JP2012166350A - Resin laminate, and resin laminated sheet - Google Patents

Abstract

When an ethylene- (meth) acrylic acid copolymer resin is used as a resin component of a foamed resin layer, the surface strength of foamed wallpaper and the like is further increased while maintaining the resin film formability of the foamed resin layer. Provided are a resin laminate and a resin laminate sheet that can be improved and maintain good productivity.
An unfoamed intermediate having a layer structure in which a metal compound-containing resin layer is laminated on one side or both sides of a foaming agent-containing resin layer is heat-treated, and the foaming agent-containing resin layer is obtained as a foamed resin layer. A resin laminate,
(1) The foaming agent-containing resin layer contains an ethylene- (meth) acrylic acid copolymer resin as a resin component,
(2) The resin component of the metal compound-containing resin layer is a copolymer composed of monomers that do not contain hydrogen bonds,
(3) The foaming agent-containing resin layer and the metal compound-containing resin layer are combined by the heat treatment or a separate heat treatment,
The resin laminated body characterized by the above-mentioned.
[Selection figure] None

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.).

  In order to improve the surface strength (scratch resistance, etc.) of the foamed resin layer of the foamed wallpaper, it is known to use an ethylene- (meth) acrylic acid copolymer resin as the foamed resin of the foamed resin layer. It is also known to provide a non-foamed resin layer on the foamed resin layer for the purpose of improving the physical properties of the foamed wallpaper.

  However, if the resin forming the foamed resin layer is hardened (adjusting the degree of polymerization, etc.) with the aim of further improving the surface strength of the foam wallpaper, the film-forming property of the foamed resin layer is poor (manufactured in a temperature range where the foaming agent does not foam). There is a problem that leads to inferior productivity. In addition, even if the film can be formed, there is a problem that it is difficult to form a foam (it is difficult to foam).

  Therefore, when ethylene- (meth) acrylic acid copolymer resin is used as the foamed resin for the foamed resin layer, the surface strength of foamed wallpaper and the like is further improved while maintaining the resin film formability of the foamed resin layer. Development of a resin laminate and a resin laminate sheet that can be maintained and can maintain good productivity is desired.

Japanese Patent Laid-Open No. 6-47875 JP 2000-255011 A JP 2001-347611 A

  In the present invention, when ethylene- (meth) acrylic acid copolymer resin is used as the resin component of the foamed resin layer, the surface strength of the foamed wallpaper and the like is improved while maintaining the resin film formability of the foamed resin layer. It is another object of the present invention to provide a resin laminate and a resin laminate sheet that can be further improved and can maintain good productivity.

  As a result of intensive studies, the present inventors have found that the resin laminate in which the foaming agent-containing resin layer containing the ethylene- (meth) acrylic acid copolymer resin as the resin component and the metal compound-containing resin layer are combined is the above. The inventors have found that the object can be achieved and have completed the present invention. This is because the foaming agent-containing resin layer containing the ethylene- (meth) acrylic acid copolymer resin is in contact with the metal compound-containing resin layer, so that both resin layers are combined during heat treatment, and the toughness of the foamed resin layer is reduced. This is because it increases.

That is, this invention relates to the following resin laminated body and resin laminated sheet.
Item 1. A resin laminate obtained by heat-treating an unfoamed intermediate having a layer structure in which a metal compound-containing resin layer is laminated on one side or both sides of a foaming agent-containing resin layer, and making the foaming agent-containing resin layer a foamed resin layer Because
(1) The foaming agent-containing resin layer contains an ethylene- (meth) acrylic acid copolymer resin as a resin component,
(2) The resin component of the metal compound-containing resin layer is a copolymer composed of monomers that do not contain hydrogen bonds,
(3) The foaming agent-containing resin layer and the metal compound-containing resin layer are combined by the heat treatment or a separate heat treatment,
The resin laminated body characterized by the above-mentioned.
Item 2. 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, silicon oxide, boron nitride, aluminum nitride, and metal soap. The resin laminate according to 1.
Item 3. The resin laminate according to claim 1 or 2, wherein the metal compound-containing resin layer contains 5% by weight or more of the metal compound.
Item 4. The resin laminated sheet formed by laminating | stacking the resin laminated body in any one of Claims 1-3 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 obtained by heat-treating an unfoamed intermediate having a layer structure in which a metal compound-containing resin layer is laminated on one side or both sides of a foaming agent-containing resin layer, and making the foaming agent-containing resin layer a foamed resin layer Because
(1) The foaming agent-containing resin layer contains an ethylene- (meth) acrylic acid copolymer resin as a resin component,
(2) The resin component of the metal compound-containing resin layer is a copolymer composed of monomers that do not contain hydrogen bonds,
(3) The foaming agent-containing resin layer and the metal compound-containing resin layer are combined by the heat treatment or a separate heat treatment,
It is characterized by that.

