JP4992364B2 - wallpaper - Google Patents

Description

  The present invention relates to a wallpaper used as an interior material such as a wall or a ceiling of a house or the like, and particularly relates to a wallpaper that cannot be folded during construction and has excellent workability.

In general, the wallpaper is composed of an upper layer portion having design properties and a backing material that supports the upper layer portion and imparts workability. When constructing these wallpapers, flexibility and anti-curling properties are required. Flexibility facilitates workability when enhancing design by embossing, etc., and curl prevention occurs when moisture in the glue used during wallpaper construction is absorbed by the backing material. This is an important requirement for preventing curling.
Various attempts have been made for the purpose of such flexibility and curl prevention. For example, wallpaper using glossy paper having a Steecht size of 10 seconds or more as a backing paper (see Patent Document 1), surface There has been proposed a wallpaper (see Patent Document 2) in which the surface tension of the resin coating layer is 40 mN / m or less, the lateral underwater elongation of the backing material is 1.3% or less, and the sizing degree is 70 seconds or less.

  By the way, in order to increase the construction efficiency of the wallpaper, usually, the adhesive is collectively applied at the construction site, and the wallpaper is folded and the adhesive surfaces are kept in close contact with each other so that the adhesive does not dry and solidify. Then, the folded portion of the wallpaper is returned to the original position, and is applied to the wall surface. However, after being attached to the wall surface, it is necessary that the trace of the bent portion is not visible. However, in order to sufficiently adhere the adhesive surfaces of the wallpaper, it is necessary to crimp the folded portion so that a crease is formed, and there is a problem that the crease is noticeable after the wallpaper is attached. In particular, this wrinkle was noticeable and problematic for wallpaper with film.

JP 2004-292990 A JP 2005-171457 A

  An object of this invention is to provide the wallpaper which was excellent in the construction property which is hard to produce a crease when constructing a wallpaper in such a condition, and its manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above problem can be solved by using a specific backing material and controlling the Clark stiffness of the backing material. The present invention has been completed based on such findings.

That is, the present invention
(1) A wallpaper having a base sheet in which a foamed resin layer made of a thermoplastic resin containing a foaming agent and an inorganic filler and a pattern layer are laminated on a backing material, and the surface protection is provided on the base sheet. Layers are laminated, the surface protection layer is obtained by crosslinking and curing an ionizing radiation curable resin, a concavo-convex pattern is applied from the surface side of the foamed resin layer, and the Clark stiffness of the backing material is 75% or less. Wallpaper, characterized by
(2) The wallpaper according to (1), wherein the thermoplastic resin constituting the foamed resin layer is a vinyl chloride resin,
(3) In the above (1) or (2), a surface protective sheet is laminated on the substrate sheet, and the surface protective sheet is obtained by laminating a surface protective layer on a film layer made of a thermoplastic resin. The described wallpaper,
(4) The wallpaper according to (3) above, wherein the thermoplastic resin constituting the film layer is an ethylene-vinyl alcohol copolymer resin,
(5) The wallpaper according to any one of (1) to (4) above, wherein a concavo-convex pattern is applied from the surface protective layer side to the foamed resin layer, and (6) one surface of the film layer made of a thermoplastic resin. A step of providing a surface protective layer obtained by crosslinking and curing an ionizing radiation curable resin and providing an adhesive layer on the other surface as necessary, and foaming on a backing material having a Clark stiffness of 75% or less A foamed resin composition comprising a thermoplastic resin containing an agent and an inorganic filler is applied, and after a pattern layer is provided thereon, the foamed resin composition is foamed in a heating foaming furnace to form a foamed resin layer. The step of obtaining a sheet, and the substrate sheet and the surface protective sheet are bonded together by a pressure roll or a pressure plate having an embossed mold formed on the surface, and at the same time, an uneven pattern is formed from the surface protective layer side to the foamed resin layer. Including the step of forming Wallpaper method of manufacture, wherein the door,
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, when constructing a wallpaper, the wallpaper excellent in the construction property which is hard to generate | occur | produce a folding line, and its manufacturing method can be provided.

