JP6155762B2 - Laminated sheet and foam laminated sheet - Google Patents

Description

  The present invention relates to a laminated sheet and a foam laminated sheet. The foamed laminated sheet has a foamed resin layer and is useful as foamed wallpaper, various decorative materials, and the like. Moreover, the said laminated sheet is a state before foaming of the said foaming laminated sheet, and means what is called an unfoamed original fabric.

  Conventionally, foamed wallpaper is known in which a foamed resin layer containing an olefin-based resin not containing halogen is formed on a paper-based substrate (for example, backing paper). In particular, foamed wallpaper using an ethylene-vinyl acetate copolymer (EVA) is well known as an olefin resin not containing halogen.

  The foamed wallpaper in which the foamed resin layer containing the olefin-based resin not containing halogen is considered more environmentally friendly than the foamed wallpaper having the foamed resin layer containing the vinyl chloride resin, but the surface strength is inferior. Therefore, the foamed wallpaper requires a means for imparting surface strength. As such means, for example, a method of suppressing the expansion ratio of the foamed resin layer can be mentioned.

  However, the above method has a problem that it is not possible to conceal the underlying unevenness during construction.

  On the other hand, as a method for improving the above-mentioned problem and producing a foam wallpaper having excellent surface strength, Patent Document 1 is formed of a resin composition containing an ethylene-methacrylic acid copolymer (EMAA) as a foam resin layer. A foam wallpaper having a layer has been proposed.

  However, the foamed wallpaper lacks ductility and spreadability (spreadability) because of the cohesive force unique to EMAA resin. Therefore, the follow-up property (hereinafter referred to as “under-ground follow-up”) due to secular change of the building after the construction of foam wallpaper, shaking of the building, or the opening of the under-ground (hereinafter “under-ground followability”) is insufficient, and cracks are likely to occur. There is a problem.

JP 2008-156811 A

  Even when the present invention uses an unsaturated carboxylic acid polymer containing, as a monomer component, at least one unsaturated carboxylic acid selected from the group consisting of acrylic acid and methacrylic acid such as EMAA as the resin component of the foamed resin layer. An object of the present invention is to provide a foamed laminated sheet having excellent foundation followability and having a superior surface strength, and a laminated sheet (unfoamed raw fabric) useful for producing the foamed laminated sheet.

  As a result of intensive research, the inventor obtained by foaming a laminated sheet having a foaming agent-containing resin layer containing a specific inorganic filler together with the specific resin component, and the foaming agent-containing resin layer. The present inventors have found that the above object can be achieved by the foamed laminated sheet, and have completed the present invention.

That is, the present invention relates to the following laminated sheet and foamed laminated sheet.
1. a laminated sheet in which at least a foaming agent-containing resin layer is formed on a substrate,
(1) The foaming agent-containing resin layer contains an unsaturated carboxylic acid polymer containing at least one unsaturated carboxylic acid selected from the group consisting of acrylic acid and methacrylic acid as a monomer component, and an inorganic filler. ,
(2) The inorganic filler has been subjected to at least one surface treatment selected from the group consisting of a rosin acid treatment and a surface treatment for introducing an amino group ,
(3) The content of the unsaturated carboxylic acid component in the unsaturated carboxylic acid polymer is 10% by mass or more and 15% by mass or less.
A laminated sheet characterized by that.
2. The laminated sheet according to Item 1, wherein the foaming agent-containing resin layer is resin-crosslinked by electron beam irradiation.
3. The laminated sheet according to Item 1 or 2 , wherein the non-foamed resin layer B, the foaming agent-containing resin layer, and the non-foamed resin layer A are sequentially formed on the substrate.
4. A foamed laminated sheet obtained by foaming the foaming agent-containing resin layer of the laminated sheet according to any one of Items 1 to 3 .
5. The foamed laminated sheet according to item 4 , wherein embossing is performed from the top surface layer.

  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 a laminated sheet in which at least a foaming agent-containing resin layer is formed on a substrate,
(1) The foaming agent-containing resin layer contains an unsaturated carboxylic acid polymer containing at least one unsaturated carboxylic acid selected from the group consisting of acrylic acid and methacrylic acid as a monomer component, and an inorganic filler. ,
(2) The inorganic filler has been subjected to at least one surface treatment selected from the group consisting of resin acid treatment and hydrophilization treatment,
It is characterized by that.