Since the resin laminate of the present invention having the above characteristics is obtained by combining a foaming agent-containing resin layer containing an ethylene- (meth) acrylic acid copolymer resin as a resin component and a metal compound-containing resin layer by heat treatment, While maintaining the resin film-forming property of the foamed resin layer, the surface strength of the foamed wallpaper and the like can be further improved, and the productivity can be maintained well. This effect, by heat treatment, ethylene - (meth) melted acrylic acid copolymer resin, an ethylene - (meth) ionic group due to the acrylic acid copolymer resin (-COO ^-, etc.) is adjacent metal compound It is considered that the surface strength is improved by forming (compositing) an ionic cross-linked structure (pseudo cross-linked structure) with the metal compound in the containing resin layer.

Unfoamed intermediate The resin laminate of the present invention has a layer structure in which a metal compound-containing resin layer is laminated on one or both sides of a foaming agent-containing resin layer before the foaming agent-containing resin layer is made into a foamed resin layer by heat treatment. Having an unfoamed intermediate. And the resin laminated body of this invention is obtained by heat-processing the unfoamed intermediate body and making a foaming agent containing resin layer into a foamed resin layer.

Foaming agent-containing resin layer The foaming agent-containing resin layer is an unfoamed foamed resin layer before heat treatment.

As the resin component, ethylene- (meth) acrylic acid copolymer resin is used. This is a polymer obtained using at least one of acrylic acid (CH ₂ ═CHCOOH) and methacrylic acid (CH ₂ ═C (CH ₃ ) COOH) as a monomer, for example, at least one of acrylic acid and methacrylic acid. It is a copolymer obtained by a combination of a monomer and ethylene. By using such a resin component, it is possible to form a strong layer resulting from hydrogen bonding in the resin, and thus excellent scratch resistance, wear resistance, and the like can be obtained.

  In the present invention, when expressed as an ethylene- (meth) acrylic acid copolymer resin, it means both an ethylene-acrylic acid copolymer resin and an ethylene-methacrylic acid copolymer resin.

  A resin other than the ethylene- (meth) acrylic acid copolymer resin may be used in combination. For example, polyolefin resin such as polypropylene, polystyrene and ethylene-vinyl acetate copolymer resin (EVA), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene copolymer resin, nylon, polyacetal resin And at least one of acrylic resins, polycarbonate resins, polyester resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyurethane resins, and polyvinyl chloride resins.

  When the other resin is used in combination, the content of the ethylene- (meth) acrylic acid copolymer resin in the resin component of the ethylene- (meth) acrylic acid copolymer resin-containing resin layer is 60% by mass. The above is preferable, 70 mass% or more is more preferable, and 100 mass% may be sufficient. By using ethylene- (meth) acrylic acid copolymer resin as a main component as a resin component of the ethylene- (meth) acrylic acid copolymer resin-containing resin layer, the surface strength of the foamed resin layer of the foam wallpaper is improved. be able to.

  The melt flow rate value (MFR) of the ethylene- (meth) acrylic acid copolymer (JIS K7210: 190 ° C., 2.16 kg) depends on the type of polymer used, but is usually 100 g / 10 min or less. Is preferred. Considering the workability and the foamed state when the foamed resin layer described below is taken into consideration, it is preferable to set it in the range of 10 to 60 g / 10 minutes. By using a material having such a numerical range, more excellent scratch resistance, wear resistance and the like can be obtained. When the MFR is within the above range, there is little increase in temperature when the resin layer containing the ethylene- (meth) acrylic acid copolymer resin is formed by extrusion film formation, and the film can be formed in a non-foamed state. When a layer is formed, a printing process can be performed on a smooth surface, and pattern loss or the like is small. Moreover, when MFR is too large, there exists a possibility that the flaw resistance at the time of forming as a foamed resin layer may become inadequate because resin is too soft.

  The foaming agent-containing resin layer contains a foaming agent.

  It is preferable to use a pyrolytic foaming agent as the foaming agent. 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. .

  A foaming aid can be further used for the resin composition forming the foaming agent-containing resin layer. As the foaming aid, for example, a hydrazide compound is preferably used.

As a hydrazide compound, general formula (1):
R—CO—NHNH ₂ (1)
And a monohydrazide compound represented by formula (2):
_{H 2 NHN-X-NHNH 2} (2)
The dihydrazide compound shown by can be used suitably.

