JP5982957B2 - Laminated sheet and foam laminated sheet - Google Patents

Description

  The present invention relates to a laminated sheet and a foam laminated sheet. The foamed laminated sheet has a foamed resin layer, and is useful as foamed wallpaper and various decorative materials. 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, in the residential environment, highly airtight houses with improved energy efficiency are increasing. However, if the indoor airtightness becomes high, the smell generated from cigarette smoke or human beings is worrisome. Therefore, development of an interior material for building having a deodorizing function is demanded. In particular, it is considered effective to provide a deodorizing function to a wall material having the largest area as an interior member.

  For example, a building material (for example, wallpaper) provided with a layer containing a photocatalyst, an adsorbent, and a binder on the surface has been proposed for the purpose of adsorbing and removing odor components and exhibiting an antibacterial action with a photocatalyst (Patent Literature). 1). Thus, when a photocatalyst and an adsorbent are blended in the surface layer, the odor component adsorbed by the adsorbent can be oxidatively decomposed by the photocatalyst.

  However, since the photocatalyst decomposes organic matter, the organic adsorbent with high deodorizing ability cannot be used at the same time for the layer containing the photocatalyst constituting the wallpaper, and the binder (binder) made of organic resin is also used at the same time. Cannot be used. As a result, the layer containing the photocatalyst must use an inorganic adsorbent and an inorganic binder, and there is a problem that the deodorizing ability and the stain resistance are insufficient.

  Therefore, in the foamed laminated sheet in which the deodorant-containing resin layer is formed on the base material, the foamed laminated sheet having excellent deodorizing performance and odor component decomposition performance and having high stain resistance, and the foamed laminated sheet Development of a laminated sheet (unfoamed raw fabric) useful for sheet production is desired.

Japanese Patent Laid-Open No. 9-300515

  The present invention provides a foamed laminated sheet in which a deodorant-containing resin layer is formed on a base material, which has excellent deodorizing performance and odor component decomposition performance, and is highly resistant to contamination. With the goal. Moreover, it aims at providing the lamination sheet (unfoamed original fabric) useful for manufacture of the said foaming lamination sheet.

  As a result of intensive research, the inventor has formed at least a foaming agent-containing resin layer and a deodorant-containing resin layer in order on the substrate, and the deodorant-containing resin layer carries an inorganic substance or In order to complete the present invention, it is found that an oxide semiconductor and / or a non-photocatalyst coated with an inorganic substance, an organic adsorbent that adsorbs an odor component, and a laminated sheet containing a resin component can solve the above problems. It came.

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 and a deodorant-containing resin layer are sequentially formed on a substrate,
The deodorant-containing resin layer is a laminated sheet which is a layer containing an oxide semiconductor carrying an inorganic substance or coated with an inorganic substance and / or a non-photocatalyst, an organic adsorbent that adsorbs an odor component, and a resin component.
2. The laminated sheet according to Item 1, wherein the inorganic substance is at least one selected from the group consisting of calcium phosphate, calcium silicate, magnesium phosphate, and magnesium silicate.
3. Item _3. The laminated sheet according to Item 1 or 2, wherein the oxide semiconductor is at least one selected from the group consisting of TiO ₂ , CdS, CdSc, WO ₃ , Fe ₂ O ₃ , SrTiO ₃ and KNbO ₃ .
4). Item 4. The laminated sheet according to any one of Items 1 to 3, wherein the non-photocatalyst is a phosphate containing at least one metal selected from the group consisting of titanium, cerium, and zirconium.
5. Item 5. The laminated sheet according to any one of Items 1 to 4, wherein the resin component is an aqueous resin.
6). Item 6. The laminated sheet according to any one of Items 1 to 5, wherein the organic adsorbent is an organic-inorganic composite adsorbent.
7). Item 7. The laminated sheet according to Item 6, wherein the organic-inorganic composite adsorbent contains an amine compound.
8). Item 8. The laminated sheet according to any one of Items 1 to 7, wherein an intermediate layer is formed between the foaming agent-containing resin layer and the deodorant-containing resin layer.
9. Item 9. The laminated sheet according to Item 8, wherein the intermediate layer contains an organic adsorbent that adsorbs odor components.
10. Item 10. The laminated sheet according to Item 9, wherein the intermediate layer further comprises an oxide semiconductor carrying an inorganic substance or coated with an inorganic substance and / or a non-photocatalyst.
11 Item 11. The laminated sheet according to any one of Items 1 to 10, wherein the substrate is a fibrous sheet.
12 The foaming lamination sheet obtained by foaming the said foaming agent containing resin layer of the lamination sheet in any one of said items 1-11.

  Hereinafter, the 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 and a deodorant-containing resin layer are sequentially formed on a substrate, and the deodorant-containing resin layer is an oxide that carries an inorganic substance or is coated with an inorganic substance. It is a layer containing a physical semiconductor and / or a non-photocatalyst, an organic adsorbent that adsorbs odor components, and a resin component. Hereinafter, the “organic adsorbent that adsorbs odor components” is simply abbreviated as “organic adsorbent”.

  The laminated sheet of the present invention having the above characteristics comprises a deodorant-containing resin layer on a foaming agent-containing resin layer, and the deodorant-containing resin layer carries an inorganic substance or is coated with an inorganic substance and By containing a non-photocatalyst, an organic adsorbent and a resin component, it has excellent deodorization performance and odor component decomposition performance, has high contamination resistance, and can be expected to improve adhesion between layers. .

  Furthermore, in the laminated sheet of the present invention, an intermediate layer may be formed between the foaming agent-containing resin layer and the deodorant-containing resin layer, and the intermediate layer carries an organic adsorbent and an inorganic substance. Or an oxide semiconductor coated with an inorganic substance and / or a non-photocatalyst. By providing such a configuration, higher deodorization performance and odor component decomposition performance can be obtained.