  The wallpaper of this invention is a wallpaper which has a base material sheet, Comprising: A surface protection sheet is laminated | stacked on it as needed. The base sheet has a structure in which a foamed resin layer and a pattern layer are laminated on a backing material, and the surface protective sheet is preferably a laminate of a surface protective layer on a film layer made of a thermoplastic resin. Hereinafter, a typical structure of the wallpaper of the present invention will be described with reference to FIG.

FIG. 1 is a schematic view showing a cross section of a wallpaper 1 of the present invention. In the example shown in FIG. 1, the wallpaper 1 of the present invention has a surface protection sheet 30 laminated on a base sheet 20.
The base sheet 20 has a foamed resin layer 22 and a pattern layer 23 made of a thermoplastic resin containing a foaming agent and an inorganic filler on a backing material 21. On the other hand, the surface protective sheet 30 is formed by laminating a film layer 31 and a surface protective layer 32. In the example shown in FIG. 1, the film layer 31 and the surface protective layer 32 are laminated via a primer layer 33 for improving adhesiveness.
In the example shown in FIG. 1, the base material sheet 20 and the surface protection sheet 30 are bonded via an adhesive layer 40.

Hereinafter, the present invention will be described in detail with reference to FIG. 1 showing one preferred embodiment of the present invention.
As the material of the backing material 21 used in the present invention, ordinary pulp paper, pulp-based flame retardant paper impregnated with a water-soluble flame retardant such as guanazine sulfanilate and guanazine phosphate, calcium carbonate, aluminum hydroxide, hydroxide Inorganic paper mixed with inorganic agents such as magnesium, paper mixed with acrylic fiber or polyester fiber, etc. can be used, and these materials may be used alone or in any combination such as composites of paper A laminated body may be sufficient.

The backing material in the wallpaper of the present invention must have a Clark stiffness of 75% or less. If the Clark stiffness of the backing material exceeds 75%, it is difficult to suppress the occurrence of creases. The Clark stiffness of the backing material is more preferably 70% or less from the viewpoint of effect.
In addition, the measurement of Clark stiffness is based on JIS P-8143.

Examples of a method for controlling the Clark stiffness of the backing material include a method of controlling the thickness of the backing material, the degree of beating of the pulp, and the fiber length of the pulp. Since the stiffness of the paper tends to increase in proportion to the cube of the thickness of the paper when the basis weight is constant, a method of adjusting the thickness of the paper is effective. Beating also increases stiffness by increasing the density of the sheet and reducing the space in which the fibers can stretch, thereby increasing the bond between the fibers. Therefore, Clark stiffness can be weakened by loosening the beating condition and reducing the number of times. Further, regarding the fiber length of the pulp, the short fiber pulp paper tends to be more stiff than the long fiber pulp paper. Therefore, the Clark stiffness can be reduced by selecting a longer fiber pulp paper.
By combining these control methods, the Clark stiffness of the backing material can be controlled within the range specified by the present invention.

In addition, the backing material in the present invention preferably has an underwater elongation of 1% or less from the viewpoint of curling prevention. Incidentally, the elongation in water is determined by the JAPAN TAPPI paper pulp test method No. It is a value measured according to 27: 2000.
Further, a flame retardant, an inorganic agent, a dry paper strength enhancer, a wet paper strength enhancer, a colorant, a sizing agent, a fixing agent and the like may be appropriately added to the backing material as necessary.
Although there is no restriction | limiting in particular about the thickness of the backing material 21, Basic weight is about 50-300 g / m < ² > normally, Preferably it is the range of 55-160 g / m < ² >. In particular, the range of 60 to 160 g / m ² is preferable in order to pick up the unevenness of the base during the construction of the wallpaper, so that so-called unevenness is not noticeable.

