JP2007092223A - Wall paper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wall paper having uneven pattern, excellent in unevenness followability by embossing and excellent in stain resistance. <P>SOLUTION: The wall paper is obtained by laminating a surface-protecting film onto a substrate sheet, and the substrate sheet is obtained by laminating a foaming resin layer composed of a thermoplastic resin containing a foaming agent and an inorganic filler, and a design layer in turn, and the surface-protecting film is obtained by laminating a surface resin layer on a film layer composed of an olefinic thermoplastic resin and applying uneven pattern from the surface protecting side to the foaming resin layer. In the wall paper, an ionizing radiation-curable resin containing a mono or bi-functional silicone methacrylate having high lifting effect (effect floating to the surface) is crosslinked and cured. The wall paper keeping characteristics having compensating tendency excellent in unevenness followability by embossing and excellent in stain resistance is obtained thereby. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a wallpaper having an ionizing radiation curable resin in a surface protective layer, which is excellent in uneven followability by embossing and excellent in stain resistance.

  Building interior materials such as wallpaper are required to be flame retardant from the standpoint of fire safety, and are often required to have a certain level of flame resistance by the Building Standards Act. In addition, architectural interior materials are required to have high designability in order to enhance comfort as an indoor living space. In particular, in order to have a three-dimensional design, a material that can be highly foamed as well as flexible. Is advantageous. As a material that meets these requirements, there is a material in which a pattern layer is provided by printing on a vinyl chloride resin layer, or a material in which an uneven pattern is formed by foaming and embossing the vinyl chloride resin layer. Widely used. However, these wallpapers have a problem that the stain resistance and the surface strength are not sufficient. This is because the wallpaper is made of a vinyl chloride resin having a problem of contamination and the like, and for the purpose of improving workability and design, it is applied to the surface of the wallpaper by forming a foam or a concavo-convex pattern. This is because fine irregularities and voids are generated.

  In order to solve the above problems, a surface protective layer is provided on the surface of the wallpaper to improve surface properties such as stain resistance. For example, urethane or acrylic resin is applied to the surface of the wallpaper to protect the surface. Layered methods are taken. However, the surface protective layer thus provided does not follow the foam or concavo-convex pattern when processed to form foam or concavo-convex pattern, resulting in uneven thickness of the surface protective layer, and the surface protective layer partially There arises a problem in manufacturing stability such that a crack is formed in the film and the foamed layer is exposed.

  A film having a foamed resin layer made of a thermoplastic resin containing a foaming agent and having excellent antifouling properties on the surface of the wallpaper, such as an acrylic resin film, a polyurethane resin film, a fluorine resin film, an ethylene-vinyl alcohol copolymer A method has been proposed in which a film or the like is bonded with an adhesive or the like to form a surface protective layer (for example, Patent Documents 1 and 2). However, just using these films as a surface protective layer is insufficient from the viewpoint of contamination resistance, and further improvements are desired.

JP 2001-260287 A JP 2001-260261 A

  Under such circumstances, the present invention provides a wallpaper having an ionizing radiation curable resin in a surface protective layer, which is excellent in unevenness followability by embossing and excellent in stain resistance, and a method for producing the wallpaper. Objective.

  As a result of intensive studies to achieve the above object, the present inventors have added emulsification by adding a specific silicone (meth) acrylate into the ionizing radiation curable resin forming the surface protective layer. It was possible to obtain a wallpaper that maintains a high level of characteristics that tend to cancel each other out, which is excellent in unevenness followability and excellent in stain resistance.

