JP5262023B2 - Foam wallpaper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a foamed wall paper which enables prevention of curling in sticking to the wall surface and opening in butt laying adhesion. <P>SOLUTION: The foamed wall paper includes a foamed resin layer, a pattern layer, a film layer and a surface protective layer overlying the substrate in this order. The substrate is a one-side-glazed lined paper of a surface smoothness of &le;40 s, measured by JIS P8119, and the film layer has a water absorption of 2-15%, measured by JIS K7209 method A at a modified immersion temperature of 30&deg;C. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to foam wallpaper.

General foamed wallpaper such as vinyl foamed wallpaper, paper foamed wallpaper, and olefin foamed wallpaper is mainly composed of a two-layer structure of an upper layer that imparts designability and a backing paper that supports the upper layer and imparts workability. These foamed wallpaper is bonded to the wall with water-based glue such as starch or vinyl acetate at the time of construction, but the water in the glue is absorbed by the backing paper in this gluing process, and the foamed wallpaper becomes soft or backing paper. May grow due to increased moisture. As a result, the occurrence of curling is increased, which makes it difficult to apply the foamed wallpaper to the wall surface, and the wallpaper after the application tends to curl. In addition, when the glue dries, the backing paper shrinks, and when pasting with good construction productivity is performed, there is a problem (opening) in which a gap is created in the joint portion between adjacent wallpaper, There were drawbacks such as impaired designability.
For this reason, it is difficult to curl even with gluing, and as a backing paper for foamed wallpaper that has improved dimensional stability, the drying section in the paper-making process generally has a large-diameter dryer shell having a large-diameter dryer shell with a diameter of 3 m or more. Backing paper formed by drying with a machine (hereinafter referred to as “Yankee dryer”) has been used. (See Patent Documents 1 and 2)
However, even when such a backing paper is used, the problem of curling and opening is still not solved.

JP 2005-82894 A JP 2007-92223 A

  Under such circumstances, an object of the present invention is to provide a foamed wallpaper that can prevent the occurrence of curling at the time of affixing the foamed wallpaper to the wall surface and the opening at the time of attachment.

As a result of intensive studies to achieve the above object, the present inventors have used a glossy backing paper having a specific surface smoothness as a substrate and a film layer having a specific water absorption rate. The object of the present invention could be achieved.
That is, the present invention is a foamed wallpaper in which at least a foamed resin layer, a pattern layer, a film layer, and a surface protective layer are sequentially laminated on a substrate, and the substrate has a surface smoothness of 40 seconds or less (according to JIS P8119). And the film layer has a water absorption of 2 to 15% (measured by changing the immersion temperature to 30 ° C. according to JIS K7209 A method). The present invention provides a foam wallpaper characterized by the above.

  ADVANTAGE OF THE INVENTION According to this invention, the foaming wallpaper which can prevent the generation | occurrence | production of the curl at the time of the sticking operation | work to the wall surface of a foaming wallpaper, or the opening at the time of attachment pasting construction can be provided.

  A typical structure of the foam wallpaper of the present invention will be described with reference to FIG. FIG. 1 is a schematic view showing a cross section of a foamed wallpaper 1 of the present invention. In the example shown in FIG. 1, a foamed wallpaper 1 of the present invention has a foamed resin layer 3 made of a thermoplastic resin containing a foaming agent and preferably an inorganic filler on a base 2, and a foamed resin layer 3 on the foamed resin layer 3. The image layer 4 is formed on the image layer 4 through an adhesive layer 5 that is optionally laminated, the film layer 6 is formed on the film layer 6 through a primer layer 7 that is optionally laminated, and the surface. The protective layer 8 is sequentially laminated. And the surface of the foam wallpaper 1 is embossed mechanically from the surface protective layer 8 side, and has the uneven | corrugated pattern 10 which gives the foam wallpaper 1 the design feeling excellent. Here, the surface protective layer 8 is preferably formed by crosslinking and curing the ionizing radiation curable resin composition.

