JP2021112833A - Laminated sheet and method for producing laminated sheet - Google Patents

Abstract

To provide a laminated sheet which prevents peeling between layers while having high non-combustibility and hardness, and a method for producing a laminated sheet.SOLUTION: A laminated sheet 1 includes a raw fabric layer 12 containing a resin material and an inorganic material 12a, a surface protective layer 14 formed on one surface of the raw fabric layer 12, and an anchor layer 16b formed on at least a surface on the side of the surface protective layer 14 of the raw fabric layer 12. In the laminated sheet 1, the raw fabric layer 12 has a first raw fabric layer and a second raw fabric layer, and the surface protective layer 14 may be constituted so as to be formed on the second raw fabric layer. An average particle diameter of the inorganic material 12a is within a range of 1 μm or more and 3 μm or less, and a maximum particle size of the inorganic material 12a is preferably 50 μm or less. A content of the inorganic material in the first raw fabric layer is within a range of 20 mass% or more and 90 mass% or less, and a content of the inorganic material in the second raw fabric layer is preferably within a range of 1 mass% or more and 50 mass% or less.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a laminated sheet and a method for manufacturing a laminated sheet.

Conventionally, for the purpose of improving nonflammability and hardness, a sheet for building materials in which an inorganic material such as calcium carbonate is highly filled in a raw fabric layer has been proposed (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2009-13208

However, when another layer such as a surface protection layer is laminated on the surface of the raw fabric layer highly filled with an inorganic material, the raw fabric layer and the other layer are combined regardless of the lamination method such as the laminating method or the coextrusion method. In some cases, the adhesion strength was weak and it was easy to peel off between layers. In the laminated sheet used for building materials, tape may be attached or peeled off from the laminated sheet during construction or use by a resident, and it is a problem that peeling easily occurs between layers.

The present disclosure has been made in view of such a problem, and an object of the present invention is to obtain a laminated sheet and a method for producing a laminated sheet, which have high nonflammability and hardness but are less likely to be peeled between layers. There is.

In order to solve the above problems, the laminated sheet according to one aspect of the present disclosure includes a raw fabric layer containing a resin material and an inorganic material, a surface protective layer formed on one surface of the raw fabric layer, and at least. It is characterized by including an anchor layer formed on the surface of the raw fabric layer on the surface protective layer side.

Further, in the method for producing a laminated sheet according to another aspect of the present disclosure, an inorganic material and a resin material are mixed, a resin film containing the inorganic material and the resin material is formed to form a raw fabric layer, and the raw fabric layer is formed. Anchor material is applied to at least one surface of the above to form an anchor layer, and a resin material is applied onto the anchor layer and cured to form a surface protective layer.

According to the aspect of the present disclosure, it is possible to obtain a laminated sheet and a method for producing a laminated sheet, which have high nonflammability and hardness and are less likely to be peeled between layers.

It is sectional drawing which shows one structural example of the laminated sheet which concerns on 1st Embodiment of this disclosure. It is sectional drawing which shows one structural example of the laminated sheet which concerns on 2nd Embodiment of this disclosure. It is sectional drawing which shows one structural example of the laminated sheet which concerns on 3rd Embodiment of this disclosure.

Hereinafter, the present disclosure will be described through embodiments, but the following embodiments do not limit inventions within the scope of claims. Also, not all combinations of features described in the embodiments are essential to the means of solving the invention. Further, the drawings schematically show the invention according to the claims, and the dimensions such as the width and thickness of each part are different from the actual ones, and the ratios thereof are also different from the actual ones.

The laminated body according to the first embodiment of the present disclosure will be described. The laminated sheet according to the present disclosure is, for example, a laminated sheet applied to a wall surface, fittings, furniture, or the like. In the following description, the side in contact with the sticking surface of the laminated sheet may be referred to as "bottom", and the side opposite to the side in contact with the sticking surface of the laminated sheet (surface) may be referred to as "top".
Hereinafter, each aspect of each embodiment of the present disclosure will be described with reference to the drawings.

1. 1. First Embodiment (1.1) Basic Configuration of Laminated Sheet FIG. 1 is a cross-sectional view for explaining a configuration example of the laminated sheet 1 according to the embodiment of the present disclosure. As shown in FIG. 1, the laminated sheet 1 includes an adhesive layer 11, a raw fabric layer 12, a pattern pattern layer 13, and a surface protective layer 14. The laminated sheet 1 is configured by laminating an adhesive layer 11, a raw fabric layer 12, a pattern layer 13 and a surface protective layer 14 in this order.

The adhesive layer 11 is a layer provided to improve the adhesiveness between the laminated sheet 1 and the base on which the laminated sheet 1 is attached. The raw fabric layer 12 is a layer that serves as a base material for the laminated sheet 1, absorbs irregularities and steps on the sticking surface to improve the construction finish of the laminated sheet 1, and makes the laminated sheet 1 nonflammable and hard. It is a layer that gives. The pattern pattern layer 13 is a layer that imparts a desired color or pattern to the laminated sheet 1. The surface protective layer 14 is provided on the uppermost surface of the laminated sheet 1 and is provided for protecting the laminated sheet 1 and adjusting the gloss of the surface of the laminated sheet 1.
Hereinafter, each layer of the adhesive layer 11, the raw fabric layer 12, the pattern pattern layer 13, and the surface protective layer 14 will be described in detail.

(Original layer)
The raw fabric layer 12 is a layer containing one or more kinds of resin materials and one or more kinds of inorganic materials.
The ratio of the contents of the resin material to the inorganic material (resin material: inorganic material) in the raw fabric layer 12 is preferably in the range of 80:20 to 10:90 by mass ratio, and from 40:60 by mass ratio. More preferably, it is in the range of 20:80. That is, the content of the inorganic material in the raw fabric layer 12 with respect to the total amount of the resin material and the inorganic material is preferably in the range of 20% by mass or more and 90% by mass or less, and is in the range of 60% by mass or more and 80% by mass or less. Is more preferable.

Within 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 is obtained, and when the surface of the raw fabric layer 12 is scratched with a Hoffman scratch tester, it is less likely to be scratched to the extent that it can be visually recognized.
On the other hand, when the proportion of the resin material is small outside the above range, when the anchor materials to be the anchor layers 16a and 16b are applied to the surface of the raw fabric layer 12, so-called "powder blowing" is applied to the surface of the raw fabric layer 12. Can be suppressed from occurring. Further, when the ink that becomes the pattern pattern layer 13 is printed on the surface of the raw fabric layer 12, it is possible to suppress the occurrence of so-called “powder blowing” on the surface of the raw fabric layer 12. Here, "powder blowing" means that the inorganic material contained in the raw fabric layer 12 emerges on the surface of the raw fabric layer 12. Further, the laminating suitability when laminating the sheet on which the anchor layer 16a or 16b is formed on the raw fabric layer 12 is improved, and cracks are prevented from occurring in the bent portion and the inorganic material is suppressed from peeling off. be able to.

As described above, when the content ratio of the resin material and the inorganic material is in the range of 80:20 to 10:90 in terms of mass ratio, it is sufficient while improving the nonflammability or flame retardancy of the laminated sheet 1. Surface hardness can be obtained. Further, it is possible to improve the laminating suitability of the laminated sheet 1 and reduce the occurrence of powder blowing and the occurrence of cracks.

