Decorative sheet and decorative member

Abstract

The present disclosure provides a decorative sheet having a substrate layer, a design layer, a second protective layer, and a first protective layer in this order in the thickness direction. The first protective layer contains a biomass-derived resin and particles, the ratio of the thickness T1 of the first protective layer to the thickness T2 of the second protective layer (T1 / T2) is 1.0 to 7.0, and the ratio of the average particle diameter C of the particles to the thickness T1 of the first protective layer (C / T1) is 0.7 to 1.8.

Description

Decorative sheets and decorative components

[0001] This disclosure relates to decorative sheets and decorative components.

[0002] Conventionally, decorative sheets are sometimes placed on the surface of articles such as building materials and furniture to give them an aesthetic appearance. Patent Document 1 discloses a decorative sheet comprising, in this order, a colored base layer, an adhesive layer, and a transparent thermoplastic resin layer, wherein the colored base layer is a resin layer formed from a resin composition containing a biomass-derived polyolefin obtained by polymerizing monomers containing biomass-derived olefins, and the colored base layer further contains inorganic material, and the specific gravity of the colored base layer is within a predetermined range.

[0003] Japanese Patent Publication No. 2023-022311

[0004] Numerous decorative sheets have been proposed with a protective layer (surface protective layer) to improve their surface properties. In recent years, there has been a demand for designs with a matte finish in decorative sheets and other decorative materials. For example, decorative sheets that exhibit a low gloss finish by incorporating particles into the protective layer have been proposed.

[0005] The protective layer is often formed from petroleum-derived resin, and such decorative sheets have room for improvement in reducing their environmental impact. The inventors of this invention considered using biomass-derived resin as the material for the protective layer in order to reduce the environmental impact. However, since biomass-derived resins require that at least a portion of the resin material be made from biomass raw materials, the selection of resins is limited. As a result, it may be difficult to obtain good surface properties and a good low gloss. Furthermore, even if a low gloss is obtained, uneven gloss may occur.

[0006] This disclosure is made in view of the above circumstances, and its main purpose is to provide a decorative sheet that has good low gloss and good surface properties, and can suppress gloss unevenness, while reducing environmental impact.

[0007] This disclosure provides a decorative sheet having a base layer, a design layer, a second protective layer, and a first protective layer in this order in the thickness direction, wherein the first protective layer contains a biomass-derived resin and particles, the ratio of the thickness T1 of the first protective layer to the thickness T2 of the second protective layer (T1 / T2) is 1.0 or more and 7.0 or less, and the ratio of the average particle size C of the particles to the thickness T1 of the first protective layer (C / T1) is 0.7 or more and 1.8 or less.

[0008] This disclosure provides a decorative member having a member to be adhered to and the decorative sheet described above.

[0009] This disclosure offers the advantage of providing a decorative sheet that reduces environmental impact while possessing good low gloss and good surface properties, and that can suppress uneven gloss.

[0010] This is a schematic cross-sectional view illustrating a decorative sheet in this disclosure. This is a schematic cross-sectional view illustrating a decorative sheet in this disclosure. This is a schematic cross-sectional view illustrating a decorative sheet in this disclosure. This is a schematic cross-sectional view illustrating a decorative component in this disclosure.

[0011] The embodiments will be described below with reference to the drawings, etc. However, this disclosure can be implemented in many different ways and is not limited to the embodiments described below. In addition, the drawings may schematically represent the width, thickness, and shape of each part compared to the actual form in order to make the explanation clearer, but this is merely an example and should not be interpreted as limiting.

[0012] In this specification, when describing a configuration in which one member is placed on top of another member, the terms "on top" or "below" include, unless otherwise specified, both cases: when the other member is placed directly above or directly below the member so as to be in contact with it, and when the other member is placed above or below the member via yet another member. Furthermore, in this specification, when describing a configuration in which one member is placed on the surface of another member, the terms "on the surface" or "on the side of the surface" include, unless otherwise specified, both cases: when the other member is placed directly above or directly below the member so as to be in contact with it, and when the other member is placed above or below the member via yet another member.

[0013] Furthermore, in this specification, the terms “board,” “sheet,” and “film” are not distinguished from each other solely on the basis of their names. For example, “sheet” includes components that are also called “board” or “film.”

[0014] The decorative sheets and decorative components described herein will be explained in detail below.

[0015] A. Decorative Sheet The decorative sheet in this disclosure is a decorative sheet having a base layer, a design layer, a second protective layer, and a first protective layer in this order in the thickness direction, wherein the first protective layer contains a biomass-derived resin and particles, the ratio of the thickness T1 of the first protective layer to the thickness T2 of the second protective layer (T1 / T2) is 1.0 or more and 7.0 or less, and the ratio of the average particle size C of the particles to the thickness T1 of the first protective layer (C / T1) is 0.7 or more and 1.8 or less.

[0016] Figure 1 is a schematic cross-sectional view illustrating a decorative sheet in this disclosure. The decorative sheet 10 shown in Figure 1 comprises a base layer 1, a design layer 2, a second protective layer 4, and a first protective layer 3, in the thickness direction D Ｔ In this disclosure, the first protective layer 3 comprises a biomass-derived resin and particles. Furthermore, the ratio of the thickness T1 of the first protective layer 3 to the thickness T2 of the second protective layer 4 (T1 / T2) is within a predetermined range, and the ratio of the average particle size C of the particles to the thickness T1 of the first protective layer 3 (C / T1) is within a predetermined range.

[0017] The decorative sheet of this disclosure, by having a first protective layer containing a biomass-derived resin, can reduce the environmental impact compared to conventional decorative sheets having a surface protective layer.

[0018] On the other hand, the biomass-derived resin included in the first protective layer requires that at least a portion of the resin material be made from biomass raw materials, thus limiting the selection of resins. As a result, even if the first protective layer contains particles, it may be difficult to obtain a low-gloss finish. Also, uneven gloss may occur. In this disclosure, the decorative sheet 10 has a second protective layer 4, and by setting the ratio (T1 / T2) of the thickness T1 of the first protective layer 3 to the thickness T2 of the second protective layer 4 within a predetermined range, even if the first protective layer 3 contains a biomass-derived resin, a decorative sheet with good low gloss and suppressed uneven gloss is obtained.

[0019] Furthermore, because the selection of resins for the first protective layer is limited, it may be difficult to obtain a decorative sheet with good surface properties (e.g., scratch resistance and solvent resistance) using only the first protective layer. By having a second protective layer 4 in the decorative sheet 10, the reduction in surface properties caused by using only the first protective layer 3 can be compensated for, and the surface properties of the decorative sheet can be improved. In addition, good scratch resistance can be obtained if the ratio of the average particle size C to the thickness T1 of the first protective layer 3 (C / T1) is within a predetermined range.

[0020] In this disclosure, as shown in Figure 1, it is preferable that the decorative sheet 10 does not have a transparent resin layer between the base layer 1 and the first protective layer 3. As shown in Figure 1, the second protective layer 4 and the first protective layer 3 may be in direct contact, the design layer 2 and the second protective layer 4 may be in direct contact, and the base layer 1 and the design layer 2 may be in direct contact. Generally, decorative sheets are sometimes provided with a relatively thick transparent resin layer for the purpose of improving strength. In this disclosure, by not having a transparent resin layer in the decorative sheet, the number of layers constituting the decorative sheet can be reduced, and manufacturing costs can be reduced. In addition, conventional transparent resin layers often contain petroleum-derived resins. Therefore, by not having a transparent resin layer in the decorative sheet, the biomass content of the entire decorative sheet can be increased.

