Cosmetic sheet, method for manufacturing the same, and cosmetic material

Abstract

To provide a cosmetic sheet that has low glossiness and weather resistance.SOLUTION: The present disclosure provides a cosmetic sheet comprising: a base layer 1; a decorative layer 2 arranged on one surface of the base layer; and a matte layer 3 arranged on the surface of the decorative layer opposite to the base layer, wherein a surface S1 of the matte layer opposite to the decorative layer has a surface shape having a wrinkle structure. The matte layer has a curing resin and an ultraviolet absorbent X; a light absorption spectrum of the ultraviolet absorbent X has a first absorption peak having a peak wavelength λP1 in a wavelength range of 200 nm or more and 380 nm or less; and when the absorbance at the peak wavelength λP1 is expressed as Amax, the wavelength λ10 at which the absorbance A10 is 10% of the absorbance Amax is 385 nm or less on the wavelength side higher than the peak wavelength λP1.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a cosmetic sheet, a method for manufacturing the cosmetic sheet, and a cosmetic material.

Background Art

[0002] For a cosmetic sheet used as a cosmetic material, for example, low gloss may be required for the purpose of improving the design.

[0003] Patent Document 1 discloses a method of forming unevenness on the film surface by irradiating a curable composition with excimer light to form a wrinkled uneven structure on the cured film, and it is described that a cured film having a matting property can be obtained.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] As a method of forming a matting layer having a surface shape with a wrinkle structure, for example, after applying a composition for a matting layer to form a coating layer, (1) an ultraviolet irradiation treatment for pre-curing, (2) an irradiation treatment with wavelength light having a peak wavelength of 100 nm or more and less than 200 nm, and (3) an electron beam irradiation treatment are performed in this order. The above (1) ultraviolet irradiation treatment for pre-curing imparts appropriate viscosity to the composition for the matting layer, and suppresses the sagging of the wrinkle structure formed by the subsequent (2) irradiation treatment with wavelength light having a peak wavelength of 100 nm or more and less than 200 nm, and is performed to obtain a wrinkle structure capable of exhibiting low gloss.

[0006] Here, weather resistance may be required for decorative materials. For example, members used outdoors (exterior members) are exposed to harsh environments, so high weather resistance is required. When an ultraviolet absorber is blended into the matte layer composition to obtain weather resistance, (1) the effect of ultraviolet irradiation treatment for preliminary curing is inhibited, it becomes difficult to form unevenness in the wrinkle structure, and the matte effect tends to decrease. Such a problem of matte effect reduction is a problem peculiar to the matte layer obtained by performing the irradiation treatment with the ionizing radiation of the above (1) to (3).

[0007] The present disclosure has been made in view of the above problems, and the main object is to provide a decorative sheet that achieves both low glossiness and weather resistance.

Means for Solving the Problems

[0008] In the present disclosure, there is provided a decorative sheet having a base material layer, a decorative layer disposed on one surface of the base material layer, and a matte layer disposed on the surface of the decorative layer opposite to the base material layer, wherein the surface of the matte layer opposite to the decorative layer has a surface shape having a wrinkle structure, the matte layer has a cured resin and an ultraviolet absorber X, and the light absorption spectrum of the ultraviolet absorber X has a peak wavelength λ in the wavelength range of 200 nm or more and 380 nm or less. P1 having a first absorption peak, and when the absorbance at the peak wavelength λ P1 is A max at a wavelength higher than the peak wavelength λ P1 the absorbance A max is 10% of the absorbance A 10 the wavelength λ 10 is 385 nm or less, a decorative sheet is provided.

[0009] In the present disclosure, there is provided a method for manufacturing the above-described cosmetic sheet, including a decorative layer forming step of forming the decorative layer on one surface of the base material layer, and a matting layer forming step of applying a matting layer composition to the surface of the decorative layer opposite to the base material layer to form a coating layer, and curing the coating layer by irradiation with ionizing radiation to form the matting layer. The irradiation treatment with ionizing radiation in the matting layer forming step includes (1) ultraviolet irradiation treatment for preliminary curing, (2) irradiation treatment with wavelength light having a peak wavelength of 100 nm or more and less than 200 nm, and (3) electron beam irradiation treatment, which are performed in this order.

[0010] In the present disclosure, there is provided a decorative material having an adherend and a cosmetic sheet disposed on the surface of the adherend, wherein the cosmetic sheet is the above-described cosmetic sheet.

Advantages of the Invention

[0011] In the present disclosure, there is an effect that a cosmetic sheet having both low gloss and weather resistance can be provided.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Best Mode for Carrying Out the Invention

[0013] Embodiments will be described below with reference to the drawings and the like. However, the present disclosure can be implemented in many different modes and should not be limited to the description of the embodiments illustrated below. Also, for the purpose of making the description clearer, the drawings may schematically represent the width, thickness, and shape of each part compared to the actual form, but this is merely an example and should not be construed as limiting.

[0014] In this specification, when expressing the mode of arranging one member on another member, if simply expressed as "on" or "under", unless otherwise specified, it includes both the case where another member is arranged directly above or directly below so as to be in contact with a certain member, and the case where another member is arranged above or below a certain member with yet another member interposed therebetween. Also, in this specification, when expressing the mode of arranging one member on the surface of another member, if simply expressed as "on the surface" or "on the surface side", unless otherwise specified, it includes both the case where another member is arranged directly above or directly below so as to be in contact with a certain member, and the case where another member is arranged above or below a certain member with yet another member interposed therebetween.

[0015] Also, in this specification, the terms "plate", "sheet", and "film" are not distinguished from each other based only on the difference in name. For example, a "sheet" includes a member called a "plate" or a "film".

[0016] Hereinafter, the cosmetic sheet, the method for manufacturing the cosmetic sheet, and the cosmetic material in the present disclosure will be described in detail.

[0017] A. Cosmetic Sheet The decorative sheet in the present disclosure is a decorative sheet having a base material layer, a decorative layer disposed on one surface of the base material layer, and a matting layer disposed on the surface of the decorative layer opposite to the base material layer, wherein the surface of the matting layer opposite to the decorative layer has a surface shape having a wrinkle structure, the matting layer has a cured resin and an ultraviolet absorber X, and the light absorption spectrum of the ultraviolet absorber X has a peak wavelength λ in the wavelength range of 200 nm or more and 380 nm or less. P1 has a first absorption peak, and the absorbance at the peak wavelength λ P1 is A max When this is the case, on the higher wavelength side than the peak wavelength λ P1 the absorbance A max at 10% of A 10 is the wavelength λ 10 which is 385 nm or less.

[0018] FIGS. 1 and 2 are schematic cross-sectional views illustrating the decorative sheet in the present disclosure. The decorative sheet 10 shown in FIG. 1 has a base material layer 1, a decorative layer 2, and a matting layer 3 in this order in the thickness direction Dt. Further, as shown in FIG. 2, in the decorative sheet 10 of the present disclosure, a transparent resin layer 4 may be disposed between the decorative layer 2 and the matting layer 3. Further, a primer layer 7 may be disposed between the matting layer 3 and the transparent resin layer 4. Further, an adhesive layer 5 and a separator layer 6 may be disposed on the side of the base material layer 1 opposite to the decorative layer 2.

[0019] FIG. 3 is a microscopic image of the surface of the matting layer 3 of the decorative sheet in the present disclosure. As shown in FIG. 3, the surface S1 of the matting layer 3 opposite to the decorative layer has a surface shape having a wrinkle structure. Further, the matting layer 3 has a cured resin and an ultraviolet absorber X having a specific absorption peak.

[0020] According to the decorative sheet in the present disclosure, since the surface of the matting layer opposite to the decorative layer has a wrinkle structure, light reflection can be suppressed by the light diffusion effect at the refractive index difference interface between the matting layer and air. Thereby, a matting effect is exhibited.

[0021] Furthermore, according to the cosmetic sheet in the present disclosure, since the matting layer contains the ultraviolet absorber X having the first absorption peak with the peak wavelength λ in the wavelength range of 200 nm or more and 380 nm or less, it has excellent weather resistance. As described above, when an ultraviolet absorber is blended in the matting layer-forming composition, the effect of the ultraviolet irradiation treatment for (1) pre-curing in the matting layer-forming step may be inhibited. However, in the present disclosure, when the absorbance at the peak wavelength λ is A, the absorbance A at a wavelength longer than the peak wavelength λ is 10% of A, and the wavelength λ is 385 nm or less. Therefore, it is possible to suppress the inhibition of the effect of the ultraviolet irradiation treatment for (1) pre-curing, and a low glossiness can be obtained. P1 Since the matting layer contains the ultraviolet absorber X having the first absorption peak with the peak wavelength λ, it has excellent weather resistance. As described above, when an ultraviolet absorber is blended in the matting layer-forming composition, the effect of the ultraviolet irradiation treatment for (1) pre-curing in the matting layer-forming step may be inhibited. However, in the present disclosure, P1 when the absorbance at the peak wavelength λ is A max and P1 at a wavelength longer than the peak wavelength λ max the absorbance A 10 is 10% of A 10 the wavelength λ is 385 nm or less, so it is possible to suppress the inhibition of the effect of the ultraviolet irradiation treatment for (1) pre-curing, and a low glossiness can be obtained.

[0022] Hereinafter, each component of the cosmetic sheet in the present disclosure will be described.

[0023] 1. Matting layer In the present disclosure, the surface S1 on the side opposite to the decorative layer of the matting layer has a surface shape having a wrinkle structure. Further, the matting layer contains a cured resin and the ultraviolet absorber X. The cosmetic sheet in the present disclosure preferably has the matting layer as the outermost layer. That is, it is preferable that the outermost surface of the cosmetic sheet has the above surface shape.

[0024] (1) Material of the matting layer (a) Ultraviolet absorber The matting layer in the present disclosure contains the ultraviolet absorber X. Since the matting layer has the ultraviolet absorber X, the weather resistance is improved. The light absorption spectrum of the ultraviolet absorber X has the first absorption peak with the peak wavelength λ in the wavelength range of 200 nm or more and 380 nm or less. The peak wavelength λ of the first absorption peak P1 has P1It is preferably present in a wavelength range of 250 nm or more and 380 nm or less, more preferably present in a wavelength range of 300 nm or more and 380 nm or less, and even more preferably present in a wavelength range of 300 nm or more and 350 nm or less.

[0025] The light absorption spectrum of the ultraviolet absorber X has a peak wavelength λ P1 and the absorbance at this wavelength is A max When this is the case, on the higher wavelength side than the peak wavelength λ P1 the wavelength λ max at which the absorbance A 10 becomes 10% of the absorbance A 10 is 385 nm or less. Since the wavelength λ 10 is 385 nm or less, it is possible to suppress the inhibition of the effect by the ultraviolet irradiation treatment for pre-curing described above, and a low gloss can be obtained. The wavelength λ 10 may be 380 nm or less, and is preferably 375 nm or less.

[0026] Fig. 4(a) shows the light absorption spectrum of the ultraviolet absorber X1, which is an example of the ultraviolet absorber X, measured using a spectrophotometer. The ultraviolet absorber X1 has a first absorption peak P1 having a peak wavelength λ P1 at about 319 nm. The absorbance A P1 at this peak wavelength λ max is about 2.0. Also, on the higher wavelength side than the peak wavelength λ P1 the wavelength λ max at which the absorbance A 10 becomes 10% of the absorbance A 10 , that is, the wavelength λ

[0027] at which the absorbance becomes 0.2 in Fig. 4(a) is about 364 nm. P1 The ultraviolet absorber X may have two or more absorption peaks in the wavelength range of 200 nm or more and 380 nm or less. In this case, the absorption peak on the highest wavelength side in the wavelength range of 200 nm or more and 380 nm or less is defined as the first absorption peak P1. Also in this case, the light absorption spectrum of the ultraviolet absorber X has a peak wavelength λP2 It may have a second absorption peak having

[0028] On the other hand, the ultraviolet absorber X may have only the first absorption peak P1 in the wavelength range of 200 nm or more and 380 nm or less. That is, the ultraviolet absorber X has a wavelength of 200 nm or more and does not have to have an absorption peak having a peak wavelength on the shorter wavelength side than the peak wavelength λ P1 either.

[0029] FIG. 4(b) shows an optical absorption spectrum measured using a spectrophotometer of an ultraviolet absorber X2 which is another example of the ultraviolet absorber X. The ultraviolet absorber X2 has two absorption peaks in the wavelength range of 200 nm or more and 380 nm or less, and the peak wavelengths thereof are about 340 nm and about 290 nm, respectively. In the present disclosure, the absorption peak having a peak wavelength of about 340 nm is defined as the first absorption peak P1. That is, the ultraviolet absorber X2 has the first absorption peak P1 having a peak wavelength λ P1 at about 340 nm, and the absorbance A P1 at this peak wavelength λ max is about 0.6. Also, on the higher wavelength side than the peak wavelength λ P1 , the absorbance A max at 10% of the absorbance A 10 , that is, the wavelength λ 10 at which the absorbance becomes 0.06 is about 372 nm.

[0030] The content of the ultraviolet absorber X contained in the matting layer is, for example, 0.1 part by mass or more, preferably 0.3 part by mass or more, and more preferably 0.5 part by mass or more with respect to 100 parts by mass of the cured resin. If the content of the ultraviolet absorber X is within the above range, there is a possibility that good weather resistance cannot be exhibited. On the other hand, the content of the ultraviolet absorber X is, for example, 15 parts by mass or less, preferably 12 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the cured resin. If the content of the ultraviolet absorber X is within the above range, the matting effect can be sufficiently exhibited.

[0031] The ultraviolet absorber can be used alone or in combination of two or more kinds. The matting layer may have an ultraviolet absorber other than the ultraviolet absorber X. Examples of the ultraviolet absorber other than the ultraviolet absorber X include the ultraviolet absorber Y. The light absorption spectrum of the ultraviolet absorber Y has an absorption peak having a peak wavelength λ Q1 in the wavelength range of 200 nm or more and 380 nm or less, and the absorbance at the peak wavelength λ Q1 is B max . When the absorbance at the peak wavelength λ Q1 is B max , the wavelength at which the absorbance becomes 10% of the absorbance B 10 is greater than 385 nm. Since the matting layer having the ultraviolet absorber Y can absorb ultraviolet rays in a wide wavelength range, the weather resistance is improved.

