JP5760471B2 - Resin laminate and resin laminate sheet - Google Patents

Description

  The present invention relates to a resin laminate and a resin laminate sheet having a foamed resin layer, which are useful as foamed wallpaper, various decorative materials, and the like.

  Conventionally, foamed wallpaper is known in which a foamed resin layer of vinyl chloride resin is formed on a fibrous sheet and a pattern layer is further formed. In recent years, in consideration of the environment, halogen-free resins such as ethylene-vinyl acetate copolymer, acrylic resin, and olefin resin have been used for the foamed resin layer (Patent Documents 1 to 3, etc.).

  It is also known to form a non-foamed resin layer on the foamed resin layer in order to increase the surface strength of the foamed wallpaper and increase the production efficiency during film formation. When the non-foamed resin layer is formed on the foamed resin layer, the foamed resin layer is protected, and as a result, the surface strength of the foamed wallpaper can be increased. As a method for producing a foamed wallpaper in which a non-foamed resin layer is formed on a foamed resin layer, for example, the foaming agent-containing resin layer and the non-foamed resin layer are coextruded and formed, and then the foaming agent-containing resin layer is foamed. The method is known.

  However, when the hardness of the resin component in the non-foamed resin layer is increased in order to increase the surface strength of the foamed wallpaper, a difference in fluidity occurs between the foaming agent-containing resin and the non-foamed resin. There is a drawback that the coextrusion film-forming property is deteriorated, for example, the thickness of the foaming agent-containing resin layer and the non-foamed resin layer varies or the resin is cut.

  Accordingly, it is desired to develop a resin laminate and a resin laminate sheet that are excellent in coextrusion film-forming properties of the foaming agent-containing resin layer and the non-foamed resin layer and have good surface strength.

JP-A-6-47875 JP 2000-255011 A JP 2001-347611

  An object of this invention is to provide the resin laminated body and resin laminated sheet which are excellent in the coextrusion film forming property of a foaming agent containing resin layer and a non-foamed resin layer, and are excellent in surface strength.

  As a result of intensive studies, the inventor formed a foaming agent-containing resin layer and an ethylene (meth) acrylic acid copolymer resin-containing layer by coextrusion film formation, and further the ethylene (meth) acrylic acid copolymer. By laminating a metal compound-containing resin layer on the resin-containing layer and by heat treatment, the ethylene (meth) acrylic acid copolymer resin-containing layer and the metal compound-containing resin layer are combined to form a composite surface protective layer. The present inventors have found that the above object can be achieved and have completed the present invention.

That is, this invention relates to the following resin laminated body and resin laminated sheet.
1. On the foamed resin layer, a resin laminate double focus type surface protective layer and the picture pattern layer are sequentially laminated,
The composite surface protective layer contains an ethylene (meth) acrylic acid copolymer resin and a metal compound,
The metal compound is at least one selected from the group consisting of magnesium oxide, zinc oxide, aluminum oxide, zirconium oxide, antimony oxide, titanium oxide, boron nitride, aluminum nitride, and metal soap,
The foamed resin layer is obtained by foaming a foaming agent-containing resin layer described later,
The resin laminate has the following steps (i) to (iii):
(I) At least a foaming agent-containing resin layer and an ethylene (meth) acrylic acid copolymer resin-containing layer are formed by coextrusion film formation,
(Ii) laminating a metal compound-containing resin layer on the ethylene (meth) acrylic acid copolymer resin-containing layer,
(Iii) A resin laminate obtained by combining the ethylene (meth) acrylic acid copolymer resin-containing layer and the metal compound-containing resin layer into a composite surface protective layer by heat treatment.
2 . Item 2. The resin laminate according to Item 1, wherein the metal compound-containing resin layer contains 5% by weight or more of the metal compound.
3 . Item 3. The resin laminate according to Item 1 or 2 , wherein the foamed resin layer has an adhesive resin layer on the back surface side.
4 . Item 4. The resin laminate according to any one of Items 1 to 3 , wherein the heat treatment is a heat treatment for using the foaming agent-containing resin layer as the foamed resin layer.
5 . The resin laminated sheet formed by laminating | stacking the said foamed resin layer side of the resin laminated body in any one of said items 1-4 on a fibrous sheet.