Moreover, the foamed wallpaper of this invention may have a non-foamed resin layer as needed.
FIG.2 and FIG.3 is a schematic diagram which shows the cross section of the other embodiment of the foaming wallpaper of this invention, respectively.
In the example shown in FIG. 2, the foamed wallpaper 1 of the present invention includes a non-foamed resin layer 9, a foamed resin layer 3, a pattern layer 4, an adhesive layer 5, a film layer 6, a primer layer 7, and a base material 2. The surface protective layer 8 is sequentially laminated.
In the example shown in FIG. 3, the foamed wallpaper 1 of the present invention has a non-foamed resin layer 9 </ b> A, a foamed resin layer 3, a non-foamed resin layer 9 </ b> B, a pattern layer 4, an adhesive layer 5, and a film on a substrate 2. Layer 6, primer layer 7, and surface protective layer 8 are sequentially laminated.
Also in the example shown in FIGS. 2 and 3, the surface of the foam wallpaper 1 is embossed from the surface protective layer 8 side, and has an uneven pattern 10 that gives the foam wallpaper 1 an excellent design feeling. The surface protective layer 8 is preferably formed by crosslinking and curing an ionizing radiation curable resin composition.

[Substrate 2]
Hereinafter, the present invention will be described in detail with reference to FIGS. 1, 2 and 3 showing preferred embodiments of the present invention.
As the base material 2, glossy backing paper having a surface smoothness measured in accordance with JIS P8119 of 40 seconds or less is used from the viewpoint of production stability and production safety, in particular, curling prevention and opening prevention. It is done. Here, it shows that surface smoothness is so high that surface smoothness is large. In addition, this glossy backing paper preferably has an underwater elongation of 2.0% or less, more preferably 1.8% or less, and 1.5% or less from the viewpoint of curling prevention and opening prevention. More preferably, it is 1.2% 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.

  This glossy backing paper is produced by drying using a Yankee dryer in the paper making process. The single glossy backing paper is dried by copying the surface of a Yankee dryer having a smooth surface while the paper sheet is stretched, so that one side has a very high surface smoothness. When the glossy backing paper obtained in this way is used for wallpaper, even when paste is applied at the time of wallpaper construction, the wallpaper is hardly curled. This is presumably because the glossy backing paper is dried in the stretched state and does not stretch even when the glue is applied.

The single glossy backing paper is preferably made from wood pulp, but non-wood pulp, organic synthetic fibers, inorganic fibers, etc. other than wood pulp can also be used. 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 added as appropriate within the range in which the effects of the present invention are not impaired.
The drying conditions by the Yankee dryer are not particularly limited, but generally, a wet paper sheet having a moisture content of 30 to 70% by mass is brought into contact with a Yankee dryer shell at 80 to 140 ° C., and the moisture content is 3 to 10%. It is preferable to dry until about%.
When single glossy backing paper is used as the base material of the foam wallpaper of the present invention, the foamed resin layer, etc., which is the upper layer portion thereof, is provided on either side of the single glossy backing paper without limitation, but has no gloss It is preferable to provide an upper layer portion on the surface because the amount of paste applied can be reduced.
The thickness of the substrate 2 is not particularly limited, but the weight is about 50 to 300 g / m ² , preferably 55 to 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 groundwork during the construction of the wallpaper and make the so-called unevenness inconspicuous.

[Foamed resin layer 3]
The foamed resin layer 3 imparts flame retardancy to the foamed wallpaper of the present invention, and prevents the ink composition used for the pattern layer 4 from penetrating into the substrate 2 via the foamed resin layer 3. For this purpose, it is a layer provided, preferably a layer obtained by foaming a foamed resin composition comprising a thermoplastic resin containing an inorganic filler and other various additives as required in addition to a foaming agent. is there.

[Foamed resin layer 3: thermoplastic resin]
Examples of the thermoplastic resin include polyvinyl chloride resin, polyethylene, propylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), polyolefin resin such as ethylene- (meth) acrylic acid resin, acrylonitrile-butadiene-styrene. Copolymer (ABS resin), acrylonitrile-styrene copolymer, nylon, polyacetal resin, acrylic resin, polycarbonate resin, polyester resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyurethane resin, etc. A thermoplastic resin simple substance and a copolymer, or these mixed resins can be mentioned. Among these, polyvinyl chloride-based thermoplastic resins (particularly, vinyl chloride resin) are preferable because they have film-forming properties, flexibility, processability at low temperatures, and can be used as a relatively low-cost wallpaper. From the viewpoint of environmental protection, polyolefin resins are preferable, and at least one of ethylene-vinyl acetate copolymer resin (EVA) and ethylene-methyl methacrylate copolymer resin (EMMA) is preferably used. Ethylene-vinyl acetate copolymer resin (EVA) has excellent performance such as stain resistance, scratch resistance, chemical resistance, etc., and exhibits excellent unevenness followability in embossing, that is, sufficient longitudinal tensile elongation It is preferable because it is large and does not collapse due to ionizing radiation, has a low production cost, and has a low smoke density during combustion.