[0032] Fig. 5 shows the light absorption spectrum of the ultraviolet absorber Y1, which is an example of the ultraviolet absorber Y, measured using a spectrophotometer. The ultraviolet absorber Y1 has a first absorption peak Q1 having a peak wavelength λ Q1 at about 358 nm, and the absorbance B Q1 at this peak wavelength λ max is about 1.1. Further, on the higher wavelength side than the peak wavelength λ Q1 , the absorbance B max at 10% of the absorbance B 10 , that is, the wavelength λ 10 at which the absorbance becomes about 0.1 is about 390 nm.

[0033] The content of the ultraviolet absorber Y contained in the matting layer is, for example, 0.1 part by mass or more, and may be 0.5 part by mass or more with respect to 100 parts by mass of the cured resin. On the other hand, the content of the ultraviolet absorber Y is, for example, 5 parts by mass or less with respect to 100 parts by mass of the cured resin.

[0034] The matting layer may contain an ultraviolet absorber other than the ultraviolet absorber X and the ultraviolet absorber Y.

[0035] The total content of the ultraviolet absorber contained in the matting layer is, for example, 0.1 part by mass or more, preferably 0.3 part by mass or more, and more preferably 0.5 part by mass or more with respect to 100 parts by mass of the curable resin. If the content of the ultraviolet absorber is too small, it may not exhibit good weather resistance. On the other hand, the total content of the ultraviolet absorber is, for example, 15 parts by mass or less, preferably 12 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the curable resin. By the total content of the ultraviolet absorber being within the above range, an increase in cost, coloring by the ultraviolet absorber, bleeding, and poor adhesion can be suppressed.

[0036] The ultraviolet absorber X, the ultraviolet absorber Y, and other ultraviolet absorbers are not particularly limited, and examples thereof include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and the like. The ultraviolet absorber X and the ultraviolet absorber Y are each preferably a triazine-based ultraviolet absorber, and more preferably a hydroxyphenyltriazine-based ultraviolet absorber.

[0037] Further, the ultraviolet absorber X, the ultraviolet absorber Y, and other ultraviolet absorbers may have a reactive functional group having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, or an allyl group in the molecule.

[0038] (b) Curable resin The matting layer contains a curable resin. The curable resin is a cured product of a curable resin composition. The resin contained in the curable resin composition is preferably a radiation-curable resin. This is because it is easy to form a specific surface shape. Also, considering that the radiation-curable resin is easy to form a matting layer and is likely to improve surface properties such as scratch resistance, strength, and weather resistance, as well as processing performance, it is preferable.

[0039] The radiation-curable resin is a resin having a radiation-curable functional group, and the radiation-curable functional group is a group that crosslinks and cures upon irradiation with radiation. Examples of the radiation-curable functional group preferably include functional groups having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group.

[0040] Note that the (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. Also, (meth)acrylate refers to acrylate or methacrylate.

[0041] Also, radiation refers to those having energy quanta capable of polymerizing and / or crosslinking molecules among electromagnetic waves or charged particle beams. Usually, ultraviolet rays (UV) or electron beams (EB) are used, but other electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.

[0042] Examples of the radiation-curable resin include an electron beam-curable resin and an ultraviolet ray-curable resin. Among them, the ultraviolet ray-curable resin is preferable. It can reduce the internal haze of the matting layer. In addition, the formation of wrinkles by a wrinkle-forming stabilizer can be stabilized, and the matting effect can be stably improved.

[0043] Specifically, the radiation-curable resin can be appropriately selected and used from conventionally used polymerizable monomers and polymerizable oligomers as the radiation-curable resin.

[0044] As the polymerizable monomer, a (meth)acrylate-based monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate monomer is preferable. Examples of the polyfunctional (meth)acrylate monomer include (meth)acrylate monomers having two or more radiation-curable functional groups in the molecule and having at least a (meth)acryloyl group as the radiation-curable functional group.

[0045] The number of functional groups of the polyfunctional (meth)acrylate monomer is, for example, 2 or more and 8 or less, and may be 2 or more and 6 or less. Also, with the above number of functional groups, a wrinkle structure is likely to be obtained. These polyfunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0046] The polymerizable monomer can be used alone or in combination of two or more kinds, and it is preferable to use a combination of two or more kinds of polymerizable monomers. By using a combination of two or more kinds of polymerizable monomers, a specific surface shape is likely to be obtained.

[0047] When using a combination of two or more kinds of polymerizable monomers, a combination of a monofunctional monomer and a polyfunctional monomer, or a combination of two or more kinds of polyfunctional monomers is preferable, and a combination of polyfunctional monomers is more preferable.

[0048] When using a polyfunctional monomer, the number of functional groups is preferably 2 or more. Also, the number of functional groups may be 8 or less, 6 or less, or 4 or less.

[0049] When using a combination of a monofunctional monomer and a polyfunctional monomer, the number of functional groups of the polyfunctional monomer is preferably 3 or less. Also, in this case, the monofunctional monomer and the polyfunctional monomer are preferably (meth)acrylate monomers.

[0050] Also, when using two or more kinds of polyfunctional monomers, it is preferable to combine a monomer with 2 functional groups and a monomer with 3 functional groups. Also, in this case, the polyfunctional monomer is preferably a (meth)acrylate monomer.

[0051] Examples of the polymerizable oligomers include (meth)acrylate oligomers having two or more radiation-curable functional groups in the molecule and having at least a (meth)acryloyl group as the radiation-curable functional group. For example, 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 can be mentioned.

[0052] Furthermore, examples of the polymerizable oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers having a (meth)acrylate group in the side chain of polybutadiene oligomers, silicone (meth)acrylate oligomers having a polysiloxane bond in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in a small molecule, and oligomers having a cation-polymerizable functional group in the molecule such as novolac-type epoxy resins, bisphenol-type epoxy resins, aliphatic vinyl ethers, and aromatic vinyl ethers.

[0053] Examples of the polymerizable oligomers 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. Urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are preferable, and urethane (meth)acrylate oligomers are more preferable.

[0054] The polymerizable oligomers can be used alone or in combination of two or more kinds, and it is preferable to use one kind of polymerizable oligomer alone.

[0055] The number of functional groups of the polymerizable oligomer is, for example, 2 or more and 8 or less, may be 2 or more and 6 or less, or may be 2 or more and 4 or less.

[0056] The weight-average molecular weight of the polymerizable oligomer is, for example, 2,500 or more and 7,500 or less, may be 3,000 or more and 7,000 or less, or may be 3,500 or more and 6,000 or less.

[0057] Here, the weight-average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.

[0058] As the resin, it is preferable to use a combination of a polymerizable oligomer and a polymerizable monomer. In this case, the polymerizable oligomer is preferably a polyfunctional urethane (meth) acrylate oligomer, and more preferably a polyfunctional urethane acrylate oligomer. Also, the polymerizable monomer is preferably a polyfunctional polymerizable monomer, more preferably a polyfunctional (meth) acrylate monomer, and even more preferably a polyfunctional acrylate monomer. It is also possible to stabilize the formation of wrinkles, stably improve the matting effect, reduce the internal haze of the matting layer, and further improve surface properties such as processing characteristics, scratch resistance, and weather resistance.

[0059] When using a combination of a polymerizable oligomer and a polymerizable monomer, the content of the polymerizable oligomer with respect to a total of 100 parts by mass of the polymerizable oligomer and the polymerizable monomer is, for example, 20 parts by mass or more, may be 25 parts by mass or more, or may be 30 parts by mass or more. Also, the content of the above polymerizable oligomer is, for example, 90 parts by mass or less, may be 80 parts by mass or less, or may be 70 parts by mass or less.

[0060] Also, a polymerizable oligomer can be used in combination, and it is preferable to use a combination of two types of polymerizable oligomers having different numbers of functional groups. In this case, the content of the polymerizable oligomer having a larger number of functional groups with respect to 100 parts by mass of the total amount of the polymerizable oligomers is, for example, 50 parts by mass or more, may be 55 parts by mass or more, may be 60 parts by mass or more, or may be 65 parts by mass or more.

[0061] (c) Other components (c-1) Photoinitiator and photopolymerization accelerator When the resin is an ultraviolet curable resin, the resin composition can contain a photoinitiator, a photopolymerization accelerator, etc.

[0062] Examples of the photoinitiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethylketal, benzoyl benzoate, α-acyl oxime ester, thioxanthones, etc.

[0063] In the present disclosure, it is preferable to contain a photoinitiator having an absorption peak with a peak wavelength in the range of 350 nm or more and 400 nm or less. More preferably, the photoinitiator has a peak wavelength in the range of 365 nm or more and 395 nm or less. This is because the effect of the ultraviolet irradiation treatment for preliminary curing can be efficiently obtained as described above in (1).

[0064] The content of the photoinitiator is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, and still more preferably 0.5 part by mass or more with respect to 100 parts by mass of the resin. When the content of the photoinitiator is within the above range, preliminary curing occurs sufficiently, the viscosity of the composition (ink) for the matting layer increases sufficiently, and a uniform wrinkle can be formed. Also, the content of the photoinitiator is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2.5 parts by mass or less with respect to 100 parts by mass of the resin. When the content of the photoinitiator is within the above range, coloring and deterioration of the coating film physical properties caused by the photoinitiator can be suppressed.

[0065] Also, the photopolymerization accelerator can reduce the polymerization inhibition by air during curing and increase the curing rate. Examples of the photopolymerization accelerator include one or more selected from isopentyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, etc. Also, the content of the photopolymerization accelerator is the same as that of the above photoinitiator.

[0066] (c-2) Wrinkling stabilizer The matting layer in the present disclosure may or may not contain a wrinkling stabilizer.

[0067] When the matting layer does not contain a wrinkling stabilizer, the internal haze can be reliably reduced.

[0068] On the other hand, when the matting layer contains a wrinkling stabilizer, wrinkles can be stably formed on the surface of the matting layer. Note that a wrinkle structure can be formed in the matting layer even without using a wrinkling stabilizer, but by using a wrinkling stabilizer, the formed wrinkle structure is stabilized, and a stable matting effect and uniformity of the surface state due to the stable formation of wrinkles over the entire surface of the matting layer can be imparted. In this case, in order to reduce the internal haze, it is preferable to perform at least one or both of making the refractive index difference between the resin and the wrinkling stabilizer in the matting layer comparable and increasing the sphericity of the wrinkling stabilizer.

[0069] Note that "wrinkling stabilization" means that, with respect to the shape of the wrinkles, the geometric characteristic values of the wrinkles (the length, width, and the ratio of length to width of each protrusion), and the surface properties of the wrinkles (Ra, RSm, Spc, etc.), the in-plane distribution (dispersion σ) converges by adding a wrinkling stabilizer as compared to the case without addition. As a result, the in-plane distribution (dispersion σ) of the 60° gloss value of the surface shape described later also converges. The wrinkling stabilizer is not for diffusing light to suppress light reflection and perform matting, but is added to stabilize the wrinkle structure.

[0070] Therefore, even when the so-called "matting agent" in the prior art and the "wrinkling stabilizer" in the present disclosure have the same or similar constituent materials and average particle diameters, their mechanisms (actions) of suppressing light reflection and matting, the structures for expressing light reflection suppression and matting, as well as the relationship between the usage amount and the degree of surface gloss (gloss value) are different.

[0071] In the prior art, the matting agents that have been used for light reflection suppression and dulling have their own dulling effects due to the light diffusion effect caused by their physical shapes. Specifically, the particles generally referred to as matting agents generally have a refractive index difference between the particles and the surrounding resin and air, and exhibit a dulling effect due to the reflection of light rays corresponding to the contour shape of the particles and the light diffusion effect by the refractive interface. Therefore, if a matting agent is used in the dulling layer, external light (incident light) will be diffused by the matting agent, resulting in a decrease in contrast.

[0072] On the other hand, the wrinkle formation stabilizer does not exhibit a dulling effect due to the reflection and refraction of light rays by the particles themselves. Instead, it stabilizes the formation of wrinkles on the surface of the dulling layer due to the wrinkle formation stabilizer, and thereby stably imparts a dulling effect to the decorative sheet by the light diffusion effect at the refractive index difference interface between such a surface and air. Therefore, the wrinkle formation stabilizer used in the present disclosure is different from the matting agent that exhibits a dulling effect by itself (even if the constituent materials and average particle sizes of both are the same or similar) in terms of the mechanisms (actions) of light reflection suppression and dulling, the structures for exhibiting light reflection suppression and dulling, etc.

[0073] Furthermore, the "wrinkle formation stabilizer" and the "matting agent" also differ in the relationship between the content and the gloss (gloss value) of the surface. When the same substance A is used as the wrinkle formation initiator AW (W: wrinkle), and a specific amount C is contained therein to form wrinkles on the surface, the 60° gloss value G 60° AW (C) of the surface is significantly lower than the 60° gloss value G 60° AM (C) of the surface when the same substance A is used simply as the matting agent AM and contained in a specific amount C without forming wrinkles on the surface. That is, the following relational expression holds. G 60° AW (C) < G 60° AM (C)

[0074] As the wrinkle formation stabilizer, not a matting agent, specifically, any one having an average particle size with the smaller value of 100% or less of the thickness of the matting layer and 30 μm or less can be used without particular limitation.

[0075] Here, the average particle size of particles such as the wrinkle formation stabilizer is the average value (arithmetic mean diameter) of the particle sizes measured for 100 non-aggregated particles randomly selected by observing a cross-section in the thickness direction of the matting layer using a scanning electron microscope (SEM) under the conditions of an acceleration voltage of 3.0 kV and a magnification of 50,000 times. The particle size is a value measured as the distance between two straight lines in a combination of two straight lines that gives the maximum distance between the two straight lines when the cross-section of the particle is sandwiched between any two parallel straight lines.

[0076] As the wrinkle formation stabilizer, for example, organic particles and inorganic particles can be used. Examples of the organic substance constituting the organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluororesin, and polyester resin. In order to reduce the refractive index difference between the resin and the wrinkle formation stabilizer and reduce the internal haze of the matting layer, it is preferable to use organic particles. Examples of the inorganic substance constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate. Among them, silica having excellent transparency is preferable. In order to improve the strength of the matting layer, it is preferable to use inorganic particles.

[0077] The shape of the wrinkle formation stabilizer is not particularly limited, and examples include spherical, polyhedral, scaly, and amorphous. In order to reduce the internal haze of the matting layer, a spherical shape is preferable. This is because when it is spherical, the diffusion of reflected light by the wrinkle formation stabilizer is suppressed, and a decrease in contrast is less likely to occur.