That is, the present invention
(1) A wallpaper in which a surface protective film is laminated on a base sheet, wherein the base sheet is a foamed resin layer made of a thermoplastic resin containing a foaming agent and an inorganic filler, and a pattern layer. A surface protective layer is laminated on a film layer made of an olefin-based thermoplastic resin, and a concavo-convex pattern is applied from the surface protective layer side to the foamed resin layer. Wallpaper characterized by being a layer obtained by crosslinking and curing an ionizing radiation curable resin containing a functional silicone (meth) acrylate;
(2) The wallpaper according to (1), wherein the surface protective film has a tensile elongation (longitudinal direction) of 30% or more,
(3) The wallpaper according to (1) or (2) above, wherein the thermoplastic resin constituting the film layer is an ethylene-vinyl alcohol copolymer resin,
(4) The wallpaper according to any one of (1) to (3), wherein the thermoplastic resin constituting the foamed resin layer is a vinyl chloride resin.
(5) The wallpaper according to any one of (1) to (5) above, wherein the content of the silicone (meth) acrylate is 1 part by mass or more with respect to 100 parts by mass of the ionizing radiation curable resin. ,
(6) The wallpaper according to any one of (1) to (5) above, wherein an adhesive layer is provided between the pattern layer and the film layer, and (7) from the thermoplastic resin Providing a surface protective layer comprising an ionizing radiation curable resin on one surface of the film layer and preparing a surface protective film provided with an adhesive layer on the other surface, if necessary, and a foaming agent and Applying a foamed resin composition comprising a thermoplastic resin containing an inorganic filler, providing a pattern layer, and then foaming the foamed resin composition in a heating foaming furnace to obtain a foamed resin layer, thereby obtaining a base sheet; And a step of forming a concavo-convex pattern from the surface protective layer side to the foamed resin layer at the same time as the base sheet and the surface protective sheet are bonded together by a pressure roll having an embossed mold formed on the surface. A method for producing wallpaper,
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, the wallpaper which has the ionizing radiation curable resin excellent in the uneven | corrugated followable | trackability by embossing and excellent in stain resistance in a surface protective layer can be provided.

  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 the wallpaper 1 of the present invention. In the example shown in FIG. 1, the wallpaper 1 of the present invention has a picture layer 4 on the lower surface of a film layer 6 on a base material 2 via a foamed resin layer 3 made of a thermoplastic resin containing a foaming agent and an inorganic filler. The surface protective layer 8 is formed by sequentially laminating the primer layer 7 and the ionizing radiation curable resin containing 1 to 2 functional silicone methacrylate on the upper surface. Further, the silicone methacrylate 9 shown in the figure has a feature that the concentration in the outermost layer portion of the surface protective layer 5 is high and becomes thinner as going to the substrate side.

[Substrate 2]
Hereinafter, the present invention will be described in detail with reference to FIG. 1 showing one preferred embodiment of the present invention.
The base material 2 used in the present invention is not particularly limited as long as it is usually used as wallpaper. For example, backing paper, flame retardant paper, synthetic resin sheet, woven fabric, non-woven fabric, knitted fabric and the like are used depending on the application. It can be selected appropriately. Each of these materials may be used alone, but may be a laminate of any combination such as a composite of paper. In addition, 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 as necessary. Above all, for regular wallpaper such as pulp-based flame retardant paper impregnated with water-soluble flame retardant such as guanazine sulfanilate and guanazine phosphate, inorganic paper mixed with inorganic agent such as calcium carbonate, aluminum hydroxide, magnesium hydroxide, etc. It is said to be a backing paper, and from the viewpoint of curling prevention, the underwater elongation is preferably 1% or less. 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.
Although there is no restriction | limiting in particular about the thickness of the base material 2, Basic weight is about 50-300 g / m < ² > normally, Preferably it is the range of 60-160 g / m < ² >.

[Foamed resin layer 3]
A foamed resin layer 3 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 for imparting flame retardancy to wallpaper. Thermoplastic resins such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, acrylonitrile / butadiene / styrene, acrylonitrile / styrene, nylon, polyacetal, acrylic, polycarbonate, polyester, polyvinyl acetate, polyvinyl alcohol, polyurethane, etc. And a copolymer or a mixed resin thereof. Among them, a vinyl chloride thermoplastic resin has a film-forming property, flexibility, low-temperature processability, and a relatively low-cost wallpaper. This is preferable.
The thickness of the foamed resin layer 3 of the present invention is preferably 500 to 1200 μm.

[Foaming agent]
Examples of the foaming agent used in the foamed resin layer 3 of the present invention include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, 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'-diphenyl azide, such as azide compounds such as p- toluenesulfonyl azide and the like. Low cost, low heat of decomposition, excellent flame retardancy and self-extinguishing properties, stable in water, non-toxic, and capable of processing heat decomposition chemical foaming agent below decomposition temperature Therefore, 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 of the foamed resin layer 3. 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.

