Decorative sheets and decorative materials

Abstract

To provide decorative sheets and decorative materials that are moisture-resistant and have high printability. [Solution] The decorative sheet 1 is formed by laminating a second anchor coat layer 7, a colored base layer 2, a first anchor coat layer 3, a pattern printing layer 4, a first transparent protective layer 5, and a second transparent protective layer 6 in this order. The colored base layer 2 has a thickness in the range of 40 μm to 150 μm and contains thermoplastic resin and calcium carbonate, with calcium carbonate contained in an amount of 60% to 80% by mass relative to the total mass of the colored base layer 2. The first anchor coat layer 3 contains a urethane resin containing vinyl chloride or an acrylic resin containing the aforementioned vinyl chloride, and the first transparent protective layer 5 and the second transparent protective layer 6 contain an ultraviolet curing resin containing modified silicone, with modified silicone contained in a proportion of 50% by mass or less in the resin solids content of the ultraviolet curing resin.

Description

Technical Field

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

Background Art

[0002] For the purpose of preventing warping of fittings, there have also been proposed methods such as a moisture-proof cosmetic sheet obtained by laminating a moisture-proof film using a sheet of a polyolefin-based resin substrate or a vapor deposition film, or preventing warping by laminating a moisture-proof sheet on the back surface of a wooden substrate of a cosmetic material that becomes a fitting (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Generally, compared with cosmetic paper, a cosmetic sheet made of a resin substrate has better moisture-proof properties and better performance such as scratch resistance, and is therefore used as a facing material for fittings such as doors. However, in the case of a polyester-based resin substrate sheet, compared with a polyolefin-based resin substrate sheet, the moisture-proof property is low, and there is a problem that warping occurs due to moisture or humidity in a decorative board obtained by bonding a resin substrate sheet to a wooden substrate for use in fittings such as doors. This is because fittings such as doors are usually created by bonding a decorative board obtained by bonding a cosmetic sheet to a wooden substrate to the front and back surfaces of a member having a flush structure, and warping occurs due to differences in temperature and humidity between the front and back surfaces and moisture movement.

[0005] Furthermore, when imparting moisture-proof properties to a decorative sheet made of polyester resin substrate, moisture-proof properties can be achieved by laminating it with a moisture-proof film such as a vapor-deposited film. However, this requires a separate primer layer to ensure adhesion with the wood substrate. Similarly, providing a moisture-proof sheet on the back of the wood substrate also increases the manufacturing process, and the method of laminating a moisture-proof sheet on the back of the wood substrate also increases the manufacturing process.

[0006] This invention has been made in view of these points, and aims to provide decorative sheets and decorative materials that have moisture resistance and high printability. [Means for solving the problem]

[0007] According to one aspect of the present invention, a decorative sheet is provided which comprises a laminate in which at least a base layer, an anchor coat layer, and a surface protection layer are laminated in this order, the laminate is a moisture-proof decorative sheet which does not include a moisture-proof layer, the base layer having a thickness in the range of 40 μm to 150 μm and containing a thermoplastic resin and calcium carbonate, with calcium carbonate contained in the range of 60% to 80% by mass relative to the total mass of the base layer, the anchor coat layer containing a urethane resin containing vinyl chloride or an acrylic resin containing vinyl chloride, and the surface protection layer containing an ultraviolet-curing resin containing modified silicone, with modified silicone contained in a proportion of 50% by mass or less in the resin solids content of the ultraviolet-curing resin.

[0008] Furthermore, according to another aspect of the present invention, a decorative material is provided comprising a base material and a decorative sheet of the above aspect provided on at least one side of the base material, wherein the base material is one of a wood-based base material, a resin-based base material, a non-combustible base material, or a metal-based base material. [Effects of the Invention]

[0009] According to one embodiment of the present invention, decorative sheets and decorative materials that are moisture-resistant and have high printability can be easily obtained. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic cross-sectional view showing an example of a decorative sheet according to one embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view showing an example of a decorative material according to one embodiment of the present invention. [Modes for carrying out the invention]

[0011] The embodiments of this technology will be described below with reference to the drawings. Here, 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. Within the scope of this disclosure, the layers do not necessarily have to be stacked in the order shown in the drawings. Furthermore, additional layers not shown in these drawings may be added. Also, the embodiments described below are illustrative of configurations for embodying the technical concept of this disclosure, and the technical concept of this disclosure is not limited to the materials, shapes, and structures of the components described below. The technical concept of this disclosure can be modified in various ways within the technical scope defined by the claims described in the patent claims.