  The laminated sheet of the present invention having the above characteristics is at least one selected from the group consisting of acrylic acid and methacrylic acid as a resin component of the foamed resin layer, particularly by containing a specific inorganic filler in the foaming agent-containing resin layer. Even when an unsaturated carboxylic acid polymer containing a kind of unsaturated carboxylic acid as a monomer component is used, a foamed laminated sheet having excellent surface followability and superior surface strength can be obtained.

  Hereinafter, each layer of the laminated sheet will be described. In addition, the layer structure of the lamination sheet of this invention will not be specifically limited if it is a layer structure which has a foaming agent containing resin layer on a base material. In the laminated sheet of the present invention, the foaming agent-containing resin layer (the protective layer in the case of having a protective layer) is a so-called “front surface” (surface visually recognized after construction). Therefore, in this specification, the direction in which the foaming agent-containing resin layer is present with respect to the substrate is referred to as “front” or “upper”, and the opposite side is referred to as “back” or “lower”.

Not limited as the substrate base material, a known fibrous substrate (backing sheet), etc. 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 .

Foaming agent-containing resin layer The foaming agent-containing resin layer used in the present invention is an unsaturated carboxylic acid polymer (hereinafter, referred to as “monomer component”) containing at least one unsaturated carboxylic acid selected from the group consisting of acrylic acid and methacrylic acid. (It may be expressed as “unsaturated carboxylic acid polymer”).

  The unsaturated carboxylic acid polymer may be either a homopolymer or a copolymer. When the unsaturated carboxylic acid polymer is a copolymer, it may be a binary copolymer or a ternary or higher copolymer. The unsaturated carboxylic acid polymer can be used alone or in combination of two or more.

  As said unsaturated carboxylic acid polymer of a homopolymer, polyacrylic acid or polymethacrylic acid is mentioned.

  As the unsaturated carboxylic acid polymer of the copolymer, monomer components (comonomer components) other than the unsaturated carboxylic acid are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene- Examples include α-olefins such as 1,1-octene, 1-decene, and 1-dodecene. Moreover, an acrylic acid-methacrylic acid copolymer can also be used as the unsaturated carboxylic acid polymer.

  The unsaturated carboxylic acid polymer is preferably at least one selected from the group consisting of an ethylene-acrylic acid copolymer (EAA) and an ethylene-methacrylic acid copolymer (EMAA).

  The content of the unsaturated carboxylic acid component in the unsaturated carboxylic acid polymer is preferably 5% by mass or more, and more preferably 10 to 15% by mass. By adopting such a copolymerization ratio, it is possible to obtain a foamed laminated sheet having excellent surface followability and superior surface strength.

  As the detailed copolymerization ratio in the binary copolymer, in the case of EAA or EMAA, the acrylic acid (AA) content or the methacrylic acid (MAA) content is preferably 5% by mass or more, and 10 to 15 More preferred is mass%.

  In the present invention, together with the unsaturated carboxylic acid polymer, an inorganic filler subjected to at least one surface treatment selected from the group consisting of resin acid treatment and hydrophilization treatment (hereinafter referred to as “surface-treated inorganic filler”). (Also referred to as “filler”). Due to the strong interaction between the carboxyl group of the unsaturated carboxylic acid polymer and the surface-treated portion of the inorganic filler, as a result, even when the unsaturated carboxylic acid polymer is used, the substrate followability It is thought that a foamed laminated sheet having excellent surface strength and superior surface strength can be obtained. In the present invention, the surface treatment refers to an operation for changing the properties of the surface of the inorganic filler with the surface treatment agent.

  A typical example of the resin acid treatment is rosin acid treatment. Examples of rosin acid include abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, dehydroabietic acid and the like. The resin acid treatment may be performed according to a conventional method. For example, the rosin acid treatment can be performed by adding an alkali solution of rosin acid to an aqueous slurry in the state of preparing an inorganic filler, and then adding an acid or an alkaline earth metal salt.

