JP2017043009A - Laminate sheet, foam laminate sheet, and manufacturing method of these sheets - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foam laminate sheet simultaneously realizing excellent flow properties of a resin composition when depositing a foaming agent-containing resin layer and good strength of a foam resin layer of the foam laminate sheet, and a manufacturing method thereof.SOLUTION: A laminate sheet at least includes a foaming agent-containing resin layer on a substrate. In the laminate sheet, (1) the foaming agent-containing resin layer has a melt volume flow rate of 15-30 cm/10 min. at 130°C with regard to a resin composition for forming the layer, and (2) the foaming agent-containing resin layer contains an azodicarbonamide-based foaming agent and an oxybisbenzenesulfonyl hydrazide-based foaming agent.SELECTED DRAWING: None

Description

  The present invention relates to a laminated sheet, a foam laminated sheet, and a method for producing them.

  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 means the state (what is called an unfoamed raw material) before foaming of the said foaming laminated sheet.

  Conventionally, a foam laminated sheet in which at least a foamed resin layer is provided on a substrate has been used as foam wallpaper, various decorative materials, and the like. The foamed resin layer is formed by foaming a foaming agent-containing resin layer. The foaming agent-containing resin layer is formed by a coating method such as comma coating, a calendering method in which a resin composition is stretched into a sheet shape, and a T-die. It is known to form by extrusion film formation using an extruder such as.

  Among the methods for forming the foaming agent-containing resin layer, extrusion film formation is superior from the viewpoint of production efficiency. As an example of extrusion film formation, a three-layer coextrusion film formation in which a foaming agent-containing resin layer is sandwiched between non-foamed resin layers is known. However, when forming an extruded film, in order to prevent the foaming agent from unintentionally foaming before and after extrusion, the temperature, pressure, sheet take-up speed, foaming agent, etc. during extrusion are adjusted, Adopting a fluid resin composition is required.

  Therefore, in general, the strength of the foamed resin layer of the foamed laminated sheet as the final product tends to be insufficient due to the adoption of a highly fluid resin composition.

  In relation to the above, for example, Patent Document 1 is a specific example of the foamed laminated sheet. Patent document 1 discloses a method for producing wallpaper, and claim 1 includes the following: “100 parts by weight of a polyolefin resin having a melt flow rate (MFR) of 0.1 to 10 g / 10 min and 0.1 parts by weight of a foaming agent. As described above, a molding raw material resin containing 0.01 to 5 parts by weight of a processing aid (lubricant) is kneaded at a temperature lower than the decomposition temperature of the foaming agent, flame-retardant paper is laminated on the calendared unfoamed sheet, and then the foaming agent A method for producing wallpaper, which is characterized by heating to a decomposition temperature or higher and causing foaming, is disclosed. Patent Document 1 discloses that a molding material resin containing a polyolefin resin having low MFR having a relatively low value and low fluidity is combined with calender molding, so that foamed cells are crushed and curled (curved). It is said that a small amount of wallpaper can be provided ([0033] paragraph, etc.).

  Although the wallpaper of Patent Document 1 adopts calendar molding, as described above, it is desirable to use extrusion film formation from the viewpoint of production efficiency. For this purpose, a resin composition for forming a foaming agent-containing resin layer is used. It is necessary to adopt a highly liquid material. Therefore, it is required to develop a foamed laminated sheet and a method for producing the same, which have both good fluidity of the resin composition when forming the foaming agent-containing resin layer and good strength of the foamed resin layer of the foamed laminated sheet. ing.

Japanese Patent Laid-Open No. 11-91049

  The present invention provides a foamed laminated sheet and a method for producing the same, which satisfy both good fluidity of the resin composition when forming the foaming agent-containing resin layer and good strength of the foamed resin layer of the foamed laminated sheet. For the purpose. Another object of the present invention is to provide an original fabric (laminated sheet) suitable for manufacturing the foamed laminated sheet and a method for manufacturing the same.

  As a result of extensive research, the inventor has set the melt volume flow rate of the resin composition for forming the foaming agent-containing resin layer to a specific range, and further includes an azodicarbonamide-based foaming agent and oxybisbenzenesulfonylhydrazide. The present inventors have found that the above object can be achieved by using a foaming agent in combination, and have completed the present invention.