[Inorganic filler]
There is no restriction | limiting in particular as the inorganic filler used for the foamed resin layer 3 of this invention, A various thing can be used.
Examples of inorganic fillers include 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, water Aluminum oxide, alumina, magnesium hydroxide, 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 balloon, glass flake, glass balloon, silica, iron slag, copper, iron, iron oxide, carbon black, sendust, alnico magnet, magnetic powder 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 add 100 parts by mass or more of an inorganic additive to 100 parts by mass of the thermoplastic resin of the foamed resin layer 3.
5-25 micrometers is preferable and, as for the average particle diameter of the inorganic filler used in this invention, 5-15 micrometers is more preferable.

  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 3 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.

[Picture layer 4]
The pattern layer 4 shown in FIG. 1 gives decorativeness to the base material 2 and is formed by printing various patterns using ink and a printing machine. In general, it can be formed with 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 4, 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 4 preferably has a thickness of about 1 to 20 μm.

[Film layer 6]
The film layer 6 of the present invention is a layer that is laminated on the upper surface of the picture layer 4 through the adhesive layer 5 as necessary, and is required for the wallpaper of the present invention, stain resistance, cellophane tape resistance, It is provided to provide performance such as scratch resistance and chemical resistance.
Examples of the thermoplastic resin used in the film layer 6 of the present invention include polyethylene, polypropylene, polybutene, methacrylic, 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.
The thickness of the film used for the film layer 6 of the present invention is preferably 10 to 25 μm. 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.

[Surface protective layer 8]
The surface protective layer 8 of the present invention is obtained by crosslinking and curing an ionizing radiation curable resin containing a mono- or bifunctional silicone (meth) acrylate, and is laminated on the upper surface of the film layer 6. The wallpaper of the present invention is provided for the purpose of improving surface properties such as stain resistance.
Here, the ionizing radiation curable resin composition is one having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, crosslinking or curing by irradiating ultraviolet rays or electron beams. Refers to a resin composition. “(Meth) acrylate” means “acrylate or methacrylate”.

[Silicone (meth) acrylate 9]
The monofunctional or bifunctional silicone (meth) acrylate contained in the ionizing radiation curable resin of the surface protective layer mainly imparts stain resistance to the wallpaper due to a synergistic effect with the ionizing radiation curable resin. Silicone (meth) acrylate is one of silicone oils made of polysiloxane or modified silicone oil in which (meth) acrylic groups are introduced at one or both ends. As the mono- or bifunctional silicone (meth) acrylate used for the silicone (meth) acrylate 9, conventionally known ones can be used, and the modified silicone oil has one or two organic groups in which the organic group is a meth) acrylic group. If it is, it will not be specifically limited. The structure of the modified silicone oil is roughly divided into a side chain type, a both-end type, a single-end type, and a side-chain both-end type depending on the bonding position of the organic group to be substituted. There is no particular limitation.
The content of the 1 to 2 functional silicone (meth) acrylate is preferably 1 to 4 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin, from the viewpoint of sufficiently obtaining the contamination resistance and the effect of using the same. 1-2 mass parts 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.

[Ionizing radiation curable resin]
As the ionizing radiation curable resin used for the surface protective layer 8, 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 phosphate di ( (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.

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 novolac type epoxy resin, bisphenol type 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.

Moreover, various additives can be mix | blended with the ionizing radiation-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. Moreover, as an organic type ultraviolet absorber, benzotriazole type, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-) is specifically mentioned. 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, a polymerizable monomer, a polymerizable oligomer and various additives, which are the ionizing radiation curable components, are uniformly mixed at predetermined ratios to prepare a coating liquid composed of an ionizing radiation curable resin composition. To do. 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 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.

[Adhesive layer 5]
When the adhesiveness between the film layer 6 and the foamed resin layer 3 is low, for example, when the ethylene-vinyl alcohol copolymer resin film is used, it is preferable to provide an adhesive layer 5 between both layers as necessary. Although there is no restriction | limiting in particular as an adhesive agent used for the adhesive bond layer 5, 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, polyurethane resin, polyester, polyamide resin, (meth) acrylic ester-olefin copolymer resin, vinyl chloride resin, ethylene-vinyl acetate copolymer resin, ionomer Resin, olefin-α olefin copolymer resin and other easy-adhesive resins alone, thermoplastic resins that are the main components of olefin resins and foamed resin compositions, and blends with thermoplastic resins that are the main components of the film layer .

