JP2013208715A - Laminated sheet and foamed laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new laminated sheet and foamed laminated sheet, which exhibits a superior deodorant function, and have a superior design.SOLUTION: In a laminated sheet, at least a foaming agent containing resin layer, an absorbent containing resin layer for absorbing volatile compounds, and a picture pattern layer are sequentially laminated on a substrate. (1) The absorbent containing resin layer includes an inorganic absorbent. (2) The content of the inorganic absorbent is 50 pts.mass or more with respect to 100 pts.mass of resin component of the absorbent containing resin layer.

Description

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

  In recent years, with the improvement of energy conservation orientation, there is a demand for highly airtight houses with improved energy efficiency. For example, it is known that in a house using the outer heat insulation method, airtightness is improved and air conditioning efficiency in summer and winter is improved.

  As the airtightness of a house is improved, for example, a problem that a bad odor caused by a volatile compound generated from tobacco smoke, human beings, furniture, garbage, and the like is likely to be swallowed indoors.

  As measures against the above problems, there is an increasing need for interior materials for buildings having a deodorizing function. Examples of building interior materials include wall materials, ceiling materials, floor materials, etc., but it is considered effective for deodorization to add a deodorizing function to wall materials having the largest area as interior materials. Various wallpaper containing an adsorbent for volatile compounds has been proposed.

  For example, in Patent Document 1, a resin layer containing a formaldehyde scavenger (adsorbent) such as dicyandiamide is provided on a paper base, and the resin layer is foamed for the purpose of giving a soft touch to the surface. A layered wallpaper (foamed laminated sheet) is disclosed.

  Since the foamed resin layer occupies most of the volume of the wallpaper, the foamed laminated sheet of Patent Document 1 can contain a large amount of adsorbent. However, since the foamed resin layer is a relatively thick layer, the foamed laminated sheet containing the adsorbent in the foamed resin layer as described above is difficult to make the adsorbent unevenly distributed in the vicinity of the surface, and has a deodorizing function corresponding to the addition amount. It is difficult to obtain. Further, since the adsorbent is present in the same layer as the foaming agent, the adsorption of the foaming gas to the adsorbent proceeds in the foaming step, and it is difficult to obtain a desired deodorizing function. In addition, since organic adsorbents such as dicyandiamide generally have low heat resistance, they are easily decomposed and altered in the resin layer forming process such as resin coating and molding, and the heating process such as foaming. There is a problem that the odor function is greatly reduced.

  Patent Document 2 includes a base material layer and a surface layer, and a deodorant (adsorbent) made of a porous inorganic substance, an amine compound, and a metal oxide is permeated by a binder resin above the surface layer. Deodorant wallpaper (laminated sheet) fixed together with the agent is described.

  However, in such a laminated sheet, a picture layer is provided below the surface layer to which the adsorbent is fixed. In such a laminated sheet, when a large amount of inorganic particles are fixed to the surface layer in order to obtain a high deodorizing function, there is a problem that the transparency of the surface layer is lost and the design is impaired.

  Therefore, development of a new laminated sheet and a foamed laminated sheet that have a high deodorizing function and excellent in design is demanded.

Japanese Patent Application Laid-Open No. 10-1003004 JP 2006-348430 A

  An object of the present invention is to provide a new laminated sheet and a foamed laminated sheet that exhibit a high deodorizing function and are excellent in design.

  As a result of earnest research to achieve the above object, the present inventor has, on the base material, a laminate having at least a foaming agent-containing resin layer, an adsorbent-containing resin layer that adsorbs a volatile compound, and a pattern layer in this order. In the sheet, the adsorbent contained in the adsorbent-containing resin layer is an inorganic adsorbent, and the adsorbent-containing resin layer contains 50 parts by mass or more of the inorganic adsorbent with respect to 100 parts by mass of the resin component. The present inventors have found that the above object can be achieved, and have completed the present invention.