The inorganic material is preferably surface-treated. The inorganic material is surface-treated using, for example, a saturated fatty acid having 10 to 30 carbon atoms, more preferably 12 to 26 carbon atoms, an unsaturated fatty acid and a salt thereof as a surface treatment agent. By surface-treating the inorganic material with such a surface treatment agent, it is possible to suppress the aggregation of the inorganic material in the resin material, which is a concern when the inorganic material is highly filled.

Examples of saturated fatty acids include palmitic acid, stearic acid, lauric acid, myristic acid, alignic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid, and examples of salts include sodium salt, potassium salt, and magnesium. Examples include salt and calcium salt. The inorganic material is surface-treated by a known method.

The inorganic material is preferably in a powder shape (powder shape), and its average particle size is preferably in the range of 1 μm or more and 3 μm or less, and the maximum particle size is preferably 50 μm or less. When the average particle size and the maximum particle size of the inorganic material are within the above-mentioned numerical ranges, the flatness of the surface of the raw fabric layer 12 can be maintained while improving the dispersibility of the inorganic material with respect to the thermoplastic resin. If the average particle size of the inorganic material is less than 1 μm, the cohesive force between the inorganic materials may increase, and the dispersibility in the thermoplastic resin described later may decrease. Further, when the average particle size of the inorganic material exceeds 3 μm, the flatness of the surface of the raw fabric layer 12 is lowered, and the thicknesses of the anchor layers 16a and 16b, which will be described later, become uneven, and unevenness and chipping occur. Sometimes. Further, when the maximum particle size of the inorganic material exceeds 50 μm, the flatness of the surface of the raw fabric layer 12 is lowered, and the thicknesses of the anchor layers 16a and 16b, which will be described later, become uneven, and unevenness and chipping occur. Sometimes. In this embodiment, the "average particle size" means the mode diameter.

Inorganic materials include antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borosand, zinc borate, calcium carbonate, molybdenum trioxide or antimony dimolybate and water. Complexes with aluminum oxide, complexes with antimony trioxide and silica, complexes with antimony trioxide and zinc flower, silicic acid of zirconium, and complexes of zirconium compounds with antimony trioxide, and salts thereof, as well as silica. It is preferable to contain at least one of alumina, hollow glass beads, and acrylic beads.

Among them, the inorganic material is preferably a powder containing at least one of calcium carbonate and calcium carbonate salt, for example. Calcium carbonate and calcium carbonate salts are suitable because it is easy to control the particle size and the compatibility with the thermoplastic resin. Further, calcium carbonate and calcium carbonate are suitable from the viewpoint of reducing the cost of fireproof building members because they are inexpensive. Further, the inorganic material preferably contains calcium carbonate in the range of 50% by mass or more and 100% by mass or less. If it is an inorganic material having a calcium carbonate content of 50% by mass or more, it is possible to impart sufficient nonflammability or sufficient flame retardancy to the raw fabric layer 12, and also impart sufficient mechanical strength. Can be done.

Further, the inorganic material may be a powder material having crystallinity, so-called crystalline powder, or a powder material having no crystallinity, so-called amorphous type powder material. If the inorganic material is a crystalline powder material, the powder itself is homogeneous and has isotropic properties, so that the mechanical strength of the powder itself is improved, and the scratch resistance and durability of the fireproof building member tend to be improved. Further, if the inorganic material is an amorphous type powder material, the electrical conductivity and thermal conductivity of the powder itself, or the light transmittance and light absorption rate can be appropriately adjusted, so that there are variations such as tactile sensation and luster. It is possible to give abundant design.

As the resin material, for example, a thermoplastic resin is used, and a propylene homopolymer, an ethylene homopolymer, an ester homopolymer, ethylene and / or a copolymer of ethylene and / or another α-olefin copolymerizable with them, It contains at least one selected from the group consisting of ethylene-ethyl acrylate copolymers and ethylene-vinyl acetate copolymers. Specifically, polypropylene, polyethylene, polyester, polybutene, polymethylpentene and the like can be used, and polypropylene, polyethylene and polyester are preferable, and polypropylene, polyethylene and polyester are more preferable. By using at least one of polypropylene, polyethylene and polyester as the thermoplastic resin, the dispersibility of the inorganic material is improved. Further, by using polypropylene as the thermoplastic resin, the dispersibility of the inorganic material is further improved.

The total content of the resin material and the inorganic material is preferably in the range of 90% by mass or more and 100% by mass or less with respect to the mass of the raw fabric layer 12. When the total content of the resin material and the inorganic material is within the above-mentioned numerical range, the laminating suitability can be improved while obtaining sufficient nonflammability or sufficient flame retardancy. If the total content of the resin material and the inorganic material is less than 90% by mass with respect to the mass of the raw fabric layer 12, sufficient nonflammability or sufficient flame retardancy may not be obtained. In addition, the laminating suitability may be reduced, or cracks may occur in the bent portion of the sheet.

The thickness of the raw fabric layer 12 is preferably in the range of 50 μm or more and 12500 μm or less, and more preferably in the range of 70 μm or more and 10000 μm or less. When the thickness of the raw fabric layer 12 is within the above-mentioned numerical range, the laminating suitability can be improved. If the thickness of the raw fabric layer 12 is less than 50 μm, the laminating suitability tends to decrease. Further, if the thickness of the raw fabric layer 12 exceeds 12500 μm, it becomes difficult to handle in terms of workability and workability.

Further, the raw fabric layer 12 is formed by uniaxial stretching or biaxial stretching. In this case, as shown in FIG. 1, the raw fabric layer 12 is formed between the inorganic material 12a and the resin material and is planar (horizontal direction) so as to extend in a direction parallel to the front and back surfaces of the raw fabric layer 12. ) Has a void 12b in the shape of. A plurality of voids 12b are scattered throughout the original fabric layer 12.

The raw fabric layer 12 of the present embodiment may be formed by adding a foaming agent to a resin material and an inorganic material. As a result, a void having a shape extending in the thickness direction of the raw fabric layer 12 can be formed in the raw fabric layer 12. The voids formed by the foaming agent are larger than the voids formed by the voids connected to each other. Therefore, the laminated sheet 1 provided with the raw fabric layer 12 in which such voids are scattered throughout has a higher heat insulating property.

As the foaming agent, at least one of a decomposition gas generating foaming agent, an expandable capsule foaming agent and the like can be used. Preferred examples of the decomposition gas generating foaming agent are azodicarboxylic amide, dinitrosopentamethylenetetramine, paratoluenesulfonyl hydrazide, benzenesulfonyl hydrazide, sodium bicarbonate and ammonium carbonate, azobisisobutyronitrile, 4,4-oxybis. At least one of (benzenesulfonic acid hydrazide), diphenylsulfon-3,3'-disulfohydrazide, benzene-1,3-disulfohydrazide, p-toluenesulfonyl semicarbazide, and effervescent hollow microspheres. .. Further, as the expandable capsule foaming agent, hydrocarbon-based materials such as ethane, butane, pentane, neopentane, hexane, and heptane are contained in fine particles having a resin material such as acrylic acid ester, vinylidene chloride, acrylonitrile, and urethane as a coating. Examples include those containing a volatile expansion component.