  Examples of the hydrophilic treatment include a surface treatment for introducing a hydrophilic functional group, and a cationic surfactant treatment. Surface treatment for introducing a hydrophilic functional group includes a surface for introducing at least one functional group selected from the group consisting of an amino group, a carbonyl group, a carboxyl group, a hydroxyl group, a thiol group, and a quaternary ammonium group. Treatment is preferred. The surface treatment for introducing the functional group may be performed according to a conventional method. For example, a surface treatment with a silane coupling agent having the functional group can be suitably exemplified.

  Although it does not specifically limit as a cationic surfactant process, For example, surface treatment by a quaternary ammonium salt, a tertiary amine, etc. is mentioned. Examples of the quaternary ammonium salt include dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, and tetradecyldimethylbenzylammonium chloride. Examples of the tertiary amine include tetradecylamine hydrochloride and octadecylamine acetate. The cationic surfactant treatment may be carried out according to a conventional method, and the treatment can be performed by adding a cationic surfactant as described above to an inorganic filler suspension and adsorbing it.

  The inorganic filler used for the surface-treated inorganic filler is not particularly limited as long as a part or all of the surface of the inorganic filler is surface-treated. For example, calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, molybdenum compound, silica, talc, mica, wollastonite, zonotolite, sepiolite, kaolin, glass beads, alumina, diatomaceous earth, etc. . Among the inorganic fillers, at least one selected from the group consisting of calcium carbonate, talc, mica and wollastonite is preferable. In addition, the surface-treated inorganic filler can be used 1 type or in combination of 2 or more types.

  As the surface-treated inorganic filler, those obtained by performing the above surface treatment on an unfilled inorganic filler (hereinafter also referred to as “untreated inorganic filler”) can be used. Further, surface treatments other than those described above may be performed as long as the object of the present invention is not impaired. Examples of the surface treatment other than the above include fatty acid treatment and surfactants other than cationic surfactants (nonionic surfactants and anionic surfactants). Moreover, the commercially available inorganic filler which has already been surface-treated can be used as it is.

  The content of the surface-treated inorganic filler is not particularly limited, but is preferably 5 to 100 parts by mass and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin component contained in the foaming agent-containing resin layer. When the surface-treated inorganic filler content is within the above range, it is possible to obtain a foamed laminated sheet that is more efficient, has excellent base followability, and has superior surface strength.

  Examples of the resin composition forming the foaming agent-containing resin layer include, in addition to the resin component and the surface-treated inorganic filler, pigments, pyrolytic foaming agents, foaming aids, untreated inorganic fillers, and the like. A resin composition containing 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 3 times or more, preferably about 5 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, unsaturated carboxylic acid polymers, and ADCA foaming agents are used in combination, the foamed resin layer and the substrate may be yellowed due to burning or chromophore formation in the foaming process. is there. Therefore, when an unsaturated carboxylic acid polymer and an ADCA foaming agent are used in combination, it is preferable to use a carboxylic acid hydrazide compound as a foaming aid as described in JP-A-2009-197219. 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.

  In the present invention, an untreated inorganic filler may be used together with the surface-treated inorganic filler. Examples of the untreated inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including an untreated inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained. When using an untreated inorganic filler, the content is preferably about 5 to 100 parts by mass, 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). When the pigment is used, the content thereof is preferably about 10 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 the resin-crosslinking of the foaming agent-containing resin layer, further excellent base followability can be obtained. This effect is due to (1) the foaming agent-containing resin layer becoming pseudo-polymerized by resin crosslinking, and (2) the interface generated between the resin in the foaming agent-containing resin layer and the surface-treated inorganic filler. The reason is that the adhesiveness has been improved.

  Examples of the method for crosslinking the foaming agent-containing resin layer include (1) irradiating the foaming agent-containing resin layer with ionizing radiation, (2) containing a crosslinking agent in the foaming agent-containing resin layer, and the like. The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing / crosslinking molecules, and usually ultraviolet rays, electron beams and the like are used. As the ultraviolet light source, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, or a metal halide lamp can be used. As the electron beam source, various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type may be used.

  Among the methods for cross-linking the foaming agent-containing resin layer, the unsaturated carboxylic acid polymer, which is the resin component of the foaming agent-containing resin layer, is easily cross-linked by electron beam irradiation. From the viewpoint of being remarkably produced, a method of irradiating an electron beam is preferable.