That is, the present invention relates to the following laminated sheet and foamed laminated sheet.
1. A laminated sheet in which at least a foaming agent-containing resin layer, an adsorbent-containing resin layer that adsorbs a volatile compound, and a design pattern layer are sequentially laminated on a substrate,
(1) The adsorbent-containing resin layer contains an inorganic adsorbent,
(2) The content of the inorganic adsorbent is 50 parts by mass or more with respect to 100 parts by mass of the resin component of the adsorbent-containing resin layer.
1. A laminated sheet characterized by Item 2. The laminated sheet according to Item 1, wherein a surface protective layer is provided on the design pattern layer.
3. The said foaming agent containing resin layer is a lamination sheet of said claim | item 1 or 2 which has a non-foaming resin layer in the single side | surface or both surfaces.
4). Item 4. The laminated sheet according to any one of Items 1 to 3, wherein the foaming agent-containing resin layer is resin-crosslinked by electron beam irradiation.
5. The foaming lamination sheet obtained by making the said foaming agent containing resin layer of the lamination sheet in any one of said items 1-4 foam.

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

≪Laminated sheet≫
In the laminated sheet of the present invention, at least a foaming agent-containing resin layer, an adsorbent-containing resin layer that adsorbs a volatile compound, and a pattern layer are sequentially laminated on a substrate.
(1) The adsorbent-containing resin layer contains an inorganic adsorbent,
(2) The content of the inorganic adsorbent is 50 parts by mass or more with respect to 100 parts by mass of the resin component of the adsorbent-containing resin layer.
It is characterized by that.

  In the laminated sheet of the present invention having the above characteristics, the adsorbent is not a foaming agent-containing resin layer, but is contained in a resin layer (adsorbent-containing resin layer) separately provided on the surface side of the foaming agent-containing resin layer. The foaming gas generated at the time of foaming of the foaming agent-containing resin layer is difficult to be adsorbed by the adsorbent, and the deterioration of the deodorizing function can be suppressed.

  Moreover, since an adsorbent can be arrange | positioned in the surface vicinity of a lamination sheet, the high deodorizing function according to content of an adsorbent can be expressed.

  In addition, since the laminated sheet of the present invention uses an inorganic adsorbent as the adsorbent, it is difficult for the adsorbent to be decomposed in the resin layer forming step and the heating step such as foaming, so the deodorizing function is reduced by heating. Can be suppressed.

  Furthermore, since the laminated sheet of the present invention has an adsorbent-containing resin layer under the pattern layer, even if the content of the inorganic adsorbent is a predetermined amount or more in order to obtain a high deodorizing function, it depends on the pattern layer. Since it is difficult to impair the design, it is possible to exhibit a high deodorizing function and to exhibit an excellent design.

  These effects are also the same in the foamed laminated sheet obtained by foaming the foaming agent-containing resin layer.

It does not limit as a base material 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.

Although the basis weight of the substrate is not critical, preferably about 50 to 300 g / ^{m 2,} about 50 to 120 / ^{m 2} is more preferable.

Foaming agent-containing resin layer For the foaming agent-containing resin layer used in the present invention, vinyl chloride resins, olefin resins, and the like conventionally used for wall coverings can be widely adopted as resin components. From the viewpoint of enhancing the durability of the laminated 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 ethylene (hereinafter abbreviated as “ethylene copolymer”).

  Ethylene copolymers are suitable for extrusion film formation from the viewpoints of melting point and melt flow rate (MFR). Examples of the ethylene copolymer include an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene-acrylic acid copolymer (EAA), and an ethylene-ethyl acrylate copolymer ( EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-methacrylic acid copolymer (EMAA) 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 and ethylene-methyl methacrylate copolymer are particularly preferred. When any one of these is used in combination with one or more other resins, ethylene -The content of the vinyl acetate copolymer and the ethylene-methyl methacrylate copolymer is preferably 70% by mass or more, and more preferably 80% by mass or more.

  Moreover, 5-25 mass% is preferable as content of monomers other than ethylene, and, as for ethylene copolymer, 9-20 mass% 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 mass, more preferably 9 to 20% by mass. Moreover, 5-25 mass% is preferable as a copolymerization ratio (MMA amount) of a methyl methacrylate, and, as for the ethylene-methyl methacrylate copolymer, 5-15 mass% is more preferable.

  In the present invention, the resin component contained in the foaming agent-containing resin layer preferably has an MFR measured at 190 ° C. and a load of 21.18 N described in JIS K 6922 of 10 to 25 g / 10 minutes. When the MFR is within the above range, there is little increase in temperature when the foaming agent-containing resin layer is formed by extrusion film formation, and the film can be formed in a non-foamed state. It can be printed on any surface and there are few patterns missing. If the MFR is too large, the resin is too soft, and the formed foamed resin layer may have insufficient scratch resistance.