For the purpose of improving the interlayer adhesion, the adhesive layer 5 is provided between the foamed resin layer 3 and the film layer 6 as described above and as shown in FIG. It can also be provided between the foamed resin layer 3. 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.
Further, for the purpose of strengthening the interlayer adhesion, a treatment such as forming a primer layer between the surface protective layer 8 and the film layer 6 and between the foamed resin layer 3 and the film layer 6 is performed as necessary. You can also.

[Uneven pattern 10]
The wallpaper of the present invention is characterized by being provided with a concavo-convex pattern by embossing in order to make the wallpaper excellent in design. From the viewpoint of obtaining a sharp concavo-convex pattern excellent in design properties, the tensile elongation (longitudinal direction) of the surface protective film comprising the pattern layer 4, the film layer 6, and the surface protective layer 8 is preferably 30% or more. If the tensile elongation (longitudinal direction) is 30% or more, when forming a concavo-convex pattern by embossing, a minute crack is generated in the surface protective layer 8 and the 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 10 of the present invention is obtained by applying heat and pressure with an embossed plate from the upper surface of the surface protective layer 8, that is, the outermost layer side, when the wallpaper in the manufacturing process is at a temperature at which embossing can be performed by any means. Can be formed. For the formation of the concavo-convex pattern 10, a well-known sheet or rotary embossing machine is used. The shape of the concavo-convex pattern 10 includes a wood grain conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain texture, a hairline. , There are many strips.

[Production method]
The wallpaper of the present invention is manufactured, for example, by the following manufacturing method.
An ionizing radiation curable resin containing a predetermined amount of mono- or bifunctional silicone methacrylate is applied to one surface of the film layer 6 made of thermoplastic resin, and an adhesive and / or primer layer is applied to the other surface as necessary. A constituent resin is applied, and then a predetermined ionizing radiation is applied to cure the ionizing radiation curable resin to obtain a surface protective sheet. Moreover, the foamed resin composition which consists of a thermoplastic resin which contains a foaming agent, an inorganic filler, and another additive as needed on the base material 2 was coated by the comma coater method, and also the pattern layer 4 was printed and applied. Then, the said foamed resin composition is foamed at about 250 degreeC using a heating foaming furnace, the foamed resin layer 3 is formed, and a base material sheet is obtained. Next, after the substrate sheet is cooled, it is reheated to about 150 ° C., and then between the cooling roll (surface protective sheet side) on which the embossed plate is formed from the outermost layer side of the surface protective sheet and the pressure roll. Both the sheets are thermocompression-bonded by passing, and after forming the concavo-convex pattern 10, cooling is performed to obtain the wallpaper of the present invention in which the concavo-convex pattern 10 is formed from the outermost layer side of the surface protective layer 8 to the foamed resin layer 3. be able to. As described above, the primer layer 7 and the adhesive layer 5 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 methods)
The decorative sheet obtained in each example was evaluated by the following methods.
(1) Evaluation of stain resistance In accordance with JIS K-6902, water-based pen (black), water-based pen (red), red crayon, lipstick, whiteboard marker, and oily magic are attached to the wallpaper as contaminants. After 24 hours, dry wiping was performed with a soft cloth (gauze), and the remaining contaminants were evaluated visually. Judgment criteria were evaluated as follows.
○ Pollutants can be completely wiped out △ Contaminants remain slightly but are minor and have no practical problems × Contaminant remains remarkable (2) Measurement of tensile elongation In accordance with JIS K-7127 , Using a universal tensile testing machine (ORIENTEC Co., Ltd., TRC-1250A-PL), pulling the wallpaper at a constant speed, measuring the elongation until the specimen breaks, and calculating the ratio of length before and after tension did.
(3) Evaluation of concavo-convex pattern (embossing formability) Evaluation of the concavo-convex pattern of the wallpaper obtained in the Example and the comparative example was performed visually. Judgment criteria were evaluated as follows.
○ The concavo-convex pattern is sharp and has excellent design. △ Some parts of the concavo-convex pattern are not sharp, but there is no problem.

