Laminated sheet and method for manufacturing a laminated sheet

Abstract

To provide a laminated sheet which hardly causes interlayer peeling while having high nonflammability and hardness and a method for producing a laminated sheet.SOLUTION: There is provided a laminated sheet comprising a base material layer containing a resin material and an inorganic material, a surface protective layer formed on one surface of the base material layer and an anchor layer formed on at least a surface on the side of the surface protective layer of the base material layer. In the laminated sheet, the base material layer has a first base material layer and a second base material layer and the surface protective layer may be configured to be formed on the second base material layer. It is preferred that the inorganic material have an average particle diameter in the range of 1 μm or more and 3 μm or less and a maximum particle diameter of 50 μm or less. It is preferred that the content of the inorganic material be in the range of 20 mass% or more and 90 mass% or less based on the total amount of the resin material and the inorganic material in the first base material layer and the content of the inorganic material is in the range of 1 mass% or more and 50 mass% or less based on the total amount of the resin material and the inorganic material in the second base material layer.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] Conventionally, for the purpose of improving nonflammability and hardness, a building material sheet with a high filling of an inorganic material such as calcium carbonate in a base layer has been proposed (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] However, when laminating another layer such as a surface protection layer on the surface of a base layer with a high filling of an inorganic material, regardless of the lamination method such as a laminating method or a coextrusion method, the adhesion strength between the base layer and the other layer is weak and peeling between layers may easily occur. In a laminated sheet used for building materials, tape may be attached to or peeled off from the laminated sheet during construction or when the occupant uses it, and the easy occurrence of peeling between layers becomes a problem.

[0005] The present disclosure has been made in view of such problems, and an object thereof is to obtain a laminated sheet and a method for manufacturing the laminated sheet that have high nonflammability and hardness and are less likely to peel between layers.

Means for Solving the Problems

[0006] In order to solve the above problems, a laminated sheet according to one aspect of the present disclosure includes a base layer containing a resin material and an inorganic material, a surface protection layer formed on one surface of the base layer, and an anchor layer formed at least on the surface of the base layer on the surface protection layer side.

[0007] Furthermore, a method for manufacturing a laminated sheet according to another aspect of the present disclosure is characterized by mixing an inorganic material and a resin material to form a resin film containing the inorganic material and the resin material to form a base layer, coating at least one surface of the base layer with an anchor material to form an anchor layer, coating the anchor layer with a resin material and curing it to form a surface protective layer. [Effects of the Invention]

[0008] According to aspects of this disclosure, it is possible to obtain a laminated sheet that has high non-flammability and hardness, and is resistant to delamination between layers, as well as a method for manufacturing a laminated sheet. [Brief explanation of the drawing]

[0009] [Figure 1] This is a cross-sectional view showing an example of the configuration of a laminated sheet according to the first embodiment of this disclosure. [Figure 2] This is a cross-sectional view showing an example of the configuration of a laminated sheet according to the second embodiment of this disclosure. [Figure 3] This is a cross-sectional view showing an example of the configuration of a laminated sheet according to the third embodiment of this disclosure. [Modes for carrying out the invention]

[0010] The present disclosure will be described below through embodiments, but these embodiments are not intended to limit the invention as defined in the claims. Furthermore, not all combinations of features described in the embodiments are necessarily essential to the solution of the invention. Also, the drawings schematically illustrate the invention as defined in the claims, and the dimensions such as width and thickness of each part may differ from those of actual objects. These ratios also differ from those in reality.

[0011] A laminate according to the first embodiment of this disclosure will now be described. The laminated sheet according to this disclosure is, for example, a laminated sheet that is applied to walls, fixtures, furniture, etc. In the following description, the side of the laminated sheet that contacts the adhesive surface may be referred to as "bottom," and the side opposite to the adhesive surface (the surface) may be referred to as "top." The following describes the various aspects of each embodiment of this disclosure with reference to the drawings.

[0012] 1. First Embodiment (1.1) Basic structure of laminated sheets Figure 1 is a cross-sectional view illustrating an example of the configuration of a laminated sheet 1 according to an embodiment of the present disclosure. As shown in Figure 1, the laminated sheet 1 comprises an adhesive layer 11, a base material layer 12, a pattern layer 13, and a surface protection layer 14. The laminated sheet 1 is constructed by laminating the adhesive layer 11, the base material layer 12, the pattern layer 13, and the surface protection layer 14 in this order.

[0013] The adhesive layer 11 is provided to improve the adhesion between the laminated sheet 1 and the substrate to which the laminated sheet 1 is attached. The base layer 12 is the base layer of the laminated sheet 1, and absorbs unevenness and steps on the application surface to improve the finish of the laminated sheet 1, as well as providing the laminated sheet 1 with fire resistance and hardness. The pattern layer 13 is a layer that imparts the desired color and pattern to the laminated sheet 1. The surface protection layer 14 is provided on the top surface of the laminated sheet 1 and is provided to protect the laminated sheet 1 and to adjust the gloss of the surface of the laminated sheet 1. The adhesive layer 11, the base material layer 12, the pattern layer 13, and the surface protection layer 14 will be described in detail below.

[0014] (Primitive layer) The base layer 12 is a layer containing one or more types of resin materials and one or more types of inorganic materials. The ratio of the content of the resin material to the inorganic material in the base layer 12 (resin material:inorganic material) is preferably in the range of 80:20 to 10:90 by mass ratio, and more preferably in the range of 40:60 to 20:80 by mass ratio. That is, the content of the inorganic material in the total amount of the resin material and the inorganic material in the base layer 12 is preferably in the range of 20% by mass or more and 90% by mass or less, and more preferably in the range of 60% by mass or more and 80% by mass or less. When in the above range, the nonflammability or flame retardancy of the laminated sheet 1 tends to be improved. When the content of the inorganic material is within the above range, sufficient surface hardness can be obtained, and it becomes difficult for scratches visible to the naked eye to occur when the surface of the base layer 12 is scratched using a Hoffman scratch tester. Preferably.

[0015] On the other hand, when the proportion of the resin material is less than the above range, when applying an anchor material to form the anchor layers 16a and 16b on the surface of the base layer 12, it is possible to suppress the occurrence of so-called "powder blowing" on the surface of the base layer 12. Further, when printing ink or the like to form the pattern layer 13 on the surface of the base layer 12, it is possible to suppress the occurrence of so-called "powder blowing" on the surface of the base layer 12. Here, "powder blowing" means that the inorganic material contained in the base layer 12 protrudes to the surface of the base layer 12. Furthermore, the lamination suitability when laminating the sheet on which the anchor layer 16a or 16b is formed to the base layer 12 is improved, and it is possible to suppress the occurrence of cracks or peeling of the inorganic material in the bent portion. In this way, when the ratio of the content of the resin material to the inorganic material is in the range of 80:20 to 10:90 by mass ratio, it is possible to obtain sufficient surface hardness while improving the nonflammability or flame retardancy of the laminated sheet 1. Further, the lamination suitability of the laminated sheet 1 can be improved, and the occurrence of powder blowing and the occurrence of cracks can be reduced.