  As the resin composition for forming the foaming agent-containing resin layer, for example, a resin composition containing the above resin component, inorganic filler, pigment, pyrolytic foaming agent, foaming aid, crosslinking aid, cell modifier and the like. It can be suitably used. In addition, stabilizers, lubricants and the like can be used as additives.

  Examples of the thermally decomposable foaming agent include azo series such as azodicarbonamide (ADCA) and azobisformamide; hydrazide series such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide. The content of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. From the viewpoint of the expansion ratio, it is 7 times or more, preferably about 7 to 10 times, and the pyrolytic foaming agent is preferably about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

  The foaming aid is preferably a metal oxide and / or a fatty acid metal salt. For example, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, laurin Magnesium acid, zinc oxide, magnesium oxide and the like can be used. About 0.001-20 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of these foaming adjuvants, about 0.001-10 mass parts is more preferable.

  When these foaming aids, EMAA, and ADCA foaming agents are used in combination, the effect of the original foaming aid is impaired by the reaction of the acrylic acid portion of EMAA with the foaming aid in the foaming step. There is a problem. Therefore, when EMAA and ADCA foaming agent are used in combination, it is preferable to use a carboxylic acid hydrazide compound as a foaming aid as described in JP-A-2009-197219. At this time, it is preferable to use about 0.2-1 mass part of carboxylic acid hydrazide compounds with respect to 1 mass part of ADCA foaming agent.

  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. About 0-100 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of an inorganic filler, about 20-70 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). About 10-50 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of a pigment, about 15-30 mass parts is more preferable.

  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 manufacturing method mentioned later as the method of irradiating an electron beam to a foaming agent containing resin layer, and the method of making it foam. The thickness of the foaming agent-containing resin layer is preferably about 40 to 100 μm, and the thickness of the foamed resin layer after foaming is preferably about 300 to 700 μm.

Non-foamed resin layer A
In order to protect the foaming agent-containing resin layer mainly on the top surface of the foaming agent-containing resin layer and to prevent the functional degradation of the inorganic adsorbent due to volatile components such as gas generated in the process of foaming the foaming agent-containing resin layer The non-foamed resin layer A may be formed. In addition, the formation of the non-foamed resin layer A suppresses a decrease in the deodorizing function of the inorganic adsorbent due to bleeding out of the plasticizer even when the plasticizer is included in the foaming agent-containing resin layer. can do. The effect of suppressing the deterioration of the deodorizing function of the inorganic adsorbent due to the bleed-out of the plasticizer is that the plasticizer bleed-out occurs in the layer constituting the laminated sheet of the present invention such as the foaming agent-containing resin layer. This is particularly noticeable when an easy vinyl chloride resin is used.

  Examples of the resin component of the non-foamed resin layer A include polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, fluorine resins, and the like, among which polyolefin resins are preferable.

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-olefin 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 thereof 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.
The thickness of the non-foamed resin layer A is not limited, but is preferably about 2 to 50 μm.

  In the present invention, also from the viewpoint of production described later, when the foaming agent-containing resin layer is provided, an embodiment in which the non-foaming resin layer B, the foaming agent-containing resin layer, and the non-foaming resin layer A are sequentially formed is preferable. The non-foamed resin layer B and / or the non-foamed resin layer A may be formed by extrusion film formation, or may be formed by heat laminating each film.

Non-foamed resin layer B
In the present invention, a non-foamed resin layer B (adhesive resin layer) may be further provided on the back surface (surface on which the base material is laminated) of the foaming agent-containing resin layer for the purpose of improving the adhesive force with the base material. Good.

The resin component of the adhesive resin layer is not particularly limited, but an ethylene-vinyl acetate copolymer (EVA) is preferable. EVA can be a known or commercially available one. In particular, the vinyl acetate component (VA component) is preferably 10 to 46 mass%, more preferably 15 to 41 mass%.
The thickness of the adhesive resin layer is not limited, but is preferably about 5 to 50 μm.

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

Adsorbent-containing resin layer An adsorbent-containing resin layer is formed between the foam-containing resin layer and the pattern layer. This adsorbent-containing resin layer is provided separately from the foaming agent-containing resin layer, thereby suppressing a decrease in deodorizing function due to the foaming gas adsorbing to the inorganic adsorbent. Moreover, the said adsorbent containing resin layer is suppressing the fall of the designability of the pattern pattern layer by an inorganic type adsorption agent by being provided under a pattern pattern layer.

