JP2022056213A - Decorative sheet and decorative material using the same - Google Patents

Abstract

To suppress deterioration over time due to ultraviolet rays in a decorative sheet formed by laminating a layer containing a polypropylene-based resin.SOLUTION: A decorative sheet 100 includes a surface protective layer 10, a transparent resin layer 20, and a substrate layer 40 in this order. The substrate layer 40 contains a polypropylene-based resin. At least one of the surface protective layer 10 and the transparent resin layer 20 contains an ultraviolet absorber. The absorbance A1 at a wavelength of 270 nm or more and 300 nm or less of the surface protective layer 10 and the transparent resin layer 20 is 2.7 or more as measured according to JIS K0115:2004. The absorbance A2 at a wavelength of 360 nm or more and 380 nm or less of the surface protective layer 10 and the transparent resin layer 20 is 0.3 or more as measured according to JIS K0115:2004.SELECTED DRAWING: Figure 1

Description

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

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

The decorative sheet may be used in places exposed to sunlight, such as outdoors and indoors near windows. When the decorative sheet is used in a place exposed to sunlight, the color tone of the decorative sheet changes or the resin deteriorates due to the influence of ultraviolet rays. Therefore, for the purpose of improving the weather resistance of the decorative sheet, an ultraviolet absorber is added to the surface protective layer of the decorative sheet.

However, there is a problem that the ultraviolet absorber tends to be bleed out from the surface protective layer over time. When the ultraviolet absorber bleeds out from the surface protective layer, there is a problem that the appearance of the decorative sheet surface is spoiled and the concentration of the ultraviolet absorber in the surface protective layer decreases with time, resulting in insufficient weather resistance. For example, Patent Document 1 has been proposed in order to eliminate the bleed-out of the ultraviolet absorber.

Japanese Unexamined Patent Publication No. 2000-117905

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

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

The present invention has been made under such circumstances, and an object of the present invention is to suppress deterioration over time due to ultraviolet rays in a decorative sheet obtained by laminating layers containing a polypropylene 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] A decorative sheet having a surface protective layer, a transparent resin layer, and a base material layer in this order.
The base material layer contains a polypropylene resin and contains
At least one of the surface protective layer and the transparent resin layer contains an ultraviolet absorber and contains an ultraviolet absorber.
The absorbance A1 of the surface protective layer and the transparent resin layer measured in accordance with JIS K0115: 2004 at a wavelength of 270 nm or more and 300 nm or less is 2.7 or more.
The absorbance A2 of the surface protective layer and the transparent resin layer measured in accordance with JIS K0115: 2004 at a wavelength of 360 nm or more and 380 nm or less is 0.3 or more.
Cosmetic sheet.
[2] A decorative material having the adherend and the decorative sheet according to the above [1].

According to the present invention, in a decorative sheet in which a layer containing a polypropylene-based resin is laminated, deterioration over time due to ultraviolet rays can be suppressed.

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

[Cosmetic sheet]
The decorative sheet of the present invention has a surface protective layer, a transparent resin layer, and a base material layer in this order.
The base material layer contains a polypropylene resin and contains
At least one of the surface protective layer and the transparent resin layer contains an ultraviolet absorber and contains an ultraviolet absorber.
The absorbance A1 of the surface protective layer and the transparent resin layer measured in accordance with JIS K0115: 2004 at a wavelength of 270 nm or more and 300 nm or less is 2.7 or more.
The absorbance A2 of the surface protective layer and the transparent resin layer measured in accordance with JIS K0115: 2004 at a wavelength of 360 nm or more and 380 nm or less is 0.3 or more.

In the present specification, "absorbance A1 at a wavelength of 270 nm or more and 300 nm or less of the surface protective layer and the transparent resin layer measured in accordance with JIS K0115: 2004" is referred to as "absorbance A1" and "JIS K0115: 2004". The "absorbance A2" of the surface protective layer and the transparent resin layer at a wavelength of 360 nm or more and 380 nm or less measured in accordance with "Asorbance A2" and "JIS K0115: 2004" was measured in accordance with the above-mentioned surface protection. The "absorbance A3" of the layer and the transparent resin layer at a wavelength of 310 nm may be referred to as "absorbance A3".