In the raw fabric layer 12 formed from a mixture containing an inorganic material, a resin material and a foaming agent, a plurality of voids formed by the foaming agent are scattered throughout the raw fabric layer 12.
The content of the foaming agent may be an amount that can obtain heat insulating properties as a building member and has the interlayer strength of the resin composition and the strength as a building member, and may be adjusted as necessary. For example, the amount of foaming agent may be at least 10%, 25%, 50%, 100%, 150%, 200% or more in volume when the raw fabric layer 12 is heated. It may be foamed. The content of the foaming agent is, for example, in the range of 5% by mass or more and 10% by mass or less with respect to the mass of the raw fabric layer 12.

Further, the raw fabric layer 12 has voids having a shape that extends in the thickness direction due to the foaming agent when the mixture containing the foaming agent is uniaxially stretched or biaxially stretched, regardless of the position of the inorganic material 12a. .. As a result, the raw fabric layer 12 has a void 12b having a shape extending in the lateral direction in FIG. 1 around the inorganic material 12a, and as a result, the raw fabric layer 12 has a shape extending in the lateral direction in FIG. It is possible to obtain the original fabric layer 12 in which a plurality of voids 12b are scattered throughout.
The raw fabric layer 12 on which such a three-dimensional void 12b is formed can enhance the heat insulating effect.

Anchor layers 16a and 16b are provided on both sides of the raw fabric layer 12. The anchor layers 16a and 16b will be described later. It is preferable that both surfaces of the raw fabric layer 12 are subjected to surface treatment such as corona treatment or plasma treatment before forming the anchor layers 16a and 16b described later. Adhesion (adhesion) between the anchor layers 16a and 16b formed on the surface treated surface by applying surface treatment such as corona treatment or plasma treatment to both surfaces of the raw fabric layer 12 and the raw fabric layer 12. ) Is improved.
Further, before forming the anchor layers 16a and 16b, both sides of the raw fabric layer 12 may be brushed to remove the powder-blown inorganic material in advance.

(Anchor layer)
The anchor layers 16a and 16b are layers formed so as to cover the entire surface of the raw fabric layer 12, and are layers for preventing powder falling of the inorganic material contained in the raw fabric layer 12. The inorganic material contained in the raw fabric layer 12 is powdered in the printing system, specifically in the printing apparatus, at the time of forming the pattern layer 13 (during ink printing) or forming the surface protective layer 14 (during resin coating). It may fall off and contaminate the inside of the printing system. Further, if the inorganic material contained in the raw fabric layer 12 is powdered off, problems such as ink loss may occur in the pattern layer 13. Here, "ink missing" means that the ink is not partially printed.

Further, the anchor layer 16b also has a function of improving the adhesion between the raw fabric layer 12 and the ink forming the pattern layer 13 or the resin material forming the surface protection layer 14. If the anchor layer 16b is not provided on the upper surface of the raw fabric layer 12, the ink or resin material may peel off without adhering to the raw fabric layer 12.

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

Further, the "urethane resin containing salt and vinegar" and the "urethane resin containing salt and vinegar" may contain a curing agent in addition to the above-mentioned salt and vinegar and urethane resin or acrylic resin. This curing agent is added to reliably cure the urethane resin containing vinyl acetate or the acrylic resin containing vinyl acetate, and the content thereof is not particularly limited. For example, the ratio of the content of urethane resin or acrylic resin containing salt and vinegar to the content of curing agent (content of urethane or acrylic resin containing salt and vinegar: content of curing agent) May be in the range of 99: 1 to 1:99 in terms of mass ratio, preferably in the range of 99: 1 to 50:50, and even more preferably in the range of 95: 5 to 90:10. ..

The content of the urethane resin containing salt and vinegar or the acrylic resin containing salt and vinegar in the anchor layers 16a and 16b (hereinafter, may be referred to as the resin content) is the mass of the anchor layers 16a and 16b. On the other hand, the range of 15% by mass or more and 100% by mass or less is preferable, the range of 80% by mass or more and 100% by mass or less is more preferable, and the range of 85% by mass or more and 95% by mass or less is further preferable. When the resin content is within the above-mentioned numerical range, the anchor layers 16a and 16b are uniform and have no unevenness or chipping while ensuring sufficient interlayer strength between the raw fabric layer 12 and the pattern layer 13 or the surface protection layer 14. Can be formed.

On the other hand, if the resin content is less than 15% by mass, the above-mentioned interlayer strength may be insufficient. Further, when the resin content is less than 80% by mass, there is no problem in use, but the ratio of the anchor layers 16a and 16b to the raw fabric layer 12 decreases. For this reason, the interlayer strength between the anchor layers 16a and 16b and the raw fabric layer 12 is slightly reduced.

If the resin content of the anchor layers 16a and 16b is 100% by mass or less with respect to the mass of the anchor layers 16a and 16b, there is no problem in use. However, if the resin content described above exceeds 95% by mass, or more accurately 98% by mass, the anchor layers 16a and 16b may be chipped due to insufficient curing. Further, the interlayer strength between the anchor layers 16a and 16b and the raw fabric layer 12 or the anchor layer 16b and the pattern layer 13 may decrease.

Further, it is preferable that the resin contents of the anchor layers 16a and 16b provided on both surfaces of the raw fabric layer 12 are the same. In this case, it is possible to reduce the occurrence of distortion and warpage of the raw fabric layer 12, and as a result, it is possible to reduce the occurrence of distortion and warpage of the entire laminated sheet 1. Further, since the coating liquid for forming the anchor layers 16a and 16b can be shared, the manufacturing cost can be reduced and the work efficiency can be improved.

The thickness of the anchor layers 16a and 16b is, for example, in the range of 0.5 μm or more and 20 μm or less, and preferably in the range of 0.5 μm or more and 10 μm or less. Further, it is preferable that the thicknesses of the anchor layers 16a and 16b are the same as each other. When the thicknesses of the anchor layers 16a and 16b are the same, the physical properties of the anchor layers 16a and 16b are almost the same, so that the occurrence of distortion and warpage of the original fabric layer 12 can be reduced.

In the case of the extrusion laminating method, the anchor layers 16a and 16b are coextruded with a heat-adhesive resin such as a maleic acid-modified olefin resin together with the raw fabric layer 12, and the layers between the raw fabric layer 12 and the anchor layers 16a and 16b are formed. Adhesion may be improved.
When the adhesive layer 11 is not provided on the back surface of the raw fabric layer 12, the anchor layer 16a may not be provided on the back surface of the raw fabric layer 12 (the backmost surface of the laminated sheet 1). This is because there is no problem even if the anchor layer is not provided on the outermost back surface of the laminated sheet 1 depending on the construction method or the like on the base of the laminated sheet 1.