  Furthermore, when the foaming agent-containing resin layer contains an azo-based foaming agent such as azodicarbonamide (ADCA), there is a concern that the undecomposed foaming agent remains and yellowing remains in the foamed resin layer. According to the invention, since a large amount of an inorganic adsorbent is used in the upper layer of the foaming agent-containing resin, yellowing can be concealed by the inorganic adsorbent, and the design can be improved.

Examples of the resin component of the adsorbent-containing resin layer include an acrylic resin, a urethane resin, a urethane-acrylic resin, and the like as the resin component. From these resins, the adsorbent content and an adjacent layer are formed. What is necessary is just to select suitably from an adhesive viewpoint in consideration of the kind of resin component. Although not limiting the coating amount of the adsorbent-containing resin composition for forming an adsorbent-containing resin layer is preferably about 0.2~5.0g / ^{m 2,} about 0.5 to 2.0 g / ^{m 2} is More preferred.

  The adsorbent-containing resin layer contains an inorganic adsorbent. Examples of the inorganic adsorbent include aldehydes such as formaldehyde and acetaldehyde; basic compounds such as ammonia; sulfur compounds such as hydrogen sulfide; acidic compounds such as acetic acid and isovaleric acid; As long as it has an adsorptive power to compounds and does not cause discoloration or the like, it can be widely used. In the present invention, by using an inorganic adsorbent having excellent heat resistance, it is possible to suppress a decrease in deodorizing function due to decomposition of the adsorbent in a resin layer forming step or a heating step such as foaming.

  In the present invention, the volatile compound adsorption mechanism of the inorganic adsorbent may be either chemical adsorption or physical adsorption, but the chemical adsorption type adsorbent that hardly releases the adsorbed volatile compound again. Is preferably used. Here, “chemical adsorption” is adsorption of volatile compounds by chemical bonds, and “physical adsorption” is adsorption of volatile compounds by van der Waals force.

  As the inorganic adsorbent, a known inorganic adsorbent can be used, and an organic-inorganic composite adsorbent is included in addition to the inorganic adsorbent. These inorganic adsorbents can be used singly or in appropriate combination of two or more.

  Examples of the inorganic adsorbent include porous inorganic compounds such as zeolite, silica gel (silicon dioxide), activated carbon, and mica, hydroxyapatite, and compounds carrying metals (silver, copper, zinc, etc.). .

  From the viewpoint of adsorption performance, the zeolite is preferably a mordenite type, Y type, or ZSM-5 type, and more preferably a metal-supported ZSM-5 type zeolite.

  Examples of the organic-inorganic composite adsorbent include composite materials in which organic compounds such as amines, ureas, amides, imides, hydrazides, azoles and azines are supported on inorganic compounds. In particular, when considering adsorption of aldehydes, etc., adsorption with organic compounds such as amines is generally effective, but when using organic-inorganic composite adsorbents in which the above organic compounds are supported on inorganic compounds It is preferable in that both deodorizing performance and heat resistance can be achieved.

  Examples of the inorganic compound that can be used as the carrier include silicon dioxide, activated carbon, sepiolite, and mica from the viewpoint of heat resistance. Among these inorganic compounds, it is particularly preferable to use a porous body of silicon dioxide from the viewpoint of adsorption performance.

More specifically, as the organic-inorganic composite adsorbent, as described in paragraph [0016] of JP-A-2003-52800, an amine compound having a primary amino group is supported on the above-described inorganic compound. And composite materials. As compounds of amines having a primary amino group, as described in paragraph [0020] of the same publication, aliphatic compounds include “H ₂ N— (CH ₂ CH ₂ —NH) n—CH ₂ CH”. ₂ NH ₂ (n is an integer of 0 or more and 3 or less) ”is preferable, and aniline is preferable as the aromatic compound.

  The average particle size of the inorganic adsorbent is preferably 1 to 7 μm, and more preferably 2 to 5 μm. Here, the average particle diameter of the inorganic adsorbent in the present specification is a value measured by a laser diffraction scattering method.