That is, the present invention relates to the following laminated sheets, foamed laminated sheets, and methods for producing them. 1. a laminated sheet having at least a foaming agent-containing resin layer on a substrate,
(1) the blowing agent-containing resin layer has a melt volume flow rate at 130 ° C. of the resin composition for forming the layer is 15 to 30 cm ^3/10 min,
(2) The foaming agent-containing resin layer contains an azodicarbonamide foaming agent and an oxybisbenzenesulfonyl hydrazide foaming agent.
A laminated sheet characterized by that.
2. The laminated sheet according to Item 1, wherein the foaming agent-containing resin layer contains 1 to 10 parts by mass of the azodicarbonamide-based foaming agent with respect to 100 parts by mass of the resin component of the layer.
3. The laminated sheet according to Item 1 or 2, wherein the foaming agent-containing resin layer contains 1 to 10 parts by mass of the oxybisbenzenesulfonylhydrazide-based foaming agent with respect to 100 parts by mass of the resin component of the layer. .
4. The laminated sheet according to any one of Items 1 to 3, wherein the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides.
5. A method for producing a laminated sheet comprising a step of laminating at least a foaming agent-containing resin layer on a substrate,
The resin composition for forming a foaming agent-containing resin layer has a melt volume flow rate at 130 ° C. is 15 to 30 cm ^3/10 min, and azodicarbonamide foaming agent and oxybisbenzenesulfonylhydrazide foaming Containing an agent,
A method for producing a laminated sheet.
6. The production method according to item 5, wherein the foaming agent-containing resin layer is laminated by extrusion film formation.
7. The production method according to Item 5, wherein the foaming agent-containing resin layer and the non-foamed resin layer laminated on one or both sides thereof are laminated by extrusion film formation.
8. 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 4.
9. A method for producing a foamed laminated sheet, wherein the foaming agent-containing resin layer of the laminated sheet according to any one of items 1 to 4 is foamed by heating.
10. The foamed laminated sheet as described in 8 above, which has an embossed uneven pattern on the front surface.

  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 has at least a foaming agent-containing resin layer on the substrate,
(1) the blowing agent-containing resin layer has a melt volume flow rate at 130 ° C. of the resin composition for forming the layer is 15 to 30 cm ^3/10 min,
(2) The foaming agent-containing resin layer contains an azodicarbonamide foaming agent and an oxybisbenzenesulfonyl hydrazide foaming agent.
It is characterized by that.

Laminated sheet of the present invention having the above characteristics, the blowing agent-containing resin layer melt volume flow rate at 130 ° C. of the resin composition for forming (hereinafter referred to as "MVR") is 15cm ^3/10 minutes or more Therefore, it has high fluidity, and the foaming agent-containing resin layer can be suitably formed by extrusion film formation without decomposing the foaming agent.

Further, the laminated sheet of the present invention, MVR at 130 ° C. of the resin composition for forming a foaming agent-containing resin layer is not more than 30 cm ^3/10 min, and azodicarbonamide foaming agent and oxy as blowing agent Since the bisbenzenesulfonyl hydrazide-based foaming agent is contained, it is possible to combine the good strength of the foamed resin layer of the foamed laminated sheet and the good fluidity of the resin composition. The foamed laminated sheet of the present invention can be widely used as various decorative materials including foamed wallpaper.

  The MVR of the resin composition for forming the foaming agent-containing resin layer is a value measured under the conditions of 130 ° C. and a load of 21.18 N by the method described in JIS K7210 B method. In the present specification, MVR is a value measured under the above conditions.

  Hereinafter, each layer which comprises a lamination sheet is demonstrated. In this specification, the direction in which the foaming agent-containing resin layer is laminated as viewed from the base material is referred to as “upper” or “front surface”, and the foaming agent-containing resin layer is laminated from the base material. The side opposite to the direction in which it is located is referred to as “down” or “back surface”.

Base material (fibrous sheet)
It does not limit as a base material, A well-known fiber sheet (backing paper) etc. can be utilized.
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 is included in the fibrous sheet used for this invention on classification.

Although the basis weight of the substrate is not critical, preferably about 50 to 300 g / m ^2, about 50~130g / m ² is more preferable.

Foaming agent-containing resin layer The laminated sheet of the present invention has at least a blowing agent-containing resin layer on the substrate.
As the resin component contained in the foaming agent-containing resin layer, vinyl chloride resins and olefin resins conventionally used for foamed sheets can be widely used. However, the vinyl chloride resin may cause the plasticizer to bleed over time. Therefore, from the viewpoint of enhancing the durability of the foamed sheet, an olefin resin is preferable to a vinyl chloride resin, and specifically, an ethylene resin is preferably contained.

