JP2015066898A - Laminated sheet and foamed laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet which is usable as a wall paper excellent in adhesiveness when re-sticking after temporarily fixing by applying an aqueous paste even when using a non-vinyl chloride-based resin layer.SOLUTION: There is provided a laminated sheet which has at least a non-vinyl chloride-based resin layer on a paper base material having a Stockigt sizing degree of 5 seconds or less.

Description

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

  Conventionally, a wallpaper on which a resin layer containing a vinyl chloride resin is formed (hereinafter also referred to as a vinyl chloride wallpaper) is known. Vinyl chloride wallpaper (also referred to as vinyl chloride foam wallpaper) having a foam resin layer as the resin layer is particularly widely used. Generally, a vinyl chloride wallpaper is prepared by directly applying a sol-like resin composition containing a vinyl chloride resin on a backing paper, and then, if necessary, foaming a foaming agent by means such as heating. There are many (patent document 1).

  On the other hand, in recent years, in consideration of the environment, it is considered preferable to use a non-vinyl chloride resin layer (non-vinyl chloride resin layer) that does not use vinyl chloride resin or polyvinyl chloride for the resin layer. Generally, wallpaper having a non-vinyl chloride resin layer (hereinafter also referred to as non-vinyl chloride wallpaper) and foam wallpaper having a non-vinyl chloride foam resin layer as a resin layer (also referred to as non-vinyl chloride foam wallpaper) are non-vinyl chloride. If necessary, melt-extrusion of a resin composition containing a foaming agent or the like in a base resin and laminating the resin composition on a backing paper to form a resin layer, and then heat-foaming the foaming agent-containing resin layer if necessary (Patent Document 2).

JP 2004-292990 A JP 2004-277986 A

  However, the non-vinyl chloride wallpaper backing paper obtained by the production method described in Patent Document 2 is less likely to penetrate when water-based glue is applied, compared to the above-mentioned vinyl chloride wallpaper backing paper. As a result, a large amount of glue remains on the surface layer of the adhesive, and the amount of glue remaining on the adherend increases when temporarily attached to an adherend such as a mortar wall or gypsum board. There is a problem that the adhesive strength when re-applying the wallpaper is greatly reduced.

  The reason why such a difference occurs between the vinyl chloride wallpaper and the non-vinyl chloride wallpaper is not clear, but according to the knowledge of the present inventors, in the case of vinyl chloride wallpaper, by the above-described manufacturing method, Highly moisture-permeable vinyl chloride resin and plasticizer contained in the resin composition soak into the backing paper for modification, and the diluent (solvent) contained in the sol-like resin composition volatilizes. This is considered to make the backing paper more porous. As a result, in the case of vinyl chloride wallpaper, the moisture permeability of the backing paper has been improved. As a result, water-based glue can easily 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 non-vinyl chloride wallpaper, it is considered that the above-described problems are caused because improvement in moisture permeability to the backing paper is not expected for the same reason as in the case of vinyl chloride wallpaper. Based on such a background, the present invention is excellent in adhesiveness when reattaching after applying a water-based paste and temporarily fixing even when a non-vinyl chloride resin layer is used, and for wallpaper. An object of the present invention is to provide a laminated sheet that can be used as wallpaper that satisfies the required performance.

  In addition, even when a non-vinyl chloride resin layer is used, the present invention has excellent adhesiveness when reattaching after applying a water-based paste and temporarily fixing, and has the performance required for wallpaper. An object of the present invention is to provide a foamed laminated sheet that can be used as a foamed wallpaper that satisfies the requirements, and to provide a foamed laminated sheet raw material (unfoamed raw material) that is useful for producing the foamed laminated sheet. .

  As a result of intensive studies, the present inventor has found that the above object can be achieved by using a specific paper-based substrate, and has completed the present invention.

