like.
Examples of raw materials for the ceramic members include glass, ceramics such as ceramics, non-cement ceramic materials such as gypsum, and non-ceramic ceramic materials such as ALC (light aerated concrete) plates. Examples of the shape of the ceramic member include plate materials and three-dimensional articles.
Raw materials for resin members include acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, rubber, etc. is mentioned. The shape of the resin member includes a plate material, a three-dimensional article, a sheet, and the like.
The members constituting the adherend can be used singly or in combination. The decorative material of the present disclosure is preferable in that the weather resistance of the adherend can be improved when the adherend contains a polypropylene-based resin.

The adherend may be appropriately selected from the above according to the application.
In addition, interior or exterior members of buildings such as walls, ceilings, floors; The material of the adhesive material is preferably at least one member selected from wooden members, metal members and resin members. In addition, when the adherend is used as an exterior member such as an entrance door, a window frame, a fitting such as a door, the material of the adherend is preferably made of at least one member selected from metal members and resin members. .

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

<Adhesive Layer 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.
Moreover, an adhesive can also be used for the adhesive layer B. 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.

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 A laminate was prepared by forming a surface protective layer on a transparent resin layer. Using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Hitachi, Ltd., trade name: U-4000), in accordance with JIS K0115: 2004, the absorbance of the laminate "absorbance A1", "absorbance A2". and "Absorbance A3" were measured.

1-2. Weather resistance Using the super accelerated weather resistance tester described below, the decorative sheets obtained in Examples and Comparative Examples were subjected to an accelerated weather resistance test (after irradiating with ultraviolet rays for 20 hours under the following irradiation conditions, A test in which the cycle is repeated for 1,500 hours, with the process of dew condensation for 4 hours as one cycle. After 1500 hours, 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.)
<Irradiation conditions>
・Black panel temperature: 63℃
・Illuminance: 100mW/ ^cm2
・ Humidity in tank: 50% RH
・Time: 20 hours <condensation conditions>
・Illuminance: 0mW/ ^cm2
・ Humidity in tank: 98% RH
・ Time: 4 hours <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 observed.

1-3. Bleed-out The decorative sheets obtained in Examples and Comparative Examples were immersed in hot water at 40° C. for 1 week, taken out, dried, and then visually observed from the surface protective layer side. 20 people, with 3 points indicating no change in appearance, 2 points indicating slight bleeding but no practical problem, and 1 point indicating significant bleeding. of subjects evaluated. The average score of 20 evaluations was calculated and ranked according to the following criteria.
<Bleed-out evaluation criteria>
AA: Average score of 2.7 or more A: Average score of 2.5 or more and less than 2.7 B: Average score of 2.0 or more and less than 2.5 C: Average score of 1.5 or more and less than 2.0 D: Average score less than 1.5

2. Preparation of decorative sheet [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, 0.12 mass of an ultraviolet absorber (hydroxyphenyltriazine-based ultraviolet absorber (trade name: Tinuvin 400, BASF), maximum absorption wavelength: 290 nm) is added to 100 parts by mass of the polypropylene resin. The composition containing 1 part was heated and melt-extruded with a T-die extruder to form a transparent resin layer having a thickness of 80 μm.

After the surface of the transparent resin layer was subjected to corona discharge treatment, the following primer layer composition was applied onto the transparent resin layer and dried to form a primer layer having a thickness of 4 μm.
<Composition B for Primer Layer>
100 parts by mass of composition X (a composition obtained by mixing a composition comprising a polycarbonate-based urethane-acrylic copolymer and acrylic polyol and hexamethylene diisocyanate at a mass ratio of 100:5) and a diluent solvent. A composition consisting of

Then, the following surface protective layer composition was applied onto the primer layer and irradiated with an electron beam to crosslink and cure the surface protective layer composition to form a surface protective layer having a thickness of 5 μm. 1 cosmetic sheet was obtained.