  Examples of the ethylene-based resin include not only polyethylene (PE) but also an ethylene copolymer having monomers other than ethylene and components (hereinafter abbreviated as “ethylene copolymer”).

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

  Ethylene copolymers are suitable for extrusion film formation in terms of melting point and MVR. Examples of the ethylene copolymer include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer ( EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-methacrylic acid copolymer (EMAA), ethylene-α olefin copolymer, and the like. These ethylene copolymers can be used alone or in admixture of two or more. Among these ethylene copolymers, ethylene-vinyl acetate copolymer is particularly preferable. When any one of these and one or more other resins are used in combination, the ethylene-vinyl acetate copolymer is contained. The amount is preferably 70% by weight or more, and more preferably 80% by weight or more.

  Moreover, as for content of monomers other than ethylene, 5-25 weight% is preferable and, as for ethylene copolymer, 9-20 weight% is more preferable. By adopting such a copolymerization ratio, the extrusion film forming property is further enhanced. As a specific example, the ethylene-vinyl acetate copolymer has a vinyl acetate copolymerization ratio (VA amount) of preferably 9 to 25% by weight, more preferably 9 to 20% by weight. The ethylene-methyl methacrylate copolymer has a methyl methacrylate copolymerization ratio (MMA amount) of preferably 5 to 25% by weight, more preferably 5 to 15% by weight. Further, the ethylene-methacrylic acid copolymer is preferably 2 to 15% by mass, more preferably 5 to 11% by mass as the copolymerization ratio (MAA amount) of acrylic acid.

  As the ethylene resin, at least one selected from polyethylene (PE) and ethylene-vinyl acetate copolymer (EVA) is preferably used.

Further, it is preferred MVR of the resin component contained in the foaming agent-containing resin layer is 10 to 40 cm ^3/10 min. If the MVR is too large, the resin is too soft and the resulting resin layer may have insufficient scratch resistance.

  In the present invention, the resin composition forming the foaming agent-containing resin layer contains at least an azodicarbonamide (ADCA) foaming agent and an oxybisbenzenesulfonylhydrazide (OBSH) foaming agent in addition to the resin component. Specifically, a resin composition containing the above resin component, ADCA type foaming agent and OBSH type 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 ADCA foaming agent is a foaming agent mainly composed of azodicarbonamide. The azodicarbonamide is preferable in that it has a large amount of gas generation and is easy to handle.

  The OBSH foaming agent is a foaming agent mainly composed of oxybisbenzenesulfonyl hydrazide. As the above-mentioned OBSH-based blowing agent, the amount of gas generated is small compared to the ADCA-based blowing agent, but 4,4′-oxybisbenzenesulfonyl hydrazide is easy to form fine cells because the decomposition temperature is relatively fast. Is preferred.

  The content of the ADCA foaming agent in the foaming agent-containing resin layer is preferably 1 to 10 parts by weight and more preferably 2 to 6 parts by weight with respect to 100 parts by weight of the resin component of the foaming agent-containing resin layer. If the content of the ADCA foaming agent is too large, the foamed cell shape may be maximized due to excessive foaming, and coloring may be caused by the foaming residue. If the content of the ADCA foaming agent is too small, the foam volume may not be sufficient.

  The content of the OBSH-based foaming agent in the foaming agent-containing resin layer is preferably 1 to 10 parts by mass and more preferably 2 to 6 parts by mass with respect to 100 parts by mass of the resin component of the foaming agent-containing resin layer. When there is too much content of the OBSH type | system | group foaming agent, there exists a possibility that the fluidity | liquidity of a resin composition may fall. If the content of the OBSH foaming agent is too small, the foaming volume may not be sufficient, and the foam cell shape may be maximized due to excessive foaming due to the combined use with the ADCA foaming agent. Yes, there is a risk of coloring due to foaming residue.

  The content ratio of the ADCA foaming agent and the OBSH foaming agent in the foaming agent-containing resin layer is not limited, but ADCA foaming agent: OBSH foaming agent = 9.5: 0.5-1: 1 (mass ratio) It is preferable to set it to about 9: 1 to 3: 1 (mass ratio).