That is, the present invention relates to the following laminated sheet and foamed laminated sheet.
1. A laminated sheet having at least a non-vinyl chloride resin layer on a paper-based substrate having a Steecht sizing degree of 5 seconds or less.
2. The laminated sheet according to item 1, wherein the non-vinyl chloride resin layer is formed by extrusion film formation.
3. The laminated sheet according to item 1 or 2, wherein the resin constituting the non-vinyl chloride resin layer is a polyolefin resin.
4. The laminated sheet according to any one of Items 1 to 3, wherein the non-vinyl chloride resin layer is a foaming agent-containing resin layer or a layer comprising a laminate including the foaming agent-containing resin layer.
5. The laminated sheet according to item 4, wherein the non-vinyl chloride resin layer is a layer composed of a laminate in which a non-foamed resin layer B, a foaming agent-containing resin layer, and a non-foamed resin layer A are laminated in order.
6. The laminated sheet according to item 4 or 5, wherein the foaming agent-containing resin layer is resin-crosslinked by electron beam irradiation.
7. A foamed laminated sheet obtained by foaming the foaming agent-containing resin layer of the laminated sheet according to any one of Items 4 to 6.

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

≪Laminated sheet≫
The laminated sheet of the present invention is characterized in that it has at least a non-vinyl chloride resin layer on a paper-based substrate having a Steecht sizing degree of 5 seconds or less.

  Since the laminated sheet of the present invention having the above characteristics uses a paper-based substrate having a Steecht sizing degree of 5 seconds or less, it has excellent moisture permeability even when a non-vinyl chloride resin layer is used. 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 above laminated sheet or foamed laminated sheet is temporarily applied to the adherend after applying a water-based paste to the laminated sheet or foamed laminated sheet for the purpose of alignment or the like. Is bonded to the entire surface or partially. Further, “re-sticking” means that the laminated sheet or foamed 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 and foamed laminated sheet of the present invention will be described. In the laminated sheet of the present invention, the non-vinyl chloride resin layer is a so-called “front surface” (a surface visually recognized after construction). Therefore, in this specification, the direction in which the non-vinyl chloride resin layer is laminated as viewed from the paper substrate is referred to as “upper” or “front surface”, and the opposite direction as viewed from the paper substrate is “ It is called “bottom” or “back”.

Paper quality substrates conventionally, wallpaper, Stockigt sizing degree was generally considered to be preferable to use paper quality substrate is at least 10 seconds (e.g., Japanese Patent Laid-Open No. 2004-292990), but the present invention Then, a paper-based substrate having a Steecht sizing degree of 5 seconds or less is used. Since the laminated sheet of the present invention includes a paper-based substrate having a Steecht sizing degree of 5 seconds or less, the moisture permeability is excellent even when a non-vinyl chloride resin layer is used. Therefore, even if it reapplies after application | coating of a water-based glue, and temporary fixing, it is excellent in adhesiveness.

  Steecht sizing is a kind of sizing indication method for paper-based substrates, and is an index related to water permeability.

In the present specification, the Steecht sizing degree is a value measured in accordance with JIS P8122. Specifically, the following (1) to (5):
(1) Create a test piece by folding four corners of the paper base material,
(2) Put 2% ammonium thiocyanate aqueous solution of 23 ± 1 ℃ on the petri dish,
(3) Float the test piece of (1) above the aqueous solution of (2) above,
(4) Immediately drop a drop of 1% iron (III) chloride solution at the same temperature onto the test piece using a pipette,
(5) Measure the time (seconds) until three red spots appear in the drop with a stopwatch in units of 0.1 second.
Is measured by

  The paper-based substrate is not particularly limited as long as the Steecht sizing degree is 5 seconds or less, and for example, a fibrous substrate (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.

  Stekithite sizing degree is determined by (i) additives other than pulp (sizing agent such as rosin and synthetic resin) added in the paper substrate manufacturing process (specifically before the paper making process); filler; paper strength enhancer; The content of the dye, pigment, etc.) can be appropriately set, and (ii) a synthetic resin can be applied to the surface layer of the paper substrate.