Hereinafter, the resin laminate and the resin laminate sheet of the present invention will be described in detail.
≪Resin laminate≫
The resin laminate of the present invention is a resin laminate in which a composite surface protective layer containing an ethylene (meth) acrylic acid copolymer resin and a metal compound is laminated on a foamed resin layer,
The foamed resin layer is obtained by foaming a foaming agent-containing resin layer described later,
The resin laminate has the following steps (i) to (iii):
(I) At least a foaming agent-containing resin layer and an ethylene (meth) acrylic acid copolymer resin-containing layer are formed by coextrusion film formation,
(Ii) laminating a metal compound-containing resin layer on the ethylene (meth) acrylic acid copolymer resin-containing layer,
(Iii) It is obtained by compounding the ethylene (meth) acrylic acid copolymer resin-containing layer and the metal compound-containing resin layer into a composite surface protective layer by heat treatment.

The resin laminate of the present invention having the above characteristics is obtained by forming a foaming agent-containing resin layer and an ethylene (meth) acrylic acid copolymer resin-containing layer by coextrusion film formation, and the ethylene (meth) acrylic acid copolymer resin. Since the metal compound-containing resin layer is provided on the containing layer, the fluidity is more stable than the case where the metal compound is added to the ethylene (meth) acrylic acid copolymer resin-containing layer and the foaming agent-containing resin layer is formed. And there exists an effect that it is excellent in the coextrusion film forming property of an ethylene (meth) acrylic acid copolymer resin content layer. Moreover, since the resin laminate of the present invention has a composite surface protective layer obtained by combining an ethylene (meth) acrylic acid copolymer resin-containing layer and a metal compound-containing resin layer by heat treatment, the surface strength is good. is there. This effect is due to the fact that the ethylene (meth) acrylic acid copolymer resin in the ethylene (meth) acrylic acid copolymer resin-containing layer is melted by heat treatment, resulting in an ionic group originating from the ethylene (meth) acrylic acid copolymer resin. It is considered that (-COO ^- etc.) is based on the surface strength being improved by forming an ionic crosslinked structure (pseudo-crosslinked structure) with the metal compound in the adjacent metal compound-containing resin layer.

Foamed resin layer The foamed resin layer is obtained by foaming a foaming agent-containing resin layer. For example, the foamed resin layer is obtained by foaming a foaming agent-containing resin layer by heat treatment.

  Although it does not limit as a resin component of a foaming agent containing resin layer, For example, it is preferable to contain polyethylene and ethylene-alpha olefin copolymer resin. Specifically, the ethylene-α-olefin copolymer resin is preferably contained in an amount of 1 to 150 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of polyethylene.

  The polyethylene and ethylene-α-olefin copolymer resin preferably has an MFR (melt flow rate) of 10 to 40 g / 10 min measured under the conditions of 190 ° C. and a load of 21.18 N described in JIS K 6922. If the MFR is too large, the resin is too soft and the resulting foamed resin layer may have insufficient scratch resistance.

  In addition, you may use resin other than the said polyethylene and ethylene-alpha olefin copolymer resin together. For example, polyolefin resins such as polypropylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), ethylene (meth) acrylic acid copolymer resin, acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene A copolymer resin, nylon, polyacetal resin, acrylic resin, polycarbonate resin, polyester resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyurethane resin, polyvinyl chloride resin, etc. Can be mentioned.

  When the other resins are used in combination, the content of polyethylene and ethylene-α-olefin copolymer resin in the resin component (total amount of the two components) is 60% by weight or more, preferably 70% by weight or more. It is preferable to set to.

  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.

  The foamed state of the foamed resin layer (for example, the size of the foamed cell, the foamed cell density, etc.) is not limited, and can be appropriately designed according to the type and use of the resin laminate and the resin laminate sheet.