[0016] In this way, when the ratio of the content of the resin material to the inorganic material is in the range of 80:20 to 10:90 by mass ratio, while improving the nonflammability or flame retardancy of the laminated sheet 1, sufficient surface hardness can be obtained. Also, the lamination suitability of the laminated sheet 1 can be improved, and the occurrence of powder blowing and the occurrence of cracks can be reduced. Occurrence can be reduced.

[0017] The inorganic material is preferably surface-treated. The inorganic material is surface-treated, for example, using a saturated fatty acid, unsaturated fatty acid, or a salt thereof having 10 to 30 carbon atoms, more preferably 12 to 26 carbon atoms, as a surface treatment agent. By surface-treating the inorganic material using such a surface treatment agent, aggregation of the inorganic material in the resin material, which is a concern when highly filling the inorganic material, can be suppressed.

[0018] Examples of the saturated fatty acid include palmitic acid, stearic acid, lauric acid, myristic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid. Examples of the salt include sodium salt, potassium salt, magnesium salt, calcium salt, etc. The inorganic material is surface-treated by a known method.

[0019] The inorganic material is preferably in a powder shape (powder form), and its average particle diameter is preferably in the range of 1 μm or more and 3 μm or less, and the maximum particle diameter is preferably 50 μm or less. If the average particle diameter and the maximum particle diameter of the inorganic material are within the above-described numerical ranges, the dispersibility of the inorganic material in the thermoplastic resin can be improved while maintaining the flatness of the surface of the base layer 12. If the average particle diameter of the inorganic material is less than 1 μm, the cohesive force between the inorganic materials increases, and the dispersibility in the thermoplastic resin described later may decrease. Also, if the average particle diameter of the inorganic material exceeds 3 μm, the flatness of the surface of the base layer 12 decreases, and the thicknesses of the anchor layers 16a and 16b described later may become non-uniform, or unevenness or chipping may occur. Further, if the maximum particle diameter of the inorganic material exceeds 50 μm, the flatness of the surface of the base layer 12 decreases, and the thicknesses of the anchor layers 16a and 16b described later may become non-uniform, or unevenness or chipping may occur. In the present embodiment, the "average particle diameter" means the mode diameter.

[0020] Preferably, the inorganic material includes antimony trioxide, antimony soda, zirconium silicate, zirconium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, calcium carbonate, complexes of molybdenum trioxide or antimony dimolybdate with aluminum hydroxide, complexes of antimony trioxide with silica, complexes of antimony trioxide with zinc oxide, zirconium silicate, and complexes of zirconium compounds with antimony trioxide, as well as salts thereof, and further preferably, at least one of silica, alumina, hollow glass beads, and acrylic beads.

[0021] In particular, the inorganic material is preferably a powder containing at least one of calcium carbonate and calcium carbonate salt. Calcium carbonate and calcium carbonate salt are suitable because their particle size and compatibility with thermoplastic resins are easily controlled. Furthermore, calcium carbonate and calcium carbonate salt are inexpensive, making them suitable from the viewpoint of reducing the cost of fire-resistant building materials. In addition, the inorganic material is preferably one that contains calcium carbonate in the range of 50% by mass or more and 100% by mass or less. If the inorganic material has a calcium carbonate content of 50% by mass or more, it is possible to impart sufficient non-combustibility or sufficient flame retardancy to the base material layer 12, as well as sufficient mechanical strength.

[0022] Furthermore, the inorganic material may be a crystalline powder material, so-called crystalline powder, or a non-crystalline powder material, so-called amorphous type powder material. If the inorganic material is a crystalline powder material, the powder itself is homogeneous and isotropic, which improves the mechanical strength of the powder itself and tends to improve the scratch resistance and durability of the fire-resistant building material. If the inorganic material is an amorphous type powder material, it is possible to appropriately adjust the electrical conductivity, thermal conductivity, light transmittance, and light absorption rate of the powder itself, making it possible to impart a wide variety of design features such as texture and gloss.

[0023] As the resin material, for example, a thermoplastic resin is used, and it includes at least one selected from the group consisting of propylene homopolymer, ethylene homopolymer, ester homopolymer, copolymer of ethylene and / or propylene with other α-olefins copolymerizable therewith, ethylene-ethyl acrylate copolymer, and ethylene-vinyl acetate copolymer. Specifically, polypropylene, polyethylene, polyester, polybutene, or polymethylpentene can be used, with polypropylene, polyethylene, and polyester being preferred, and polypropylene, polyethylene, or polyester being more preferred. By using at least one of polypropylene, polyethylene, and polyester as the thermoplastic resin, the dispersibility of the inorganic material is improved. Furthermore, by using polypropylene as the thermoplastic resin, the dispersibility of the inorganic material is further improved.

[0024] Furthermore, the total content of resin material and inorganic material is preferably within the range of 90% to 100% by mass relative to the mass of the base layer 12. If the total content of resin material and inorganic material is within the above numerical range, sufficient non-flammability or sufficient flame retardancy can be obtained while improving lamination suitability. If the total content of resin material and inorganic material is less than 90% by mass relative to the mass of the base layer 12, sufficient non-flammability or sufficient flame retardancy may not be obtained. In addition, lamination suitability may decrease, or cracks may occur at the bent parts of the sheet.

[0025] The thickness of the base layer 12 is preferably within the range of 50 μm to 12,500 μm, and more preferably within the range of 70 μm to 10,000 μm. If the thickness of the base layer 12 is within the above numerical range, the lamination suitability can be improved. If the thickness of the base layer 12 is less than 50 μm, the lamination suitability tends to decrease. Furthermore, if the thickness of the base layer 12 exceeds 12,500 μm, it becomes difficult to handle in terms of processability and workability.

[0026] Furthermore, the raw material layer 12 is formed by uniaxial or biaxial stretching. In this case, as shown in Figure 1, the raw material layer 12 has planar (lateral) voids 12b formed between the inorganic material 12a and the resin material, extending in a direction parallel to the front and back surfaces of the raw material layer 12. Multiple voids 12b are scattered throughout the raw material layer 12.

[0027] The base layer 12 in this embodiment may be formed by adding a foaming agent to a resin material and an inorganic material. This makes it possible to form voids within the base layer 12 that extend in the thickness direction of the base layer 12. The voids formed by the foaming agent connect with each other, resulting in larger voids than those formed individually. Therefore, a laminated sheet 1 having a base layer 12 in which such voids are scattered throughout has even higher thermal insulation properties.

[0028] As a blowing agent, at least one of the following can be used: a decomposition gas generating blowing agent, an expandable capsule blowing agent, etc. Preferred examples of decomposition gas generating blowing agents include azodicarbonamide, dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, benzenesulfonyl hydrazide, sodium bicarbonate and ammonium carbonate, azobisisobutyronitrile, 4,4-oxybis(benzenesulfonic acid hydrazide), diphenylsulfon-3,3'-disulfohydrazide, benzene-1,3-disulfohydrazide, p- Toluene sulfonyl semicarbazide, and a small amount of foamed hollow microspheres At least one type can be mentioned. In addition, examples of expandable capsule foaming agents include those containing hydrocarbon-based volatile expanding components such as ethane, butane, pentane, neopentane, hexane, and heptane, encased in fine particles coated with resin materials such as acrylic acid esters, vinylidene chloride, acrylonitrile, and urethane.