  Although there is no particular limitation on the lower limit of the degree of steechite sizing, for example, a paper-based substrate of 1 second or longer can be used.

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

Non-vinyl chloride resin layer The laminated sheet of the present invention has a non-vinyl chloride resin layer on a paper substrate. The non-vinyl chloride resin layer is composed of one single layer or a plurality of two or more layers. The non-vinyl chloride resin refers to a resin that does not use vinyl chloride resin or polyvinyl chloride. That is, the non-vinyl chloride resin layer is substantially free of vinyl chloride resin or polyvinyl chloride in each layer. For example, the resin constituting the non-vinyl chloride resin layer is preferably a polyolefin resin.

The configuration of the non-vinyl chloride resin layer is not particularly limited as long as each layer contains a resin that is not a vinyl chloride resin or polyvinyl chloride. Examples of the non-vinyl chloride resin layer include a foaming agent-containing resin layer single layer and a layer made of a laminate including a foaming agent-containing resin layer. As a layer configuration of a layer composed of a laminate including a foaming agent-containing resin layer, a layer configuration having a foaming agent-containing resin layer and a non-foaming resin layer A in that order on the non-foaming resin layer B can be mentioned. 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 foaming agent-containing resin layer, and the non-foamed resin layer A are laminated in order.
In addition, in this specification, a laminated sheet in the case where the non-vinyl chloride resin layer is a foaming agent-containing resin layer or a layer made of a laminate including the foaming agent-containing resin layer is referred to as “foaming lamination” for convenience. It is also called “sheet original”. The foamed laminated sheet original fabric is a foamed laminated sheet intermediate. In the present specification, the laminated sheet of the present invention includes the foamed laminated sheet original fabric.

(Foaming agent-containing resin layer)
The non-vinyl chloride resin layer in the present invention may have a foaming agent-containing resin layer.

  The resin component contained in the foaming agent-containing resin layer is preferably a polyolefin resin, and 1) polyethylene and 2) an ethylene copolymer having monomers other than ethylene and ethylene (hereinafter referred to as “ethylene copolymer”) (Abbreviated) is more preferred.

  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.

  In addition, the foaming agent-containing resin layer may use the ethylene resin and another resin 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. Moreover, in the case of an ethylene-alpha olefin copolymer, 0.5-50 mass% is preferable as a copolymerization ratio of alpha olefin.

  In the present invention, the resin component contained in the foaming agent-containing 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 temperature rise when forming the foaming agent-containing resin layer described later by extrusion film formation, and it can be formed in a non-foamed state. In addition, printing processing can be performed on a smooth surface, and pattern loss or the like is small. If the MFR is too large, the resin is too soft and the resulting foamed resin layer may have insufficient scratch resistance.

  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 7 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 non-vinyl chloride resin layer in the present invention may have a non-foamed resin layer.

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

  The non-foamed resin layer A is provided on the upper surface of the foaming agent-containing resin layer for the purpose of clarifying the pattern when forming the pattern layer or improving the scratch resistance of the foaming agent-containing resin layer (and the foaming resin layer). You may have.

  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) acrylic ester 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 non-vinyl chloride resin layer may be formed on the non-vinyl chloride 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 top surface of the non-vinyl chloride resin layer. The pattern layer can be formed on the 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 or the foamed laminated sheet. Examples of the design pattern include a wood grain pattern, 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 or foam 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 non-vinyl chloride resin layer. The protective layer can be formed, for example, on the surface of the foaming agent-containing resin layer (or foamed resin layer), non-foamed resin layer A, or design pattern layer. A protective layer is a layer formed in order to adjust the glossiness of a lamination sheet or a foaming lamination sheet, or to give intensity | strength and contamination | pollution resistance to the surface. Moreover, when providing a picture pattern layer in a lamination sheet or a foaming lamination sheet, a protective layer is a layer formed on the said picture pattern layer as needed in order to protect the said pattern 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.

  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.