  More specific examples of the hydrazide compound of the general formula (1) include lauric acid hydrazide, salicylic acid hydrazide, form hydrazide, acetohydrazide, propionic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy- Examples include 2-naphthoic acid hydrazide.

  Specific examples of the dihydrazide compound of the general formula (2) include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecane-2-acid dihydrazide, and maleic acid. Examples include dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, dimer acid dihydrazide, and dibasic acid dihydrazide such as 2,6-naphthoic acid dihydrazide. Furthermore, various dibasic acid dihydrazide compounds described in Japanese Patent Publication No. 2-4607, 2,4-dihydrazino-6-methylamino-sym-triazine, and the like can also be used as the dihydrazide of the present invention.

  The content of the foaming aid is preferably about 0.3 to 10 parts by weight and more preferably about 1 to 6 parts by weight with respect to 100 parts by weight of the resin component.

  The resin composition forming the foaming agent-containing resin layer includes, for example, an inorganic filler, a pigment, a crosslinking aid, in addition to the resin component, the foaming agent and the foaming aid mainly composed of the ethylene-methacrylic acid copolymer. Agents, stabilizers, lubricants and the like can be used.

  Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, 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. About 0-100 weight part is preferable with respect to 100 weight part of resin components, and, as for content of an inorganic filler, about 20-70 weight part is more preferable.

  Regarding pigments, examples of inorganic pigments include titanium oxide, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), and cadmium. Examples include red, ultramarine blue, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, and mica titanium. 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 3 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.

  You may irradiate an electron beam with respect to a foaming agent containing resin layer. What is necessary is just to implement according to the method described in the manufacturing method of the postscript as the method.

  In addition, as for the thickness of a foaming agent containing resin layer, about 40-100 micrometers is preferable.

Metal compound-containing resin layer In the resin laminate of the present invention, a metal compound-containing resin layer is formed on one side or both sides of the foaming agent-containing resin layer.

  In the present invention, the metal compound-containing resin layer forms a non-foamed resin layer.

  The resin component constituting the metal compound-containing resin layer is a resin obtained from a combination of monomers that does not contain hydrogen bonds in the resin layer because the added metal compound does not contribute to the formation of an ionic crosslinked structure. Use.

  Therefore, for example, an ethylene copolymer resin obtained from a combination of ethylene and a monomer having no OH group or COOH group can be suitably used. Examples of the ethylene copolymer resin include ethylene-vinyl acetate copolymer resin (EVA), ethylene-methyl methacrylate copolymer resin (EMMA), ethylene-ethyl acrylate copolymer resin (EEA), and ethylene-methyl acrylate. A copolymer resin (EMA) or an ethylene-α olefin copolymer can be used. In addition, a polyolefin-based resin composed of a resin simple substance such as polyethylene, polypropylene, polybutene, polybutadiene, polyisoprene can also be used. In view of coextrusion with an ethylene- (meth) acrylic acid copolymer resin-containing resin layer (particularly, a foaming agent-containing resin layer), the melting point and flow characteristics are easy to match. It is preferable to use EVA and EMMA resins.

  The metal compound-containing resin layer contains a metal compound.

As the metal compound, the above-mentioned ethylene - (meth) ethylene is used as the resin component of the acrylic acid copolymer resin containing resin layer - (meth) ionic group due to the acrylic acid copolymer resin (-COO ^-, etc.) And an ionic crosslinked structure (pseudo-crosslinked structure) may be used, for example, magnesium oxide, zinc oxide, aluminum oxide, zirconium oxide, antimony oxide, titanium oxide, silicon oxide, boron nitride, aluminum nitride and There may be mentioned at least one selected from the group consisting of metal soaps.

  As the metal soap, fatty acid metal salts such as zinc stearate, magnesium stearate, zinc laurate, zinc ricinoleate and zinc octylate are preferable.

  Among these, 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 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 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.

  Although the thickness of a metal compound containing resin layer is not limited, About 5-50 micrometers is preferable.

Further, an adhesive resin layer may be provided on the back surface of the foamed resin layer (the surface on which the fibrous sheet described later is laminated) for the purpose of improving the adhesive force with the fibrous sheet.

  As the 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, and more preferably 15 to 30% by weight.

