JP2017213917A - Laminate sheet and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate sheet usable as a wallpaper excellent in adhesiveness when stuck again after temporarily stuck by applying a water-based glue, while securing a designability, even if a resin layer is formed using a method different from a method of directly applying a sol resin composition.SOLUTION: A laminate sheet includes a resin layer on a substrate. In the laminate sheet, (1) the resin layer includes a resin foam layer or a laminate including a resin foam layer, and is deposited on the substrate after deposition, and (2) the laminate sheet has an opening penetrating from a rear face of the substrate to a front face of the substrate, and the resin layer has no opening.SELECTED DRAWING: None

Description

  The present invention relates to a laminated sheet. The laminated sheet is useful as wallpaper, various decorative materials, and the like. In addition, a laminated sheet having a foamed resin layer (foamed laminated sheet) is useful as a foam wallpaper, various decorative materials, a skin material for laminated decorative plates, a cushioning floor material, a heat insulating decorative material, and the like.

  2. Description of the Related Art Conventionally, a wallpaper in which a resin layer is formed by directly applying a sol-like resin composition onto a backing paper (hereinafter also referred to as a wallpaper by a sol method) is known. A wallpaper (hereinafter, foamed wallpaper by a sol method) in which a foamed resin layer is formed by foaming the foaming agent by means of heating or the like further containing a foaming agent in the resin composition is widely used. (Patent Document 1). As the resin composition, a resin composition containing a vinyl chloride resin is often used.

  On the other hand, in recent years, in consideration of the environment, after using a non-vinyl chloride resin (non-vinyl chloride resin) that does not use vinyl chloride resin or polyvinyl chloride, the resin composition is melt-extruded, and the resin composition is Heating and foaming a wallpaper in which a resin layer is formed by laminating on a backing paper (hereinafter also referred to as a wallpaper by a film forming method) and a foaming agent-containing resin layer further containing a foaming agent in the resin composition. It is considered that a foamed wallpaper in which a foamed resin layer is formed (hereinafter also referred to as a foamed wallpaper by a film forming method) is preferable (Patent Document 2).

JP 2004-292990 A JP 2004-277986 A

  However, the backing paper of the wallpaper by the film forming method obtained by the manufacturing method as described in Patent Document 2 is less likely to penetrate when the water-based paste is applied, compared to the backing paper of the wallpaper by the sol method described above. A large amount of glue remains on the surface layer of the paper, and the amount of glue remaining on the adherend when temporarily attached to the adherend, such as a mortar wall or gypsum board, is increased. There is a problem that the adhesive strength when re-applying the wallpaper by the membrane method is greatly reduced.

  The reason why such a difference occurs between the wallpaper by the sol method and the wallpaper by the film forming method is not clear, but according to the knowledge of the present inventors, in the case of wallpaper by the sol method, by the above-described manufacturing method, In order to make the backing paper more porous by the volatilization of the diluent (solvent) contained in the sol-like resin composition, and the inorganic filler contained in the resin composition that has penetrated into the backing paper This is thought to be due to the fact that the components easily absorb moisture. As a result, in the case of wallpaper by the sol method, the moisture permeability of the backing paper has been improved. As a result, water-based glue tends to penetrate into the backing paper, so the amount of glue remaining on the surface side of the backing paper is small. Become. Therefore, even if it is peeled off after being temporarily fixed to the adherend, the amount of glue remaining on the adherend side is small, and it seems that the adhesive force necessary for re-attachment can be maintained.

On the other hand, in the case of wallpaper by the film forming method, the improvement of moisture permeability to the backing paper due to the reason as in the case of wallpaper by the sol method is not expected, so it is considered that the above-described problem occurs. Based on such a background, even when the resin layer is formed by a method different from the method of directly applying the sol-like resin composition, the present invention applies the aqueous paste and temporarily reattaches it. It is an object of the present invention to provide a laminated sheet that is excellent in adhesiveness and can be used as wallpaper that satisfies the performance required for wallpaper.

  As a result of intensive studies, the present inventor can achieve the above object by forming a resin layer by forming a resin layer after forming a resin layer and then forming a laminated sheet with a specific structure. As a result, the present invention has been completed.

That is, this invention relates to the following laminated sheet and its manufacturing method.
1. a laminated sheet having a resin layer on a substrate,
(1) The resin layer is laminated on the substrate after film formation,
(2) In the laminated sheet, a hole that does not penetrate the laminated sheet is formed on the back surface of the base material.
A laminated sheet characterized by that.
2. The laminated sheet according to item 1, wherein the film formation is film formation by extrusion molding or calendar molding.
3. The laminated sheet according to item 1 or 2, wherein the resin constituting the resin layer is a polyolefin resin.
4. The laminated sheet according to any one of items 1 to 3, wherein the hole has a diameter of 40 to 300 μm.
5. The laminated sheet according to any one of Items 1 to 4, wherein the holes are formed at intervals of 2 to 10 mm.
6. The laminated sheet according to any one of Items 1 to 5, wherein the resin layer is a foamed resin layer or a layer formed of a laminate including the foamed resin layer.
7. A method for producing a laminated sheet having a resin layer on a substrate,
(i) Step 1 of preparing the base material in which the through hole is formed, and
(ii) Step 2 of laminating the resin layer on the substrate after forming the resin layer,
In order, The manufacturing method of a lamination sheet characterized by the above-mentioned.
8. A method for producing a laminated sheet having a resin layer on a substrate, comprising:
(i) Step 1 of laminating the resin layer on the substrate after forming the resin layer, and
(ii) Step 2 of forming a hole that does not penetrate the resin layer from the back surface of the substrate;
In order, The manufacturing method of a lamination sheet characterized by the above-mentioned.
9. A method for producing a laminated sheet having a resin layer on a substrate,
(i) Step 1 of laminating the resin layer on the substrate after forming the resin layer,
(ii) Step 2 of forming a hole penetrating the resin layer from the back surface of the base material, and
(iii) Step 3 of forming a pattern and / or protective layer on the resin layer,
A method for producing a laminated sheet, comprising:
10. A method for producing a laminated sheet having a layer made of a foamed resin layer or a laminate comprising a foamed resin layer on a substrate,
(i) A step of laminating the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer on the substrate after forming the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer. 1,
(ii) forming a hole not penetrating the foaming agent-containing resin layer or the laminate including the foaming agent-containing resin layer from the back surface of the substrate; and
(iii) Step 3 of forming a foamed resin layer by foaming the foaming agent-containing resin layer,
In order, The manufacturing method of a lamination sheet characterized by the above-mentioned.
11. A method for producing a laminated sheet having a layer made of a foamed resin layer or a laminate comprising a foamed resin layer on a substrate,
(i) A step of laminating the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer on the substrate after forming the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer. 1,
(ii) forming a hole penetrating the foaming agent-containing resin layer or a laminate including the foaming agent-containing resin layer from the back surface of the substrate; and
(iii) Step 3 of forming the foamed resin layer by foaming the foaming agent-containing resin layer so that the penetrating hole is a hole that does not penetrate the foamed resin layer or the laminate including the foamed resin layer
,
In order, The manufacturing method of a lamination sheet characterized by the above-mentioned.