[0029] The base layer 12, formed from a mixture containing inorganic material, resin material, and foaming agent, is made by the foaming agent Multiple voids are scattered throughout the entire raw material layer 12. The amount of foaming agent should be such that it provides sufficient thermal insulation for a building material, as well as sufficient interlayer strength and strength for the resin composition, and can be adjusted as needed. For example, the amount of foaming agent should be such that when the base layer 12 is heated, it expands to a volume of at least 10%, 25%, 50%, 100%, 150%, 200%, or more. The amount of foaming agent is, for example, within the range of 5% by mass to 10% by mass relative to the mass of the base layer 12.

[0030] Furthermore, when the raw material layer 12 is formed by uniaxial or biaxial stretching of a mixture containing a foaming agent, it has voids that extend in the thickness direction due to the foaming agent, regardless of the position of the inorganic material 12a. As a result, the raw material layer 12 has voids 12b that extend laterally in Figure 1 around the inorganic material 12a, and consequently, a raw material layer 12 can be obtained in which multiple voids 12b that extend laterally in Figure 1 are scattered throughout the entire layer. The raw material layer 12, in which such three-dimensional voids 12b are formed, can enhance its thermal insulation effect.

[0031] Anchor layers 16a and 16b are provided on both sides of the base layer 12. The anchor layers 16a and 16b will be described later. It is preferable to apply surface treatment such as corona treatment or plasma treatment to both sides of the base layer 12 before forming the anchor layers 16a and 16b, which will be described later. By applying surface treatment such as corona treatment or plasma treatment to both sides of the base layer 12, the adhesion (bonding) between the anchor layers 16a and 16b formed on the surface-treated surfaces and the base layer 12 is improved. Alternatively, before forming the anchor layers 16a and 16b, both sides of the raw material layer 12 may be brushed to remove any powdered inorganic material beforehand.

[0032] (Anchor layer) The anchor layers 16a and 16b are layers formed to cover the entire surface of the base layer 12 and are layers to prevent powder from falling off the inorganic material contained in the base layer 12. The inorganic material contained in the base layer 12 may fall off as powder within the printing system, specifically within the printing device, when the pattern layer 13 is formed (during ink printing) or when the surface protection layer 14 is formed (during resin coating), and contaminate the printing system. Furthermore, if the inorganic material contained in the base layer 12 falls off as powder, defects such as ink bleed may occur in the pattern layer 13. Here, "ink bleed" refers to the ink not being printed in some areas.

[0033] Furthermore, the anchor layer 16b also has the function of improving the adhesion between the base material layer 12 and the ink that forms the pattern layer 13 or the resin material that forms the surface protective layer 14. If the anchor layer 16b is not provided on the upper surface of the base material layer 12, the ink or resin material may peel off without adhering to the base material layer 12.

[0034] The anchor layers 16a and 16b preferably contain a urethane resin containing vinyl chloride or an acrylic resin containing vinyl chloride. Here, "vinyl chloride" means a copolymer of vinyl chloride and vinyl acetate. Furthermore, "urethane resin containing vinyl chloride" means a composition containing vinyl chloride and a urethane resin, and "acrylic resin containing vinyl chloride" means a composition containing vinyl chloride and an acrylic resin. The ratio of the content of vinyl chloride to the content of urethane resin or acrylic resin (content of vinyl chloride: content of urethane resin or acrylic resin) is preferably in the range of 80:20 to 1:99 by mass ratio, more preferably in the range of 50:50 to 5:95, and even more preferably in the range of 20:80 to 10:90.

[0035] Furthermore, "urethane resin containing polyvinyl chloride" and "urethane resin containing polyvinyl chloride" are as described above. In addition to vinyl chloride and urethane resin or acrylic resin, the mixture may also contain a curing agent. This curing agent is added to ensure the curing of the urethane resin containing vinyl chloride or the acrylic resin containing vinyl chloride, and its content is not particularly limited. For example, the ratio of the content of the urethane resin or acrylic resin containing vinyl chloride to the content of the curing agent (content of urethane resin or acrylic resin containing vinyl chloride: content of curing agent) should be within the range of 99:1 to 1:99 by mass ratio, preferably within the range of 99:1 to 50:50, and even more preferably within the range of 95:5 to 90:10.

[0036] The content of urethane resin containing vinyl chloride or acrylic resin containing vinyl chloride in the anchor layers 16a and 16b (hereinafter sometimes referred to as the resin content) is preferably in the range of 15% to 100% by mass, more preferably in the range of 80% to 100% by mass, and even more preferably in the range of 85% to 95% by mass, relative to the mass of the anchor layers 16a and 16b. When the resin content is within the above numerical range, it is possible to form uniform anchor layers 16a and 16b without unevenness or chipping while ensuring sufficient interlayer strength between the base layer 12 and the pattern layer 13 or surface protection layer 14.

[0037] On the other hand, if the resin content is less than 15% by mass, the interlaminar strength described above may be insufficient. Also, if the resin content is less than 80% by mass, there is no problem in terms of use, but the penetration ratio of the anchor layers 16a and 16b into the base material layer 12 decreases. As a result, the interlaminar strength between the anchor layers 16a and 16b and the base material layer 12 may decrease slightly.

[0038] Furthermore, there are no problems in use as long as the resin content in anchor layers 16a and 16b is 100% by mass or less relative to the mass of anchor layers 16a and 16b. However, if the resin content exceeds 95% by mass, or more precisely, 98% by mass, chipping of anchor layers 16a and 16b may occur due to insufficient curing. In addition, the interlayer strength between anchor layers 16a and 16b and the base material layer 12, or between anchor layer 16b and the pattern layer 13 may decrease.

[0039] Furthermore, it is preferable that the resin content in the anchor layers 16a and 16b provided on both sides of the base layer 12 is the same. In this case, the occurrence of distortion and warping of the base layer 12 can be reduced, and as a result, the occurrence of distortion and warping of the entire laminated sheet 1 can be reduced. In addition, since the coating liquid for forming the anchor layers 16a and 16b can be common, manufacturing costs can be reduced and work efficiency can be improved.

[0040] The thickness of the anchor layers 16a and 16b is, for example, within the range of 0.5 μm to 20 μm, and preferably within the range of 0.5 μm to 10 μm. Furthermore, it is preferable that the thicknesses of the anchor layers 16a and 16b are the same. When the thicknesses of the anchor layers 16a and 16b are the same, the physical properties of the anchor layers 16a and 16b become almost the same, thereby reducing the occurrence of distortion and warping of the raw material layer 12.

[0041] In the case of the extrusion lamination method, the anchor layers 16a and 16b may be co-extruded together with the base layer 12 using a heat-adhesive resin such as a maleic acid-modified olefin resin to improve the interlayer adhesion between the base layer 12 and the anchor layers 16a and 16b. Furthermore, if the adhesive layer 11 is not provided on the back surface of the raw material layer 12, the anchor layer 16a does not need to be provided on the back surface of the raw material layer 12 (the outermost surface of the laminated sheet 1). This is because, depending on the installation method of the laminated sheet 1 to the substrate, it is not a problem if the outermost surface of the laminated sheet 1 does not have an anchor layer.