  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 1.5 times or more, preferably about 3 to 7 times, and the pyrolytic foaming agent is preferably about 1 to 20 parts by weight with respect to 100 parts by weight of the resin component.

  As the foaming aid, for example, a metal soap such as zinc stearate can be used. The content of the foaming aid is preferably about 0.3 to 10 parts by weight, and more preferably about 1 to 5 parts by weight with respect to 100 parts by weight of the resin component.

  Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. 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 weight and more preferably about 20 to 70 parts by weight with respect to 100 parts by weight 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 10 to 50 parts by weight and more preferably about 15 to 30 parts by weight with respect to 100 parts by weight of the resin component.

  The foaming agent-containing resin layer may be irradiated with an electron beam. 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 with respect 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 is preferably about 300 to 700 μm.

  The foamed resin layer of the present invention may have a non-foamed resin layer (adhesive resin layer) on the back surface (surface on which a fibrous sheet described later is laminated) for the purpose of improving the adhesive strength with the fibrous sheet. Good.

  As a resin component of the adhesive resin layer, an ethylene-vinyl acetate copolymer (EVA) is preferable. EVA is not particularly limited, and known or commercially available EVA can be used. In particular, the vinyl acetate component (VA component) is preferably 10 to 30% by weight, more preferably 15 to 30% by weight.

  The thickness of the adhesive resin layer is not limited, but is preferably about 10 to 50 μm.

A composite type surface protective layer containing an ethylene (meth) acrylic acid copolymer resin and a metal compound is formed on the composite type surface protective layer foamed resin layer. In the present invention, the composite surface protective layer is obtained by compositing an ethylene (meth) acrylic acid copolymer resin-containing layer and a metal compound-containing resin layer, which are sequentially laminated on the foaming agent-containing resin layer.

The ethylene (meth) acrylic acid copolymer resin-containing layer is formed on the foaming agent-containing resin layer. The ethylene (meth) acrylic acid copolymer resin-containing layer contains ionic groups (-COO ^- etc.) such as ethylene (meth) acrylic acid copolymer resin (EMAA) and ethylene-acrylic acid copolymer resin (EAA). Although it may be formed only from resin which has, other resin may be used together to such an extent that the effect of this invention is not impaired. In addition, when using 2 or more types of resin, it is preferable that content of ethylene (meth) acrylic acid copolymer resin shall be 70 weight% or more in consideration of the surface strength of a composite-type surface protective layer.

  The (meth) acrylic acid content (copolymerization ratio) in the ethylene (meth) acrylic acid copolymer resin is not particularly limited, but is preferably 2 to 15% by weight. When an ethylene (meth) acrylic acid copolymer resin having a (meth) acrylic acid content within such a range is used, the coextrusion film forming property with the foaming agent-containing resin layer is particularly excellent.

  Although the thickness of an ethylene (meth) acrylic acid copolymer resin content layer is not limited, 5-20 micrometers is preferred and 5-15 micrometers is more preferred.

The metal compound-containing resin layer is formed on the ethylene (meth) acrylic acid copolymer resin-containing layer. Any metal compound may be used as long as it can form an ionic group (such as —COO 2 ^— ) and an ionic cross-linked structure (pseudo cross-linked structure) resulting from the ethylene (meth) acrylic acid copolymer resin. Examples thereof include at least one selected from the group consisting of magnesium oxide, zinc oxide, aluminum oxide, zirconium oxide, antimony oxide, titanium oxide, silicon oxide, boron nitride, aluminum nitride, and metal soap. Examples of the metal soap include zinc stearate and magnesium stearate. Among these metal compounds, at least one of magnesium oxide and zinc oxide is preferable.

  Although the particle diameter of a metal compound is not limited, 3.5 micrometers or less are preferable and 0.6 micrometers or less are more preferable from an ionic viewpoint. The lower limit is about 0.02 μm. However, in the case of a metal soap, it is in a molten state at the time of layer formation or at the time of compounding, so the lower limit of the particle size is not particularly limited. Further, the content of the metal compound in the metal compound-containing resin layer is preferably 5% by weight or more, more preferably 10% by weight or more, and the upper limit is about 40% by weight.