  In the laminated sheet of the present invention, the content of the inorganic adsorbent contained in the adsorbent-containing resin layer is 50 parts by mass or more with respect to 100 parts by mass of the resin component of the adsorbent-containing resin layer. When the adsorbent-containing resin layer contains 50 parts by mass or more of the inorganic adsorbent, the deodorizing function can be sufficiently exhibited. Furthermore, when the foaming agent-containing resin layer contains an azo foaming agent such as azodicarbonamide (ADCA), there is a concern that the undecomposed foaming agent remains and yellowing remains in the foamed resin layer. Since it has an adsorbent-containing resin layer containing 50 parts by mass or more of an inorganic adsorbent in the upper layer of the adsorbent-containing resin layer, the yellowness can be concealed by the inorganic adsorbent, and the design can be improved. .

  The content of the inorganic adsorbent contained in the adsorbent-containing resin layer is preferably 120 parts by mass or less and 100 parts by mass or less with respect to 100 parts by mass of the resin component of the adsorbent-containing resin layer. Is more preferable. When there is too much content of the said inorganic type adsorption agent, there exists a possibility that it may be inferior to the printability at the time of forming a pattern pattern layer.

Picture Pattern Layer A picture pattern layer is laminated on the front surface of the adsorbent-containing resin layer.
The pattern layer imparts design properties to the foamed laminated sheet. Examples of the design pattern include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern. The pattern can be selected according to the 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 can be known or commercially available.

  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.
As the colorant, a pigment used in a foaming agent-containing resin layer can be used as appropriate.

  The thickness of the design pattern layer varies depending on the type of design pattern, but is generally preferably about 0.1 to 10 μm.

As needed between each layer, such as between the primer layer non-foamed resin layer A and the adsorbent-containing resin layer, between the adsorbent-containing resin layer and the pattern layer, between the pattern layer and the surface protective layer, etc. A primer layer may be formed.

  Examples of the resin contained in the primer layer include an acrylic resin, a urethane resin, a urethane-acrylic resin, and the like. Among these resins, an adhesive is used depending on the type of the adjacent layer of the primer layer. It can be appropriately selected in consideration of improvement.

Although the coating amount of the primer layer is not critical, preferably about 0.2~5.0g / ^{m 2,} about 0.5 to 2.0 g / ^{m 2} is more preferable.

Surface Protective Layer In the laminated sheet of the present invention, a surface protective layer may be further formed on the adsorbent-containing resin layer for the purpose of gloss adjustment and surface protection.

  The kind of surface protective layer is not limited. A one-component curable resin or a two-component curable resin using a binder resin or solvent equivalent to the pattern layer, such as an acrylic resin or a urethane resin, can be used.

  In the case of forming a surface protective layer for the purpose of surface strength (scratch resistance, etc.) of foamed wallpaper, contamination resistance, and protection of the pattern layer, the one containing an ionizing radiation curable resin as a resin component Is preferred.

  The ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation. The ionizing radiation curable resin is not particularly limited, and a prepolymer (including an oligomer) containing a radical polymerizable double bond capable of undergoing a polymerization and crosslinking reaction by irradiation of an electron beam in the molecule and / or a transparent mainly composed of a monomer. Resin can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a cross-linking curing reaction. Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group. It is desirable to include a silicone resin for the purpose of improving contamination.

  For gloss adjustment, it is desirable to form a surface protective layer containing a known filler such as silica. In addition, an additive such as silicone can be added in order to impart slipperiness and easy wiping of dirt. In addition, an adsorbent, an antibacterial agent, an antiallergen agent, etc. may be added as needed and the functionality may be provided. Here, when using an inorganic material as these additives, the content of the inorganic material is 20 parts by mass or less with respect to 100 parts by mass of the resin component of the surface protective layer so as not to impair the design of the pattern layer. It is preferable that

  As a method for forming the surface protective layer, a known method such as gravure printing can be employed. In addition, when the adhesiveness of a pattern pattern layer and a surface protective layer is not fully acquired, a surface protective layer can also be provided after carrying out the adhesion process (primer process) of the surface of a pattern pattern layer.

  The thickness of the surface protective layer is not limited, but is preferably about 0.1 to 15 μm.

≪Foamed laminated sheet≫
The foamed laminated sheet of the present invention can be obtained by foaming the foaming agent-containing resin layer of the laminated sheet. The heating conditions at the time of foaming are not limited as long as the foamed resin layer is formed by the decomposition of the foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds.

The foamed laminated sheet of the present invention may be embossed from the top surface layer.
Examples of the embossed pattern include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain texture, a hairline, and a multiline groove.