[0012] 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".

[0013] [Composition of decorative sheet] A decorative sheet 1 according to one embodiment of the present invention is a multi-layered decorative sheet, and as shown in Figure 1 for example, it is formed by laminating a colored base layer (base layer) 2, a first anchor coat layer (anchor coat layer) 3, a pattern printing layer 4, a first transparent protective layer (surface protective layer) 5, and a second transparent protective layer (surface protective layer) 6 in that order. In addition, on the side of the colored base layer 2 opposite to the first anchor coat layer 3, a second anchor coat layer 7 and a primer coat layer 8 are laminated in that order.

[0014] An adhesive resin layer may be provided between the pattern printing layer 4 and the first transparent protective layer 5, if necessary. Providing an adhesive resin layer improves the adhesion between the pattern printing layer 4 and the first transparent protective layer 5. The material of the adhesive resin layer is not particularly limited, but can be appropriately selected from acrylic, polyester, polyurethane, epoxy, etc. The coating method can be appropriately selected depending on the viscosity of the adhesive.

[0015] [Colored original fabric layer] The colored base layer 2 consists of a thermoplastic resin and calcium carbonate. The colored base layer 2 contains thermoplastic resin in an amount of 20% to 40% by mass relative to its total mass, and calcium carbonate in powder form in an amount of 60% to 80% by mass relative to its total mass. The thermoplastic resin contains at least one of the following: polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, etc.

[0016] Preferably, the calcium carbonate has an average particle size within the range of 1 μm to 3 μm, and a maximum particle size of 50 μm or less. The colored base layer 2 preferably has a thickness of 40 μm to 150 μm in order to ensure moisture resistance and the processing suitability of the decorative sheet 1. If the thickness of the colored base layer 2 is less than 40 μm, the moisture permeability of the decorative sheet 1 will be 15 g / m². 2 If the moisture permeability exceeds 24 hours and the thickness of the colored raw material layer 2 is greater than 150 μm, the moisture permeability of decorative sheet 1 is 10 g / m². 2 Although the shelf life is less than 24 hours, the reduced processability makes it difficult to use as a decorative sheet.

[0017] The colored base fabric layer 2 is a uniaxially or biaxially stretched base fabric layer. In particular, when the colored base fabric layer 2 is a biaxially stretched base fabric layer, it is preferable because the strength and heat resistance of the entire decorative sheet 1 can be made more suitable.

[0018] The colored base fabric layer 2 may further contain at least one of antimony trioxide, sodium antimonate, zirconium silicate, zirconium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, molybdenum trioxide or a complex of antimony dimolybdate and aluminum hydroxide, a complex of antimony trioxide and silica, a complex of antimony trioxide and zinc white, zirconium silicate, and a complex of a zirconium compound and antimony trioxide, and salts thereof. When containing these, the colored base fabric layer 2 preferably contains calcium carbonate in powder form in the range of 60% to 80% by mass based on the total mass of at least the colored base fabric layer 2.

[0019] 〔First Anchor Coat Layer〕 The first anchor coat layer 3 is made of a urethane resin containing vinylidene chloride or an acrylic resin containing vinylidene chloride. The first anchor coat layer 3 is provided for improving printing suitability. By providing the first anchor coat layer 3, it is possible to prevent the calcium carbonate contained in the colored base fabric layer 2 from falling off. During the manufacturing process, if the calcium carbonate in the colored base fabric layer 2 falls off, it may contaminate the printing system or cause problems such as ink bleeding. Here, "ink bleeding" means that the ink is not partially printed.

[0020] Furthermore, by providing the first anchor coat layer 3, the adhesion between the ink for forming the pattern printing layer 4 and the colored base layer 2 can be improved. If the pattern is printed directly onto the colored base layer 2 without using the first anchor coat layer 3, the ink will not adhere to the colored base layer 2. If, for example, cellophane tape is pressed onto the printed material and then peeled off, delamination will occur between the printed material and the colored base layer 2, resulting in insufficient adhesion strength between layers, which is a problem for building materials. By providing the first anchor coat layer 3, the insufficient adhesion strength between layers can be resolved.

