Decorative sheets and decorative materials

Abstract

The present invention provides decorative sheets and decorative materials that can suppress a decrease in surface hardness and flexibility, even when formed using plant-derived polyolefin resin. [Solution] A colored base layer 2, a pattern layer 3, an adhesive resin layer 4, and a transparent resin layer 5 are laminated in this order to form the structure. The colored base layer 2 and the transparent resin layer 5 are each formed using a resin composition containing a plant-derived polyolefin resin, and the transparent resin layer 5 has a Martens hardness HM of 30 N / mm² in the cross-sectional direction. 2 More than 60N / mm 2 The following range was used. As a result, the surface hardness of the decorative sheet 1 can be improved, and the suitability for bending can also be improved.

Description

Technical Field

[0001] The present invention relates to a cosmetic sheet and a cosmetic material.

Background Art

[0002] As a cosmetic sheet replacing a cosmetic sheet made of polyvinyl chloride, for example, as disclosed in Patent Document 1, a cosmetic sheet using an olefin resin has been proposed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In recent years, due to environmental issues, the substitution with biomass plastics has attracted attention. In the field of cosmetic sheets, it is desired to reduce the use amount of fossil fuels by substituting raw materials derived from biomass for conventional petroleum-derived materials. As plant-derived materials that can be used for cosmetic sheets, biomass polyethylene and the like can be mentioned. However, this biomass polyethylene has a problem in that it tends to be inferior in terms of surface hardness and bending processability compared to polypropylene, which has been conventionally used as a material for cosmetic sheets.

[0005] The present invention has been made in view of such points, and an object thereof is to provide a cosmetic sheet and a cosmetic material capable of suppressing a decrease in surface hardness and bending processability even when formed using a plant-derived polyolefin resin.

Means for Solving the Problems

[0006] According to one aspect of the present invention, a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order, and the colored thermoplastic resin layer and the transparent thermoplastic resin layer are each formed using a resin composition containing a plant-derived polyolefin resin, and the transparent thermoplastic resin layer has a Martens hardness HM of 30 N / mm² in the cross-sectional direction. 2 More than 60N / mm 2 The following decorative sheets are provided:

[0007] Furthermore, according to another embodiment, a decorative material is provided comprising a base material and a decorative sheet according to the above embodiment laminated on at least one surface of the base material. [Effects of the Invention]

[0008] According to one embodiment of the present invention, it is possible to realize decorative sheets and decorative materials that can suppress a decrease in surface hardness and flexibility even when formed with plant-derived polyolefin resin. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic cross-sectional view showing an example of a decorative sheet according to one embodiment of the present invention. [Modes for carrying out the invention]

[0010] The embodiments of this technology will be described below with reference to the drawings. In the drawings, identical or similar parts are denoted by the same or similar reference numerals, and redundant explanations are omitted. The drawings are schematic, and the relationship between thickness and planar dimensions, the ratio of the thickness of each layer, etc., may differ from reality. The layers do not necessarily have to be stacked in the order shown in the drawings, as long as they are within the scope of this disclosure. Additional layers not shown in these drawings may also be added. Furthermore, the embodiments shown below are illustrative of configurations for realizing the technical idea of ​​this disclosure, and the technical idea of ​​this disclosure is not limited to the materials, shapes, and structures of the components described below. The technical idea of ​​this disclosure can be modified in various ways within the technical scope defined by the claims described in the patent claims.

[0011] Furthermore, the terms "left / right" and "up / down" in the following explanation are merely definitions for the sake of explanation and do not limit the technical concept of this disclosure. Therefore, for example, if the page is rotated 90 degrees, "left / right" and "up / down" will be swapped when read, and if the page is rotated 180 degrees, "left" will become "right" and "right" will become "left". The composition of the decorative material 10 will be explained below with reference to Figure 1.

[0012] As shown in Figure 1, the decorative material 10 comprises a decorative sheet 1 and a base material 9. The specific configuration of the decorative sheet 1 will be described later. The base material 9 is formed in a plate shape using, for example, wood-based boards, inorganic boards, or metal plates, and a decorative sheet 1 is laminated to one side (the upper side in Figure 1). In other words, the decorative material 10 comprises the base material 9 and the decorative sheet 1 laminated to one side of the base material 9.

[0013] (Composition of decorative sheet) As shown in Figure 1, the decorative sheet 1 comprises a colored base layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive resin layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface protection layer 6, an uneven surface 7, and a primer layer 8.

[0014] <Colored base material layer> The colored base layer 2 is a resin layer formed using a thermoplastic resin, and is formed using a resin composition containing a biomass-derived (plant-derived) polyolefin resin. Specifically, it is a colored resin layer formed from a resin composition containing, for example, biomass-derived (plant-derived) polyethylene, fossil fuel-derived ethylene, and fossil fuel-derived polyethylene obtained by polymerizing monomers containing at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin. In this specification, "biomass-derived" means "plant-derived." The composition of the colored substrate layer 2 will be described in detail below.

[0015] (Biomass-derived polyethylene) Biomass-derived polyethylene is formed by the polymerization of monomers containing biomass-derived ethylene. The biomass-derived ethylene is not particularly limited, and ethylene produced by conventionally known methods can be used. Because biomass-derived ethylene is used as the raw material monomer, the resulting polyethylene is biomass-derived. Furthermore, the raw material monomer for polyethylene does not necessarily have to contain 100% by mass of biomass-derived ethylene.

[0016] The monomers used as raw materials for biomass-derived polyethylene may further include at least one of ethylene derived from fossil fuels and α-olefins derived from fossil fuels, or may further include α-olefins derived from biomass.

[0017] The above-mentioned α-olefin is not particularly limited in terms of the number of carbon atoms, but typically those with 3 to 20 carbon atoms can be used, and butylene, hexene, or octene are preferred. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a biomass-derived raw material. Furthermore, by including such an α-olefin, the polymerized polyethylene has alkyl groups as branched structures, making it more flexible than simple linear polyethylene. By using ethylene, a biomass-derived raw material, it is theoretically possible to manufacture the product using 100% biomass-derived components.

[0018] The biomass-derived ethylene concentration in polyethylene (hereinafter sometimes referred to as "biomass content") is a value measured by radiocarbon (C14) measurement of the biomass-derived carbon content. Since atmospheric carbon dioxide contains C14 at a certain percentage (105.5 pMC), it is known that the C14 content in plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in the total carbon atoms in polyethylene, the proportion of biomass-derived carbon can be calculated. In this embodiment, when the C14 content in polyethylene is PC14, the biomass-derived carbon content Pbio can be determined as follows.