[Foamed resin layer 3: foaming agent]
Examples of the foaming agent used in the foamed resin layer 3 according to 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′— Nitroso compounds such as dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine, azodicarbonamide, azobisformamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, etc. Azo compounds, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), sulfonyl hydrazide compounds such as diphenylsulfone-3,3'-disulfonyl hydrazide, calcium Disilazide, 4,4'-diphenyl disulfonyl azide and 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 constituting 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. The foaming aid varies depending on the type of foaming agent used. For example, when azodicarbonamide is used as the foaming agent, zinc oxide, lead sulfate, urea, zinc stearate, etc. may be used as the foaming aid. .

[Foamed resin layer 3: inorganic filler]
The inorganic filler preferably used for the foamed resin layer 3 according to the present invention is not particularly limited, and various types 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. These inorganic fillers can be used alone or in combination of two or more.

Many of these inorganic fillers have an effect of imparting flame retardancy to the foamed wallpaper of the present invention, and the effect is further increased when incorporated in a large amount.
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 used as they are, but the inorganic fillers are previously silane-based, titanate-based, aluminate-based, zircoaluminum-based coupling agents, phosphate-based, fatty acid-based surfactants, You may process by fats and oils, wax, a stearic acid, a silane coupling agent, etc.

  Moreover, the foamed resin composition which comprises the foamed resin layer 3 can contain various additives according to the physical property requested | required. Examples of the various additives include a fungicide, an insecticide, an antiseptic, an antibacterial agent, a diluent, a deodorant, a light stabilizer, and a plasticizer.

[Foamed resin layer 3: forming method]
The foamed resin layer 3 is obtained by, for example, emulsifying a foamed resin composition containing the resin as described above into an emulsion composition, or by pelletizing a foamed resin composition by a comma coater method or a T-die extrusion film forming method. The film can be formed by a known method such as a calendering method or a dry lamination method using an adhesive. Here, the emulsification can be performed by a usual method. For example, the emulsion composition is obtained by emulsifying the thermoplastic resin in the foamed resin composition by an emulsion polymerization method or the like, and then adding a predetermined amount of other components. Can be obtained.

The foamed resin layer 3 can be foamed by a known foaming method. For example, the foamed resin layer 3 can be foamed at a temperature of about 180 to 240 ° C. using a foaming heating furnace. The foaming treatment can be performed without particular limitation as long as the foamed resin composition is formed into a film as the foamed resin layer 3, but is usually performed after the surface protective layer is provided.
Further, the thickness of the foamed resin layer 3 is not particularly limited and can be appropriately set according to desired characteristics and the like, but is preferably 50 to 300 μm in the film forming state, and the thickness after foaming is preferably 350 to 1500 μm. 500 to 1200 μm is more preferable. Further, the foaming ratio in forming the foamed resin layer is not particularly limited, but is usually about 3 to 7 times. If the expansion ratio is within the above range, good surface strength, workability and the like can be obtained.

  The foamed resin composition may be subjected to a crosslinking treatment for the purpose of improving the surface characteristics. The method for the crosslinking treatment is not limited, but crosslinking treatment (curing treatment) with ionizing radiation is preferable. For example, a layer made of the above foamed resin composition is formed on a substrate, and cross-linked by irradiating with ionizing radiation such as an electron beam in order to widen the temperature range of foamable viscosity. Thereby, productivity is stabilized and the surface of the foamed resin layer 3 is hardened to improve surface characteristics. When the foamed resin composition is subjected to a crosslinking treatment, the foamed resin composition can preferably contain a crosslinking agent. Any crosslinking agent can be used without particular limitation as long as it can crosslink the resin constituting the foamed resin layer.

  As ionizing radiation, ultraviolet rays, electron beams and the like are usually used. As the ultraviolet light source, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, or a metal halide lamp can be used. Further, as the electron beam source, for example, various electron beam accelerators such as a Cockloft Walton type, a pandegraph type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type may be used. The irradiation dose 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).

[Picture layer 4]
The pattern layer 4 is a layer that is preferably provided in order to give decorativeness to the substrate 2, and is formed by printing various patterns using an ink composition and a printing machine. In general, it can be formed with ink by a known printing method such as gravure printing, flexographic printing, offset printing, silk screen printing, transfer printing from a transfer sheet, and 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 and cloth patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. These patterns are formed not only by multicolor printing with normal yellow, red, blue and black process colors, but also by multicolor printing performed by preparing individual color plates constituting the pattern. .