[0021] Before forming the first anchor coat layer 3 on the colored base layer 2, it is preferable to perform corona treatment or plasma treatment on the surface of the colored base layer 2 on which the first anchor coat layer 3 will be formed. "Vinyl chloride copolymer" refers to a copolymer of vinyl chloride and vinyl acetate. "Urethane resin containing vinyl chloride" refers to a composition containing vinyl chloride and a urethane resin. "Urethane resin containing vinyl chloride" may also contain a curing agent in addition to vinyl chloride and the urethane resin. This curing agent is added to ensure the curing of the urethane resin containing vinyl chloride, and its content is not particularly limited. "Acrylic resin containing vinyl chloride" refers to a composition containing vinyl chloride and an acrylic resin. "Acrylic resin containing vinyl chloride" may also contain a curing agent in addition to vinyl chloride and the acrylic resin. This curing agent is added to ensure the curing of the acrylic resin containing vinyl chloride, and its content is not particularly limited.

[0022] [Image printing layer] The pattern printing layer 4 is provided as needed to give the decorative sheet 1 a design aesthetic, and is formed by printing various patterns using ink and a printing press. Patterns for the pattern printing layer 4 include wood grain patterns, marble patterns (e.g., travertine marble patterns) that mimic the surface of rocks, fabric patterns that mimic the texture of cloth or cloth, tile patterns, brick patterns, and patterns that combine these, such as marquetry and patchwork. These patterns are formed by multicolor printing using the usual yellow, red, blue, and black process colors, as well as by multicolor printing using spot colors, where individual plates for each color that makes up the pattern are prepared.

[0023] The ink used for the pattern printing layer 4 is a mixture of a binder with appropriate amounts of colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, and curing agents. There are no particular restrictions on the binder; for example, any of the following can be used, either alone or in mixtures of two or more: polyurethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc.

[0024] Ink colorants include inorganic pigments such as carbon black, iron black, titanium white, antimony white, lead yellow, titanium yellow, iron oxide, cadmium red, ultramarine, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metallic pigments consisting of flaky foil pieces of aluminum, brass, etc.; and pearlescent pigments consisting of flaky foil pieces of titanium dioxide-coated mica, basic lead carbonate, etc.

[0025] [First transparent protective layer] The first transparent protective layer 5 is a solid printing layer that covers the entire surface of the pattern printing layer 4 opposite to the first anchor coat layer 3. The first transparent protective layer 5 is made of a material (resin) that is transparent or translucent enough to allow the pattern of the pattern printing layer 4 to be seen through the first transparent protective layer 5, and is formed of a UV-curable resin containing modified silicone. The content of modified silicone in the solid content of the UV-curable resin containing modified silicone is preferably 50% by mass or less. The thickness of the first transparent protective layer 5 is preferably in the range of, for example, 2 μm to 10 μm.

[0026] The first transparent protective layer 5 may contain a triazine-based ultraviolet absorber UVA as a weathering agent and a photopolymerization initiator that does not have an absorption peak in the 260nm to 330nm range as a photopolymerization initiator. By using a UV-curable resin containing modified silicone as the resin constituting the first transparent protective layer 5, it is possible to prevent cohesive failure caused by adding calcium carbonate to the colored base layer 2, and to improve stain resistance and peel strength against cellophane tape. Furthermore, by using modified silicone, cohesive failure can be prevented for a longer period of time.

[0027] [Second transparent protective layer] The second transparent protective layer 6 is a layer partially provided on the side of the first transparent protective layer 5 opposite to the pattern printing layer 4, and is a layer for adding design to the decorative sheet 1. The second transparent protective layer 6 is formed using the same resin as the first transparent protective layer 5, except that it is partially printed. The second transparent protective layer 6 may also be given a triazine-based ultraviolet absorber UVA as a weathering agent and a photopolymerization initiator that does not have an absorption peak in the 260nm to 330nm range as a photopolymerization initiator.

[0028] By using a UV-curable resin containing modified silicone as the resin constituting the second transparent protective layer 6, it is possible to prevent cohesive failure that occurs when calcium carbonate is added to the colored base layer 2, and to improve stain resistance and peel strength against cellophane tape. Furthermore, by using modified silicone, cohesive failure can be prevented for a longer period of time.