[0078] In order to reduce the internal haze of the matting layer, the sphericity of the wrinkle-forming stabilizer is, for example, 10% or less, may be 8% or less, and may be 5% or less. The lower limit of the sphericity of the wrinkle-forming stabilizer is not particularly limited, but from the viewpoint of easy availability, it is, for example, 0.1% or more, and may be 0.5% or more.

[0079] Here, the "sphericity" is a value obtained by averaging the degree of deviation of the outer shape of each of 10 arbitrarily selected particles from a perfect circle. Specifically, it refers to the ratio (%) of the maximum value of the radial distance between the minimum circumscribed circle (minimum circumscribed circle) in contact with the surface of each particle in the electron micrograph of each particle to the radius of the minimum circumscribed circle.

[0080] When silica is used as the wrinkle-forming stabilizer, it is preferable that the specific surface area by the BET method using the nitrogen adsorption method is small. This is because light diffusion can be suppressed. The specific surface area is, for example, 50 m 2 / g or more and 800 m 2 / g or less, and may be 100 m 2 / g or more and 500 m 2 / g or less.

[0081] Similarly, since light diffusion can be suppressed, it is preferable that the oil absorption amount is small. The oil absorption amount is, for example, 700 ml / 100 g or less, and may be 600 ml / 100 g or less. Here, the oil absorption amount is determined by the method described in JIS K6217-4 "Method for Determining Oil Absorption Amount".

[0082] The surface of the wrinkle formation stabilizer may be coated with an organic compound in order to suppress light diffusion. For the purpose of a matting effect and reducing the internal haze of the matting layer, it is preferable to use at least one of two types of wrinkle formation stabilizers distinguished by their average particle size, with the upper limit being the smaller of 100% or less of the thickness of the matting layer and 30 μm or less. Specifically, the two types of wrinkle formation stabilizers are a first wrinkle formation stabilizer having an average particle size of 1 μm or more and the upper limit being the smaller of 100% or less of the thickness of the matting layer and 30 μm or less, and a second wrinkle formation stabilizer having an average particle size of less than 1 μm. By using at least one of the two types of wrinkle formation stabilizers, the formation of wrinkles is stabilized and a stable and excellent matting effect can be obtained.

[0083] The average particle size of the first wrinkle formation stabilizer is 1 μm or more and the upper limit is the smaller of 100% or less of the thickness of the matting layer and 30 μm or less. Since it can stably improve the matting effect and reduce the internal haze of the matting layer, the average particle size of the first wrinkle formation stabilizer is, for example, 1.3 μm or more, and may be 1.5 μm or more, or may be 1.8 μm or more. Also, with respect to the thickness of the matting layer, the average particle size of the first wrinkle formation stabilizer is, for example, 90% or less of the thickness of the matting layer, and may be 80% or less of the thickness of the matting layer, or may be 70% or less of the thickness of the matting layer. Also, with respect to the absolute value, the average particle size of the first wrinkle formation stabilizer is, for example, 20 μm or less, and may be 10 μm or less, may be 8 μm or less, or may be 7 μm or less. The average particle size of the first wrinkle formation stabilizer may be the smaller of any combination of the upper limit with respect to the thickness of the matting layer and the upper limit of the absolute value. For example, the upper limit may be the smaller of 90% or less of the thickness of the matting layer and 20 μm or less, or the upper limit may be the smaller of 90% or less of the thickness of the matting layer and 10 μm or less. Note that the thickness of the matting layer will be described later.

[0084] Further, the average particle size of the second wrinkle-forming stabilizer is less than 1 μm. In order to stabilize the formation of wrinkles, stably improve the matting effect, and reduce the internal haze of the matting layer, the average particle size of the second wrinkle-forming stabilizer is, for example, 1 nm or more, may be 3 nm or more, and may be 5 nm or more. Further, the average particle size of the second wrinkle-forming stabilizer is, for example, 900 nm or less, may be 700 nm or less, and may be 500 nm or less. It is preferable that the average particle size is near or below visible light because the internal haze of the matting layer with respect to visible light decreases.

[0085] In order to stabilize the formation of wrinkles by the wrinkle-forming stabilizer, stably improve the matting effect, and reduce the internal haze of the matting layer, the content of the wrinkle-forming stabilizer (when the first wrinkle-forming stabilizer and the second wrinkle-forming stabilizer are used in combination, the total content thereof) is, for example, 0.5 part by mass or more, may be 0.75 part by mass or more, may be 1.0 part by mass or more, and may be 1.2 part by mass or more with respect to 100 parts by mass of the resin. Further, the upper limit of the content of the above wrinkle-forming stabilizer is not particularly limited in order to stably improve the matting effect and reduce the internal haze of the matting layer. However, for example, in order to improve the coatability of the resin composition and efficiently improve the matting effect, it is, for example, 25.0 parts by mass or less, may be 15.0 parts by mass or less, may be 10.0 parts by mass or less, may be 7.5 parts by mass or less, and may be 6.0 parts by mass or less with respect to 100 parts by mass of the resin.

[0086] When the first anti-wrinkle stabilizer and the second anti-wrinkle stabilizer are used in combination, the content of each of the first anti-wrinkle stabilizer and the second anti-wrinkle stabilizer is not particularly limited as long as the total content is within the above range. The content of the second anti-wrinkle stabilizer is, for example, 0.1 part by mass or more, may be 0.5 part by mass or more, and may be 1.0 part by mass or more with respect to 100 parts by mass of the resin. Also, the content of the second anti-wrinkle stabilizer is, for example, 10.0 parts by mass or less, may be 7.5 parts by mass or less, may be 5.0 parts by mass or less, and may be 3.5 parts by mass or less with respect to 100 parts by mass of the resin. Further, when the first anti-wrinkle stabilizer and the second anti-wrinkle stabilizer are used in combination, as the blending ratio of the first anti-wrinkle stabilizer and the second anti-wrinkle stabilizer, when the total amount thereof is 100 parts by mass, the blending amount of the first anti-wrinkle stabilizer may be, for example, 0 parts by mass or more and 95 parts by mass or less, may be 10 parts by mass or more and 90 parts by mass or less, may be 20 parts by mass or more and 80 parts by mass or less, and may be 30 parts by mass or more and 70 parts by mass or less.

[0087] As the anti-wrinkle stabilizer, as described above, organic particles and inorganic particles can be used, and it can be said that the types of these particles themselves include those that have also been conventionally used as matting agents. In order for the matting agent to exhibit a matting effect by itself due to the light diffusion effect caused by its physical shape, it needs to be used in a large amount. However, in the present disclosure, even with a small content as described above, that is, even with a content less than the content required for the matting agent to exhibit a matting effect by itself due to the light diffusion effect caused by its physical shape, an extremely excellent matting effect is obtained compared to the effect obtained by the matting agent. Therefore, it can be said that the cosmetic sheet in the present disclosure, although substantially free of a matting agent, stably forms wrinkles on the surface, so that a more excellent low glossiness can be stably obtained compared to the case where a matting agent is used, and the internal haze of the matting layer can be reduced.

[0088] (c-3) Light stabilizer The matting layer can contain a light stabilizer. This improves the weather resistance of the matting layer. The light stabilizer is not particularly limited, and examples thereof include hindered amine light stabilizers such as piperidinyl sebacate-based light stabilizers. Further, the light stabilizer may have a reactive functional group having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, or an allyl group in the molecule. The light stabilizer can be used alone or in combination of two or more.

[0089] The content of the light stabilizer is preferably 0.1 part by mass or more, more preferably 1.0 part by mass or more, based on 100 parts by mass of the resin. Further, the content of the light stabilizer is preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, still more preferably 7.0 parts by mass or less, and particularly preferably 6.0 parts by mass or less, based on 100 parts by mass of the resin. When the content of the light stabilizer is within the above range, the effect of efficiently using the light stabilizer can be obtained.

[0090] (2) Surface shape The surface shape of the matting layer in the present disclosure has a wrinkle structure.

[0091] The wrinkle structure preferably has an uneven shape due to irregular wrinkles. The irregular wrinkles preferably have a plurality of convex portions formed by a plurality of protrusions and a plurality of concave portions formed by being surrounded by the plurality of protrusions. Further, the protrusions preferably have linear protrusions.

[0092] In the present specification, the "linear protrusion" means that the ratio of the length to the width (length / width) of the protrusion is 3 or more, preferably 5 or more, and more preferably 10 or more. The method for determining the length and width of the protrusion will be described later. Hereinafter, the linear protrusion may be referred to as a linear protrusion.

[0093] As a specific aspect of the wrinkle structure, for example, the aspect shown in FIG. 3 can be cited. In FIG. 3, as the surface shape of the matte layer, having irregular wrinkles in plan view; the irregular wrinkles having a plurality of convex portions 9 formed by a plurality of curved linear protrusions, and a concave portion 8 formed by being surrounded by the plurality of protrusions (the plurality of convex portions 9); at least a part of the plurality of curved convex portions 9 being formed by meandering linear protrusions, and a meandering concave portion 8 being formed so as to be surrounded by the meandering linear protrusions; are also shown. The surface shape of the matte layer has a wrinkle structure composed of irregular wrinkles as shown in FIG. 3, thereby improving the matte effect.

[0094] Here, "curved" means having at least one portion in which the extending direction of the convex portion 9 of the continuous linear stripe is reversed from one side to the other side in plan view. Hereinafter, the portion in which the extending direction of the convex portion 9 of the continuous linear stripe is reversed from one side to the other side may be referred to as an inversion portion. As an example of the inversion portion, for example, when approximated by a continuous curve when the width of the planar shape of the convex portion 9 of the linear stripe is ignored (when the width is regarded as 0), a form having an inflection point and the like can be cited. Further, as another example of the inversion portion, when approximated by a straight line when the width of the planar shape of the convex portion 9 of the linear stripe is ignored, a form having a V-shaped broken line or a portion approximated by two sides sandwiching one vertex of a triangle can be cited.

[0095] Also, "meandering" means having two or more inversion portions in plan view, and when the convex portion 9 of the linear stripe advances in its extending direction, at two adjacent inversion portions, the extending direction of the convex portion 9 of the linear stripe is alternately reversed in the opposite direction. For example, when approximated by a continuous curve when the width of the planar shape of the convex portion 9 of the linear stripe is ignored, a form having a portion approximated by the Roman letter "S" can be cited. Further, when approximated by a straight line when the width of the planar shape of the convex portion 9 of the linear stripe is ignored, a form having a portion approximated by the Roman letter "W" can be cited.

[0096] In this specification, "irregular" means not having a shape with a certain law or being arranged according to a certain law, that is, not being so-called patterned. Typical examples of shapes that are not irregular (regular shapes) include, for example, a shape arranged with a plurality of cylindrical unit lenses adjacent to each other in a direction perpendicular to their longitudinal direction, such as a so-called lenticular lens, which has a certain periodicity in a specific direction. Therefore, in the present disclosure, the irregular wrinkles that the surface shape of the anti-glare layer can have mean that the shape of one protrusion itself is not a shape formed according to a certain law such as periodicity and is irregular; the shapes of a plurality of convex portions formed by a plurality of protrusions are not formed and arranged according to a certain law and are irregular; the shape of the concave portion surrounded by such a plurality of protrusions is also irregular.

[0097] In the wrinkle structure forming the surface shape, if any of the shape of one protrusion (one convex portion), the shape and arrangement of each of a plurality of protrusions (a plurality of convex portions), and the shape of the concave portion surrounded by the plurality of protrusions is irregular, the surface of the anti-glare layer is likely to have a specific surface shape. For the same reason as this, it is more preferable that all are irregular.

[0098] As described above, the surface of the anti-glare layer has a wrinkle structure and substantially has an uneven shape. The convex and concave portions in the uneven shape are defined with reference to the median value of the height distribution in the uneven shape, and the region with a height exceeding the median value is defined as the convex portion, and the region with a height below the median value is defined as the concave portion. For example, using the density difference (i.e., brightness difference) of an image having a density corresponding to 1:1 with the height of the surface of the anti-glare layer, taking the darkest part in the density distribution image as gradation 255 and the lightest part in the density distribution image as gradation 0, for gradations 0 to 255, gradations 0 to 127 can be defined as the concave portion and gradations 128 to 255 can be defined as the convex portion, and they can be separated by binarization processing. In this case, the median value of the density with respect to the median value of the height is 127.

[0099] Further, as also shown in, for example, FIG. 3, the wrinkle structure preferably has a plurality of convex portions formed by a plurality of protrusions having a certain degree of homogeneity although irregular, and concave portions surrounded by the convex portions. Therefore, in the convex portions (protrusions) shown in FIG. 3, a shape in which the width of the convex portion extremely varies or a shape in which the height of the convex portion extremely varies cannot be said to be a preferable aspect in obtaining a matting effect. Specific aspects that can be effective in improving the matting effect will be described below with respect to the shape of the wrinkles constituting the wrinkle structure, that is, the shapes of the convex portions (protrusions) and the concave portions.

[0100] The shape of the concave portion may be an acute angle shape, a semi-circular shape or a semi-elliptical shape, or a combination thereof in a cross-sectional view. Further, the shape of the concave portion may be a shape in which one convex portion has a concave portion in part in a cross-sectional view.

[0101] On the other hand, the shape of the convex portion can have a semi-circular or semi-elliptical shape although there is a difference in width in a cross-sectional view.

[0102] The height of the convex portion (the height of the protrusion) is, for example, 0.5 μm or more, and may be 1 μm or more. Further, the height of the convex portion is, for example, 10 μm or less.

[0103] The depth of the concave portion is, for example, 0.5 μm or more, and may be 1 μm or more. Further, the depth of the concave portion is, for example, 10 μm or less.

[0104] The distance from the top of the convex portion to the bottom of the concave portion (the height difference between the convex portion and the concave portion) is, for example, 1 μm or more, and may be 2 μm or more. Further, the above distance is, for example, 20 μm or less, may be 18 μm or less, and may be 16 μm or less. When the above distance is within the above range, the matting effect is improved.

[0105] Here, the dimensions of the convex portions are the average values of any 10 convex portions (protrusions) at any 10 locations (100-μm square regions × 10 locations) on the surface of the matte layer, that is, a total of 100 convex portions. The height of one convex portion (protrusion) is the average value of the heights at any 5 locations on one convex portion (protrusion).

[0106] Also, the dimensions of the concave portions are determined in the same manner as the dimensions of the convex portions described above.

[0107] The occupancy ratio of the convex portions is, for example, 15% or more, may be 20% or more, or may be 30% or more. Also, the occupancy ratio of the convex portions is, for example, 80% or less, may be 70% or less, or may be 60% or less. When the occupancy ratio of the convex portions is within the above range, due to the relationship with the occupancy ratio of the concave portions surrounded by the convex portions, the surface of the matte layer is likely to have a specific surface shape, and the matte effect is improved.