Next, a foamed resin layer 22 obtained by foaming a foamed resin composition comprising a thermoplastic resin containing a foaming agent and an inorganic filler shown in FIG. 1 is provided to impart flame retardancy to wallpaper. It is. Thermoplastic resins include polyvinyl chloride (polyvinyl chloride resin), polyethylene, polypropylene, polystyrene, acrylonitrile / butadiene / styrene, acrylonitrile / styrene, nylon, polyacetal, acrylic, polycarbonate, polyester, polyvinyl acetate, polyvinyl alcohol, polyurethane, etc. The thermoplastic resin simple substance and copolymer of these, or these mixed resin can be mentioned, Among these, a vinyl chloride thermoplastic resin has film formability, flexibility, low temperature workability, and relatively Since it can be set as a low-cost wallpaper, it is preferable.
The thickness of the foamed resin layer 22 of the present invention is preferably 500 to 1200 μm.

  Examples of the foaming agent used in the foamed resin layer 22 of the present invention include inorganic foaming agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, and ammonium nitrite; N, N′-dimethyl-N, N′-dinitroso Nitroso compounds such as terephthalamide, N, N'-dinitrosopentamethylenetetramine; azo such as azodicarbonamide, azobisformamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate Compounds; sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3'-disulfonyl hydrazide; calcium azide 4,4'-diphenyl disulfonyl azide and azide compounds such as p- toluenesulfonyl azide and the like. Of these, low cost, low heat of decomposition, excellent flame retardancy and self-extinguishing properties, stable to water, non-toxic, and thermal decomposition chemical foaming agent can be processed at decomposition temperature or lower. Since it is possible, a thermally decomposable foaming agent of an azo compound such as azodicarbonamide or azobisformamide is preferable.

  The addition amount of the foaming agent may be appropriately determined depending on the required design properties, but is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic resin constituting the foamed resin layer 22. If necessary, a foaming aid that accelerates the decomposition of the foaming agent can be used in combination in order to obtain a further foaming effect. For example, when azodicarbonamide is used as the foaming agent, zinc oxide, lead sulfate, urea, zinc stearate, or the like is used as the foaming aid.

  There is no restriction | limiting in particular as the inorganic filler used for the foamed resin layer 22 of this invention, A various thing can be used. For example, calcium carbonate, magnesium carbonate, fly ash, dehydrated sludge, natural silica, synthetic silica, kaolin, clay, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, barium sulfate, calcium hydroxide, aluminum hydroxide, alumina, water Magnesium oxide, talc, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite, aluminum borate, silica Balloons, glass flakes, glass balloons, silica, iron slag, copper, iron, iron oxide, carbon black, sendust, alnico magnets, magnetic powders such as various ferrites, cement, glass powder, diatomaceous earth Antimony trioxide, magnesium oxysulfate, hydrated aluminum, hydrated gypsum, alum, and the like. Among these, aluminum hydroxide is preferable because it has a low decomposition temperature, a large endothermic amount, and low cost. In addition, although these inorganic fillers may be used independently, 2 or more types may be used together.

Many of these inorganic fillers have the effect of imparting flame retardancy to the wallpaper of the present invention, and the effect is further increased when incorporated in a large amount. In order to sufficiently obtain the flame retardancy of the wallpaper, it is preferable to blend 100 parts by mass or more of an inorganic filler with respect to 100 parts by mass of the thermoplastic resin constituting the foamed resin layer 22.
The average particle size of the inorganic filler used in the present invention is preferably 5 to 25 μm, more preferably 5 to 15 μm.

  These inorganic fillers may be blended as they are, but the inorganic filler is previously a silane-based, titanate-based, aluminate-based, zircoaluminum-based coupling agent, phosphoric acid-based, fatty acid-based surfactant, You may process by fats and oils, wax, a stearic acid, a silane coupling agent, etc.

  Moreover, the foamed resin layer 22 can mix | blend various additives according to the physical property requested | required. Examples of the additive include a fungicide, an insecticide, an antiseptic, an antibacterial agent, a diluent, a deodorant, a light stabilizer, and a plasticizer.

  Next, the pattern layer 23 shown in FIG. 1 gives decorativeness to the backing material 2 and is formed by printing various patterns using ink and a printing machine. In general, it can be formed with a commonly used ink by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, or the like. As patterns, there are stone patterns imitating the surface of rocks, such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns imitating cloth or cloth-like patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done.