[0042] (Pattern layer) The pattern layer 13 is formed on the base layer 12 to give the laminated sheet 1 a design feature. This is the layer that adds the image. There are no particular restrictions on the type of pattern formed by the pattern layer 13. For example, wood grain patterns, stone patterns, fabric patterns, abstract patterns, geometric figures, letters, symbols, etc., may be formed individually or in combination of two or more types. Furthermore, the pattern layer 13 may be a layer to which a single color has been applied.

[0043] The pattern layer 13 is a layer formed by printing with, for example, a urethane resin-based ink. As the urethane resin-based ink, for example, one containing urethane resin, vinyl chloride vinyl acetate copolymer resin, organic pigment, and inorganic pigment can be used. Preferably, the composition of the pattern layer 13 contains, for example, urethane resin in a range of 50.9% to 76.7% by mass, vinyl chloride vinyl acetate copolymer resin in a range of 10.2% to 23.3% by mass, organic pigment in a range of 0% to 37.7% by mass, and inorganic pigment in a range of 0% to 20.0% by mass.

[0044] As a method for forming the pattern layer 13, any printing method such as inkjet printing, gravure printing, screen printing, offset printing, or flexographic printing can be used. Furthermore, the mass of the pattern layer 13 is, for example, 8.36 [g / m³]. 2 ] or less (solid amount) (organic mass 6.71 [g / m 2 It is preferable that the following conditions are met. Furthermore, the ratio of the formation area (ink printing area) per unit area (e.g., 300 mm square) of the pattern layer 13 is preferably 50% or less, and more preferably 90% or more. In particular, if the pattern layer 13 is a layer formed by solid printing, the ratio of the formation area (area covered by ink) per unit area of ​​the pattern layer 13 is preferably 90% or less. The unit area is not limited to 300 mm square, but may be, for example, 200 mm square or more and 400 mm square or less. The unit area of ​​the pattern layer 13 is specified in order to ensure an appropriate light transmittance, and may be set based on, for example, the location where the laminated sheet 1 is placed and the brightness of the light source.

[0045] (Surface protective layer) The surface protection layer 14 is formed on the pattern layer 13 and is a layer for protecting the surface of the laminated sheet 1. The surface protection layer 14 is preferably a transparent layer in order to allow the pattern and colors of the pattern layer 13 to be displayed on the surface of the laminated sheet 1. The surface protection layer 14 may also be, for example, a top coat layer or a top resin layer.

[0046] When the laminated sheet 1 is for interior use, the surface protective layer 14 is formed by applying a coating resin onto the pattern layer 13 in order to produce a visual gloss-matt effect on the surface of the laminated sheet 1. Depending on the required performance, the coating resin may be a urethane resin, acrylic resin, UV-curing resin, ionizing radiation-curing resin, etc. The surface protective layer 14 is formed by applying the coating resin in one or more layers. When the surface protective layer 14 is formed in multiple layers, two or more layers of different coating resins may be applied, or two or more layers of the same resin may be applied.

[0047] Furthermore, even when the laminated sheet 1 is for interior use, if the laminated sheet 1 requires abrasion resistance or scratch resistance, the surface protection layer 14 is formed by applying a thermoplastic resin or the like onto the pattern layer 13. In this case, the design can be improved by providing an uneven pattern on the surface of the surface protection layer 14. Examples of uneven patterns include wood grain grooves, stone slab surface irregularities (granite cleavage surfaces, etc.), fabric surface textures, pearlescent finishes, sand textures, and hairline finishes. As a method for forming the uneven pattern, for example, an embossing method using a known sheet-fed or rotary embossing machine can be employed.

[0048] To stably maintain performance such as scratch resistance and abrasion resistance, while also considering bendability and cost-effectiveness. The thickness of the surface protective layer 14 is preferably 60 μm or more and 200 μm or less, and more preferably 60 μm or more and 150 μm or less. When the laminated sheet 1 is used for exterior applications, it is preferable to add an ultraviolet absorber such as a benzotriazole, benzoate, benzophenone, or triazine type, and a light stabilizer such as a hindered amine type to the surface protective layer 14.

[0049] (Adhesive layer) The adhesive layer 11 has the function of ensuring adhesion to the substrate to which the laminated sheet 1 is attached. The thickness of the adhesive layer 11 is preferably in the range of 0.1 μm to 3.0 μm. By having the thickness of the adhesive layer 11 within the above range, adhesion to the substrate is enhanced, and the adhesive layer 11 can be prevented from protruding from the laminated sheet 1 when the laminated sheet 1 is attached.

[0050] The materials constituting the adhesive layer 11 are not particularly limited, but can be appropriately selected from adhesive resins such as acrylic, polyester, polyurethane, and epoxy. The coating method can be appropriately selected depending on the viscosity of the adhesive resin, but for example, gravure coating can be used.

[0051] The adhesive layer 11 may also be a primer. In this case, the materials constituting the adhesive layer 11 can be appropriately selected from among nitrated cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc., either individually or as modified versions of each, as binders. These can be in any form, such as aqueous, solvent-based, or emulsion type. The curing method can also be appropriately selected from a one-component type that cures on its own, a two-component type that uses a curing agent in combination with a main component, or a type that cures by irradiation with ultraviolet light or electron beams. A common curing method is a two-component type in which an isocyanate-based curing agent is combined with a urethane-based main component for curing. This method is preferable in terms of workability, cost, and the cohesive strength of the resin itself. In addition to the binders mentioned above, colorants such as pigments and dyes, extender pigments, solvents, various additives, inorganic fillers, etc., may be added.

[0052] In particular, the adhesive layer 11 preferably contains an inorganic filler such as silica, alumina, magnesia, titanium oxide, or barium sulfate. The adhesive layer 11 is located on the back of the laminated sheet 1. Therefore, when considering winding the laminated sheet 1 as a continuous plastic film (web-like), it is necessary to prevent blocking, such as the films sticking together and becoming difficult to slide or unable to peel apart. By including an inorganic filler in the adhesive layer 11, it is possible to suppress adhesion and blocking between the laminated sheets (films).

[0053] Furthermore, the adhesive layer 11 is not necessarily required. Depending on the installation method of the laminated sheet 1 to the substrate, it is not a problem if the adhesive layer 11 is not provided on the back surface of the laminated sheet 1.

[0054] (1.2) Method for manufacturing laminated sheets The following describes an example of a manufacturing method for the laminated sheet 1. First, a raw material layer 12 is formed. The inorganic material and resin material contained in the raw material layer 12 are mixed using a known mixer such as a super mixer, Henschel mixer, tumbler mixer, or ribbon blender. Inorganic materials and resin materials are heated and kneaded, and the mixture of each component contained in the raw material layer 12 is extruded using a known molding machine such as a T-die extruder to form a resin film containing inorganic materials and resin materials. A film is formed. Then, the formed resin film is stretched uniaxially or biaxially using a single-screw or twin-screw extruder to form a raw material layer 12 having a uniform micropore diameter.