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

<Asorbance>
The decorative sheet of the present invention has an absorbance 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.
The polypropylene-based resin absorbs ultraviolet rays having a wavelength of 270 nm or more and 300 nm or less and is significantly deteriorated. Therefore, it is considered that if the cut rate of ultraviolet rays having a wavelength of 270 nm or more and 300 nm or less is increased, deterioration of the polypropylene-based 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 by the present inventors, there were frequent cases where the weather resistance of the decorative sheet could not be 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 present inventors have found that the cause of the above-mentioned case is that the absorption wavelength range of ultraviolet rays is changed by a part of the deteriorated polypropylene-based resin or the like. Then, it has been found that the weather resistance of the decorative sheet containing the polypropylene-based resin can be improved by considering the absorbance of the wavelength of 360 nm or more and 380 nm or less in addition to the absorbance of the wavelength of 270 nm or more and 300 nm or less.

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.
The absorbance A1 is preferably 3.0 or more, more preferably 3.4 or more, and further preferably 3.8 or more. If 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.
The absorbance A2 is preferably 0.4 or more, more preferably 0.5 or more, and further preferably 0.6 or more. If 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 further preferably 0.8 or less.

Both the absorbance A1 and the absorbance A2 are the absorbances of 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, but the total absorbance of the surface protective layer and the transparent resin layer. In the present invention, since the absorbance A1 and the absorbance A2 mean the total absorbance of the surface protective layer and the transparent resin layer, an excessive amount of the ultraviolet absorber is contained in either the surface protective layer or the transparent resin layer. Can be suppressed. Therefore, in the present invention, it is possible to easily suppress the bleed-out of the ultraviolet absorber.

The absorbance A1 and the absorbance A2 can be adjusted, for example, by the content ratio of the ultraviolet absorber and the thickness of the layer containing the ultraviolet absorber. Further, in order to facilitate the absorbance A1 to be 2.7 or more and the absorbance A2 to be 0.3 or more, it is preferable to include two or more kinds of ultraviolet absorbers having different maximum absorption wavelengths as the ultraviolet absorber.

The absorbance A1 can be measured, for example, as follows.
First, a laminate in which a surface protective layer is formed on a transparent resin layer is produced. Then, in accordance with JIS K0115: 2004, the average value of the absorbances measured at the wavelength of 270 nm or more and 300 nm or less of the laminate can be defined as the absorbance A1. The average value of the absorbance at a wavelength of 270 to 300 nm is the average value when the absorbance (a total of 31 absorbances) is measured for each 1 nm for a wavelength of 270 nm or more and 300 nm or less.
The absorbance A2 can be calculated as an average value of the absorbances measured at a wavelength of 360 nm or more and 380 nm or less of the laminate in accordance with JIS K0115: 2004. The average value of the absorbances having a wavelength of 360 nm or more and 380 nm or less is the average value when the absorbances (total of 21 absorbances) are measured for each 1 nm for the wavelengths of 360 nm or more and 380 nm or less.

As described above, the absorbance A1 and the absorbance A2 mean the total absorbance of the surface protective layer and the transparent resin layer.
When the absorbance A1 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 in the following ranges.
The absorbance A1I is preferably 0.5 or more, more preferably 1.0 or more, and further preferably 1.5 or more in order to suppress deterioration of the transparent resin layer. If the absorbance A1I 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 A1I is preferably 5.0 or less, more preferably 4.5 or less, and further preferably 4.0 or less.
The absorbance A1II is preferably 0.5 or more, more preferably 1.0 or more, and further preferably 1.5 or more. If the absorbance A1II is too large, 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 further preferably 4.5 or less.
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 the absorbances measured at a wavelength of 270 nm or more and 300 nm or less of the transparent resin layer.

When the absorbance A2 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 in the following ranges.
The absorbance A2I is preferably 0.15 or more, more preferably 0.2 or more, and further 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 further preferably 0.7 or less.
The absorbance A2II is preferably 0.05 or more, more preferably 0.07 or more, and further 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 further preferably 0.8 or less.
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 the absorbances measured at a wavelength of 360 nm or more and 380 nm or less of the transparent resin layer.

In order to improve the weather resistance, the decorative sheet of the present invention preferably has an absorbance A3 at a wavelength of 310 nm of 1.1 or more, more preferably 1.6 or more, and more preferably 2.0 or more. Is even more preferable. If 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 further preferably 2.6 or less.

When the absorbance A3 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 in the following ranges.
The absorbance A3I is preferably 0.3 or more, more preferably 0.5 or more, and further preferably 0.7 or more in order to suppress deterioration of the transparent resin layer. If the absorbance A3I 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 A3I is preferably 2.8 or less, more preferably 2.5 or less, and further preferably 2.2 or less.
The absorbance A3II is preferably 0.1 or more, more preferably 0.2 or more, and further 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 even more preferably 2.3 or less.
Absorbance A3I is obtained by measuring the absorbance A3II at a wavelength of 310 nm of the transparent resin layer 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 surface opposite to the base material layer of the transparent resin layer. The surface protective layer may be formed of a single layer or may be formed of two or more layers as shown in FIG.
In the present specification, the layer of the surface protective layer farthest from the transparent resin layer is referred to as a "top coat layer". That is, when the surface protective layer is formed from a single layer, the surface protective layer has a single layer structure of the top coat layer. When the surface protective layer is formed of two or more layers, the layer located between the top coat layer and the transparent resin layer is a layer other than the top coat layer among the layers constituting the surface protective layer. It means that there is.
The top coat layer preferably contains a cured product of the curable resin composition.