≪Foamed laminated sheet≫
The foamed laminated sheet of the present invention is a laminated sheet in the case where the non-vinyl chloride resin layer is a foaming agent-containing resin layer or a layer comprising a laminate containing a foaming agent-containing resin layer (that is, the foamed laminated sheet raw material). It is obtained by foaming the antifoaming resin layer.

  The foamed laminated sheet of the present invention may be embossed from the top surface layer. The embossing method, the embossed pattern, and the like are the same as in the embossing in the laminated sheet of the present invention described above.

≪Laminated sheet and foamed laminated sheet manufacturing method≫
The production method of the laminated sheet of the present invention is not particularly limited, and a method of previously preparing a paper base material having a steecht degree of 5 seconds or less and laminating a non-vinyl chloride resin layer on the paper base material is provided. Can be mentioned. In addition, the method for producing the foamed laminated sheet is not particularly limited, and a non-vinyl chloride system in which a paper-based substrate having a steecht degree of sizing of 5 seconds or less is prepared in advance and a foaming agent-containing resin layer is included on the paper-based substrate There is a method in which a resin layer is laminated to produce a laminated sheet (foamed laminated sheet original fabric), and then a heat treatment is performed to turn the foaming agent-containing resin layer into a foamed resin layer. In addition, you may laminate | stack a pattern layer and / or a protective layer sequentially on the non-vinyl chloride-type resin layer of a lamination sheet or a foaming lamination sheet as needed.

  The method for forming the non-vinyl chloride resin layer is not particularly limited, and examples thereof include extrusion molding (extrusion film formation), calender molding, and coating molding (application of a resin emulsion-containing resin composition). Of these, extrusion film formation is preferred. When the non-vinyl chloride resin layer is a layer composed of a laminate of a foaming agent-containing 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 preferred. For example, when the non-vinyl chloride resin layer is a layer made of a laminate having non-foamed resin layers on both sides of the foaming agent-containing resin layer, the molten resin corresponding to the three layers is extruded 3 at the same time. A multi-manifold type T-die capable of forming layers simultaneously and a T-die having a feed block can be used.

  The non-vinyl chloride resin layer includes a foaming agent-containing resin layer, the resin composition forming the foaming agent-containing resin layer contains an inorganic filler, and the foaming agent-containing resin layer is In the case of forming by extrusion film formation, 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.

  When the non-vinyl chloride resin layer is a layer comprising a foaming agent-containing resin layer or a foaming agent-containing resin layer, electron beam irradiation is performed as necessary after forming the foaming agent-containing resin layer. Can do. 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 the pattern layer or the surface protective layer.

  When the non-vinyl chloride resin layer is a layer composed of a foaming agent-containing resin layer or a laminate including a foaming agent-containing resin layer, on the foaming agent-containing resin layer, as described above, a pattern layer as necessary And a protective layer can be laminated | stacked one by one. 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.

  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.

  The laminated sheet of the present invention can be used as wallpaper, various decorative materials and the like. In addition, the foamed laminated sheet of the present invention can be used for applications such as foamed wallpaper, various decorative materials, skin materials for laminated decorative plates, cushioning floor materials, and heat insulating decorative materials.

  Since the laminated sheet of the present invention uses a paper-based base material having a Steecht sizing degree of 5 seconds or less, even when a non-vinyl chloride resin layer is used, affixing after applying a water-based paste and temporarily fixing it. Excellent adhesion when repairing.

  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
Using a three-type three-layer T-die extruder, a three-layer coextrusion film was formed so that the thickness was 5 μm / 50 μm / 5 μm in the order of non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B. . As a result, a non-vinyl chloride resin layer in which non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B were sequentially laminated was obtained. The composition of each layer is shown in Table 1 below.

  Next, a backing paper (paper base material) having a Steecht sizing degree of 1 second was heated to 120 ° C. and laminated on the non-foamed resin layer B side of the non-vinyl chloride resin layer. The lamination was performed by thermocompression using a laminate roll. As a result, a laminated sheet composed of the backing paper and the non-vinyl chloride resin layer 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 laminated sheet. Then, it heated at 220 degreeC for 30 second, and made the foaming agent containing resin layer the foamed resin layer. This obtained the foaming lamination sheet.