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 The foaming agent-containing resin layer used in the present invention preferably contains an olefin resin as a resin component, and is an ethylene copolymer containing 1) polyethylene and 2) ethylene and components other than ethylene as monomers. It is preferable to contain at least one (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. Among these, low-density polyethylene is preferable.

  The ethylene copolymer is suitable for extrusion film formation from the viewpoint of melting point and MFR. Examples of the ethylene copolymer include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), 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, at least one of ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer and ethylene-methacrylic acid copolymer is preferable, and when these are used in combination with other resins. The content of at least one of ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer and ethylene-methacrylic acid 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. The ethylene-methyl methacrylate copolymer has a methyl methacrylate copolymerization ratio (MMA amount) of preferably 5 to 25% by mass, more preferably 5 to 15% by mass. Moreover, 2-15 mass% is preferable as a copolymerization ratio (MAA amount) of methacrylic acid, and, as for an ethylene-methacrylic acid copolymer, 5-11 mass% is more preferable.

  The resin component contained in the foaming agent-containing resin layer preferably has an MFR (melt flow rate) measured at 190 ° C. and a load of 21.18 N described in JIS K 6922 of 10 to 100 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 used suitably. 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.

  Moreover, metal soaps, such as a zinc stearate, etc. can be used as a cell regulator, for example. The content of the cell regulator is preferably about 0.3 to 10 parts by mass, more preferably about 1 to 5 parts by mass with respect to 100 parts by weight of the resin component.

  When these foaming aids, EMAA, and ADCA foaming agents are used in combination, there is a problem that the effect of the original foaming aid is impaired by the reaction of the carboxyl group of EMAA with the foaming aid. 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 (titanium dioxide), zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chromium titanium yellow, oxidized Examples thereof include iron (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. By performing resin cross-linking by electron beam irradiation, the surface strength of the resin layer can be improved, and the foaming characteristics can be adjusted. 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. 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 It is preferable to have the non-foamed resin layer A on the front surface of the foaming agent-containing resin layer. The non-foamed resin layer A has a function of preventing deterioration in deodorizing performance and odor component decomposition performance due to volatile components such as foaming gas generated from the foaming agent in the foaming step when forming the foamed resin layer.

  Specifically, the foaming gas to the substance (surface) having a catalytic function and an adsorbing function, such as an oxide semiconductor and / or a non-photocatalyst supported with or coated with an inorganic substance, and an organic adsorbent described later. Can prevent adverse effects caused by. Moreover, by having the non-foamed resin layer A, it is possible to clarify the pattern when forming the pattern layer or to improve the scratch resistance of the foamed resin layer (protect 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, fluorine resins, and the like, among which polyolefin resins are preferable.

  Examples of polyolefin resins include polyethylene, polypropylene, polybutene, polybutadiene, polyisoprene, and other resins, copolymers of ethylene and α-olefins having 4 or more carbon atoms (linear low-density polyethylene), and ethylene-acrylic acid copolymers. Polymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene- (meth) acrylic acid copolymer such as ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer ( EVA), ethylene-vinyl acetate copolymer saponified product, ionomer and the like. In addition, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and the same applies to other parts described as (meth).

  The thickness of the non-foamed resin layer A is not limited, but is preferably about 3 to 50 μm, and more preferably about 3 to 20 μm.

  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 non-foamed resin layer B (adhesive resin layer) is not limited, but is preferably about 3 to 50 μm, and more preferably about 3 to 20 μm.

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

It is necessary between the pattern-pattern layer foaming agent-containing resin layer (when the front surface of the foaming agent-containing resin layer is provided with the non-foaming resin layer A) and the deodorant-containing resin layer. Depending on the pattern pattern layer may be formed.

  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 may be known or commercially available.

  As the colorant, for example, a pigment used in the 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, 2-methoxyethyl acetate, and 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 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 varies depending on the type of design pattern, but is generally preferably about 0.1 to 10 μm.

Deodorant-containing resin layer The laminated sheet of the present invention has an excellent deodorization performance and odor component decomposition performance, and has a foaming agent-containing resin layer (of the foaming agent-containing resin layer) for the purpose of improving stain resistance. When the non-foamed resin layer A is provided on the front surface, a deodorant-containing resin layer is formed on the non-foamed resin layer A). This deodorant-containing resin layer catalyzes odorous components (formaldehyde, acetaldehyde, ammonia, etc.) that cause daily odors such as organic gas sick houses, pet odors, cigarette smoke and human odors. It has a deodorizing function by decomposing and a deodorizing function by adsorbing odor components. In particular, the mechanism of decomposing the odor component captured by the adsorption action by the catalytic action expresses the deodorizing function very efficiently by the synergistic effect of each action.

  The deodorant-containing resin layer is a layer containing an oxide semiconductor carrying an inorganic substance or coated with an inorganic substance and / or a non-photocatalyst, an organic adsorbent, and a resin component.

  An oxide semiconductor carrying an inorganic substance or coated with an inorganic substance will be described.

“Supported” is a state in which an inorganic substance is bound to the surface of the oxide semiconductor, and “coating” is a state in which the inorganic substance is bound to the entire surface of the oxide semiconductor. Then, an oxide semiconductor (e.g., TiO ₂₎ constitutes a central portion (core portion), the inorganic material on the surface (e.g. hydroxyapatite) is present. While exhibiting the odor component decomposition performance by the catalytic activity of the oxide semiconductor, the decomposition of the organic resin binder and the organic adsorbent is suppressed by providing an inorganic substance on the surface.

The inorganic substance is preferably at least one selected from the group consisting of calcium phosphate, calcium silicate, magnesium phosphate and magnesium silicate because it is stable without resin decomposing ability and excellent in protein adsorption ability. Examples of calcium phosphate include fluorapatite Ca ₅ (PO ₄ ) ₃ F, chlorapatite Ca ₅ (PO ₄ ) ₃ Cl, hydroxyapatite (hydroxyapatite) Ca ₅ (PO ₄ ) ₃ (OH), and fluoroapatite Ca ₅ ( There are PO ₄ , CO ₃ ) ₃ F and carbonate apatite Ca ₅ (PO ₄ , CO ₃ ) ₃ (OH). Apatite is apatite.