(Pattern pattern layer)
The pattern pattern layer 13 is a layer formed on the original fabric layer 12 and imparting a pattern to the laminated sheet 1 in order to give it a design.
There are no particular restrictions on the type of pattern pattern formed by the pattern pattern layer 13, and for example, wood grain pattern, stone pattern, cloth pattern, abstract pattern, geometric figure, character, symbol, etc. may be used alone or in combination of two or more. May be formed in combination. Further, the pattern pattern layer 13 may be a layer to which a single color is imparted.

The pattern pattern layer 13 is a layer formed by printing with, for example, urethane resin ink. As the urethane resin-based ink, for example, an ink containing a urethane resin, a vinyl chloride vinyl acetate copolymer resin, an organic pigment, and an inorganic pigment can be used. The composition of the pattern layer 13 contains, for example, urethane resin in the range of 50.9% by mass or more and 76.7% by mass or less, and vinyl chloride vinyl acetate copolymer resin in an amount of 10.2% by mass or more and 23.3% by mass. It may be contained in the range of% or less, the organic pigment in the range of 0% by mass or more and 37.7% by mass or less, and the inorganic pigment in the range of 0% by mass or more and 20.0% by mass or less. preferable.

As a method for forming the pattern layer 13, any printing method such as an inkjet printing method, a gravure printing method, a screen printing method, offset printing, or flexographic printing can be used.
Further, the mass of the pattern layer 13 is preferably 8.36 [g / m ² ] or less (solid amount) (organic mass 6.71 [g / m ² ] or less), for example.
The ratio of the formed area (printed area of ink) per unit area (for example, 300 [mm] square) of the pattern layer 13 is preferably 50% or less, and more preferably 90% or more. .. In particular, when the pattern layer 13 is a layer formed by solid printing, the ratio of the formed area (area covered with ink) per unit area of the pattern layer 13 is preferably 90% or less. The unit area is not limited to 300 [mm] squares, and may be, for example, 200 [mm] squares or more and 400 [mm] squares or less. The unit area of the pattern layer 13 is defined in order to secure an appropriate light transmittance, and may be set based on, for example, the place where the laminated sheet 1 is arranged, the brightness of the light source, and the like.

(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 protective layer 14 is preferably a transparent layer in order to express the pattern and color of the pattern pattern layer 13 on the surface of the laminated sheet 1. Further, the surface protection layer 14 may be, for example, a top coat layer or an upper base resin layer.

When the laminated sheet 1 is used for interior use, the surface protective layer 14 is formed by applying a coating resin on the pattern layer 13 in order to exhibit a visual gloss matte effect on the surface of the laminated sheet 1. As the coating resin, a urethane resin, an acrylic resin, an ultraviolet curable resin, an ionizing radiation curable resin, or the like is used depending on the required performance. The surface protective layer 14 is formed by applying a coating resin to a single layer or a plurality of layers. When the surface protective layer 14 is formed of a plurality of layers, two or more different coating resins may be applied, or two or more layers of the same resin may be applied.

Further, even when the laminated sheet 1 is used for interior use, when the laminated sheet 1 requires abrasion resistance and scratch resistance, the surface protective layer 14 is coated with a thermoplastic resin or the like on the pattern layer 13. Is formed. In this case, the design can be improved by providing an uneven pattern on the surface of the surface protective layer 14. Examples of the uneven pattern include wood grain conduit grooves, stone plate surface irregularities (granite cleavage surface, etc.), cloth surface texturer, satin finish, sand grain, hairline, and the like. As a method for forming the uneven pattern, for example, an embossing method using a known single-wafer type or rotary type embossing machine can be adopted.

The thickness of the surface protective layer 14 is preferably 60 μm or more and 200 μm or less, preferably 60 μm or more and 150 μm or less, while stably maintaining performance such as scratch resistance and wear resistance, and considering bending workability and economy. Is more preferable.
When the laminated sheet 1 is used for exterior use, for example, an ultraviolet absorber such as benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, and a light stabilizer such as hindered amine-based are added to the surface protective layer 14. It is preferable to let it.

(Adhesive layer)
The adhesive layer 11 has a function of ensuring adhesion to the base on which the laminated sheet 1 is attached. The thickness of the adhesive layer 11 is preferably in the range of, for example, 0.1 μm or more and 3.0 μm or less. When the thickness of the adhesive layer 11 is within the above range, the adhesion to the base can be improved and the adhesive layer 11 can be prevented from protruding from the laminated sheet 1 when the laminated sheet 1 is attached.

The material constituting the adhesive layer 11 is 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 and the like, and for example, a gravure coat is used.

The adhesive layer 11 may be a primer. In this case, the material constituting the adhesive layer 11 may be, for example, nitrified cotton as a binder, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester or the like alone or in each modified product. Can be appropriately selected and used. These are not particularly limited in their form such as water-based, solvent-based, and emulsion type. The curing method can also be appropriately selected from a one-component type that cures independently, a two-component type that uses a curing agent in combination with the main agent, and a type that cures by irradiation with ultraviolet rays, electron beams, or the like. As a general curing method, a two-component type that cures by combining an isocyanate-based curing agent with a urethane-based main agent is used, and this method has workability, price, and cohesive force of the resin itself. It is suitable from the viewpoint. In addition to the above binders, colorants such as pigments and dyes, extender pigments, solvents, various additives, inorganic fillers and the like may be added.

In particular, the adhesive layer 11 preferably contains an inorganic filler such as silica, alumina, magnesia, titanium oxide, and barium sulfate. The adhesive layer 11 is located on the innermost back surface of the laminated sheet 1. Therefore, considering that the laminated sheet 1 is wound as a continuous plastic film (web-like), it is necessary to prevent the films from sticking to each other to prevent slipping and blocking such as not peeling off. There is. Since the adhesive layer 11 contains an inorganic filler, it is possible to suppress adhesion and blocking between laminated sheets (films).

The adhesive layer 11 does not necessarily have to be provided. This is because there is no problem even if the adhesive layer 11 is not provided on the outermost back surface of the laminated sheet 1 depending on the construction method or the like on the base of the laminated sheet 1.

(1.2) Method for Manufacturing Laminated Sheet An example of the method for manufacturing the laminated sheet 1 will be described below.
First, the raw fabric layer 12 is formed.
The inorganic material and the resin material contained in the raw fabric layer 12 are mixed using a known mixer such as a super mixer, a Henschel mixer, a tumbler mixer, or a ribbon blender.
The inorganic material and the resin material are heat-kneaded, and the mixture containing each component contained in the raw fabric layer 12 is extruded using a known molding machine such as T-die extrusion to obtain a resin film containing the inorganic material and the resin material. Form a film. Then, the formed resin film is stretched uniaxially or biaxially with a uniaxial extruder or a twin screw extruder to form a raw fabric layer 12 having a uniform fine pore size.

Anchor materials are applied to the lower surface and the upper surface of the raw fabric layer 12 to form anchor layers 16a and 16b, respectively. At this time, the anchor layers 16a and 16b may be formed on both sides of the raw fabric layer 12 at the same time, the anchor layer 16a is formed on the lower surface of the raw fabric layer 12, and the anchor layer 16a is different from the anchor layer 16a on the upper surface of the raw fabric layer 12. The anchor layer 16b may be formed at the timing.
For example, urethane resin-based ink is applied to the upper surface of the raw fabric layer 12 (the surface of the anchor layer 16b) so as to obtain a desired pattern, and dried to form the pattern layer 13.
A resin material such as a coating resin or a thermoplastic resin is applied onto the surface of the pattern layer 13 and cured to form the surface protective layer 14.