[0019] Pbio(%) = PC14 / 105.5 × 100 In this embodiment, theoretically, if all ethylene derived from biomass is used as the raw material for polyethylene, the concentration of biomass-derived ethylene will be 100%, and the biomass degree of biomass-derived polyethylene will be 100. Furthermore, the concentration of biomass-derived ethylene in fossil fuel-derived polyethylene produced solely from fossil fuel-derived raw materials will be 0%, and the biomass degree of fossil fuel-derived polyethylene will be 0.

[0020] In this embodiment, the biomass-derived polyethylene and the decorative sheet composed of that polyethylene do not need to have a biomass content of 100%. In this embodiment, the polymerization method for monomers containing biomass-derived ethylene is not particularly limited and can be carried out by conventionally known methods. The polymerization temperature and polymerization pressure should be adjusted as appropriate depending on the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited and can be conventionally known apparatus. An example of a polymerization method for monomers containing ethylene is described below.

[0021] The polymerization method for ethylene polymers and copolymers of ethylene and α-olefins can be appropriately selected depending on the type of polyethylene to be polymerized, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE), depending on differences in density and branching. For example, it is preferable to use a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as the polymerization catalyst, and to carry out the polymerization in one or more stages using one of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, or high-pressure ionic polymerization. Furthermore, as the biomass-derived polyethylene, ethylene polymers or copolymers of ethylene and α-olefins may be used individually or in combination of two or more types.

[0022] (Resin composition containing biomass-derived polyethylene) In this embodiment, the resin composition mainly contains the above-mentioned polyethylene. The above resin composition may contain two or more types of polyethylene with different biomass concentrations, and the concentration of biomass-derived ethylene in the resin composition as a whole should be within the above range.

[0023] (Ethylene derived from fossil fuels, polyethylene derived from fossil fuels) The colored substrate layer 2 contains biomass-derived polyethylene made from the above resin composition, and further contains fossil fuel-derived polyethylene obtained by polymerizing ethylene derived from fossil fuels and monomers containing at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefins. In other words, in this embodiment, the resin composition consists of a mixture of biomass-derived polyethylene and fossil fuel-derived polyethylene. The mixing method is not particularly limited and can be mixed by conventionally known methods. For example, it may be a dry blend or a melt blend.

[0024] According to this embodiment, the resin composition forming the colored substrate layer 2 preferably contains 5 to 90% by mass, more preferably 25 to 75% by mass of biomass-derived polyethylene and preferably 10 to 95% by mass, more preferably 25 to 75% by mass of fossil fuel-derived polyethylene. Even when using a resin composition of a mixture containing biomass-derived polyethylene, fossil fuel-derived ethylene, and fossil fuel-derived polyethylene obtained by polymerizing monomers containing at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin, the concentration of biomass-derived ethylene in the resin composition as a whole only needs to be within the above range.

[0025] In the resin composition manufactured in the above manufacturing process, various additives may be added to the resin composition in addition to the main component polyethylene, to the extent that its properties are not impaired. Examples of additives include plasticizers, UV stabilizers, color inhibitors, matting agents, deodorizers, flame retardants, weather-resistant agents, antistatic agents, thread friction reducers, slip agents, mold release agents, antioxidants, ion exchange agents, and coloring pigments. These additives are added to the entire resin composition in an amount of preferably 1 to 20% by mass, more preferably 1 to 10% by mass.

[0026] As described above, the colored base material layer 2 contains biomass-derived ethylene at a concentration of 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass, relative to the entire colored base material layer 2. If the concentration of biomass-derived ethylene in the colored base material layer 2 is 5% by mass or more, the amount of fossil fuels used can be reduced compared to conventional methods, and a carbon-neutral decorative sheet can be realized.

[0027] The colored substrate layer 2 is 0.92 [g / cm³] 3 ] or more than 1.16[g / cm 3 ]Within the range below, preferably 0.98 [g / cm³] 3 ] or more 1.10[g / cm 3It has a density within the following range. The density of the colored base material layer 2 is a value measured according to the method specified in Method A of JIS K7112-1980 after annealing as described in JIS K6760-1995. When the density of the colored base material layer 2 is 0.92 [g / cm 3 or more, the rigidity of the colored base material layer 2 can be increased. Also, when the density of the colored base material layer 2 is 1.16 [g / cm 3 or less, the transparency and mechanical strength of the colored base material layer 2 can be increased.

[0028] The colored base material layer 2 may be any of those containing biomass-derived high-density polyethylene and biomass-derived low-density polyethylene as biomass-derived polyethylene, those containing biomass-derived high-density polyethylene and fossil fuel-derived low-density polyethylene, and those containing biomass-derived low-density polyethylene in fossil fuel-derived high-density polyethylene.

[0029] The biomass content of the entire colored base material layer 2 may be within the range of 10% or more and 90% or less. Note that biomass-derived high-density polyethylene refers to polyethylene with a density exceeding 0.94 [g / cm 3 . Also, biomass-derived low-density polyethylene refers to polyethylene with a density of 0.94 [g / cm 3 or less. The colored base material layer 2 is preferably a blend of biomass-derived high-density polyethylene and low-density polyethylene (which may be either biomass-derived or fossil fuel-derived) within the range of 95:5 to 70:30 as biomass-derived polyethylene. If the content of low-density polyethylene is too low, the film-forming stability is poor, and if the content of low-density polyethylene is too high, there is a problem that it becomes too soft.

[0030] The manufacturing method of the colored base material layer 2 is not particularly limited and can be manufactured by a conventionally known method. In this embodiment, it is preferably formed by calender molding. Furthermore, as described above, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, friction reducers, light scattering agents, and gloss adjusters may be added to the colored substrate layer 2 as needed.

[0031] The thickness of the colored base material layer 2 is preferably in the range of 55 [μm] to 150 [μm], more preferably 60 [μm] to 120 [μm], and even more preferably 65 [μm] to 100 [μm]. This is because, when the thickness of the colored base material layer 2, which is made of biomass-derived polyethylene, is 55 [μm] or more, it is possible to absorb unevenness and steps in the underlying flooring material, etc., and improve the finish of the decorative sheet 1. Also, when the thickness of the colored base material layer 2 is 150 [μm] or less, it is possible to reduce the manufacturing cost of the decorative sheet 1 by not forming the colored base material layer 2 to be unnecessarily thick.

[0032] In this embodiment, biomass-derived polyethylene was described as the biomass-derived resin constituting the colored base material layer 2, but the present invention is not limited thereto. For example, biomass-derived polypropylene or biomass-derived polybutylene may be used instead of the biomass-derived polyethylene described above. In other words, in this embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin constituting the colored base material layer 2.

[0033] <Pattern layer> The pattern layer 3 is laminated on one side of the colored substrate layer 2 (the upper side in Figure 1) and is a layer for adding a pattern to enhance the design. Furthermore, the pattern layer 3 is formed using printing ink or paint. The printing ink or paint that forms the pattern layer 3 is formed, for example, by dissolving or dispersing a coloring agent such as a dye or pigment together with a suitable binder resin in a suitable diluent solvent.