[0055] Anchor material is applied to the lower and upper surfaces of the raw material layer 12 to form anchor layers 16a and 16b, respectively. At this time, anchor layers 16a and 16b may be formed simultaneously on both sides of the raw material layer 12, or anchor layer 16a may be formed on the lower surface of the raw material layer 12 and anchor layer 16b may be formed on the upper surface of the raw material layer 12 at a different timing than anchor layer 16a. On the upper surface of the raw material layer 12 (the surface of the anchor layer 16b), for example, a urethane resin-based ink is applied to form a desired pattern, and then dried to form the pattern layer 13. A resin material, such as a coating resin or thermoplastic resin, is applied to the surface of the pattern layer 13 and cured to form a surface protective layer 14.

[0056] Next, an adhesive resin or primer is applied to the lower surface of the raw material layer 12 (the surface of the anchor layer 16a) to form an adhesive layer 11. The laminated sheet 1 according to this embodiment is manufactured as described above. If anchor layers 16a and 16b are formed at different times, the anchor layer 16a may be formed after the surface protection layer 14 is formed, and then the adhesive layer 11 may be formed.

[0057] (1.3) Effects of the first embodiment The laminated sheets described above have the following effects. (1) The laminated sheet of this embodiment contains inorganic particles in the base layer and has an anchor layer on the surface of the base layer. This configuration improves the non-flammability and hardness of the laminated sheet, and also improves the interlayer adhesion between the base layer and the layers provided on the surface of the base layer (pattern printing layer, surface protection layer), making it less likely for the layers to peel off from each other.

[0058] (2) The laminated sheet of this embodiment has multiple voids formed around the inorganic material in the base layer, and the voids are scattered throughout the base layer. This configuration creates three-dimensional voids within the raw material layer, thereby enhancing the thermal insulation effect.

[0059] (3) In this embodiment, it is preferable that the average particle size of the inorganic material contained in the raw material layer is in the range of 1 μm to 3 μm, and the maximum particle size of the inorganic material is 50 μm or less. This configuration allows for a flattening of the raw material layer surface and suppression of unevenness and chipping in the raw material layer.

[0060] (4) In this embodiment, it is preferable that the amount of inorganic material in the laminated sheet relative to the total amount of resin material and inorganic material in the base layer is in the range of 20% by mass or more and 90% by mass or less. This configuration improves the non-flammability and hardness of the laminated sheet, as well as the smoothness and processability of the raw material layer surface.

[0061] (5) In this embodiment, it is preferable to use calcium carbonate or a calcium carbonate salt as inorganic particles in the laminated sheet. This configuration allows for easy control of the particle size of inorganic particles and their compatibility with thermoplastic resins, and is also preferable from the viewpoint of reducing the cost of laminated sheets.

[0062] 2. Second Embodiment The laminated sheet according to the second embodiment of this disclosure will be described below with reference to Figure 2. Figure 2 is a cross-sectional view illustrating one example of the configuration of the laminated sheet 2 according to the second embodiment of this disclosure. That is the case.

[0063] The laminated sheet 2 comprises an adhesive layer 11, a base layer 22 having a first base layer 22a and a second base layer 22b, a pattern layer 13, and a surface protection layer 14. The laminated sheet 2 is constructed by laminating the adhesive layer 11, the first base layer 22a, the second base layer 22b, the pattern layer 13, and the surface protection layer 14 in this order. The pattern layer 13 and the surface protection layer 14 are formed on the side of the second base layer 22b. In other words, the laminated sheet 2 differs from the laminated sheet 1 according to the first embodiment in that it has a base layer 22 having a first base layer 22a and a second base layer 22b instead of the base layer 12.

[0064] The first raw material layer 22a and the second raw material layer 22b will be described below. Note that the other layers (adhesive layer 11, pattern layer 13, and surface protection layer 14) have the same configuration as the other layers of the laminated sheet 1, so their descriptions will be omitted.

[0065] (2.1) Basic structure of laminated sheets <First fabric layer, second fabric layer> The first raw material layer 22a has the same configuration as the raw material layer 12 described in the first embodiment. Anchor layers 26a and 26b are provided on both sides of the first raw material layer 22a. The second base layer 22b is a layer containing one or more types of resin materials and one or more types of inorganic materials. The inorganic material content in the second base layer 22b is preferably less than the inorganic material content in the second base layer. The ratio of resin material to inorganic material content (resin material:inorganic material) in the second base layer 22b is preferably in the range of 99:1 to 50:50 by mass ratio, and more preferably in the range of 90:10 to 60:40 by mass ratio. That is, the inorganic material content relative to the total amount of resin material and inorganic material in the second base layer 22b is preferably in the range of 1% by mass or more and 50% by mass or less, and 10% by mass or less. It is more preferable that the amount is in the range of 40% by mass or less.

[0066] It is preferable to use the same inorganic material as the base layer 12. Furthermore, it is preferable to use at least one of calcium carbonate and calcium carbonate salt as the inorganic material for the first base layer 22a. It is also preferable to use a different inorganic material for the second base layer 22b than the inorganic material contained in the first base layer 22a. For example, if the first base layer 22a contains at least one of calcium carbonate and calcium carbonate salt as the inorganic material, it is preferable that the second base layer 22b contains at least one inorganic material other than calcium carbonate, along with calcium carbonate. This allows for the use of inorganic particles in the first raw material layer 22a while reducing the manufacturing cost of the first raw material layer 22a. Furthermore, it is possible to improve the non-flammability and sheet hardness of the second raw material layer 22b.

[0067] Furthermore, the film thickness of the second raw material layer 22b is preferably the same as or thinner than that of the first raw material layer 22a. Specifically, the ratio of the film thicknesses of the first raw material layer 22a to the second raw material layer 22b is preferably 50:50 to 95:5. In this case, a decrease in the non-flammability and sheet hardness of the laminated sheet 2 can be suppressed.

[0068] As shown in Figure 2, anchor layers 26c and 26d are provided on both sides of the second raw material layer 22b. It is preferable to perform surface treatment such as corona treatment or plasma treatment on both sides of the second raw material layer 22b before forming the anchor layers 26c and 26d. The anchor layer 26c is a layer provided on the lower surface of the second raw material layer 22b, and the anchor layer 26d is a layer provided on the upper surface of the second raw material layer 22b. The anchor layers 26c and 26d have the same configuration as the anchor layers 26a and 26b described in the first embodiment.

[0069] (2.2) Effects of the second embodiment The laminated sheet described above has the following effects in addition to the effects described in the first embodiment: (6) The laminated sheet of this embodiment has a first raw material layer and a second raw material layer, each containing different inorganic particles. This configuration improves the non-flammability and hardness of the laminated sheet, and also improves the interlayer adhesion between the base layer and the layers provided on the surface of the base layer (pattern printing layer, surface protection layer), making it less likely for the layers to peel off from each other.