≪Method for producing laminated sheet and foam laminated sheet≫
As a method for producing a laminated sheet, first, a foaming agent-containing resin layer and an adsorbent-containing resin layer are formed on a substrate using an extruder or the like, and bonded to a preheated substrate to obtain a laminate. Can do. At this time, it is possible to use a multi-manifold type T-die capable of simultaneously forming two layers by extruding molten resin corresponding to two layers. In this case, the resin composition for forming the foaming agent-containing resin layer and the resin composition for forming the adsorbent-containing resin layer are placed in separate cylinders, and two types and two layers are simultaneously extruded to form and laminate do it. Alternatively, a laminate in which two types and two layers are simultaneously formed in advance may be prepared, placed on the substrate, and bonded to the substrate by thermal lamination.

  When the foaming agent-containing resin layer has non-foaming resin layers on both sides (non-foaming resin layer A / foaming agent-containing resin layer / non-foaming resin layer B), a multi-manifold type capable of simultaneously forming three layers It is preferable that the molten resin corresponding to the three layers is simultaneously extruded and formed using a T-die extruder.

  In addition, 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, an 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 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. That is, it is possible to suppress the occurrence of the above-mentioned corners by co-extrusion film formation in a mode in which the foaming agent-containing resin layer is sandwiched between non-foamed resin layers.

  After forming the foaming agent-containing resin layer, electron beam irradiation may be performed. Thereby, a resin component can be bridge | crosslinked and the surface strength of a foamed resin layer, a foaming characteristic, etc. can be adjusted. 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.

After simultaneous lamination on the substrate, a pattern layer is formed on the adsorbent-containing resin layer by a known method such as extrusion film formation. Furthermore, a surface protective layer may be provided on the adsorbent-containing resin layer.
Each of these layers can be laminated by combining printing such as coating, extrusion film formation, and the like in addition to printing.

Next, a foamed laminated sheet can be manufactured by heat-treating the foaming agent-containing resin layer into a foamed resin layer.
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 20 to 80 seconds.

  In the laminated sheet and the foamed laminated sheet of the present invention, since the inorganic adsorbent is contained in the adsorbent-containing resin layer, not the foam-containing resin layer, the gas generated when the foaming agent-containing resin layer is foamed is the inorganic adsorbent. It can hardly be adsorbed on the surface and can suppress the deterioration of the deodorizing function.

  In addition, since the laminated sheet of the present invention uses an inorganic adsorbent as the adsorbent, it is difficult to decompose in the resin layer forming step and the heating step such as foaming, and suppresses the deterioration of the deodorizing function. it can.

  Furthermore, since the laminated sheet and the foamed laminated sheet of the present invention have an adsorbent-containing resin layer under the pattern layer, in order to obtain a high deodorizing function, the content of the inorganic adsorbent is a certain amount or more. Since it is difficult to impair the design properties of the design pattern layer, it exhibits a high deodorizing function and can exhibit excellent design properties.

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, the film was extruded and formed in the order of non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B in a thickness of 5 μm / 65 μm / 5 μm. As a base material, a backing paper “WK-665 (manufactured by Kojin)” is prepared, and after heating to 90 ° C., the above three layers are laminated, whereby non-foamed resin layer A / foaming agent-containing resin A laminate composed of layer / non-foamed resin layer B / base material was obtained.

  Extrusion conditions were such that the cylinder temperature containing the resin for forming the non-foamed resin layer A was 140 ° C., the cylinder temperature containing the resin composition for forming the foaming agent-containing resin layer was 120 ° C., and non-foamed The cylinder temperature in which the resin for forming the resin layer B was accommodated was 100 ° C. The die temperature was 120 ° C. for all. Next, electron beam irradiation was performed under the conditions of an electron beam (200 kV, 50 kGy) from the non-foamed resin layer A side.

Next, the adsorbent-containing resin composition containing the following components is printed on the non-foamed layer resin layer A of the laminate by gravure printing so that the weight after drying is 1 g / m ^2, and the adsorbent-containing resin. A layer is formed, and a pattern printing layer is formed thereon using water-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Hydrick). A laminated sheet was obtained by providing a weight of 1 g / m ² .

  By heating the laminated sheet at 230 ° C. using a heating foaming furnace, the foaming agent-containing resin layer was foamed to form a foamed resin layer. Then, the foaming lamination sheet which has an uneven | corrugated pattern on the surface was obtained by embossing by passing between the cooling roll in which the embossing type | mold was formed, and a pressure roll.