[0034] The printing ink or coating that forms the pattern layer 3 is applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating. The pattern layer 3 is formed by including the above-mentioned coloring agent and binder resin. The binder resin used in the pattern layer 3 in this embodiment will be described below.

[0035] Examples of binder resins that can be used include, but are not limited to, urethane resins, acrylic resins, vinyl chloride acetate resins, polyimide resins, nitrated cotton, or mixtures thereof. Any design can be used as the pattern, such as wood grain, stone pattern, fabric pattern, abstract pattern, geometric pattern, letters, symbols, solid color, or a combination thereof. In addition, to improve the opacity of the decorative sheet 1, an opacity layer may be provided between the pattern layer 3 and the colored base material layer 2. The opacity layer is formed using, for example, an opaque printing ink or paint containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0036] The thickness of the pattern layer 3 is preferably within the range of 1 [μm] to 10 [μm]. This is because when the thickness of the pattern layer 3 is 1 [μm] or more, it is possible to make the printing clearer. Also, when the thickness of the pattern layer 3 is 10 [μm] or less, it is possible to improve the printability when manufacturing the decorative sheet 1 and to reduce manufacturing costs.

[0037] Furthermore, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, drying agents, curing agents, curing accelerators, and curing retarders may be added to the pattern layer 3 to impart various functions. Furthermore, the pattern layer 3 may have a configuration that includes, for example, a solid-colored base layer to conceal the color and pattern of the substrate to which the decorative sheet 1 is attached, and a pattern layer to add a design for aesthetic purposes. Also, if it is possible to substitute the coloring of the colored base layer 2, the pattern layer 3 does not necessarily have to be provided.

[0038] <Adhesive resin layer> The adhesive resin layer 4 is laminated on the side of the pattern layer 3 opposite to the colored base material layer 2 (the upper side in Figure 1), and is used to bond the pattern layer 3 to the transparent resin layer 5. The adhesive resin layer 4 may be made of either polypropylene or polyethylene material, but since the transparent resin layer 5 is formed from a resin composition containing biomass-derived (plant-derived) polyethylene, as described later, it is preferable to use an adhesive resin made of polyethylene material for the adhesive resin layer 4. By forming the adhesive resin layer 4 from polyethylene material, variations in thickness and quality can be suppressed when manufacturing the decorative sheet 1.

[0039] As adhesive resins, resins derived from fossil fuels are preferred, and resins such as maleic anhydride-modified polyethylene resin, urethane-based resins, acrylic-based resins, ethylene-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers, and polyester-based resins can be used. The adhesive resin layer 4 has a Martens hardness HM of 5 N / mm² in the cross-sectional direction. 2 More than 20N / mm 2 Preferably, the following: 8 N / mm 2 More than 12N / mm 2 It is more preferable that the following conditions are met (temperature 23°C, humidity 50%RH): Martens hardness HM of adhesive resin layer 4 is 5 N / mm². 2 If the size is smaller, the deformation stress during peeling may not be absorbed by the adhesive resin layer 4, potentially leading to a decrease in adhesion. Also, the Martens hardness HM is 20 N / mm². 2 If the size is too large, the adhesive resin layer 4 may not be able to absorb the deformation stress during peeling, causing the adhesive resin layer 4 to break and potentially leading to a decrease in adhesion.

[0040] Martens hardness is a type of index that indicates the hardness (hardness) of a material. Martens hardness is defined as the quotient between the indentation force calculated from the load and the surface area of ​​the indentation calculated from the indentation depth, obtained by applying a load to an indenter, pressing the indenter into the surface of a sample, and measuring the depth of the indentation formed in the sample. To avoid the influence of resin layers other than the adhesive resin layer 4, the Martens hardness is measured from the cross-section of the decorative sheet 1. Specifically, a sample of the decorative sheet 1 is embedded in a resin such as a cold-curing epoxy resin or a UV-curing resin and allowed to cure completely. Then, the decorative sheet 1 is cut so that its cross-section is exposed, and the cut surface is mechanically polished to obtain the measurement surface. An indenter is then pressed into the adhesive resin layer 4, and the Martens hardness is calculated from the indentation depth and load. More detailed measurement methods are specified in "ISO 14577".

[0041] Methods for adjusting the Martens hardness include, for example, adjusting the extrusion temperature when forming the adhesive resin layer 4, or adding a nucleating agent to the resin constituting the adhesive resin layer 4 to adjust the degree of crystallinity of the resin. The adhesive resin layer 4 preferably has a restorative power ηIT in the range of 50% to 75%, and more preferably in the range of 55% to 70%.

[0042] If the restoring power ηIT is less than 50%, the elastic deformation during peeling will be small, and the adhesion strength may decrease because the stress changes during deformation cannot be fully absorbed. Conversely, if the restoring power ηIT is greater than 75%, the elastic deformation during peeling will be excessively large, and the adhesion strength may decrease. Methods for adjusting the restoration power include adjusting the extrusion temperature during resin film formation to create the adhesive resin layer 4, or adding a nucleating agent to the resin constituting the adhesive resin layer 4, as described above, to adjust the degree of crystallinity of the resin.

[0043] Here, the recovery power ηIT is measured using, for example, a Martens hardness measuring device (Fischerscope HM2000; Fischer Instruments Co., Ltd.) compliant with ISO 14577. Alternatively, the recovery power may be measured from the cross-section of the substrate to avoid the influence of the core layer of the laminated substrate other than the adhesive resin layer 4 during measurement. Specifically, the decorative sheet may be embedded in a resin such as a cold-curing epoxy resin or UV-curing resin, allowed to cure sufficiently, then cut so that the cross-section of the decorative sheet is exposed, and mechanically polished to obtain the measurement surface. Furthermore, a specific measurement method involves pressing an indenter into the measurement surface of the adhesive resin layer, deriving Wplast (plastic deformation work) and Welast (elastic deformation work) from the area enclosed by the curve of the indentation depth displacement and load, and deriving the recovery power (ηIT) from the ratio of elastic deformation work to Wtotal (total deformation work) using equations (1) and (2) below. The measurement conditions are, for example, a test force of 10 mN, a test force application time of 10 seconds, and a test force holding time of 5 seconds.

[0044] Wtotal = Wplast + Welast …(1) ηIT = Welast / Wtotal …(2)

[0045] Furthermore, in order to improve the adhesion between the pattern layer 3 and the transparent resin layer 5, an additional adhesive layer (not shown) may be provided between the pattern layer 3 and the adhesive resin layer 4. For example, urethane-based adhesives, polyester-based resins, polyisocyanate-based resins, polyester polyol-based resins, etc., can be used as the material for the adhesive layer.