As the ink used for forming the pattern layer 23, an ink in which a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used. The binder is not particularly limited, and examples thereof include polyurethane resins, vinyl acetate resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polyethylene resins, Any one of chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc., alone or 2 A mixture of seeds or more is used. Among these, for the purpose of the present invention, it is preferable to use one kind of polyurethane resin, vinyl acetate resin, acrylic resin, polyester resin, cellulose resin, polyamide resin, or a mixture of two or more kinds. .
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metallic pigments composed of scaly foil pieces such as aluminum and brass, pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.
The pattern layer 23 preferably has a thickness of about 1 to 20 μm.

In the wallpaper 1 of the present invention, the surface protective sheet 30 is preferably laminated on the base sheet 20, and the surface protective sheet 30 is preferably composed of a film layer 31 and a surface protective layer 32 made of a thermoplastic resin.
The film layer 31 is a layer that is laminated on the upper surface of the pattern layer 23 through an adhesive layer 40 as necessary. Usually, the stain resistance, cellophane tape resistance, scratch resistance, It is provided to provide performance such as chemical resistance.
Examples of the thermoplastic resin used in the film layer 31 of the present invention include polyethylene, polypropylene, polybutene, methacryl, thermoplastic polyester, polyvinyl alcohol, fluorine, and other thermoplastic resins and various copolymer resins. A transparent or translucent commercially available film made of the above resin can be used.
Examples of the commercially available film include an ethylene-vinyl alcohol copolymer film, a fluorine resin film such as polyvinyl fluoride, polyvinylidene fluoride, and ethylene tetrafluoroethylene, and an olefin film coated with a urethane or acrylic coating agent. Is mentioned. Above all, it excels in performance such as contamination resistance, scratch resistance, chemical resistance, etc., and exhibits excellent unevenness followability in embossing, that is, it has a sufficiently large longitudinal tensile elongation and is produced without collapsing by ionizing radiation. An ethylene-vinyl alcohol copolymer resin film having a low cost and a low smoke density during combustion is preferred.
Moreover, it is preferable that the thickness of the film used for the film layer 31 of this invention is 10-25 micrometers. If the thickness of the film is within the above range, it is possible to ensure the unevenness followability of the wallpaper by embossing without being restricted in the production of the film.

The surface protective layer 32 of the present invention is provided on the wallpaper of the present invention for the purpose of improving surface properties such as stain resistance by being laminated on the upper surface of the film layer 31. The resin constituting the surface protective layer 32 is not particularly limited, and a resin obtained by crosslinking and curing the curable resin composition is preferable. Examples of the curable resin composition include a thermosetting resin composition and an ionizing radiation curable resin composition, and an ionizing radiation curable resin composition, particularly an electron beam curable resin composition is preferable.
Here, the ionizing radiation curable resin composition is one having an energy quantum capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, by irradiating with ultraviolet rays or electron beams. The resin composition which hardens | cures.

  Thermosetting resin compositions include phenolic resins, phenol-formalin resins, urea resins, urea-formalin resins, melamine resins, melamine-formalin resins, alkyd resins, epoxy resins, unsaturated polyester resins, and general-purpose two-component curing types. An acrylic resin (acrylic polyol hardened | cured material) etc. can be illustrated.

  As the ionizing radiation curable resin used for the surface protective layer 32, a conventionally known compound may be appropriately used. Among the polymerizable monomers and polymerizable oligomers or prepolymers conventionally used as ionizing radiation curable resin compositions. Can be appropriately selected and used. Specifically, representative examples will be described below, but among these, it is preferable to use a polymerizable oligomer from the viewpoint of unevenness followability of embossing.

  Typically, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable as the polymerizable monomer, and among them, a polyfunctional (meth) acrylate is preferable. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( (Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Examples include ethylene oxide-modified bisphenol A diacrylate. These polyfunctional (meth) acrylates may be used singly or in combination of two or more. The notation of (meth) acrylate indicates acrylate or methacrylate.