Example 1
As the substrate 2, rice weighing 60 g / m ² of wallpaper for backing paper (Kojin Co., WK-FKKD) used to prepare a foamed resin composition in the following composition on the substrate, the composition The pattern layer 4 is coated by gravure printing with a coating amount of 3 g / m ² using an ink having an acrylic resin as a binder and carbon black and a petal as a colorant. Formed.
Separately 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 6 is used. The primer layer 7 is formed by gravure printing a urethane-acrylic copolymer resin at a coating amount of 2.0 g / m ² on the upper surface (side where the adhesive is not applied) of the film layer 6, An ionizing radiation curable resin having the following composition was coated on the surface by a gravure offset coater method at a coating amount of 2.0 g / m ² . After coating, the surface protective layer 5 was formed by irradiating an electron beam with a pressurization voltage of 125 kV and an irradiation dose of 30 kGy (3 Mrad) to cure the ionizing radiation curable resin, thereby obtaining a surface protective sheet.
The base material obtained by applying the pattern layer 4 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 3. After obtaining the sheet, the surface protection sheet obtained above and the embossing mold are passed through between the cooling roll and the pressure roll, and the surface is subjected to thermocompression bonding while embossing, thereby forming a concavo-convex pattern on the surface. Got a wallpaper with.
Foamed resin composition composition PVC resin (manufactured by Tosoh, trade name: R-720): 100 parts by mass Calcium carbonate (manufactured by Shiroishi Kogyo, trade name: Whiten H): 100 parts by weight Foaming agent (manufactured by Otsuka Chemical, trade name: Uniform AZ Ultra): 3 parts by weight Antifungal agent (manufactured by Taisho Technos, trade name: Biosite 7663DS): 0.2 parts by weight Light stabilizer (manufactured by Adeka Argus Chemical, trade name: O-1305): 5 parts by weight Dilution Agent (manufactured by Shell Petroleum, trade name: Shellsol S): 20 parts by mass Plasticizer (diisononyl phthalate): 38 parts by mass Ionizing radiation curable resin composition Hexafunctional urethane acrylate: 80 parts by mass Trifunctional urethane acrylate: 20 parts by mass Silica (particle size: about 3 μm): 20 parts by mass Bifunctional silicone methacrylate: 2 parts by mass

Example 2
As the substrate 2, rice weighing 60 g / m ² of wallpaper for backing paper (Kojin Co., WK-FKKD) used to prepare a foamed resin composition with the composition of Example 1 on the substrate, The composition is coated by a comma coating method, and is further applied by gravure printing with an application amount of 2.0 g / m ² using an ink having an acrylic resin as a binder and carbon black and a petal as a colorant. The pattern layer 4 was formed.
Separately 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 6 is used. The primer layer 7 is formed by gravure printing on the upper surface of the film layer 6 (the side on which the adhesive is not applied) with a urethane-acrylic copolymer resin at a coating amount of 2.0 g / m ^2. An ionizing radiation curable resin having the following composition was coated at a coating amount of 2.0 g / m ² by a gravure offset coater method. After coating, the surface protective layer 5 was formed by irradiating an electron beam with a pressurization voltage of 125 kV and an irradiation dose of 30 kGy (3 Mrad) to cure the ionizing radiation curable resin, thereby obtaining a surface protective sheet.
The base material obtained by applying the pattern layer 4 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 3. After obtaining the sheet, the surface protection sheet obtained above and the embossing mold are passed through between the cooling roll and the pressure roll, and the surface is subjected to thermocompression bonding while embossing, thereby forming a concavo-convex pattern on the surface. Got a wallpaper with.
Ionizing radiation curable resin composition Hexafunctional urethane acrylate: 60 parts by mass Trifunctional urethane acrylate: 40 parts by mass Silica (particle size: about 3 μm): 20 parts by mass Bifunctional silicone methacrylate: 2 parts by mass

Example 3
A wallpaper was obtained in the same manner as in Example 2 except that the ionizing radiation curable resin composition was changed to the following composition.
Ionizing radiation curable resin composition Hexafunctional urethane acrylate: 70 parts by mass Trifunctional urethane acrylate: 30 parts by mass Silica (particle size: about 3 μm): 20 parts by mass Bifunctional silicone methacrylate: 2 parts by mass

Comparative Example 1
As the substrate 2, rice weighing 60 g / m ² of wallpaper for backing paper (Kojin Co., WK-FKKD) used to prepare a foamed resin composition with the composition of Example 1 on the substrate, The composition is coated by a comma coating method, and is further applied by gravure printing with an application amount of 2.0 g / m ² using an ink having an acrylic resin as a binder and carbon black and a petal as a colorant. The pattern layer 4 is formed, and further an acrylic resin (manufactured by Matsui Dye Chemical Co., Ltd., trade name: Mica Primer EC-CRWD) is applied by gravure printing with a coating amount of 2.0 g / m ² , and the surface protective layer 8 Formed. The printed sheet obtained above was foamed with a foamed resin composition at 230 ° C. using a heating foaming furnace to form a foamed resin layer 3 to obtain a base sheet, and then the surface protective sheet obtained above. At the same time, a wallpaper having a concavo-convex pattern on the surface was obtained by passing between a cooling roll having an embossed mold and a pressure roll and thermocompression bonding while embossing.