As the ink composition used for forming the picture layer 4, a binder and a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed. 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 is a layer that is laminated on the upper surface of the picture layer 4, preferably via the adhesive layer 5, and is required for the foamed wallpaper of the present invention. It is provided for imparting surface properties such as stain resistance, cellophane tape resistance, scratch resistance, chemical resistance and the like, as well as imparting characteristics for preventing opening of the time.
The film layer 6 of the present invention needs to have a water absorption of 2 to 15% (in accordance with JIS K7209 A method, the immersion temperature is changed to 30 ° C.) from the viewpoint of curling prevention and opening prevention. The water absorption is preferably 3 to 12%. Here, the JIS K7209 A method is to measure the water absorption after the test piece is immersed in water at 23 ° C. for 24 ± 1 hour.
Further, the sum of the elongation rate (%) in the flow direction and the elongation rate (%) in the width direction of the film layer after 10 minutes of water immersion (23 ° C.) is 0.2% or more. The content is preferably 0.2 to 2%. If it is 0.2% or more, it is possible to offset the elongation of the glossy backing paper, which is the base material, and the elongation of the film layer during the construction of the foam wallpaper. obtain. Moreover, if it is 2% or less, it will be a grade which does not exceed the elongation of a backing paper, and is more preferable.
The absolute value of the difference between the elongation of the backing paper and the sum of the elongation (%) in the flow direction and the elongation (%) in the width direction is preferably 1 or less.
When the absolute value of the difference is 1 or less, the elongation of the backing paper and the elongation of the film layer can be offset more, so that further prevention of curling and opening can be suitably achieved.
Here, the flow direction refers to the longitudinal direction of unwinding and winding of the original film, and the width direction refers to a direction perpendicular to the flow direction.

The thermoplastic resin used for the film layer 6 includes the water absorption rate described above and the elongation (%) in the flow direction and the elongation (%) in the width direction after 10 minutes of water immersion (23 ° C.). In order to satisfy the sum, ethylene-vinyl alcohol copolymer (EVOH), polylactic acid, aliphatic polyamide, polyether polyurethane and the like are preferable, and ethylene-vinyl alcohol copolymer, polylactic acid, aliphatic polyamide are more preferable. . As the aliphatic polyamide, nylon 6 having a high water absorption rate is preferable. Among the above-mentioned, it is excellent in performance such as contamination resistance, scratch resistance, chemical resistance, etc., exhibits excellent unevenness followability in embossing, that is, the tensile elongation in the longitudinal direction is sufficiently large and collapses by ionizing radiation. In particular, an ethylene-vinyl alcohol copolymer resin film having a low production cost and a low smoke concentration during combustion is particularly preferable.
From the viewpoint of production efficiency, a transparent or translucent commercially available film made of the above resin can be preferably used.
The thickness of the film used for the film layer 6 according to 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 is laminated on the outermost surface of the foam wallpaper 1 of the present invention to improve the surface characteristics of the foam wallpaper 1 such as stain resistance, cellophane tape resistance, scratch resistance, chemical resistance and the like. is there. The surface tension of the surface protective layer 8 is preferably 30 dyne / cm or less. If the surface tension of the surface protective layer is within the above range, particularly excellent stain resistance against electric burn can be obtained. The surface tension is a value measured according to JIS K6768.
As the surface protective layer 8, a resin such as LLDPE (linear low density polyethylene), EMAA (ethylene-methacrylic acid copolymer), and polypropylene is heated and melted to the front surface of the pattern layer 4 by extrusion formation. If necessary, it may be laminated via an adhesive layer 5, or it may be laminated by laminating a film of the resin by a known dry lamination method, if necessary, via an adhesive layer 5. However, it is preferable that the ionizing radiation curable resin composition is crosslinked and cured. 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. It is a composition comprising ionizing radiation curable resin, other components added as necessary, and various additives. In the specification, for example, when the ionizing radiation curable resin in the ionizing radiation curable resin composition is an electron beam curable resin, this is referred to as an electron beam curable resin composition.

[Surface protective layer 8: ionizing radiation curable resin]
As the ionizing radiation curable resin preferably used for the surface protective layer 8, those having a surface tension of preferably 30 dyne / cm or less can be appropriately used as the ionizing radiation curable resin. It can be suitably selected from conventionally used polymerizable monomers, polymerizable oligomers and prepolymers. In particular, it is preferable to use a polymerizable (meth) acrylate monomer and / or a polymerizable oligomer. Typical examples are described below. “(Meth) acrylate” means “acrylate or methacrylate”.