Moreover, in this invention, from the viewpoint of uneven | corrugated followable | trackability, the polyfunctional (meth) acrylate (henceforth (meth) acrylate A) whose functional group number of (meth) acrylate is 2-3, Preferably it is 3; The polyfunctional (meth) acrylate (hereinafter also referred to as (meth) acrylate B) having 4 to 6, preferably 5 to 6 functional groups is preferably used in combination.
The blending ratio (mass ratio) of (meth) acrylate A and (meth) acrylate B is preferably 5:95 to 20:80, and preferably 10:90 to 20:80, from the viewpoint of unevenness followability and stain resistance. Further preferred. In addition, (meth) acrylate A and (meth) acrylate B may be used individually by 1 type, and may combine 2 or more types.

  In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate The system etc. are mentioned. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

When an ultraviolet curable resin composition is used as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin composition. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 - 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -Tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal It is done.
Examples of the polymerizable oligomer having a cationic polymerizable functional group in the molecule include aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.
In the present invention, it is preferable to use an electron beam curable resin composition as the ionizing radiation curable resin composition. This is because the electron beam curable resin composition can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator and can provide stable curing characteristics.

  In addition, the surface protective layer 32 in the present invention preferably contains a monofunctional or bifunctional silicone (meth) acrylate for the purpose of further imparting stain resistance to the wallpaper. The content of the mono- or bifunctional silicone (meth) acrylate is preferably 1 to 4 parts by mass with respect to 100 parts by mass of the curable resin, from the viewpoint of sufficiently improving the stain resistance and obtaining the effect of use. 2 parts by mass is more preferable. Moreover, as a functional group equivalent (molecular weight / functional group number) of silicone (meth) acrylate, what has the conditions of 1000-20000 is mentioned, for example.

Moreover, various additives can be mix | blended with the curable resin composition in this invention according to the desired physical property of the cured resin layer obtained. Examples of this additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, A plasticizer, an antifoamer, a filler, a solvent, a coloring agent, etc. are mentioned.
Here, as the weather resistance improving agent, an ultraviolet absorber or a light stabilizer can be used. The ultraviolet absorber may be either inorganic or organic, and as the inorganic ultraviolet absorber, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle diameter of about 5 to 120 nm can be preferably used. Examples of the organic ultraviolet absorber include benzotriazole-based compounds, specifically 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-). Amylphenyl) benzotriazole, 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of polyethylene glycol, and the like. On the other hand, examples of the light stabilizer include hindered amines, specifically 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1,2,2). , 6,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate and the like. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

Examples of the wear resistance improver include, for inorganic substances, spherical particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable. Organic materials include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is usually about 30 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles.
Examples of the polymerization inhibitor include hydroquinone, p-benzoquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. Examples of the crosslinking agent include a polyisocyanate compound, an epoxy compound, a metal chelate compound, an aziridine compound, and an oxazoline compound. Used.
As the filler, for example, barium sulfate, talc, clay, calcium carbonate, aluminum hydroxide and the like are used.
Examples of the colorant include known coloring pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue, phthalocyanine green, titanium oxide, and carbon black.
As the infrared absorber, for example, a dithiol metal complex, a phthalocyanine compound, a diimmonium compound, or the like is used.

In the present invention, the above-mentioned curing component and various additives are homogeneously mixed at a predetermined ratio, respectively, to prepare a coating liquid composed of a curable resin composition. The viscosity of this coating solution is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the substrate by the coating method described later, but a solvent may be added as necessary. Good.
In the present invention, the coating liquid prepared in this way is applied to the surface of the substrate so that the thickness after curing is 1 to 20 μm, gravure coating, bar coating, roll coating, reverse roll coating, Coating is performed by a known method such as comma coating, preferably gravure coating, to form an uncured resin layer. When the thickness after curing is 1 μm or more, a cured resin layer having a desired function is obtained. The thickness of the surface protective layer after curing is preferably about 2 to 20 μm.

In the present invention, the uncured resin layer thus formed is heated, or the uncured resin layer is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excessive electron beam.
The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.

When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.
The cured resin layer thus formed has various functions by adding various additives, for example, a so-called hard coat function, anti-fogging coat function, and anti-fouling coat having high hardness and scratch resistance. A function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can also be imparted.