[0046] <Transparent resin layer> The transparent resin layer 5 is laminated on the side of the adhesive resin layer 4 opposite to the pattern layer 3 (the upper side in Figure 1), and is a transparent resin layer formed from a resin composition containing the biomass-derived (plant-derived) polyethylene described above. More specifically, the transparent resin layer 5 is a resin layer formed from a resin composition containing biomass-derived polyethylene polymerized from monomers containing biomass-derived ethylene, fossil fuel-derived ethylene, and fossil fuel-derived polyethylene polymerized from monomers containing at least one of fossil fuel-derived ethylene and α-olefin. In other words, the transparent resin layer 5 may use the same biomass-derived polyethylene resin composition used in the colored substrate layer 2.

[0047] The transparent resin layer 5 may contain 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass, of the biomass-derived ethylene mentioned above, relative to the entire transparent resin layer 5. If the concentration of biomass-derived ethylene in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuels used can be reduced compared to conventional methods, and a carbon-neutral decorative sheet can be realized.

[0048] The biomass-derived polyethylene that forms the transparent resin layer 5 is further enriched with a polyethylene crystallization nucleating agent. The polyethylene crystallization nucleating agent is preferably added to polyethylene in an amount of 2% to 5% based on the mass of polyethylene, and more preferably in an amount of 3% to 4% based on the mass of polyethylene. By adding the polyethylene crystallization nucleating agent to the transparent resin layer 5, the extrusion stability during manufacturing can be improved and good haze can be obtained.

[0049] The transparent resin layer 5 has a Martens hardness HM of 30 N / mm² in the cross-sectional direction. 2 More than 60N / mm 2 The following is preferable: 40 N / mm 2 More than 50N / mm 2It is more preferable that the following ranges apply (temperature 23°C, humidity 50%RH): Martens hardness HM of transparent resin layer 5 is 30 N / mm². 2 If the size is smaller, the surface performance deteriorates, resulting in insufficient durability in practical use. Also, the Martens hardness HM is 60 N / mm². 2 If the size is too large, it can lead to surface cracks when bending the molded product, reducing workability.

[0050] Furthermore, the transparent resin layer 5 preferably has a recovery power ηIT within the range of 25% to 50%, and more preferably within the range of 30% to 45%. If the recovery power ηIT is less than 25%, the elastic deformation will be small in response to the stress during deformation (such as during bending), which may reduce the surface performance. Also, if the recovery power ηIT is greater than 50%, elastic deformation will be dominant, which may cause curling in the decorative sheet itself, potentially reducing workability.

[0051] One method for adjusting the Martens hardness HM of the transparent resin layer 5 is to change the ratio of low-density polyethylene to high-density polyethylene in the transparent resin layer 5. When the ratio of high-density polyethylene to low-density polyethylene is relatively high, the Martens hardness of the transparent resin layer 5 becomes harder. In addition, methods for adjusting the Martens hardness HM and the restoring power ηIT of the transparent resin layer 5 include, for example, adjusting the extrusion temperature when forming the transparent resin layer 5, or adjusting the amount of nucleating agent added to the resin constituting the transparent resin layer 5 to adjust the degree of crystallinity of the resin.

[0052] The density of the transparent resin layer 5 is 0.92 [g / cm³]. 3 ] or more 0.99[g / cm 3 Within the following range, preferably 0.94 [g / cm³] 3 ] or more 0.98[g / cm 3 ]Within the range below, more preferably 0.95 [g / cm³] 3 ] or more 0.97[g / cm 3The density of the transparent resin layer 5 is the value measured according to the method specified in Method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1995. The density of the transparent resin layer 5 is 0.92 [g / cm³]. 3 If the density is 0.99 [g / cm³] or higher, the rigidity of the transparent resin layer 5 can be increased. Also, if the density of the transparent resin layer 5 is 0.99 [g / cm³], the rigidity of the transparent resin layer 5 can be increased. 3 If the following conditions are met, the transparency and mechanical strength of the transparent resin layer 5 can be improved.

[0053] The transparent resin layer 5 has a thickness of 55 to 150 [μm], preferably 55 to 100 [μm], and more preferably 60 to 80 [μm]. The transparent resin layer 5 may contain biomass-derived high-density polyethylene as biomass-derived polyethylene. High-density polyethylene is preferred from the viewpoint of extrusion suitability, transparency, and mechanical properties.

[0054] Furthermore, the transparent resin layer 5 may also contain polyethylene, as biomass-derived polyethylene, which is a blend of biomass-derived high-density polyethylene and biomass-derived low-density polyethylene in a range of 100:0 to 20:80. Furthermore, the transparent resin layer 5 may have a biomass content of 10% to 90% of the entire transparent resin layer 5.

[0055] The method for manufacturing the transparent resin layer 5 is not particularly limited and can be manufactured by conventionally known methods. In this embodiment, it is preferable to form it by extrusion molding, and it is more preferable that the extrusion molding is carried out by the T-die method or the inflation method. In this embodiment, it is preferable that the transparent resin layer 5 and the colored substrate layer 2 satisfy the following specific relationships with respect to density, thickness, and biomass content (ethylene concentration derived from biomass).

[0056] In this embodiment, it is preferable that the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 satisfy d2 > d1. This is because shapeability is required for the transparent resin layer 5 to function, and productivity is required for the colored substrate layer 2 to function. Furthermore, the ratio of the density d1 of the transparent resin layer 5 to the density d2 of the colored base material layer 2 (d2 / d1) is preferably within the range of 1.1 to 1.5, more preferably within the range of 1.1 to 1.3, and even more preferably within the range of 1.1 to 1.2. By having the density ratio of the transparent resin layer to the colored base material layer within this range, even when biomass-derived polyethylene is used, the material can have the necessary extrusion suitability and bending suitability as a decorative sheet.

[0057] In this embodiment, it is preferable that the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored substrate layer 2 satisfy t1 ≥ t2. This is because the transparent resin layer 5 requires a certain thickness to function, while the colored substrate layer 2 does not need to be as thick as the transparent resin layer 5 to function. Furthermore, the ratio (t1 / t2) of the thickness t1 of the transparent resin layer 5 to the thickness t2 of the colored substrate layer 2 is preferably within the range of 1.1 to 3, more preferably within the range of 1.1 to 2, and even more preferably within the range of 1.1 to 1.5.

[0058] In this embodiment, it is preferable that the biomass-derived ethylene concentration C1 in the transparent resin layer 5 and the biomass-derived ethylene concentration C2 in the colored substrate layer 2 satisfy the condition C1 > C2. This is because, since the transparent resin layer 5 is thick and requires a large amount of ethylene to function, increasing the biomass content of the transparent resin layer 5 can further reduce the amount of fossil fuels used.