  Hereinafter, the laminated sheet of the present invention will be described in detail.

≪Laminated sheet≫
The laminated sheet of the present invention is a laminated sheet having a resin layer on a substrate,
(1) The resin layer is laminated on the substrate after film formation,
(2) In the laminated sheet, a hole that does not penetrate the laminated sheet is formed on the back surface of the base material.
It is characterized by that.

  In particular, the laminated sheet of the present invention having the above-described characteristics is a sol-like resin for forming the laminated sheet on the base material by forming the resin layer and then forming the resin layer on the substrate. Even when the resin layer is formed by a method different from the method of directly applying the composition, the water permeability is excellent while ensuring the design. Therefore, even if it reapplies after apply | coating water-based glue and temporarily fixing, it is excellent in adhesiveness.

  In this specification, “temporary fixing” means that the laminated sheet is temporarily bonded to the adherend temporarily or partially on the adherend after applying the aqueous paste of the laminated sheet for the purpose of alignment or the like. That means. Further, “re-sticking” means that the laminated sheet that has been temporarily fixed is bonded to the adherend again without applying aqueous paste again.

  Hereinafter, the layer structure of the laminated sheet of the present invention will be described. In the laminated sheet of the present invention, the resin layer is a so-called “front surface” (surface visually recognized after construction). Therefore, in this specification, the direction in which the resin layers are laminated as viewed from the substrate is referred to as “up” or “front surface”, and the opposite direction as viewed from the substrate is “down” or “back surface”. Called.

Laminated sheet substrate present invention has a base material.

  The substrate is not limited. For example, a known fibrous base material (backing paper) can be used.

  Specifically, wallpaper general paper (pulp-based sheet sized with a known sizing agent); flame-retardant paper (pulp-based sheet treated with a flame retardant such as guanidine sulfamate or guanidine phosphate) ); Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper; fiber mixed paper (paper made by mixing pulp and synthetic fiber). In addition, what corresponds to a nonwoven fabric on classification is included in these fibrous base materials.

The basis weight of the substrate is not limited, but is preferably about 50 to 300 g / m ^2, more preferably about 50 to 120 g / m ² .

Resin layer The laminated sheet of the present invention has a resin layer on a substrate. The resin layer is composed of one single layer or a plurality of two or more layers.

  The resin layer is not particularly limited as long as each layer contains a resin. For example, the resin constituting the resin layer is preferably a polyolefin resin.

  The structure of the resin layer is not particularly limited. Examples of the resin layer include a single layer of a foamed resin layer and a layer made of a laminate including a foamed resin layer. As a layer configuration of a layer formed of a laminate including a foamed resin layer, a layer configuration having a foamed resin layer and a non-foamed resin layer A on the non-foamed resin layer B in that order can be given. Hereinafter, each layer will be described by taking as an example a layer made of a laminate in which the non-foamed resin layer B, the foamed resin layer, and the non-foamed resin layer A are laminated in order. In the present specification, a laminated sheet in the case where the resin layer is a foamed resin layer or a layer composed of a laminate including the foamed resin layer is also referred to as a “foamed laminated sheet” for convenience. The laminated sheet of the present invention includes the foamed laminated sheet.

(Foamed resin layer)
The resin layer in the present invention may have a foamed resin layer.

The resin component contained in the foamed resin layer is preferably a polyolefin-based resin, and 1) polyethylene and 2) an ethylene copolymer having monomers other than ethylene and ethylene (
Hereinafter, at least one kind of “ethylene copolymer” is abbreviated.

As the polyethylene, low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), and the like can be widely used. Among these, low-density polyethylene is preferable.

Ethylene polymers are suitable for extrusion film formation from the viewpoint of melting point and MFR. Examples of the ethylene copolymer include an ethylene-vinyl acetate copolymer (EVA), an ethylene-acrylic acid copolymer (EAA), an ethylene-methacrylic acid copolymer (EMAA), and an ethylene-methyl methacrylate copolymer ( EMMA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-α olefin copolymer, and the like.

  Moreover, the foamed resin layer may use the ethylene resin and another resin in combination as a resin component. When used in combination, the content of the ethylene-based resin is preferably 70% by mass or more, and more preferably 80% by mass or more.

In addition, the content of monomers other than ethylene in the ethylene copolymer can further enhance the extrusion film forming property by adopting an appropriate copolymerization ratio depending on the components to be copolymerized. Specifically, in the case of an ethylene-vinyl acetate copolymer, the copolymerization ratio (VA amount) of vinyl acetate is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. In the case of an ethylene-acrylic acid copolymer, the copolymerization ratio (AA amount) of acrylic acid is preferably 2 to 15% by mass, and more preferably 5 to 11% by mass. In the case of an ethylene-methacrylic acid copolymer, the copolymerization ratio (MAA amount) of methacrylic acid is preferably 2 to 15% by mass, and more preferably 5 to 11% by mass. Ethylene-α
In the case of an olefin copolymer, the α-olefin copolymerization ratio is preferably 0.5 to 50% by mass.

In the present invention, the resin component contained in the foamed resin layer preferably has an MFR (melt flow rate) measured at 190 ° C. and a load of 21.18 N described in JIS K 6922 of 10 to 35 g / 10 min. When the MFR is within the above range, there is little increase in temperature when forming the foaming agent-containing resin layer, which will be described later, by extrusion film formation, etc., and the film can be formed in a non-foamed state. Can print on a smooth surface and has less pattern loss. If the MFR is too large,
If the resin is too soft, the foamed resin layer to be formed may have insufficient scratch resistance.

The foamed resin layer in the present invention is obtained by foaming the foaming agent-containing resin layer. That is, the foamed laminate sheet is obtained by foaming the foaming agent-containing resin layer of the foamed laminate sheet intermediate having a foaming agent-containing resin layer or a laminate including the foaming agent-containing resin layer on a base material. It is done. In this specification, the said foaming laminated sheet intermediate body is called foaming laminated sheet original fabric.

  As the resin composition for forming the foaming agent-containing resin layer, for example, a resin composition containing the above resin component, inorganic filler, pigment, pyrolytic foaming agent, foaming aid, crosslinking aid and the like can be suitably used. . In addition, stabilizers, lubricants and the like can be used as additives.

Examples of the thermally decomposable foaming agent include azo series such as azodicarbonamide (ADCA) and azobisformamide; hydrazide series such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide. The content of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. From the viewpoint of the expansion ratio, it is 5 times or more, preferably about 7 to 10 times, and the pyrolytic foaming agent is preferably about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

  The foaming aid is preferably a metal oxide and / or a fatty acid metal salt. For example, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, laurin Magnesium acid, zinc oxide, magnesium oxide and the like can be used. About 0.3-10 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of these foaming adjuvants, about 1-5 mass parts is more preferable.

