Decorative sheet and decorative material

Abstract

The present invention provides a decorative sheet and a decorative material which have moisture-proof properties and high printability. In order to achieve the above, a decorative sheet (1) is formed by stacking a second anchor coat layer (7), a colored base layer (2), a first anchor coat layer (3), a pattern print 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 within the range of 40 µm to 150 µm inclusive, contains a thermoplastic resin and calcium carbonate, and contains calcium carbonate within the range of 60 mass% to 80 mass% inclusive with respect to the total mass of the colored base layer (2). The first anchor coat layer (3) contains a urethane resin containing a vinyl chloride-vinyl acetate copolymer resin or an acrylic resin containing the vinyl chloride-vinyl acetate copolymer resin. The first transparent protective layer (5) and the second transparent protective layer (6) contain an ultraviolet curable resin that contains a modified silicon. The modified silicon is contained in a proportion of 50 mass% or less in the resin solid content of the ultraviolet curable resin.

Description

Decorative sheets and decorative materials

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

[0002] In order to prevent warping of building materials, methods have been proposed, such as moisture-proof decorative sheets laminated with moisture-proof films using polyolefin resin substrate sheets or vapor-deposited films, and methods of preventing warping by laminating a moisture-proof sheet on the backside of the wooden substrate of the decorative material that will become the building material (see, for example, Patent Document 1).

[0003] Japanese Patent Application Laid-Open No. 2001-193267

[0004] In general, resin-based decorative sheets are more moisture-proof and scratch-resistant than decorative paper, and are therefore used as facings for doors and other fixtures. However, polyester-based resin-based sheets have lower moisture resistance than polyolefin-based resin-based sheets, and decorative panels made by bonding a resin-based sheet to a wood substrate for doors and other fixtures have the problem of warping due to moisture and humidity. This is because doors and other fixtures are usually made by bonding a decorative panel made by bonding a decorative sheet to a wood substrate to the front and back surfaces of flush-structured components, and warping occurs due to differences in temperature and humidity between the front and back surfaces and moisture movement.

[0005] Furthermore, when adding moisture-proofing properties to decorative sheets with polyester resin substrates, it is possible to impart moisture-proofing properties by laminating them with a moisture-proof film such as a vapor-deposited film, but when a moisture-proof film is laminated onto a decorative sheet, a separate primer layer must be applied to ensure that the decorative sheet adheres to the wood substrate. Applying a moisture-proof sheet to the backside of a wood substrate increases the number of manufacturing steps.

[0006] The present invention has been made in view of the above points, and has as its object to provide a decorative sheet and decorative material that are moisture-proof and highly suitable for printing.

[0007] According to one aspect of the present invention, there is provided a decorative sheet comprising a laminate in which at least a base fabric layer, an anchor coat layer, and a surface protection layer are laminated in this order, the laminate being a moisture-proof decorative sheet without a moisture-proof layer, wherein the base fabric layer has a thickness in the range of 40 μm to 150 μm and contains a thermoplastic resin and calcium carbonate, the calcium carbonate content being in the range of 60% by mass to 80% by mass relative to the mass of the entire base fabric layer, the anchor coat layer contains a urethane-based resin containing vinyl chloride and acetate or an acrylic-based resin containing vinyl chloride and acetate, and the surface protection layer contains an ultraviolet-curable resin containing modified silicon, and the modified silicon is contained in a proportion of 50% by mass or less in the resin solid content of the ultraviolet-curable resin.

[0008] According to another aspect of the present invention, there is provided a decorative material comprising a substrate and a decorative sheet of the above-described aspect provided on at least one side of the substrate, wherein the substrate is any one of a wood substrate, a resin substrate, a non-flammable substrate, and a metal substrate.

[0009] According to one embodiment of the present invention, decorative sheets and decorative materials that are moisture-proof and highly suitable for printing can be easily obtained.