[0108] Here, the occupancy ratio of the convex portions is the average value of the occupancy ratios of the convex portions at any 10 locations (100-μm square regions × 10 locations) on the matte layer.

[0109] The convex portions and the concave portions may have portions in substantially the same direction and substantially the same width, but it is preferable that the length of such portions is short. When the above length is short, the surface of the matte layer is likely to have a specific surface shape, and the matte effect is improved. Specifically, the length in which the convex portions and the concave portions in substantially the same direction and substantially the same width are continuous is, for example, 95 μm or less, may be 80 μm or less, or may be 70 μm or less. Also, the above length is, for example, 5 μm or more, may be 10 μm or more, or may be 15 μm or more. When the above length is within the above range, the wrinkles become more irregular, so the matte effect is improved.

[0110] Here, for any 10 convex portions and concave portions (that is, a total of 100 convex portions and concave portions) at any 10 locations (100-μm square regions × 10 locations) on the matte layer, it is preferable that 80% or more of them satisfy the above conditions. The above ratio may be 85% or more, may be 90% or more, or may be 95% or more.

[0111] In addition, the "substantially" in "substantially the same" in this specification means being generally the same. Without branching, the substantially same direction means within ±3°, and the substantially same width means within ±5%.

[0112] Also, the number of convex portions (protrusions) in a 100 μm square region is, for example, 10 or more, may be 20 or more, and may be 30 or more. The number of the above convex portions is, for example, 200 or less, may be 100 or less, and may be 70 or less. When the number of the above convex portions is within the above range, the surface of the matting layer is likely to have a specific surface shape, and the matting effect is improved.

[0113] Here, the number of convex portions in a 100 μm square region is the average value of the number of convex portions at 10 locations (100 μm square region × 10 locations) of the matting layer.

[0114] The surface of the matting layer preferably has a wrinkle structure at least in part thereof, and more preferably has a wrinkle structure over the entire surface.

[0115] In the surface shape of the matting layer in the present disclosure, the wrinkle structure preferably has the following surface properties.

[0116] (3) Surface properties of the wrinkle structure The wrinkle structure preferably has the following surface properties. The surface properties of the wrinkle structure are controlled by adjusting the type of material used for the matting layer, the thickness of the matting layer, and the conditions of the irradiation treatment described later.

[0117] (a) Spc (arithmetic mean curvature of the apex of the protrusion) The Spc (arithmetic mean curvature of the apex of the protrusion) of the wrinkle structure defined in ISO 25178-2:2021 is, for example, 27000 mm -1 or less, may be 26000 mm -1 or less, and may be 25000 mm -1 or less. On the other hand, the above Spc (arithmetic mean curvature of the apex of the protrusion) is, for example, 1000 mm -1 or more, and 1200 mm-1 It may be the above, 1400 mm -1 It may be the above.

[0118] Spc (arithmetic mean curvature of the apex of the protrusion) is one of the three-dimensional surface property parameters defined in ISO 25178-2:2021, and is obtained from the arithmetic mean value of the curvature radii of the peaks (apexes of the protrusions) of the parts classified as mountains (convex parts) in the shape image included in the reference area. It is the average curvature (average sharpness) of the tip of the peak. Therefore, Spc (arithmetic mean curvature of the apex of the protrusion) is the reciprocal of the radius (mm) -1 ) and becomes.

[0119] The larger the value of Spc (arithmetic mean curvature of the apex of the protrusion), the larger the curvature of the tip of the peak (convex part) (the curvature radius of its reciprocal is smaller, and the shape of the tip becomes sharper). On the other hand, the smaller the value of Spc (arithmetic mean curvature of the apex of the protrusion), the smaller the curvature of the apex of the protrusion (the curvature radius of its reciprocal is larger, and the shape of the tip becomes blunter). That is, the smaller Spc (arithmetic mean curvature of the apex of the protrusion) is, the rounder the protrusion is and it approaches a flat surface. Therefore, the matting effect by the matting layer of the decorative sheet decreases.

[0120] In addition, in the measurement of Spc (arithmetic mean curvature of the apex of the protrusion) in this specification, the cut-off value is 0.8 mm. Also, in this specification, Spc (arithmetic mean curvature of the apex of the protrusion) is the average value of the measured values at any 10 locations.

[0121] (b) Rz (maximum height) The Rz (maximum height) of the wrinkle structure defined in JIS B0601:2013 is, for example, 12.5 μm or less, and may be 12.0 μm or less, or may be 11.0 μm or less. On the other hand, the above Rz (maximum height) is, for example, 2.0 μm or more, and may be 2.2 μm or more, or may be 2.5 μm or more.

[0122] Rz (Maximum height) is one of the peak and height parameters of the contour curve, and is the sum of the height of the highest peak and the depth of the deepest valley in the contour curve at the reference length. The larger the value of Rz (Maximum height), the larger (higher) convex portions exist as viewed from the valley (concave portion), and it becomes an index indicating that there tends to be many such convex portions.

[0123] In addition, in the measurement of Rz (Maximum height) in this specification, the cut-off value is 0.8 mm. Also, in this specification, Rz (Maximum height) is the average value of the measured values at any 10 locations.

[0124] (c) Ra (Arithmetic mean roughness) The Ra (Arithmetic mean roughness) of the wrinkle structure defined in JIS B0601:2013 is, for example, 2.5 μm or less, may be 2.3 μm or less, and may be 2.0 μm or less. On the other hand, the above Ra (Arithmetic mean roughness) is, for example, 0.1 μm or more, may be 0.2 μm or more, and may be 0.3 μm or more.

[0125] Ra (Arithmetic mean roughness) is one of the height direction parameters of the contour curve, and is the average value of the height difference from the average plane in the contour curve at the reference length. The smaller the value of Ra (Arithmetic mean roughness), the smaller the height difference between the convex portion in the wrinkle structure and the concave portion formed accordingly, and it is an index indicating that it tends to have a smoother and more uniform shape.

[0126] In addition, in the measurement of Ra (Arithmetic mean roughness) in this specification, the cut-off value is 0.8 mm. Also, in this specification, the above Ra (Arithmetic mean roughness) is the average value of the measured values at any 10 locations.

[0127] (d) RSm (Average length of curve elements) In JIS B0601:2013, the RSm (average length of curve elements) of the wrinkle structure is, for example, 150 μm or less, and may be 130 μm or less, or may be 120 μm or less. On the other hand, the above RSm (average length of curve elements) is, for example, 2 μm or more, and may be 4 μm or more, or may be 8 μm or more.

[0128] RSm (average length of curve elements) is a horizontal parameter of the contour curve and is the average of the lengths of the contour curve elements at the reference length. The smaller the RSm, the more convex portions are included in the reference length. Therefore, for a surface shape with a small RSm, since the apexes of the protrusions are densely present, the matting effect becomes larger.

[0129] In the measurement of RSm (average length of curve elements) in this specification, the cut-off value is 0.8 mm. Also, in this specification, RSm (average length of curve elements) is the average value of the measured values at any 10 locations.

[0130] (e) Sa (arithmetic mean height) In JIS B0601:2013, the Sa (arithmetic mean height) of the wrinkle structure is, for example, 2.5 μm or less, and may be 2.0 μm or less, or may be 1.5 μm or less. On the other hand, the above Sa (arithmetic mean height) is, for example, 0.1 μm or more, and may be 0.3 μm or more. Sa (arithmetic mean height) is an index indicating the undulation state over the entire surface of the wrinkle structure.

[0131] (f) Ssk (skewness) In ISO 25178-2:2021, the Ssk (skewness) of the wrinkle structure is, for example, 1.5 μm or less, and may be 1.0 μm or less. On the other hand, the above Ssk (skewness) is, for example, -0.8 μm or more, and may be -0.6 μm or more.

[0132] Ssk (Skewness) is an index indicating the degree of bias in the height distribution from the average plane. When Ssk is 0, the surface shape is symmetric (normal distribution) with respect to the average plane. When Ssk exceeds 0, it can be understood that the surface shape is biased downward, i.e., the lower height side, with respect to the average plane, and the vicinity of the top of the convex part tends to be sharp and narrow. On the other hand, when Ssk is less than 0, it can be understood that the surface shape is biased upward, i.e., the higher height side, with respect to the average plane, and the vicinity of the top of the convex part tends to be blunt and thick.

[0133] (g) Sku (Kurtosis) The Sku (Kurtosis) of the wrinkle structure defined in ISO 25178-2:2021 is, for example, 4 or less, may be 3.7 or less, or may be 3.5 or less. On the other hand, the above Sku (Kurtosis) is, for example, 0.1 or more, may be 0.3 or more, or may be 0.5 or more.

[0134] Sku (Kurtosis) is one of the three-dimensional surface property parameters defined in ISO 25178-2:2021 and is an index indicating the degree of sharpness of the height distribution from the average plane. When Sku is 3, the surface shape is symmetric (normal distribution) with respect to the average plane. When Sku exceeds 3, the height distribution has a sharp shape, and when Sku is less than 3, it can be understood that the height distribution tends to have a flattened shape.

[0135] In addition, when measuring Sku (Kurtosis) in this specification, the cut-off value is 0.8 mm. Also, in this specification, Sku (Kurtosis) is the average value of the measured values at any 10 locations.

[0136] (4) Physical properties of the matte layer The cosmetic sheet in the present disclosure has a matte layer with a specific surface shape, thereby obtaining a good matte effect. Due to the matte effect, it becomes difficult to visually recognize the gloss, and a low glossiness is obtained.

[0137] The 60° gloss value of the surface having the surface shape of the matting layer may be, for example, 10.0 or less, 7.5 or less, 5.0 or less, 4.0 or less, or 3.6 or less.

[0138] Here, the 60° gloss value of the surface shape of the matting layer is the 60° specular glossiness measured in accordance with JIS K5600-4-7:1999, and can be measured, for example, using a gloss meter. The 60° gloss value of the surface shape of the matting layer is the average value of the measured values at any 10 locations.

[0139] The internal haze of the matting layer is, for example, 4.0% or less, and may be 3.6% or less. On the other hand, the lower limit of the internal haze of the matting layer is not particularly limited, but it is preferably substantially 0% or more. Note that "substantially" means taking into account measurement errors.

[0140] Here, the internal haze of the matting layer can be measured in accordance with JIS K7136:2000. When measuring the internal haze of the matting layer, for example, by arranging a transparent layer on the surface having a specific surface shape of the matting layer, the uneven shape can be filled and flattened. Thereby, the influence of haze caused by the surface shape can be eliminated. Also, when measuring the internal haze of the matting layer, only the matting layer constituting the decorative sheet is prepared separately.

[0141] (5) Thickness of the matting layer The thickness of the matting layer is not particularly limited as long as it can form a specific surface shape. For example, it is 3 μm or more, and may be 3.2 μm or more, or 3.4 μm or more. Also, the thickness of the matting layer is, for example, 300 μm or less, and may be 200 μm or less, 150 μm or less, or 100 μm or less. When the thickness of the matting layer is within the above range, the surface shape is likely to be a specific surface shape.

[0142] Here, the thickness of the matting layer is determined as the average value of the thicknesses at 20 locations measured from an image taken using a scanning electron microscope (SEM) of the cross-section of the decorative sheet. The acceleration voltage of the SEM is set to 3 kV, and the magnification is set according to the thickness. The same applies to the thicknesses of other layers.

[0143] In the present disclosure, the matting layer may be partially disposed or entirely disposed with respect to the base material layer described later. Among these, it is preferable that the matting layer is disposed entirely on the base material layer.

[0144] (6) Method for forming the matting layer As a method for forming the matting layer, for example, a matting layer composition is applied to the surface of the decorative layer opposite to the base material layer to form a coating layer, and the coating layer is cured by irradiation treatment with ionizing radiation to form the matting layer. The irradiation treatment with ionizing radiation preferably includes, in this order, (1) ultraviolet irradiation treatment for pre-curing, (2) irradiation treatment with wavelength light having a peak wavelength of 100 nm or more and less than 200 nm, and (3) electron beam irradiation treatment.

[0145] (a) Formation of the coating layer Examples of the method for applying the matting layer composition include known methods such as the gravure printing method, bar coating method, roll coating method, reverse roll coating method, comma coating method, etc.

[0146] The thickness of the coating layer can be the same as that of the matting layer.

[0147] Further, when the matting layer composition contains a solvent, the solvent may be dried after applying the matting layer composition.

[0148] (b) Irradiation treatment with ionizing radiation The above coating layer is cured by irradiation treatment with ionizing radiation to form a matting layer having a specific surface shape. The irradiation treatment preferably includes, at least, in this order, (1) ultraviolet irradiation treatment for pre-curing, (2) irradiation treatment with wavelength light having a peak wavelength of 100 nm or more and less than 200 nm, and (3) electron beam irradiation treatment.

[0149] (1) By performing an ultraviolet irradiation treatment for pre-curing, the coating layer is pre-cured as a whole, thereby imparting appropriate viscosity to the matte layer composition (pre-gelling). Therefore, the sagging of the wrinkle structure formed by the irradiation treatment described in (2) below is suppressed, and a wrinkle structure capable of exhibiting low glossiness can be obtained.

[0150] In the ultraviolet irradiation treatment for pre-curing in (1) above, the peak wavelength of the ultraviolet light employed is, for example, 365 nm or more, preferably 375 nm or more, and more preferably 385 nm or more. On the other hand, the peak wavelength is, for example, 410 nm or less, may be 405 nm or less, or may be 400 nm or less. The peak half-value width of the ultraviolet light is, for example, 25 nm or less, may be 20 nm or less, or may be 15 nm or less. By using the light of the above wavelength in the ultraviolet irradiation treatment in (1) above, the overall pre-curing of the coating layer can be efficiently performed.

[0151] The ultraviolet illuminance in the irradiation treatment in (1) above is preferably 0.01 W / cm 2 or more, more preferably 0.1 W / cm 2 or more, and even more preferably 0.3 W / cm 2 or more. Also, the ultraviolet illuminance is preferably 5 W / cm 2 or less, more preferably 3 W / cm 2 or less, and even more preferably 2 W / cm 2 or less. When the ultraviolet illuminance is within the above range, the coating layer can be efficiently pre-cured as a whole without being completely cured.