Example 2
A laminated sheet and a foamed laminated sheet were obtained in the same manner as in Example 1 except that a backing paper having a Steecht sizing degree of 4 seconds was used.

Comparative Example 1
A laminated sheet and a foamed laminated sheet were obtained in the same manner as in Example 1 except that a backing paper having a Steecht sizing degree of 10 seconds was used.

Comparative Example 2
A laminated sheet and a foamed laminated sheet were obtained in the same manner as in Example 1 except that a backing paper (WK-665, manufactured by KJ Special Paper Co., Ltd.) having a Steecht sizing degree of 20 seconds was used.

Comparative Example 3
A laminated sheet and a foamed laminated sheet were obtained in the same manner as in Example 1 except that a backing paper having a Steecht sizing degree of 25 seconds was used.

Evaluation Test 1: Measurement of Residual Glue The foamed laminated sheets obtained in the above examples and comparative examples were cut into a size of 10 cm × 10 cm, and the mass (M _S (unit: g)) of each foamed laminated sheet 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: Measurement of drying time of glue Each foamed laminated sheet obtained in the above examples and comparative examples was cut into a size of 20 cm x 30 cm. Next, in the same manner as in Evaluation Test 1, water-based paste was applied to each of the foamed laminated sheets and left for 60 minutes.

  Subsequently, each said foaming lamination sheet was affixed on the gypsum board (Tiger board, Yoshino gypsum Co., Ltd. product) or mortar. Thereafter, each of the above-mentioned foamed laminated sheets was cut into 5 cm × 5 cm at regular intervals, and each of the foamed laminated sheets was peeled off from the gypsum board or mortar. Next, the foamed laminated sheets were left until the peeled surface of the peeled laminated sheets was completely dried. Subsequently, the time (drying time) when the peeling surface was completely dried was measured.

  The results are shown in Table 2 below. As a reference example, the remaining amount of glue (%) in the case of a vinyl chloride foam laminate sheet composed of backing paper / foamed resin layer containing vinyl chloride resin / pattern pattern layer / protective layer in order from the bottom. Table 2 shows. In addition, Table 2 also shows the degree of sticky sizing of the backing paper in each of Examples, Comparative Examples, and Reference Examples.

  Generally, it is preferable that the wallpaper does not take (short) the time from the time when it is applied to the adherend to the time when the aqueous paste is completely dried (the time from the start of construction to the completion of construction). In this regard, it was found that the drying time in the foamed laminated sheets of Examples 1 and 2 was equivalent to the drying time in the foamed laminated sheet of Comparative Example 2 on the market (Table 2). Therefore, the foamed laminated sheets of Examples 1 and 2 are suitable for being used as foamed wallpaper by being attached to an adherend.

Claims (7)

  A laminated sheet having at least a non-vinyl chloride resin layer on a paper-based substrate having a Steecht sizing degree of 5 seconds or less.   2. The laminated sheet according to claim 1, wherein the non-vinyl chloride resin layer is formed by extrusion film formation.   3. The laminated sheet according to claim 1, wherein the resin constituting the non-vinyl chloride resin layer is a polyolefin resin.   The laminated sheet according to any one of claims 1 to 3, wherein the non-vinyl chloride resin layer is a foaming agent-containing resin layer or a layer comprising a laminate including the foaming agent-containing resin layer.   5. The laminated sheet according to claim 4, wherein the non-vinyl chloride resin layer is a layer made of a laminate in which a non-foamed resin layer B, a foaming agent-containing resin layer, and a non-foamed resin layer A are laminated in order.   6. The laminated sheet according to claim 4, wherein the foaming agent-containing resin layer is resin-crosslinked by electron beam irradiation.   A foamed laminated sheet obtained by foaming the foaming agent-containing resin layer of the laminated sheet according to any one of claims 4 to 6.