[0010] 1 is a cross-sectional view schematically showing an example of a decorative sheet according to an embodiment of the present invention; 2 is a cross-sectional view schematically showing an example of a decorative material according to an embodiment of the present invention;

[0011] Hereinafter, embodiments of the present technology will be described with reference to the drawings. The drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, and the like differ from the actual ones. The layers do not necessarily need to be stacked in the order shown in the drawings, as long as they fall within the scope of the present disclosure. Layers not shown in the drawings may also be added. The embodiments shown below exemplify configurations for embodying the technical idea of ​​the present disclosure, and the technical idea of ​​the present disclosure is not limited to the materials, shapes, structures, and the like of the components described below. Various modifications can be made to the technical idea of ​​the present disclosure within the technical scope defined by the claims.

[0012] Furthermore, the directions of "left and right" and "up and down" in the following explanation are merely definitions for the convenience of explanation and do not limit the technical idea of ​​the present disclosure. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left."

[0013] [Configuration of Decorative Sheet] A decorative sheet 1 according to one embodiment of the present invention is a decorative sheet having a multi-layer configuration, and is formed by laminating, in this order, a colored base fabric layer (base fabric layer) 2, a first anchor coat layer (anchor coat layer) 3, a picture print layer 4, a first transparent protective layer (surface protective layer) 5, and a second transparent protective layer (surface protective layer) 6, as shown in Fig. 1. Furthermore, on the surface of the colored base fabric layer 2 opposite the first anchor coat layer 3, a second anchor coat layer 7 and a primer coat layer 8 are laminated, in this order.

[0014] An adhesive resin layer may be provided between the picture print layer 4 and the first transparent protective layer 5, if necessary. By providing an adhesive resin layer, it is possible to improve the adhesion between the picture print 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, etc.

[0015] [Colored Raw Fabric Layer] The colored raw fabric layer 2 is composed of a thermoplastic resin and calcium carbonate. It contains 20% to 40% by mass of thermoplastic resin relative to the total mass of the colored raw fabric layer 2, and 60% to 80% by mass of powdered calcium carbonate relative to the total mass of the colored raw fabric layer 2. The thermoplastic resin contains at least one of 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, and the like.

[0016] The calcium carbonate preferably has an average particle size in the range of 1 μm to 3 μm and a maximum particle size of 50 μm or less. The colored raw fabric layer 2 preferably has a thickness in the range of 40 μm to 150 μm in order to ensure moisture resistance and processability of the decorative sheet 1. If the colored raw fabric layer 2 is thinner than 40 μm, the moisture permeability of the decorative sheet 1 will be 15 g / m or less. ２ When the time exceeds 24 hours and the thickness of the colored raw fabric layer 2 is greater than 150 μm, the moisture permeability of the decorative sheet 1 is 10 g / m ２ Although it lasts for less than 24 hours, the processability is reduced, making it difficult to use as a decorative sheet.

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

[0018] The colored raw fabric layer 2 may further contain at least one of antimony trioxide, antimony sodium, zirconium silicate, zirconium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, a complex of molybdenum trioxide or antimony dimolybdate with aluminum hydroxide, a complex of antimony trioxide with silica, a complex of antimony trioxide with zinc oxide, zirconium silicate, a complex of a zirconium compound with antimony trioxide, and salts thereof. If these are contained, the colored raw fabric layer 2 preferably contains at least powdered calcium carbonate in an amount ranging from 60% to 80% by mass relative to the total mass of the colored raw fabric layer 2.

[0019] [First Anchor Coat Layer] The first anchor coat layer 3 is made of a urethane resin containing vinyl chloride and acetate or an acrylic resin containing vinyl chloride and acetate. The first anchor coat layer 3 is provided to improve printability, and by providing the first anchor coat layer 3, it is possible to prevent calcium carbonate contained in the colored raw fabric layer 2 from falling off. If calcium carbonate in the colored raw fabric layer 2 falls off during the manufacturing process, it may contaminate the printing system or cause problems such as ink loss. Here, "ink loss" refers to a situation where ink is not printed in parts.