[0152] The light of the wavelength employed in the irradiation treatment in (1) above can be irradiated, for example, using an ultraviolet irradiation device having a light source such as an LED light, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp. Among them, it is preferable to use an ultraviolet irradiation device having an LED light as the light source. This is because light of a single wavelength can be irradiated, and the effect of this treatment is less likely to be inhibited by an ultraviolet absorber.

[0153] Furthermore, by performing the irradiation treatments (2) and (3) described later, the surface shape is likely to become a specific surface shape, and the scratch resistance is likely to be improved.

[0154] Although the details of the mechanism by which a specific surface shape is likely to be obtained by performing at least the irradiation treatments (2) and (3) are unknown, it is presumed to be due to the following mechanism.

[0155] First, when the irradiation treatment with ultraviolet rays of low wavelength (short wavelength) in the above (2) is performed, the energy of the ultraviolet rays penetrates only the surface portion, and the energy does not reach the lower layer. Therefore, only the surface portion of the coating layer starts to harden, and it is considered that a wrinkle structure is formed by the surface alone undergoing hardening shrinkage. Thus, it is considered that the formation of the wrinkle structure occurs in a state where only a certain thickness direction from the surface of the coating layer is hardened by the irradiation with ultraviolet rays of low wavelength (short wavelength).

[0156] Subsequently, by performing the electron beam irradiation treatment in the above (3), it is possible to promote the hardening from the surface vicinity portion where the progress of hardening is slow to the deep portion away from the surface in a state where the wrinkle structure formed on the surface of the coating layer is maintained.

[0157] Even by the irradiation treatment in the above (2), the coating layer becomes a cured product over the entire thickness and can become a matting layer. However, by further combining the irradiation treatment in the above (3), the curing state is improved. As a result, a wrinkle structure appears on the surface of the matting layer, and it is considered that a specific surface shape is likely to be obtained. Furthermore, it is considered that the scratch resistance is also improved because the coating layer becomes a cured product over the entire thickness and the curing state is improved.

[0158] In the irradiation treatment of (2) above, as the wavelength light having a peak wavelength of 100 nm or more and less than 200 nm, for example, noble gases such as Ar, Kr, Xe, Ne, etc., gases such as halides of noble gases by halogens such as F, Cl, I, Br, etc., or excited dimers formed by the discharge of these mixed gases, that is, "excimer light" including light in the ultraviolet wavelength range from an excimer is preferable. As the wavelength of the excimer light and the excimer serving as the light source, for example, light with a peak wavelength of 126 nm radiated from the excimer of Ar 2 (hereinafter abbreviated as "126 nm (Ar 2 )").), 146 nm (Kr 2 ), 157 nm (F 2 ), 172 nm (Xe 2 ), 193 nm (ArF), etc. can be preferably adopted. As the excimer light, either spontaneous emission light or laser light with high coherence (interference ability) by induced emission can be used, but usually spontaneous emission light is sufficient. Note that the discharge lamp that emits these lights (ultraviolet rays) is also referred to as an "excimer lamp".

[0159] The excimer light is characterized in that it has a single wavelength peak and a narrower half-value width of the wavelength compared to ordinary ultraviolet rays (for example, ultraviolet rays emitted from metal halide lamps, mercury lamps, etc.). By using such excimer light, it becomes easier to develop a wrinkle structure.

[0160] For the same reason as above, the peak wavelength of the above wavelength light is preferably 120 nm or more, more preferably 140 nm or more, still more preferably 150 nm or more, and even more preferably 155 nm or more. Also, the peak wavelength of the above wavelength light is less than 200 nm, and particularly preferably, 172 nm (Xe 2) That is. Thus, in order to easily develop the wrinkle structure, it is preferable to use light with a lower wavelength (shorter wavelength), and among the ultraviolet rays with a lower wavelength (shorter wavelength) (wavelength: 280 nm or less), ultraviolet rays in the region of less than 200 nm with a lower wavelength (shorter wavelength) are preferable. The full width at half maximum of the above wavelength light is, for example, 25 nm or less, and may be 20 nm or less.

[0161] The integrated light quantity of the above wavelength light is preferably 1 mJ / cm 2 or more, more preferably 2 mJ / cm 2 or more, still more preferably 5 mJ / cm 2 or more. Also, the upper limit of the integrated light quantity of the above wavelength light is not particularly limited. Considering productivity such as reducing the number of lamps required for irradiating the above wavelength light and improving production efficiency, the integrated light quantity of the above wavelength light is preferably 1,000 mJ / cm 2 or less, more preferably 300 mJ / cm 2 or less, still more preferably 100 mJ / cm 2 or less, particularly preferably 10 mJ / cm 2 or less.

[0162] The ultraviolet illuminance is preferably 1 mW / cm 2 or more, more preferably 5 mW / cm 2 or more, still more preferably 10 mW / cm 2 or more. Also, the ultraviolet illuminance is preferably 10 W / cm 2 or less, more preferably 3 W / cm 2 or less, still more preferably 1 W / cm 2 or less. Particularly considering productivity, the ultraviolet illuminance is preferably 500 mW / cm 2 or less, more preferably 300 mW / cm 2 or less, still more preferably 150 mW / cm 2 or less.

[0163] Also, the oxygen concentration when irradiating the above wavelength light is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, still more preferably 500 ppm or less, particularly preferably 300 ppm or less.

[0164] The wavelength light having a peak wavelength of 100 nm or more and less than 200 nm employed in the irradiation treatment of (2) above can also be irradiated using, for example, an ultraviolet irradiation device using a low-pressure mercury lamp or the like as a light source.

[0165] After the irradiation treatment with the wavelength light having a peak wavelength of 100 nm or more and less than 200 nm in (2) above, it is preferable to perform the electron beam irradiation treatment of (3) above.

[0166] The irradiation conditions of the electron beam employed in the irradiation treatment of (3) above are not particularly limited as long as the curable composition is cured. The acceleration voltage of the electron beam is preferably 10 kV or more, more preferably 30 kV or more, still more preferably 50 kV or more, and even more preferably 75 kV or more. Also, the acceleration voltage of the electron beam is preferably 300 kV or less, more preferably 250 kV or less, and still more preferably 200 kV or less. When the acceleration voltage of the electron beam is within the above range, it is likely to become a cured product while maintaining the shape of the wrinkle structure as it is. Also, the scratch resistance is improved. Also, for the same reason as above, the irradiation dose of the electron beam is preferably 5 kGy or more, more preferably 10 kGy or more, and still more preferably 15 kGy or more. Also, the irradiation dose of the electron beam is preferably 150 kGy or less, more preferably 125 kGy or less, and still more preferably 100 kGy or less.

[0167] The electron beam source is not particularly limited as long as it can exhibit the above irradiation conditions. For example, various electron beam accelerators such as a Cockcroft-Walton type, a Van de Graaff type, a resonant transformer type, an insulated core transformer type, a linear type, a dynatron type, and a high-frequency type can be used.

[0168] In the above manner, a matte layer having a specific surface shape is obtained.

[0169] 2. Substrate layer The cosmetic sheet in the present disclosure has a base material layer. The base material layer is a member that supports the matte layer. By disposing the matte layer on one surface of the base material layer, the matte layer can be easily formed. Further, since the cosmetic sheet has the base material layer, various performances such as mechanical strength, post-processing suitability, and designability are improved, so the usability as a sheet is improved.

[0170] The base material layer is not particularly limited, and examples thereof include a resin base material, a glass base material, a metal base material, and a fiber base material. The type of the base material layer is appropriately selected according to the use of the cosmetic sheet.

[0171] Examples of the resin used for the resin base material include various synthetic resins and various natural resins. Examples of the synthetic resin include a thermoplastic resin and a curable resin. Considering the manufacturing suitability, handling suitability, and post-processing suitability of the cosmetic sheet, a thermoplastic resin is preferable.

[0172] Examples of the thermoplastic resin include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomer, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, and polyester-based thermoplastic elastomers; acrylic resins such as poly(meth)acrylic acid methyl, poly(meth)acrylic acid ethyl, poly(meth)acrylic acid butyl, and (meth)acrylic acid methyl-(meth)acrylic acid butyl copolymer; polyamide resins typified by nylon 6 and nylon 66; cellulose resins such as triacetate cellulose, cellophane, and celluloid; styrene resins such as polystyrene, acrylonitrile-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer (ABS resin); polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate resin, and polyimide resin.

[0173] Examples of natural resins include natural rubber, rosin, and amber.

[0174] Examples of curable resins include radiation curable resins and thermosetting resins.

[0175] Examples of metals used for the metal substrate include aluminum alloys such as aluminum or duralumin; iron alloys such as iron, carbon steel, or stainless steel; copper alloys such as copper or brass, bronze; gold, silver, chromium, nickel, cobalt, tin, titanium. The metal substrate may have a plating film or an anodized film on its surface.

[0176] Examples of fibrous materials used for the fiber substrate include papers such as tissue paper, kraft paper, fine paper, Japanese paper, titanium paper, lint paper, sulfuric acid paper, paraffin paper, parchment paper, glassine paper, backing paper for wallpaper, cardboard, base paper for gypsum board; woven or non-woven fabrics made of fibers such as protein or cellulose-based natural fibers like polyester resin fibers, acrylic resin fibers, silk, cotton, and hemp, glass fibers, and carbon fibers. Various resins such as acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin may be added to the fiber substrate. When the fiber substrate is a paper substrate, the strength between the fibers of the paper substrate or the interlayer strength between the paper substrate and other substrates can be improved. Also, fuzzing can be suppressed. As a method of adding the resin, the resin may be impregnated after papermaking or filled inside during papermaking. Examples of paper substrates added with resin include paper-interlayer reinforced paper and resin-impregnated paper.

[0177] In the case of a fiber substrate, it is preferable that a resin layer for preventing transmission is disposed on the surface of the fiber substrate on the dulling layer side. Examples of the resin used for the resin layer for preventing penetration include two-component curable urethane resin. The resin layer for preventing transmission can be formed by a method such as coating.

[0178] The base material layer may contain additives as necessary. In the case of a resin base material, examples of the additives include inorganic fillers, flame retardants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, light stabilizers, and colorants. The various additives can be used alone or in combination of multiple types. The content of the additives is not particularly limited as long as it does not inhibit the surface characteristics and processing characteristics, and can be appropriately set according to the required characteristics.

[0179] In order to improve the weather resistance, among the above additives, it is preferable to use weathering agents such as ultraviolet absorbers and light stabilizers. The ultraviolet absorbers and light stabilizers can be the same as those used in the above matte layer.

[0180] The base material layer may be a single layer or a laminate of two or more layers. In the case of a laminate, the base material layer may have two or more layers of the same type of base material or two or more layers of different types of base materials.

[0181] In the present disclosure, the base material layer can also serve as the decorative layer described later.

[0182] The base material layer may be transparent or opaque. When the base material layer is opaque, the base material layer can become the decorative layer.

[0183] Also, the base material layer may be colored. When the base material layer is colored, the base material layer can become the decorative layer. The mode of coloring is not particularly limited, and it may be transparent coloring or opaque coloring (concealing coloring), and these can be arbitrarily selected.

[0184] When the base material layer is colored, it can contain a colorant. Examples of the colorant include white pigments such as titanium white; inorganic pigments such as iron black, lead yellow, titanium yellow, chrome yellow, cadmium red, ultramarine blue, cobalt blue, etc.; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, nickel - azo complex, azomethine azo - based black pigment, perylene - based black pigment, etc.; metallic pigments composed of flaky foil pieces such as aluminum and brass; and pearl (pearlescent) pigments composed of flaky foil pieces such as titanium dioxide - coated mica and basic lead carbonate. For example, when the surface hue of the adherend to which the decorative sheet is laminated varies and it is desired to conceal the surface hue and improve the stability of the color tone of the decorative layer, inorganic pigments such as white pigments can be used.

[0185] The base material layer may be surface - treated in order to enhance the adhesion with the layer in contact with the base material layer, for example, the adhesion with the decorative layer and the adhesion with the adhesive layer. Examples of the surface treatment include physical surface treatments such as oxidation method and roughening method, and chemical surface treatments. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone - ultraviolet treatment method. Examples of the roughening method include sandblasting method and solvent treatment method. These surface treatments are appropriately selected according to the type of the base material layer. Considering the effect and operability of the surface treatment, generally, corona discharge treatment is preferred.

[0186] Also, when the base material layer is a laminate, an adhesive layer or a primer layer may be disposed between the adjacent layers in order to improve the adhesion of each adjacent layer.

[0187] The thickness of the base material layer is not particularly limited and is appropriately selected according to the material of the base material layer. In the case of a base material layer containing resin, the thickness of the base material layer is, for example, 10 μm or more and 500 μm or less, and may be 20 μm or more and 300 μm or less, or may be 40 μm or more and 200 μm or less. Also, when the base material layer is a paper base material, the basis weight is, for example, 20 g / m 2 or more and 150 g / m 2 or less, and may be 30 g / m 2 or more and 100 g / m 2 or less.

[0188] 3. Decorative layer The decorative sheet in the present disclosure has a decorative layer on one surface of the base material layer. The decorative layer can impart a design to the decorative sheet. The decorative layer may be disposed on the surface side opposite to the surface having a specific surface shape of the matte layer. For example, the decorative layer may be disposed between the base material layer and the matte layer. Also, when the decorative sheet has a transparent resin layer as described later, the decorative layer may be disposed between the base material layer and the transparent resin layer.

[0189] As the decorative layer, for example, it may be a colored layer, a pattern layer, or a metal layer. Further, the decorative layer may have a colored layer and a pattern layer.

[0190] The colored layer may be a so-called solid colored layer disposed on the entire surface of the decorative sheet. The colored layer can contain a binder resin and a colorant. The colored layer can be formed by a coating method.

[0191] The pattern of the pattern layer (pattern) is not particularly limited, and examples include wood grain patterns such as annual rings and conduit grooves on the surface of a wood board; stone grain patterns on the surface of stone slabs such as marble and granite; cloth grain patterns on the surface of cloth; leather grain patterns on the surface of leather; geometric patterns; characters; figures; combinations thereof.

[0192] The pattern layer contains, for example, a binder resin and a colorant. The pattern layer can be formed by a printing method.

[0193] The binder resin used for the colored layer and the pattern layer is not particularly limited. For example, it includes resin such as urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, etc. Also, various resins can be used, such as one-component curable resins and two-component curable resins accompanied by curing agents such as isocyanate compounds.