The oxide semiconductor is preferably at least one selected from the group consisting of TiO ₂ , CdS, CdSc, WO ₃ , Fe ₂ O ₃ , SrTiO ₃ and KNbO ₃ because of its high catalytic activity.

  The particle diameter of the oxide semiconductor is preferably 5 to 500 nm, more preferably 10 to 400 nm, and still more preferably 20 to 250 nm because it is easy to support an inorganic substance or be easily coated with an inorganic substance in terms of material design.

  The content of the oxide semiconductor supporting or coated with an inorganic substance in the deodorant-containing resin layer is compatible with the adhesion between the deodorant-containing resin layer and the adjacent lower layer and the odor component decomposition performance. From the viewpoint, 0.1 to 80 parts by mass is preferable and 5 to 50 parts by mass is more preferable with respect to 100 parts by mass of the resin component described later.

  The non-photocatalyst will be described.

  A non-photocatalyst is a catalyst that does not require light (ultraviolet rays or visible light) when decomposing odor components.

The non-photocatalyst is preferably a phosphate containing at least one metal selected from the group consisting of titanium, cerium and zirconium, and more preferably a titanium phosphate-based compound, because of its high activity. Examples of the titanium phosphate compound include Ti (OH) (H ₂ PO ₄ ) ₂ (OR), Ti (OH) (PO ₄ ), Ti (OH) ₂ (H ₂ PO ₄ ) (OR), Ti (OH) (HPO ₄ ) (OR), Ti (OH) (HPO ₄ ) (H ₂ PO ₄ ), Ti (OH) ₂ (H ₂ PO ₄ ) ₂ , Ti (OH) ₃ (H ₂ PO ₄ ) Or these condensates etc. can be used. Here, R is an alkyl group having 1 to 4 carbon atoms.

  The particle size of the non-photocatalyst is preferably 1 to 500 nm, more preferably 5 to 400 nm, and still more preferably 10 to 250 nm because the ink stability and catalytic activity are high.

  The content of the non-photocatalyst in the deodorant-containing resin layer is based on 100 parts by mass of the resin component described later from the viewpoint of coexistence of adhesion between the deodorant-containing resin layer and the adjacent lower layer and deodorization performance. 0.1 to 80 parts by mass is preferable, and 5 to 50 parts by mass is more preferable.

  The organic adsorbent will be described.

  The organic adsorbent is an adsorbent composed of an organic substance and having a deodorizing action by adsorbing an odor component. In the present invention, by using an organic adsorbent, an odor component can be adsorbed by a chemical bond, so that the adsorbed odor component is less likely to be released again.

Examples of organic adsorbents include natural product adsorbents derived from plant or animal fats and oils, and styrene-divinylbenzene copolymers with functional groups such as SO ₃ H, COOH, NH ₂ (ion) Synthetic polymer adsorbent of (exchange resin). In the present invention, the organic adsorbent includes an organic-inorganic composite adsorbent described later. The organic adsorbent is preferably an organic-inorganic composite adsorbent for reasons such as high heat resistance and little color change.

An organic-inorganic composite adsorbent is an adsorbent in which an organic functional group is exposed from the surface of an inorganic substance. Specifically, for example, a hydroxyl group, amines, ureas, amides, imides, hydrazides are added to an inorganic material. And those carrying organic compounds such as azoles and azines. Examples of the inorganic material that can be used as the carrier include silicon dioxide, activated carbon, sepiolite, and mica from the viewpoint of heat resistance. What is necessary is just to select the said functional group according to the target odor component, for example, when aiming at aldehyde adsorption | suction, it is preferable to use the organic inorganic composite adsorption agent containing an amine compound. By using an organic / inorganic composite adsorbent containing an amine compound, the amino group at the end of the amine compound reacts with the aldehyde (CH ₃ CHO + H ₂ N− → CH ₃ CH (OH) NH— <Schiff reaction>), and the aldehyde is removed. Is done.

The average particle size of the organic / inorganic composite adsorbent is not limited, but is preferably 1 to 12 μm, and more preferably 2 to 5 μm. Here, the average particle diameter in the present specification is a value measured by a laser diffraction scattering method. Moreover, although the specific surface area of an organic inorganic composite adsorption agent is not limited, 400-900 m < ² > / g is preferable and 500-900 m < ² > / g is more preferable. Here, the specific surface area in this specification is a value measured by the BET method.

  As an organic-inorganic composite adsorbent containing an amine compound, for example, “Kesmon NS-231” manufactured by Toagosei Co., Ltd. is known.

  The content of the organic adsorbent in the deodorant-containing resin layer is 100 mass parts of the resin component described later from the viewpoint of compatibility between the deodorant-containing resin layer and the adhesion between the adjacent lower layer and the deodorizing performance. 1-100 mass parts is preferable with respect to it, and 20-80 mass parts is more preferable.

  The resin component (film-forming resin component) will be described.

  The resin component is not limited as long as it is a film-forming resin component that forms a deodorant-containing resin layer, and ionizing radiation curable resins, thermosetting resins, or thermoplastic resins can be widely used.

  Among them, ionizing radiation curable resins are suitable as the resin component for the purpose of surface strength (scratch resistance, etc.), contamination resistance, and protection of the pattern layer of the foamed laminated sheet (foamed wallpaper). .

  The ionizing radiation curable resin is mainly composed of a prepolymer (including oligomer) and / or a monomer containing a radical polymerizable double bond that can be polymerized and cross-linked by irradiation with ionizing radiation such as ultraviolet rays and electron beams. A transparent 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.

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. Among these prepolymers, urethane (meth) acrylate is preferable. These molecular weights are usually preferably about 250 to 100,000.

  As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  Examples of the prepolymer having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.