[0059] The transparent resin layer 5 may contain, if necessary, one or more additives selected from various sources such as colorants, fillers, UV absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, friction reducers, light scattering agents, and gloss adjusters. The transparent resin layer 5 preferably has a degree of transparency (colorless, colored, or semi-transparent) that allows the pattern of the pattern layer 3 to be seen through the surface (top surface) of the decorative sheet 1.

[0060] In this embodiment, biomass-derived polyethylene was described as the biomass-derived resin constituting the transparent resin layer 5, but the present invention is not limited thereto. For example, biomass-derived polypropylene or biomass-derived polybutylene may be used instead of the biomass-derived polyethylene described above. In other words, in this embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin constituting the transparent resin layer 5.

[0061] <Surface protective layer> The surface protection layer 6 is laminated on the side of the transparent resin layer 5 opposite to the adhesive resin layer 4 (the upper side in Figure 1), and is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design properties to the decorative sheet 1. Furthermore, the surface protective layer 6 can be made of a thermosetting resin or an ionizing radiation-curable resin, and is formed using, for example, an acrylic resin composition.

[0062] Furthermore, the surface protective layer 6 may contain various additives as needed, such as weathering agents, plasticizers, stabilizers, fillers, dispersants, colorants such as dyes and pigments, solvents, UV absorbers, heat stabilizers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss adjusters. In addition, the surface protective layer 6 may contain functional additives as needed, such as antibacterial agents and antifungal agents.

[0063] <Uneven part> The uneven portion 7 is formed by recesses provided at multiple locations from the surface protective layer 6 to the transparent resin layer 5. The uneven portion 7 is not necessarily required.

[0064] <Primer layer> The primer layer 8 is a base layer that improves the adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9. Furthermore, the primer layer 8 is laminated on the side of the colored substrate layer 2 opposite to the pattern layer 3 (the lower side in Figure 1). Furthermore, the primer layer 8 is formed using, for example, a polyester resin, an organic additive, a pigment, etc.

[0065] Furthermore, the primer layer 8 may contain rust-preventive pigments to improve corrosion resistance. The thickness of the primer layer 8 is, for example, within the range of 1 [μm] to 10 [μm]. The embodiments described above are merely examples of the present invention, and the present invention is not limited to the embodiments described above. Various modifications can be made to forms other than those described above, as long as they do not depart from the technical spirit of the present invention, depending on the design and other factors.

[0066] (Effects of this embodiment) The decorative sheet 1 of this embodiment can achieve the following effects.

[0067] (1) In a decorative sheet 1 in which a colored base layer 2, a pattern layer 3, an adhesive resin layer 4, a transparent resin layer 5, and a surface protection layer 6 are laminated in this order, the colored base layer 2 and the transparent resin layer 5 are resin layers formed using a resin composition containing a biomass-derived polyolefin resin, and the transparent resin layer 5 has a Martens hardness HM of 30 N / mm² in the cross-sectional direction. 2 More than 60N / mm 2 It is within the following range. Here, biomass-derived polyethylene tends to be inferior to polypropylene, which is conventionally used as a material for decorative sheets, in terms of surface hardness and flexibility. As described above, by adjusting the Martens hardness HM in the cross-sectional direction of the transparent resin layer 5, the surface hardness of the decorative sheet 1 can be improved, and the flexibility can also be improved. As a result, by using biomass-derived materials as the materials for the colored base material layer 2 and the transparent resin layer 5, the amount of fossil fuels used can be reduced, and a decorative sheet 1 with surface hardness and flexibility equivalent to conventional decorative sheets can be realized.

[0068] (2) The transparent resin layer 5 is designed so that the recovery power ηIT in an indentation test using a Martens hardness tester is within the range of 25% to 50%. Therefore, it is possible to suppress the occurrence of problems such as reduced surface performance due to small elastic deformation in response to stress during deformation (such as during bending), or reduced workability due to curling of the decorative sheet itself when elastic deformation becomes dominant.

[0069] (3) The transparent resin layer 5 contains a crystallization nucleating agent for polyolefins in an amount of 2% to 5% based on the mass of the plant-derived polyolefin, thereby improving extrusion stability during manufacturing and obtaining good haze, and suppressing a decrease in extrusion stability, transparency, and mechanical properties.

[0070] (4) The transparent resin layer 5 contains 5% by mass or more of plant-derived polyethylene relative to the total amount of the transparent resin layer 5, thus reducing the amount of fossil fuels used compared to conventional methods and enabling the realization of a carbon-neutral decorative sheet. In addition, the transparent resin layer 5 has a density of 0.92 g / cm³. 3 More than 0.99g / cm 3 Because it has a density within the following range, the transparency and mechanical strength of the transparent resin layer 5 can be improved. Furthermore, since the colored base material layer 2 contains 5% by mass or more of plant-derived polyethylene relative to the total amount of the colored base material layer 2, the amount of fossil fuels used can be reduced compared to conventional methods, enabling the realization of a carbon-neutral decorative sheet. In addition, the colored base material layer 2 has a density of 0.92 g / cm³. 3 More than 1.16g / cm 3 Because it has a density within the following range, the transparency and mechanical strength of the colored substrate layer 2 can be increased.

[0071] (5) Furthermore, the decorative material 10 comprises a base material 9 and a decorative sheet 1 laminated on at least one surface of the base material 9. As a result, even when a decorative sheet 1 made of biomass-derived polyethylene resin is used, it is possible to provide a decorative material 10 that can suppress a decrease in surface hardness and flexibility. [Examples]

[0072] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the examples below. (Example 1) A 60 μm thick colored substrate layer made of biomass-derived polyethylene resin was subjected to corona discharge treatment on one side. Then, a pattern layer made of urethane-based printing ink, a layer made of urethane-based adhesive, an adhesive resin layer, a transparent resin layer made of biomass-derived polyethylene resin, and a surface protection layer mainly composed of an acrylic resin composition were laminated in this order on the corona-discharge-treated side to obtain the decorative sheet of Example 1. The biomass-derived polyethylene resin and adhesive resin that will form the transparent resin layer, and maleic anhydride-modified polyethylene that will form the adhesive resin layer, were co-extruded onto the pattern layer after the urethane-based adhesive was applied, thereby laminating the adhesive resin layer and the transparent resin layer on top of the pattern layer. The thickness of the transparent resin layer (including the adhesive resin layer) was 70 μm.

[0073] At this time, the Martens hardness HM in the cross-sectional direction of the transparent resin layer is 30 N / mm². 2 The thickness of the colored substrate layer is 45 μm, the recovery power of the transparent resin layer in the indentation test using a Martens hardness tester is 20%, the amount of polyethylene crystallization nucleating agent added to the transparent resin layer is 6% by mass, the plant-derived polyethylene content of the transparent resin layer is 3% by mass, and the density of the transparent resin layer is 0.8 g / cm³. 3 The colored base layer contains 3% by mass of plant-derived polyethylene, and the density of the colored base layer is 1.3 g / cm³. 3 I made it so that it would be like that.