<Composition for Surface Protective Layer>
・Ionizing radiation curable resin composition: 100 parts by mass (trifunctional urethane acrylate oligomer with a weight average molecular weight of 4000)
・The following ultraviolet absorber a: 1 part by mass ・The following ultraviolet absorber b: 5 parts by mass ・Reactive radical scavenger: 1.5 parts by mass (pentamethylpiperidinyl methacrylate)
- Non-reactive radical scavenger: 1.5 parts by mass (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate)

<Detailed information on UV absorbers a to c>
- Ultraviolet absorber a: hydroxyphenyltriazine-based ultraviolet absorber (trade name: TINUVIN479, BASF), maximum absorption wavelength: 320 nm
・Ultraviolet absorber b: hydroxyphenyltriazine-based ultraviolet absorber (trade name: ADEKA STAB LA-46, ADEKA), maximum absorption wavelength: between 280 and 300 nm ・Ultraviolet absorber c: hydroxyphenyltriazine-based ultraviolet absorber (product Name: TINUVIN477, BASF), maximum absorption wavelength: 350 ~ 360 nm

[Examples 2 to 15], [Comparative Examples 1 to 10]
Example 1 except that the type and content of the ultraviolet absorber in the composition for the surface protective layer and the content of the radical scavenger in the composition for the surface protective layer were changed as shown in Tables 1 to 4. Decorative sheets of Examples 2 to 15 and Comparative Examples 1 to 10 were obtained in the same manner.

From the results in Tables 1 to 4, it can be confirmed that the decorative sheets of the examples can suppress deterioration of the decorative sheet over time due to ultraviolet rays, and can suppress bleeding out of the ultraviolet absorber and the radical scavenger.

Since the decorative sheet of the present invention has excellent weather resistance and can suppress bleeding out, it can be 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. It is preferably used.

10: base material layer 20: decorative layer 30: resin layer 31: transparent resin layer 32: primer layer 33: surface protective layer 20: transparent resin layer 100: decorative sheet

Claims (9)

A decorative sheet having a resin layer on a base material layer,
The resin layer has a transparent resin layer and a surface protective layer in this order from the substrate layer side,
The base material layer contains a polyolefin resin,
The surface protective layer is a crosslinked cured product layer of a surface protective layer composition containing an ionizing radiation curable resin composition, an ultraviolet absorber 1 and a radical scavenger,
As the ultraviolet absorber 1, at least two ultraviolet absorbers having different maximum absorption wavelengths are included,
The radical scavenger includes a reactive radical scavenger and a non-reactive radical scavenger,
The content of the radical scavenger is 0.5 parts by mass or more and less than 10.0 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition,
Absorbance A1 of the resin layer at a wavelength of 270 nm or more and 300 nm or less is 2.7 or more,
Absorbance A2 of the resin layer at a wavelength of 360 nm or more and 380 nm or less is 0.3 or more,
cosmetic sheet. The decorative sheet according to claim 1, wherein the resin layer has an absorbance A3 of 1.1 or more at a wavelength of 310 nm. 3. The decorative sheet according to claim 1, wherein said UV absorber 1 is a triazine-based UV absorber. The content of the ultraviolet absorber 1 is more than 0.5 parts by mass and 10.0 parts by mass or less with respect to 100 parts by mass of the ionizing radiation curable resin composition, according to any one of claims 1 to 3. cosmetic sheet. The decorative sheet according to any one of claims 1 to 4, wherein the resin layer has a primer layer between the transparent resin layer and the surface protective layer. The decorative sheet according to any one of claims 1 to 5, wherein the transparent resin layer contains an ultraviolet absorber 2. 7. The decorative sheet according to claim 6, wherein the content of said ultraviolet absorber 2 is 0.05 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the resin constituting said transparent resin layer. The decorative sheet according to any one of claims 1 to 7, comprising a decorative layer between the base layer and the resin layer. A decorative material comprising an adherend and the decorative sheet according to any one of claims 1 to 8.

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