[0021] I. Parameters 1. T1 / T2 In this disclosure, the ratio of the thickness T1 of the first protective layer to the thickness T2 of the second protective layer (T1 / T2) is 7.0 or less, and may be 6.0 or less. By setting the above ratio (T1 / T2) to the above range, the penetration of the resin material of the first protective layer (e.g., a curable resin composition) into the lower layer (the layer located on the substrate layer side of the first protective layer) can be uniformly controlled in the in-plane direction of the decorative sheet, resulting in a decorative sheet with suppressed gloss unevenness. Furthermore, the above ratio (T1 / T2) is 1.0 or more, and may be 2.0 or more. A first protective layer containing a biomass-derived resin (especially when the resin material contains a biomass oligomer) has lower penetration of the resin material into the lower layer compared to a protective layer that does not contain a biomass-derived resin. By setting the above ratio (T1 / T2) within the above range, the resin material of the first protective layer (e.g., a curable resin composition) can be appropriately penetrated into the lower layer, making it easier for the particles to emerge and resulting in a low gloss finish.

[0022] 2. C / T1 In this disclosure, the ratio of the average particle size C to the thickness T1 of the first protective layer 3 (C / T1) is 0.7 or more, and may be 0.9 or more. Setting the above ratio (C / T1) within the above range makes it easier to form surface irregularities by the particles, and makes it easier to obtain a low gloss feel. On the other hand, the above ratio (C / T1) is 1.8 or less, and may be 1.4 or less. Setting the above ratio (C / T1) within the above range is preferable because there is no risk of particles falling off the first protective layer in the event of scratches, abrasions, etc.

[0023] II. Layer Structure As shown in Figure 1, the decorative sheet 10 in this disclosure consists of a base layer 1, a design layer 2, a second protective layer 4, and a first protective layer 3, in the thickness direction D Ｔ In this order, the layers are present. As shown in Figure 1, it is preferable that the design layer 2 has a pattern layer 21. Alternatively, the design layer 2 may have a solid layer 22 on the base layer 1 side of the pattern layer 21.

[0024] Furthermore, as shown in Figure 2, the decorative sheet 10 may have a low-gloss pattern layer 5 between the first protective layer 3 and the second protective layer 4. In this case, the thickness direction D ＴFrom this perspective, it is preferable that the low-gloss pattern layer 5 is arranged according to the pattern of the pattern layer 21.

[0025] 1. First protective layer The first protective layer is positioned on the side of the design layer opposite to the base layer. The decorative sheet may have the first protective layer as its outermost layer. The first protective layer can protect the design layer and the base layer. The first protective layer contributes to improving the surface properties of the decorative sheet (e.g., scratch resistance and solvent resistance).

[0026] (1) Materials (a) Resin The first protective layer contains a biomass-derived resin. A biomass-derived resin is a resin in which biomass raw materials are used in at least a part of the resin material.

[0027] The biomass-derived resin is preferably a cured product of a curable resin composition containing a biomass-derived curable compound (hereinafter also simply referred to as the curable resin composition). The biomass-derived curable compound is, for example, a monomer, oligomer, or prepolymer produced solely from biomass raw materials, or a monomer, oligomer, or prepolymer produced from raw materials containing biomass raw materials. The biomass content of the biomass-derived curable compound is, for example, 10% or more, and may be 20% or more. On the other hand, the biomass content of the biomass-derived curable compound is, for example, 100% or less, and may be 90% or less. The method for measuring the biomass content is the same as the method for measuring the biomass content of the first protective layer described later.

[0028] The biomass-derived resin may be a cured product of a curable resin composition containing a biomass-derived curable compound but not a petroleum-derived curable compound, or it may be a cured product of a curable resin composition containing both a biomass-derived curable compound and a petroleum-derived curable compound. The ratio of the biomass-derived curable compound to all curable compounds in the curable resin composition is, for example, 50% by mass or more, may be 60% by mass or more, or may be 70% by mass or more. On the other hand, the ratio of the biomass-derived curable compound to all curable compounds in the curable resin composition is, for example, 100% by mass or less, may be 90% by mass or less, or may be 80% by mass or less.

[0029] The cured product may be a cured product obtained by curing the curable resin composition with ionizing radiation, or a cured product obtained by curing the curable resin composition with heat. Examples of the curable resin composition include ionizing radiation-curable resin compositions and thermosetting resin compositions. From the viewpoint of durability, design (low gloss), and production efficiency, ionizing radiation-curable resin compositions are preferred. Specific examples of ionizing radiation-curable resin compositions include electron beam-curable resin compositions and ultraviolet-curable resin compositions. Among these, electron beam-curable resin compositions have advantages such as less odor because they do not require polymerization initiators, and less discoloration.

[0030] An ionizing radiation-curable resin composition is a composition containing a compound having an ionizing radiation-curable functional group (hereinafter also referred to as "ionizing radiation-curable compound"). An ionizing radiation-curable functional group is a group that crosslinks and hardens upon irradiation with ionizing radiation. Specific examples include functional groups having an ethylenically double bond, such as (meth)acryloyl groups, vinyl groups, and allyl groups. Other specific examples of ionizing radiation-curable functional groups include epoxy groups and oxetanyl groups. In this specification, (meth)acryloyl group means acryloyl group or metacloyl group. In this specification, (meth)acrylate means acrylate or methacrylate. Ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or crosslinking molecules. Specific examples of ionizing radiation include ultraviolet rays (UV) and electron beams (EB). Other specific examples of ionizing radiation include electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0031] The ionizing radiation-curable resin composition may contain only one ionizing radiation-curable compound, or it may contain two or more. The type of ionizing radiation-curable compound is not particularly limited, and polymerizable monomers, polymerizable oligomers, and polymerizable prepolymers can be used. In this disclosure, from the viewpoint of reducing environmental impact, it is preferable that some or all of the ionizing radiation-curable compounds contained in the ionizing radiation-curable resin composition are derived from biomass.

[0032] The ionizing radiation-curable resin composition preferably contains a compound having two or more ethylenically unsaturated bonding groups as the ionizing radiation-curable compound. In particular, it is preferable to contain a polyfunctional (meth)acrylate compound having two or more ethylenically unsaturated bonding groups. In this disclosure, from the viewpoint of reducing environmental impact, it is preferable that some or all of the polyfunctional (meth)acrylate compound is derived from biomass.

[0033] Examples of biomass-derived polyfunctional (meth)acrylate compounds include biomass (meth)acrylate monomers and biomass (meth)acrylate oligomers. The ionizing radiation-curable resin composition preferably contains at least one of the above-mentioned biomass-derived curable compounds: biomass (meth)acrylate monomers and biomass (meth)acrylate oligomers. When the ionizing radiation-curable resin composition contains only biomass (meth)acrylate monomers, the molecular weight and viscosity of the ionizing radiation-curable resin composition before application can be reduced, thus improving coating properties even without solvents. On the other hand, when the ionizing radiation-curable resin composition contains only biomass (meth)acrylate monomers, there are limitations in the selection of biomass (meth)acrylate monomers to function as a protective layer, thus limiting the improvement of the biomass content of the first protective layer. When the ionizing radiation-curable resin composition contains both biomass (meth)acrylate monomers and biomass (meth)acrylate oligomers, the range of curable compounds can be broadened, further increasing the biomass content of the first protective layer.

[0034] The proportion of biomass (meth)acrylate oligomers to the total amount of biomass-derived polyfunctional (meth)acrylate compounds contained in the ionizing radiation-curable resin composition is, for example, 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more. On the other hand, the proportion of biomass (meth)acrylate oligomers is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. By keeping the proportion of oligomers within the above range, it is possible to suppress the increase in molecular weight and viscosity of the ionizing radiation-curable resin composition before coating, and to maintain appropriate penetration of the ionizing radiation-curable resin composition into the lower layer. By maintaining appropriate penetration into the lower layer, if the first protective layer composition contains particles, the tops of the particles become more visible, and a low gloss finish is easily achieved. In other words, by keeping the ratio of biomass (meth)acrylate oligomers to the total number of biomass-derived polyfunctional (meth)acrylate compounds within the above range, it becomes possible to achieve both a high biomass content and low gloss.