The surface protective layer preferably has a top coat layer and a primer layer located on the transparent resin layer side of the top coat layer. By forming the surface protective layer from the top coat layer and the primer layer and containing the ultraviolet absorber in both the top coat layer and the primer layer, the bleed-out of the ultraviolet absorber is suppressed while suppressing the deterioration with time due to the ultraviolet rays. Can be easily suppressed.

The surface protective layer is mainly composed of resin.
It is preferable that the resin constituting the surface protective layer does not substantially contain a polypropylene-based resin. It is preferable that the polypropylene-based resin is not substantially contained as the resin constituting the surface protective layer, so that the weather resistance of the surface protective layer can be easily improved.
The fact that the polypropylene-based resin is substantially not contained means that the ratio of the polypropylene-based resin to the total resin components constituting the surface protective layer is 1% by mass or less, preferably 0.1% by mass or less. , More preferably 0.01% by mass or less, still more preferably 0% by mass.

《UV absorber》
The decorative sheet needs to contain an ultraviolet absorber in at least one of the surface protective layer and the transparent resin layer. The decorative sheet preferably contains an ultraviolet absorber in both the surface protective layer and the transparent resin layer.
When the surface protective layer is formed from two or more layers, it is preferable that at least the top coat layer contains an ultraviolet absorber, and it is more preferable that all the layers constituting the surface protective layer contain an ultraviolet absorber.
Unless otherwise specified, the following embodiments relating to the ultraviolet absorber are common to the ultraviolet absorber of the surface protective layer and the ultraviolet absorber of the transparent resin layer.

The decorative sheet preferably contains two or more kinds of ultraviolet absorbers having different maximum absorption wavelengths as the ultraviolet absorber so that the absorbance A1 and the absorbance A2 can be easily set in a predetermined range.
Of the two types of UV absorbers, when the UV absorber with a small maximum absorption wavelength is defined as the UV absorber 1 and the UV absorber with a large maximum absorption wavelength is defined as the UV absorber 2, the UV absorber 1 and the UV absorber 1 are defined. The maximum absorption wavelength of 2 is preferably in the following range.
The maximum absorption wavelength of the ultraviolet absorber 1 is preferably 270 nm or more and 310 nm or less, and more preferably 280 nm or more and 300 nm or less. The maximum absorption wavelength of the ultraviolet absorber 2 is preferably 330 nm or more and 370 nm or less, and more preferably 340 nm or more and 360 nm or less.

Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, and the like, and a triazine-based ultraviolet absorber is preferable. Further, among the triazine-based ultraviolet absorbers, the hydroxyphenyltriazine-based ultraviolet absorber is preferable from the viewpoint of weather resistance.
That is, it is preferable that the decorative sheet of the present invention contains a triazine-based ultraviolet absorber in at least one of the surface protective layer and the transparent resin layer. Further, it is more preferable that the decorative sheet of the present invention contains a hydroxyphenyltriazine-based ultraviolet absorber in at least one of the surface protective layer and the transparent resin layer.
Further, an ultraviolet absorber having a reactive functional group such as a (meth) acryloyl group, a vinyl group or an allyl group is preferable because it is easy to suppress bleed-out.

Examples of the hydroxyphenyltriazine-based ultraviolet absorber include those of the following general formula (1).

In the general formula (1), R ¹¹ is a divalent organic group, R ¹² is an acyloxy group represented by —OC (= O) R ¹⁵ , and R ¹³ , R ¹⁴ and R ¹⁵ are independent of each other. It is a hydrogen atom or a monovalent organic group, and n ₁₁ and n ₁₂ are independently integers of 0 to 5. Further, when there are a plurality of R ¹³ and R ¹⁴ , they may be the same or different.
Examples of the divalent organic group of R ¹¹ include an aliphatic hydrocarbon group such as an alkylene group and an alkaneylene group. From the viewpoint of weather resistance, an alkylene group is preferable, 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, still more preferably 8 or less, and particularly preferably 4 or less. These aliphatic hydrocarbon groups may be linear, branched or cyclic, and are preferably linear or branched from the viewpoint of weather resistance, and more preferably linear.