When these foaming aids, a copolymer having a carboxyl group in the molecule such as EMAA, and the ADCA foaming agent are used in combination, the acrylic acid portion of the copolymer and the foaming aid are used in the foaming step. There is a problem that the effect of the original foaming aid is impaired by the reaction of the agent. Therefore, when used in combination with a copolymer having a carboxyl group in the molecule, such as EMAA, and an ADCA foaming agent, as explained in Japanese Laid-Open Publication No. 2009-197219, as a foaming aid It is preferable to use a carboxylic acid hydrazide compound. At this time, the carboxylic acid hydrazide compound is preferably used in an amount of about 0.2 to 1 part by mass with respect to 1 part by mass of the ADCA foaming agent.

Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, molybdenum compound, and talc. By including an inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained. The content of the inorganic filler is preferably about 0 to 100 parts by mass and more preferably about 20 to 70 parts by mass with respect to 100 parts by mass of the resin component.

  For pigments, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve) ), Cadmium red, ultramarine, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide. Examples of organic pigments include aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone. Perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine). The content of the pigment is preferably about 5 to 50 parts by mass, more preferably about 15 to 30 parts by mass with respect to 100 parts by mass of the resin component.

  In the present invention, the foaming agent-containing resin layer may be resin-crosslinked by electron beam irradiation. What is necessary is just to implement according to the method described in the postscript manufacturing method as a method of irradiating an electron beam to a foaming agent containing resin layer, and the method of making it foam. In addition, the thickness of the foaming agent-containing resin layer is preferably about 40 to 100 μm, and the thickness of the foamed resin layer after foaming is preferably about 300 to 700 μm.

(Non-foamed resin layers A and B)
The resin layer in the present invention may have a non-foamed resin layer.

  For example, the back surface of the foamed resin layer (the surface on which the base material is laminated) may have a non-foamed resin layer B (adhesive resin layer) for the purpose of improving the adhesive force with the base material.

  The resin component of the adhesive resin layer is not particularly limited, but is preferably a polyolefin resin, and more preferably an ethylene-vinyl acetate copolymer (EVA). As the EVA, a known or commercially available EVA can be used. In particular, the vinyl acetate component (VA component) is preferably 10 to 46% by mass, more preferably 15 to 41% by mass.

  The thickness of the adhesive resin layer is not limited, but is preferably about 5 to 50 μm.

  On the upper surface of the foamed resin layer, a non-foamed resin layer A may be provided for the purpose of clarifying the pattern when forming the pattern layer or improving the scratch resistance of the foamed resin layer.

Examples of the resin component of the non-foamed resin layer A include polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, and fluorine resins. Of these, polyolefin resins are preferred.

Examples of polyolefin resins include polyethylene (PE), polypropylene (PP), polybutene, polybutadiene, polyisoprene, and the like; copolymers of ethylene and α-olefins having 4 or more carbon atoms (linear low density polyethylene) Ethylene (meth) acrylic acid copolymer resins such as ethylene-acrylic acid copolymer resin and ethylene-methacrylic acid copolymer resin; ethylene-methyl acrylate copolymer resin, ethylene-ethyl acrylate copolymer Examples thereof include at least one of ethylene (meth) acrylate copolymer resin such as resin; ethylene-vinyl acetate copolymer (EVA); saponified ethylene-vinyl acetate copolymer resin; ionomer. Among these polyolefin resins, ethylene (meth) acrylic acid copolymer resins such as ethylene-acrylic acid copolymer resins and ethylene-methacrylic acid copolymer resins are preferable. Note that “(meth) acryl” means acryl or methacryl, and the same applies to other similar portions.

The thickness of the non-foamed resin layer A is not limited, but is preferably about 3 to 50 μm, more preferably about 5 to 20 μm.

Other Layers In the laminated sheet of the present invention, a layer different from the resin layer may be formed on the resin layer. Hereinafter, the layer will be described.

(Pattern pattern layer)
The laminated sheet of the present invention may have a pattern layer on the upper surface of the resin layer. The pattern layer can be formed on the foamed resin layer (or foaming agent-containing resin layer) or the non-foamed resin layer A, for example.

The design pattern layer imparts design properties to the laminated sheet. Examples of design patterns include wood grain patterns,
Examples include a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern. A design pattern can be selected according to the kind of laminated sheet.

  The pattern pattern layer can be formed, for example, by printing a pattern pattern. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, offset printing, and the like. As the printing ink, a printing ink containing a colorant, a binder resin, and a solvent can be used. These inks may be known or commercially available.

  As the colorant, for example, a pigment used in the above-described foaming agent-containing resin layer can be appropriately used.

The binder resin can be set according to the type of the non-foamed resin layer A. For example, acrylic resin,
Styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy resin, melamine resin , Fluorine resin, silicone resin, fiber derivative, rubber resin and the like.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. Containing organic solvent; and water. These solvents (or dispersion media) can be used alone or in the form of a mixture.

  The thickness of the design pattern layer is different from the type of design pattern, but is generally preferably about 0.1 to 10 μm.

(Protective layer)
The laminated sheet of the present invention may have a protective layer on the resin layer. The protective layer can be formed, for example, on the surface of the foamed resin layer (or foaming agent-containing resin layer), the non-foamed resin layer A, or the pattern layer. A protective layer is a layer formed in order to adjust the gloss of the surface of a laminated sheet or the above-mentioned foamed laminated sheet original fabric, or to give strength and contamination resistance to the surface. Moreover, when providing a pattern layer on the laminated sheet or the foamed laminated sheet original fabric, the protective layer is a layer formed on the pattern layer as necessary in order to protect the pattern layer. Further, depending on the product, a protective layer may be formed on the non-foamed resin layer A, and a pattern layer may be formed on the protective layer.

  What is necessary is just to select suitably from well-known resin components, such as a thermoplastic resin and a curable resin, as a resin component used for formation of a protective layer.

Examples of the thermoplastic resin used for forming the protective layer include polyolefin resins, acrylic resins, polyvinyl alcohol resins, and fluorine resins. Among these thermoplastic resins, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer are preferable. Ethylene (meth) acrylic acid copolymer resin such as ethylene-vinyl acetate copolymer (EVA); Saponified ethylene-vinyl acetate copolymer resin; Ionomer; Ethylene copolymer such as ethylene-olefin copolymer And polyolefin resins such as polyethylene and polypropylene. These thermoplastic resins may be used alone or in combination of two or more. Further, when a crosslinkable thermoplastic resin such as an ethylene copolymer is used for forming the protective layer, the thermoplastic resin may be subjected to a crosslinking treatment as necessary.

In addition, the curable resin used for forming the protective layer is not particularly limited, for example, room temperature curable resin, heat curable resin, one liquid reaction curable resin, two liquid reaction curable resin, ionizing radiation curing. Any one of curable resins may be used, but a one-component reaction curable resin is preferable. Among these curable resins, acrylic resins, urethane resins, and the like are preferable, and one-component reaction curable acrylic resins are more preferable. These curable resins may be used alone or in combination of two or more. Moreover, when using curable resin for formation of a protective layer, in order to advance hardening reaction, you may use a crosslinking agent, a polymerization initiator, a polymerization accelerator, etc. as needed.

  The protective layer may contain a colorant. As the colorant, for example, a pigment used in the above-described foaming agent-containing resin layer can be appropriately used.