[0035] The ratio of biomass (meth)acrylate monomer to the biomass-derived polyfunctional (meth)acrylate compound contained in the ionizing radiation-curable resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more. By having the ratio of biomass (meth)acrylate monomer within the above range, the molecular weight and viscosity of the ionizing radiation-curable resin composition before application can be reduced, and the permeability of the ionizing radiation-curable resin composition to the lower layer can be appropriately maintained. For this reason, a low gloss finish is easily achieved. On the other hand, the ratio of biomass (meth)acrylate monomer may be 100% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less.

[0036] When the ionizing radiation-curable resin composition is a mixture of biomass (meth)acrylate monomer and biomass (meth)acrylate oligomer, for the reasons described above, the mass ratio of biomass (meth)acrylate monomer to biomass (meth)acrylate oligomer is preferably, for example, 100:0 or more and 50:50 or less.

[0037] The polyfunctional (meth)acrylate compounds may be difunctional (meth)acrylate monomers or trifunctional or more functional (meth)acrylate monomers. Examples of difunctional (meth)acrylate monomers include glycerin di(meth)acrylate, ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate. Examples of trifunctional or more functional (meth)acrylate monomers include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, isocyanuric acid modified tri(meth)acrylate, and diglycerin EO modified tetraacrylate.

[0038] Examples of polyfunctional (meth)acrylate oligomers include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and sorbitol EO (ethylene oxide) modified acrylate.

[0039] Urethane (meth)acrylate is obtained, for example, by a reaction of a polyhydric alcohol, an organic diisocyanate, and hydroxy (meth)acrylate. In the present disclosure, it is preferable that at least any one of the polyhydric alcohol, the organic diisocyanate, and the hydroxy (meth)acrylate is derived from biomass. Further, epoxy (meth)acrylate is obtained, for example, by a reaction of an epoxy resin and (meth)acrylic acid. In this case, it is preferable that at least any one of the epoxy resin and the (meth)acrylic acid is derived from biomass. In this reaction, at least one of a polybasic acid and a phenol may be further used. The epoxy resin may be difunctional, or may be trifunctional or higher functional. Further, examples of the epoxy resin include aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

[0040] As the biomass-derived polyfunctional (meth)acrylate-based compound, commercially available products can be used. For example, the ARONIX series manufactured by Toagosei Co., Ltd. can be used, and specific examples thereof include glycerin ditriacrylate (product number: M-930), diglycerin EO-modified tetraacrylate (product number: M-460), sorbitol EO-modified acrylate (product number: M-926), and glycerin diacrylate (product number: M-920).

[0041] When the ionizing radiation-curable compound is an ultraviolet-curable compound, the ionizing radiation-curable resin composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. Examples of the photopolymerization initiator include acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, and thioxanthone. Examples of the photopolymerization accelerator include isoamyl p-dimethylaminobenzoate and ethyl p-dimethylaminobenzoate.

[0042] On the other hand, the thermosetting resin composition may be a composition containing a thermosetting resin. This resin composition is cured by heating. In the present disclosure, it is preferable that part or all of the thermosetting resin is a biomass-derived thermosetting resin (curable compound). Examples of the thermosetting resin include acrylic resins, urethane resins, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. The thermosetting resin composition may optionally contain additives such as a curing agent and a curing catalyst.

[0043] The first protective layer may contain a resin other than biomass-derived resin, that is, a petroleum-derived resin. The proportion of the biomass-derived resin in the first protective layer is, for example, 70% by mass or more, may be 90% by mass or more, may be 95% by mass or more, and may be 100% by mass, relative to all resin components constituting the first protective layer. The petroleum-derived resin refers to, for example, a resin produced using only fossil fuel as a raw material.

[0044] (b) Particles The first protective layer contains particles. When the first protective layer contains particles, the particles form irregularities on the surface of the first protective layer, which enables imparting design with low gloss and tactile sensation. It is preferable that the first protective layer contains at least one of inorganic particles and organic particles as particles. Examples of the material of the inorganic particles include inorganic materials such as silica, alumina, zirconia, titania (titanium dioxide), kaolinite, calcium carbonate, and barium sulfate. On the other hand, examples of the material of the organic particles include resins such as (meth)acrylic resins, urethane resins, silicone resins, and amide resins.

[0045] In this disclosure, the average particle size C is not particularly limited as long as the ratio (C / T1) is within the range described above. For example, the average particle size C may be 3.0 μm or more and 9.0 μm or less, or 4.0 μm or more and 7.0 μm or less. Having the average particle size C within the above range makes it easier to adjust the ratio (C / T1) to the range described later. The average particle size C of the particles contained in the first protective layer is determined by measuring the particle sizes of multiple particles from a cross-sectional image taken using a scanning electron microscope (SEM) and taking the average value. It is preferable to have a large number of samples, for example, 100 or more.

[0046] The particle content in the first protective layer is preferably, for example, 10 parts by mass or more and 25 parts by mass or less, and more preferably 15 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of biomass-derived resin contained in the first protective layer. If the particle content is too low, it is difficult to obtain a good low gloss finish.

[0047] (c) The first protective layer of additives may further contain at least one of the following as additives: an antioxidant, a light stabilizer, an ultraviolet absorber, an antibacterial agent, an antiviral agent, or an anti-allergen agent.

[0048] (2) Biomass content The biomass content of the first protective layer is preferably 5% or more, more preferably 15% or more, and particularly preferably 20% or more, from the viewpoint of reducing environmental impact. On the other hand, the biomass content of the first protective layer may be, for example, 60% or less, 50% or less, 40% or less, or 30% or less. By having a biomass content of the first protective layer that is below the above values, the first protective layer can be formed without making significant changes from conventional materials and equipment.

[0049] In this specification, "biomass content" is the value obtained by measuring the amount of carbon derived from biomass using radiocarbon (C14) measurement. Since atmospheric carbon dioxide contains C14 at a certain percentage (105.5 pMC), it is known that the C14 content of plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. On the other hand, it is known that fossil fuels contain almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in the total carbon atoms in the first protective layer of this disclosure. That is, if the C14 content in the first protective layer of this disclosure is PC14, the biomass-derived carbon content Pbio can be determined as follows: Pbio (%) = (PC14 / 105.5) × 100

[0050] (3) Thickness The thickness T1 of the first protective layer is not particularly limited as long as the ratio (T1 / T2) is within the range described above. For example, the thickness T1 of the first protective layer may be 3.0 μm or more, or 3.5 μm or more. Having the thickness T1 of the first protective layer within the above range makes it easier to adjust the ratio (T1 / T2) within the above range, and also improves surface properties (scratch resistance and solvent resistance). On the other hand, having the thickness T1 of the first protective layer may be 8.0 μm or less, or 7.5 μm or less. Having the thickness T1 of the first protective layer within the above range makes it easier to adjust the ratio (T1 / T2) within the above range. In addition, the processability of the decorative sheet (for example, processability for wrapping and lamination) is improved, and leveling properties are improved when forming the coating film. In addition, the visibility of the design layer is improved, and the production cost of the decorative sheet can be reduced.

[0051] (4) Formation method A method for forming the first protective layer is, for example, a method in which a composition for the first protective layer obtained by mixing a curable resin composition containing a biomass-derived curable compound with particles, solvents and additives as needed is applied to the side of the design layer opposite to the base material layer, and is dried and cured as needed.