R ¹³ and R ¹⁴ are preferably hydrogen atoms from the viewpoint of weather resistance. When R ¹³ and R ¹⁴ are monovalent organic groups, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like are preferably mentioned, and an aryl group and an arylalkyl group are preferably mentioned from the viewpoint of weather resistance. Such aromatic hydrocarbon groups are preferable, and aryl groups, especially phenyl groups, are preferable.
The R ¹⁵ is preferably a monovalent organic group from the viewpoint of weather resistance, preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, and from the viewpoint of weather resistance, an alkyl group and an alkenyl group. Such as an aliphatic hydrocarbon group is more preferable, and an alkyl group is further preferable. When the monovalent organic group of ^R15 is an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, it may be linear, branched or cyclic, and may be linear or branched from the viewpoint of weather resistance. The shape is preferable, and the number of carbon atoms thereof is preferably 2 or more, more preferably 4 or more, and the upper limit is preferably 16 or less, more preferably 12 or less, still more preferably 10 or less, from the viewpoint of weather resistance.

Further, examples of the hydroxyphenyltriazine-based ultraviolet absorber include those having the following general formula (2).
Since the hydroxyphenyltriazine compound represented by the general formula (2) does not contain an ester bond in the molecule, the molecular structure is not easily displaced. Therefore, the hydroxyphenyltriazine compound represented by the general formula (2) is preferable to the hydroxyphenyltriazine compound represented by the general formula (1) in that it is superior in suppressing bleed-out and maintaining long-term weather resistance.
It is considered that the variation in the molecular structure starting from the ester bond is caused by acidic conditions. Therefore, the hydroxyphenyltriazine compound represented by the general formula (2) can exert an excellent effect when used outdoors exposed to acid rain.

In the general formula (2), R ²¹ is a monovalent organic group, R ²¹ is a hydrogen atom or a monovalent organic group, and R ²² and R ²³ are independently hydroxyl groups or monovalent organic groups. Yes, n ₂₁ , n ₂₂ and n ₂₃ are independently integers of 1-5. Further, when there are a plurality of R ²¹ , R ²² and R ²³ , they may be the same or different.

As the monovalent organic group of R ²¹ , R ²² and R ²³ , those exemplified as the monovalent organic group of R ¹³ and R ¹⁴ in the above general formula (1) are preferably mentioned, and from the viewpoint of weather resistance. , An aliphatic hydrocarbon group such as an alkyl group or an alkenyl group is more preferable, and an alkyl group is further preferable. In this case, the monovalent organic group of R ²¹ , R ²² and R ²³ may be linear, branched or cyclic, and is preferably linear or branched from the viewpoint of weather resistance, and is directly formed. Chain form is more preferable. Further, from the viewpoint of weather resistance, the carbon number is preferably 2 or more, more preferably 3 or more, and the upper limit is preferably 16 or less, more preferably 12 or less, still more preferably 8 or less.
Further, n ₂₁ , n ₂₂ and n ₂₃ are preferably 2 or more, and a plurality of R ²¹ , R ²² and R ²³ may be the same or different, and the plurality of R ^21s are the same from the viewpoint of weather resistance. It is preferable that R ²² and R ²³ are different. It is preferable that one of the different R ²² and R ²³ is a hydrogen atom. When R ²¹ , R ²² and R ²³ are monovalent organic groups, they are preferably the same organic group.

The content of the ultraviolet absorber in the surface protective layer is not particularly limited as long as the absorbances A1 and A2 are within the above ranges. By setting the content of the ultraviolet absorber in the surface protective layer to a predetermined amount or more, the absorbances A1 and A2 can be easily set in the above range. Further, by setting the content of the ultraviolet absorber in the surface protective layer to a predetermined amount or more, deterioration of the transparent resin layer can be easily suppressed. Further, by setting the content of the ultraviolet absorber in the surface protective layer to a predetermined amount or less, bleed-out can be easily suppressed.
The content of the ultraviolet absorber in the top coat layer constituting the surface protective layer 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 resin constituting the top coat layer, and is 1.0. It is more preferably 20 parts by mass or more and 8.0 parts by mass or less, further preferably 2.0 parts by mass or more and 7.0 parts by mass or less, and further preferably 3.0 parts by mass or more and 6.5 parts by mass or less.
When the other layer constituting the surface protective layer contains an ultraviolet absorber, the content of the ultraviolet absorber in the other layer is 1 part by mass with respect to 100 parts by mass of the resin constituting the other layer. 40 parts by mass or more is preferable, 5 parts by mass or more and 30 parts by mass or less are more preferable, and 7 parts by mass or more and 25 parts by mass or less are further preferable. Examples of the other layer include a primer layer.