Each resin layer was formed using the following components.
(Non-foamed resin layer A)
・ Low density polyethylene (product name: Petrocene 202, manufactured by Tosoh Corporation)
(Non-foamed resin layer B)
・ Ethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical, trade name: Evertate CV5053)
(Foaming agent-containing resin layer)
・ 50 parts by mass of low density polyethylene (manufactured by Tosoh, trade name: Petrocene 202) ・ 50 parts by weight of ultra low density polyethylene (manufactured by Tosoh, trade name: LUMITAC 54-1) ・ Foaming agent (manufactured by Otsuka Chemical, trade name: Uniform Ultra AZ3050) ) 4 parts by weight / light calcium carbonate (manufactured by Shiraishi Kogyo, trade name: Brilliant-15, average particle size: 0.15 μm) 40 parts by weight / titanium dioxide (pigment) (made by DuPont, trade name: Taipure R-108) 30 5 parts by mass / foaming aid (made by ADEKA, trade name: ADK STAB OF-101) 5 parts by weight / crosslinking aid (made by JSR, trade name: OPSTAR JUA702) 1 part by weight (adsorbent-containing resin layer)
・ Acrylic aqueous emulsion (non-volatile content) 100 parts by mass ・ Inorganic adsorbent (organic-inorganic composite adsorbent) (manufactured by Toagosei, NS-231) 50 parts by mass (surface protective layer)
・ Acrylic water-based emulsion (non-volatile content) 80 parts by mass ・ Silicone resin emulsion (non-volatile content) 20 parts by mass
In Example 1, the approximate amount of inorganic adsorbent (organic / inorganic composite adsorbent) (content per 1 m ^{2 of the} adsorbent-containing resin layer) was 0.33 g / m ² .

Example 2
A foamed laminated sheet was obtained in the same manner as in Example 1 except that the approximate amount of the inorganic adsorbent (organic-inorganic composite adsorbent) in the adsorbent-containing resin layer was 0.44 g / m ² .
The content of the inorganic adsorbent (organic / inorganic composite adsorbent) was 80 parts by mass with respect to 100 parts by mass of the resin component of the adsorbent-containing resin layer.

Example 3
A foamed laminated sheet was obtained in the same manner as in Example 1 except that the approximate amount of the inorganic adsorbent (organic-inorganic composite adsorbent) in the adsorbent-containing resin layer was 0.55 g / m ² .
The content of the inorganic adsorbent (organic-inorganic composite adsorbent) was 120 parts by mass with respect to 100 parts by mass of the resin component of the adsorbent-containing resin layer.

Example 4
A foamed laminated sheet was obtained in the same manner as in Example 3, except that an inorganic adsorbent (trade name “Zeomic” manufactured by Sinanen Zeomic) was used instead of the organic-inorganic composite adsorbent.

Comparative Example 1
A foamed laminated sheet was obtained in the same manner as in Example 1 except that the adsorbent-containing resin layer did not contain an adsorbent and the surface protective layer contained an organic-inorganic composite adsorbent.
The approximate amount of the inorganic adsorbent (organic / inorganic composite adsorbent) was the content per 1 m ^{2 of} the surface protective layer, which was 0.33 g / m ² which was the same as in Example 1.

Comparative Example 2
A foamed laminated sheet was obtained in the same manner as in Comparative Example 1, except that the approximate amount of the inorganic adsorbent (organic-inorganic composite adsorbent) was 0.23 g / m ² .

Comparative Example 3
A foamed laminated sheet was obtained in the same manner as in Example 3 except that an organic adsorbent (trade name “BioFighter” manufactured by Earth Creation) was used instead of the inorganic adsorbent (organic / inorganic composite adsorbent).

Comparative Example 4
A foamed laminated sheet was obtained in the same manner as in Example 3 except that the adsorbent-containing resin layer did not contain an adsorbent and the foamed resin layer contained an inorganic adsorbent (organic-inorganic composite adsorbent). .
The approximate amount of the inorganic adsorbent (organic-inorganic composite adsorbent) was the content per 1 m ^{2 of} the foamed resin layer, which was 0.55 g / m ² which was the same as in Example 3.