[0052] (5) The first protective layer may be a single layer or a laminate of two or more layers. In the latter case, the first protective layer may have two or more layers of the same type of constituent material, or two or more layers of different types of constituent material. The gloss of each layer may be the same or different. For example, as shown in Figure 3, the first protective layer 3 may be a laminate of an overall layer 31 formed over the entire surface when the decorative sheet is viewed in the thickness direction, and a pattern layer 32 formed in a pattern. In this case, it is preferable that the gloss of the pattern layer and the gloss of the overall layer are different. This makes it possible to obtain a three-dimensional effect (glossy matte feel) due to the difference in gloss levels. The gloss can be adjusted by the presence or absence of particles and the amount of particles.

[0053] As shown in Figure 3, it is preferable that the pattern of the pattern layer 32 is in harmony with the pattern in the design layer. "Harmony" means that the shapes and positions of the two patterns in question are roughly the same. Specifically, it means that the shapes and positions of the pattern of the pattern layer 32 and the patterns of at least some of the designs that make up the design layer are in harmony to the extent that it does not impair realism and a sense of luxury. This allows the design and the glossy-matte finish to be in harmony, and a visual sense of three-dimensionality can be obtained. For example, if the design of the design layer is a wood grain pattern, by making the gloss of the pattern layer 32 lower than the gloss of the overall layer 31 and harmonizing it with the pores of the design layer, a design that closely resembles real wood grain can be obtained.

[0054] 2. Substrate Layer The substrate layer in this disclosure is a layer that supports the design layer, the second protective layer, and the first protective layer. Examples of materials for the substrate layer include paper, resin, metal, non-metallic inorganic materials, etc. Among these, paper is preferred as the material for the substrate layer from the viewpoint of further increasing the biomass content of the entire decorative sheet and significantly reducing the environmental burden. Furthermore, paper substrates have the advantage of making it easier to obtain decorative sheets with lower gloss compared to resin substrates. In other words, paper substrates are preferred for the substrate layer.

[0055] In this disclosure, examples of paper used for the base layer include tissue paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, sulfuric acid paper, paraffin paper, parchment paper, glassine paper, wallpaper backing paper, cardboard, and gypsum board base paper. The above paper may be general paper or flame-retardant paper. Flame-retardant paper is paper that contains a flame retardant in general paper. Examples of flame retardants include nitrogen compounds such as urea and ammonium compounds, hydroxides (preferably hydrates) such as magnesium hydroxide and aluminum hydroxide, and flame retardants containing phosphorus or halogen elements that have self-extinguishing properties. Among these, compounds containing crystal water, such as magnesium hydroxide, can be made flame-retardant by the heat of vaporization of crystal water during combustion decomposition.

[0056] Examples of resins used in the base layer include synthetic resins and natural resins. Examples of synthetic resins include thermoplastic resins. Examples of thermoplastic resins include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as poly(meth)acrylate, poly(meth)acrylate ethyl, poly(meth)acrylate butyl, and (meth)acrylate-(meth)acrylate butyl copolymers; polyamide resins such as nylon 6 and nylon 66; cellulose resins such as cellulose triacetate, cellophane, and celluloid; and styrene resins such as polystyrene, acrylonitrile-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer (ABD). Other examples of thermoplastic resins include polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate resin, and polyimide resin. Among these, polyester resins are preferred due to their good scratch resistance, and polyethylene terephthalate and polybutylene terephthalate are particularly preferred. Furthermore, each of the above thermoplastic resins may be partially or entirely derived from biomass. This is because it is possible to further increase the biomass content of the entire decorative sheet and reduce the environmental impact. Examples of natural resins include natural rubber, pine resin, and amber.

[0057] Examples of metals that can be used for the base layer include aluminum, aluminum alloys (e.g., duralumin), iron, iron alloys (e.g., carbon steel, stainless steel), copper, copper alloys (e.g., brass, bronze), gold, silver, chromium, nickel, cobalt, tin, and titanium. The surface of the metal may also be plated.

[0058] Examples of non-metallic inorganic materials used in the base layer include non-ceramic ceramic materials such as cement, ALC (autoclaved lightweight concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramic materials such as pottery, earthenware, glass, and enamel; and natural stones such as limestone (including marble), granite, andesite.

[0059] Other examples of materials for the base layer include woven fabrics and nonwoven fabrics. Fibers used in woven or nonwoven fabrics include, for example, resin fibers (e.g., polyester resin fibers, acrylic resin fibers), natural fibers (e.g., silk, cotton, linen), glass fibers, and carbon fibers. When a fibrous material is used for the base layer, resins such as acrylic resins, styrene-butadiene rubber, melamine resins, and urethane resins may be added (resin impregnation after papermaking, or resin filling during papermaking). The base layer may also be a wallpaper base roll in which a resin layer such as a vinyl chloride resin layer, an olefin resin layer, or an acrylic resin layer is laminated on the surface of wallpaper backing paper.

[0060] The base layer may contain additives such as flame retardants, inorganic agents, dry strength enhancers, wet strength enhancers, colorants, sizing agents, and fixing agents, as needed. The base layer may also be surface-treated, for example, to improve adhesion. Examples of surface treatments include oxidation and embossing. Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone-ultraviolet treatment. Examples of embossing methods include sandblasting and solvent treatment.

[0061] The base layer may be a single layer or a laminate of two or more layers. In the latter case, the base layer may have two or more layers of the same type of constituent material, or it may have two or more layers of different types of constituent material.

[0062] The shape of the base layer can be, for example, a sheet. The thickness of the base layer is not particularly limited, but for example, it is 10 μm or more and 300 μm or less. The basis weight of the base layer is not particularly limited, but for example, it is 25 g / m². ２ More than 300g / m ２ The following applies: 40 g / m ２ 160g / m or more２ The following is also acceptable.

[0063] 3. Design Layer The design layer is placed between the base material layer and the second protective layer. When the decorative sheet is viewed in plan in the thickness direction, the design layer may be placed over the entire surface of the decorative sheet or on a part of the decorative sheet.

[0064] The design layer includes, for example, at least one of a solid layer (a layer with solid ink coverage) and a pattern layer (a layer with printed ink). The decorative sheet may have both a solid layer and a pattern layer as its design layer.

[0065] A solid color layer can be formed on the surface of the base layer to even out the color, especially when the base layer itself is colored or has color unevenness, thereby giving the base layer the desired color. Furthermore, the placement of a solid color layer can improve the adhesion between the pattern layer and the base layer. The solid color layer may be opaque or colored transparent. A solid color layer may not be necessary if the base layer's color is utilized or if the base layer itself is appropriately colored. On the other hand, if the base layer is paper, it is preferable to include a solid color layer because it improves the oil and water resistance of the paper base material.

[0066] The ink used to form a solid layer typically consists of a binder mixed with colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, and curing agents as appropriate. In other words, the solid layer usually contains colorants and binder resin. The solid layer may also contain fillers.

[0067] Examples of binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-acrylic copolymers, chlorinated propylene resins, nitrocellulose resins, and cellulose acetate resins.

[0068] Examples of colorants include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, lead yellow, titanium yellow, reddish-brown, cadmium red, ultramarine, and cobalt blue; organic pigments (including dyes) such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azoblack; metallic pigments such as aluminum and brass; and pearl pigments such as titanium dioxide-coated mica and basic lead carbonate.

[0069] Examples of fillers include those of the same type as the particles in the first protective layer.

[0070] The pattern layer adds decorative properties to the base layer and is formed by printing various patterns using ink and a printing press. Examples of patterns in the pattern layer include wood grain, stone, sand, tile, brickwork, fabric, leather, geometric figures, letters, symbols, abstract patterns, and floral patterns. The ink used to form the pattern layer is the same as the ink used to form the solid color layer.

[0071] From the viewpoint of improving the visual sense of unevenness due to the difference in gloss, the pattern layer is preferably less glossy than the surrounding area. When a wood grain pattern is used as the pattern for the decorative sheet, the wood grain pattern has areas such as the vascular area which is less glossy, the springwood area which is more glossy, and the autumnwood area (shiny area) which is even more glossy. For example, the vascular area which is less glossy may be formed with a relatively less glossy pattern layer, and the wood grain area which is more glossy, specifically the springwood area, the autumnwood area, or both the springwood and autumnwood areas may be formed with a solid layer.