  The content of the thermally decomposable foaming agent other than the ADCA-based foaming agent and the OBSH-based foaming agent in the foaming agent-containing resin layer can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. From the viewpoint of expansion ratio, it is 5 times or more, preferably about 7 to 10 times, and the pyrolytic foaming agent is the sum of the contents of the above ADCA foaming agent and OBSH foaming agent. The amount is preferably about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component of the layer.

  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 matrix resins, and, as for content of these foaming adjuvants, about 1-5 mass parts is more preferable.

  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). These may be used alone or in combination. The content of the pigment is preferably about 1 to 50 parts by mass, more preferably about 2 to 30 parts by mass with respect to 100 parts by mass of the resin component of the foaming agent-containing resin layer, although it depends on the required color tone density.

  In the present invention, the foaming agent-containing resin layer may be resin-crosslinked by electron beam irradiation. What is necessary is just to implement according to the method described in the postscript manufacturing method as a method of irradiating an electron beam to a foaming agent containing resin layer, and the method of making it foam.

In the laminated sheet of the present invention, MVR of 130 ° C. of the resin composition (compound) to form a blowing agent-containing resin layer is 15 to 30 cm ^3/10 min. By setting the MVR of the resin composition within this range, the foaming agent-containing resin layer can be suitably formed by extrusion film formation, and the foaming characteristics can be improved. Furthermore, MVR is preferably 16~25cm ^3/10 min of the resin composition, 16~22cm ^3/10 min is more preferable.

  The thickness of the foaming agent-containing resin layer is preferably about 40 to 200 μm.

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 fibrous sheet 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 fibrous sheet. .

  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% by mass, more preferably 15 to 41% by mass.

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

  The non-foamed resin layer A may be formed on the top surface of the foaming agent-containing resin layer for the purpose of clarifying the pattern when forming the pattern layer or improving the scratch resistance of the foamed resin layer.

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

  Examples of polyolefin resins include polyethylene (low density polyethylene (LDPE) or high density polyethylene (HDPE)), polypropylene, polybutene, polybutadiene, polyisoprene, and other resins, and ethylene and α-olefins having 4 or more carbon atoms. Polymers (linear low density polyethylene (LLDPE)), ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer and other ethylene ( Examples include at least one of a (meth) acrylic acid copolymer, an ethylene-vinyl acetate copolymer (EVA), a saponified ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, and an ionomer. In the present invention, in particular, when a vinyl chloride resin is used as the resin in the foaming agent-containing resin layer, in order to obtain durability of the laminated sheet, the non-foamed resin layer A (particularly an ethylene-vinyl alcohol copolymer layer) is used. It is preferable to form. In addition, "(meth) acrylic acid" means acrylic acid and / or methacrylic acid, and the same applies to other portions described as (meth).

  The thickness of the non-foamed resin layer A is not limited, but is preferably about 2 to 50 μm, and 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 is also preferable from the viewpoint of manufacturing described later.

Pattern Pattern Layer In the laminated sheet of the present invention, a pattern pattern layer may be formed on a resin layer (foaming agent-containing resin layer, non-foamed resin layer A, etc.) or a primer layer described later, if necessary.

  The pattern layer imparts design properties to the laminated sheet and the foamed laminated sheet. Examples of the design pattern include a 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, an abstract pattern, a flower pattern, etc. You can choose according to your purpose.

  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 (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.

A primer layer may be formed as necessary on the primer layer resin layer (foaming agent-containing resin layer, non-foamed resin layer A, etc.) or the pattern layer.

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

  Examples of the acrylic include, for example, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, and (meth) acrylate methyl- (meth) acrylic acid. (Meth) such as butyl copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer An acrylic resin made of a homopolymer or a copolymer containing an acrylate ester may be mentioned.

  Polyurethane is a composition having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent).

  As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.

  As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate, or aliphatic (or alicyclic) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate ) Isocyanates are used.

  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.

Surface protective layer Resin layer (foaming agent-containing resin layer, non-foamed resin layer A, etc.), pattern layer or primer layer has a surface protective layer intended for gloss adjustment and / or pattern layer protection May be.

  The kind of surface protective layer is not limited. If it is a surface protective layer aiming at gloss adjustment, there exists a surface protective layer containing known fillers, such as a silica, for example. As a method for forming the surface protective layer, a known method such as gravure printing can be employed.