  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.

  As the crosslinking agent, a known radical generator that is decomposed by heating and generates free radicals to form a crosslinking bond between molecules or within a molecule can be used. For example, dicumyl peroxide, 1,1-ditertiarybutylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-ditertiarybutylperoxyhexane, 2,5-dimethyl-2 Organic peroxides such as 1,5-ditertiarybutylperoxyhexyne, 1,3-bis (tertiarybutylperoxyisopropyl) benzene, tertiarybutylperoxyketone, and tertiarybutylperoxybenzoate. . These crosslinking agents can be used alone or in combination of two or more.

  Although content of a crosslinking agent is not limited, 0.1-2 mass parts is preferable with respect to 100 mass parts of resin components of a foaming agent containing resin layer, and 0.1-1.5 mass parts is more preferable.

  The foaming agent-containing resin layer may contain a crosslinking aid. Examples of the crosslinking aid include polyunsaturated compounds such as polyallyl compounds and poly (meth) acryloxy compounds. For example, polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, poly (meth) such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate Examples include acryloxy compounds and divinylbenzene. These crosslinking aids can be used alone or in combination of two or more.

  Although content of a crosslinking adjuvant is not limited, 10 mass parts or less are preferable with respect to 100 mass parts of resin components of a foaming agent containing resin layer, and 0.1-3 mass parts is more preferable.

  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.

  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 increase in temperature when the foaming agent-containing resin layer is formed by extrusion film formation, and the film can be formed in a non-foamed state. It can be printed on any surface and there are few patterns missing. If the MFR is too large, the resin is too soft and the resulting foamed resin layer may have insufficient scratch resistance.

Non-foamed resin layers A and B
The foaming agent-containing resin layer may have a non-foamed resin layer on one side or both sides.

  For example, the back surface (surface on which the base material is laminated) of the foaming agent-containing resin layer 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 an ethylene-vinyl acetate copolymer (EVA) is preferable. 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 mass%, more preferably 15 to 41 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 foaming agent-containing resin layer, a non-foamed resin layer A may be provided for the purpose of clarifying the design pattern when forming the design 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 the polyolefin resin include polyethylene (PE), polypropylene, polybutene, polybutadiene, polyisoprene, and the like, a copolymer of ethylene and an α-olefin having 4 or more carbon atoms (linear low density polyethylene), ethylene- Acrylic acid copolymer resin, ethylene (meth) acrylic acid copolymer resin such as ethylene-methacrylic acid copolymer resin, ethylene-methyl acrylate copolymer resin, ethylene-ethyl acrylate copolymer resin, etc. Examples thereof include at least one of ethylene (meth) acrylate copolymer resin, ethylene-vinyl acetate copolymer (EVA), saponified ethylene-vinyl acetate copolymer resin, and 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. By using the above resin as the resin component of the non-foamed resin layer A, excellent scratch resistance can be obtained, and an effect of improving the interfacial adhesiveness by being shared with the resin component of the foaming agent-containing resin layer can be obtained.

  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.

  In the present invention, an embodiment in which the non-foamed resin layer B, the foaming agent-containing resin layer, and the non-foamed resin layer A are sequentially formed on the substrate is also preferable from the viewpoint of production described later.

A pattern layer may be formed on the pattern layer foaming agent-containing resin layer (or on the non-foamed resin layer A).

  The design pattern layer imparts design properties to the resin laminate. 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. The pattern can be selected according to the type of foam wallpaper.

  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 substrate. 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 (overcoat layer)
In the present invention, the surface of the foamed resin layer (or foaming agent-containing resin layer), the non-foamed resin layer A, or the pattern layer may have a protective layer. The protective layer is a layer formed in order to adjust the gloss of the surface of the laminated sheet or the foamed laminated sheet described later, or to impart strength and stain 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.

  As a resin component used for forming the protective layer, a resin component capable of satisfying the tear strength (and surface strength as required) is appropriately selected from known resin components such as thermoplastic resins and curable resins. That's fine.

  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 other polyolefin resins. 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.