[0070] 3. Third Embodiment The laminated sheet according to the third embodiment of this disclosure will be described below with reference to Figure 3. Figure 3 is a cross-sectional view illustrating one example of the configuration of the laminated sheet 3 according to the third embodiment of this disclosure.

[0071] Laminated sheet 3 comprises an adhesive layer 11, a base layer 22 having a first base layer 22a and a second base layer 22b, a pattern layer 13, and a surface protection layer 14 having an upper resin layer 34a, a first topcoat layer 34b, and a second topcoat layer 34c. Laminated sheet 2 is constructed by laminating the adhesive layer 11, the first base layer 22a, the second base layer 22b, the pattern layer 13, the upper resin layer 34a, the first topcoat layer 34b, and the second topcoat layer 34c in this order. That is, laminated sheet 2 differs from laminated sheet 1 according to the first embodiment in that it has a surface protection layer 34 having an upper resin layer 34a, a first topcoat layer 34b, and a second topcoat layer 34c instead of the surface protection layer 14.

[0072] The first raw material layer 22a and the second raw material layer 22b will be described below. Note that the other layers (adhesive layer 11, first raw material layer 22a, second raw material layer 22b, and pattern layer 13) have the same configuration as the other layers of the laminated sheet 2, so their descriptions will be omitted.

[0073] (3.1) Basic structure of laminated sheets <Surface protective layer> The surface protection layer 34 comprises an upper resin layer 34a, a first topcoat layer 34b, and a second topcoat layer 34c. As shown in Figure 3, the surface protection layer 34 may have an embossed shape.

[0074] The upper resin layer 34a is a layer intended for shock absorption (cushioning), and also serves as an adhesive layer for bonding the pattern layer 13 and the first topcoat layer 34b. Furthermore, the upper resin layer 34a has the function of making the pattern clearer and improving the scratch resistance of the pattern layer 13. The upper resin layer 34a is formed, for example, from a transparent polypropylene resin. The thickness of the upper resin layer 34a is, for example, approximately 150 μm to 200 μm.

[0075] The first topcoat layer 34b is a topcoat layer intended for gloss adjustment and / or protection of the pattern layer 13. The first topcoat layer 34b is preferably formed from, for example, an ultraviolet-curable resin. The thickness of the surface protection layer 34 is preferably, for example, 0.1 μm or more and 15 μm or less.

[0076] The second topcoat layer 34c is partially provided on the surface side of the first topcoat layer 34b and covers a portion of the surface of the first topcoat layer 34b. An example of the portion of the surface of the first topcoat layer 34b is the portion facing the pattern of the pattern layer 13. Furthermore, the material of the second topcoat layer 34c can be, for example, the same resin as the first topcoat layer 34b. A filler may be added to the second topcoat layer 34c. This may be done. By adding a filler, different gloss, feel, texture, surface strength, and mechanical properties such as friction can be imparted compared to the first topcoat layer 34b. As a filler, for example, a material that consumes little oxygen during combustion is preferred, and examples include calcium carbonate, antimony trioxide, antimony soda, zirconium silicate, zircon oxide and other zirconium compounds, 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 zirconium compounds and antimony trioxide. In particular, calcium carbonate is suitable from the viewpoint of reducing the cost of decorative sheets because its particle size can be easily controlled by the manufacturing method and its compatibility with polyolefin resins can be controlled by surface treatment, and it is also inexpensive as a material. Furthermore, beads or amorphous particles of resins such as acrylic, polyolefin, and silicone, as well as beads or amorphous particles of inorganic materials such as silica (especially hollow silica), alumina, and metal oxides, can be used. The method for forming the second topcoat layer 34c is not particularly limited, and known printing techniques can be employed. The second topcoat layer 34c is also generally referred to as the "tactile coating layer" or the "matt conduit printing layer."

[0077] The surface protective layer 34 has an embossed shape consisting of recesses and protrusions that are synchronized with the pattern of the pattern layer 13, thereby providing a three-dimensional feel through touch. The misalignment between the embossed shape and the pattern of the pattern layer 13 is preferably within a range of 10 mm or less in the longitudinal direction and 3 mm or less in the short direction (width direction) relative to the shape of the pattern. For example, if the pattern is wood grain, the direction in which the wood grain pores extend becomes the "longitudinal direction relative to the shape of the pattern," and the direction perpendicular to the longitudinal direction becomes the "short direction relative to the shape of the pattern." In particular, if the wood grain pores extend along the longitudinal direction of the laminated sheet 3, the longitudinal direction of the laminated sheet 3 becomes the "longitudinal direction relative to the shape of the pattern," and the short direction (width direction) of the laminated sheet 3 becomes the "short direction relative to the shape of the pattern." The embossed shape is only strongly visible due to the reflection of oblique light because the surface protective layer 34 is transparent. However, if the misalignment between the embossed shape and the pattern of the pattern layer 13 is within the above range, it is difficult to see the transmitted light of the pattern layer 13 simultaneously with the reflected light, so there is no sense of incongruity. By keeping the misalignment between the embossed shape and the pattern of the pattern layer 13 within a certain range, a laminated sheet 3 can be obtained in which the shape and distribution of the pattern are evenly and accurately matched across the entire sheet. The height difference between the recessed and raised parts of the embossed shape is preferably in the range of 3 μm to 200 μm. The height difference between the recessed and raised parts can be selected to a value suitable for the design of the laminated sheet 3. For example, a continuous multi-stage shape can be taken within the maximum height difference (200 μm). In particular, to obtain a shape as a macroscopic three-dimensional object, a height difference in the range of 10 μm to 150 μm is more preferable.

[0078] (3.2) Effects of the third embodiment In addition to the effects described in the first and second embodiments, the laminated sheet described above has the following effects. (7) The laminated sheet of this embodiment has an embossed shape and a second top coat layer provided on the portion facing the pattern of the pattern layer. This configuration allows for the addition of a tactile, three-dimensional feel to the surface of the laminated sheet. [Examples]

[0079] The laminated sheet relating to this disclosure will be described below with reference to examples. In the lamination examples, laminated sheets with the configurations described in each of the following examples and comparative examples were prepared and bonded to flooring materials for evaluation.

[0080] <Example 1> In Example 1, the raw material layer forms a single laminated sheet. First, calcium carbonate with an average particle size of 2 μm and a maximum particle size of 30 μm, and polypropylene, a resin material, were mixed using a super mixer as the inorganic material for the base layer. At this time, the calcium carbonate content was 50% by mass relative to the total amount of calcium carbonate and polypropylene. Next, the calcium carbonate and polypropylene were heated and kneaded, and the mixture was extruded using a T-die extruder to form a polypropylene film. Subsequently, the formed polypropylene film was stretched biaxially using a twin-screw extruder to form a base layer with a thickness of 400 μm and a uniform micropore size around the calcium carbonate.

[0081] A urethane resin containing vinyl chloride was coated onto both sides of the base layer and dried to form anchor layers with a thickness of 5 μm. Subsequently, a urethane resin-based ink was coated onto the upper surface of the base layer (the surface of the anchor layer) and dried to form a pattern layer. A thermoplastic resin layer was formed by coating and curing polyethylene as a thermoplastic resin onto the surface of the patterned layer, and then a coating layer was formed by coating and curing an acrylic resin as a coating resin, creating a surface protective layer with a thickness of 100 μm.