Comparative Example 2
As the substrate 2, rice weighing 60 g / m ² of wallpaper for backing paper (Kojin Co., WK-FKKD) used to prepare a foamed resin composition with the composition of Example 1 on the substrate, The composition is coated by a comma coating method, and is further applied by gravure printing with an application amount of 2.0 g / m ² using an ink having an acrylic resin as a binder and carbon black and a petal as a colorant. The pattern layer 4 was formed.
The base material obtained by applying the pattern layer 4 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 3. After obtaining the sheet, it was passed between the cooling roll and the pressure roll on which the embossing mold was formed, and thermocompression bonded while embossing was performed, thereby obtaining a wallpaper having an uneven pattern on the surface.

Table 1 shows the results of the above evaluation on the wallpaper obtained in Examples 1 to 3 and Comparative Examples 1 and 2.
The wallpaper obtained in Example 1 showed high performance in all points of stain resistance and embossing property. Moreover, Example 2 and Example 3 showed the performance equivalent to Example 1 in terms of stain resistance, and the tensile elongation was less than 30%, but there was no problem in practical use. On the other hand, Comparative Example 1 in which there was no film layer and the surface protective layer was not an ionizing radiation curable resin, and Comparative Example 2 in which there was no film layer and no surface protective layer were insufficient in terms of stain resistance.

  ADVANTAGE OF THE INVENTION According to this invention, the wallpaper which has the unevenness | corrugation followability | corrugation by embossing in the wallpaper which has an uneven | corrugated pattern, and was excellent in stain resistance can have a surface protection layer.

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

Explanation of symbols

1. Wallpaper 2. Base material 3. Foamed resin layer 4. Pattern layer 5. Adhesive layer 6. 6. Film layer Primer layer 8. Surface protective layer 9. Silicone methacrylate10. Uneven pattern

Claims (7)

  A wallpaper in which a surface protective film is laminated on a base sheet, wherein the base sheet is laminated with a foam resin layer made of a thermoplastic resin containing a foaming agent and an inorganic filler, and a pattern layer in that order. The surface protective layer is laminated on a film layer made of an olefin-based thermoplastic resin, a concavo-convex pattern is applied from the surface protective layer side to the foamed resin layer, and the surface protective layer is a 1 to 2 functional silicone ( A wallpaper comprising a layer obtained by crosslinking and curing an ionizing radiation curable resin containing a (meth) acrylate.   The wallpaper according to claim 1, wherein the surface protective film has a tensile elongation (longitudinal direction) of 30% or more.   The wallpaper according to claim 1 or 2, wherein the thermoplastic resin constituting the film layer is an ethylene-vinyl alcohol copolymer resin.   The wallpaper according to any one of claims 1 to 3, wherein the thermoplastic resin constituting the foamed resin layer is a vinyl chloride resin.   The wallpaper according to any one of claims 1 to 5, wherein the content of the silicone (meth) acrylate is 1 part by mass or more with respect to 100 parts by mass of the ionizing radiation curable resin.   The wallpaper according to any one of claims 1 to 5, wherein an adhesive layer is provided between the picture layer and the film layer.   A step of providing a surface protective film provided with a surface protective layer made of an ionizing radiation curable resin on one surface of a film layer made of a thermoplastic resin and an adhesive layer provided on the other surface as needed; and a substrate A foamed resin composition comprising a thermoplastic resin containing a foaming agent and an inorganic filler is coated on the substrate, and after providing a pattern layer, the foamed resin composition is foamed in a heating foaming furnace to form a foamed resin layer. And a step of forming a concavo-convex pattern from the surface protective layer side to the foamed resin layer at the same time as the base sheet and the surface protective sheet are bonded together by a pressure roll having an embossed mold formed on the surface. A method for producing wallpaper.

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