  The resin components include polyester resin, phenol resin, epoxy resin, polyurethane resin, amino alkyd resin, melamine resin, guanamine resin, urea resin, acrylic resin, urethane acrylic resin, etc., thermosetting vinyl acetate resin, styrene resin, etc. Resin or thermoplastic resin can also be used. Among these thermosetting resins and thermoplastic resins, acrylic resins and polyurethane resins are preferable.

  As the resin component, it is preferable to use an aqueous resin in consideration of the stability when mixed with a deodorant or the like to form an ink. As the aqueous resin, for example, an aqueous acrylic resin, polyurethane resin, or the like can be used.

  When the deodorant-containing resin layer is the outermost layer, a known filler such as silica may be contained for gloss adjustment. Further, by adding additives such as silicone resin, thickener and antifoaming agent to the deodorant-containing resin layer, for example, when a laminated sheet and a foamed laminated sheet are used as wallpaper, slipperiness and Ease of wiping off dirt can be imparted. In addition, an antibacterial agent, an antiallergen agent, etc. may be added as needed and functionality may be provided.

  The content of the silicone resin in the deodorant-containing resin layer is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the resin component from the viewpoint of imparting slipperiness and ease of wiping off dirt. 10-50 mass parts is more preferable.

  The deodorant-containing resin layer of the present invention includes, for example, a dispersion in which an inorganic semiconductor is supported or coated with an inorganic substance and / or a non-photocatalyst, an organic adsorbent, and a resin component in a solvent. , Applied on the foaming agent-containing resin layer (or on the non-foamed resin layer A or the pattern pattern layer) by a method such as gravure coating, spray coating, dip coating, or brush coating, and then the solvent in the dispersion is removed. Although the method of heating and drying at the temperature which can be removed is mentioned, it is not limited to this method. After drying is completed, aging can be performed for a required time at a temperature of about 30 to 60 ° C. Thereby, the peeling strength of the coated deodorant-containing resin layer can be improved.

  Moreover, when using ionizing radiation curable resin as a resin component, after applying the dispersion, it is irradiated with ionizing radiation such as visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-ray, electron beam, ion beam, etc. To cure. Among these, it is particularly preferable to use ultraviolet rays or electron beams.

  As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. The wavelength of ultraviolet light is about 190 to 380 nm.

  As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 kV, more preferably about 100 to 300 kV. The irradiation amount of the electron beam is preferably about 20 to 150 kGy.

The thickness of the deodorant-containing resin layer is not limited, and it is preferably applied in a range of about 0.2 to 5 g / m ² in terms of application amount (dry weight) according to the purpose and application. .

Intermediate layer The laminated sheet of the present invention comprises a foaming agent-containing resin layer (when the front surface of the foaming agent-containing resin layer is provided with a non-foaming resin layer A), a deodorant-containing resin layer, Between the foaming agent-containing resin layer (or the non-foaming resin layer A when the foaming agent-containing resin layer is provided with the non-foaming resin layer A) and the patterning layer. An intermediate layer may be formed between the layers, such as between the pattern pattern layer and the deodorant-containing resin layer, if necessary.

  By providing the intermediate layer, the foaming agent-containing resin layer (foamed resin layer) and the pattern layer can be protected, and the surface properties of the laminated sheet (foamed laminated sheet) can be further improved. Moreover, the adhesiveness between each layer can be improved. In addition, the surface of the lower layer (foaming agent-containing resin layer or non-foamed resin layer A) is melted and the upper layer deodorant is taken into the lower layer during the heat foaming (dropping of the deodorant into the resin) Sometimes it can be prevented by the intermediate layer.

  The intermediate layer may be a layer formed by applying a resin composition, or may be a layer formed by a film formed or a melt molded film. By appropriately selecting the type and forming method of the resin for forming the intermediate layer, a layer having a function according to the purpose such as a primer layer and a transparent resin layer (film layer) can be obtained.

Primer layer Examples of the resin contained in the primer layer include acrylic resins, urethane resins, urethane-acrylic resins, and the like. From these resins, adhesion is performed according to the type of the adjacent layer of the primer layer. Can be appropriately selected in consideration of the improvement of the property. In particular, high adhesion can be obtained by using an acrylic resin or a urethane-acrylic resin.

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.

Transparent resin layer (film layer)
The transparent resin layer may be colored as long as it is transparent. When the transparent resin layer is formed on the front surface of the pattern layer, it may be translucent as long as the pattern layer is visible.

  The transparent resin layer is preferably a layer containing polyethylene and / or an ethylene copolymer. As polyethylene and / or ethylene copolymer, ethylene and α-olefin copolymer having 4 or more carbon atoms (linear low density polyethylene), ethylene-acrylic acid copolymer resin, ethylene-methyl acrylate copolymer resin , Ethylene (meth) acrylic acid copolymer resins such as ethylene-ethyl acrylate copolymer resin, ethylene-methacrylic acid copolymer resin, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer Examples of the polymer (EVOH), saponified ethylene-vinyl acetate copolymer resin, and ionomer include ethylene-vinyl alcohol copolymer in the present invention.

  The thickness of the transparent resin layer is not particularly limited, but generally about 3 to 30 μm is preferable, and about 5 to 20 μm is more preferable.

  The surface of the transparent resin layer on which the surface protective layer is formed is subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment as necessary. Also good. The surface treatment may be performed according to a conventional method for each treatment.

  The intermediate layer preferably contains the organic adsorbent described in the deodorant-containing resin layer for the reasons of improving the deodorizing performance and selecting a material according to the target gas. The content of the organic adsorbent in the intermediate layer is 0.1 to 80 parts by mass with respect to 100 parts by mass of the resin component forming the intermediate layer from the viewpoint of improving the deodorizing performance and selecting a material according to the target gas. Is preferable, and 10-50 mass parts is more preferable.