[0082] Next, an adhesive resin was applied to the underside of the raw material layer (the surface of the anchor layer) to form an adhesive layer with a thickness of 1.0 μm. The laminated sheet of Example 1 was manufactured in the manner described above.

[0083] <Example 2> A raw material layer was formed in the same manner as in Example 1, and this was designated as the first raw material layer. Furthermore, a second base layer was prepared in the same manner as the base layer of Example 1, except that silica with an average particle size of 2 μm and a maximum particle size of 30 μm was used as the inorganic material, and polypropylene was used as the resin material, and the silica content relative to the total amount of silica and polypropylene was 40% by mass. At this time, the film thicknesses of the first and second base layers were adjusted so that the ratio of film thickness of the first and second base layers was 60:40. Next, the first raw material layer and the second raw material layer were laminated together using molten polyethylene. Subsequently, a pattern layer and a surface protection layer were formed on the upper surface of the second raw material layer in the same manner as in Example 1, and an adhesive layer was formed on the lower surface of the first raw material layer in the same manner as in Example 1. In this manner, a laminated sheet of Example 2 was manufactured, in which the raw material layer consisted of a first raw material layer and a second raw material layer.

[0084] <Example 3> The laminated sheet of Example 3 was manufactured in the same manner as in Example 2, except that a thermoplastic resin layer was not formed when forming the surface protective layer.

[0085] <Example 4> The laminated sheet of Example 4 was manufactured in the same manner as in Example 2, except that the average particle size of the calcium carbonate used in the first raw material layer was 4 μm and the maximum particle size was 50 μm.

[0086] <Example 5> The laminated sheet of Example 5 was manufactured in the same manner as in Example 2, except that the calcium carbonate content used in the first raw material layer was 95% by mass relative to the total amount of calcium carbonate and polypropylene.

[0087] <Example 6> The laminated sheet of Example 6 was manufactured in the same manner as in Example 2, except that the calcium carbonate content used in the first raw material layer was 15% by mass relative to the total amount of calcium carbonate and polypropylene.

[0088] <Example 7> The laminated sheet of Example 7 was manufactured in the same manner as in Example 2, except that the average particle size of the calcium carbonate used in the second base layer was 5 μm and the maximum particle size was 50 μm.

[0089] <Example 8> The laminated sheet of Example 8 was manufactured in the same manner as in Example 2, except that the calcium carbonate content used in the second raw material layer was 60% by mass relative to the total amount of calcium carbonate and polypropylene.

[0090] <Example 9> The laminated sheet of Example 9 was manufactured in the same manner as in Example 2, except that the ratio of the film thickness of the first raw material layer to the second raw material layer was set to 25:75. At this time, the total film thickness of the first raw material layer and the second raw material layer remained the same as in Example 2.

[0091] <Comparative Example 1> A laminated sheet of Comparative Example 1 was manufactured in the same manner as in Example 2, except that the first raw material layer was formed using urethane beads with an average particle size of 2 μm and a maximum particle size of 30 μm instead of calcium carbonate.

[0092] <Comparative Example 2> A laminated sheet of Comparative Example 2 was manufactured in the same manner as in Example 2, except that aramid fibers were used instead of silica to form the second base layer.

[0093] <Comparative Example 3> A laminated sheet of Comparative Example 3 was manufactured in the same manner as in Example 2, except that a second raw material layer was formed using urethane beads with a uniform particle size of 2 μm and a maximum particle size of 30 μm instead of silica.

[0094] <Comparative Example 4> A laminated sheet of Comparative Example 3 was manufactured in the same manner as in Example 2, except that no anchor layers were provided on the surfaces of the first and second raw material layers.

[0095] [evaluation] (a) Interlayer adhesion The adhesion between layers constituting each example and comparative example of the laminated sheet was evaluated using an adhesion (cross-cut method) test in accordance with JIS K 5600-5-6. In the test, a result of "○" was given when the number of peeled squares was 0 or more and 2 or less, "△" when the number of peeled squares was 3 or more and 5 or less, and "×" when the number of peeled squares was 6 or more.

[0096] (b) Nonflammable The non-combustibility of the laminated sheets of each example and comparative example was evaluated by exothermic testing using a cone calorimeter testing machine compliant with ISO 5660-1. In the test, a score of "○" was given if all of the following requirements 1 to 3 were met, "△" if two of the requirements 1 to 3 were met, and "×" if one of the requirements 1 to 3 was met or none of the requirements were met. Gypsum board was used as the non-combustible substrate. 1. Total heat output is 8 MJ / m³ 2 below 2. The maximum heat generation rate remains at 200 kW / m² for 10 seconds or more. 2 Do not exceed 3. No cracks or holes that penetrate to the back surface, which would be harmful from a fire-retardant standpoint, will occur.

[0097] (c) Sheet hardness The sheet hardness of each example and comparative example laminate was evaluated using a scratch hardness (pencil method) test in accordance with JIS K 5600-5-4. Sheet hardness was determined by scratching the surface of the laminate with a pencil and visually checking whether tearing occurred. In the test, "○" was used to indicate that no significant defects occurred on the surface of the laminate, "△" was used to indicate that defects occurred on the surface of the laminate but did not pose a problem for use, and "×" was used to indicate that significant defects occurred on the surface of the laminate.

[0098] (d) Smoothness In the manufacturing process of the laminated sheets of each example and comparative example, when applying the anchor material (urethane resin containing vinyl chloride), the surface formation state of the base layer, or the first and second base layers, was visually inspected to evaluate the smoothness of the base layer. In the evaluation, "○" was used if it was possible to form a uniform, even, and free coated surface without clogging due to powder shedding of inorganic material from the base layer, "△" was used if clogging, unevenness, or gaps occurred due to powder shedding depending on the printing or lamination conditions, and "×" was used if clogging occurred due to powder shedding or if it was extremely difficult to form a uniform coated surface.

[0099] (e) Surface powdering In the manufacturing process of the laminated sheets for each example and comparative example, the surface of the raw material layer or the surfaces of the laminated first and second raw material layers were dry-rubbed by hand, and the presence or absence of powdering or shedding of inorganic material (calcium carbonate or silica) was visually evaluated. In the evaluation, "○" was used when no inorganic particles were observed on the surface of the hand, "△" was used when inorganic material was observed on the surface of the hand, and "×" was used when inorganic material was observed on the entire surface of the hand.

[0100] (f) Ink adhesion In the manufacturing process of the laminated sheets for each example and comparative example, Nichiban cellophane tape was pressed onto the surface of the base layer (second base layer) after the pattern layer was formed, and then peeled off with a force of 10N. The presence or absence of delamination within the pattern layer or between the base layer and the pattern layer was visually evaluated. In the evaluation, "○" was used if no delamination occurred within the pattern layer or between the base layer and the pattern layer, "△" was used if delamination occurred in part within the pattern layer or between the base layer and the pattern layer, and "×" was used if the pattern layer adhered to the entire surface of the cellophane tape and significant delamination occurred within the pattern layer or between the base layer and the pattern layer.