  Further, the curable resin used for forming the protective layer is not particularly limited, and for example, a room temperature curable resin, a heat curable resin, an ionizing radiation curable resin, a one-component reaction curable resin, and a two-component reaction curable resin. Any of a curable resin, an ionizing radiation curable resin and the like 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 the foamed resin layer (or foaming agent-containing resin layer), non-foamed resin layer A, or pattern pattern layer by a method such as coating or comma coating, the resin composition is dried by heating or the like as necessary. This is done by curing.

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

  Examples of the resin contained in the primer layer include acrylic resin, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, and chlorinated polyethylene. However, acrylic resin, chlorinated polypropylene and the like are particularly 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.

≪Foamed laminated sheet≫
The foamed laminated sheet of the present invention can be obtained by foaming the foaming agent-containing resin layer of the laminated sheet.

  The foamed laminated sheet of 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.

≪Method for producing foam laminated sheet≫
As a manufacturing method of a foaming laminated sheet, for example, after forming a picture pattern layer on a base material and a foaming agent-containing resin layer, a protective layer is formed on the picture pattern layer to form a laminated sheet, and then heat treatment is performed. It can manufacture by making a containing resin layer into a foamed resin layer.

  When the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides, simultaneous extrusion film formation by a T-die extruder is suitable. For example, in the case of having non-foamed resin layers on both sides, a multi-manifold type T die capable of simultaneously forming three layers by simultaneously extruding molten resins corresponding to the three layers can be used.

  In addition, when the foaming agent-containing resin layer is formed by extrusion film formation, a residue (so-called eyes) of an inorganic filler surface-treated is easily generated at the extrusion port (so-called die) of the extruder. It tends to be a foreign matter on the surface of the resin layer. Therefore, 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.

  After forming the foaming agent-containing resin layer, electron beam irradiation may be performed. 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.

  On the foaming agent-containing resin layer, a pattern layer and a protective layer are sequentially laminated 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.

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

  The laminated sheet of the present invention contains, in particular, an inorganic filler that has been subjected to at least one surface treatment selected from the group consisting of resin acid treatment and hydrophilization treatment in the foaming agent-containing resin layer. Even when using an unsaturated carboxylic acid polymer containing as a monomer component at least one unsaturated carboxylic acid selected from the group consisting of acrylic acid and methacrylic acid as the resin component of the foamed resin layer, the substrate followability is excellent. And the foaming lamination sheet which has the outstanding surface strength is obtained.

  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
The material of the resin and the other foaming agent-containing resin layer was melt-kneaded according to the following composition, then formed into a film having a thickness of 100 μm, and bonded to the backing paper.

  Next, electron beam irradiation was performed under the conditions of 200 kV and 35 kGy.

  Next, a protective layer is formed on the foaming agent-containing resin layer by coating an acrylic aqueous emulsion (manufactured by Dainichi Seika Kogyo Co., Ltd.) with a gravure printing machine and heated in a gear oven (220 ° C x 35 seconds) Then, the foaming agent-containing resin layer was foamed to obtain a desired foamed laminated sheet.

<Foaming agent-containing resin composition>
・ EMAA "N1110H: Mitsui DuPont Polychemical Co., Ltd. MAA content = 10% by mass"
: 100 parts by mass-Calcium carbonate "Shiroka Hana O (calcium carbonate that has been surface treated by rosin acid treatment): Shiraishi Kogyo Co., Ltd.": 10 parts by mass-Titanium dioxide "Tai Pure R-108: DuPont Co., Ltd." :: 30 parts by mass-Foaming agent "Vinyl Hall AC # 3: made by Eiwa Kasei Kogyo Co., Ltd.":: 4.0 parts by mass-Foaming aid "ADHS: made by Otsuka Chemical Co., Ltd."
Example 2
The same procedure as in Example 1 was performed except that calcium carbonate “Actifort 700 (calcium carbonate subjected to surface treatment for introducing an amino group): manufactured by Shiroishi Kogyo Co., Ltd.” was used instead of calcium carbonate “Hakuenka O”. A foamed laminated sheet was obtained.

Example 3
Example 1 is used except that calcium carbonate “Shiraka Hana U (calcium carbonate surface-treated with a quaternary ammonium salt and fatty acid): manufactured by Shiraishi Kogyo Co., Ltd.” is used instead of calcium carbonate “Hakuen Hana O”. Similarly, a foamed laminated sheet was obtained.