  When the adhesiveness between the film layer 31 and the foamed resin layer 22 is low, for example, when the ethylene-vinyl alcohol copolymer resin film is used, it is preferable to provide an adhesive layer 40 between both layers as necessary. Although there is no restriction | limiting in particular as an adhesive agent used for the adhesive bond layer 40, a heat sensitive adhesive is preferable from the manufacturing process of this invention. A heat-sensitive adhesive is generally an adhesive that is a solid at normal temperature, melts or softens when heated, expresses adhesiveness, and solidifies and solidifies when cooled, with a thermoplastic resin as the main component. Say. This is dissolved in an appropriate solvent or melted by heating, applied to one or both adhesive surfaces of the adherend, and the two are overlapped and heated and pressed to bond them. Specifically, (meth) acrylic resin system, polyurethane resin system, polyester system, polyamide resin system, (meth) acrylic ester-olefin copolymer resin, vinyl chloride resin, ethylene-vinyl acetate copolymer resin, Easy-adhesive resins such as ionomer resins and olefin-α-olefin copolymer resins, and blends with thermoplastic resins that are the main components of olefin resins and foamed resin compositions, and thermoplastic resins that are the main components of film layers Can be mentioned.

The adhesive layer 40 is provided between the foamed resin layer 22 and the film layer 31 as described above and as shown in FIG. 1 for the purpose of improving the interlayer adhesive force. It can also be provided between the foamed resin layer 22. In addition to providing an adhesive layer, a physical or chemical surface treatment such as an oxidation method or a concavo-convex method can be applied to one or both sides as desired in order to improve the interlayer adhesion.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
In addition, for the purpose of strengthening the interlayer adhesive force, a treatment such as forming a primer layer between the surface protective layer 32 and the film layer 31 and between the foamed resin layer 22 and the film layer 31 is performed as necessary. You can also.

The wallpaper of the present invention is provided with a concavo-convex pattern by embossing in order to make the wallpaper excellent in design. The embossing is performed from the surface side of the foamed resin layer 22 in the base sheet 20, that is, from the surface protective sheet side. This concavo-convex pattern is provided on the base material sheet 20, and then the surface protection sheet 30 can be laminated. After the surface protection sheet 30 is laminated on the base material sheet 20, the surface protection layer side is applied to the foamed resin layer. An uneven pattern can also be provided. From the viewpoint of designability, as shown in FIG. 1, it is preferable to provide the concavo-convex pattern 50 after laminating the surface protective sheet on the base sheet.
Furthermore, it is preferable that the tensile elongation (longitudinal direction) of the surface protective sheet 30 composed of the film layer 31 and the surface protective layer 32 is 30% or more from the viewpoint of obtaining a sharp uneven pattern with excellent design. If the tensile elongation (longitudinal direction) is 30% or more, when forming a concavo-convex pattern by embossing, minute cracks are generated in the surface protective layer 32, and surface properties such as contamination resistance are significantly reduced. There is no.
Here, the tensile elongation (longitudinal direction) refers to the ratio (%) of the length before pulling the surface protective film in the vertical direction and the length after pulling.
The concavo-convex pattern 50 of the present invention is heated by an embossing roll or an embossing plate from the upper surface of the surface protective layer 32, that is, the outermost layer side, when the wallpaper in the manufacturing process is at a temperature that can be embossed by any means. It can be formed by pressing. A well-known sheet or rotary embossing machine is used to form the concavo-convex pattern 50. The shape of the concavo-convex pattern 50 includes a wood grain pipe groove, stone surface unevenness, cloth surface texture, satin, sand, hairline. , There are many strips.
In addition, when providing the uneven | corrugated pattern in the above-mentioned base material sheet 20, and laminating | stacking the surface protection sheet 30 after that, when it is the temperature which can be embossed similarly, it is the embossing roll from the surface side of a foamed resin layer. Alternatively, it can be formed by heating and pressing with an embossed plate.