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

Even if a pattern layer is formed between the foaming agent-containing resin layer containing the ethylene- (meth) acrylic acid copolymer resin and the metal compound-containing resin layer or on the metal compound-containing resin layer Good. When the pattern layer is formed between the foaming agent-containing resin layer containing the ethylene- (meth) acrylic acid copolymer resin and the metal compound-containing resin layer, the metal compound contained in the metal compound-containing resin layer and It is preferable to add the same metal compound 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. These solvents are used alone or as 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.

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≫
A resin laminate sheet can be obtained by laminating the resin laminate of the present invention 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,} about 50 to 120 / ^{m 2} is more preferable.

≪Method for producing resin laminate≫
The resin laminate of the present invention comprises (i) a monomer in which the resin component does not contain hydrogen bonds on one or both sides of a foaming agent-containing resin layer containing an ethylene- (meth) acrylic acid copolymer resin as a resin component. Laminating a metal compound-containing resin layer that is a copolymer, (ii) heat-treating the unfoamed intermediate having a layer structure in this way, and making the foaming agent-containing resin layer a foamed resin layer, and (iii) the heat treatment or It can be manufactured by combining the foaming agent-containing resin layer and the metal compound-containing resin layer by separate heat treatment.

  Thus, a foamed resin layer can be obtained by heat-treating and foaming the foaming agent-containing resin layer. 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.

  The thickness of the foamed resin layer after foaming after heat-treating the foaming agent-containing resin layer is preferably about 300 to 700 μm.

  The heat treatment for the composite may be performed under the condition that the foaming agent-containing resin layer containing the ethylene- (meth) acrylic acid copolymer resin is melted. Therefore, if the foaming agent-containing resin layer containing the ethylene- (meth) acrylic acid copolymer resin is melted by the heat treatment for forming (foaming) the foaming agent-containing resin layer, the foaming agent-containing resin layer is foamed. This heat treatment can be used as a heat treatment for compounding.

In the present invention, by such heat treatment, the foaming agent-containing resin layer containing the ethylene- (meth) acrylic acid copolymer resin is melted, and the ionic group ( -COO ^-, etc.) is believed to surface strength by forming metal compound and an ionic cross-linking structure (pseudo crosslinking structure) of adjacent metal compound-containing resin layer is improved.

  As a manufacturing method of the resin laminate, as described above, for example, a foaming agent-containing resin layer containing a (I) ethylene- (meth) acrylic acid copolymer resin and a metal compound-containing resin layer are simultaneously formed on a fibrous sheet. After forming, or (II) after sequentially forming a foaming agent-containing resin layer and a metal compound-containing resin layer containing an ethylene- (meth) acrylic acid copolymer resin, the resin layer is heat-treated (heated and melted). It can be produced by (melt extrusion film formation). Thus, the foaming agent-containing resin layer containing the ethylene- (meth) acrylic acid copolymer resin and the metal compound-containing resin layer may be laminated separately or by coextrusion film formation. In the case of coextrusion film formation, for example, in the case of having a metal compound-containing resin layer on both sides, three layers of simultaneous film formation (three-layer coextrusion production) are performed by simultaneously extruding molten resin corresponding to the three layers. A multi-manifold type T die capable of forming a film) can be used.

  After forming the foaming agent-containing resin layer containing the ethylene- (meth) acrylic acid copolymer resin, electron beam irradiation can be performed before foaming. 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 formation of a pattern layer to be described later.

  Next, a pattern layer is formed on the metal compound-containing resin layer.

  Next, the foamed resin layer is formed by heating the foaming agent-containing resin layer. The heating conditions are not limited as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds. In addition, the heat treatment makes the ethylene- (meth) acrylic acid copolymer resin-containing resin layer and the metal compound-containing resin layer complex.

Since the resin laminate of the present invention is a composite of a foaming agent-containing resin layer and a metal compound-containing resin layer containing an ethylene- (meth) acrylic acid copolymer resin as a resin component by heat treatment, the resin of the foamed resin layer The surface strength of foamed wallpaper and the like can be further improved while maintaining the film forming property, and the productivity can be maintained well. This effect, by heat treatment, ethylene - (meth) melted acrylic acid copolymer resin, an ethylene - (meth) ionic group due to the acrylic acid copolymer resin (-COO ^-, etc.) is adjacent metal compound 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 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) non-foamed resin layer (metal compound-containing resin layer) / ii) foaming agent-containing resin layer / iii) non-foamed resin The layers were formed in the order of the layers so as to have a thickness of 10 μm / 70 μm / 10 μm.

  After the film formation, the surface of the iii) layer is laminated on a backing paper (WK-665DO, manufactured by Kojin Co., Ltd.) heated to 90 ° C., and i) an electron beam (195 kV, 30 kGy) is irradiated from above the layer to obtain a laminated resin The layer was resin cross-linked. Thereby, the laminated resin sheet original fabric was produced.