Subsequently, for example, an adhesive resin or a primer is applied to the lower surface of the raw fabric layer 12 (the surface of the anchor layer 16a) to form the adhesive layer 11.
As described above, the laminated sheet 1 according to the present embodiment is manufactured.
When the anchor layers 16a and 16b are formed at different timings, the anchor layer 16a may be formed after the surface protective layer 14 is formed, and then the adhesive layer 11 may be further formed.

(1.3) Effect of First Embodiment The above-mentioned laminated sheet has the following effects.
(1) The laminated sheet of the present embodiment contains inorganic particles in the raw fabric layer and has an anchor layer on the surface of the raw fabric layer.
According to this configuration, the nonflammability and sheet hardness of the laminated sheet are improved, and the interlayer adhesion between the raw fabric layer and the layers (pattern printing layer, surface protective layer) provided on the surface of the raw fabric layer is improved. It is possible to prevent the layers from peeling off from each other.

(2) The laminated sheet of the present embodiment has a plurality of voids formed around the inorganic material in the raw fabric layer, and the voids are scattered throughout the raw fabric layer.
According to this configuration, three-dimensional voids are formed in the raw fabric layer, and the heat insulating effect can be enhanced.

(3) In the laminated sheet of the present embodiment, it is preferable that the average particle size of the inorganic material contained in the raw fabric layer is within the range of 1 μm or more and 3 μm or less, and the maximum particle size of the inorganic material is 50 μm or less.
According to this configuration, the surface of the raw fabric layer can be flattened, and the occurrence of unevenness and chipping of the raw fabric layer can be suppressed.

(4) In the laminated sheet of the present embodiment, the content of the inorganic material with respect to the total amount of the resin material and the inorganic material in the raw fabric layer is preferably in the range of 20% by mass or more and 90% by mass or less.
According to this configuration, the nonflammability and sheet hardness of the laminated sheet can be improved, and the smoothness and processability of the surface of the raw fabric layer can be improved.

(5) In the laminated sheet of the present embodiment, it is preferable to use calcium carbonate or calcium carbonate salt as the inorganic particles.
According to this configuration, it is easy to control the particle size of the inorganic particles and the compatibility with the thermoplastic resin, and it is also preferable from the viewpoint of reducing the cost of the laminated sheet.

2. Second Embodiment Hereinafter, the laminated sheet according to the second embodiment of the present disclosure will be described with reference to FIG.
FIG. 2 is a cross-sectional view for explaining a configuration example of the laminated sheet 2 according to the second embodiment of the present disclosure.

The laminated sheet 2 includes an adhesive layer 11, a raw fabric layer 22 having a first raw fabric layer 22a and a second fabric fabric layer 22b, a pattern layer 13, and a surface protective layer 14. The laminated sheet 2 is composed of an adhesive layer 11, a first raw fabric layer 22a, a second raw fabric layer 22b, a pattern layer 13 and a surface protection layer 14 laminated in this order. The pattern pattern layer 13 and the surface protection layer 14 are formed on the surface on the second original fabric layer 22b side. That is, the laminated sheet 2 is different from the laminated sheet 1 according to the first embodiment in that the laminated sheet 2 is provided with the raw fabric layer 22 having the first raw fabric layer 22a and the second raw fabric layer 22b instead of the raw fabric layer 12. ..

Hereinafter, the first original fabric layer 22a and the second original fabric layer 22b will be described. Each layer (adhesive layer 11, pattern pattern layer 13 and surface protection layer 14) other than the first original fabric layer 22a and the second original fabric layer 22b has the same configuration as each layer of the laminated sheet 1, and thus will be described. Omit.

(2.1) Basic configuration of laminated sheet <1st raw fabric layer, 2nd raw fabric layer>
The first raw fabric layer 22a has the same configuration as the raw fabric layer 12 described in the first embodiment. Anchor layers 26a and 26b are provided on both sides of the first raw fabric layer 22a.
The second raw fabric layer 22b is a layer containing one or more kinds of resin materials and one or more kinds of inorganic materials.
The content of the inorganic material in the second raw fabric layer 22b is preferably smaller than the content of the inorganic material in the second raw fabric layer. The content ratio of the resin material to the inorganic material (resin material: inorganic material) in the second raw fabric layer 22b is preferably in the range of 99: 1 to 50:50 by mass ratio, and 90: by mass ratio. More preferably, it is in the range of 10 to 60:40. That is, the content of the inorganic material in the second raw fabric layer 22b with respect to the total amount of the resin material and the inorganic material is preferably in the range of 1% by mass or more and 50% by mass or less, and 10% by mass or more and 40% by mass or less. It is more preferable that the range is.

As the inorganic material, it is preferable to use the same material as the raw fabric layer 12. It is preferable to use at least one of calcium carbonate and calcium carbonate salt as the inorganic material for the first raw fabric layer 22a. Then, it is preferable to use an inorganic material different from the inorganic material contained in the first raw fabric layer 22a for the second raw fabric layer 22b. For example, when the first raw fabric layer 22a contains at least one of calcium carbonate and calcium carbonate salt as an inorganic material, the second raw fabric layer 22b is at least one kind of inorganic material other than calcium carbonate and calcium carbonate as an inorganic material. Is preferably included.
As a result, the production cost of the first raw fabric layer 22a can be reduced while forming inorganic particles in the first raw fabric layer 22a. Further, the second raw fabric layer 22b can improve nonflammability and sheet hardness.

Further, the film thickness of the second raw fabric layer 22b is preferably equal to or thinner than that of the first raw fabric layer 22a. Specifically, the ratio of the film thickness of the first raw fabric layer 22a to the second raw fabric layer 22b is preferably 50:50 to 95: 5. In this case, the nonflammability of the laminated sheet 2 and the decrease in sheet hardness can be suppressed.

As shown in FIG. 2, anchor layers 26c and 26d are provided on both sides of the second raw fabric layer 22b. It is preferable that both surfaces of the second raw fabric layer 22b are subjected to surface treatment such as corona treatment or plasma treatment before forming the anchor layers 26c and 26d. The anchor layer 26c is a layer provided on the lower surface of the second original fabric layer 22b, and the anchor layer 26d is a layer provided on the upper surface of the second original fabric layer 22b. The anchor layers 26c and 26d have the same configuration as the anchor layers 26a and 26b described in the first embodiment.

(2.2) Effects of the Second Embodiment The above-mentioned laminated sheet has the following effects in addition to the effects described in the first embodiment.
(6) The laminated sheet of the present embodiment has a first raw fabric layer and a second raw fabric layer containing different inorganic particles, respectively.
According to this configuration, the nonflammability and sheet hardness of the laminated sheet are further improved, and the interlayer adhesion between the raw fabric layer and the layers (pattern printing layer, surface protective layer) provided on the surface of the raw fabric layer is improved. It is possible to prevent the layers from peeling off from each other.