[0074] The Martens hardness HM in the cross-sectional direction of the transparent resin layer can be increased or decreased by adjusting the type of resin and degree of crystallinity. The recovery power of the transparent resin layer in the indentation test using a Martens hardness tester can be increased or decreased by adjusting the type of resin and degree of crystallinity. The density of the transparent resin layer can be increased or decreased by adjusting the type of resin and additives. The density of the colored substrate layer can be increased or decreased by adjusting the type of resin and additives.

[0075] (Example 2) In the decorative sheet of Example 1, the Martens hardness HM in the cross-sectional direction of the transparent resin layer is 45 N / mm². 2 Aside from the fact that it was made as described above, the decorative sheet for Example 2 was created using the same procedure as the decorative sheet for Example 1. (Example 3) In the decorative sheet of Example 1, the Martens hardness HM in the cross-sectional direction of the transparent resin layer is 60 N / mm². 2 The decorative sheet of Example 3 was created using the same procedure as the decorative sheet of Example 1, except that the result was as described above.

[0076] (Example 4) The decorative sheet of Example 4 was prepared using the same procedure as the decorative sheet of Example 1, except that the thickness of the colored substrate layer was set to 45 μm. (Example 5) The decorative sheet of Example 5 was prepared using the same procedure as the decorative sheet of Example 2, except that the thickness of the colored substrate layer was set to 100 μm.

[0077] (Example 6) The decorative sheet of Example 6 was prepared using the same procedure as the decorative sheet of Example 3, except that the thickness of the colored substrate layer was set to 150 μm. (Example 7) The decorative sheet of Example 7 was prepared using the same procedure as the decorative sheet of Example 1, except that the restoration power of the transparent resin layer was set to 25%.

[0078] (Example 8) The decorative sheet of Example 8 was prepared using the same procedure as the decorative sheet of Example 2, except that the restoration work rate of the transparent resin layer was set to 40%. (Example 9) The decorative sheet of Example 9 was prepared using the same procedure as the decorative sheet of Example 3, except that the restoration work rate of the transparent resin layer was set to 50%.

[0079] (Example 10) The decorative sheet of Example 10 was prepared using the same procedure as the decorative sheet of Example 1, except that the amount of polyethylene crystallization nucleating agent added to the transparent resin layer was 2% by mass. (Example 11) The decorative sheet of Example 11 was prepared using the same procedure as the decorative sheet of Example 2, except that the amount of polyethylene crystallization nucleating agent added to the transparent resin layer was 3% by mass.

[0080] (Example 12) The decorative sheet of Example 12 was prepared using the same procedure as the decorative sheet of Example 3, except that the amount of polyethylene crystallization nucleating agent added to the transparent resin layer was 5% by mass. (Example 13) In the decorative sheet of Example 1, the Martens hardness HM in the cross-sectional direction of the transparent resin layer is 40 N / mm². 2 The decorative sheet of Example 13 was prepared using the same procedure as the decorative sheet of Example 1, except that the content of plant-derived polyethylene in the transparent resin layer was set to 5% by mass.

[0081] (Example 14) In the decorative sheet of Example 1, the Martens hardness HM in the cross-sectional direction of the transparent resin layer is 50 N / mm². 2 Except for setting the transparent resin layer to contain 10% by mass of plant-derived polyethylene, the decorative sheet of Example 14 was prepared using the same procedure as the decorative sheet of Example 1. (Example 15) In the decorative sheet of Example 1, the density of the transparent resin layer is 0.92 g / cm³. 3 The decorative sheet of Example 15 was created using the same procedure as the decorative sheet of Example 1, except that the result was as described above.

[0082] (Example 16) In the decorative sheet of Example 2, the density of the transparent resin layer is 0.95 g / cm³. 3Aside from the fact that it was made as described above, the decorative sheet of Example 16 was prepared using the same procedure as the decorative sheet of Example 2. (Example 17) In the decorative sheet of Example 3, the density of the transparent resin layer is 0.99 g / cm³. 3 Aside from the fact that it was made as described above, the decorative sheet of Example 17 was prepared using the same procedure as the decorative sheet of Example 3.

[0083] (Example 18) In the decorative sheet of Example 1, the content of plant-derived polyethylene in the transparent resin layer was 5% by mass, and the density of the transparent resin layer was 0.92 g / cm³. 3 The decorative sheet of Example 18 was prepared using the same procedure as the decorative sheet of Example 1, except that the result was as described above. (Example 19) In the decorative sheet of Example 2, the content of plant-derived polyethylene in the transparent resin layer was set to 10% by mass, and the density of the transparent resin layer was 0.95 g / cm³. 3 The decorative sheet of Example 19 was created using the same procedure as the decorative sheet of Example 2, except that the result was as described above.

[0084] (Example 20) In the decorative sheet of Example 3, the content of plant-derived polyethylene in the transparent resin layer was 15% by mass, and the density of the transparent resin layer was 0.99 g / cm³. 3 Aside from the fact that it was made as described above, the decorative sheet of Example 20 was prepared using the same procedure as the decorative sheet of Example 3. (Example 21) In the decorative sheet of Example 1, the Martens hardness HM in the cross-sectional direction of the transparent resin layer is 40 N / mm². 2 The decorative sheet of Example 21 was prepared using the same procedure as the decorative sheet of Example 1, except that the plant-derived polyethylene content in the colored base material layer was set to 5% by mass.

[0085] (Example 22) In the decorative sheet of Example 1, the Martens hardness HM in the cross-sectional direction of the transparent resin layer is 50 N / mm². 2The decorative sheet of Example 22 was prepared using the same procedure as the decorative sheet of Example 1, except that the plant-derived polyethylene content in the colored base material layer was set to 10% by mass. (Example 23) In the decorative sheet of Example 1, the density of the colored base material layer is 0.92 g / cm³. 3 Aside from the fact that it was made as described above, the decorative sheet of Example 23 was created using the same procedure as the decorative sheet of Example 1.

[0086] (Example 24) In the decorative sheet of Example 2, the density of the colored substrate layer is 0.95 g / cm³. 3 The decorative sheet of Example 24 was created using the same procedure as the decorative sheet of Example 2, except that the result was as described above. (Example 25) In the decorative sheet of Example 3, the density of the colored base material layer is 1.16 g / cm³. 3 Aside from the fact that it was made as described above, the decorative sheet of Example 25 was prepared using the same procedure as the decorative sheet of Example 3.