  Further, the intermediate layer further includes an oxide semiconductor and / or a non-photocatalyst that supports or is coated with an inorganic substance, as described in the deodorant-containing resin layer, for the reason of imparting the above-described decomposition ability. Is preferred. The content of the oxide semiconductor and / or the non-photocatalyst that supports or is coated with an inorganic substance in the intermediate layer is 0.000 parts by mass with respect to 100 parts by mass of the resin component forming the intermediate layer from the viewpoint of imparting decomposition ability. 1-80 mass parts is preferable and 10-50 mass parts is more preferable.

≪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 pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds.

Embossing The laminated sheet 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 heat softening the front surface of the deodorant-containing resin layer. Examples of the embossed pattern include a wood grain plate conduit groove, a stone plate surface irregularity (such as granite cleaved surface), a cloth surface texture, a satin texture, a grained grain, a hairline, and a ridge line.

≪Method for producing foam laminated sheet≫
As a method for producing a foamed laminated sheet, for example, a foaming agent-containing resin layer and a deodorant-containing resin layer are sequentially formed on a substrate to form a laminated sheet, and then heat-treated to form the foaming agent-containing resin layer as a foamed resin. It can be manufactured by layering.

  When the foaming agent-containing resin layer has the non-foaming resin layer A on the front surface, the foaming agent-containing resin layer and the non-foaming resin layer A are co-extruded on the base material by a T-die extruder and preheated. To obtain a laminate. When extruding molten resin corresponding to two layers at the same time, a multi-manifold type T-die capable of simultaneously forming two layers can be used. In this case, the resin composition for forming the foaming agent-containing resin layer and the resin composition for forming the non-foamed resin layer A are placed in separate cylinders, and two types and two layers are simultaneously extruded to form and laminate. do it. In this method, the coextruded laminate is simultaneously laminated (film formation) on the substrate. Since the resin layer laminated simultaneously with extrusion on the base material has adhesiveness by heat melting, it is bonded to the base material. 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 Using a T-die extruder, a molten resin corresponding to three layers is simultaneously extruded to form a laminate, which is then placed on the substrate and thermally laminated to adhere to the substrate. (Non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B / base material).

  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. This electron beam irradiation may be performed after the pattern layer or the surface protective layer is formed.

  After laminating on the base material, on the foaming agent-containing resin layer (when the non-foamed resin layer A is simultaneously laminated (film formation), on the non-foamed resin layer A), if necessary, the pattern layer and the intermediate layer After forming, the deodorant-containing resin layer can be formed by applying a deodorant-containing resin coating liquid. Each of these layers can also be laminated by combining coating such as printing and coating, extrusion film formation, and the like. Coating such as printing and application can be performed according to a conventional method.

  Next, the foamed resin layer is formed by heating the foaming agent-containing resin layer to obtain a foamed laminated sheet. 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.

  Next, you may emboss from the front surface of a foaming lamination sheet. Embossing can be performed by means such as pressing an embossed plate. For example, an embossed pattern can be formed by pressing the embossed plate after heat softening the front surface of the deodorant-containing resin layer.

Forming Form of Laminated Sheet (Foamed Laminated Sheet) In the laminated sheet (foamed laminated sheet) of the present invention, for example, as shown in FIGS. 1 to 3, a deodorant-containing resin layer is formed on the foaming agent-containing resin layer. Yes.

Form 1
As shown in FIG. 1, the foaming agent-containing resin layer 3 and the deodorant-containing resin layer 6 can be formed on the substrate 1. Furthermore, it is preferable that the foaming agent-containing resin layer 3 has non-foaming resin layers on both sides (from the base material 1 side, non-foaming resin layer B2 / foaming agent-containing resin layer 3 / non-foaming resin layer A4). Moreover, the aspect which forms the pattern pattern layer 5 may be sufficient.

Form 2
As shown in FIG. 2, it is preferable to provide a film layer 7 as an intermediate layer between the pattern layer 5 and the deodorant-containing resin layer 6. The film layer 7 is preferably a layer made of, for example, an ethylene-vinyl alcohol copolymer (EVOH) resin. At this time, like the deodorant-containing resin layer 6, the film layer 7 preferably contains an oxide semiconductor carrying an inorganic substance or coated with an inorganic substance and / or a non-photocatalyst, and an organic adsorbent. By providing the film layer 7, it is possible to obtain the effect of improving the adhesion between the layers and preventing the deodorant from dropping into the resin. Furthermore, the film layer 7 contains the oxide semiconductor which supported the inorganic substance or was coat | covered with the inorganic substance, and / or a non-photocatalyst, and an organic type adsorption agent, and can obtain the effect of deodorant performance improvement.

Form 3
As shown in FIG. 3, a primer layer 8 is preferably provided as an intermediate layer between the pattern layer 5 and the deodorant-containing resin layer 6. The primer layer 8 is preferably a layer made of, for example, an acrylic resin or a urethane resin. At this time, like the deodorant-containing resin layer 6, the primer layer 8 preferably contains an oxide semiconductor and / or a non-photocatalyst supported with or coated with an inorganic substance, and an organic adsorbent. By providing the primer layer 8, the adhesion between the layers can be improved. Furthermore, when the primer layer 8 includes an oxide semiconductor and / or a non-photocatalyst supported with or coated with an inorganic substance, and an organic adsorbent, an effect of improving the deodorizing performance can be obtained.

  The laminated sheet of the present invention is a laminated sheet in which at least a foaming agent-containing resin layer and a deodorant-containing resin layer are sequentially formed on a substrate, and the deodorant-containing resin layer carries an inorganic substance or is an inorganic substance. By including a coated oxide semiconductor and / or a non-photocatalyst, an organic adsorbent, and a resin component, it has excellent deodorizing performance and odor component decomposition performance, and can improve stain resistance. .

It is sectional drawing of the lamination sheet of the formation aspect 1. FIG. It is sectional drawing of the lamination sheet of the formation aspect 2. FIG. It is sectional drawing of the lamination sheet of the formation aspect 3. FIG.

  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
A foamed laminated sheet (wallpaper) having deodorizing performance was produced by the method described below.