[0072] The thickness of the design layer is, for example, 0.5 μm or more and 20 μm or less, and may be 1 μm or more and 10 μm or less, or 2 μm or more and 5 μm or less. If the design layer includes both a solid layer and a patterned layer, the thickness of the design layer refers to the total thickness.

[0073] One method for forming the design layer is to apply an ink containing a colorant, a binder resin, and a solvent, and then dry it. An example of a coating method is gravure printing.

[0074] 4. Second Protective Layer The decorative sheet in this disclosure has a second protective layer between the design layer and the first protective layer. When the decorative sheet is viewed in plan in the thickness direction, it is preferable that the second protective layer is arranged over the entire surface of the decorative sheet. By arranging the second protective layer, the reduction in surface properties caused by the first protective layer alone can be compensated for, and the surface properties of the decorative sheet (e.g., scratch resistance and solvent resistance) can be improved. The second protective layer contributes to improving the adhesion between the first protective layer and the design layer. Furthermore, by setting the thickness T2 of the second protective layer to a thickness such that the above ratio (T1 / T2) is within the above range, the penetration of the resin material of the first protective layer into the lower layer can be appropriately adjusted, resulting in a decorative sheet with good low gloss and suppressed gloss unevenness. Furthermore, the second protective layer and the first protective layer may be arranged in direct contact, or they may be arranged via other layers.

[0075] The second protective layer contains, for example, a resin component. Preferred resin components include, for example, acrylic resin, urethane resin, acrylic polyol resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate bond in the polymer main chain and two or more hydroxyl groups in the terminals and side chains), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin (nitrified cotton), and cellulose acetate resin. These can be used individually or in combination. Furthermore, the resin component may be obtained by adding a curing agent such as an isocyanate-based curing agent to these resins and then crosslinking and curing them. Among these, a polyol-based resin such as acrylic polyol resin crosslinked and cured with an isocyanate-based curing agent is preferred, and an acrylic polyol resin crosslinked and cured with an isocyanate-based curing agent is more preferred.

[0076] The thickness of the second protective layer is not particularly limited as long as the ratio (T1 / T2) is within the range described above. The thickness T2 of the second protective layer may be, for example, 1.0 μm or more, or 1.5 μm or more. Having the thickness T2 of the second protective layer within the above range makes it easier to adjust the ratio (T1 / T2) within the above range and improves surface properties (scratch resistance and solvent resistance). On the other hand, the thickness T2 of the second protective layer may be, for example, 5.0 μm or less, or 4.0 μm or less. Having the thickness T2 of the second protective layer within the above range makes it easier to adjust the ratio (T1 / T2) within the above range and also reduces the production cost of the decorative sheet.

[0077] The second protective layer may contain particles. Examples of particle types include those similar to those in the first protective layer. The second protective layer may further contain at least one of the following as an additive: an antioxidant, a light stabilizer, an ultraviolet absorber, an antibacterial agent, an antiviral agent, or an anti-allergen agent.

[0078] 5. The low-gloss patterned decorative sheet preferably has a patterned low-gloss patterned layer between the first protective layer and the second protective layer. The low-gloss patterned layer is preferably positioned on the side of the second protective layer opposite to the design layer. The low-gloss patterned layer is a layer that creates a partial difference in gloss on the decorative sheet. When the decorative sheet has a low-gloss patterned layer, when the decorative sheet is viewed from the first protective layer side, the parts where the low-gloss patterned layer exists are represented as relatively low-gloss regions (low-gloss areas), and the parts where the low-gloss patterned layer does not exist are represented as relatively high-gloss regions (high-gloss areas). The low-gloss areas appear to the observer as recesses, and the high-gloss areas appear to the observer as convex parts. This makes it possible to create a decorative sheet with a visually uneven surface.

[0079] When a first protective layer composition containing a resin material (e.g., a curable resin composition) and particles is applied onto a low-gloss pattern layer, the resin material of the first protective layer composition penetrates the low-gloss pattern layer, and the particles remaining directly above the low-gloss pattern layer become exposed. As a result, it is presumed that irregularities are formed on the surface directly above and near the low-gloss pattern layer, and a low-gloss region is created.

[0080] When viewed from the thickness direction of the decorative sheet, it is preferable that the low-gloss pattern layer is arranged to cover an area of ​​1% to 50% of the base layer. By covering the above area range with the low-gloss pattern layer, a visually good gloss-matt appearance can be obtained.

[0081] From the viewpoint of obtaining a low-gloss region, it is preferable that the curable resin composition forming the first protective layer has high permeability to the low-gloss pattern layer. The low-gloss pattern ink for forming the low-gloss pattern layer preferably contains a urethane resin or a polyvinyl acetal resin as a binder resin. The content of the above urethane resin or polyvinyl acetal resin in the low-gloss pattern ink is preferably 50% by mass or more. Among the urethane resins, thermoplastic (non-crosslinkable) urethane resins such as polyester urethane resins are preferred.

[0082] As the thermoplastic (non-crosslinkable) urethane resin, it is preferable to select a non-crosslinked type, that is, a thermoplastic resin having a linear molecular structure rather than a three-dimensional crosslinked, network-like three-dimensional molecular structure. Such a non-crosslinked urethane resin is, for example, a urethane resin obtained by reacting a polyol component with an isocyanate component. Examples of polyol components include acrylic polyols, polyester polyols, and polyether polyols. Examples of isocyanate components include aromatic isocyanates such as tolylene diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate, and aliphatic or alicyclic isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated tolylene diisocyanate. It is preferable that the average number of hydroxyl groups in one polyol molecule and the average number of isocyanate groups in one isocyanate molecule are both 2. Furthermore, the average molecular weight of the urethane resin is preferably, for example, around 10,000 to 50,000, and the glass transition temperature (Tg) is preferably, for example, around -70 to -40°C, for the expression of the interaction region.

[0083] Polyvinyl acetal resins are obtained by the condensation (acetalization) of polyvinyl alcohol and aldehydes. Examples of polyvinyl acetal resins include polyvinyl formal (formal resin), polyvinyl acetal, polyvinyl propional, polyvinyl butyral (butyral resin), and polyvinyl hexyral. Polyvinyl butyral is particularly preferred because it is soluble in solvents, easily formed into inks, and exhibits good visual texture (visually recognized as recessed areas).

[0084] Furthermore, the low-gloss pattern ink may be mixed with unsaturated polyester resin, acrylic resin, or vinyl chloride-vinyl acetate copolymer, as needed, to adjust the degree of low-gloss areas and the contrast of gloss between the low-gloss areas and their surroundings. It is preferable that the low-gloss pattern ink does not contain a curing agent.

[0085] The low-gloss pattern layer may or may not contain a coloring agent. The coloring agent may be of the same type as that used in the design layer.

[0086] Low-gloss pattern inks preferably contain extender pigments. This is because the addition of extender pigments promotes light scattering, further enhancing the low-gloss effect. While there are no particular limitations on the extender pigments, examples include silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, and magnesium carbonate. Among these, silica is preferred because it offers a high degree of freedom in material design, such as oil absorption, particle size, and pore volume, and is excellent in terms of design, whiteness, and ink application stability. Finely powdered silica is particularly preferred. The average particle size of the extender pigment is, for example, 0.1 μm to 5 μm. The content of the extender pigment in the low-gloss pattern ink is preferably 5% to 15% by mass. By keeping the content within this range, sufficient thixotropy is imparted to the low-gloss pattern ink while maintaining an appropriate viscosity, thereby suppressing a decrease in the productivity of the low-gloss pattern layer and deterioration of the surface properties of the low-gloss pattern layer.