[0029] The second transparent protective layer 6 is formed, for example, on the portion of the pattern printing layer 4 that faces the printing ink. Fillers may be added to the second transparent protective layer 6. By adding fillers, different gloss, feel, texture, surface strength, friction, and other mechanical properties can be imparted to the second transparent protective layer 6. Examples of fillers include zirconium compounds such as antimony trioxide, antimony soda, zircon silicate, and zircon oxide; complexes of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, molybdenum trioxide, or antimony dimolybdate and aluminum hydroxide; complexes of antimony trioxide and silica; complexes of antimony trioxide and zinc oxide; zirconium silicate; and complexes of zirconium compounds and antimony trioxide. In addition, beads or amorphous particles of resins such as acrylic, polyolefin, and silicone, or beads or amorphous particles of inorganic materials such as silica (especially hollow silica), alumina, and metal oxides can be used. Furthermore, the method for forming the second transparent protective layer 6 is not particularly limited, and known printing techniques can be used. The second transparent protective layer 6 is also commonly referred to as the "tactile coating layer" or the "matte conduit printing layer."

[0030] [Second anchor coat layer] The second anchor coat layer 7, like the first anchor coat layer 3, is made of a urethane resin containing vinyl chloride or an acrylic resin containing vinyl chloride. The second anchor coat layer 7 is provided to improve printability, and by providing the second anchor coat layer 7, it is possible to prevent the shedding of calcium carbonate powder contained in the colored base layer 2. If calcium carbonate powder sheds from the colored base layer 2 during the manufacturing process, it may contaminate the printing system or cause problems such as ink leakage. Before forming the second anchor coat layer 7 on the colored base layer 2, it is preferable to perform corona treatment or plasma treatment on the surface of the colored base layer 2 on which the second anchor coat layer 7 will be formed.

[0031] [Primer coat layer] As shown in Figure 2, the primer coat layer 8 is a layer provided to improve the adhesion between the decorative sheet 1 and the base material 9 when laminating the decorative sheet 1 to the base material 9 to form the decorative material 10.

[0032] The primer coat layer 8 can be made of, for example, ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, etc., when the substrate 9 to which the decorative sheet 1 is bonded is a wood-based substrate. These resins can be used individually or in combination to form an adhesive composition, which can then be formed using appropriate coating methods such as roll coating or gravure printing. Urethane-acrylate resins are preferred as the resin constituting the primer coat layer 8, and it is particularly preferred to form it with a resin consisting of a copolymer of acrylic resin and urethane resin and an isocyanate.

[0033] As described above, the primer coat layer 8 is formed to improve the adhesion between the substrate 9 and the decorative sheet 1, so the primer coat layer 8 does not need to be provided.

[0034] [Moisture permeability of decorative sheets] Moisture permeability refers to the amount of moisture transferred after 24 hours in an environment with a temperature of 40°C and a humidity of 90%, as measured in accordance with JIS Z0208 1976 "Test Method for Moisture Permeability of Moisture-Proof Packaging Materials (Cup Method)". The moisture permeability of decorative sheet 1 is 15 g / m². 2 It is preferable that it is less than 24hr, and 10 [g / m³] 2 It is more preferable that it be less than 24 hours.

[0035] [Manufacturing method for decorative sheets] A brief explanation of one example of a manufacturing method for decorative sheet 1 will be given. First, one side of the colored raw material layer 2 that will form the first anchor coat layer 3 is subjected to corona treatment or plasma treatment. Then, the surface that has been subjected to corona treatment or plasma treatment is coated with an ink for forming the first surface anchor coat layer 3 to form the first anchor coat layer 3.

[0036] Next, an ink for forming a pattern printing layer 4 is applied onto the first anchor coat layer 3 to form the pattern printing layer 4. Next, an ink for forming the first transparent protective layer 5 is applied to the surface of the pattern printing layer 4 to form the first transparent protective layer 5. Next, the second transparent protective layer 6 is formed by partially applying an ink for forming the second transparent protective layer 6 onto the first transparent protective layer 5 in a manner that enhances the aesthetic appearance.

[0037] Next, an ink for forming the second anchor coat layer 7 is applied to the side of the colored raw material layer 2 opposite to the first anchor coat layer 3, thereby forming the second anchor coat layer 7.

[0038] Finally, a primer coat layer forming ink is applied onto the second anchor coat layer 7 to form the primer coat layer 8.

[0039] The decorative sheet 1 is formed as described above. The second anchor coat layer 7 may be formed simultaneously with the first anchor coat layer 3. Furthermore, the primer coat layer 8 may be formed before the pattern printing layer 4, the first transparent protective layer 5, and the second transparent protective layer 6.