[0194] Examples of the colorant used for the colored layer and the pattern layer include pigments and dyes. Among them, the colorant is preferably a pigment excellent in hiding power and weather resistance. The pigments can be the same as those used for the above-mentioned base material layer. The content of the colorant is, for example, 5 parts by mass or more and 90 parts by mass or less, may be 15 parts by mass or more and 80 parts by mass or less, or may be 30 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0195] The colored layer and the pattern layer may contain additives such as weathering agents such as ultraviolet absorbers and light stabilizers, extender pigments, stabilizers, plasticizers, curing agents, catalysts, etc. as required.

[0196] Examples of the metal material used for the metal layer include aluminum, chromium, tin, and indium. The metal layer can be formed by a vapor deposition method.

[0197] The thickness of the decorative layer is appropriately selected according to the desired design and the type of the decorative layer. When the decorative layer has at least one of the colored layer and the pattern layer, considering hiding the base color of the adherend and improving the design property, the thickness of the decorative layer is, for example, 0.5 μm or more and 20 μm or less, may be 1 μm or more and 10 μm or less, or may be 2 μm or more and 5 μm or less.

[0198] 4. Other Layers As shown in FIG. 1, the cosmetic sheet in the present disclosure has at least a base material layer 1, a decorative layer 2, and a matting layer 3. On the other hand, the cosmetic sheet in the present disclosure may have other layers in addition to these layers. Examples of the other layers include a transparent resin layer, an adhesive layer, a separator layer, and a primer layer. For example, as shown in FIG. 2, the cosmetic sheet 10 has a transparent resin layer 4, an adhesive layer 5, a separator layer 6, and a primer layer 7 in addition to the base material layer 1, the decorative layer 2, and the matting layer 3.

[0199] (1) Transparent resin layer The cosmetic sheet in the present disclosure may have a transparent resin layer between the matting layer and the decorative layer. The strength of the cosmetic sheet can be enhanced by the transparent resin layer.

[0200] The transparent resin layer only needs to be transparent to the extent that the decorative layer can be visually recognized, and in addition to being colorless and transparent, it may also be colored transparent or translucent.

[0201] Examples of the resin constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, and vinyl chloride resins. Considering the processability, among them, polyolefin resins and vinyl chloride resins are preferable. The resins may be used alone or in combination of two or more.

[0202] The transparent resin layer contains additives as required. Examples of the additives include weathering agents such as ultraviolet absorbers and light stabilizers. As the weathering agent, those described above may be appropriately selected and used.

[0203] Considering the processability, the thickness of the transparent resin layer is, for example, 20 μm or more and 150 μm or less, and may be 40 μm or more and 120 μm or less, or may be 60 μm or more and 100 μm or less.

[0204] Examples of the method for forming the transparent resin layer include a method of applying a resin composition and a method of laminating a resin film by dry lamination.

[0205] (2) Adhesive layer The cosmetic sheet in the present disclosure may have an adhesive layer on the side of the base material layer opposite to the decorative layer. In this case, the adhesive layer is, for example, a member for attaching the cosmetic sheet to an adherend. Further, when the cosmetic sheet has a transparent resin layer, the adhesive layer may be disposed between the transparent resin layer and the decorative layer.

[0206] The adhesive layer may be transparent or opaque.

[0207] Examples of the adhesive used for the adhesive layer include curable adhesives and pressure-sensitive adhesives. Specific examples include urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, silicone-based adhesives, and rubber-based adhesives. Further, OCA (Optically Clear Adhesive) or OCR (Optically Clear Resin) can also be used as the adhesive layer.

[0208] From the viewpoint of efficiently obtaining a desired adhesive force, the thickness of the adhesive layer is, for example, 5 μm or more and 100 μm or less, and may be 10 μm or more and 75 μm or less, or may be 20 μm or more and 50 μm or less.

[0209] Examples of the method for forming the adhesive layer include a method of applying an adhesive composition and a method of laminating an adhesive film by dry lamination.

[0210] (3) Primer layer The cosmetic sheet in the present disclosure may have a primer layer in order to improve the interlayer adhesion of the plurality of layers constituting the cosmetic sheet. The primer layer may be disposed at any interlayer between the matting layer and the base material layer. Further, when the cosmetic sheet has a transparent resin layer, the primer layer may be disposed between the transparent resin layer and the matting layer. Further, the primer layer may be disposed on the side of the base material layer opposite to the decorative layer (back surface primer layer).

[0211] The primer layer is mainly composed of a binder resin, and may contain additives such as ultraviolet absorbers and light stabilizers as required.

[0212] Examples of the binder resin include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (a urethane-acrylic copolymer derived from a polymer having a carbonate bond in the polymer main chain and two or more hydroxyl groups at the terminals and side chains (polycarbonate polyol)), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin (nitrocellulose), and cellulose acetate resin. These can be used alone or in combination of two or more.

[0213] Also, the binder resin may be a resin obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to the above resins and subjecting them to crosslinking curing. For example, a resin obtained by crosslinking and curing a polyol-based resin such as an acrylic polyol resin with an isocyanate-based curing agent is preferable, and a resin obtained by crosslinking and curing an acrylic polyol resin with an isocyanate-based curing agent is more preferable.

[0214] The thickness of the primer layer is, for example, 0.5 μm or more, and may be 1 μm or more, or may be 2 μm or more. Also, the thickness of the primer layer is, for example, 10 μm or less, and may be 8 μm or less, or may be 6 μm or less.

[0215] Examples of the method for forming the primer layer include a method of applying a resin composition and drying and curing it as required.

[0216] (4) Separator layer The cosmetic sheet in the present disclosure may have a separator layer on the surface opposite to the base material layer of the adhesive layer. The separator layer is a member that protects the adhesive layer and is peeled off when the cosmetic sheet is attached to an adherend. As the separator layer, a conventionally known one can be used.

[0217] 5. Manufacturing method of cosmetic sheet The manufacturing method of the cosmetic sheet in the present disclosure is not particularly limited. For example, it has a decorative layer forming step of forming a decorative layer on one surface of the base material layer, and a matting layer forming step of applying a matting layer composition on the surface of the decorative layer opposite to the base material layer to form a coating layer, and curing the coating layer by irradiation treatment with ionizing radiation to form a matting layer. The irradiation treatment with ionizing radiation in the matting layer forming step is performed in this order: (1) ultraviolet irradiation treatment for pre-curing, (2) irradiation treatment with wavelength light having a peak wavelength of 100 nm or more and less than 200 nm, and (3) electron beam irradiation treatment.

[0218] (1) Decorative layer forming step Examples of the method for forming the decorative layer include a coating method using an ink for forming a decorative layer containing a colorant, a binder resin, and a solvent (or dispersion medium). For example, the ink for forming a decorative layer is applied to one surface of the base material layer and dried to obtain a decorative layer.

[0219] Examples of the above solvent (or dispersion medium) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; and chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water.

[0220] Examples of the above coating method include, for example, printing methods. Examples of printing methods include, for example, gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. Further, examples of coating methods for forming a solid layer include various coating methods such as roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating.

[0221] (2) Matte layer forming step In this step, a matte layer composition is applied to the surface of the decorative layer opposite to the base material layer to form a coating layer, and the coating layer is cured by irradiation treatment with ionizing radiation to form a matte layer. The irradiation treatment with ionizing radiation in the matte layer forming step is performed in this order: (1) ultraviolet irradiation treatment for pre-curing, (2) irradiation treatment with wavelength light having a peak wavelength of 100 nm or more and less than 200 nm, and (3) electron beam irradiation treatment.

[0222] The method for forming the matte layer is the same as the content detailed in the above-mentioned "1. Matte layer (6) Method for forming matte layer".

[0223] B. Decorative material The cosmetic material in the present disclosure has an adherend and a cosmetic sheet disposed on one surface of the adherend.

[0224] FIG. 6 is a schematic cross-sectional view illustrating the cosmetic material in the present disclosure. The cosmetic material 100 shown in FIG. 6 has an adherend 20 and a cosmetic sheet 10 disposed on the surface of the adherend 20. Based on the base material layer 1, the matte layer 3 is disposed on the side opposite to the adherend 20. In FIG. 6, the cosmetic sheet 10 and the adherend 20 are adhered via the adhesive layer 5 of the cosmetic sheet 10.

[0225] According to the present disclosure, by using the above-described cosmetic sheet, a cosmetic material having both low glossiness and weather resistance can be obtained.

[0226] 1. Adherend The shape of the adherend is not particularly limited. For example, it includes plate-like shapes such as flat plates and curved plates; three-dimensional shapes such as cylinders and prisms; and sheet-like shapes. The adherend may be a wooden member. Examples of the wooden member include wood fiberboard. Examples of the wood fiberboard include wood veneer, plywood, laminated wood, particle board, and MDF (medium density fiberboard). Examples of the material of the wooden member include woods such as cedar, cypress, pine, and lauan.

[0227] The adherend may be a metal member. Examples of the metal used for the metal member include iron, aluminum, copper, and alloys containing one or more of these metals. Further, the adherend may be a ceramic member such as glass or porcelain, or a non-ceramic member such as gypsum, cement, ALC (lightweight cellular concrete), or calcium silicate.

[0228] The adherend may be a resin member. Examples of the resin used for the resin member include acrylic resin, polyester resin, polystyrene resin, polyolefin resins such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, vinyl chloride resin, cellulose resin, and rubber.

[0229] 2. Cosmetic sheet Regarding the cosmetic sheet in the present disclosure, since it is the same as the content described in the above "A. Cosmetic Sheet", the description here is omitted.

[0230] 3. Cosmetic material The cosmetic material in the present disclosure may be a member used outdoors (exterior member) or a member used indoors (interior member), but it is preferably an exterior member. This is because the cosmetic member in the present disclosure has good weather resistance.

[0231] Exterior members are usually used for exterior (outdoor) applications. Examples of exterior applications include building materials. Building materials are used, for example, in buildings such as houses, offices, stores, hospitals, and clinics. Examples of the uses of exterior members include exterior walls, roofs, eaves ceilings, louvers, door pockets, window frames, doors, door frames, handrails, fences, and drying racks.

[0232] The present disclosure is not limited to the above embodiments. The above embodiments are examples, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits the same operational effects is included in the technical scope of the present disclosure.

Example

[0233] [Example 1] (Preparation of the composition for forming a matte layer 1) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a bifunctional acrylate monomer (bifunctional monomer) were mixed to obtain a mixture. To the obtained mixture, 3 parts by mass of an ultraviolet absorber X2 (hydroxyphenyltriazine-based ultraviolet absorber), 3 parts by mass of a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) were added, and 0.8 part by mass of a photopolymerization initiator 1 (phosphine oxide-based photopolymerization initiator) was added to obtain the composition for forming a matte layer 1. Note that the photopolymerization initiator 1 has an absorption peak at 395 nm.

[0234] (Production of Cosmetic Sheet) As the base material, a 60-μm-thick polypropylene sheet subjected to corona discharge treatment on both sides was prepared. On one side of the base material, printing ink containing a two-component curable acrylic-urethane resin and a colorant was applied by the gravure printing method to form a wood grain pattern decorative layer. On the other side of the base material, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (hardener: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a primer layer (back primer layer) with a thickness of 3 μm. A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form an adhesive layer with a thickness of 3 μm. A transparent polypropylene was heat-melt extruded by a T-die extruder onto the adhesive layer to form a transparent resin layer with a thickness of 80 μm. A mixture of 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a hardener, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied to the treated surface by the gravure printing method and dried to form a primer layer with a thickness of 4 μm. On the primer layer, Composition 1 for forming a matte layer was applied at a coating amount of 5 g / m 2 to form a coating layer. The coating layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2 , integrated light quantity 30 to 100 mJ / cm 2 ) for pre-curing. Next, the coating layer was irradiated with ultraviolet rays using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet output density 30 mW / cm 2 , integrated light quantity 5 to 100 mJ / cm 2 , nitrogen atmosphere). Further, electron beams were irradiated (acceleration voltage 100 to 150 kV, irradiation dose 30 to 100 kGy) to form a matte layer. Thus, a cosmetic sheet having a back primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matte layer was obtained.

[0235] [Example 2] (Preparation of the composition for forming a matting layer 2) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a bifunctional acrylate monomer (bifunctional monomer) were mixed to obtain a mixture. To the obtained mixture, 3 parts by mass of an ultraviolet absorber X1 (hydroxyphenyltriazine-based ultraviolet absorber), 3 parts by mass of a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) were added, and 0.8 part by mass of a photopolymerization initiator 1 was added to obtain the composition for forming a matting layer 2.

[0236] (Production of a cosmetic sheet) As a base material, a 60-μm-thick polypropylene sheet subjected to corona discharge treatment on both sides was prepared. On one surface of the base material, a printing ink containing a two-component curable acrylic-urethane resin and a colorant was applied by a gravure printing method to form a wood grain pattern decorative layer. On the other surface of the base material, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (curing agent: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a 3-μm-thick primer layer (back primer layer). A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form a 3-μm-thick adhesive layer. Transparent polypropylene was heat-melted and extruded by a T-die extruder onto the adhesive layer to form an 80-μm-thick transparent resin layer. 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a curing agent, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied to the treated surface by a gravure printing method and dried to form a 4-μm-thick primer layer. Onto the primer layer, the composition for forming a matting layer 2 was applied at a coating amount of 5 g / m 2 during drying to form a coating layer. The coating layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2, integrated light quantity: 30 to 100 mJ / cm 2 ), pre-curing was performed. Then, ultraviolet rays were irradiated using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet output density: 30 mW / cm 2 , integrated light quantity: 5 to 100 mJ / cm 2 , nitrogen atmosphere). Further, electron beams were irradiated (acceleration voltage: 100 to 150 kV, irradiation dose: 30 to 100 kGy) to form a matting layer. As a result, a decorative sheet having a back primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matting layer was obtained.

[0237] [Example 3] (Preparation of matting layer forming composition 3) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a bifunctional acrylate monomer (bifunctional monomer) were mixed at a ratio to obtain a mixture. To the obtained mixture, 0.5 part by mass of ultraviolet absorber X1, 3 parts by mass of a wrinkle formation stabilizer (silica particles, average particle diameter: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) were added, and 0.8 part by mass of photopolymerization initiator 1 was added to obtain matting layer forming composition 3.