Using a three-type three-layer multi-manifold T-die extruder, the film was extruded to have a thickness of 15 μm / 100 μm / 10 μm in the order of non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B. As a base material, a backing paper “WK-FKKD (manufactured by Kojin Co., Ltd.), basis weight: 60 g / m ² ” was prepared, and after heating this to 90 ° C., the above three layers were laminated, A laminate comprising non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B / substrate 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, for the purpose of improving the surface strength of the laminate, an electron beam (200 kV, 50 kGy) was irradiated from the non-foamed resin layer A side to crosslink the foaming agent-containing resin layer and the non-foamed resin layers A and B.

As shown in FIG. 1 (formation mode 1), a water-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Hydrick) is formed on the non-foamed resin layer A of the laminate by gravure printing. A pattern (pattern pattern layer) was printed. Next, as the outermost layer, a deodorant-containing resin layer (deodorant-containing coating liquid) was printed and provided so that the mass after drying was 1 g / m ² to obtain a laminated sheet.

  Next, the laminated sheet was heated in a foaming furnace (at 230 ° C. for 35 seconds) to foam the foaming agent-containing resin layer. Next, embossing was performed on the front side of the foam using an embossed plate to form a texture pattern, and a foamed laminated sheet (foamed wallpaper) was obtained.

  Each resin layer was formed using the following components.

  The non-foamed resin layers A and B were formed of an ethylene-vinyl acetate copolymer (EVA resin) “Evertate CV5053 (VA content: 20 mass%, MFR = 70), manufactured by Sumitomo Chemical Co., Ltd.”.

  The foaming agent-containing resin layer is composed of an ethylene-vinyl acetate copolymer (EVA resin) “Evatate CV5053 (VA content: 20 mass%, MFR = 70), manufactured by Sumitomo Chemical Co., Ltd.”, 100 parts by mass, 4 parts by mass of ADCA # 3, manufactured by Eiwa Kasei Co., Ltd., 30 parts by mass of filler (calcium carbonate) “Whiteon H, manufactured by Shiroishi Kogyo”, 20 parts by mass of pigment (titanium dioxide) “Typure R-108, manufactured by DuPont”, foamed It was formed by 1 part by mass of an auxiliary agent “Adeka Stub OF-101, manufactured by ADEKA Corporation” and 1 part by mass of a crosslinking agent “OPSTAR JUA-702, manufactured by JSR Corporation”.

  The deodorant-containing resin layer (deodorant-containing coating liquid) is an organic adsorbent (organic / inorganic composite adsorbent) “Kesmon NS-231, manufactured by Toagosei Co., Ltd.”, 70 parts by mass, oxidized with an inorganic substance. 30 parts by mass of a semiconductor (apatite (calcium phosphate) -coated titanium oxide “F4T-20AF, manufactured by Nanowave Co., Ltd.”), 20 parts by mass of a silicone resin “KP-361, manufactured by Shin-Etsu Silicone” and a resin component (aqueous acrylic resin) 100 It formed with the ink containing a mass part.

Example 2
A foamed laminated sheet was obtained in the same manner as in Example 1 except that the deodorant-containing coating liquid was formed without containing a silicone resin in the deodorant-containing coating liquid.

Example 3
Example 1 except that a non-photocatalyst (titanium phosphate compound “Eco Chimera, manufactured by YOO Corporation”) was used in the deodorant-containing coating solution instead of the oxide semiconductor coated with an inorganic substance. Thus, a foamed laminated sheet was obtained.

Example 4
A foamed laminated sheet was obtained in the same manner as in Example 3, except that the deodorant-containing coating liquid was formed without containing a silicone resin in the deodorant-containing coating liquid.

Example 5
As shown in FIG. 2 (formation mode 2), the same procedure as in Example 1 was performed except that a film layer (ethylene-vinyl alcohol copolymer EVOH) was provided between the pattern layer and the deodorant-containing resin layer. Thus, a foamed laminated sheet was obtained. The product name “EVAL FILM HF-ME” (film thickness: 12 μm, ethylene content 44 mol%) manufactured by Kuraray Co., Ltd. was used for the film layer.

Example 6
Foaming is carried out in the same manner as in Example 1 except that an organic adsorbent (natural adsorbent) “High Cut B-50T, manufactured by Takamatsu Yushi Co., Ltd.) is used as the organic adsorbent contained in the deodorant-containing coating liquid. A laminated sheet was obtained.

Example 7
A foamed laminated sheet was obtained in the same manner as in Example 6 except that the deodorant-containing resin layer was formed without containing the silicone resin in the deodorant-containing coating liquid.

Example 8
As shown in FIG. 3 (formation mode 3), a foamed laminated sheet was obtained in the same manner as in Example 1 except that a primer layer was provided between the pattern layer and the deodorant-containing resin layer. For the primer layer, 100 parts by mass of an aqueous polyurethane resin “TAP162, manufactured by Arakawa Chemical Industry Co., Ltd.” and 40 masses of organic adsorbent (organic-inorganic composite adsorbent) “Kesmon NS-231, manufactured by Toagosei Co., Ltd.” What added the part was used.

Example 9
A foamed laminated sheet was obtained in the same manner as in Example 8, except that the primer layer was further added with 20 parts by mass of an oxide semiconductor (apatite (calcium phosphate) -coated titanium oxide) coated with an inorganic substance. .

Example 10
As a resin component contained in the deodorant-containing coating liquid, an ionizing radiation curable resin (bifunctional urethane acrylate oligomer: weight average molecular weight 720) is used in place of the aqueous acrylic resin, and after applying the deodorant-containing coating liquid A foamed laminated sheet was obtained in the same manner as in Example 1 except that the deodorant-containing resin layer was formed by irradiation with an electron beam (165 kV, 30 kGy).

Example 11
A foamed laminated sheet was obtained in the same manner as Example 10 except that the deodorant-containing resin layer was formed without containing the silicone resin in the deodorant-containing coating liquid.