[0040] [Decorative materials] As shown in Figure 2, the decorative material 10 comprises a base material 9 and a decorative sheet 1. (base material) The base material 9 is a plate-shaped member formed using, for example, a metallic material, a wood-based material, or an inorganic material. Examples of metallic materials include aluminum, steel, stainless steel, and composite panels. Composite panels can include, for example, a resin layer serving as a core material, with metal plates (aluminum, galvalume, stainless steel, etc.) attached to both sides of the resin layer. Examples of wood-based materials include MDF (Medium Density Fiberboard), plywood, and particleboard. Examples of inorganic materials include gypsum board and fiber-reinforced calcium silicate board.

[0041] [Method of manufacturing decorative materials] A brief explanation will be given of an example of a manufacturing method for the cosmetic material 10. First, the primer coat layer 8 of the decorative sheet 1 is positioned facing the substrate 9. Next, this laminate is subjected to, for example, heat lamination. In this way, the primer coat layer 8 and the substrate 9 are welded together to form the decorative material 10.

[0042] In addition to the method of pressing the laminated material with a metal plate, a continuous lamination method using circular pressure can also be used for thermal lamination of the above-mentioned laminate. In particular, using a continuous lamination method that uses an endless metal belt or a heat drum made of metal or a hardening resin allows for the continuous production of a decorative material 10 that is free from surface warping or undulation, has good interlayer adhesion, and is densely hardened and integrated, at high speed.

[0043] [Effects of this embodiment] (1) According to the decorative sheet 1 of this embodiment, the colored base layer 2 contains a thermoplastic resin and calcium carbonate, has a thickness in the range of 40 μm to 150 μm, and a first anchor coat layer 3 containing a urethane resin containing vinyl chloride or an acrylic resin containing vinyl chloride and a second anchor coat layer 7 are provided on both sides of the colored base layer 2, so that a highly moisture-resistant decorative sheet 1 can be easily obtained without adding any manufacturing steps. In other words, for example, if a separate moisture-proof layer is provided to obtain a highly moisture-resistant decorative sheet, it will increase the manufacturing process, but since moisture resistance can be obtained without providing a moisture-proof layer, a highly moisture-resistant decorative sheet 1 can be easily obtained without increasing the manufacturing process. Therefore, a decorative sheet that does not rely on petroleum-derived products and is in line with solving environmental issues can be obtained. Furthermore, since the first anchor coat layer 3 and the second anchor coat layer 7 are provided on both sides of the colored base layer 2, it is possible to suppress the shedding of calcium carbonate contained in the colored base layer 2 during the manufacturing process, and a decorative sheet with high printability can be obtained.

[0044] The term "moisture barrier" here refers to a moisture-proof layer measured according to JIS Z0208 1976 "Method for testing moisture permeability of moisture-proof packaging materials (cup method)," where, under conditions of 40°C and 90% humidity, the amount of moisture transferred after 24 hours is 15 g / m³. 2 This refers to layers that are less than 24 hours old.

[0045] (2) Since the first transparent protective layer 5 and the second transparent protective layer 6 contain a UV-curing resin containing modified silicone, cohesive failure can be suppressed in the colored raw material layer 2 containing calcium carbonate, which is placed beneath the first transparent protective layer 5 and the second transparent protective layer 6. Furthermore, improved stain resistance can also be achieved.

[0046] [Variation] (1) In this embodiment, the design is described in which the second transparent protective layer 6 is partially applied on the first transparent protective layer 5 to create a design feature, but the invention is not limited to this. The second transparent protective layer 6 may be applied as a solid layer on the first transparent protective layer 5. Also, although the transparent protective layer is described as a multi-layer structure, the transparent protective layer may be a single layer.

[0047] (2) In this embodiment, the decorative sheet 1 has been described as having a structure in which a primer coat layer 8, a second anchor coat layer 7, a colored base layer 2, a first anchor coat layer 3, a pattern printing layer 4, a first transparent protective layer 5, and a second transparent protective layer 6 are laminated in this order, but it is not limited to this. The decorative sheet 1 only needs to include at least a colored base layer 2, a first anchor coat layer 3, and a first transparent protective layer 5.

[0048] In this embodiment, the decorative sheet 1 also includes cases where it does not have a pattern printing layer 4, and for example, a single-color sheet in which the color of the colored base layer is visible is also included in the decorative sheet 1. [Examples]

[0049] The present invention will be described in detail below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[0050] [Preparation of decorative sheets for the examples and comparative examples] (Example 1) A base layer consisting of 60% by mass of calcium carbonate and 40% by mass of polypropylene resin (PP resin) relative to the total mass of the base layer was used as the colored base layer 2. The thickness of the colored base layer 2 was set to 80 μm.