  When a surface protective layer is formed for the purpose of surface strength (scratch resistance, etc.), contamination resistance, pattern layer protection, etc. of laminated sheets, those containing ionizing radiation curable resins as resin components are suitable. is there. The ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation.

An embossed pattern may be provided on the front surface of the embossed laminated sheet or the foamed laminated sheet. In this case, what is necessary is just to emboss from the uppermost surface layer (opposite side to the fibrous sheet). Embossing can be performed by known means such as pressing an embossed plate. For example, when the outermost surface layer is a surface protective layer, a desired embossed pattern can be formed by pressing the embossed plate after heat-softening the front surface. 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 sand texture, a hairline, a geometric pattern, a multi-row groove, and a contour pattern.

≪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.

≪Laminated sheet and foamed laminated sheet manufacturing method≫
As a manufacturing method of a lamination sheet, the manufacturing method which laminates | stacks the said foaming agent containing resin layer at least on a base material is mentioned, for example.

  Moreover, as a manufacturing method of a foaming laminated sheet, the manufacturing method of a laminated sheet WHEREIN: After laminating | stacking the said foaming agent containing resin layer, the manufacturing method which foams the said foaming agent containing resin layer by heat processing and makes it a foaming resin layer is mentioned. It is done.

  When the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides, the non-foamed resin layer B and / or the non-foamed resin layer A may be formed by extrusion film formation, Although it may be formed by heat lamination, co-extrusion film formation using 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 an inorganic substance such as a pigment is contained in the resin composition forming the foaming agent-containing resin layer, when forming the foaming agent-containing resin layer by extrusion film formation, the extrusion port (so-called die lip) of the extruder is used. An inorganic residue (so-called eyes) is likely to be generated, and this tends to be a foreign matter on the surface of the foaming agent-containing resin layer. Therefore, when an inorganic substance such as a pigment is contained in the resin composition forming the foaming agent-containing resin layer, it is preferable to form a three-layer coextrusion film as described above so that the non-foamed resin layer does not contain an inorganic substance. . That is, it is possible to suppress the occurrence of the eyes by co-extrusion film formation in a mode in which the foaming agent-containing resin layer is sandwiched between non-foamed resin layers not containing an inorganic substance.

  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.

  On the foaming agent-containing resin layer, if necessary, a pattern layer and a primer layer are formed in any order, and if necessary, a surface protective layer is formed to form a laminated sheet, and then heat-treated. A foaming laminated sheet is obtained by making the foaming agent-containing resin layer into a foamed resin layer. FIG. 1 illustrates a layer structure of a laminated sheet in which a non-foamed resin layer B, a foaming agent-containing resin layer, a non-foamed resin layer A, a design pattern layer, a primer layer, and a surface protective layer are sequentially formed on a fibrous sheet. . Each of these layers can be laminated by combining coating such as printing and coating, extrusion film formation and the like, and coating such as printing and coating can be performed according to a conventional method.

  The heat treatment conditions may be any conditions 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 25 to 80 seconds. Further, when an embossed pattern is added, it is carried out by a known means such as pressing an embossed plate.

Laminated sheet of the present invention, since MVR at 130 ° C. of the resin composition for forming a foaming agent-containing resin layer is 15cm ^3/10 minutes or more, has a high fluidity, to decompose the blowing agent The foaming agent-containing resin layer can be suitably formed by extrusion film formation. Further, the laminated sheet of the present invention, MVR at 130 ° C. of the resin composition for forming a foaming agent-containing resin layer is not more than 30 cm ^3/10 min, and azodicarbonamide foaming agent and oxy as blowing agent Since the bisbenzenesulfonyl hydrazide-based foaming agent is contained, it is possible to combine the good strength of the foamed resin layer of the foamed laminated sheet and the good fluidity of the resin composition. The foamed laminated sheet of the present invention can be widely used as various decorative materials including foamed wallpaper.

It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the lamination sheet of this invention.

  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.

Examples 1-4 and Comparative Examples 1-3
≪Preparation of resin composition containing foaming agent≫
Seven types of resin compositions shown in Table 1 below were prepared by kneading.