[0101] (g) Processability The laminated sheets of each example and comparative example were folded and then unfolded, and the occurrence of cracks and powder shedding in the folded portion was visually evaluated. In the evaluation, "○" was used if no cracks or powder shedding occurred in the folded portion, "△" was used if slight cracks or powder shedding occurred in the folded portion, and "×" was used if cracks or powder shedding occurred significantly in the folded portion. Table 1 below shows excerpts of the configurations for each example and comparative example. Table 2 below shows the evaluation results for each example and comparative example.

[0102] [Table 1]

[0103] [Table 2]

[0104] As shown in Table 1, the laminated sheets of each embodiment, which contain inorganic particles in the base layer, or the first and second base layers, and have an anchor layer on the surface of the base layer, or the first and second base layers, did not receive any "×" ratings in interlayer adhesion, non-flammability, and sheet hardness, demonstrating that all properties were compatible. On the other hand, in each comparative example, the laminated sheets in which the base layer, or at least one of the first and second base layers, did not contain inorganic particles, or in which no anchor layer was provided on the surface of the base layer, or the first and second base layers, received a "×" rating for at least one of the interlayer adhesion, non-flammability, and sheet hardness.

[0105] Furthermore, the laminated sheets of Examples 1-3, in which the average particle size of the inorganic material contained in the first raw material layer was 2 μm and the content was 50% by mass, exhibited higher smoothness and less inorganic material powdering than the laminated sheet of Example 4, in which the average particle size of the inorganic material was 4 μm, and the laminated sheet of Example 5, in which the inorganic material content was 95% by mass. In addition, the laminated sheets of Examples 1-3 showed higher ink adhesion and processability than the laminated sheet of Example 5, in which the inorganic material content was 95% by mass. On the other hand, the laminated sheets of Examples 1 to 3 had higher non-flammability and sheet hardness than the laminated sheet of Example 6, which contained 5% by mass of inorganic material.

[0106] Furthermore, the laminated sheets of Examples 2 and 3, in which the average particle size of the inorganic material contained in the second raw material layer was 2 μm and the content was 40% by mass, had higher smoothness, were less prone to powdering of the inorganic material, and had higher processability than the laminated sheet of Example 7, in which the average particle size of the inorganic material was 5 μm, and the laminated sheet of Example 8, in which the content of the inorganic material was 60% by mass.

[0107] Furthermore, the laminated sheets of Examples 2 and 3, in which the film thickness ratio of the first and second raw material layers was 60:40, showed higher non-flammability, sheet hardness, and processability compared to the laminated sheet of Example 9, in which the film thickness ratio of the first and second raw material layers was 25:75.

[0108] Based on the above evaluation results, it was confirmed that laminated sheets containing inorganic materials in the base layers (first base layer and second base layer) and equipped with an anchor layer exhibit higher interlayer adhesion, non-flammability, and sheet hardness compared to laminated sheets that do not contain inorganic materials in the base layers or are not equipped with an anchor layer.

[0109] The scope of this disclosure is not limited to the illustrative and described exemplary embodiments, but also includes all embodiments that produce an effect equivalent to that which is intended by this disclosure. Furthermore, the scope of this disclosure is not limited to the combination of features of the invention defined by the claims, but may be defined by any desired combination of specific features from all disclosed features. [Explanation of Symbols]

[0110] 1,2,3 Laminated Sheet 11 Adhesive layer 12 Anti-nuclear layer 12a Inorganic materials 12b void 13 Pattern Layers 14 Surface protective layer 16id, 16b anchor layer 22 Anti-nuclear layer 22a First fabric layer 22b Second primary fabric layer 26a~26d Anchor layer 34 Surface protective layer 34a Upper resin layer 34b First top coat layer 34c Second top coat layer

Claims

1. A base layer containing resin material and inorganic material, A surface protective layer formed on one surface of the aforementioned raw material layer, An anchor layer formed on the surface of the raw material layer on the side of the surface protection layer, Equipped with, The aforementioned resin material is a thermoplastic resin, The thermoplastic resin is at least one selected from the group consisting of propylene homopolymer, ethylene homopolymer, copolymer of ethylene and / or propylene with copolymerizable α-olefins, ethylene-ethyl acrylate copolymer, and ethylene-vinyl acetate copolymer. The anchor layer contains a urethane resin containing a copolymer of vinyl chloride and vinyl acetate, or an acrylic resin containing a copolymer of vinyl chloride and vinyl acetate, and the ratio of the content of the vinyl chloride and vinyl acetate copolymer to the content of the urethane resin or acrylic resin is in the range of 80:20 to 1:99 by mass ratio. Laminated sheet.

2. The aforementioned raw material layer has multiple voids formed around the inorganic material, The aforementioned voids are scattered throughout the entire raw material layer. The laminated sheet according to claim 1.

3. The voids formed in the raw material layer have a shape that extends in the thickness direction of the raw material layer, and the voids are connected to other voids. The laminated sheet according to claim 2.

4. The inorganic material contains calcium carbonate in an amount of 50% by mass or more and 100% by mass or less. A laminated sheet according to any one of claims 1 to 3.

5. The inorganic material is at least one of the following: antimony trioxide, antimony soda, 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 zirconium compounds with antimony trioxide, as well as salts thereof, and furthermore, hollow glass beads and acrylic beads. A laminated sheet according to any one of claims 1 to 3.

6. The thermoplastic resin is at least one of polypropylene and polyethylene. A laminated sheet according to any one of claims 1 to 5.

7. The surface protective layer contains a urethane resin, an acrylic resin, an ultraviolet-curable resin, or an ionizing radiation-curable resin. A laminated sheet according to any one of claims 1 to 6.

8. The ratio of the content of the vinyl chloride-vinyl acetate copolymer to the content of the urethane resin or acrylic resin is within the range of 80:20 to 1:99 by mass (excluding 1:1). A laminated sheet according to any one of claims 1 to 7.

9. The ratio of the content of the vinyl chloride-vinyl acetate copolymer to the content of the urethane resin or acrylic resin is in the range of 20:80 to 10:90 by mass ratio. A laminated sheet according to any one of claims 1 to 8.

10. Inorganic materials and resin materials are mixed together. A resin film containing inorganic materials and resin materials is formed to create a base layer. An anchor layer is formed by coating at least one side of the base layer with an anchor material containing a urethane resin containing a copolymer of vinyl chloride and vinyl acetate, or an acrylic resin containing a copolymer of vinyl chloride and vinyl acetate, wherein the ratio of the content of the copolymer of vinyl chloride and vinyl acetate to the content of the urethane resin or acrylic resin is in the range of 80:20 to 1:99 by mass ratio. The process includes applying a resin material onto the anchor layer and curing it to form a surface protective layer. The aforementioned resin material is a thermoplastic resin, The thermoplastic resin is at least one selected from the group consisting of propylene homopolymer, ethylene homopolymer, copolymer of ethylene and / or propylene with copolymerizable α-olefins, ethylene-ethyl acrylate copolymer, and ethylene-vinyl acetate copolymer. A method for manufacturing laminated sheets.

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