[0051] Next, corona treatment was performed on one side of this colored raw material layer 2. Next, an anchor coating agent made of a urethane resin containing vinyl chloride was applied to the corona-treated surface of the colored base material layer 2 to form a first anchor coating layer 3 with a coating thickness of 1 to 2 μm. Subsequently, a solid ink layer and a pattern ink layer were formed on the first anchor coating layer 3 using an ink made of a urethane resin to form a pattern printing layer 4.

[0052] On top of the patterned print layer 4, an acrylic UV-curing resin containing modified silicone was first applied to the entire surface, then partially applied on top of that, and then UV light was irradiated to crosslink the resin, forming a first transparent protective layer 5 and a second transparent protective layer 6. The thickness of the transparent protective layer consisting of the first transparent protective layer 5 and the second transparent protective layer 6 was 5 μm. This created a moisture-resistant decorative sheet 1. A vinyl acetate adhesive was applied to the surface of a base material 9 made of a 2.5 mm thick MDF board, and a decorative sheet 1 and the base material 9 were bonded together so that the colored base material layer 2 was in contact with the vinyl acetate adhesive applied to the base material 9, thereby creating a moisture-resistant decorative material 10.

[0053] (Example 2) The decorative material of Example 2 was prepared using the same procedure as the decorative material 10 of Example 1, except that in the decorative sheet 1 of Example 1, a colored film consisting of 80% by mass of calcium carbonate and 20% by mass of PP resin relative to the total mass of the colored film was used as the colored raw material layer 2.

[0054] (Comparative Example 1) The decorative material of Comparative Example 1 was prepared using the same procedure as the decorative material 10 of Example 1, except that in the decorative sheet 1 of Example 1, a base material consisting of 100% by mass of PP resin relative to the total mass of the base material, which does not contain calcium carbonate, was used as the colored base material layer 2. (Comparative Example 2) The decorative material of Comparative Example 2 was prepared using the same procedure as the decorative material 10 of Example 1, except that the decorative sheet 1 of Example 1 used a base roll consisting of 100% by mass of polybutylene terephthalate resin (PBT resin) relative to the total mass of the base roll, which does not contain calcium carbonate, as the colored base roll layer 2.

[0055] (Comparative Example 3) In the decorative sheet 1 of Example 1, the decorative material of Comparative Example 3 was prepared using the same procedure as the decorative material 10 of Example 1, except that corona treatment was not performed on the colored raw material layer 2 and the first anchor coat layer 3 was not applied. (Comparative Example 4) The decorative material of Comparative Example 4 was prepared using the same procedure as the decorative material 10 of Example 1, except that the first transparent protective layer 5 and the second transparent protective layer 6 in the decorative sheet 1 of Example 1 were formed using an acrylic ultraviolet curing resin that does not contain modified silicone.

[0056] (Comparative Example 5) In the decorative sheet 1 of Example 1, a base material consisting of 100% by mass of PP resin relative to the total mass of the base material, which does not contain calcium carbonate, was used as the colored base material layer 2. Corona treatment was not performed on this colored base material layer, and the first anchor coat layer 3 was not applied on the colored base material layer. The first transparent protective layer 5 and the second transparent protective layer 6 were formed using an acrylic ultraviolet curing resin that does not contain modified silicone. The decorative material of Comparative Example 5 was prepared using the same procedure as the decorative material 10 of Example 1. (Comparative Example 6) In the decorative sheet 1 of Example 1, a base material consisting of 100% by mass of PP resin relative to the total mass of the base material, which does not contain calcium carbonate, was used as the colored base material layer 2, and the first anchor coat layer 3 was not applied on this colored base material layer. The decorative material of Comparative Example 6 was prepared using the same procedure as the decorative material 10 of Example 1.

[0057] (Comparative Example 7) The decorative material of Comparative Example 7 was prepared using the same procedure as the decorative material 10 of Example 1, except that the first transparent protective layer 5 and the second transparent protective layer 6 in the decorative sheet 1 of Example 1 were formed using an acrylic ultraviolet curing resin that does not contain modified silicone. (Comparative Example 8) The decorative material of Comparative Example 8 was prepared using the same procedure as the decorative material 10 of Example 1, except that in the decorative sheet 1 of Example 1, a base material consisting of 100% by mass of PP resin relative to the total mass of the base material, which does not contain calcium carbonate, was used as the colored base material layer 2, and the first transparent protective layer 5 and the second transparent protective layer 6 were formed using an acrylic ultraviolet curing resin that does not contain modified silicone.