[0087] The thickness of the low-gloss pattern layer is not particularly limited, but is preferably between 0.5 μm and 8.0 μm. A thickness of the low-gloss pattern layer greater than or equal to the above value makes it easier to achieve sufficient gloss difference on the surface of the decorative sheet. On the other hand, a thickness of the low-gloss pattern layer less than or equal to the above value eliminates mechanical constraints when printing the low-gloss pattern ink and is also economically advantageous.

[0088] When the design layer has a pattern layer, a pattern with visual recesses due to the difference in gloss can be obtained by matching the parts of the pattern layer's design where gloss is to be reduced to create a visually recessed appearance with a low-gloss pattern layer. For example, when the design layer has a wood grain pattern layer, a pattern can be obtained where the wood grain pores appear visually recessed due to the difference in gloss by matching the low-gloss pattern layer with the wood grain pores.

[0089] 6. Other Layers (1) Back Adhesive Layer The decorative sheet in this disclosure may have a back adhesive layer on the side of the base layer opposite to the design layer. The back adhesive layer is, for example, a component for attaching the decorative sheet to a substrate. The back adhesive layer may be transparent or opaque.

[0090] Examples of adhesives used for the back adhesive layer include curing-type adhesives and pressure-sensitive adhesives. Specific examples include urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, and rubber-based adhesives. Furthermore, OCA (Optically Clear Adhesive) or OCR (Optically Clear Resin) can also be used as the back adhesive layer.

[0091] From the viewpoint of efficiently obtaining the desired adhesive strength, the thickness of the back adhesive layer is, for example, 5 μm to 100 μm, may be 10 μm to 75 μm, or 20 μm to 50 μm. Methods for forming the back adhesive layer include, for example, applying an adhesive composition or laminating an adhesive film by dry lamination.

[0092] (2) In addition, it is preferable that the decorative sheet in this disclosure does not have a transparent resin layer between the base layer and the first protective layer. Generally, decorative sheets may have a relatively thick layer (for example, 20 μm or more) of transparent resin layer in order to improve strength. In this disclosure, by not having a transparent resin layer in the decorative sheet, the number of layers constituting the decorative sheet can be reduced, and manufacturing costs can be reduced. Furthermore, the biomass content of the decorative sheet as a whole can be increased.

[0093] 7. Decorative Sheet (1) Biomass Content The decorative sheet in this disclosure has a first protective layer containing the biomass-derived resin described above, so the biomass content of the decorative sheet as a whole is, for example, 0.5% or more. Furthermore, in this disclosure, the biomass content of the decorative sheet as a whole can be further improved by using a paper substrate as the base layer, or, if the base layer is a resin substrate, by replacing part or all of the resin contained in the base layer with a biomass-derived resin. For example, the biomass content of the decorative sheet as a whole can be, for example, 5.0% or more. In particular, when a paper substrate is used as the base layer, the biomass content of the decorative sheet as a whole can be 50% or more.

[0094] (2) Gloss Value The decorative sheet in this disclosure can exhibit a low gloss on the surface facing the first protective layer. The 60° gloss value of the surface facing the first protective layer of the decorative sheet is preferably 10.0 or less, and more preferably 9.0 or less. On the other hand, the 60° gloss value of the surface facing the first protective layer of the decorative sheet may be, for example, 4.0 or more, and may also be 5.0 or more.

[0095] The 75° gloss value of the surface of the decorative sheet on the first protective layer side is preferably 22.0 or less, and more preferably 20.0 or less. On the other hand, the 75° gloss value of the surface of the decorative sheet on the first protective layer side may be, for example, 5.0 or more, and may also be 10.0 or more.

[0096] In this specification, the 60° gloss value refers to the 60° specular gloss as defined in "Method 3" of JIS Z 8741:1997. The 75° gloss value refers to the 75° specular gloss measured in "Method 2" of JIS Z 8741:1997. The 60° gloss value and the 75° gloss value are measured using a gloss meter. For example, a gloss meter GMX-203 (measuring angle 60° or 75°) manufactured by Murakami Color Technology Laboratory Co., Ltd. may be used. The average of the measured values ​​at any 10 locations on the surface of the first protective layer side of the decorative sheet is taken as the 60° gloss value or 75° gloss value of the surface of the first protective layer side of the decorative sheet. If the decorative sheet has the low-gloss pattern layer described above, the 10 arbitrary measurement locations may or may not include the area where the low-gloss pattern layer exists.

[0097] (3) Other decorative sheets may have an embossed pattern on the outermost surface on the side of the first protective layer relative to the base material layer. In particular, it is preferable that the embossed pattern is arranged on the side of the first protective layer opposite to the base material layer. Examples of embossed patterns include wood grain grooves, stone surface irregularities, fabric surface texture, pearlescent finish, sand texture, hairline finish, and fine grooves. An example of a method for forming an embossed pattern is to heat the decorative sheet and press an embossing plate onto it.

[0098] B. Decorative Members The decorative member in this disclosure comprises a member to be adhered to and the decorative sheet described above. Figure 4 is a schematic cross-sectional view illustrating a decorative member in this disclosure. The decorative member 100 shown in Figure 4 comprises a member to be adhered to 50, an adhesive layer 40, and the decorative sheet 10 described above, in this order. As shown in Figure 4, the first protective layer 3 of the decorative sheet 10 constitutes the outermost layer of the decorative member 100. The decorative sheet 10 is arranged so that the surface facing the base material layer 1 faces the member to be adhered to 50.

[0099] According to this disclosure, the decorative sheet described above makes it a decorative component that can reduce environmental impact.

[0100] 1. Decorative Sheets The decorative sheets in this disclosure are the same as those described in "A. Decorative Sheets" above.

[0101] 2. Adhered Member The adhered member in this disclosure is a member that is decorated with a decorative sheet. Examples of adhered members include resin members, wood members, metal members, ceramic members, etc. The shape of the adhered member is not particularly limited and examples include plate-shaped, sheet-shaped, and three-dimensional shapes.

[0102] 3. Adhesive Layer The decorative member in this disclosure may have an adhesive layer between the adherend and the decorative sheet. As the adhesive layer disposed between the adherend and the decorative sheet, for example, an adhesive conventionally known as an adhesive for the decorative sheet can be used. Furthermore, if the decorative sheet has the above-mentioned back adhesive layer, the decorative sheet and the adherend may be in direct contact.

[0103] 4. Decorative Members The decorative members in this disclosure comprise the decorative sheet and adherend described above. The uses of the decorative members in this disclosure are not particularly limited, but examples include building components such as walls, ceilings, floors, roofs, eaves, fences, and gates; joinery or construction components such as window frames, doors, handrails, baseboards, moldings, and trim; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; various furniture used in wet areas such as kitchens, toilets, bathrooms, and washbasins; surface decorative panels for cabinets of home appliances, office automation equipment, etc.; and interior or exterior components for vehicles. Furthermore, the decorative materials in this disclosure may be components used outdoors (exterior components) or components used indoors (interior components).

[0104] The decorative member in this disclosure can be obtained, for example, by laminating a decorative sheet and an adherend. Specifically, the surface of the adherend (the surface requiring decoration) and the surface of the decorative sheet facing the base material layer are laminated together. Examples of methods for laminating the adherend and the decorative sheet include lamination, wrapping, and vacuum forming.

[0105] This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and achieves similar effects is included within the technical scope of this disclosure.

[0106] [Example 1] Paper substrate "CHPS (product number)", manufactured by TENTOKU Co., Ltd., basis weight: 45 g / m² ２ Next, a solid color layer was formed on the paper substrate using gravure printing with an ink for forming a solid color layer. Then, a pattern layer with a wood grain design was formed on the solid color layer using gravure printing with an ink for forming a pattern layer. In this way, a design layer having a solid color layer and a pattern layer was formed on the paper substrate.