<< Radical scavenger >>
It is preferable that at least one of the surface protective layer and the transparent resin layer contains a radical scavenger. Since the surface protective layer is the layer to which ultraviolet rays are first incident among the layers constituting the decorative sheet, it is preferable to contain a radical scavenger. When the surface protective layer has a multi-layer structure, it is preferable that the top coat layer contains a radical scavenger.
Unless otherwise specified, the following embodiments relating to the radical scavenger are common to the radical scavenger of the surface protective layer and the radical scavenger of the transparent resin layer.

Examples of the radical scavenger include aromatic radical scavengers, amine radical scavengers, organic acid radical scavengers, catechin radical scavengers and hindered amine radical scavengers. preferable. The hindered amine radical scavenger has a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.

When the surface protective layer contains a radical scavenger, the radical scavenger includes a radical scavenger i having a polymerizable double bond with a resin constituting the surface protective layer and a resin constituting the surface protective layer. It preferably contains at least one of the radical scavengers ii that do not have a polymerizable ethylenic double bond. Further, the top coat layer has a radical scavenger i having an ethylenic double bond that can be polymerized with the resin constituting the top coat, and an ethylenic double bond that can be polymerized with the resin constituting the top coat layer. It is more preferable to contain at least one of the radical scavengers ii.
The ethylenic double bond has, for example, a functional group such as a (meth) acryloyl group, a vinyl group and an allylic group.

When only the radical scavenger i is used, almost all the radical scavengers in the surface protective layer are in an immobilized state, and there is almost no radical scavenger that can move freely in the surface protective layer, so that the radicals are captured. Performance is less likely to be exhibited. On the other hand, since the radical trapping agent i polymerizes with the resin constituting the surface protective layer, when the resin constituting the surface protective layer contains a cured product (particularly a cured product of the ionizing radiation curable resin composition), the radical trapping agent i As a result, the crosslink density of the cured product (particularly the cured product of the ionizing radiation curable resin composition) decreases, and the scratch resistance tends to decrease.
Therefore, it is preferable that the surface protective layer contains the radical scavenger i and the radical scavenger ii in an appropriate blending ratio, so that "radical scavenger", "scratch resistance", and "suppression of bleed-out" can be easily improved. .. When the surface protective layer has a multilayer structure, it is preferable that the top coat layer contains both the radical scavenger i and the radical scavenger ii as the radical scavenger, or the top coat layer contains only the radical scavenger ii as the radical scavenger. ..

The blending ratio of the radical scavenger i and the radical scavenger ii based on the mass is preferably 8: 2 to 0:10.
By setting the radical scavenger i to 8 and the radical scavenger ii to 2 or more, the weather resistance can be improved and the reduction in the crosslink density of the cured product of the surface protective layer can be easily suppressed.

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

The radical scavenger i has an ethylenic double bond that can be polymerized with the resin constituting the surface protective layer. Examples of the group having an ethylenically double bond include a (meth) acryloyl group, a crotonoyl group, a vinyl group and an allylic group, and among these, a (meth) acryloyl group is preferable. That is, the radical scavenger i preferably has a (meth) acryloyl group.
The number of ethylenic double bonds in the radical scavenger i is not particularly limited, and may be one or two or more. Further, only one type of radical scavenger i may be used, or two or more types may be used.

Examples of the radical trapping agent i having one ethylenic double bond include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine and 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, Examples thereof include 2,6,6-tetramethylpiperidine, pentamethylpiperidinyl (meth) acrylate, the compound of CAS number 1010692-24-6 and the compound of CAS number 1010692-21-3.
Examples of the radical trapping agent i having two or more ethylenic double bonds include 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine and 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- Examples thereof include the compound of 42-7 and the compound of CAS number 110692-23-5.

The radical scavenger ii does not have a polymerizable double bond with the resin constituting the surface protective layer. Only one kind of radical scavenger ii may be used, or two or more kinds may be used.

Radical trapping agents ii include 4-benzoyloxy-2,2,6,6-tetramethylpiperidin, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, and bis (1,2,2). , 6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyl oshiki-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl- 4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-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.

《Top coat layer》
The top coat layer preferably contains a cured product of the curable resin composition in order to enhance the scratch resistance of the decorative sheet.
Further, the ratio of the cured product of the curable resin composition to the total resin components constituting the top coat layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass. The above is more preferable.