[0020] Furthermore, by providing the first anchor coat layer 3, it is possible to improve adhesion between the ink used to form the picture printed layer 4 and the colored raw fabric layer 2. If a picture is printed directly on the colored raw fabric layer 2 without using the first anchor coat layer 3, the ink will not adhere to the colored raw fabric layer 2. Therefore, if cellophane tape or the like is applied to the printed matter and then peeled off, interlayer delamination occurs between the printed matter and the colored raw fabric layer 2, and insufficient interlayer adhesion strength becomes an issue when used as a building material. By providing the first anchor coat layer 3, it is possible to eliminate the insufficient interlayer adhesion strength.

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

[0022] [Picture Printed Layer] The picture printed layer 4 is provided as needed to impart a design to the decorative sheet 1, and is formed by printing various patterns using ink and a printing machine. Patterns that can be used for the picture printed layer 4 include wood grain patterns, stone patterns that imitate the surface of rocks such as marble patterns (e.g., travertine marble patterns), fabric patterns that imitate fabric or cloth-like patterns, tile patterns, brickwork patterns, and the like. There are also patterns that combine these, such as marquetry and patchwork. These patterns can be formed by multicolor printing using the usual process colors of yellow, red, blue, and black, as well as by multicolor printing using special colors, in which plates for each color that makes up the pattern are prepared.

[0023] The ink used for the picture print layer 4 is a mixture of a binder with an appropriate amount of a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardener, etc. There are no particular limitations on the binder, and any of polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins, etc. may be used alone or in combination of two or more.

[0024] Examples of colorants for the ink include inorganic pigments such as carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metal pigments consisting of scaly flakes of aluminum, brass, etc.; and pearlescent pigments consisting of scaly flakes of titanium dioxide-coated mica, basic lead carbonate, etc.

[0025] [First Transparent Protective Layer] The first transparent protective layer 5 is a solid print layer that covers the entire surface of the picture printed layer 4 opposite 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 picture of the picture printed layer 4 to be seen through the first transparent protective layer 5, and is formed of a UV-curable resin containing modified silicon. The content of modified silicon in the solid content of the UV-curable resin containing modified silicon is preferably 50 mass% or less. The thickness of the first transparent protective layer 5 is preferably, for example, in the range of 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 260 nm to 330 nm range. By using a UV-curable resin containing modified silicon as the resin constituting the first transparent protective layer 5, cohesive failure caused by adding calcium carbonate to the colored raw fabric layer 2 can be prevented, and the stain resistance and peel strength against cellophane tape can be improved. Furthermore, the use of modified silicon can prevent cohesive failure for a longer period of time.

[0027] [Second Transparent Protective Layer] The second transparent protective layer 6 is a layer partially provided on the surface of the first transparent protective layer 5 opposite the picture printed layer 4, and is a layer for imparting design properties 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 contain a triazine-based ultraviolet absorber UVA as a weather resistance agent and a photopolymerization initiator that does not have an absorption peak in the range of 260 nm to 330 nm as a photopolymerization initiator.

[0028] By using a UV-curable resin containing modified silicon 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 raw fabric layer 2, and also to improve the stain resistance and peel strength against cellophane tape. Furthermore, by using modified silicon, it is possible to prevent cohesive failure for a longer period of time.

[0029] The second transparent protective layer 6 is formed, for example, on the portion of the picture-printed layer 4 facing the printing ink. A filler may be added to the second transparent protective layer 6. Adding a filler can impart different mechanical properties, such as gloss, tactile feel, texture, surface strength, and friction, to the second transparent protective layer 6. Examples of fillers include zirconium compounds such as antimony trioxide, antimony sodium, zirconium silicate, and zirconium oxide; magnesium hydroxide; aluminum hydroxide; basic magnesium carbonate; borax; zinc borate; molybdenum trioxide or a complex of antimony dimolybdate with 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 with antimony trioxide. Additionally, beads or irregular particles of resins such as acrylic, polyolefin, and silicone, as well as beads or irregular particles of inorganic materials such as silica (especially hollow silica), alumina, and metal oxides, can be used. The method for forming the second transparent protective layer 6 is not particularly limited, and any known printing method can be used. The second transparent protective layer 6 is also generally referred to as a "tactile coating layer" or a "matt conduit printing layer."