Further, the protective layer may be a single layer, or two or more layers that are the same or different may be laminated. For example, it may have a two-layer structure in which a layer formed of a curable resin is formed on the outermost surface and a layer formed of a thermoplastic resin is laminated on the lower layer.

  Although the thickness of a protective layer is not specifically limited, For example, 1-20 micrometers is preferable and 1-15 micrometers is more preferable.

  The protective layer may be formed by a method corresponding to the type of resin component used. For example, in the case of forming a protective layer using a thermoplastic resin, the protective layer may be formed by pasting a thermoplastic resin film prepared in advance to the surface of the pattern layer. The protective layer may be formed by extruding a thermoplastic resin on the surface of the layer to form a film.

In the case of forming a protective layer using a curable resin, for example, a resin composition containing various additives as required in the curable resin can be used as a gravure coat, a bar coat, a roll coat, a reverse roll. After coating on the non-foamed resin layer A, the pattern layer, etc. by a method such as coating or comma coating, the resin composition is dried and cured by heating or the like, if necessary.

In addition, before forming the protective layer, a surface treatment such as a corona treatment or a plasma treatment or a primer layer may be provided on the surface of the non-foamed resin layer A, the pattern pattern layer or the like in consideration of adhesiveness.

  As the resin contained in the primer layer, for example, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, and the like can be used. Polypropylene or the like is desirable.

The thickness of the primer layer is not limited, but is preferably about 0.1 to 10 μm, more preferably about 0.1 to 5 μm.

In addition, when the protective layer is formed of a thermoplastic resin, an adhesive resin layer may be formed between the protective layer and the non-foamed resin layer A or the pattern layer in consideration of the adhesiveness of the protective layer. Good. Examples of the resin contained in the adhesive resin layer include polyvinyl chloride, polyvinyl acetate, and resins obtained by polymerizing polyolefin with polar groups such as maleic anhydride and acrylic acid, and are appropriately selected depending on the layer to be bonded.

  The thickness of the adhesive resin layer is preferably about 1 to 10 μm, and more preferably about 3 to 5 μm.

  The laminated sheet in the present invention may be embossed from the top surface layer. Embossing can be performed by known means such as an embossed plate. For example, when the outermost surface layer is the protective layer, a desired embossed pattern can be formed by pressing the embossed plate after heat-softening the protective layer. Examples of the embossed pattern include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain texture, a hairline, and a multiline groove.

Formation of Resin Layer The resin layer in the laminated sheet of the present invention is formed on the substrate by being laminated on the substrate after film formation. Specifically, the resin layer is formed by forming a resin layer using the resin composition for forming each layer constituting the resin layer, and laminating the formed resin layer on the substrate. This improves production stability when thinning the resin layer and simplifies production facilities when multilayering the resin layer, compared to the formation method in which the sol-like resin composition is applied directly onto the substrate. Can be planned. Furthermore, it becomes easy to employ a material that is difficult to be solated, such as a polyolefin resin typified by polyethylene. In this specification, “film formation (or film formation)” means that a film-like resin layer is completely formed as in calender molding, or a semi-molten state (molten resin film shape as in extrusion molding). ) In any case of forming a resin layer, while it is clearly different from direct application of a sol-like resin composition.

  As the film formation of the resin layer, film formation by extrusion molding or calendar molding is preferable. Here, in this specification, extrusion molding includes co-extrusion molding. In addition, when the resin layer is a foamed resin layer or a layer composed of a laminate including the foamed resin layer, for example, the foaming agent-containing resin layer or the foaming agent-containing resin layer is included by extrusion molding, calendar molding, or the like. After the laminated body is formed into a film and the foamed agent-containing resin layer or the laminated body including the foamed agent-containing resin layer is laminated on the base material, the foamed agent-containing resin layer may be further foamed.

As a method of laminating a resin layer on a substrate, (a) a method of laminating a resin composition for forming each layer constituting the resin layer by extrusion molding on the substrate, (b) laminating by thermal lamination And (c) a method of laminating via an adhesive. In addition, the method of (a) above is a resin layer (in the case where the resin layer is a foamed resin layer or a layer comprising a foamed resin layer, the foaming agent-containing resin layer or the foaming agent-containing resin layer). Film formation and lamination are performed at the same time.

  The film forming method and the laminating method of the resin layer will be described later in the item of the manufacturing method of the laminated sheet.

Formation of Holes In the laminated sheet of the present invention, holes that do not penetrate the laminated sheet are formed on the back surface of the substrate. By forming the hole which does not penetrate this laminated sheet, the laminated sheet of the present invention is excellent in moisture permeability. Moreover, since the hole does not penetrate the laminated sheet, design properties can be ensured.

In this specification, the hole which does not penetrate a laminated sheet means the hole which does not reach the front surface (outermost surface) of a laminated sheet from the back surface of a base material. For example, when the resin layer is a laminate of a non-foamed resin layer B, a foamed resin layer, and a non-foamed resin layer A, and a pattern layer and / or protective layer is further formed on the resin layer, a laminated sheet The holes that do not pass through i) are holes from the back surface of the base material to the inside of the base material, ii) holes from the back surface of the base material to the front surface of the base material, iii) non-foamed resin layer from the back surface of the base material B) Hole reaching the inside of the substrate, iv) Hole extending from the back surface of the base material to the front surface of the non-foamed resin layer B, v) A hole extending from the back surface of the base material to the inside of the foam resin layer, vi) Back surface of the base material Vii) A hole from the back surface of the base material to the inside of the non-foamed resin layer A, viii) A back surface of the base material to the front surface of the non-foamed resin layer A Any of holes, ix) holes extending from the back surface of the substrate to the inside of the pattern layer and / or the protective layer are included. The holes i) to vii) are also referred to as holes that do not penetrate the resin layer. The holes viii) and ix) are holes that penetrate the resin layer and do not penetrate the laminated sheet.

  Although the diameter of a hole (opening part) is not limited, 40-300 micrometers is preferable. When the diameter of the hole is within the above range, the moisture permeability is further improved while ensuring the strength of the laminated sheet.

The interval between the holes is not limited, but is preferably formed at an interval of 2 to 10 mm (in addition,
The interval between the adjacent holes is also referred to as a pitch). When the pitch of the holes is within the above range, the moisture permeability is further improved while ensuring the strength of the laminated sheet.

  In the present invention, the diameters and intervals of the holes mean the diameters and intervals of the holes on the back surface of the base material (the backmost surface of the laminated sheet).

  As the hole pattern, a lattice shape, a staggered shape, an irregular shape, or the like can be selected as necessary.

≪Foamed laminated sheet≫
As described above, the foamed laminated sheet means a laminated sheet in the case where the resin layer is a foamed resin layer or a layer composed of a laminate including the foamed resin layer. It is obtained by foaming the foaming agent-containing resin layer. The heating conditions at the time of foaming are not limited as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds.