[0087] (Example 26) In the decorative sheet of Example 1, the plant-derived polyethylene content of the colored base material layer was 5% by mass, and the density of the colored base material layer was 0.92 g / cm³. 3 The decorative sheet of Example 26 was prepared using the same procedure as the decorative sheet of Example 1, except that the procedure was changed accordingly. (Example 27) In the decorative sheet of Example 2, the plant-derived polyethylene content of the colored base material layer was set to 10% by mass, and the density of the colored base material layer was 0.95 g / cm³. 3 Aside from the fact that it was made as described above, the decorative sheet of Example 27 was created using the same procedure as the decorative sheet of Example 2.

[0088] (Example 28) In the decorative sheet of Example 3, the plant-derived polyethylene content of the colored base material layer was 15% by mass, and the density of the colored base material layer was 1.16 g / cm³. 3 Aside from the fact that it was made as described above, the decorative sheet of Example 28 was prepared using the same procedure as the decorative sheet of Example 3. (Example 29) In the decorative sheet of Example 1, the thickness of the colored substrate layer was set to 55 μm, the recovery power of the transparent resin layer in the indentation test using a Martens hardness tester was set to 25%, the amount of polyethylene crystallization nucleating agent added to the transparent resin layer was set to 2% by mass, the content of plant-derived polyethylene in the transparent resin layer was set to 5% by mass, and the density of the transparent resin layer was 0.92 g / cm³. 3 The plant-derived polyethylene content of the colored base layer is set to 5% by mass, and the density of the colored base layer is 0.92 g / cm³. 3 Aside from the fact that it was made as described above, the decorative sheet of Example 29 was prepared using the same procedure as the decorative sheet of Example 1.

[0089] (Example 30) In the decorative sheet of Example 2, the thickness of the colored substrate layer was set to 100 μm, the recovery power of the transparent resin layer in the indentation test using a Martens hardness tester was set to 40%, the amount of polyethylene crystallization nucleating agent added to the transparent resin layer was set to 3% by mass, the content of plant-derived polyethylene in the transparent resin layer was set to 10% by mass, and the density of the transparent resin layer was set to 0.95 g / cm³. 3 The plant-derived polyethylene content of the colored base layer is set to 10% by mass, and the density of the colored base layer is set to 0.95 g / cm³. 3 Aside from the fact that it was made as described above, the decorative sheet of Example 30 was prepared using the same procedure as the decorative sheet of Example 2. (Example 31) In the decorative sheet of Example 3, the thickness of the colored substrate layer was set to 150 μm, the recovery power of the transparent resin layer in the indentation test using a Martens hardness tester was set to 50%, the amount of polyethylene crystallization nucleating agent added to the transparent resin layer was set to 5% by mass, the plant-derived polyethylene content of the transparent resin layer was set to 15% by mass, and the density of the transparent resin layer was set to 0.99 g / cm³. 3 The plant-derived polyethylene content of the colored base layer is set to 15% by mass, and the density of the colored base layer is 1.16 g / cm³. 3 Aside from the fact that it was made as described above, the decorative sheet of Example 31 was prepared using the same procedure as the decorative sheet of Example 3.

[0090] (Example 32) The decorative sheet of Example 32 was prepared using the same procedure as the decorative sheet of Example 31, except that the amount of polyethylene crystallization nucleating agent added to the transparent resin layer was 1% by mass.

[0091] (Comparative Example 1) In the decorative sheet of Example 1, the Martens hardness HM in the cross-sectional direction of the transparent resin layer is 25 N / mm². 2 The following conditions were met: the thickness of the colored substrate layer was set to 50 μm, the recovery power of the transparent resin layer in the indentation test using a Martens hardness tester was set to 40%, the amount of polyethylene crystallization nucleating agent added to the transparent resin layer was set to 1% by mass, the plant-derived polyethylene content of the transparent resin layer was set to 10% by mass, and the density of the transparent resin layer was set to 0.95 g / cm³. 3 The plant-derived polyethylene content of the colored base layer is set to 10% by mass, and the density of the colored base layer is set to 0.95 g / cm³. 3 The decorative sheet for Comparative Example 1 was prepared using the same procedure as the decorative sheet for Example 1, except that the desired result was achieved. (Comparative Example 2) The decorative sheet of Comparative Example 2 was prepared using the same procedure as the decorative sheet of Comparative Example 1, except that the thickness of the colored substrate layer was set to 100 μm.

[0092] (Comparative Example 3) In the decorative sheet of Comparative Example 1, the Martens hardness HM in the cross-sectional direction of the transparent resin layer was 65 N / mm². 2 The decorative sheet for Comparative Example 3 was prepared using the same procedure as for the decorative sheet for Comparative Example 1, except that the thickness of the colored substrate layer was set to 120 μm. (Comparative Example 4) In the decorative sheet of Comparative Example 1, the Martens hardness HM in the cross-sectional direction of the transparent resin layer was 65 N / mm². 2 The decorative sheet for Comparative Example 4 was prepared using the same procedure as for the decorative sheet for Comparative Example 1, except that the thickness of the colored substrate layer was set to 155 μm. (Comparative Example 5) The decorative sheet of Comparative Example 5 was prepared using the same procedure as the decorative sheet of Comparative Example 2, except that the content of plant-derived polyethylene in the transparent resin layer was set to 0% by mass.

[0093] (evaluation) The decorative sheets of Examples 1 to 32 and the decorative sheets of Comparative Examples 1 to 5 were evaluated for "environmental friendliness," "surface performance," "transparency," "extrusion suitability," and "bending suitability," respectively. The evaluation method used was as described below. The evaluation results are shown in Table 1.

[0094] <Environmental considerations> We relatively evaluated the dependence on fossil fuels in the production of decorative sheets. Dependence was assessed based on the amount of fossil fuel-derived materials used. A higher amount of fossil fuel use indicated a higher dependence, while a lower amount indicated a lower dependence. Specifically, we evaluated whether the transparent resin layer and the colored base layer each used plant-derived polyolefin resin.

[0095] Evaluation Criteria ○: Both the transparent resin layer and the colored substrate layer contain plant-derived polyolefin resin. △: Either the transparent resin layer or the colored substrate layer contains plant-derived polyolefin resin, while the other is made of fossil-derived polyolefin resin (does not contain plant-derived polyolefin resin).

[0096] <Surface performance> As a measure of surface performance, a pencil hardness test was conducted, and the test results were evaluated. In the pencil hardness test, in accordance with JIS K5600-5-4 (scratch hardness (pencil method)), a pencil was slid across the decorative sheet with a load applied, and it was observed whether an indentation (scratch) was formed in the surface protective layer to evaluate whether the decorative sheet had sufficient scratch resistance or poor scratch resistance.

[0097] Evaluation Criteria ◎: Damage occurred to the surface when using a hardness of 2B or higher. ○: Damage occurred to the surface when using a 3B or 4B pencil. ×: Damage occurred to the surface when using a pencil with a hardness of 5B or less.