  Examples of the resin component of the metal compound-containing resin layer include ethylene-vinyl acetate copolymer (EVA), ethylene-α olefin copolymer, ethylene-methyl methacrylate, urethane, acrylic, and the like. Resins can also be used. When the ionizing radiation curable resin is used as the resin component, one that undergoes radical polymerization (curing) by electron beam irradiation is preferable. When the metal compound-containing resin layer is provided by coating, urethane type and acrylic type are preferable from the viewpoint of adhesion of the paint binder.

  The metal compound-containing resin layer may be laminated on the ethylene (meth) acrylic acid copolymer resin-containing layer alone, but together with the foaming agent-containing resin layer and the ethylene (meth) acrylic acid copolymer resin-containing layer Lamination may be performed by coextrusion film formation. In the case of coextrusion film formation, film formation can be performed by using, for example, a multi-manifold type T die.

  Although the thickness of a metal compound containing resin layer is not limited, Usually, it is about 1-10 micrometers, and 1-5 micrometers is preferable.

  In the present invention, the two layers can be combined by heat treatment. The heat treatment may be performed under the condition that the ethylene (meth) acrylic acid copolymer resin-containing layer is melted. For example, heat treatment for making the foaming agent-containing resin layer into a foamed resin layer can be used. On the other hand, heat treatment for compositing may be performed separately from heat treatment for forming the foaming agent-containing resin layer as a foamed resin layer.

In the present invention, ethylene (meth) acrylic acid copolymer resin containing layer is melted by heat treatment, ethylene (meth) ionic group due to the acrylic acid copolymer resin ^- metal compound (-COO etc.) is adjacent containing It is considered that the surface strength is improved by forming an ionic cross-linked structure (pseudo cross-linked structure) with the metal compound in the resin layer.

  Although the thickness of a composite-type surface protective layer is not limited, 6-30 micrometers is preferable and 6-20 micrometers is more preferable.

A pattern layer may be formed on the pattern layer composite type surface protective layer or between the ethylene (meth) acrylic acid copolymer resin-containing layer and the metal compound-containing resin layer. When the pattern layer is formed between the ethylene (meth) acrylic acid copolymer resin-containing layer and the metal compound-containing resin layer, a metal compound similar to the metal compound contained in the metal compound-containing resin layer is used. It is preferable to add to the binder resin.

  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 base sheet. 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; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. Chlorinated organic solvents; and water. A solvent (or dispersion medium) can be used alone or in combination of two or more.

  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.

Embossing The resin laminate of the present invention may be embossed from the front surface. Embossing can be performed by known means such as an embossed plate. For example, a desired embossed pattern can be formed by pressing the embossed plate after heating and softening the front surface of the composite surface resin 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.
≪Resin laminated sheet≫
The resin laminate of the present invention can be made into a resin laminate sheet by laminating the foamed resin layer side on a fibrous sheet.

  The fiber sheet is not limited, and a known wallpaper 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.

The basis weight of the paper quality substrate is not limited, but preferably about 50 to 300 g / m ^2, more preferably about 50~120 g / m ^2.
≪Method for producing resin laminate≫
As a method for producing the resin laminate of the present invention, for example, at least a foaming agent-containing resin layer and an ethylene (meth) acrylic acid copolymer resin-containing layer are formed by coextrusion film formation, and then the ethylene (meth) acrylic acid A metal compound-containing resin layer is laminated on the copolymer resin-containing resin layer, and the ethylene (meth) acrylic acid copolymer resin-containing layer and the metal compound-containing resin layer are further combined by heat treatment to form a composite surface protective layer. It can be manufactured by forming. According to the said manufacturing method, it can form into a film, without an ethylene (meth) acrylic acid copolymer resin and a metal compound reacting and hardening during an extrusion film forming process, and can obtain the resin laminated body of this invention efficiently. it can.