≪Laminated sheet manufacturing method≫
The manufacturing method of the lamination sheet of this invention is not specifically limited. For example,
(1) (i) Step 1 of preparing a substrate on which a through hole is formed, and
(ii) Step 2 of laminating the resin layer on the substrate after forming the resin layer,
A manufacturing method having, in order,
(2) (i) Step 1 of laminating the resin layer on the substrate after forming the resin layer, and
(ii) Step 2 of forming a hole that does not penetrate the resin layer from the back surface of the substrate;
A manufacturing method having, in order,
(3) (i) Step 1 of laminating the resin layer on the substrate after forming the resin layer,
(ii) Step 2 of forming a hole penetrating the resin layer from the back surface of the base material, and
(iii) Step 3 of forming a pattern and / or protective layer on the resin layer,
A production method comprising:
Etc.

In addition, as a production method of the foamed laminated sheet of the present invention (the laminated sheet of the present invention in the case where the resin layer is a foamed resin layer or a layer composed of a laminate including the foamed resin layer),
(4) (i) After forming a foaming agent-containing resin layer or a laminate including a foaming agent-containing resin layer, the foaming agent-containing resin layer or a laminate including the foaming agent-containing resin layer is laminated on a substrate. Step 1,
(ii) forming a hole not penetrating the foaming agent-containing resin layer or the laminate including the foaming agent-containing resin layer from the back surface of the substrate; and
(iii) Step 3 of forming a foamed resin layer by foaming the foaming agent-containing resin layer
,
A manufacturing method having, in order,
(5) (i) After forming the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer, the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer is laminated on the substrate. Step 1,
(ii) forming a hole penetrating the foaming agent-containing resin layer or a laminate including the foaming agent-containing resin layer from the back surface of the substrate; and
(iii) Step 3 of forming the foamed resin layer so as to be a hole that does not penetrate the foamed resin layer or the laminate including the foamed resin layer by foaming the foaming agent-containing resin layer;
A manufacturing method having, in order,
(6) (i) Step 1 of preparing a substrate on which a through hole is formed,
(ii) A step of laminating the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer on the substrate after forming the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer. 2,
as well as
(iii) Step 3 of forming a foamed resin layer by foaming the foaming agent-containing resin layer
,
A manufacturing method having, in order,
(7) (i) After forming the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer, the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer is laminated on the substrate. Step 1,
(ii) Step 2 of forming the foamed resin layer by foaming the foaming agent-containing resin layer
,as well as
(iii) Step 3 of forming a hole that does not penetrate the foamed resin layer or a layer made of a laminate including the foamed resin layer from the back surface of the base material,
A manufacturing method having, in order,
(8) (i) After forming the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer, the foaming agent-containing resin layer or the laminate containing the foaming agent-containing resin layer is laminated on the substrate. Step 1,
(ii) Step 2 of forming the foamed resin layer by foaming the foaming agent-containing resin layer
,
(iii) Step 3 of forming a hole penetrating from the back surface of the base material through the foaming agent-containing resin layer or a layer made of a laminate including the foaming agent-containing resin layer, and
(iv) Step 4 of forming a pattern layer and / or protective layer on the resin layer,
And the like. The manufacturing method of (1) includes the manufacturing method of (6), the manufacturing method of (2) includes the manufacturing method of (7), and the manufacturing method of (3) is the above ( The production method of 8) is included.

  Hereinafter, (1) to (5) will be described in detail as examples.

Manufacturing method (1) (Step 1)
In step 1, a substrate on which a through hole is formed is prepared. The through hole imparts excellent moisture permeability to the laminated sheet.

  Examples of the method for forming the through hole in the substrate include a method of piercing with a needle or the like, a punching process, a burning process using a laser beam, and the like. Examples of the method of piercing with a needle or the like include pressure bonding with a needle roll. Examples of the punching process include a method using a punching machine. Examples of the tempering process using a laser beam include a method using a laser beam punch. In addition, you may use a commercial item for the base material in which the through-hole was formed.

The through hole formed in the base material becomes a hole that does not pass through the laminated sheet on the back surface of the base material in step 2 described later. Accordingly, the diameter, pitch, and pattern of the through holes are the same as the diameter, pitch, and pattern of holes that do not penetrate the laminated sheet in the laminated sheet.

(Process 2)
In step 2, after the resin layer is formed, the resin layer is laminated on the substrate. This
A resin layer is formed on the substrate.

  The resin layer closes the opening on the front surface side of the through hole of the base material. Therefore, the through hole of the base material is a hole that does not penetrate the laminated sheet on the back surface of the base material. Since the hole does not penetrate the laminated sheet, the design property can be ensured.

  As a film formation method of the resin layer, a film formation method by extrusion molding or calendar molding is preferable.

  As the calendar molding, a known calendar molding can be employed. For example, when the resin layer includes a foamed resin layer, a film-like foaming agent-containing resin layer is formed by supplying and heat-pressing the resin composition for forming a resin layer between a pair of heated calender rolls. . The foaming agent-containing resin layer obtained by calendar molding can be cooled and rolled up.

As the extrusion molding, a known extrusion molding method can be employed. For example, extrusion molding using a T-die extruder, a cylindrical extruder, or the like can be given. Examples of T-die include multi-manifold type and feed block type.

When the resin layer is a layer made of a laminate of a foamed resin layer and a non-foamed resin layer (non-foamed resin layer A and / or B), co-extrusion film formation by a T-die extruder is suitable. For example, when the resin layer is a layer made of a laminate having a non-foamed resin layer on both sides of the foamed resin layer, three layers can be simultaneously formed by simultaneously extruding molten resin corresponding to the three layers. Possible multi-manifold type T dies and T dies with feed blocks can be used.

In addition, it is a case where a resin layer contains a foamed resin layer, Comprising: An inorganic filler is contained in the resin composition which forms a foaming agent containing resin layer, and a foaming agent containing resin layer is formed by extrusion film formation. In this case, an inorganic filler residue (so-called eyes) is likely to be generated at the extrusion port (so-called die) of the extruder, and this tends to be a foreign matter on the surface of the foaming agent-containing resin layer. Therefore, when an inorganic filler is included in the resin composition forming the foaming agent-containing resin layer, it is preferable to form a three-layer coextrusion film as described above. That is, it is possible to suppress the occurrence of the above-mentioned corners by co-extrusion film formation in a mode in which the foaming agent-containing resin layer is sandwiched between non-foamed resin layers.

As a method of laminating a substrate and a resin layer (or a foaming agent-containing resin layer or a laminate including a foaming agent-containing resin layer), (a) a resin for forming each layer constituting the resin layer on the substrate Examples thereof include a method of laminating the composition by extrusion molding, (b) a method of laminating by thermal lamination, (c) a method of laminating via an adhesive, and the like. Hereinafter, each lamination method in case a resin layer is a foamed resin layer or it is a layer which consists of a laminated body containing a foamed resin layer is demonstrated.

  As a method of laminating a resin composition for forming each layer constituting a resin layer on a substrate by extrusion molding, a foaming agent-containing resin layer or a laminate including a foaming agent-containing resin layer is extruded from an extruder to form a film. Laminate on the substrate. In the lamination by extrusion molding, the laminate including the base material and the foaming agent-containing resin layer or the foaming agent-containing resin layer is bonded and laminated by the heat of the resin melted at the time of extrusion.