[0058] (Comparative Example 9) The decorative material of Comparative Example 9 was prepared using the same procedure as the decorative material 10 of Example 1, except that the decorative sheet 1 of Example 1 used a base roll with a thickness of 35 μm, consisting of 60% by mass of calcium carbonate and 40% by mass of polypropylene resin (PP resin) relative to the total mass of the base roll, as the colored base roll layer 2. (Comparative Example 10) The decorative material of Comparative Example 10 was prepared using the same procedure as the decorative material 10 of Example 1, except that the decorative sheet 1 of Example 1 used a base roll with a thickness of 200 μm, consisting of 60% by mass of calcium carbonate and 40% by mass of polypropylene resin (PP resin) relative to the total mass of the base roll, as the colored base roll layer 2.

[0059] [Evaluation Method] The decorative materials of Examples 1-2 and Comparative Examples 1-10 were evaluated for interlayer adhesion strength, peel resistance, moisture permeability, stain resistance, and petroleum dependence. The evaluation method is as follows. (Interlayer adhesion strength) The interlayer strength between the colored base layer and the patterned printing layer was evaluated as interlayer adhesion strength. Specifically, during the decorative sheet manufacturing process, at the stage when the patterned printing layer was formed, cellophane tape was pressed onto the surface of the patterned printing layer and immediately peeled off to visually check for ink peeling and delamination between the colored base layer and the patterned printing layer. The evaluation criteria were as follows: ○; No peeling. △: Some peeling occurs. ×: The peeled ink adheres to the entire surface of the cellophane tape, resulting in significant delamination.

[0060] (Peel resistance) The peel strength of the colored raw material layer was evaluated as peel resistance. Specifically, cellophane tape was pressed onto the surface of the decorative sheet and immediately peeled off to visually check for the occurrence of cohesive failure in the colored base layer. The evaluation criteria were as follows: ○: No peeling. △: Some peeling occurs. ×: Part of the peeled colored base layer adheres to the entire surface of the cellophane tape, causing significant cohesive failure of the colored base layer.

[0061] (moisture permeability) At the stage of creating the decorative sheet, the amount of moisture transfer was measured after 24 hours in an environment with a temperature of 40°C and a humidity of 90%, in accordance with JIS Z0208 1976 "Method for testing moisture permeability of moisture-proof packaging materials (cup method)".

[0062] (Stain-resistant) An oil-based marker pen was used to draw on the surface of the decorative sheet, and then the drawing was wiped off with a dried Kimwipe®. The evaluation criteria were as follows: ○: Drawings made with magic pens can be wiped away. △: Although there is some slight color residue, the marks made with the magic pen can be wiped off. ×: There is some color residue, and it cannot be wiped off.

[0063] (Oil dependence) We evaluated the petroleum dependence of cosmetic materials. The evaluation criteria are as follows: ○: Low usage rate of petroleum-derived materials, resulting in low dependence on petroleum. △: The usage rate of petroleum-derived materials is moderate, indicating a moderate level of dependence on petroleum. ×: High usage rate of petroleum-derived materials, resulting in high dependence on petroleum. The measurement and evaluation results are shown in Table 1.

[0064] [Table 1]

[0065] Table 1 shows that a decorative sheet comprising a colored base layer 2 having a thickness in the range of 40 μm to 150 μm and containing thermoplastic resin in the range of 20% to 40% by mass and calcium carbonate in the range of 60% to 80% by mass relative to the total mass of the colored base layer 2, a first anchor coat layer 3 containing a urethane resin containing vinyl chloride, and a first transparent protective layer 5 and a second transparent protective layer 6 containing a UV-curing resin containing modified silicone, with modified silicone in a ratio of 50% by mass or less in the resin solids content of the UV-curing resin, has a moisture permeability of 15 g / m² without the need for a separate moisture barrier layer. 2 It was confirmed that the shelf life was less than 24 hours, and that a decorative sheet with excellent printability, processability, interlayer adhesion strength, peel resistance, stain resistance, and petroleum dependence could be obtained.