[0107] The second protective layer ink was prepared by mixing the main ink, hardener, and diluent solvent listed below in a ratio of 100 / 15 / 40 (by mass). The second protective layer ink was applied to the image layer by gravure printing and dried (second protective layer ink layer). At this time, the plate depth was adjusted so that the thickness of the second protective layer was the value shown in Table 1. <Components of the second protective layer ink> ・Main ink Solid resin: Acrylic polyol 20% by mass Particles: Silica 10% by mass Solvent: MEK / Ethyl acetate / Butyl acetate = 5% by mass / 45% by mass / 20% by mass ・Hardener Polyisocyanate (HDI) / Ethyl acetate = 75% by mass / 25% by mass ・Diluent solvent Ethyl acetate

[0108] Next, the first protective layer composition 1, having the composition described below, was applied to the ink layer for the second protective layer by gravure printing. At this time, the plate depth was adjusted so that the thickness of the first protective layer was the value shown in Table 1. Next, it was dried by passing it through an 80°C drying oven for 3 seconds. After that, the first protective layer was formed and a laminate was produced by curing it under the conditions of a speed of 120 m / min, an irradiation dose of 120 kV, and 3 Mrad. The obtained laminate was placed in a 70°C oven to cure the second protective layer, and after 24 hours the laminate was removed from the oven to obtain a decorative sheet. The biomass content of the first protective layer was 10%.

[0109] <Composition 1 for the first protective layer> - Ionizing radiation-curable resin composition: Biomass-derived acrylate monomer (glycerin triacrylate "Aronics M-930" (molecular weight: 348, manufactured by Toagosei Co., Ltd.)) 100 parts by mass - Particles: Silica (average particle size 7 μm) 20 parts by mass - Solvent: None

[0110] [Examples 2 to 4] Decorative sheets were obtained in the same manner as in Example 1, except that the thickness of the second protective layer was set to the thickness shown in Table 1, and a first protective layer having the thickness shown in Table 1 was formed using the first protective layer composition 2 having the composition described below. The biomass content of the first protective layer was 20%.

[0111] <Composition 2 for the first protective layer> - Ionizing radiation-curable resin composition: Biomass-derived acrylate monomer (glycerin triacrylate "Aronics M-930" (molecular weight: 348, manufactured by Toagosei Co., Ltd.)) 80 parts by mass Biomass-derived acrylate oligomer ((bifunctional urethane acrylate "ART RESIN STQI-037PR" (weight-average molecular weight 4000, manufactured by Negami Kogyo Co., Ltd.)) 20 parts by mass Particles: Silica (average particle size 7 μm) 20 parts by mass Solvent: Ethyl acetate 5 parts by mass

[0112] [Example 5] A decorative sheet was obtained in the same manner as in Example 1, except that a biaxially oriented PET film ("Diafoil," manufactured by Mitsubishi Plastics, Inc.) with a thickness of 75 μm was used as the base material, and the first protective layer was formed using the first protective layer composition 2 described above. The biomass content of the first protective layer was 20%.

[0113] [Example 6] A decorative sheet was obtained in the same manner as in Example 1, except that a biaxially oriented PET film ("Diafoil," manufactured by Mitsubishi Plastics, Inc.) with a thickness of 75 μm was used as the base material, the thickness of the second protective layer was set to the thickness shown in Table 1, and a first protective layer having the thickness shown in Table 1 was formed using the first protective layer composition 3 having the composition described below. The biomass content of the first protective layer was 10%.

[0114] <Composition 3 for the first protective layer> - Ionizing radiation-curable resin composition: Biomass-derived acrylate monomer (glycerin triacrylate "Aronics M-930" (molecular weight: 348, manufactured by Toagosei Co., Ltd.)) 100 parts by mass - Particles: Silica (average particle size 4 μm) 20 parts by mass - Solvent: None

[0115] [Example 7] A decorative sheet was obtained in the same manner as in Example 1, except that the thickness of the second protective layer was set to the thickness shown in Table 1, and a first protective layer having the thickness shown in Table 1 was formed using the first protective layer composition 3 described above. The biomass content of the first protective layer was 10%.

[0116] [Examples 8-9, Comparative Example 1] A decorative sheet was obtained in the same manner as in Example 1, except that the thickness of the second protective layer was set to the thickness shown in Table 1, and a first protective layer having the thickness shown in Table 1 was formed using the first protective layer composition 2 described above. The biomass content of the first protective layer was 20%.

[0117] [Comparative Example 2] A decorative sheet was obtained in the same manner as in Example 1, except that the second protective layer was not formed, and a first protective layer having the thickness shown in Table 1 was formed on the pattern layer using the first protective layer composition 2 described above. The biomass content of the first protective layer was 20%.

[0118] [Comparative Example 3] A decorative sheet was obtained in the same manner as in Example 1, except that the thickness of the second protective layer was set to the thickness shown in Table 1, and a first protective layer having the thickness shown in Table 1 was formed using the first protective layer composition 3 described above. The biomass content of the first protective layer was 10%.

[0119] [Comparative Example 4] A decorative sheet was obtained in the same manner as in Example 1, except that the thickness of the second protective layer was set to the thickness shown in Table 1, and a first protective layer having the thickness shown in Table 1 was formed using the first protective layer composition 4 having the composition described below. The biomass content of the first protective layer was 10%. <First protective layer composition 4> ・Ionizing radiation-curable resin composition: Biomass-derived acrylate monomer (glycerin triacrylate "Aronics M-930" (molecular weight: 348, manufactured by Toagosei Co., Ltd.)) 100 parts by mass ・Particles: Silica (average particle size 11 μm) 20 parts by mass ・Solvent: None

[0120] [Reference Example 1] A decorative sheet was obtained in the same manner as in Example 1, except that the thickness of the second protective layer was changed to the thickness shown in Table 1, and the first protective layer having the thickness shown in Table 1 was formed using First Protective Layer Composition 5 having the following composition. The biomass content of the first protective layer was 0%. <First Protective Layer Composition 5> ・Ionizing radiation curable resin composition: petroleum-derived acrylate monomer (polyethylene glycol diacrylate "PEG200 diacrylate" (molecular weight: 300, manufactured by Daicel-Allnex Co., Ltd.)) 100 parts by mass ・Particles: silica (average particle diameter 7 µm) 20 parts by mass ・Solvent: none

[0121] [Reference Example 2] A decorative sheet was obtained in the same manner as in Example 1, except that the thickness of the second protective layer was changed to the thickness shown in Table 1, and the first protective layer having the thickness shown in Table 1 was formed using First Protective Layer Composition 6 having the following composition. The biomass content of the first protective layer was 0%. <First Protective Layer Composition 6> ・Ionizing radiation curable resin composition: petroleum-derived acrylate monomer (polyethylene glycol diacrylate "PEG200 diacrylate" (molecular weight: 300, manufactured by Daicel-Allnex Co., Ltd.)) 100 parts by mass ・Particles: silica (average particle diameter 11 µm) 20 parts by mass ・Solvent: none

[0122] [Gloss Unevenness Evaluation] The obtained decorative sheet was visually observed from the first protective layer side, and evaluated according to the following evaluation criteria. ・Evaluation criteria AA: No defective defects such as gloss unevenness were observed, and the quality is good. A: Although slight defective defects such as gloss unevenness are present, there is no problem in terms of quality. B: There are relatively many defective defects such as gloss unevenness, and improvement in quality is required. C: There are a large number of defective defects such as gloss unevenness, and improvement in quality is required.