[0238] (Production of decorative sheet) As a base material, a polypropylene sheet with a thickness of 60 μm that had been subjected to corona discharge treatment on both sides was prepared. On one side of the base material, printing ink containing a two-component curable acrylic-urethane resin and a colorant was applied by the gravure printing method to form a decorative layer with a wood grain pattern. On the other side of the base material, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (hardener: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a primer layer (back primer layer) with a thickness of 3 μm. A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form an adhesive layer with a thickness of 3 μm. A transparent polypropylene was heat-melt extruded by a T-die extruder onto the adhesive layer to form a transparent resin layer with a thickness of 80 μm. A mixture of 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a hardener, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied to the treated surface by the gravure printing method and dried to form a primer layer with a thickness of 4 μm. Onto the primer layer, Composition 3 for forming a matte layer was applied at a coating amount of 5 g / m 2 to form a coating layer. The coating layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2 , integrated light quantity 30 - 100 mJ / cm 2 ) for pre-curing. Next, the coating layer was irradiated with ultraviolet rays using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet ray output density 30 mW / cm 2 , integrated light quantity 5 - 100 mJ / cm 2 , nitrogen atmosphere). Further, an electron beam was irradiated (acceleration voltage 100 - 150 kV, irradiation dose 30 - 100 kGy) to form a matte layer. Thus, a decorative sheet having a back primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matte layer was obtained.

[0239] [Example 4] (Preparation of Composition 4 for Forming a Matte Layer) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a bifunctional acrylate monomer (bifunctional monomer) were mixed at a ratio to obtain a mixture. To the obtained mixture, 1.5 parts by mass of ultraviolet absorber X1, 1.5 parts by mass of ultraviolet absorber X2, and 3 parts by mass of a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) were added, and 0.8 parts by mass of photopolymerization initiator 1 was added to obtain Composition 4 for forming a matting layer.

[0240] (Production of cosmetic sheet) As a base material, a 60-μm-thick polypropylene sheet subjected to corona discharge treatment on both sides was prepared. On one surface of the base material, printing ink containing a two-component curable acrylic-urethane resin and a coloring agent was applied by a gravure printing method to form a wood grain-like decorative layer. On the other surface of the base material, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (curing agent: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a primer layer (back primer layer) with a thickness of 3 μm. A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form an adhesive layer with a thickness of 3 μm. A transparent polypropylene was heat-melt extruded by a T-die extruder onto the adhesive layer to form a transparent resin layer with a thickness of 80 μm. 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a curing agent, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied to the treated surface by a gravure printing method and dried to form a primer layer with a thickness of 4 μm. On the primer layer, Composition 4 for forming a matting layer was applied at a coating amount of 5 g / m 2 to form a coating layer. The coating layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2 , integrated light quantity 30 to 100 mJ / cm 2) Pre-curing was performed. Subsequently, ultraviolet rays were irradiated using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet output density 30 mW / cm 2 , integrated light quantity 5 - 100 mJ / cm 2 , nitrogen atmosphere). Further, electron beams were irradiated (acceleration voltage 100 - 150 kV, irradiation dose 30 - 100 kGy) to form a matte layer. As a result, a decorative sheet having a back primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matte layer was obtained.

[0241] [Example 5] (Preparation of Matte Layer Forming Composition 5) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a difunctional acrylate monomer (difunctional monomer) were mixed at a ratio to obtain a mixture. To the obtained mixture, 3.0 parts by mass of ultraviolet absorber X1, 1.0 parts by mass of ultraviolet absorber X2, a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) were added, and 0.8 parts by mass of photoinitiator 1 was added to obtain Matte Layer Forming Composition 5.

[0242] (Production of Decorative Sheet) As a base material, a polypropylene sheet with a thickness of 60 μm that had been subjected to corona discharge treatment on both sides was prepared. On one surface of the base material, printing ink containing a two-component curable acrylic-urethane resin and a colorant was applied by the gravure printing method to form a decorative layer with a wood grain pattern. On the other surface of the base material, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (hardener: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a primer layer (back primer layer) with a thickness of 3 μm. A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form an adhesive layer with a thickness of 3 μm. A transparent polypropylene was heat-melt extruded by a T-die extruder onto the adhesive layer to form a transparent resin layer with a thickness of 80 μm. A mixture of 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a hardener, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied to the treated surface by the gravure printing method and dried to form a primer layer with a thickness of 4 μm. On the primer layer, Composition 5 for forming a matte layer was applied at a coating amount of 5 g / m 2 to form a coated layer. The coated layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2 , integrated light quantity 30 - 100 mJ / cm 2 ) for pre-curing. Next, the coated layer was irradiated with ultraviolet rays using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet ray output density 30 mW / cm 2 , integrated light quantity 5 - 100 mJ / cm 2 , nitrogen atmosphere). Further, an electron beam was irradiated (acceleration voltage 100 - 150 kV, irradiation dose 30 - 100 kGy) to form a matte layer. Thereby, a decorative sheet having a back primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matte layer was obtained.

[0243] [Example 6] (Preparation of Composition 6 for Forming Matte Layer) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a difunctional acrylate monomer (difunctional monomer) were mixed at a ratio to obtain a mixture. To the obtained mixture, 2.0 parts by mass of ultraviolet absorber X1, 1.0 parts by mass of ultraviolet absorber X2, 1.0 parts by mass of ultraviolet absorber X3 (hydroxyphenyltriazine-based ultraviolet absorber), and 3 parts by mass of a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) were added, and 0.8 parts by mass of photopolymerization initiator 1 was added to obtain a composition 6 for forming a matte layer.

[0244] (Production of cosmetic sheet) As a base material, a 60-μm-thick polypropylene sheet subjected to corona discharge treatment on both sides was prepared. On one surface of the base material, printing ink containing a two-component curable acrylic-urethane resin and a colorant was applied by a gravure printing method to form a wood grain-like decorative layer. On the other surface of the base material, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (curing agent: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a primer layer (back primer layer) with a thickness of 3 μm. A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form an adhesive layer with a thickness of 3 μm. Transparent polypropylene was heat-melted and extruded by a T-die extruder onto the adhesive layer to form a transparent resin layer with a thickness of 80 μm. A mixture of 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a curing agent, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied to the treated surface by a gravure printing method and dried to form a primer layer with a thickness of 4 μm. On the primer layer, the composition 6 for forming a matte layer was applied at an application amount of 5 g / m 2 when dried to form a coating layer. The coating layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2, integrated light quantity: 30 to 100 mJ / cm 2 ), pre-curing was performed. Subsequently, ultraviolet rays were irradiated using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet output density: 30 mW / cm 2 , integrated light quantity: 5 to 100 mJ / cm 2 , nitrogen atmosphere). Further, electron beams were irradiated (acceleration voltage: 100 to 150 kV, irradiation dose: 30 to 100 kGy) to form a matting layer. As a result, a decorative sheet having a back primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matting layer was obtained.

[0245] [Example 7] (Preparation of Matting Layer Forming Composition 7) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a difunctional acrylate monomer (difunctional monomer) were mixed at a ratio to obtain a mixture. To the obtained mixture, 2.0 parts by mass of ultraviolet absorber X1, 1.0 parts by mass of ultraviolet absorber X2, 1.0 parts by mass of ultraviolet absorber Y1 (hydroxyphenyltriazine-based ultraviolet absorber), and a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) were added, and 0.8 parts by mass of photopolymerization initiator 1 was added to obtain Matting Layer Forming Composition 7.

[0246] (Production of Decorative Sheet) As a base material, a 60-μm-thick polypropylene sheet subjected to corona discharge treatment on both sides was prepared. On one side of the base material, printing ink containing a two-component curable acrylic-urethane resin and a colorant was applied by a gravure printing method to form a wood grain-like decorative layer. On the other side of the base material, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (hardener: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a primer layer (back primer layer) with a thickness of 3 μm. A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form an adhesive layer with a thickness of 3 μm. A transparent polypropylene was heat-melted and extruded by a T-die extruder onto the adhesive layer to form a transparent resin layer with a thickness of 80 μm. A mixture of 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a hardener, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied by a gravure printing method to the treated surface and dried to form a primer layer with a thickness of 4 μm. On the primer layer, Composition 7 for forming a matte layer was applied at a coating amount of 5 g / m 2 to form a coating layer. The coating layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2 , integrated light quantity 30 to 100 mJ / cm 2 ) for pre-curing. Next, the coating layer was irradiated with ultraviolet rays using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet ray output density 30 mW / cm 2 , integrated light quantity 5 to 100 mJ / cm 2 , nitrogen atmosphere). Further, an electron beam was irradiated (acceleration voltage 100 to 150 kV, irradiation dose 30 to 100 kGy) to form a matte layer. Thus, a decorative sheet having a back primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matte layer was obtained.

[0247] [Example 8] (Preparation of Composition 8 for Forming a Matte Layer) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a difunctional acrylate monomer (difunctional monomer) were mixed to obtain a mixture. To the obtained mixture, 10.0 parts by mass of an ultraviolet absorber X1, 3 parts by mass of an anti-wrinkle stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) were added, and 0.8 parts by mass of a photopolymerization initiator 1 was added to obtain a composition 8 for forming a matte layer.

[0248] (Production of cosmetic sheet) As a substrate, a polypropylene sheet with a thickness of 60 μm that had been subjected to corona discharge treatment on both sides was prepared. On one surface of the substrate, a printing ink containing a two-component curable acrylic-urethane resin and a coloring agent was applied by the gravure printing method to form a wood grain decorative layer. On the other surface of the substrate, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (curing agent: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a primer layer (back primer layer) with a thickness of 3 μm. A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form an adhesive layer with a thickness of 3 μm. A transparent polypropylene was heat-melt extruded by a T-die extruder onto the adhesive layer to form a transparent resin layer with a thickness of 80 μm. 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a curing agent, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied to the treated surface by the gravure printing method and dried to form a primer layer with a thickness of 4 μm. On the primer layer, the composition 8 for forming a matte layer was applied at an application amount of 5 g / m 2 when dried to form a coating layer. The coating layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2 , integrated light quantity 30 to 100 mJ / cm 2) Pre-curing was carried out. Subsequently, ultraviolet rays were irradiated using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet output density 30 mW / cm 2 , integrated light quantity 5 - 100 mJ / cm 2 , nitrogen atmosphere). Further, electron beams were irradiated (acceleration voltage 100 - 150 kV, irradiation dose 30 - 100 kGy) to form a matting layer. As a result, a decorative sheet having a back primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matting layer was obtained.

[0249] [Example 9] (Preparation of matting layer forming composition 9) A trifunctional urethane acrylate oligomer (trifunctional oligomer) was mixed at a ratio of 30 parts by mass, a trifunctional acrylate monomer (trifunctional monomer) was mixed at a ratio of 30 parts by mass, and a difunctional acrylate monomer (difunctional monomer) was mixed at a ratio of 40 parts by mass to obtain a mixture. To the obtained mixture, 0.1 part by mass of ultraviolet absorber X1, 3 parts by mass of a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) was added, and 0.8 part by mass of photoinitiator 1 was added to obtain matting layer forming composition 9.

[0250] (Production of decorative sheet) As a base material, a polypropylene sheet with a thickness of 60 μm that had been subjected to corona discharge treatment on both sides was prepared. On one surface of the base material, printing ink containing a two-component curable acrylic-urethane resin and a colorant was applied by the gravure printing method to form a decorative layer with a wood grain pattern. On the other surface of the base material, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (hardener: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a primer layer (back surface primer layer) with a thickness of 3 μm. A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form an adhesive layer with a thickness of 3 μm. A transparent polypropylene was heat-melt extruded by a T-die extruder onto the adhesive layer to form a transparent resin layer with a thickness of 80 μm. A mixture of 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a hardener, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied to the treated surface by the gravure printing method and dried to form a primer layer with a thickness of 4 μm. On the primer layer, Composition 9 for forming a matte layer was applied at a coating amount of 5 g / m 2 to form a coating layer. The coating layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2 , integrated light quantity 30 to 100 mJ / cm 2 ) for pre-curing. Next, the coating layer was irradiated with ultraviolet rays using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet ray output density 30 mW / cm 2 , integrated light quantity 5 to 100 mJ / cm 2 , nitrogen atmosphere). Further, an electron beam was irradiated (acceleration voltage 100 to 150 kV, irradiation dose 30 to 100 kGy) to form a matte layer. Thus, a decorative sheet having a back surface primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matte layer was obtained.

[0251] [Example 10] (Preparation of Composition 10 for Forming Matte Layer) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a difunctional acrylate monomer (difunctional monomer) were mixed at a ratio to obtain a mixture. To the obtained mixture, 15 parts by mass of an ultraviolet absorber X1, 3 parts by mass of a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) were added, and 0.8 part by mass of a photopolymerization initiator 1 was added to obtain a composition 10 for forming a matte layer.

[0252] (Production of cosmetic sheet) As a substrate, a 60-μm-thick polypropylene sheet subjected to corona discharge treatment on both sides was prepared. On one surface of the substrate, a printing ink containing a two-component curable acrylic-urethane resin and a colorant was applied by a gravure printing method to form a wood grain-like decorative layer. On the other surface of the substrate, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (curing agent: containing 5 parts by mass with respect to 100 parts by mass of the resin, hexamethylene diisocyanate) was applied to form a primer layer (back primer layer) with a thickness of 3 μm. A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form an adhesive layer with a thickness of 3 μm. A transparent polypropylene was heated and melt-extruded by a T-die extruder onto the adhesive layer to form a transparent resin layer with a thickness of 80 μm. 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a curing agent, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied by a gravure printing method to the treated surface and dried to form a primer layer with a thickness of 4 μm. On the primer layer, the composition 10 for forming a matte layer was applied at a coating amount of 5 g / m 2 to form a coating layer. The coating layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2 , integrated light quantity 30 to 100 mJ / cm 2) Pre-curing was performed. Subsequently, ultraviolet rays were irradiated using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 )), ultraviolet output density 30 mW / cm 2 , integrated light quantity 5 - 100 mJ / cm 2 , nitrogen atmosphere). Further, electron beams were irradiated (acceleration voltage 100 - 150 kV, irradiation dose 30 - 100 kGy) to form a matte layer. As a result, a decorative sheet having a back primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matte layer was obtained.

[0253] [Example 11] (Preparation of Matte Layer Forming Composition 11) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a bifunctional acrylate monomer (bifunctional monomer) were mixed at a ratio to obtain a mixture. To the obtained mixture, 3 parts by mass of an ultraviolet absorber X4 (hydroxyphenyltriazine-based ultraviolet absorber), a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) was added, and 0.8 part by mass of a photopolymerization initiator 1 was added to obtain a matte layer forming composition 11.