3. 3. Third Embodiment Hereinafter, the laminated sheet according to the third embodiment of the present disclosure will be described with reference to FIG.
FIG. 3 is a cross-sectional view for explaining a configuration example of the laminated sheet 3 according to the third embodiment of the present disclosure.

The laminated sheet 3 includes an adhesive layer 11, a raw fabric layer 22 having a first raw fabric layer 22a and a second raw fabric layer 22b, a pattern layer 13, an upper base resin layer 34a, a first top coat layer 34b, and a first layer. A surface protective layer 14 having a two-top coat layer 34c is provided. In the laminated sheet 2, the adhesive layer 11, the first raw fabric layer 22a, the second raw fabric layer 22b, the pattern layer 13, the upper base resin layer 34a, the first top coat layer 34b and the second top coat layer 34c are laminated in this order. It is composed of. That is, the laminated sheet 2 according to the first embodiment is provided with the surface protective layer 34 having the upper base resin layer 34a, the first top coat layer 34b, and the second top coat layer 34c instead of the surface protective layer 14. Different from sheet 1.

Hereinafter, the first original fabric layer 22a and the second original fabric layer 22b will be described. The layers other than the surface protective layer 34 (adhesive layer 11, first raw fabric layer 22a, second raw fabric layer 22b, pattern layer 13) have the same configuration as each layer of the laminated sheet 2, and thus will be described. Omit.

(3.1) Basic configuration of laminated sheet <Surface protective layer>
The surface protective layer 34 includes an upper base resin layer 34a, a first top coat layer 34b, and a second top coat layer 34c. As shown in FIG. 3, the surface protective layer 34 may have an embossed shape.

The upper base resin layer 34a is a layer for the purpose of shock absorption (buffering) and the like, and is also an adhesive layer for adhering the pattern pattern layer 13 and the first top coat layer 34b. Further, the upper base resin layer 34a has a function of clarifying the pattern when forming the pattern layer 13 and improving the scratch resistance of the pattern layer 13. The upper base resin layer 34a is formed of, for example, a transparent polypropylene resin. The thickness of the upper base resin layer 34a is, for example, about 150 μm or more and 200 μm or less.

The first top coat layer 34b is a top coat layer for the purpose of adjusting gloss and / or protecting the pattern layer 13. The first top coat layer 34b is preferably formed of, for example, an ultraviolet curable resin. The thickness of the surface protective layer 34 is preferably 0.1 μm or more and 15 μm or less, for example.

The second topcoat layer 34c is a layer that is partially provided on the surface side of the first topcoat layer 34b and covers a part of the surface of the first topcoat layer 34b. As a part of the surface of the first top coat layer 34b, for example, a portion facing the pattern pattern of the pattern pattern layer 13 can be mentioned. Further, as the material of the second top coat layer 34c, for example, the same resin as that of the first top coat layer 34b can be adopted. A filler may be added to the second top coat layer 34c. By adding the filler, mechanical properties such as gloss, touch, texture, surface strength, and friction different from those of the first top coat layer 34b can be imparted. As the filler, for example, a material that consumes less oxygen during combustion is preferable, and for example, zirconium compounds such as calcium carbonate, antimony trioxide, antimony soda, zircon silicate, and zircon oxide, magnesium hydroxide, aluminum hydroxide, and base. Antimony trioxide and silica complex, antimony trioxide and zinc flower complex, silicic acid of zirconium, zirconium compound, such as magnesium carbonate, borosand, zinc borate, molybdenum trioxide or antimony dimolybate and aluminum hydroxide complex. And antimony trioxide complex and the like. In particular, calcium carbonate is suitable from the viewpoint of reducing the cost of the decorative sheet because it is easy to control the particle size by the manufacturing method and the compatibility with the polyolefin resin by the surface treatment, and the material cost is low. Is. Further, resin beads and amorphous particles such as acrylic, polyolefin and silicone, and inorganic beads and amorphous particles such as silica (particularly hollow silica), alumina and metal oxide can be used. Further, the method for forming the second top coat layer 34c is not particularly limited, and a known printing method can be adopted. The second top coat layer 34c is also generally referred to as a "tactile coat layer" or a "matte conduit printing layer".

The surface protective layer 34 has, for example, an embossed shape composed of concave portions and convex portions synchronized with the pattern of the pattern pattern layer 13, so that a three-dimensional effect can be imparted by tactile sensation. The deviation between the embossed shape and the pattern of the pattern pattern layer 13 is preferably within a range of 10 mm or less in the longitudinal direction and 3 mm or less in the lateral direction (width direction) with respect to the shape of the pattern pattern, for example. For example, when the pattern is wood grain, the direction in which the wood grain conduit extends is the "longitudinal direction with respect to the shape of the pattern", and the direction orthogonal to the longitudinal direction is the "short direction with respect to the shape of the pattern". Become. In particular, when the wood grain conduit extends along the longitudinal direction of the laminated sheet 3, the longitudinal direction of the laminated sheet 3 is the "longitudinal direction with respect to the shape of the pattern", and the lateral direction (width direction) of the laminated sheet 3 ) Is the "short direction with respect to the shape of the pattern". Since the surface protective layer 34 is transparent, the embossed shape is strongly visible for the first time due to the reflection of oblique light. However, if the deviation between the embossed shape and the pattern of the pattern pattern layer 13 is within the above range, the pattern is displayed at the same time as the reflected light. Since it is difficult to visually recognize the transmitted light of the pattern layer 13, there is no sense of discomfort. By suppressing the deviation between the embossed shape and the pattern of the pattern pattern layer 13 within a certain range, it is possible to obtain a laminated sheet 3 in which the shape and distribution of the pattern are equally matched on the entire surface of the sheet. The height difference between the embossed concave portion and the convex portion is preferably in the range of, for example, 3 μm or more and 200 μm or less. For the height difference between the concave portion and the convex portion, a numerical value suitable for the design of the target laminated sheet 3 can be selected. For example, it is possible to take a continuous multi-stage shape within the maximum height difference (200 μm). In particular, in order to obtain a shape as a macroscopic three-dimensional object, the height difference is more preferably in the range of 10 μm or more and 150 μm or less.

(3.2) Effects of the Third Embodiment The above-mentioned laminated sheet has the following effects in addition to the effects described in the first embodiment and the second embodiment.
(7) The laminated sheet of the present embodiment has an embossed shape and has a second top coat layer provided at a portion of the pattern pattern layer facing the pattern pattern.
According to this configuration, it is possible to give a three-dimensional effect by touch to the surface of the laminated sheet.

Hereinafter, the laminated sheet according to the present disclosure will be described with reference to examples. In the laminated example, a laminated sheet having the configuration described in each of the following examples and each comparative example will be produced, and the laminated sheet will be laminated on the floor material. Was evaluated.

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

Urethane-based resin containing vinyl acetate was applied to both sides of the raw fabric layer and dried to form anchor layers having a thickness of 5 μm. Subsequently, a urethane resin-based ink was applied to the upper surface of the raw fabric layer (the surface of the anchor layer) and dried to form a pattern layer.
Polyethylene as a thermoplastic resin is applied and cured on the surface of the pattern layer to form a thermoplastic resin layer, and then an acrylic resin is further applied and cured as a coating resin to form a coat layer. A surface protective layer having a size of 100 μm was formed.