[0098] <Transparency> The haze percentage of the transparent resin layer was measured using an ultraviolet-visible-near-infrared spectrophotometer (Shimadzu Corporation: "UV-3600"). To measure the haze percentage of the transparent resin layer, a resin film was first formed by extruding a resin with the same composition as the transparent resin layer of the decorative sheet in each example and comparative example, with a thickness set to between 70 μm and 80 μm. Next, the haze at a wavelength of 555 nm was measured using a spectrophotometer (integrating sphere) to evaluate the haze.

[0099] Evaluation Criteria ◎: Haze is less than 15% ○: Haze is between 15% and less than 25% ×: Haze is 25% or more

[0100] <Extrusion suitability> We evaluated whether there were any problems during the extrusion molding of the colored base material layer and the transparent resin layer on the production line. ○: Products that did not cause any problems during the extrusion molding of the colored base material layer and transparent resin layer on the production line (products that could be molded without any issues). △: Items that had some issues during the extrusion molding process (items that may result in defects). ×: Products that caused problems during the extrusion molding process (products with a very high probability of producing defects). In this example, "○" was considered a passing grade.

[0101] <Suitability for bending processes> We evaluated whether there were any problems with the suitability of the V-cut processing using decorative material laminated to MDF. Specifically, we checked for (the presence or absence of whitening when bent). Evaluation Criteria ○: Those that did not undergo bleaching. △: Slightly bleached. ×: Shows signs of bleaching. Here, a circle (〇) or triangle (△) was considered a passing grade.

[0102] [Table 1]

[0103] In a decorative sheet in which a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order, and the colored thermoplastic resin layer and the transparent thermoplastic resin layer are each formed using a resin composition containing a plant-derived polyolefin resin, the Martens hardness HM in the cross-sectional direction of the transparent thermoplastic resin layer is 30 N / mm². 2 More than 60N / mm 2 It was confirmed that by keeping the following ranges, a decorative sheet could be obtained that met the requirements in terms of "environmental friendliness," "surface performance," "transparency," "extrusion suitability," and "bending suitability," although "extrusion suitability" and "bending suitability" were slightly inferior. Furthermore, it was confirmed that surface performance and transparency could be improved by adjusting the Martens hardness HM in the cross-sectional direction of the transparent thermoplastic resin layer, the thickness of the colored thermoplastic resin layer, and the amount of polyolefin crystallization nucleating agent added to the transparent thermoplastic resin layer.

[0104] Furthermore, the present invention can take the following configuration, for example. (1) A colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order. The colored thermoplastic resin layer and the transparent thermoplastic resin layer are each formed using a resin composition containing a plant-derived polyolefin resin. The aforementioned transparent thermoplastic resin layer has a Martens hardness HM of 30 N / mm² in the cross-sectional direction. 2 More than 60N / mm 2 A decorative sheet characterized by being within the following range.

[0105] (2) The decorative sheet according to (1) above, characterized in that the colored thermoplastic resin layer has a thickness within the range of 55 μm to 150 μm. (3) The decorative sheet according to (1) or (2) above, characterized in that the transparent thermoplastic resin layer has a recovery power ηIT in the range of 25% to 50% in an indentation test using a Martens hardness tester.

[0106] (4) The decorative sheet according to any one of (1) to (3) above, characterized in that the transparent thermoplastic resin layer contains a crystallization nucleating agent for polyolefins in an amount of 2% by mass or more and 5% by mass or less relative to the mass of the plant-derived polyolefin. (5) The transparent thermoplastic resin layer contains 5% by mass or more of plant-derived ethylene relative to the mass of the transparent thermoplastic resin layer, at a concentration of 0.92 g / cm³. 3 More than 0.99g / cm 3 A decorative sheet according to any one of the above items (1) to (4), characterized in having a density within the following range.

[0107] (6) The colored thermoplastic resin layer contains 5% by mass or more of plant-derived ethylene relative to the mass of the colored thermoplastic resin layer, at a concentration of 0.92 g / cm³. 3 More than 1.10g / cm 3 A decorative sheet according to any one of the above items (1) to (5), characterized in having a density within the following range. (7) The decorative sheet according to any one of (1) to (6) above, characterized in that it has a pattern layer between the colored thermoplastic resin layer and the adhesive resin layer.

[0108] (8) The decorative sheet according to any one of (1) to (7) above, characterized by comprising a primer layer laminated on the side of the colored thermoplastic resin layer opposite to the adhesive resin layer. (9) Substrate and A decorative sheet according to any one of the above items (1) to (8) laminated on at least one surface of the substrate, A decorative material characterized by having the following features. [Explanation of Symbols]

[0109] 1 Decorative sheet 2 Colored base material layer (colored thermoplastic resin layer) 3 Pattern Layers 4 Adhesive resin layer 5 Transparent resin layer (transparent thermoplastic resin layer) 6 Surface protective layer 7 Uneven part 8. Primer layer 9 Base material 10 Decorative materials

Claims

1. A colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order. The colored thermoplastic resin layer and the transparent thermoplastic resin layer are each formed using a resin composition containing a plant-derived polyolefin resin. The aforementioned transparent thermoplastic resin layer has a Martens hardness HM of 30 N / mm² in the cross-sectional direction. ２ More than 60N / mm ２ A decorative sheet characterized by being within the following range.

2. The decorative sheet according to claim 1, characterized in that the colored thermoplastic resin layer has a thickness in the range of 55 μm to 150 μm.

3. The decorative sheet according to claim 1 or 2, characterized in that the transparent thermoplastic resin layer has a recovery power ηIT in an indentation test using a Martens hardness tester that is in the range of 25% to 50%.

4. The decorative sheet according to claim 1 or 2, characterized in that the transparent thermoplastic resin layer contains a crystallization nucleating agent for polyolefins in an amount of 2% by mass or more and 5% by mass or less relative to the mass of the plant-derived polyolefin.

5. The transparent thermoplastic resin layer contains 5% by mass or more of plant-derived ethylene relative to the mass of the transparent thermoplastic resin layer, at a concentration of 0.92 g / cm³. ３ 0.99g / cm or more ３ The decorative sheet according to claim 1 or 2, characterized in that it has a density within the following range.

6. The colored thermoplastic resin layer contains 5% by mass or more of plant-derived ethylene relative to the mass of the colored thermoplastic resin layer, at a concentration of 0.92 g / cm³. ３ 1.10g / cm or more ３ The decorative sheet according to claim 1 or 2, characterized in that it has a density within the following range.

7. The decorative sheet according to claim 1 or 2, characterized in that it has a pattern layer between the colored thermoplastic resin layer and the adhesive resin layer.

8. The decorative sheet according to claim 1 or 2, further comprising a primer layer laminated on the side of the colored thermoplastic resin layer opposite to the adhesive resin layer.

9. Substrate and A decorative sheet according to claim 1 or claim 2 laminated on at least one surface of the substrate, A decorative material characterized by having the following features.

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