[0030] [Second Anchor Coat Layer] Like the first anchor coat layer 3, the second anchor coat layer 7 is made of a urethane resin containing vinyl chloride and acetate or an acrylic resin containing vinyl chloride and acetate. 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 calcium carbonate contained in the colored raw fabric layer 2 from powdering off. If calcium carbonate in the colored raw fabric layer 2 powders off during the manufacturing process, it may contaminate the printing system or cause problems such as ink loss. Before forming the second anchor coat layer 7 on the colored raw fabric layer 2, it is preferable to perform a corona treatment or plasma treatment on the surface of the colored raw fabric layer 2 on which the second anchor coat layer 7 is to 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 substrate 9 when the decorative sheet 1 is laminated onto the substrate 9 to form the decorative material 10.

[0032] For example, when the substrate 9 to which the decorative sheet 1 is attached is a wood-based substrate, examples of resins that make up the primer coat layer 8 include ester-based resins, urethane-based resins, acrylic-based resins, polycarbonate-based resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral-based resins, and nitrocellulose-based resins. These resins can be used alone or in combination to form an adhesive composition, which can be applied using an appropriate application method such as roll coating or gravure printing. Urethane-acrylate resins are preferred as the resin that makes up the primer coat layer 8; in other words, it is particularly preferred to form the primer coat layer from a resin composed of a copolymer of an acrylic resin and a urethane resin and an isocyanate.

[0033] As described above, the primer coating layer 8 is a layer formed to improve the adhesion between the substrate 9 and the decorative sheet 1, and therefore the primer coating layer 8 does not necessarily have to be provided.

[0034] [Moisture permeability of decorative sheet] The moisture permeability is measured in accordance with JIS Z0208 1976 "Test method for moisture permeability of moisture-proof packaging materials (cup method)" and refers to the amount of moisture transferred after 24 hours in an environment of a temperature of 40°C and a humidity of 90%. The moisture permeability of the decorative sheet 1 is 15 g / m ２ 24 hr] or less, and 10 [g / m ２ It is more preferable that the time is less than 24 hours.

[0035] [Manufacturing method of decorative sheet] A brief description will be given of an example of a manufacturing method of the decorative sheet 1. First, a corona treatment or plasma treatment is performed on one side of the colored raw fabric layer 2, on which the first anchor coat layer 3 is to be formed. Then, a first surface anchor coat layer forming ink for forming the first anchor coat layer 3 is applied to the corona-treated or plasma-treated side, thereby forming the first anchor coat layer 3.

[0036] Next, a picture printing layer forming ink for forming a picture printing layer 4 is applied onto the first anchor coat layer 3 to form the picture printing layer 4. Next, a first transparent protective layer forming ink for forming a first transparent protective layer 5 is applied solidly onto the surface of the picture printing layer 4 to form the first transparent protective layer 5. Next, a second transparent protective layer forming ink for forming a second transparent protective layer 6 is applied partially onto the first transparent protective layer 5 so that the design is expressed, to form the second transparent protective layer 6.

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

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

[0039] In this way, the decorative sheet 1 is formed. The second anchor coat layer 7 may be formed simultaneously with the first anchor coat layer 3. The primer coat layer 8 may be formed before the pattern print layer 4, the first transparent protective layer 5, and the second transparent protective layer 6 are formed.