[0123] [Solvent Resistance Evaluation] Solvent resistance evaluation was performed on the obtained decorative sheet by the following method. A gauze impregnated with a methyl ethyl ketone solvent was wrapped around one surface of a columnar weight, and the weight was rubbed back and forth 100 times with the gauze-wrapped surface in contact with the surface on the first protective layer side of the decorative sheet (load 200 g / cm ２). The 60° gloss value of the rubbing portion before and after the test was measured using the method described above, and the gloss change rate (%) was calculated using the following formula and evaluated according to the following evaluation criteria. Gloss change rate (%) = (Gloss value after test / Gloss value before test) × 100 (%) ・Evaluation criteria AA: No change in gloss (Gloss change rate: 100% or more and less than 105%) A: Slight change in gloss (Gloss change rate: 105% or more and less than 115%) B: Moderate change in gloss (Gloss change rate: 115% or more and less than 120%) C: Large change in gloss (Gloss change rate: 120% or more)

[0124] [Scratch Resistance Evaluation] The scratch resistance of the obtained decorative sheet was evaluated using the following method. Donster steel wool (#0000) was wrapped around one side of a cylindrical weight, and with the wrapped side in contact with the surface of the first protective layer of the decorative sheet, the weight was rubbed back and forth 50 times (load 200 g / cm). ２ ). The 60° gloss value of the rubbing portion before and after the test was measured using the method described above, and the gloss change rate (%) was calculated using the following formula and evaluated according to the following evaluation criteria. Gloss change rate (%) = (Gloss value after test / Gloss value before test) × 100 (%) ・Evaluation criteria AA: No change in gloss (Gloss change rate: 100% or more and less than 105%) A: Slight change in gloss (Gloss change rate: 105% or more and less than 115%) B: Moderate change in gloss (Gloss change rate: 115% or more and less than 120%) C: Large change in gloss (Gloss change rate: 120% or more)

[0125]

[0126]

[0127] As shown in Table 1, in all examples, the composition for the first protective layer contained a biomass-derived monomer or biomass-derived oligomer, resulting in a decorative sheet containing a biomass-derived resin, which is expected to reduce environmental impact. As shown in Table 2, when T1 / T2 was too large, uneven gloss occurred (Comparative Examples 1 and 4). This is presumed to be because the thickness of the second protective layer was too thin, causing the curable resin composition of the first protective layer composition to penetrate excessively into the lower layer. Furthermore, the decorative sheet without the second protective layer had poor surface properties (solvent resistance and scratch resistance) and also exhibited uneven gloss (Comparative Example 2). Also, when C / T1 was too high and T1 / T2 was too low, scratch resistance decreased (Comparative Example 3). For example, as in Reference Examples 1 and 2, it was confirmed that the gloss of the decorative sheet decreased to some extent when the first protective layer did not contain a biomass-derived resin.

[0128] Thus, the present disclosure provides, for example, the following inventions.

[0129] [1] A decorative sheet having a base layer, a design layer, a second protective layer, and a first protective layer in this order in the thickness direction, wherein the first protective layer contains a biomass-derived resin and particles, the ratio of the thickness T1 of the first protective layer to the thickness T2 of the second protective layer (T1 / T2) is 1.0 or more and 7.0 or less, and the ratio of the average particle size C of the particles to the thickness T1 of the first protective layer (C / T1) is 0.7 or more and 1.8 or less. [2] The decorative sheet according to [1], wherein the particles are at least one of inorganic particles and resin particles. [3] The decorative sheet according to [1] or [2], wherein the 60° gloss value of the surface of the decorative sheet on the first protective layer side is 4.0 or more and 10.0 or less, and the 75° gloss value of the surface of the decorative sheet on the first protective layer side is 5.0 or more and 22.0 or less. [4] The decorative sheet according to any one of [1] to [3], wherein the base layer is a paper base or a polyester base. [5] The decorative sheet according to any one of [1] to [4], wherein the first protective layer comprises a cured product of an ionizing radiation-curable resin composition containing a biomass-derived curable compound. [6] The decorative sheet according to [5], wherein the ionizing radiation-curable resin composition comprises at least one of a biomass (meth)acrylate monomer and a biomass (meth)acrylate oligomer as the biomass-derived curable compound. [7] The decorative sheet according to [6], wherein the mass ratio of the biomass (meth)acrylate monomer to the biomass (meth)acrylate oligomer in the ionizing radiation-curable resin composition is 100:0 or more and 50:50 or less. [8] The decorative sheet according to any one of [1] to [7], wherein the average particle size C of the particles is 3.0 μm or more and 9.0 μm or less. [9] The decorative sheet according to any one of [1] to [8], wherein the thickness T1 of the first protective layer is 3.0 μm or more and 8.0 μm or less.

[10] The decorative sheet according to any one of [1] to [9], wherein the thickness T2 of the second protective layer is 1.0 μm or more and 5.0 μm or less.

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

[10] , wherein the content of the particles in the first protective layer is 10 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the resin in the first protective layer.

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

[11] , wherein the decorative sheet has a low-gloss pattern layer between the second protective layer and the first protective layer.

[13] The decorative sheet according to

[12] , wherein the design layer comprises a pattern layer having a pattern, and the low-gloss pattern layer is arranged according to the pattern when viewed from the thickness direction.

[14] A decorative member comprising a adherend and the decorative sheet according to any one of [1] to

[13] .

[0130] 1...Base layer 2...Design layer 21...Pattern layer 22...Solid layer 3...First protective layer 4...Second protective layer 5...Low-gloss pattern layer 10...Decorative sheet 50...Adhered material 100...Decorative material

Claims

1. A decorative sheet having a base layer, a design layer, a second protective layer, and a first protective layer in this order in the thickness direction, wherein the first protective layer contains a biomass-derived resin and particles, the ratio of the thickness T1 of the first protective layer to the thickness T2 of the second protective layer (T1 / T2) is 1.0 or more and 7.0 or less, and the ratio of the average particle size C of the particles to the thickness T1 of the first protective layer (C / T1) is 0.7 or more and 1.8 or less.

2. The decorative sheet according to claim 1, wherein the particles are at least one of inorganic particles and resin particles.

3. The decorative sheet according to claim 1, wherein the 60° gloss value of the surface of the decorative sheet on the first protective layer side is 4.0 or more and 10.0 or less, and the 75° gloss value of the surface of the decorative sheet on the first protective layer side is 5.0 or more and 22.0 or less.

4. The decorative sheet according to claim 1, wherein the base material layer is a paper base material or a polyester base material.

5. The decorative sheet according to claim 1, wherein the first protective layer comprises a cured product of an ionizing radiation-curable resin composition containing a biomass-derived curable compound.

6. The decorative sheet according to claim 5, wherein the ionizing radiation-curable resin composition comprises at least one of a biomass (meth)acrylate monomer and a biomass (meth)acrylate oligomer as the biomass-derived curable compound.

7. The decorative sheet according to claim 6, wherein the mass ratio of the biomass (meth)acrylate monomer to the biomass (meth)acrylate oligomer in the ionizing radiation-curable resin composition is 100:0 or more and 50:50 or less.

8. The decorative sheet according to claim 1, wherein the average particle size C of the particles is 3.0 μm or more and 9.0 μm or less.

9. The decorative sheet according to claim 1, wherein the thickness T1 of the first protective layer is 3.0 μm or more and 8.0 μm or less.

10. The decorative sheet according to claim 1, wherein the thickness T2 of the second protective layer is 1.0 μm or more and 5.0 μm or less.

11. The decorative sheet according to claim 1, wherein the content of the particles in the first protective layer is 10 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the resin in the first protective layer.

12. The decorative sheet according to claim 1, wherein the decorative sheet has a low-gloss pattern layer between the second protective layer and the first protective layer.

13. The decorative sheet according to claim 12, wherein the design layer comprises a pattern layer having a pattern, and the low-gloss pattern layer is arranged according to the pattern when viewed from the thickness direction.

14. A decorative member comprising a member to be adhered to and a decorative sheet according to any one of claims 1 to 13.

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