≪Preparation of foamed laminated sheet: extrusion film formation≫
Using a T-die extruder capable of forming three types and three layers of each resin composition, the thickness of the non-foamed resin A, the foaming agent-containing resin, and the non-foamed resin B is 5 μm, 60 μm, and 5 μm. To form a film. Film formation was performed at an extrusion cylinder temperature of 130 ° C. and a T-die temperature of 130 ° C. Lamination was carried out so that the non-foamed resin layer B would come on 65 g / m ² backing paper (WK-665 KJ special paper) to obtain a laminated sheet having 3 types and 3 layers of resin layers.
Non-foamed resin A: Novatec LC701: LDPE (Nippon Polyethylene)
Non-foamed resin B: EVAFLEX EV150: EVA (Mitsui DuPont Polychemical)

  Furthermore, the laminated sheet was heated at 220 ° C. for 35 seconds to foam the foaming agent-containing resin layer to obtain a foamed laminated sheet.

≪Evaluation of each foam laminated sheet≫
Table 2 shows the MVR (130 ° C.) and expansion ratio of the resin composition containing the foaming agent used in each Example and Comparative Example, and also relates to the extrusion film formability of each resin composition and each foamed laminated sheet. Table 2 shows the evaluation results of the surface condition and scratch resistance.

  Evaluation methods and evaluation criteria were as follows.

Extrusion film forming property For each example and comparative example, the screw rotation speed of the extruder was set so that the predetermined thickness was obtained, and the three types and three layers of resin layers were extruded and formed, and the rotation speed was fixed. The take-up speed was changed as it was, and the evaluation was made at the take-out speed.
○: The take-up speed was 30 m / min or more.
Δ: The take-up speed was 20 m / min or more and less than 30 m / min.
X: The take-up speed was less than 20 m / min.

The surface state of the surface state foamed laminated sheet was visually observed and evaluated according to the following evaluation criteria.
○: The surface was flat and there were no holes due to foam breakage of the foamed cells.
X: There was a hole due to foam breakage of the foam cell.

The foamed laminated sheets prepared in the scratch-resistant examples and comparative examples were tested according to the performance evaluation method of the surface-enhanced wallpaper established by the Wallpaper Industry Association, and evaluated based on the following evaluation criteria.
○: A slight change is observed on the surface.
Δ: The surface layer was slightly broken and reached the foamed resin layer.
X: The surface layer was greatly broken and the foamed resin layer was damaged.

1. Base material (fibrous sheet)
2. Non-foamed resin layer B
3. Foaming agent-containing resin layer
4. Non-foamed resin layer A
5. Pattern pattern layer
6. Primer layer
7. Surface protective layer

Claims (10)

A laminated sheet having at least a foaming agent-containing resin layer on a substrate,
(1) the blowing agent-containing resin layer has a melt volume flow rate at 130 ° C. of the resin composition for forming the layer is 15 to 30 cm ^3/10 min,
(2) The foaming agent-containing resin layer contains an azodicarbonamide foaming agent and an oxybisbenzenesulfonyl hydrazide foaming agent.
A laminated sheet characterized by that.   2. The laminated sheet according to claim 1, wherein the foaming agent-containing resin layer contains 1 to 10 parts by mass of the azodicarbonamide-based foaming agent with respect to 100 parts by mass of the resin component of the layer.   3. The laminated sheet according to claim 1, wherein the foaming agent-containing resin layer contains 1 to 10 parts by mass of the oxybisbenzenesulfonylhydrazide-based foaming agent with respect to 100 parts by mass of the resin component of the layer.   4. The laminated sheet according to claim 1, wherein the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides. A method for producing a laminated sheet comprising a step of laminating at least a foaming agent-containing resin layer on a substrate,
The resin composition for forming a foaming agent-containing resin layer has a melt volume flow rate at 130 ° C. is 15 to 30 cm ^3/10 min, and azodicarbonamide foaming agent and oxybisbenzenesulfonylhydrazide foaming Containing an agent,
A method for producing a laminated sheet.   6. The production method according to claim 5, wherein the foaming agent-containing resin layer is laminated by extrusion film formation.   6. The production method according to claim 5, wherein the foaming agent-containing resin layer and the non-foamed resin layer laminated on one or both sides thereof are laminated by extrusion film formation.   A foamed laminated sheet obtained by foaming the foaming agent-containing resin layer of the laminated sheet according to any one of claims 1 to 4.   5. A method for producing a foamed laminated sheet, wherein the foaming agent-containing resin layer of the laminated sheet according to any one of claims 1 to 4 is foamed by heating.   9. The foamed laminated sheet according to claim 8, which has an embossed uneven pattern on the front surface.

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