[0040] [Decorative Material] As shown in FIG. 2, the decorative material 10 includes a substrate 9 and a decorative sheet 1. (Substrate) The substrate 9 is a plate-shaped member formed using, for example, a metal-based material, a wood-based material, or an inorganic material. Examples of metal-based materials that can be used include aluminum, steel, stainless steel, and composite panels. Examples of composite panels that can be used include a resin layer serving as a core material and metal plates (aluminum, galvalume, stainless steel, etc.) attached to both sides of the resin layer. Examples of wood-based materials that can be used include MDF (medium density fiberboard), plywood, and particle board. Examples of inorganic materials that can be used include gypsum board and fiber-mixed calcium silicate board.

[0041] [Method of Manufacturing the Decorative Material] An example of a method of manufacturing the decorative material 10 will now be briefly described. First, the primer coating layer 8 of the decorative sheet 1 is placed facing the substrate 9. Next, this laminate is, for example, thermally laminated. In this way, the primer coating layer 8 and the substrate 9 are welded together to form the decorative material 10.

[0042] As a method for thermally laminating the above-mentioned laminate, in addition to a method of pressing with a metal plate in contact with the laminate using a flat pressure, a continuous lamination method using a circular pressure can also be used. In particular, when a continuous lamination method using an endless metal belt or a heat drum made of metal or curable resin is used, it is possible to continuously produce at high speed a decorative material 10 that is free from warping or waviness on the surface, has good adhesion between the layers, and is densely cured and integrated.

[0043] [Advantages of the Present Embodiment] (1) According to the decorative sheet 1 of this embodiment, the colored raw fabric layer 2 contains a thermoplastic resin and calcium carbonate and has a thickness ranging from 40 μm to 150 μm. The colored raw fabric layer 2 is provided with a first anchor coat layer 3 and a second anchor coat layer 7, each containing a urethane resin containing vinyl chloride and acetate or an acrylic resin containing vinyl chloride and acetate, on both sides. This allows for easy production of a highly moisture-proof decorative sheet 1 without additional manufacturing steps. For example, providing a separate moisture-proof layer to obtain a highly moisture-proof decorative sheet would require additional manufacturing steps. However, since moisture resistance can be achieved without providing a moisture-proof layer, a highly moisture-proof decorative sheet 1 can be easily obtained without additional manufacturing steps. This allows for the production of a decorative sheet that does not rely on petroleum-derived products and contributes to solving environmental issues. Furthermore, the provision of the first anchor coat layer 3 and the second anchor coat layer 7 on both sides of the colored raw fabric layer 2 prevents the calcium carbonate contained in the colored raw fabric layer 2 from powdering during the manufacturing process, resulting in a decorative sheet with high printability.

[0044] The "moisture-proof layer" referred to here is a layer that has a moisture permeability test of moisture-proof packaging materials (cup method) in accordance with JIS Z0208 1976, where the moisture permeability test is performed in an environment of 40°C and 90% humidity, and the moisture permeability test is 15 g / m2 or less after 24 hours. ２ 24 hours or less.

[0045] (2) The first transparent protective layer 5 and the second transparent protective layer 6 contain an ultraviolet curable resin containing modified silicon, which can prevent cohesive failure in the colored base fabric layer 2 containing calcium carbonate disposed below the first transparent protective layer 5 and the second transparent protective layer 6. Furthermore, the stain resistance can be improved.

[0046] [Modifications] (1) In the present embodiment, a case has been described in which the second transparent protective layer 6 is partially coated on the first transparent protective layer 5 to provide a design, but the present invention is not limited to this. The second transparent protective layer 6 may be coated solidly on the first transparent protective layer 5. Furthermore, although the transparent protective layer is formed as a multi-layer structure, the transparent protective layer may also be a single layer.

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

[0048] The decorative sheet 1 in this embodiment also includes a case where it does not have a picture printed layer 4, and includes, for example, a single-color sheet through which the color of the colored base fabric layer shows through.