[0066] Furthermore, the present invention can take the following configuration, for example. (1) The laminate consists of at least a base layer, an anchor coat layer, and a surface protection layer laminated in this order, and the laminate is a decorative sheet that does not include a moisture-proof layer having moisture-proof properties. The aforementioned base layer has a thickness in the range of 40 μm to 150 μm, contains a thermoplastic resin and calcium carbonate, and contains calcium carbonate in an amount of 60% to 80% by mass relative to the total mass of the base layer. The anchor coat layer contains a urethane resin containing vinyl chloride or an acrylic resin containing vinyl chloride. The decorative sheet is characterized in that the surface protective layer contains an ultraviolet-curing resin containing modified silicone, and the modified silicone is contained in the resin solids content of the ultraviolet-curing resin at a ratio of 50% by mass or less. (2) Moisture permeability of 15g / m 2 The decorative sheet described in (1) above, characterized in that it is less than 24 hours. (3) The decorative sheet according to (1) or (2) above, characterized in that the base layer further contains at least one of the following: antimony trioxide, antimony soda, zirconium silicate, zirconium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, molybdenum trioxide or a complex of antimony dimolybdate and aluminum hydroxide, a complex of antimony trioxide and silica, a complex of antimony trioxide and zinc oxide, zirconium silicate, and a complex of a zirconium compound and antimony trioxide, as well as salts thereof. (4) The decorative sheet according to any one of (1) to (3) above, characterized in that the thermoplastic resin contains at least one of the following: polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, etc. (5) The decorative sheet according to (1) or (2) above, characterized in that the base layer contains the thermoplastic resin in an amount of 20% by mass or more and 40% by mass or less. (6) The decorative sheet according to any one of (1) to (5) above, characterized in that the calcium carbonate is in powder form, has an average particle diameter in the range of 1 μm to 3 μm, and a maximum particle diameter of 50 μm or less. (7) The decorative sheet according to any one of (1) to (6) above, characterized in that the surface protective layer contains a weather-resistant agent and a photopolymerization initiator. (8) Substrate and The base material comprises a decorative sheet according to any one of the above items (1) to (7), provided on at least one side of the base material, The aforementioned base material is characterized in that it is one of the following: a wood-based base material, a resin-based base material, a non-combustible base material, or a metal base material. [Explanation of symbols]

[0067] 1 Decorative sheet 2 Colored original fabric layer 3. First anchor coat layer 4. Pattern printing layer 5 First transparent protective layer 6 Second transparent protective layer 7. Second anchor coat layer 8. Primer coat layer 9 Base material 10 Decorative materials

Claims

1. The laminate consists of at least a base layer, an anchor coat layer, and a surface protection layer laminated in this order, and the laminate is a decorative sheet that does not include a moisture-proof layer having moisture-proof properties. The aforementioned base layer has a thickness in the range of 40 μm to 150 μm, contains a thermoplastic resin and calcium carbonate, and contains calcium carbonate in an amount of 60% to 80% by mass relative to the total mass of the base layer. The anchor coat layer contains a urethane resin containing vinyl chloride or an acrylic resin containing vinyl chloride. The decorative sheet is characterized in that the surface protective layer contains an ultraviolet-curing resin containing modified silicone, and the modified silicone is contained in the resin solids content of the ultraviolet-curing resin at a ratio of 50% by mass or less.

2. Moisture permeability of 15 g / m ２ The decorative sheet according to claim 1, characterized in that it is 24 hours or less.

3. The decorative sheet according to claim 1 or 2, characterized in that the base layer further contains at least one of the following: antimony trioxide, antimony soda, zirconium silicate, zirconium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, molybdenum trioxide or a complex of antimony dimolybdate and aluminum hydroxide, a complex of antimony trioxide and silica, a complex of antimony trioxide and zinc oxide, zirconium silicate, and a complex of a zirconium compound and antimony trioxide, as well as salts thereof.

4. The decorative sheet according to claim 1 or 2, characterized in that the thermoplastic resin contains at least one of the following: polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, etc.

5. The decorative sheet according to claim 1 or 2, characterized in that the base layer contains the thermoplastic resin in an amount of 20% by mass or more and 40% by mass or less.

6. The decorative sheet according to claim 1 or 2, characterized in that the calcium carbonate is in powder form, has an average particle diameter within the range of 1 μm to 3 μm, and a maximum particle diameter of 50 μm or less.

7. The decorative sheet according to claim 1 or 2, characterized in that the surface protective layer contains a weather-resistant agent and a photopolymerization initiator.

8. Substrate and The base material comprises a decorative sheet according to claim 1 or claim 2 provided on at least one side of the base material, The aforementioned base material is characterized in that it is one of the following: a wood-based base material, a resin-based base material, a non-combustible base material, or a metal base material.

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