The wallpaper of the present invention is manufactured, for example, by the following manufacturing method.
An ionizing radiation curable resin is applied to one surface of the film layer 31 made of a thermoplastic resin, and a resin constituting an adhesive and / or primer layer is applied to the other surface as necessary, The surface protection sheet 30 is obtained by irradiating ionizing radiation to cure the ionizing radiation curable resin. Further, a foamed resin composition made of a thermoplastic resin containing a foaming agent, an inorganic filler, and other additives as necessary was coated on the backing material 21 by a comma coater method, and a pattern layer 23 was further printed and applied. Then, the said foamed resin composition is foamed at about 250 degreeC using a heating foaming furnace, the foamed resin layer 22 is formed, and the base material sheet 20 is obtained. Next, after cooling the base sheet 20, it is reheated to about 150 ° C., and then a cooling roll (surface protective sheet 30 side) on which an embossed plate is formed from the outermost layer side of the surface protective sheet 30 and pressurization Both sheets are thermocompression bonded by passing between the rolls, and the concavo-convex pattern 50 is formed. Then, the wallpaper of this invention which formed the uneven | corrugated pattern 50 from the outermost layer side of the surface protective layer 32 to the foamed resin layer 22 can be obtained by cooling. As described above, the primer layer 33 and the adhesive layer 40 can be provided between desired layers as necessary.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation method)
The decorative sheet obtained in each example was evaluated by the following methods.
(1) Clark stiffness This was measured according to JIS P8143.
(2) Evaluation of crease properties A commercially available adhesive for wallpaper (Yayoi) was used on the back side of the wallpaper 20 m ² produced in each example and comparative example, using a gluing machine (manufactured by Yayoi Chemical Industry Co., Ltd.). Chemical industry Co., Ltd. “Luo Mild”) was applied at 120 g / m ^2, and the adhesive surfaces were bonded together and folded. A load of 15 kg was applied to the folded part and left for 15 minutes. Next, the wallpaper was applied to a gypsum board (Yoshino Gypsum Co., Ltd. “Non-combustible Tiger Board” thickness 12.5 mm) and visually evaluated.

Example 1
As the backing material 21, using a backing paper having a rice weighing of 60 g / m ² and a thickness of 90 μm and adjusted to a Clark stiffness of 63.2%, a foamed resin composition having the following composition was prepared on the substrate. The composition is coated by a comma coating method, and further applied by gravure printing with a coating amount of 3 g / m ² using an ink containing acrylic resin as a binder, carbon black and a petrol as a colorant. Layer 23 was formed.
Apart from the above, an ethylene-vinyl alcohol copolymer resin (manufactured by Kuraray Co., Ltd., Eval Film HF-ME (thickness: 12 μm), ethylene content 44 mol%) coated with an adhesive in advance as the film layer 31 is used. The primer layer 33 is formed by gravure printing the urethane-acrylic copolymer resin at a coating amount of 2.0 g / m ² on the upper surface (the side where the adhesive is not applied) of the film layer 31, It was coated by gravure offset coater method in the ionizing radiation-curable resin having the following composition on coating amount 2.0 g / m ^2. After coating, an electron beam with a pressurization voltage of 125 kV and an irradiation dose of 30 kGy (3 Mrad) was irradiated to cure the ionizing radiation curable resin to form the surface protective layer 32, thereby obtaining the surface protective sheet 30.
The backing material 21 obtained by applying the pattern layer 23 and coating the foamed resin composition is foamed with the foamed resin composition at 230 ° C. using a heating foaming furnace to form the foamed resin layer 22. A material sheet 20 was obtained. Next, the substrate sheet 20 and the surface protective sheet 30 obtained above are simultaneously passed between a cooling roll and a pressure roll on which an embossing mold is formed, and subjected to thermocompression bonding while embossing is performed. A wallpaper having a concavo-convex pattern was obtained.
Foamed resin composition composition PVC resin (manufactured by Tosoh Corporation, trade name: R-720): 100 parts by mass Calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Whiten H): 100 parts by weight Foaming agent (Otsuka Product name: Uniform AZ Ultra, manufactured by Kagaku Co., Ltd .: 3 parts by mass Antifungal agent (manufactured by Taisho Technos Co., Ltd., product name: Biosite 7663DS): 0.2 parts by mass Light stabilizer (Adeka Argus Chemical Co., Ltd.) ), Trade name: O-1305): 5 parts by weight Diluent (manufactured by Shell, trade name: Shellsol S): 20 parts by weight Plasticizer (diisononyl phthalate): 38 parts by weight Ionizing radiation curable resin composition 6 Functional urethane acrylate: 80 parts by weight Trifunctional urethane acrylate: 20 parts by weight Silica (particle size: about 3 μm): 20 parts by weight Bifunctional silicone methacrylate: 2 parts by weight Was evaluated by the above method, broken wrinkles was observed.