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

[0050] [Creation of decorative sheets in examples and comparative examples] (Example 1) A raw fabric consisting of 60% by mass of calcium carbonate and 40% by mass of polypropylene resin (PP resin) relative to the mass of the entire fabric was used as the colored raw fabric layer 2. The thickness of the colored raw fabric layer 2 was 80 μm.

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

[0052] An acrylic UV-curable resin containing modified silicone was first applied to the entire surface of this pattern printed layer 4, and then partially applied thereon, after which 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. In this way, a moisture-proof decorative sheet 1 was produced. A vinyl acetate adhesive was applied to the surface of a substrate 9 made of a 2.5 mm thick MDF substrate, and the decorative sheet 1 and the substrate 9 were bonded together so that the colored raw fabric layer 2 was in contact with the vinyl acetate adhesive applied to the substrate 9, thereby producing a moisture-proof decorative material 10.

[0053] (Example 2) The decorative material of Example 2 was prepared in the same manner 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) A decorative material of Comparative Example 1 was produced using the same procedure as decorative material 10 of Example 1, except that in decorative sheet 1 of Example 1, a base fabric containing no calcium carbonate and made of 100% by mass of PP resin relative to the mass of the entire base fabric was used as colored base fabric layer 2. (Comparative Example 2) A decorative material of Comparative Example 2 was produced using the same procedure as decorative material 10 of Example 1, except that in decorative sheet 1 of Example 1, a base fabric containing no calcium carbonate and made of 100% by mass of polybutylene terephthalate resin (PBT resin) relative to the mass of the entire base fabric was used as colored base fabric layer 2.

[0055] (Comparative Example 3) A decorative material of Comparative Example 3 was produced using the same procedure as decorative material 10 of Example 1, except that in decorative sheet 1 of Example 1, the colored raw fabric layer 2 was not subjected to corona treatment and the first anchor coat layer 3 was not applied. (Comparative Example 4) A decorative material of Comparative Example 4 was produced using the same procedure as decorative material 10 of Example 1, except that in decorative sheet 1 of Example 1, the first transparent protective layer 5 and second transparent protective layer 6 were formed using an acrylic ultraviolet-curable resin that did not contain modified silicone.

[0056] (Comparative Example 5) In the decorative sheet 1 of Example 1, a base fabric containing no calcium carbonate and made of 100% by mass of PP resin relative to the mass of the entire base fabric was used as the colored base fabric layer 2, this colored base fabric layer was not subjected to corona treatment, and further, the first anchor coat layer 3 was not applied onto the colored base fabric layer, and the first transparent protective layer 5 and the second transparent protective layer 6 were formed using an acrylic ultraviolet-curable resin containing no modified silicone, except that a decorative material of Comparative Example 5 was produced in the same manner as decorative material 10 of Example 1. (Comparative Example 6) In the decorative sheet 1 of Example 1, a base fabric containing no calcium carbonate and made of 100% by mass of PP resin relative to the mass of the entire base fabric was used as the colored base fabric layer 2, and the first anchor coat layer 3 was not applied onto the colored base fabric layer, except that a decorative material of Comparative Example 6 was produced in the same manner as decorative material 10 of Example 1.

[0057] (Comparative Example 7) A decorative material of Comparative Example 7 was produced using the same procedure as decorative material 10 of Example 1, except that in the decorative sheet 1 of Example 1, the first transparent protective layer 5 and the second transparent protective layer 6 were formed using an acrylic UV-curable resin that did not contain modified silicone. (Comparative Example 8) A decorative material of Comparative Example 8 was produced using the same procedure as decorative material 10 of Example 1, except that in the decorative sheet 1 of Example 1, a base fabric that did not contain calcium carbonate and was made of 100% by mass of PP resin relative to the mass of the entire base fabric was used as the colored base fabric layer 2, and the first transparent protective layer 5 and the second transparent protective layer 6 were formed using an acrylic UV-curable resin that did not contain modified silicone.