Subsequently, an adhesive resin was applied to the lower surface of the raw fabric layer (the surface of the anchor layer) to form an adhesive layer having a thickness of 1.0 μm.
As described above, the laminated sheet of Example 1 was manufactured.

<Example 2>
A raw fabric layer was formed in the same manner as in Example 1 to form a first raw fabric layer.
Further, except that silica having 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 was 40% by mass based on the total amount of silica and polypropylene. A second raw fabric layer was prepared in the same manner as the raw fabric layer of Example 1. At this time, the film thicknesses of the first and second raw fabric layers were adjusted so that the ratio of the film thicknesses of the first and second raw fabric layers was 60:40.
Subsequently, the first raw fabric layer and the second raw fabric layer were laminated and bonded together via molten polyethylene. Subsequently, a pattern pattern layer and a surface protective layer are formed on the upper surface of the second raw fabric layer in the same manner as in Example 1, and an adhesive layer is formed on the lower surface of the first raw fabric layer in the same manner as in Example 1. Formed.
As described above, the laminated sheet of Example 2 in which the raw fabric layer was composed of the first raw fabric layer and the second raw fabric layer was manufactured.

<Example 3>
The laminated sheet of Example 3 was produced in the same manner as in Example 2 except that the thermoplastic resin layer was not formed when the surface protective layer was formed.

<Example 4>
The laminated sheet of Example 4 was produced in the same manner as in Example 2 except that the average particle size of calcium carbonate used for the first raw fabric layer was 4 μm and the maximum particle size was 50 μm.

<Example 5>
The laminated sheet of Example 5 was produced in the same manner as in Example 2 except that the content of calcium carbonate used in the first raw fabric layer was 95% by mass with respect to the total amount of calcium carbonate and polypropylene. did.

<Example 6>
The laminated sheet of Example 6 was produced in the same manner as in Example 2 except that the content of calcium carbonate used in the first raw fabric layer was set to 15% by mass with respect to the total amount of calcium carbonate and polypropylene. did.

<Example 7>
The laminated sheet of Example 7 was produced in the same manner as in Example 2 except that the average particle size of calcium carbonate used for the second raw fabric layer was 5 μm and the maximum particle size was 50 μm.

<Example 8>
The laminated sheet of Example 8 was produced in the same manner as in Example 2 except that the content of calcium carbonate used in the second raw fabric layer was 60% by mass with respect to the total amount of calcium carbonate and polypropylene. did.

<Example 9>
The laminated sheet of Example 9 was produced in the same manner as in Example 2 except that the ratio of the film thicknesses of the first raw fabric layer and the second raw fabric layer was 25:75. At this time, the total film thickness of the first raw fabric layer and the second raw fabric layer remained the same as in Example 2.

<Comparative example 1>
The laminated sheet of Comparative Example 1 was produced in the same manner as in Example 2 except that the first raw fabric layer was formed by using urethane beads having an average particle size of 2 μm and a maximum particle size of 30 μm instead of calcium carbonate. ..

<Comparative example 2>
The laminated sheet of Comparative Example 2 was produced in the same manner as in Example 2 except that the second raw fabric layer was formed by using aramid fibers instead of silica.

<Comparative example 3>
The laminated sheet of Comparative Example 3 was produced in the same manner as in Example 2 except that the second raw fabric layer was formed by using urethane beads having a uniform particle size of 2 μm and a maximum particle size of 30 μm instead of silica.

<Comparative example 4>
The laminated sheet of Comparative Example 3 was produced in the same manner as in Example 2 except that the anchor layer was not provided on the surfaces of the first raw fabric layer and the second raw fabric layer.

[evaluation]
(A) Adhesion between layers By an adhesion (cross-cut method) test based on JIS K 5600-5-6, the adhesion between layers constituting the laminated sheets of each example and each comparative example was evaluated. In the test, "○" is when the number of squares to be peeled is 0 or more and 2 or less, "△" is when the number of squares to be peeled is 3 or more and 5 or less, and the number of squares to be peeled is The case of 6 or more was evaluated as "x".

(B) Nonflammability The nonflammability of the laminated sheets of each Example and each Comparative Example was evaluated by a heat generation test using a cone calorie meter tester conforming to ISO5660-1. In the test, "○" is when all of the following requirements 1 to 3 are satisfied, "△" is when two of the requirements 1 to 3 are satisfied, and one of the requirements 1 to 3 is satisfied, or 1 The case where none of them were satisfied was evaluated as "x". A gypsum board was used as the nonflammable base material.
1. 1. Total calorific value is 8MJ / m ² or less 2. 2. The maximum heat generation rate does not exceed ^{200 kW / m 2 continuously for 10 seconds or more.} No cracks or holes that penetrate to the back surface, which is harmful for flame protection

(C) Sheet hardness The sheet hardness of the laminated sheets of each Example and each Comparative Example was evaluated by a scratch hardness (pencil method) test according to JIS K 5600-5-4. The sheet hardness was determined by scratching the surface of the laminated sheet with a pencil and visually confirming whether or not the laminated sheet was torn. In the test, "○" indicates that there is no significant defect on the surface of the laminated sheet, "△" indicates that there is a defect on the surface of the laminated sheet but there is no problem in use, and "△" indicates that there is a significant defect on the surface of the laminated sheet. Was evaluated as "x".

(D) Smoothness In the manufacturing process of the laminated sheet of each example and each comparative example, when the anchor material (urethane resin containing vinyl acetate) is applied, the raw fabric layer or the first raw fabric layer and The smoothness of the raw fabric layer was evaluated by visually confirming the formation state of the surface of the second raw fabric layer. In the evaluation, if it is possible to form a uniform coated surface without unevenness or omission without causing plate clogging due to powder falling of the inorganic material from the raw fabric layer, "○", printing conditions or lamination conditions As a result, the case where plate clogging, unevenness, or omission occurs due to powder dropping is evaluated as "Δ", and the case where plate clogging due to powder dropping occurs or it is extremely difficult to form a uniform coated surface is evaluated as "x". ..

(E) Surface powder blowing In the manufacturing process of the laminated sheet of each example and each comparative example, the surface of the raw fabric layer or the surfaces of the laminated first raw fabric layer and the second raw fabric layer are dry-rubbed by hand to be inorganic. The presence or absence of powder blowing or falling off of the material (calcium carbonate or silica) was visually evaluated. In the evaluation, "○" is the case where no inorganic particles can be confirmed on the surface of the hand, "△" is the case where the inorganic material can be confirmed on the surface of the hand, and the case where the inorganic material can be confirmed on the entire surface of the hand. Was evaluated as "x".

(F) Ink Adhesion In the manufacturing process of the laminated sheet of each example and each comparative example, Nichiban cellophane tape was pressed onto the surface of the raw fabric layer (second raw fabric layer) after the pattern layer was formed, and then 10 N. It was peeled off by force, and the presence or absence of peeling inside the pattern layer or between the original fabric layer and the pattern layer was visually evaluated. In the evaluation, "○" indicates that peeling does not occur inside the pattern layer or between the original fabric layer and the pattern layer, and peeling occurs inside the pattern layer or partly between the original fabric layer and the pattern layer. The case where it occurred was defined as “Δ”, and the case where the pattern layer adhered to the entire surface of the cellophane tape and remarkable peeling occurred inside the pattern layer or between the original fabric layer and the pattern layer was evaluated as “x”.