  As a method of heat laminating, a foaming agent-containing resin layer obtained by molding or a laminate containing the foaming agent-containing resin layer is laminated on a substrate and heat-laminated. In the lamination by thermal lamination, the base material and the laminate containing the foaming agent-containing resin layer or the foaming agent-containing resin layer are bonded and laminated by thermocompression bonding using a laminate roll.

  As a method of laminating through an adhesive, an adhesive is applied on a base material or a foamed agent-containing resin layer obtained by molding or a laminate including a foaming agent-containing resin layer, and molded on the coated surface. The obtained foaming agent-containing resin layer or a laminate or a substrate containing the foaming agent-containing resin layer is bonded and laminated. It does not specifically limit as an adhesive agent, A well-known adhesive agent (For example, a urethane type adhesive agent, an acrylic adhesive agent, etc.) can be used.

(Other processes)
As described above, a pattern layer and / or a protective layer can be sequentially laminated on the resin layer as necessary. In this case, the layers can be laminated by combining coating such as printing and coating, extrusion film formation, and the like. Coating such as printing and application can be performed according to a conventional method.

  When the resin layer is a foamed resin layer or a layer composed of a laminate including the foamed resin layer, after forming and laminating the foaming agent-containing resin layer, or the laminate of the foaming agent-containing resin layer in Step 2, In step 3, the foamed resin layer is formed by foaming the foaming agent-containing resin layer (the production method of (6) above).

When the resin layer is a foamed resin layer or a layer composed of a laminate including the foamed resin layer, electron beam irradiation can be performed as necessary after forming the foaming agent-containing resin layer. Thereby, the resin component can be cross-linked to adjust the surface strength, foaming characteristics, etc. of the foamed resin layer. The energy of the electron beam is preferably about 150 to 250 kV, more preferably about 175 to 200 kV. The irradiation amount is preferably about 10 to 100 kGy, and more preferably about 10 to 50 kGy. A known electron beam irradiation apparatus can be used as the electron beam source. In addition, this electron beam irradiation may be after forming a pattern layer or a protective layer.

  Next, the foamed resin layer is formed by heating the foaming agent-containing resin layer. The heating conditions are not limited as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds.

  When the resin layer is a foamed resin layer or a layer comprising a foamed resin layer, the pattern layer and / or protective layer is laminated by a foaming agent-containing resin layer or a foaming agent-containing resin layer. Can be carried out at any time after the film formation of the laminate including, and is usually carried out before foaming of the foaming agent-containing resin layer.

After step 2 (when the resin layer is a foamed resin layer or a layer comprising a foamed resin layer, after step 3 for foaming the foaming agent-containing resin layer), on the outermost surface layer May be embossed. The means and pattern for embossing are the same as the means and pattern described in the description of embossing in the laminated sheet.

Manufacturing method (2) (Step 1)
In step 1, after the resin layer is formed, the resin layer is laminated on the substrate. Thereby, a resin layer is formed on the substrate.

The film forming method and the laminating method of the resin layer are the same as the methods described in the description of the film forming method and the laminating method in step 2 of the manufacturing method (1).

(Process 2)
In step 2, a hole that does not penetrate the resin layer is formed from the back surface of the substrate. The hole that does not penetrate the resin layer can be said to be a hole that does not penetrate the laminated sheet as described above. The hole that does not penetrate through the resin layer (hole that does not penetrate through the laminated sheet) provides excellent moisture permeability while ensuring the design of the laminated sheet. In addition, the hole which does not penetrate the said resin layer includes all the holes of said i) -vii).

  The method for forming the hole from the back surface of the substrate is the same as the method for forming the through hole in the manufacturing method of (1). The diameter, pitch, and pattern of the holes are the same as the diameter, pitch, and pattern of holes that do not penetrate the laminated sheet in the description of the laminated sheet.

(Other processes)
When the resin layer is a foamed resin layer or a layer composed of a laminate including the foamed resin layer, after forming and laminating the foaming agent-containing resin layer or the foamed agent-containing resin layer laminate in Step 1, Before the step 2 (prior to the step 2), the foamed resin layer is formed by foaming the foaming agent-containing resin layer (the production method of (7) above). The foaming method is the same as the foaming method in the production method (1).

In the manufacturing method of (2), lamination of a pattern layer and / or a protective layer, electron beam irradiation, embossing, etc. can be performed by the same method as described in the manufacturing method of (1). The pattern layer and / or the protective layer can be laminated at any time after the formation of the resin layer, and the electron beam irradiation can be performed to produce a foaming agent-containing resin layer or a laminate containing the foaming agent-containing resin layer. After filming, it can be performed at any time before foaming of the foaming agent-containing resin layer, and embossing can be performed at any time after step 1 (the laminate is a foamed resin layer or a laminate including a foamed resin layer). In the case of a layer composed of, it can be carried out after foaming of the foaming agent-containing resin layer.

Manufacturing method (3) (Step 1)
In step 1, after the resin layer is formed, the resin layer is laminated on the substrate. Thereby, a resin layer is formed on the substrate.

The film forming method and the laminating method of the resin layer are the same as the methods described in the description of the film forming method and the laminating method in step 2 of the manufacturing method (1).

(Process 2)
Step 2 is performed after step 1. In step 2, a hole (through hole) penetrating the resin layer is formed from the back surface of the substrate. The hole penetrating the resin layer becomes a hole that does not penetrate the laminated sheet after performing steps 1 to 3 in the manufacturing method of (3). The hole that does not penetrate the laminated sheet provides excellent moisture permeability while ensuring the design of the laminated sheet. Note that the holes that do not penetrate the laminated sheet include both the holes of viii) and ix).

  The method for forming the hole from the back surface of the substrate is the same as the method for forming the through hole in the manufacturing method of (1). The diameter, pitch, and pattern of the holes are the same as the diameter, pitch, and pattern of holes that do not penetrate the laminated sheet in the description of the laminated sheet.

(Process 3)
Step 3 is performed after step 1. In step 3, a pattern layer and / or a protective layer is formed on the resin layer. The said pattern pattern layer and / or protective layer block | close the opening part by the side of the front surface of the through-hole of a resin layer. Therefore, the through hole of the resin layer is a hole that does not penetrate the laminated sheet on the back surface of the base material in the laminated sheet. Since the hole does not penetrate the laminated sheet, the design property can be ensured. As a method for forming the pattern / pattern layer and / or the protective layer, all are the same as the method for forming the pattern / pattern layer and / or the protective layer in the description of the laminated sheet.

Step 3 is performed at any time with respect to step 2. That is, step 3 is performed before step 2 or step 2.
Can be implemented after. When step 3 is carried out before step 2, in step 2, holes penetrate the resin layer and do not penetrate the laminated sheet (so that no through-hole is formed in the pattern layer and / or protective layer). Form. On the other hand, when step 3 is performed after step 2, in step 3, the pattern layer and / or the protective layer is formed on the resin layer having the through hole so as to close the opening on the front surface side of the through hole. Form. In the case where the opening is closed with a pattern layer, it is preferable that the printing ink forming the pattern layer has a high viscosity. In the case of closing the opening with a protective layer, from the viewpoint of ensuring designability, the protective layer contains a colorant, or the resin layer is a foamed resin layer or a laminate including a foamed resin layer. A layer is preferred.