  Moreover, when the foamed resin layer has an adhesive resin layer on its back surface, the adhesive resin layer is formed by a known coating method, and a foaming agent-containing resin layer and an ethylene (meth) acrylic acid copolymer resin are contained thereon. Although it is possible to co-extrusion and form the layers, it is preferable to co-extrusion and form the adhesive resin layer together with the foaming agent-containing resin layer and the ethylene (meth) acrylic acid copolymer resin-containing layer. In this case, it is possible to use a multi-manifold type T die capable of simultaneously forming three layers by simultaneously extruding molten resins corresponding to the three layers.

  In particular, when an inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer, and the foaming agent-containing resin layer is formed by extrusion film formation, the extrusion port (so-called die) of the extruder is used. Inorganic filler residues (so-called eyes and eyes) are easily generated, 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, by forming the foaming agent-containing resin layer in a form in which the foaming agent-containing resin layer is sandwiched between the adhesive resin layer and the ethylene (meth) acrylic acid copolymer resin-containing layer, it is possible to suppress the occurrence of the eyes.

  After forming the foaming agent-containing resin layer and the ethylene (meth) acrylic acid copolymer resin-containing 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. This electron beam irradiation may be performed after the pattern layer is formed.

  On the ethylene (meth) acrylic acid copolymer resin-containing layer, a metal compound-containing resin layer is laminated. Under the present circumstances, although a metal compound containing resin layer may be laminated | stacked independently, you may form by coextrusion film forming with a foaming agent containing resin layer and an ethylene (meth) acrylic acid copolymer resin containing layer. When laminating a metal compound-containing resin layer alone, combining foaming agent-containing resin layer and ethylene (meth) acrylic acid copolymer resin-containing layer by combining coating such as printing and coating, extrusion film formation, etc. They can be stacked separately. 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. In this case, a foamed resin layer is formed by heat treatment and a composite surface protective layer is also formed.

In the resin laminate of the present invention, a foaming agent-containing resin layer and an ethylene (meth) acrylic acid copolymer resin-containing layer are formed by coextrusion film formation, and the ethylene (meth) acrylic acid copolymer resin-containing layer is formed on the ethylene (meth) acrylic acid copolymer resin-containing layer. Since the metal compound-containing resin layer is provided, the fluidity is more stable than when a metal compound is added to the ethylene (meth) acrylic acid copolymer resin-containing layer to form a film, and the foaming agent-containing resin layer and the ethylene (meta) ) There is an effect that the coextrusion film forming property of the acrylic acid copolymer resin-containing layer is excellent. Moreover, since the resin laminate of the present invention has a composite surface protective layer obtained by combining an ethylene (meth) acrylic acid copolymer resin-containing layer and a metal compound-containing resin layer by heat treatment, the surface strength is good. is there. This effect is due to the fact that the ethylene (meth) acrylic acid copolymer resin in the ethylene (meth) acrylic acid copolymer resin-containing layer is melted by heat treatment, resulting in an ionic group originating from the ethylene (meth) acrylic acid copolymer resin. It is considered that (-COO ^- etc.) is based on the surface strength being improved by forming an ionic crosslinked structure (pseudo-crosslinked structure) with the metal compound in the adjacent metal compound-containing resin layer.

  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 multi-manifold T-die extruder, i) ethylene (meth) acrylic acid copolymer resin-containing layer / ii) foaming agent-containing resin layer / iii) adhesive resin layer in order of 10 μm / 70 μm / 10 μm The film was formed as follows. After the film formation, the surface of the layer iii) was laminated on a backing paper (WK-665DO, manufactured by Kojin Co., Ltd.) heated to 90 ° C., and an electron beam (195 kV, 30 kGy) was irradiated from the i) layer. Thereby, the laminated resin sheet original fabric was produced.

  Next, the i) layer was subjected to corona discharge treatment, and 100 parts by weight of EVA-containing water-based ink ("Ode EV Primer" manufactured by DIC Graphics Co., Ltd.) was added with 10 parts of magnesium oxide (particle size: 0.5 μm). This was applied to form a metal compound-containing resin layer (metal compound content: 33.3% by weight).

  Next, a texture pattern was printed on the metal compound-containing resin layer using a water-based ink ("Hydric", manufactured by Dainichi Seika Kogyo Co., Ltd.) as a pattern print by a gravure printer.