(G) Workability When the laminated sheets of each Example and each Comparative Example were bent and reopened, the presence or absence of cracks and powder falling in the bent portion was visually evaluated. In the evaluation, "○" indicates that no cracking or powder falling occurs in the bent part, "△" indicates that a slight amount of cracking or powder falling occurs in the bent part, and cracking or powder falling is remarkable in the bent part. The case where it occurred was marked as "x".
Table 1 below shows an excerpt of the configuration of each Example and each Comparative Example. In addition, Table 2 below shows the evaluation results of each Example and each Comparative Example.

As shown in Table 1, the raw fabric layer, or the first and second raw fabric layers contains inorganic particles, and an anchor layer is formed on the surface of the raw fabric layer, or the first and second raw fabric layers. The laminated sheet of each example having the above was not evaluated as "x" in all of the interlayer adhesion, nonflammability and sheet hardness, and each characteristic could be compatible.
On the other hand, the raw fabric layer, or at least one of the first and second raw fabric layers does not contain inorganic particles, or an anchor layer is formed on the surface of the raw fabric layer or the first and second raw fabric layers. In each of the laminated sheets of the comparative examples not provided with, at least one of interlayer adhesion, nonflammability and sheet hardness was evaluated as "x".

Further, the laminated sheets of Examples 1 to 3 having an average particle size of 2 μm and a content of 50% by mass of the inorganic material contained in the first raw fabric layer are laminated with Example 4 having an average particle size of 4 μm of the inorganic material. The smoothness was higher than that of the laminated sheet of Example 5 in which the content of the sheet and the inorganic material was 95% by mass, and powder blowing of the inorganic material was less likely to occur. Further, the laminated sheets of Examples 1 to 3 had higher ink adhesion and workability than the laminated sheets of Example 5 having an inorganic material content of 95% by mass.
On the other hand, the laminated sheets of Examples 1 to 3 had higher nonflammability and sheet hardness than the laminated sheets of Example 6 having an inorganic material content of 5% by mass.

Further, the laminated sheets of Examples 2 and 3 having an average particle size of 2 μm and a content of 40% by mass of the inorganic material contained in the second raw fabric layer are laminated with Example 7 having an average particle size of 5 μm of the inorganic material. The smoothness was higher than that of the laminated sheet of Example 8 in which the content of the sheet and the inorganic material was 60% by mass, powder blowing of the inorganic material was less likely to occur, and the workability was further high.

Further, in the laminated sheets of Examples 2 and 3 in which the film thickness ratio of the first raw fabric layer to the second raw fabric layer is 60:40, the film thickness ratio of the first raw fabric layer to the second raw fabric layer is 25: Compared with the laminated sheet of Example 9 of 75, the nonflammability, the sheet hardness and the workability were high.

From the above evaluation results, the laminated sheet in which the raw fabric layer (first raw fabric layer and the second raw fabric layer) contains an inorganic material and the anchor layer is provided does not contain an inorganic material in the raw fabric layer or is an anchor layer. It was confirmed that the interlayer adhesion, nonflammability, and sheet hardness were higher than those of the laminated sheet not provided with.

The scope of the present disclosure is not limited to the exemplary embodiments illustrated and described, but also includes all embodiments that provide an equivalent effect to that of the present disclosure. Furthermore, the scope of the present disclosure is not limited to the combination of the features of the invention defined by the claims, but may be defined by any desired combination of the specific features of all the disclosed features.

1,2,3 Laminated sheet 11 Adhesive layer 12 Original fabric layer 12a Inorganic material 12b Void 13 Pattern layer 14 Surface protection layer 16a, 16b Anchor layer 22 Original fabric layer 22a First original fabric layer 22b Second original fabric layer 26a ~ 26d Anchor layer 34 Surface protection layer 34a Upper base resin layer 34b First top coat layer 34c Second top coat layer

Claims (14)

A raw fabric layer containing a resin material and an inorganic material,
A surface protective layer formed on one surface of the raw fabric layer and
At least an anchor layer formed on the surface of the original fabric layer on the surface protective layer side,
Laminated sheet with. The raw fabric layer has a plurality of voids formed around the inorganic material, and has a plurality of voids.
The laminated sheet according to claim 1, wherein the voids are scattered throughout the raw fabric layer. The inorganic materials include antimony trioxide, antimony soda, zircon silicate, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borosand, zinc borate, calcium carbonate, molybdenum trioxide or antimony dimolybate and water. Complexes with aluminum oxide, complexes with antimony trioxide and silica, complexes with antimony trioxide and zinc flower, silicic acid of zirconium, and complexes of zirconium compounds with antimony trioxide, and salts thereof, as well as silica. The laminated sheet according to claim 1 or 2, which is at least one of alumina, hollow glass beads, and acrylic beads. The laminated sheet according to any one of claims 1 to 3, wherein the average particle size of the inorganic material is in the range of 1 μm or more and 3 μm or less, and the maximum particle size of the inorganic material is 50 μm or less. The anchor layer according to any one of claims 1 to 4, which 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. The laminated sheet described. The raw fabric layer has a first raw fabric layer and a second raw fabric layer.
The laminated sheet according to any one of claims 1 to 5, wherein the surface protective layer is formed on the upper surface of the second raw fabric layer. The laminated sheet according to claim 6, wherein the content of the inorganic material in the first raw fabric layer is larger than the content of the inorganic material in the second raw fabric layer. The first raw fabric layer contains at least one of calcium carbonate and calcium carbonate as the inorganic material.
The laminated sheet according to claim 6 or 7, wherein the second raw fabric layer contains at least one of the inorganic materials other than calcium carbonate and calcium carbonate as the inorganic material. The content of the inorganic material in the first raw fabric layer with respect to the total amount of the resin material and the inorganic material is in the range of 20% by mass or more and 90% by mass or less.
The content of the inorganic material with respect to the total amount of the resin material and the inorganic material in the second raw fabric layer is in the range of 1% by mass or more and 50% by mass or less according to any one of claims 6 to 8. The laminated sheet described. The laminated sheet according to any one of claims 6 to 9, wherein the ratio of the film thickness of the first raw fabric layer to the second raw fabric layer is 50:50 to 95: 5. The laminated sheet according to any one of claims 1 to 10, wherein the resin material is a thermoplastic resin. The laminated sheet according to claim 11, wherein the thermoplastic resin is at least one of polypropylene, polyethylene, and polyester. The laminated sheet according to any one of claims 1 to 12, wherein the number of squares to be peeled off is 0 or more and 2 or less in the adhesion test according to JIS K 5600-5-6. Mix inorganic material and resin material,
A resin film containing an inorganic material and a resin material is formed to form a raw fabric layer.
Anchor material is applied to at least one surface of the raw fabric layer to form an anchor layer.
A method for producing a laminated sheet in which a resin material is applied onto the anchor layer and cured to form a surface protective layer.

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