Examples of the cured product of the curable resin include a cured product of a thermosetting resin, a cured product of an ionizing radiation curable resin, or a mixture thereof. Among these, a cured product of an ionizing radiation curable resin composition is preferable from the viewpoint of increasing the crosslink density of the top coat layer and improving scratch resistance and weather resistance. Further, from the viewpoint that it can be applied without a solvent and is easy to handle, the cured product of the electron beam curable resin composition is more preferable among the ionizing radiation curable resin compositions.

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

-Ionizing radiation curable resin-
The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as “ionizing radiation curable compound”). Examples of the ionizing radiation curable functional group include a group that is crosslinked and cured by irradiation with ionizing radiation, and a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group is preferable.
Further, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet (UV) or electron beam (EB) is used, but other than that, Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays are also included.
Specifically, the ionizing radiation curable compound can be appropriately selected and used from the polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.

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

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

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

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

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

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

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

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

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

<Transparent resin layer>
The transparent resin layer is located between the surface protective layer and the base material layer.
Examples of the resin constituting the transparent resin layer include polypropylene-based resin, polyolefin-based resin other than polypropylene-based resin (polyethylene, polymethylpentene, polybutene, etc.), polyester resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin (hereinafter, "" Also referred to as "ABS resin"), acrylic resin, vinyl chloride resin and the like. Among these, polypropylene-based resins are preferable from the viewpoint of processability.

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 the polypropylene-based resin of the transparent resin layer include a propylene homopolymer, an ethylene-propylene copolymer, a propylene-butene copolymer, and an ethylene-propylene-butene copolymer. Among these, a propylene homopolymer, an ethylene-propylene copolymer, and a propylene-butene copolymer are preferable, and a propylene homopolymer is more preferable.

It is preferable that the transparent resin layer contains an ultraviolet absorber and a radical scavenger.
The content of the ultraviolet absorber in the transparent resin layer is not particularly limited as long as the absorbances A1 and A2 are within the above range.
The content of the ultraviolet absorber in the transparent resin layer is preferably 0.05 parts by mass or more and 10 parts by mass or less, and 0.07 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the resin constituting the transparent resin layer. The following is more preferable, 0.09 parts by mass or more and 3 parts by mass or less is further preferable, and 0.10 parts by mass or more and 1 part by mass or less is further preferable. In particular, when the thickness of the transparent resin layer is in the range described later, it is preferable that the content of the ultraviolet absorber is in the above range.
The content of the radical scavenger in the transparent resin layer is preferably 0.1 part by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 8 parts by mass with respect to 100 parts by mass of the resin constituting the transparent resin layer. The following is more preferable, 1 part by mass or more and 5 parts by mass or less is further preferable, and 1.5 parts by mass or more and 3 parts by mass or less is further preferable. In particular, when the thickness of the transparent resin layer is in the range described later, it is preferable to set the content of the radical scavenger in the above range.

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

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

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

Examples of the polypropylene-based resin of the base material layer include a propylene homopolymer, an ethylene-propylene copolymer, a propylene-butene copolymer, and an ethylene-propylene-butene copolymer. Among these, a propylene homopolymer, an ethylene-propylene copolymer, and a propylene-butene copolymer are preferable, and a propylene homopolymer is more preferable.

When the base material layer contains a resin other than the polypropylene resin, for example, a polyolefin resin other than the polypropylene resin (polyethylene, polymethylpentene, polybutene, etc.), a polyester resin, a polycarbonate resin, and an acrylonitrile-butadiene-styrene resin (hereinafter, A thermoplastic resin such as "ABS resin"), acrylic resin, vinyl chloride resin and the like can be used.

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

The content of the colorant is, for example, preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 40 parts by mass or less, and 5 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the resin constituting the base material layer. More preferably, it is 5 parts by mass or less and 20 parts by mass or less.

Additives may be added to the base material layer, if necessary. Examples of the additive include an inorganic filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, an ultraviolet absorber, and a radical scavenger. The blending amount of the additive can be appropriately adjusted as long as the effect of the present invention is not impaired.
In the present invention, since the absorbances A1 and A2 are within a predetermined range, the weather resistance of the base material layer can be improved even if the base material layer does not contain an ultraviolet absorber and a radical scavenger.

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

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

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

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

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

As the colorant, a pigment having excellent hiding power and weather resistance is preferable. As the pigment, the same pigment as those exemplified for the substrate layer can be used.
The content of the colorant in the base material layer is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the resin constituting the decorative layer. More than 70 parts by mass is more preferable.