[0058] (Comparative Example 9) A decorative material of Comparative Example 9 was produced using the same procedure as decorative material 10 of Example 1, except that in decorative sheet 1 of Example 1, a base fabric having a thickness of 35 μm and consisting of 60 mass % calcium carbonate and 40 mass % polypropylene resin (PP resin) relative to the mass of the entire base fabric was used as colored base fabric layer 2. (Comparative Example 10) A decorative material of Comparative Example 10 was produced using the same procedure as decorative material 10 of Example 1, except that in decorative sheet 1 of Example 1, a base fabric having a thickness of 200 μm and consisting of 60 mass % calcium carbonate and 40 mass % polypropylene resin (PP resin) relative to the mass of the entire base fabric was used as colored base fabric layer 2.

[0059] [Evaluation and Judgment Method] The decorative materials of Examples 1 and 2 and Comparative Examples 1 to 10 were evaluated for interlayer adhesion strength, peel resistance, moisture permeability, stain resistance, and petroleum dependency. The evaluation methods are as follows. (Interlayer Adhesion Strength) The interlayer strength between the colored base fabric layer and the picture printed layer was evaluated as interlayer adhesion strength. Specifically, in the decorative sheet production process, at the stage when the picture printed layer was formed, cellophane tape was pressed onto the surface of the picture printed layer and immediately peeled off, and the presence or absence of ink peeling and interlayer delamination between the colored base fabric layer and the picture printed layer was visually confirmed. The evaluation criteria are as follows: ○: No peeling. △: Partial peeling occurred. ×: Peeled ink was attached to the entire surface of the cellophane tape, and significant interlayer delamination occurred.

[0060] (Peel Resistance) The peel strength of the colored raw fabric layer was evaluated as peel resistance. Specifically, cellophane tape was pressed onto the surface of the decorative sheet and immediately peeled off, and the occurrence of cohesive failure of the colored raw fabric layer was visually confirmed. The evaluation criteria are as follows: ○: No peeling. △: Partial peeling occurred. ×: Part of the peeled colored raw fabric layer adhered to the entire surface of the cellophane tape, and significant cohesive failure occurred in the colored raw fabric layer.

[0061] (Moisture Permeability) After the decorative sheet was prepared, the amount of moisture transferred after 24 hours in an environment of 40°C and 90% humidity was measured in accordance with JIS Z0208 1976 "Test method for moisture permeability of moisture-proof packaging materials (cup method)."

[0062] (Stain resistance) Drawings were made on the surface of the decorative sheet using an oil-based marker pen, and then the drawing was wiped off with dried Kimwipes (registered trademark). The evaluation criteria are as follows: ○: The drawing made with the marker pen could be wiped off. △: The drawing made with the marker pen could be wiped off, although some color remained. ×: The color remained and the drawing could not be wiped off.

[0063] (Petroleum Dependence) The cosmetic materials were evaluated for their petroleum dependency. The evaluation criteria are as follows: ○: The proportion of petroleum-derived materials used is low, and petroleum dependency is low. △: The proportion of petroleum-derived materials used is intermediate, and petroleum dependency is moderate. ×: The proportion of petroleum-derived materials used is high, and petroleum dependency is high. The measurement and evaluation results are shown in Table 1.

[0064]

[0065] From Table 1, it can be seen that a decorative sheet having a thickness in the range of 40 μm or more and 150 μm or less, containing a thermoplastic resin in the range of 20% by mass or more and 40% by mass or less and calcium carbonate in the range of 60% by mass or more and 80% by mass or less relative to the mass of the entire colored raw fabric layer 2, a first anchor coat layer 3 containing a urethane resin including vinyl chloride acetate, and a first transparent protective layer 5 and a second transparent protective layer 6 containing an ultraviolet curing resin containing modified silicon, the modified silicon being contained in a proportion of 50% by mass or less in the resin solid content of the ultraviolet curing resin, has a moisture permeability of 15 [g / m] without providing a separate moisture-proof layer. ２ 24 hours] or less, and it was confirmed that a decorative sheet excellent in printability, processability, interlayer adhesion strength, peel resistance, stain resistance, petroleum dependency, etc. could be obtained.