  Next, a corona discharge treatment was performed on the i) layer, and a texture pattern was printed using a water-based ink (“Hydric”, manufactured by Dainichi Seika Kogyo Co., Ltd.) as a pattern print by a gravure printing machine.

  Next, it is heated in an oven (220 ° C. × 35 seconds) to melt the resin layer, and at the same time, the foaming agent contained in the foaming agent-containing resin layer is foamed into a foamed resin layer, and the foaming agent-containing resin layer And the metal compound containing resin layer was compounded and the resin laminated sheet was formed.

  Next, the foam was embossed with a textured pattern to obtain a resin laminated sheet.

  Each layer was formed using the following components.

Example 2
Example 1 i) A non-foamed resin layer (metal compound-containing resin layer) was prepared in the same manner as in Example 1 except that the metal compound was changed to zinc oxide (particle diameter 0.6 μm).

Example 3
Iii of Example 1) Example 1 except that 30 parts of magnesium oxide (particle diameter 0.5 μm) was added to 100 parts of the ethylene-vinyl acetate copolymer resin of the non-foamed resin layer to obtain a metal compound-containing resin layer. It produced similarly.

Comparative Example 1
Example 1 i) A non-foamed resin layer (metal compound-containing resin layer) was prepared in the same manner as in Example 1 except that the metal compound was not included.

Comparative Example 2
It was produced in the same manner as in Example 1 except that the ethylene-methacrylic acid copolymer resin in the ii) foaming agent-containing resin layer of Example 1 was replaced with “polyethylene resin (Petrocene 208 manufactured by Tosoh Corporation)”.

Comparative Example 3
In Example 1, i) a non-foamed resin layer (metal compound-containing resin layer) polyethylene resin was prepared as an “ethylene-methacrylic acid copolymer resin (Nucrel N1560, Mitsui / DuPont Polychemical)” layer. Others are the same.

Test example 1
About the resin lamination sheet obtained by the Example and the comparative example, the scratch resistance and resin film-forming property were investigated.

Each test method and evaluation criteria are as follows.
(Resin film-forming properties)
The state of film formation during extrusion film formation of the outermost resin layer (single layer or two layers) of the wallpaper was observed. The evaluation criteria are as follows. ○: Resin cut, no hole. X: The film could not be formed due to the resin being cut or perforated.

(Scratch resistance)
This was performed in accordance with the performance evaluation method for surface-enhanced wallpaper established by the Wallpaper Industry Association. The evaluation criteria are as follows. ○: No change on the surface. Δ: Only the surface layer is damaged. X: Scratches reach the foamed resin layer.

  The evaluation results are as shown in Table 2 below.

In Examples 1 to 3, an ethylene- (meth) acrylic acid copolymer resin-containing resin layer is used as the foamed resin layer, and a metal compound-containing resin layer is used as the non-foamed resin layer. For this reason, in Examples 1-3, the ethylene- (meth) acrylic acid copolymer resin-containing resin layer and the metal compound-containing resin layer are combined (integrated) by heat treatment (heating and melting), and ethylene- ( The (meth) acrylic acid copolymer resin and the metal compound-containing non-foamed resin layer react to harden the foamed resin layer, forming a tougher resin layer than the conventional foamed resin layer containing ethylene-methacrylic acid copolymer resin. It was done. As a result, a resin laminated sheet having excellent scratch resistance could be produced, and the film could be formed without any trouble during extrusion film formation.

Claims (4)

A resin laminate obtained by heat-treating an unfoamed intermediate having a layer structure in which a metal compound-containing resin layer is laminated on one side or both sides of a foaming agent-containing resin layer, and making the foaming agent-containing resin layer a foamed resin layer Because
(1) The foaming agent-containing resin layer contains an ethylene- (meth) acrylic acid copolymer resin as a resin component,
(2) The resin component of the metal compound-containing resin layer is a copolymer composed of monomers that do not contain hydrogen bonds,
(3) The foaming agent-containing resin layer and the metal compound-containing resin layer are combined by the heat treatment or a separate heat treatment,
The resin laminated body characterized by the above-mentioned.   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, silicon oxide, boron nitride, aluminum nitride, and metal soap. The resin laminate according to 1.   The resin laminate according to claim 1 or 2, wherein the metal compound-containing resin layer contains 5% by weight or more of the metal compound.   The resin laminated sheet formed by laminating | stacking the resin laminated body in any one of Claims 1-3 on a fibrous sheet.