Example 12
A foamed laminated sheet was obtained in the same manner as in Example 8 except that an aqueous urethane-acrylic resin was used as the resin for forming the primer layer.

Example 13
A foamed laminated sheet was obtained in the same manner as in Example 8 except that an aqueous acrylic resin was used as the resin for forming the primer layer.

Example 14
A foamed laminated sheet was obtained in the same manner as in Example 13 except that the amount of deodorant added to the primer layer was 10 parts by mass.

Example 15
A foamed laminated sheet was obtained in the same manner as in Example 14 except that the amount of deodorant added to the primer layer was 50 parts by mass.

Example 16
Other than changing the oxide semiconductor (apatite (calcium phosphate) -coated titanium oxide) coated with an inorganic substance in the deodorant-containing resin layer to a non-photocatalyst (titanium phosphate compound “Eco Chimera, manufactured by YOO Corporation”) Obtained a foamed laminated sheet in the same manner as in Example 15.

Example 17
The deodorant-containing resin layer (deodorant-containing coating liquid) is an organic adsorbent (organic-inorganic composite adsorbent) “Kesmon NS-231, manufactured by Toagosei Co., Ltd.”, 20 parts by mass, oxidized with an inorganic substance. 50 parts by mass of a semiconductor (apatite (calcium phosphate) -coated titanium oxide “F4T-20AF, manufactured by Nanowave Co., Ltd.”), 20 parts by mass of a silicone resin “KP-361, manufactured by Shin-Etsu Silicone” and a resin component (aqueous acrylic resin) 100 A foamed laminated sheet was obtained in the same manner as in Example 15 except that it was formed with an ink containing parts by mass.

Example 18
The non-foamed resin layer B and the foaming agent-containing resin layer are formed of the following resin or resin composition, and the thickness of each of the non-foaming resin layer A / foaming agent-containing resin layer / non-foaming resin layer B is 8 μm / 75 μm in order. A foamed laminated sheet was obtained in the same manner as in Example 15 except that the thickness was / 8 μm.
(A) Resin used for forming the non-foamed resin layer B:
・ Low density polyethylene "Petrocene 202, manufactured by Tosoh Corporation"
(B) Resin composition used for forming the foaming agent-containing resin layer:
・ 50 parts by mass of low density polyethylene “Petrocene 202, manufactured by Tosoh Corporation” ・ 50 parts by mass of ultra-low density polyethylene “LUMITAC54-1, manufactured by Tosoh Corporation” ・ Foaming agent “Uniform Ultra AZ3050, manufactured by Otsuka Chemical Co., Ltd.” 4 parts by weight Filler (light calcium carbonate) “Brilliant-15, average particle size 0.15 μm, manufactured by Shiroishi Kogyo Co., Ltd.” 40 parts by weight Pigment (titanium dioxide) “Tai Pure R-108, manufactured by DuPont” 30 Part by mass-Foaming aid "ADK STAB OF-101, manufactured by ADEKA Corporation" 5 parts by mass-Crosslinking agent "OPSTAR JUA-702, manufactured by JSR Co., Ltd."
Example 19
A foamed laminated sheet was obtained in the same manner as in Example 18 except that the resin forming the non-foamed resin layer A was low-density polyethylene “Petrocene 202, manufactured by Tosoh Corporation”.

Comparative Example 1
As an adsorbent contained in the deodorant-containing coating liquid, instead of the organic / inorganic composite adsorbent, a foamed laminate was used in the same manner as in Example 1 except that zeolite “HSZ800 series 890HOA type, manufactured by Tosoh Corporation” was used. A sheet was obtained.

Comparative Example 2
A foamed laminated sheet was obtained in the same manner as in Comparative Example 1 except that the deodorant-containing coating liquid was formed without containing the silicone resin in the deodorant-containing coating liquid.

Comparative Example 3
Example 1 except that a visible light type photocatalyst “MPT-623, manufactured by Ishihara Sangyo Co., Ltd.” was used as the catalyst contained in the deodorant-containing coating solution instead of the oxide semiconductor coated with an inorganic substance. Similarly, a foamed laminated sheet was obtained.

Comparative Example 4
A foamed laminated sheet was obtained in the same manner as in Comparative Example 3 except that the deodorant-containing resin layer was formed without containing the silicone resin in the deodorant-containing coating liquid.

Comparative Example 5
As a deodorant-containing coating solution, a titanium oxide photocatalyst coating agent “TC-S4115 (with inorganic binder), nonvolatile component 5 mass%, titanium oxide particle size: 100 nm, manufactured by Sumitomo Chemical Co., Ltd.”, an organic adsorbent (Organic-inorganic composite adsorbent) “Kesmon NS-231, manufactured by Toagosei Co., Ltd.” is 70 parts by mass per 100 parts by mass of the nonvolatile component, and silicone resin “KP-361, manufactured by Shin-Etsu Silicone” is 100 masses of the nonvolatile component. A foamed laminated sheet was obtained in the same manner as in Example 1 except that 20 parts by mass added per part was used.

Comparative Example 6
A foamed laminated sheet was obtained in the same manner as in Comparative Example 5 except that the deodorant-containing coating liquid was formed without containing the silicone resin in the deodorant-containing coating liquid.

<Evaluation test>
(1) Acetaldehyde deodorization performance test The sample (10 cm x 10 cm) of the foam laminated sheet obtained in the examples and comparative examples was inserted into a Tedlar bag having an internal volume of 5 liters (L). 1 L of synthetic air [(nitrogen: oxygen) volume ratio: 4/1, 50% RH] is fed into the tedlar bag, and acetaldehyde is fed into the tedlar bag so that the acetaldehyde concentration is 60 ppm, and acetaldehyde deodorizing performance Test gas was used.