[0066] The present invention can take the following configurations, for example: (1) A decorative sheet comprising a laminate in which at least a base fabric layer, an anchor coat layer, and a surface protective layer are laminated in this order, the laminate not including a moisture-proof layer having moisture-proof properties, wherein the base fabric layer has a thickness in the range of 40 μm to 150 μm, contains a thermoplastic resin and calcium carbonate, and the calcium carbonate content is in the range of 60% by mass to 80% by mass based on the total mass of the base fabric layer, the anchor coat layer contains a urethane-based resin containing vinyl chloride and acetate or an acrylic-based resin containing vinyl chloride and acetate, and the surface protective layer contains an ultraviolet-curable resin containing modified silicon, and the modified silicon is contained in a proportion of 50% by mass or less of the resin solid content of the ultraviolet-curable resin. (2) A decorative sheet having a moisture permeability of 15 g / m ２(3) The decorative sheet according to (1) above, characterized in that the base layer further contains at least one of antimony trioxide, antimony sodium, zirconium silicate, zirconium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, a complex of molybdenum trioxide or antimony dimolybdate with aluminum hydroxide, a complex of antimony trioxide with silica, a complex of antimony trioxide with zinc white, silicic acid of zirconium, and a complex of a zirconium compound with antimony trioxide, and salts thereof. (4) The decorative sheet according to any one of (1) to (3), wherein the thermoplastic resin contains at least one of 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), wherein the base layer contains the thermoplastic resin in an amount of 20% by mass to 40% by mass. (6) The decorative sheet according to any one of (1) to (5), wherein the calcium carbonate is in powder form, has an average particle size of 1 μm to 3 μm, and a maximum particle size of 50 μm or less. (7) The decorative sheet according to any one of (1) to (6), wherein the surface protective layer contains a weathering agent and a photopolymerization initiator. (8) A decorative material comprising: a substrate; and a decorative sheet according to any one of (1) to (7) above, provided on at least one surface of the substrate, wherein the substrate is any one of a wood substrate, a resin substrate, a non-flammable substrate, and a metal substrate.

[0067] REFERENCE SIGNS LIST 1 decorative sheet 2 colored base layer 3 first anchor coat layer 4 picture printed layer 5 first transparent protective layer 6 second transparent protective layer 7 second anchor coat layer 8 primer coat layer 9 substrate 10 decorative material

Claims

1. A decorative sheet consisting of a laminate of at least a base fabric layer, an anchor coat layer, and a surface protection layer laminated in this order, the laminate not including a moisture-proof layer with moisture-proof properties, wherein the base fabric layer has a thickness within the range of 40 μm to 150 μm, contains a thermoplastic resin and calcium carbonate, and the calcium carbonate content is within the range of 60% to 80% by mass based on the mass of the entire base fabric layer, the anchor coat layer contains a urethane-based resin containing vinyl chloride and acetate or an acrylic-based resin containing vinyl chloride and acetate, and the surface protection layer contains an ultraviolet-cured resin containing modified silicon, and the modified silicon is contained in a proportion of 50% by mass or less of the resin solid content of the ultraviolet-cured resin.

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

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

4. A decorative sheet according to claim 1 or 2, characterized in that the thermoplastic resin contains at least one of 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. A decorative sheet according to claim 1 or 2, characterized in that the base layer contains the thermoplastic resin in the range of 20% by mass or more and 40% by mass or less.

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

7. The decorative sheet according to claim 1 or 2, wherein the surface protective layer contains a weathering agent and a photopolymerization initiator.

8. A decorative material comprising: a substrate; and a decorative sheet according to claim 1 or claim 2 provided on at least one side of the substrate, wherein the substrate is any one of a wood substrate, a resin substrate, a non-flammable substrate, and a metal substrate.

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