(Other processes)
When the resin layer is a foamed resin layer or a layer composed of a laminate including the foamed resin layer, after forming and laminating the foaming agent-containing resin layer or the foamed agent-containing resin layer laminate in Step 1, Before step 2 (prior to step 2), the foamed resin layer is formed by foaming the foaming agent-containing resin layer (the production method of (8) above). The foaming method is the same as the foaming method in the production method (1). Step 3 is performed at an arbitrary time with respect to the step of foaming the foaming agent-containing resin layer. That is, step 3 can be performed before the foaming step or after the foaming step.

In the manufacturing method of (3), electron beam irradiation, embossing, etc. can be performed by the same method as the method described in the manufacturing method of (1). The electron beam irradiation can be performed at any time before foaming of the foaming agent-containing resin layer after film formation of the foaming agent-containing resin layer or the laminate including the foaming agent-containing resin layer. It can be performed at any later time (after foaming of the foaming agent-containing resin layer in the case where the resin layer is a foamed resin layer or a layer made of a laminate including the foamed resin layer).

Manufacturing method (4) (Step 1)
In step 1, after forming a foaming agent-containing resin layer or a laminate including the foaming agent-containing resin layer,
The said foaming agent containing resin layer or the laminated body containing a foaming agent containing resin layer is laminated | stacked on a base material. Thereby, the laminated body containing a foaming agent containing resin layer or a foaming agent containing resin layer is formed on a base material.

Regarding the film forming method and the laminating method of the foaming agent-containing resin layer or the laminate including the foaming agent-containing resin layer, Each is the same.

(Process 2)
In step 2, a hole that does not penetrate the foaming agent-containing resin layer or the laminate including the foaming agent-containing resin layer is formed from the back surface of the substrate. When forming a laminate of the non-foamed resin layer B, the foaming agent-containing resin layer, and the non-foamed resin layer A in Step 1, the holes that do not penetrate are I) a hole that extends from the back surface of the base material to the inside of the base material, II ) A hole from the back surface of the base material to the front surface of the base material, III) A hole from the back surface of the base material to the inside of the non-foamed resin layer B, IV) A main surface of the non-foamed resin layer B from the back surface of the base material V) A hole from the back of the substrate to the inside of the foam-containing resin layer, VI) A hole from the back of the substrate to the front of the foam-containing resin layer, VII) Any of holes extending from the back surface to the inside of the non-foamed resin layer A is included.

  The method of forming a hole that does not penetrate from the back surface of the substrate is the same as the method of forming the through hole in the manufacturing method of (1). The diameters, pitches, and patterns of the holes that do not penetrate are the same as the diameters, pitches, and patterns of the holes that do not penetrate the laminated sheet in the laminated sheet.

(Process 3)
In step 3, the foamed resin layer is formed by foaming the foaming agent-containing resin layer. Specifically, the foamed resin layer can be formed by heating the foaming agent-containing resin layer as in the production method (1). In the process 3, the part of the non-penetrating hole obtained in the above-mentioned process 2 may be filled with the foam of the foamed resin layer, but at least the hole (opening) formed on the back surface of the substrate Is retained. The hole that does not penetrate through the resin layer formed by the foaming step of Step 3 (hole that does not penetrate through the laminated sheet) provides excellent moisture permeability while ensuring the design of the laminated sheet.

  In the manufacturing method of (4), lamination of a pattern layer and / or a protective layer, electron beam irradiation, embossing, etc. can be performed by the same method as described in the manufacturing method of (1). In addition, lamination | stacking of a pattern pattern layer and / or a protective layer can be performed at any time after film-forming of a foaming agent containing resin layer or a laminated body containing a foaming agent containing resin layer, and electron beam irradiation contains a foaming agent After the formation of the resin layer, it can be performed at any time before Step 3, and the embossing can be performed after Step 3.

Manufacturing method (5) (Step 1)
In step 1, after forming a foaming agent-containing resin layer or a laminate including the foaming agent-containing resin layer,
The said foaming agent containing resin layer or the laminated body containing a foaming agent containing resin layer is laminated | stacked on a base material. Thereby, the laminated body containing a foaming agent containing resin layer or a foaming agent containing resin layer is formed on a base material.

Regarding the film forming method and the laminating method of the foaming agent-containing resin layer or the laminate including the foaming agent-containing resin layer, the method described in the description of the film forming method and the laminating method in step 2 of the manufacturing method of (1) Each is the same.

(Process 2)
In step 2, a hole penetrating the foaming agent-containing resin layer or the laminate including the foaming agent-containing resin layer is formed from the back surface of the substrate.

  The method for forming the through hole from the back surface of the substrate is the same as the method for forming the through hole in the manufacturing method of (1). The pitch and pattern of the through holes are the same as the pitch and pattern of holes that do not penetrate the laminated sheet in the laminated sheet. What is necessary is just to set suitably so that the said through-hole may be a hole which does not penetrate the resin layer (hole which does not penetrate a lamination sheet), for example, it is good to make it 400 micrometers or less. From the viewpoint of increasing, it is more preferably 40 to 300 μm.

(Process 3)
In step 3, the foamed resin layer is formed by foaming the foaming agent-containing resin layer so that the through hole is a hole that does not penetrate the foamed resin layer or the laminate including the foamed resin layer. Specifically, as in the manufacturing method of (1), by heating the foaming agent-containing resin layer, a part of the through-hole is filled with the foamed resin layer, and before step 3 (before foaming) The through hole becomes a hole that does not penetrate through the foamed resin layer or the laminate including the foamed resin layer after Step 3. Here, even if the through hole is deformed into the non-penetrating hole in the process of step 3, at least the hole (opening) formed in the back surface of the base material is retained. By this step 3, a foamed resin layer having holes that do not penetrate the laminated sheet can be formed. The hole that does not penetrate through the resin layer formed by the foaming step of Step 3 (hole that does not penetrate through the laminated sheet) provides excellent moisture permeability while ensuring the design of the laminated sheet.

  In the manufacturing method of (5), lamination of a pattern layer and / or a protective layer, electron beam irradiation, embossing and the like can be performed by the same method as described in the manufacturing method of (1). In addition, lamination | stacking of a pattern pattern layer and / or a protective layer can be performed at any time after film-forming of a foaming agent containing resin layer or a laminated body containing a foaming agent containing resin layer, and electron beam irradiation contains a foaming agent The resin layer or the laminate including the foaming agent-containing resin layer can be formed at any time before foaming of the foaming agent-containing resin layer, and embossing can be performed after Step 3.

  The laminated sheet of the present invention can be used as wallpaper, various decorative materials and the like. In addition, the laminated sheet (foamed laminated sheet) of the present invention having a foamed resin layer can be used for applications such as foamed wallpaper, various decorative materials, laminated decorative skin materials, cushioning flooring materials, and heat insulating decorative materials. .