Example 2
A wallpaper was obtained in the same manner as in Example 1 except that a backing paper having a weight of rice of 60 g / m ² and a thickness of 94 μm and adjusted to a Clark stiffness of 67.1% was used as the backing material 21. When evaluated in the same manner as in Example 1, no creases were observed.

Example 3
A wallpaper was obtained in the same manner as in Example 1 except that a backing paper having a weight of rice of 60 g / m ² and a thickness of 108 μm and adjusted to a Clark stiffness of 73.2% was used as the backing material 21. When evaluated in the same manner as in Example 1, a slight crease was observed immediately after sticking, but the crease became inconspicuous after 1 day.

Comparative Example 1
A wallpaper was obtained in the same manner as in Example 1 except that a backing paper having a weight of rice of 60 g / m ² and a thickness of 111 μm and adjusted to a Clark stiffness of 78.6% was used as the backing material 21. When evaluated in the same manner as in Example 1, creases were confirmed and creases were confirmed even after 2 days.

  ADVANTAGE OF THE INVENTION According to this invention, when constructing a wallpaper, the wallpaper excellent in the construction property which is hard to generate | occur | produce a folding line, and its manufacturing method can be provided.

It is a schematic diagram which shows the cross section of the wallpaper of this invention.

Explanation of symbols

1. Wallpaper 20 Base sheet 21. Backing material 22. Foamed resin layer 23. Pattern layer 30. Surface protection sheet 31. Film layer 32. Surface protective layer 33. Primer layer 40. Adhesive layer 50. Uneven pattern

Claims (6)

  A wallpaper having a base sheet in which a foamed resin layer made of a thermoplastic resin containing a foaming agent and an inorganic filler and a pattern layer are sequentially laminated on a backing material, and a surface protective layer is laminated on the base sheet The surface protective layer is obtained by crosslinking and curing an ionizing radiation curable resin, is provided with an uneven pattern from the surface side of the foamed resin layer, and the Clark stiffness of the backing material is 75% or less. Wallpaper.   The wallpaper according to claim 1, wherein the thermoplastic resin constituting the foamed resin layer is a vinyl chloride resin.   The wallpaper according to claim 1 or 2, wherein a surface protective sheet is laminated on the base sheet, and the surface protective sheet is obtained by laminating a surface protective layer on a film layer made of a thermoplastic resin.   The wallpaper according to claim 3, wherein the thermoplastic resin constituting the film layer is an ethylene-vinyl alcohol copolymer resin.   The wallpaper in any one of Claims 1-4 with which the uneven | corrugated pattern was given from the surface protective layer side to the foamed resin layer. A step of providing a surface protective layer obtained by crosslinking and curing an ionizing radiation curable resin on one surface of a film layer made of a thermoplastic resin, and preparing a surface protective sheet provided with an adhesive layer on the other surface, if necessary; A foamed resin composition comprising a thermoplastic resin containing a foaming agent and an inorganic filler is applied to a backing material having a Clark stiffness of 75% or less, and a pattern layer is provided thereon, and then the foamed resin composition is heated in a heating foaming furnace. At the same time, the base sheet and the surface protective sheet are bonded together by a step of obtaining a base sheet by foaming a product to obtain a base sheet, and a pressure roll or pressure plate having an embossed mold formed on the surface. A method for producing wallpaper, comprising a step of forming an uneven pattern from the surface protective layer side to the foamed resin layer.

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