The concentration of acetaldehyde was measured immediately after the test gas was introduced (0 hour) and after storage for 24 hours in the dark. Further, the acetaldehyde concentration was measured immediately after the test gas was introduced (0 hour) and after irradiation with 2.0 mW / cm ² of black light (BL) for 24 hours. The acetaldehyde concentration was measured with a detector tube in a Tedlar bag.

(2) Contamination resistance test Coffee and soy sauce were each dropped as a contaminant on the gauze placed on the samples of the foamed laminated sheets obtained in the above Examples and Comparative Examples, and wiped with water after 24 hours. .

  Furthermore, the lines of the water-based sign pen were directly written on the samples of the foamed laminated sheets obtained in the examples and comparative examples, and after 24 hours, they were wiped with a neutral detergent.

  As a result of visual evaluation, “◯” was indicated when wiping was possible, “Δ” was indicated when wiping residue was observed, and “X” was indicated when wiping was not possible.

(3) EM (embossing) suitability test The samples of the foamed laminated sheets obtained in the examples and comparative examples were placed in a heating furnace at 220 ° C. for 60 seconds and then embossed to obtain a state of embossed shape transfer. (Embossability) is judged visually. “◯” when the shape was transferred, “Δ” when the uneven shape was sweet, and “X” when the uneven shape was not transferred or cracked and the surface protective film could not maintain the shape.

Discussion Consider the acetaldehyde deodorization performance test.

  In Comparative Examples 1 and 2, zeolite was used as the adsorbent, the aldehyde concentration was not sufficiently lowered, and good deodorizing performance was not exhibited. In Comparative Examples 3-6, the high deodorizing performance was shown in the dark place by using an organic type adsorbent for the adsorbent. However, since a photocatalyst was used as the catalyst, the organic component of the organic adsorbent was decomposed by the photocatalyst under black light irradiation, and the deodorizing performance was lowered.

  On the other hand, Examples 1-5 and 8-19 use the organic type adsorbent (organic-inorganic composite adsorbent) as the adsorbent, and a good decrease in aldehyde concentration is observed, showing high deodorizing performance. It was. In Examples 8, 9 and 12 to 19, an organic adsorbent (organic / inorganic composite adsorbent) was also added to the intermediate layer, a good decrease in aldehyde concentration was observed, and high deodorizing performance was exhibited. . Particularly in Examples 8, 9, 12, 13, 15, 16, 18 and 19, the total amount of deodorant added in the intermediate layer and the surface protective layer is higher than that in Examples 14 and 17, and thus in the dark. It showed the highest performance. In Examples 6 and 7, natural organic organic adsorbents were used among organic adsorbents, and a good decrease in aldehyde concentration was observed, indicating high deodorizing performance. Moreover, Examples 1-19 showed the performance equivalent to a dark place atmosphere or higher performance than a dark place by the activation of a catalyst also in a black light irradiation atmosphere. As described above, in Examples 1 to 19, the organic adsorbent exhibits deodorization performance by efficiently adsorbing acetaldehyde, and then an oxide semiconductor that supports an inorganic substance or is coated with an inorganic substance and / or It is considered that the acetaldehyde adsorbed by the non-photocatalyst is efficiently decomposed (odor component decomposition performance).

  Consider the anti-contamination test.

  In Comparative Examples 5 and 6, an inorganic binder was used in order to suppress decomposition of the organic resin by the photocatalyst, and pollutant adsorption occurred, resulting in poor contamination.

  On the other hand, Examples 1 to 19 showed good contamination resistance. In Examples 10 and 11, an electron beam curable resin was used as a resin component, and very good contamination resistance was exhibited. In Examples 1 to 9 and 12 to 19 using a thermosetting resin (aqueous acrylic resin), the addition of the silicone resin improved the repelling of the aqueous sign pen and improved the stain resistance.

  Consider the EM (emboss) suitability test.

  In Comparative Examples 5 and 6, an inorganic binder was used, and the cracking resistance was deteriorated due to the occurrence of cracks due to embossing.

1. Base material 2. Non-foamed resin layer B
3. 3. Foaming agent-containing resin layer Non-foamed resin layer A
5. Pattern layer 6 6. Deodorant-containing resin layer Film layer8. Primer layer

Claims (11)

A laminated sheet in which at least a foaming agent-containing resin layer and a deodorant-containing resin layer are sequentially formed on a substrate,
The deodorant-containing resin layer is a laminated sheet which is a layer containing an oxide semiconductor carrying an inorganic substance or coated with an inorganic substance and / or a non-photocatalyst, an organic adsorbent that adsorbs an odor component, and a resin component.   The laminated sheet according to claim 1, wherein the inorganic substance is at least one selected from the group consisting of calcium phosphate, calcium silicate, magnesium phosphate, and magnesium silicate. The laminated sheet according to claim 1 or 2, wherein the oxide semiconductor is at least one selected from the group consisting of TiO ₂ , CdS, CdSc, WO ₃ , Fe ₂ O ₃ , SrTiO ₃ and KNbO ₃ .   The laminated sheet according to any one of claims 1 to 3, wherein the non-photocatalyst is a phosphate containing at least one metal selected from the group consisting of titanium, cerium, and zirconium. The laminated sheet according to any one of claims 1 to 4 , wherein the organic adsorbent is an organic-inorganic composite adsorbent. The laminated sheet according to claim 5 , wherein the organic-inorganic composite adsorbent contains an amine compound. The laminated sheet according to any one of claims 1 to 6 , wherein an intermediate layer is formed between the foaming agent-containing resin layer and the deodorant-containing resin layer. The laminated sheet according to claim 7 , wherein the intermediate layer includes an organic adsorbent that adsorbs odor components. The laminated sheet according to claim 8 , wherein the intermediate layer further comprises an oxide semiconductor carrying an inorganic substance or coated with an inorganic substance and / or a non-photocatalyst. The laminated sheet according to any one of claims 1 to 9 , wherein the substrate is a fibrous sheet. The foaming lamination sheet obtained by making the said foaming agent containing resin layer of the lamination sheet in any one of Claims 1-10 foam.

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