From the viewpoint of improving weather resistance, the decorative layer preferably contains a weather resistant 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 ground color of the adherend and improving the design, it is preferably 0.5 μm or more and 20 μm or less, and 1 μm or more and 10 μm. The following is more preferable, and 2 μm or more and 5 μm or less is further preferable.

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

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

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

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

The decorative sheet of the present invention may be embossed or the like to provide unevenness.
When embossing, for example, the decorative sheet is heated to preferably 80 ° C. or higher and 260 ° C. or lower, more preferably 100 ° C. or higher and 220 ° C. or lower, and further preferably 120 ° C. or higher and 200 ° C. or lower, and the embossed plate is pressed against the decorative sheet. Then, embossing can be performed. The portion where the embossed plate is pressed is preferably on the surface protective layer side of the decorative sheet.

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

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

The adherend may be appropriately selected from the above depending on the intended use.
When an adherend is used as an interior or exterior member of a building such as a wall, ceiling, or floor; a fitting or a building member such as a window frame, a door, a handrail, a skirting board, a peripheral edge, or a mall; The material of the landing material is preferably at least one selected from a wood member, a metal member and a resin member. When an adherend is used as an exterior member such as an entrance door, a window frame, or a fitting such as a door, the material of the adherend is preferably at least one selected from a metal member and a resin member. ..

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

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

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

The thickness of the adhesive layer B is not particularly limited, but from the viewpoint of obtaining excellent adhesiveness, it is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less, and further preferably 10 μm or more and 30 μm or less.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.

1. 1. Evaluation and measurement 1-1. Absorbance A laminate in which a surface protective layer was formed on a transparent resin layer was prepared. Using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Hitachi, Ltd., trade name: U-4000), "absorbance A1" and "absorbance A2", which are the absorbances of the laminate, in accordance with JIS K0115: 2004. And "absorbance A3" was measured.

1-2. Weather resistance The following super-accelerated weather resistance test equipment was used to irradiate the decorative sheets obtained in Examples and Comparative Examples with ultraviolet rays for 20 hours under the following irradiation conditions, and then the following dew condensation conditions. The step of dew condensation for 4 hours was set as one cycle, and the test) in which the cycle was repeated was carried out for 1400 hours. After 1000 hours and 1400 hours, the appearance of the decorative sheet was visually evaluated according to the following criteria.
<Ultra-accelerated weather resistance test equipment>
UV lamp (trade name: M04-L21WB / SUV, manufactured by Iwasaki Electric Co., Ltd.), lamp jacket (trade name: WJ50-SUV, manufactured by Iwasaki Electric Co., Ltd.) and illuminance meter (trade name: UVD-365PD, manufactured by Iwasaki Electric Co., Ltd.) Super accelerated weather resistance test device (trade name: Eye Super UV Tester SUV-W161 ", manufactured by Iwasaki Electric Co., Ltd.)
<Irradiation conditions>
・ Black panel temperature: 63 ° C
・ Illuminance: 100mW / cm ²
・ Humidity in the tank: 50% RH
・ Time: 20 hours <Condensation conditions>
・ Illuminance: 0mW / cm ²
・ Humidity in the tank: 98% RH
・ Time: 4 hours <Evaluation criteria>
A: No change in appearance was confirmed on the entire decorative sheet.
B: A slight whitening was confirmed on the appearance of the decorative sheet, but a change in the color tone of the transparent resin layer and / or the base material layer could not be confirmed.
C: A slight whitening was confirmed on the appearance of the decorative sheet, and a slight change in color tone of the transparent resin layer and / or the base material layer was confirmed.
D: Remarkable whitening of the appearance of the decorative sheet and a large change in color tone of the transparent resin layer and / or the base material layer were confirmed.

2. 2. Preparation of decorative sheet [Example 1]
A decorative layer was formed on one surface of a base material layer (colored polypropylene resin sheet having a thickness of 60 μm) subjected to double-sided corona discharge treatment by using a printing ink made of a two-component curable acrylic-urethane resin. Next, an adhesive layer made of a urethane resin-based adhesive having a thickness of 3 μm was formed on the decorative layer.
Next, the composition A containing the ultraviolet absorber 1, the ultraviolet absorber 2 and the ultraviolet absorber 3 was heated, melted and extruded on the adhesive layer with a T-die extruder against 100 parts by mass of the polypropylene resin to have a thickness of 80 μm. A transparent resin layer was formed.
The contents (parts by mass) of the ultraviolet absorber 1, the ultraviolet absorber 2, and the ultraviolet absorber 3 were the contents (parts by mass) shown in Table 1. Further, detailed information on the ultraviolet absorber 1, the ultraviolet absorber 2, and the ultraviolet absorber 3 is as follows.