  The foamed laminated sheets obtained in Examples and Comparative Examples were evaluated for 1) design properties, 2) acetaldehyde deodorization performance, and 3) ammonia deodorization performance. Each test method and evaluation criteria are as follows.

1) Designability The foamed laminated sheets of Examples 1 to 4 and Comparative Examples 1 to 4 were placed side by side with a comparative foamed laminated sheet to which no adsorbent was added, and the appearance of the pattern was compared. The design property was evaluated.
A when the pattern pattern looks the same as the comparative foamed laminated sheet, A when the pattern looks white when compared, B can recognize the pattern, but the surface white cannot be ignored The case where it was about was set as C.

2) Acetaldehyde deodorization performance A test piece (100 x 100 mm) was inserted into an analytic barrier bag having an internal volume of 3 liters. Using a 99.5% acetaldehyde solution and synthetic air ((nitrogen: oxygen) volume ratio: 4/1, 50% RH), a gas having an acetaldehyde concentration of 50 ppm was prepared, and 1 liter was fed into the bag into which the test piece was inserted. . The initial concentration of acetaldehyde immediately after gas injection and the concentration of acetaldehyde after storage for 24 hours in a dark place were measured with a detector tube, and the acetaldehyde removal rate (%) after 24 hours was calculated by the following formula.
Acetaldehyde removal rate (%) = [{(initial concentration) − (concentration after 24 hours)} / (initial concentration)] × 100
An acetaldehyde removal rate of 80% or more was designated as A, less than 80% and 25% or more as B, and less than 25% as C.

3) Ammonia deodorization performance The test paper (100 mm x 60 mm) was covered with an aluminum tape on the backing paper side and side surfaces, and inserted into an analytic barrier bag having an internal volume of 5 liters. An evaluation gas with an ammonia concentration of 200 ppm was prepared using 28% ammonia water and synthetic air [(nitrogen / oxygen) volume ratio: 4/1, 50% RH], and 3 L was fed into the bag into which the test piece was inserted. It is. The initial ammonia concentration immediately after gas injection and the ammonia concentration after storage for 6 hours were measured with a detector tube, and the ammonia removal rate (%) after 6 hours was calculated by the following equation.
Ammonia removal rate (%) = [{(initial concentration) − (concentration after 6 hours)} / (initial concentration)] × 100
An ammonia removal rate of 70% or more was designated as A, less than 70% and 35% or more as B, and less than 35% as C.
The results are shown in Table 1.

Results In the foamed laminated sheets of Examples 1 to 4, the inorganic adsorbent is contained in the adsorbent-containing resin layer, which is the lower layer of the pattern layer, and the content of these adsorbents is appropriate. Excellent deodorizing function.

  On the other hand, the foamed laminated sheet of Comparative Example 1 was poor in design because a large amount of inorganic adsorbent was contained in the surface protective layer. Moreover, although the foaming laminated sheet of Comparative Example 2 contains the inorganic adsorbent in the surface protective layer, since the content is small, the deterioration of the design is suppressed, but the deodorizing function is inferior. Further, since the foamed laminated sheet of Comparative Example 3 uses an organic adsorbent as the adsorbent, the organic adsorbent is decomposed in the heating step such as foaming, and the deodorizing function is greatly reduced. . Furthermore, since the foamed laminated sheet of Comparative Example 4 contains the inorganic adsorbent in the foamed resin layer, the deodorizing function is inferior despite the addition of the same amount of inorganic adsorbent as in Example 3. It was.

Claims (5)

A laminated sheet in which at least a foaming agent-containing resin layer, an adsorbent-containing resin layer that adsorbs a volatile compound, and a design pattern layer are sequentially laminated on a substrate,
(1) The adsorbent-containing resin layer contains an inorganic adsorbent,
(2) The content of the inorganic adsorbent is 50 parts by mass or more with respect to 100 parts by mass of the resin component of the adsorbent-containing resin layer.
A laminated sheet characterized by that.   The laminated sheet according to claim 1, further comprising a surface protective layer on the design pattern layer.   The said foaming agent containing resin layer is a laminated sheet of Claim 1 or 2 which has a non-foaming resin layer in the single side | surface or both surfaces.   The laminated sheet according to claim 1, wherein the foaming agent-containing resin layer is resin-crosslinked by electron beam irradiation.   The foaming lamination sheet obtained by foaming the said foaming agent containing resin layer of the lamination sheet in any one of Claims 1-4.