  Next, it was heated in an oven (220 degrees x 35 seconds) to make the foaming agent-containing resin layer into a foamed resin layer and melt the ethylene (meth) acrylic acid copolymer resin to obtain a composite surface protective layer. .

  Next, a texture pattern uneven embossing was applied from the outermost surface of the foam to obtain a resin laminated sheet.

  Each layer was formed using the following components.

Example 2
A metal compound-containing resin layer (containing a metal compound) by applying 10 parts by weight of zinc oxide (particle size: 0.6 μm) to 100 parts by weight of EVA-containing water-based ink (“Ode EV Primer” manufactured by DIC Graphics Co., Ltd.) A resin laminated sheet was obtained in the same manner as in Example 1 except that the amount was 33.3% by weight.

Comparative Example 1
A resin laminated sheet was obtained in the same manner as in Example 1 except that the metal compound-containing resin layer was not formed.

Comparative Example 2
Except for changing the ethylene (meth) acrylic acid copolymer resin (Mitsui / DuPont Polychemical Co., Ltd., trade name Nucrel N1110H) to polyethylene (made by Tosoh Corporation, trade name Petrocene 208), the same as Example 1. Thus, a resin laminated sheet was obtained.

Comparative Example 3
Resin lamination as in Example 1 except that 10 parts by weight of magnesium oxide was added to 100 parts by weight of the resin in the ethylene (meth) acrylic acid copolymer resin-containing layer without forming a metal compound-containing resin layer A sheet was obtained.

Test example 1
The resin laminated sheets obtained in the examples and comparative examples were examined for scratch resistance and resin film-forming properties.

Each test method and evaluation criteria are as follows.
(Scratch resistance)
The scratch resistance of the obtained resin laminated sheet was measured by the Gakushin type abrasion test method of JIS A6921 6.3.2 (reciprocating the friction element 400 times on the surface layer), and the surface state was observed. A surface condition of good (4th grade or 5th grade) was evaluated as ◯, a slightly bad (3rd grade or more and less than 4th grade) was evaluated as Δ, and a bad (less than 3rd grade) was evaluated as ×.
(Resin film-forming properties)
The state of film formation during extrusion film formation of the resin layer (three-layer coextrusion) of the wallpaper was observed. The case where the resin was cut and the hole was not opened was evaluated as ◯, and the case where the film was not formed due to the resin being cut or opened was evaluated as x.

  The evaluation results are as shown in Table 2 below.

Claims (5)

On the foamed resin layer, a resin laminate double focus type surface protective layer and the picture pattern layer are sequentially laminated,
The composite surface protective layer contains an ethylene (meth) acrylic acid copolymer resin and a metal compound,
The metal compound is at least one selected from the group consisting of magnesium oxide, zinc oxide, aluminum oxide, zirconium oxide, antimony oxide, titanium oxide, boron nitride, aluminum nitride, and metal soap,
The foamed resin layer is obtained by foaming a foaming agent-containing resin layer described later,
The resin laminate has the following steps (i) to (iii):
(I) At least a foaming agent-containing resin layer and an ethylene (meth) acrylic acid copolymer resin-containing layer are formed by coextrusion film formation,
(Ii) laminating a metal compound-containing resin layer on the ethylene (meth) acrylic acid copolymer resin-containing layer,
(Iii) A resin laminate obtained by combining the ethylene (meth) acrylic acid copolymer resin-containing layer and the metal compound-containing resin layer into a composite surface protective layer by heat treatment. The resin laminate according to claim 1, wherein the metal compound-containing resin layer contains 5 wt% or more of the metal compound. The said foaming resin layer is a resin laminated body of Claim 1 or 2 which has an adhesive resin layer in the back surface side. The said heat processing is a resin laminated body in any one of Claims 1-3 which is heat processing for making the said foaming agent containing resin layer into the said foamed resin layer. The resin laminated sheet formed by laminating | stacking the said foamed resin layer side of the resin laminated body in any one of Claims 1-4 on a fibrous sheet.