[0254] (Production of Decorative Sheet) As a base material, a polypropylene sheet with a thickness of 60 μm that had been subjected to corona discharge treatment on both sides was prepared. On one side of the base material, printing ink containing a two-component curable acrylic-urethane resin and a colorant was applied by the gravure printing method to form a wood grain pattern decorative layer. On the other side of the base material, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (hardening agent: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a primer layer (back surface primer layer) with a thickness of 3 μm. A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form an adhesive layer with a thickness of 3 μm. A transparent polypropylene was heat-melt extruded by a T-die extruder onto the adhesive layer to form a transparent resin layer with a thickness of 80 μm. 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a hardening agent, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied to the treated surface by the gravure printing method and dried to form a primer layer with a thickness of 4 μm. Onto the primer layer, Composition 11 for forming a matte layer was applied at a coating amount of 5 g / m 2 to form a coated layer. The coated layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2 , integrated light quantity 30 to 100 mJ / cm 2 ) for pre-curing. Next, the coated layer was irradiated with ultraviolet rays using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet ray output density 30 mW / cm 2 , integrated light quantity 5 to 100 mJ / cm 2 , nitrogen atmosphere). Further, electron beams were irradiated (acceleration voltage 100 to 150 kV, irradiation dose 30 to 100 kGy) to form a matte layer. Thus, a decorative sheet having a back surface primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matte layer was obtained.

[0255] [Comparative Example 1] (Preparation of Composition 12 for Forming a Matte Layer) 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a difunctional acrylate monomer (difunctional monomer) were mixed at a ratio to obtain a mixture. To the obtained mixture, 3 parts by mass of an ultraviolet absorber Y1, 3 parts by mass of a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area 100 m 2 / g, oil absorption rate: 40 ml / 100 g) were added, and 0.8 parts by mass of a photopolymerization initiator 1 was added to obtain a composition 12 for forming a matting layer.

[0256] (Production of cosmetic sheet) As a substrate, a 60-μm-thick polypropylene sheet subjected to corona discharge treatment on both sides was prepared. On one surface of the substrate, a printing ink containing a two-component curable acrylic-urethane resin and a colorant was applied by a gravure printing method to form a wood grain-like decorative layer. On the other surface of the substrate, a resin composition containing a two-component curable urethane-nitrocellulose mixed resin (curing agent: containing 5 parts by mass of hexamethylene diisocyanate with respect to 100 parts by mass of the resin) was applied to form a 3-μm-thick primer layer (back primer layer). A transparent urethane resin-based adhesive was applied to the decorative layer and dried to form a 3-μm-thick adhesive layer. Transparent polypropylene was heat-melt extruded by a T-die extruder onto the adhesive layer to form an 80-μm-thick transparent resin layer. 100 parts by mass of a mixture composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol, 5 parts by mass of hexamethylene diisocyanate as a curing agent, and a diluting solvent were mixed to prepare a resin composition for the primer layer. After subjecting the surface of the transparent resin layer to corona discharge treatment, the resin composition for the primer layer was applied to the treated surface by a gravure printing method and dried to form a 4-μm-thick primer layer. On the primer layer, the composition 12 for forming a matting layer was applied at a coating amount of 5 g / m 2 to form a coating layer. The coating layer was irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm 2 , integrated light amount 30 to 100 mJ / cm 2) Pre-curing was performed. Subsequently, ultraviolet rays were irradiated using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe 2 ), ultraviolet output density 30 mW / cm 2 , integrated light quantity 5 - 100 mJ / cm 2 , nitrogen atmosphere). Further, electron beams were irradiated (acceleration voltage 100 - 150 kV, irradiation dose 30 - 100 kGy) to form a matte layer. As a result, a decorative sheet having a back primer layer, a base material layer, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a matte layer was obtained.

[0257] [Absorbance] Figures 4, 5, and 7 show the light absorption spectra measured using an ultraviolet-visible near-infrared spectrophotometer for ultraviolet absorber X1, ultraviolet absorber X2, ultraviolet absorber X3, ultraviolet absorber X4, and ultraviolet absorber Y1. Also, the peak wavelength of the first absorption peak of each ultraviolet absorber and λ 10 are shown in Table 1.

[0258] [Table 1]

[0259] [Evaluation] (60° gloss value) [Evaluation method] Regarding the decorative sheets obtained in the examples and comparative examples, using a gloss meter (「Micro Gloss (model name)」, manufactured by BYK Gardner), the 60° specular glossiness was measured in accordance with JIS K 5600-4-7:1999 and evaluated according to the following evaluation criteria. [Evaluation criteria] A: Gloss is 5 or less B: Gloss is greater than 5 and 10 or less C: Gloss is greater than 10

[0260] [Weather resistance evaluation] [Evaluation method] For the cosmetic sheets obtained in the examples and comparative examples, after conducting the following accelerated weathering test (a process of irradiating ultraviolet rays for 20 hours under the following irradiation conditions and then conducting dew condensation for 4 hours under the following dew condensation conditions, with one cycle being defined as such, and repeating the cycle) using a metal halide lamp (MWOM) for 500 hours, the changes in appearance were observed as follows, and the weather resistance was evaluated. The evaluation results are shown in Table 2.

[0261] <Accelerated Weathering Test Conditions> (Test Equipment) Manufactured by Dipla Winters Co., Ltd., product name "Dipla Metal Weather" (Irradiation Conditions) Illuminance: 65 mW / cm 2 , Black panel temperature: 63°C, humidity inside the tank: 50% RH, time: 20 hours (Dew Condensation Conditions) Illuminance: 0 mW / cm 2 , humidity inside the tank: 98% RH, time: 4 hours <Evaluation Criteria> A: No change in appearance was confirmed throughout the cosmetic sheet. B: Slight color tone changes were confirmed in the appearance of the cosmetic sheet, but whitening could not be confirmed.

[0262]

Table 2

[0263] It was confirmed that the cosmetic sheets obtained in Examples 1 to 11 had a low 60° gloss value and good weather resistance.

[0264] Thus, in the present disclosure, for example, the following inventions are provided.

[0265] [1] A cosmetic sheet having a base material layer, a decorative layer disposed on one surface of the base material layer, and a matting layer disposed on the surface of the decorative layer opposite to the base material layer, wherein the surface of the matting layer opposite to the decorative layer has a surface shape having a wrinkle structure. The matting layer has a cured resin and an ultraviolet absorber X. The light absorption spectrum of the ultraviolet absorber X has a first absorption peak having a peak wavelength λ in a wavelength range of 200 nm or more and 380 nm or less. P1 and the absorbance at the peak wavelength λ P1 is A max when the absorbance A P1 at a wavelength longer than the peak wavelength λ max is 10% of the absorbance A 10 the wavelength λ 10 is 385 nm or less. A cosmetic sheet.

[0266] [2] In the matting layer, the content of the ultraviolet absorber X is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the cured resin. The cosmetic sheet according to [1].

[0267] [3] The light absorption spectrum of the ultraviolet absorber X has a second absorption peak having a peak wavelength λ in a wavelength range of 200 nm or more and shorter than the peak wavelength λ P1 The cosmetic sheet according to [1] or [2]. P2 having a peak wavelength λ

[0268] [4] The light absorption spectrum of the ultraviolet absorber X has no absorption peak having a peak wavelength in a wavelength range of 200 nm or more and shorter than the peak wavelength λ P1 The cosmetic sheet according to [1] or [2].

[0269] [5] The ultraviolet absorber X is a triazine-based ultraviolet absorber. The cosmetic sheet according to any one of [1] to [4].

[0270] [6] The matting layer contains an ultraviolet absorber other than the ultraviolet absorber X. The cosmetic sheet according to any one of [1] to [5].

[0271] [7] The matting layer contains an ultraviolet absorber Y as an ultraviolet absorber other than the ultraviolet absorber X, The light absorption spectrum of the ultraviolet absorber Y has an absorption peak with a peak wavelength λ in the wavelength range of 200 nm or more and 380 nm or less, Q1 has an absorption peak, and when the absorbance at the peak wavelength λ Q1 is B, max at a wavelength higher than the peak wavelength λ, Q1 the wavelength at which the absorbance B max is 10% of the absorbance B 10 is greater than 385 nm. The cosmetic sheet according to [6].

[0272] [8] The matting layer contains a photoinitiator having an absorption peak with a peak wavelength in the wavelength range of 350 nm or more and 400 nm or less. The cosmetic sheet according to any one of [1] to [7].

[0273] [9] The wrinkle structure is a structure having an uneven shape due to irregular wrinkles. The irregular wrinkles have a plurality of convex portions formed by a plurality of protrusions and concave portions formed by being surrounded by the plurality of protrusions. The cosmetic sheet according to any one of [1] to [8].

[0274]

[10] The 60° gloss value of the surface shape is 10.0 or less. The cosmetic sheet according to any one of [1] to [9].

[0275]

[11] A transparent resin layer is disposed between the matting layer and the decorative layer. The cosmetic sheet according to any one of [1] to

[10] .

[0276]

[12] An adhesive layer is disposed on the side of the base material layer opposite to the decorative layer. The cosmetic sheet according to any one of [1] to

[11] .

[0277]

[13] The decorative sheet according to any one of [1] to

[12] , which is used for an exterior member.

[0278]

[14] A method for manufacturing a decorative sheet according to any one of [1] to

[13] , comprising: A decorative layer forming step of forming the decorative layer on one surface of the base material layer; A matting layer forming step of applying a matting layer composition to the surface of the decorative layer opposite to the base material layer to form a coating layer, and curing the coating layer by irradiation treatment with ionizing radiation to form the matting layer. The irradiation treatment with ionizing radiation in the matting layer forming step is a method for manufacturing a decorative sheet, which sequentially performs (1) ultraviolet irradiation treatment for pre-curing, (2) irradiation treatment with wavelength light having a peak wavelength of 100 nm or more and less than 200 nm, and (3) electron beam irradiation treatment.

[0279]

[15] A decorative material having an adherend and a decorative sheet disposed on the surface of the adherend, wherein the decorative sheet is the decorative sheet according to any one of [1] to

[13] .

Explanation of reference numerals

[0280] 1... Base material layer 2... Decorative layer 3... Matting layer 4... Transparent resin layer 5... Adhesive layer 6... Separator layer 7... Primer layer 10... Decorative sheet 100... Decorative material

Claims

1. A decorative sheet having a base material layer, a decorative layer disposed on one surface of the base material layer, and a matting layer disposed on the surface of the decorative layer opposite to the base material layer, wherein the surface of the matting layer opposite to the decorative layer has a surface shape having a wrinkle structure, the matting layer has a cured resin and an ultraviolet absorber X, The light absorption spectrum of the ultraviolet absorber X has a first absorption peak having a peak wavelength λ in the wavelength range of 200 nm or more and 380 nm or less, and when the absorbance at the peak wavelength λ is A, on the higher wavelength side than the peak wavelength λ, the wavelength λ at which the absorbance becomes 10% of the absorbance A is 385 nm or less. A cosmetic sheet. Ｐ１ and has a first absorption peak having a peak wavelength λ, and when the absorbance at the peak wavelength λ is A Ｐ１ on the higher wavelength side than the peak wavelength λ, the absorbance A ｍａｘ is 10% of the absorbance A Ｐ１ and the wavelength λ ｍａｘ at which the absorbance becomes A １０ is 385 nm or less. A cosmetic sheet. １０ ​

2. The decorative sheet according to claim 1, wherein in the matting layer, the content of the ultraviolet absorber X is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the cured resin.

3. The light absorption spectrum of the ultraviolet absorber X is 200 nm or more, and has a second absorption peak having a peak wavelength λ in a wavelength range shorter than the peak wavelength λ Ｐ１ on the shorter wavelength side. The cosmetic sheet according to claim 1, having a peak wavelength λ Ｐ２ ​

4. The light absorption spectrum of the ultraviolet absorber X has no absorption peak having a peak wavelength in a wavelength range of 200 nm or more and shorter than the peak wavelength λ Ｐ１ The cosmetic sheet according to claim 1, which does not have an absorption peak having a peak wavelength in a wavelength range shorter than Ｐ１ .

5. The decorative sheet according to claim 1, wherein the ultraviolet absorber X is a triazine-based ultraviolet absorber.

6. The decorative sheet according to claim 1, wherein the matting layer contains an ultraviolet absorber other than the ultraviolet absorber X.

7. The matting layer contains an ultraviolet absorber Y as an ultraviolet absorber other than the ultraviolet absorber X, The light absorption spectrum of the ultraviolet absorber Y has an absorption peak with a peak wavelength λ in the wavelength range of 200 nm or more and 380 nm or less. Ｑ１ When the absorbance at the peak wavelength λ Ｑ１ is B ｍａｘ and the wavelength at which the absorbance is 10% of the absorbance B Ｑ１ is greater than 385 nm on the higher wavelength side than the peak wavelength λ ｍａｘ the cosmetic sheet according to claim 6. １０ ​

8. The decorative sheet according to claim 1, wherein the matting layer contains a photopolymerization initiator having an absorption peak with a peak wavelength in the wavelength range of 350 nm or more and 400 nm or less.

9. The wrinkle structure is a structure having an uneven shape due to irregular wrinkles, and the irregular wrinkles have a plurality of convex portions formed by a plurality of protrusions and concave portions formed by being surrounded by the plurality of protrusions. The decorative sheet according to claim 1.

10. The decorative sheet according to claim 1, wherein the 60° gloss value of the surface shape is 10.0 or less.

11. The decorative sheet according to claim 1, wherein a transparent resin layer is disposed between the matting layer and the decorative layer.

12. The decorative sheet according to claim 1, wherein an adhesive layer is disposed on the surface side of the base material layer opposite to the decorative layer.

13. The decorative sheet according to claim 1, which is used for an exterior member.

14. A method for manufacturing the decorative sheet according to any one of claims 1 to 13, comprising: a decorative layer forming step of forming the decorative layer on one surface of the base material layer; a matting layer forming step of applying a matting layer composition on the surface of the decorative layer opposite to the base material layer to form a coating layer, and curing the coating layer by irradiation treatment with ionizing radiation to form the matting layer. In the step of forming the matting layer, the irradiation treatment with the ionizing radiation is carried out in the following order: (1) ultraviolet irradiation treatment for pre-curing, (2) irradiation treatment with wavelength light having a peak wavelength of 100 nm or more and less than 200 nm, and (3) electron beam irradiation treatment. A method for manufacturing a decorative sheet.

15. A decorative material having an adherend and a decorative sheet disposed on the surface of the adherend, wherein the decorative sheet is the decorative sheet according to any one of claims 1 to 13. A decorative material.

Images