<Detailed information on UV absorbers 1 to 3>
-Ultraviolet absorber 1: Hydroxyphenyltriazine-based ultraviolet absorber (trade name: TINUVIN460, BASF), maximum absorption wavelength: 349 nm
-UV absorber 2: hydroxyphenyltriazine-based UV absorber (trade name: ADEKA STAB LA-46, ADEKA), maximum absorption wavelength: between 280 and 300 nm-UV absorber 3: hydroxyphenyltriazine-based UV absorber (product) Name: TINUVIN477, BASF), Maximum absorption wavelength: 356 nm

After the surface of the transparent resin layer was subjected to a corona discharge treatment, the following composition B was applied onto the transparent resin layer and dried to form a primer layer having a thickness of 4 μm.
<Composition B>
A 100 parts by mass composition X (a composition obtained by mixing a composition composed of a polycarbonate urethane-acrylic copolymer and an acrylic polyol and hexamethylene diisocyanate in a mass ratio of 100: 5) and a diluting solvent are mixed. Composition.

Next, the following composition C is applied onto the primer layer, and the ionizing radiation curable resin composition is cured by irradiating it with an electron beam to form a top coat layer having a thickness of 5 μm. I got a sheet.

<Composition C>
-Ionizing radiation curable resin composition: 100 parts by mass (trifunctional urethane acrylate oligomer having a weight average molecular weight of 4000)
-The UV absorber 1: 1 part by mass-Hinderdamine radical scavenger: 3 parts by mass (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate)

[Examples 2 to 9], [Comparative Examples 1 to 6]
Except for changing the type and content (parts by mass) of the UV absorber in the transparent resin layer and the type and content (parts by mass) of the UV absorber in the top coat layer as shown in Table 1 or Table 2. , The decorative sheets of Examples 2 to 9 and Comparative Examples 1 to 6 were obtained in the same manner as in Example 1.

From the results of Tables 1 and 2, it can be confirmed that the decorative sheet of the example having an absorbance A1 of 2.7 or more and an absorbance A2 of 0.3 or more can suppress deterioration over time due to ultraviolet rays.

Since the decorative sheet of the present invention has excellent weather 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 (11)

A decorative sheet having a surface protective layer, a transparent resin layer, and a base material layer in this order.
The base material layer contains a polypropylene resin and contains
At least one of the surface protective layer and the transparent resin layer contains an ultraviolet absorber and contains an ultraviolet absorber.
The absorbance A1 of the surface protective layer and the transparent resin layer measured in accordance with JIS K0115: 2004 at a wavelength of 270 nm or more and 300 nm or less is 2.7 or more.
The absorbance A2 of the surface protective layer and the transparent resin layer measured in accordance with JIS K0115: 2004 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 surface protective layer and the transparent resin layer have an absorbance A3 of 1.1 or more at a wavelength of 310 nm, measured in accordance with JIS K0115: 2004. When the surface protective layer is formed of one or more layers, and the layer of the surface protective layers farthest from the transparent resin layer is defined as a top coat layer, the surface protective layer is defined as a top coat layer.
The decorative sheet according to claim 1 or 2, wherein in the top coat layer, the ultraviolet absorber is contained in an amount of more than 0.5 parts by mass and not more than 10.0 parts by mass with respect to 100 parts by mass of the resin constituting the top coat. The topcoat layer has a radical scavenger i having an ethylenic double bond that can be polymerized with the resin constituting the topcoat, and an ethylenic double bond that can be polymerized with the resin constituting the topcoat layer. The decorative sheet according to claim 3, which comprises at least one of the radical scavengers ii. The decorative sheet according to claim 4, wherein the top coat layer contains only the radical scavenger ii as a radical scavenger. The decorative sheet according to any one of claims 3 to 5, which has the top coat layer and the primer layer located on the transparent resin layer side of the top coat layer as the surface protective layer. The decorative sheet according to any one of claims 1 to 6, which does not substantially contain a polypropylene-based resin as the resin constituting the surface protective layer. The present invention according to any one of claims 1 to 7, wherein the transparent resin layer contains 0.05 parts by mass or more and 10.0 parts by mass or less of the ultraviolet absorber with respect to 100 parts by mass of the resin constituting the transparent resin layer. The described cosmetic sheet. The decorative sheet according to any one of claims 1 to 8, wherein the ultraviolet absorber contains two or more types of ultraviolet absorbers having different maximum absorption wavelengths. The decorative sheet according to any one of claims 1 to 9, which has a decorative layer between the base material layer and the transparent resin layer. A decorative material having the adherend and the decorative sheet according to any one of claims 1 to 10.

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