  In particular, the laminated sheet of the present invention is applied directly to the sol-like resin composition in order to form the resin layer by forming the resin layer on the substrate after forming the resin layer, and to make the laminated sheet have a specific structure. Even when the resin layer is formed by a method different from the method of performing the method, the moisture permeability is excellent while ensuring the design. Therefore, even if it reapplies after apply | coating water-based glue and temporarily fixing, it is excellent in adhesiveness.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
Through holes (diameter 80 μm, pitch 2 mm) were formed on the backing paper (WK-665, manufactured by KJ Special Paper Co., Ltd., basis weight: 65 g / m ² ) by using ordinary needle embossing.

Next, using a three-type three-layer T-die extruder, three-layer co-extrusion made in the order of non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B Made a membrane. Thereby, the laminated body which consists of three layers by which non-foaming resin layer A / foaming agent containing resin layer / non-foaming resin layer B was laminated | stacked in order was obtained. The composition of each layer is shown in Table 1 below.

  Next, the backing paper was heated to 120 ° C. and laminated on the non-foamed resin layer B side of the laminate. The lamination was performed by thermocompression using a laminate roll. Thereby, the foaming laminated sheet original fabric which consists of backing paper and the said laminated body was obtained.

Next, electron beam irradiation (acceleration voltage 200 kV, irradiation dose 30 kGy) was performed from the resin surface side (non-foamed resin layer A side) of the foamed laminated sheet original fabric. Next, a protective layer was formed on the non-foamed resin layer A by applying water-based ink (ALTOP, acrylic one-part curable resin emulsion, manufactured by Dainichi Seika Kogyo Co., Ltd.) with a gravure printing machine. Then, it heated at 220 degreeC for 35 second using the heating foaming furnace, and made the foaming agent containing resin layer the foamed resin layer. This obtained the lamination sheet (foaming lamination sheet). The expansion ratio was about 6 to 7 times.

Example 2
Except for not forming the through holes on the backing paper (WK665, manufactured by KJ Special Paper Co., Ltd., basis weight: 65g / m ² )
In the same manner as in Example 1, a foamed laminated sheet original fabric was obtained.

  Next, in the same manner as in Example 1, irradiation with an electron beam and formation of a protective layer were performed.

Next, normal needle embossing is performed from the back side of the backing paper of the foamed laminated sheet original fabric on which the electron beam is irradiated and the protective layer is formed (from the front surface of the protective layer of the foamed laminated sheet original fabric). Was used to form through-holes (diameter 80 μm, pitch 2 mm) from the back surface of the backing paper to the front surface of the protective layer. Then, the foaming agent containing resin layer was made into the foamed resin layer by heating at 220 degreeC for 35 second using a heating foaming furnace. This obtained the lamination sheet (foaming lamination sheet). The expansion ratio was about 6 to 7 times. Further, in the process in which the foaming agent-containing resin layer becomes a foamed resin layer by heating, a part of the through hole was filled with the foam of the foamed resin layer. That is, the through hole before heating became a hole that did not penetrate due to foaming by heating.

Comparative Example 1
Except for not forming the through holes on the backing paper (WK665, manufactured by KJ Special Paper Co., Ltd., basis weight: 65g / m ² )
In the same manner as in Example 1, a foamed laminated sheet original fabric was obtained.

Next, in the same manner as in Example 1, irradiation with an electron beam, formation of a protective layer, and heating were performed. This obtained the foaming lamination sheet.

Comparative Example 2
Except for not forming the through holes on the backing paper (WK665, manufactured by KJ Special Paper Co., Ltd., basis weight: 65g / m ² )
In the same manner as in Example 1, a foamed laminated sheet original fabric was obtained.

Next, in the same manner as in Example 1, irradiation with an electron beam, formation of a protective layer, and heating were performed to obtain a foamed laminated sheet. Thereafter, through the back side of the backing sheet of the foam laminated sheet, through the use of ordinary needle embossing, a through hole (diameter 80 μm from the back side of the backing paper to the protective layer)
, Pitch 2 mm). This obtained the foaming lamination sheet in which the said through-hole was formed.

Evaluation test 1: measurement of residual adhesive amount Each foamed laminated sheet obtained in Examples 1 and 2 and Comparative Example 1 was cut into a size of 10 cm × 10 cm, and the mass of each foamed laminated sheet (M _S (unit: g)) Was measured. Next, by diluting the starch paste with water so that the ratio of starch paste (construction paste, Rua Mild, Yayoi Chemical Industry Co., Ltd.) and water is starch paste: water = 10: 7 (mass ratio), An aqueous paste was obtained. Thereafter, the aqueous paste was applied to the backing paper surface of each of the foamed laminated sheets cut out. The application amount of the aqueous paste was 130 g / m ² . Next, the foamed laminated sheets were folded so that the backing paper surfaces coated with the water-based paste were in contact with each other, and in this state, the foamed laminated sheets were left for 60 minutes in a moisture-proof curing bag. Thereafter, the mass (M _{S + G} (unit: g)) of each foamed laminated sheet was measured.
Next, after each said foaming laminated sheet was affixed on the gypsum board (Tiger board, product made by Yoshino gypsum Co., Ltd.), each said foaming laminated sheet was peeled off. Thereafter, the mass (M _{S + G} ′ (unit: g)) of each of the foamed laminated sheets peeled off was measured.
Finally, the following formula:

The remaining amount of glue was calculated by calculating

Evaluation Test 2: Designability Evaluation The designability of each foamed laminated sheet obtained in Examples 1 and 2 and Comparative Example 1 was evaluated. Specifically, after each foamed laminated sheet is affixed to gypsum board (Tiger Board, manufactured by Yoshino Gypsum Co., Ltd.), a certain distance (30 cm) is left, and when viewed from the front, holes (or through holes) Was evaluated whether or not. The evaluation criteria are as follows.
○: Holes in the foam laminated sheet are not noticeable.
X: The hole or through-hole of a foaming lamination sheet is conspicuous.

Claims (6)

A laminated sheet having a resin layer on a substrate,
(1) The resin layer is a layer made of a foamed resin layer or a laminate including the foamed resin layer, and is laminated on the substrate after film formation,
(2) The laminated sheet has a hole formed from the back surface of the base material to the front surface of the base material, and the resin layer has no holes.
A laminated sheet characterized by that.   2. The laminated sheet according to claim 1, wherein the film formation is film formation by extrusion molding or calendar molding.   3. The laminated sheet according to claim 1, wherein the resin constituting the resin layer is a polyolefin resin.   The laminated sheet according to any one of claims 1 to 3, wherein the hole has a diameter of 40 to 300 µm.   The laminated sheet according to any one of claims 1 to 4, wherein the holes are formed at intervals of 2 to 10 mm. A method for producing a laminated sheet having a resin layer on a substrate,
The resin layer is a foamed resin layer or a layer made of a laminate including a foamed resin layer,
(i) Step 1 of preparing the base material in which the through hole is formed, and
(ii) Step 2 of laminating the resin layer on the substrate after forming the resin layer,
In order, The manufacturing method of a lamination sheet characterized by the above-mentioned.