Example 4
Instead of EMAA “N1110H”, a foamed laminated sheet was obtained in the same manner as in Example 1 except that EMAA “N1560: manufactured by Mitsui DuPont Polychemical Co., Ltd., MAA content = 15 mass%” was used.

Example 5
A foamed laminated sheet was obtained in the same manner as in Example 1 except that EMAA “AN42115C: manufactured by Mitsui DuPont Polychemical Co., Ltd., MAA content = 5 mass%” was used instead of EMAA “N1110H”.

Comparative Example 1
Foamed laminated sheet in the same manner as in Example 1 except that calcium carbonate “Whiteon H (calcium carbonate not subjected to surface treatment): manufactured by Shiroishi Kogyo Co., Ltd.” is used instead of calcium carbonate “Shiraka Hana O”. Got.

Comparative Example 2
Foam lamination as in Example 1 except that calcium carbonate “Shiraka Hana CCR (calcium carbonate subjected to surface treatment with fatty acid): manufactured by Shiroishi Kogyo Co., Ltd.” is used instead of calcium carbonate “Shiraka Hana O”. A sheet was obtained.

Comparative Example 3
A foamed laminated sheet was obtained in the same manner as in Example 1 except that EVA “Evaflex EV450: manufactured by Mitsui DuPont Polychemical Co., Ltd.” was used instead of EMAA.

Comparative Example 4
A foamed laminated sheet was obtained in the same manner as in Example 1 except that LDPE “NOVATEC LJ802: manufactured by Nippon Polyethylene Co., Ltd.” was used instead of EMAA.

Test Example The scratch resistance and ground following ability of the foamed laminated sheets prepared in each Example and Comparative Example were examined. Each test method and its evaluation criteria are as follows.

≪Scratch resistance≫
In the surface strengthening performance test (Japan Vinyl Industry Association), a scratch test was performed with a load of 500 g instead of the load of 200 g instead of the normal load of 200 g performed in 5 reciprocations. Scratch trace resin with no fluff or slight fuzz 5, scratch mark fuzz but foam resin layer dent is not recognized 4, scratch mark fuzz with foam resin layer dent is recognized 3, The case where the scratching mark was large and the fluffing backing paper was partially exposed (less than 2 cm) was evaluated as 2, and the case where the scratching mark was large and the fluffing backing paper was exposed by 2 cm or more was rated as 1. In addition, evaluation 3-5 was set as the pass (5 is the highest evaluation).

≪Base followability≫
Two board papers were pasted on the backing paper side of the foam laminate sheet, and the appearance of the foam laminate sheet was observed when it was displaced 2.0 mm in the wallpaper width direction at a speed of 3 mm / min using a tensile tester. 5 with no change in appearance, no cracks (holes), 4 with slight gloss change and / or whitening, 3 with partial cracks (holes) 3, From evaluation 3, it was rated 2 when cracks (holes) were observed but did not break, and 1 when completely broken. In addition, evaluation 2-5 was set as the pass (5 is the highest evaluation).

  The results are shown in the table below.

Claims (5)

A laminated sheet in which at least a foaming agent-containing resin layer is formed on a substrate,
(1) The foaming agent-containing resin layer contains an unsaturated carboxylic acid polymer containing at least one unsaturated carboxylic acid selected from the group consisting of acrylic acid and methacrylic acid as a monomer component, and an inorganic filler. ,
(2) The inorganic filler has been subjected to at least one surface treatment selected from the group consisting of a rosin acid treatment and a surface treatment for introducing an amino group ,
(3) The content of the unsaturated carboxylic acid component in the unsaturated carboxylic acid polymer is 10% by mass or more and 15% by mass or less.
A laminated sheet characterized by that. The laminated sheet according to claim 1, wherein the foaming agent-containing resin layer is resin-crosslinked by electron beam irradiation. The laminated sheet according to claim 1 or 2 , wherein the non-foamed resin layer B, the foaming agent-containing resin layer, and the non-foamed resin layer A are sequentially formed on the substrate. The foaming lamination sheet obtained by foaming the said foaming agent containing resin layer of the lamination sheet in any one of Claims 1-3 . The foamed laminated sheet according to claim 4 , wherein embossing is performed from above the outermost surface layer.