As the polymerizable monomer, a (meth) acrylate-based monomer having a radical polymerizable unsaturated group in the molecule is preferable, 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 ionizing radiation curable resin composition can contain a monofunctional (meth) acrylate together with the above-mentioned polyfunctional (meth) acrylate for the purpose of reducing the viscosity and the like within a range not impairing the effect. 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, the polymerizable oligomer is preferably an oligomer having a radically polymerizable unsaturated group in the molecule, particularly an acrylate oligomer having a radically polymerizable unsaturated group, such as an epoxy (meth) acrylate or urethane (meth) acrylate. And oligomers such as polyester (meth) acrylate and polyether (meth) acrylate. 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 having (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers having 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, the ultraviolet curable resin composition has a photopolymerization initiator in an amount of 0.1 to 5 with respect to 100 parts by mass of the resin composition. It is preferable to contain about part by mass. 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, benzyl dimethyl ketal, acetophenone dimethyl ketal, etc. 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.

[Surface protective layer 8: silicone (meth) acrylate]
The ionizing radiation curable resin composition used for the surface protective layer 8 preferably contains silicone (meth) acrylate. Silicone (meth) acrylate is added mainly for the purpose of controlling the surface tension of the surface protective layer at the same time as providing surface properties such as stain resistance to wallpaper due to a synergistic effect with the ionizing radiation curable resin. is there. Silicone (meth) acrylate is one of modified silicone oils in which (meth) acrylic groups are introduced into one or both ends of a silicone oil composed of polysiloxane. Conventionally known silicone (meth) acrylates can be used, and are not particularly limited as long as the organic group is a (meth) acrylic group, and a modified silicone oil having 1 to 6 organic groups can be preferably used. . 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 silicone (meth) acrylate may be appropriately adjusted so that the surface tension of the surface protective layer is in a desired range. However, from the viewpoint of sufficiently improving the contamination resistance and the effect of using the ionizing radiation. 0.5-4 mass parts is preferable with respect to 100 mass parts of curable resin, more than 1.0-2.5 mass parts is more preferable, and 1.5-2.5 mass parts is still more preferable. Moreover, as a functional group equivalent (molecular weight / functional group number) of silicone (meth) acrylate, what has the conditions of 100-20000, for example, Preferably it is 100-10000 is mentioned.

[Surface protective layer 8: Various additives]
The ionizing radiation curable resin composition can contain various additives depending on the desired physical properties of the resulting surface protective layer. Examples of the 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, and a coupling agent. , Plasticizers, antifoaming agents, fillers, solvents, colorants and the like.
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. As the inorganic ultraviolet absorber, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle size 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. In addition, 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 10 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.

[Surface protective layer 8: Formation of surface protective layer using ionizing radiation curable resin composition]
In the formation of the surface protective layer 8 using the ionizing radiation curable resin composition, first, ionizing radiation curable resins such as polymerizable monomers and polymerizable oligomers, silicone (meth) acrylates added as necessary, and various types An ionizing radiation curable resin composition obtained by homogeneously mixing the additives at a predetermined ratio is prepared. The viscosity of the ionizing radiation curable resin composition is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the base material by a coating method described later. It may be added.
Solvents include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, water-insoluble organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methanol, ethanol, isopropyl alcohol, and normal propyl alcohol. Examples thereof include water-soluble organic solvents, water, and mixed solvents thereof. The amount of the solvent in the ionizing radiation curable resin composition may be appropriately selected according to the viscosity of the ionizing radiation curable resin composition, but the ionizing radiation curable resin composition is usually 65 to 85 mass on a solid basis. %.

  The ionizing radiation curable resin composition thus prepared has a gravure coat, a bar coat, a roll coat, a reverse roll coat, a comma so that the thickness after curing is 1 to 20 μm. It coats by well-known systems, such as a coat, preferably a gravure coat, and forms an uncured resin layer. A surface protective layer having desired performance is obtained when the thickness after curing is 1 μm or more. The thickness of the surface protective layer after curing is preferably 2 to 20 μm from the viewpoint of sufficiently obtaining the effect of providing the surface protective layer.

The uncured resin layer formed in this way is cured by irradiating with ionizing radiation such as an electron beam or ultraviolet rays to form a surface protective 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 crosslinking density of the ionizing radiation curable resin 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).
Furthermore, there is no restriction | limiting in particular as an electron beam source, For example, various electron beam accelerators, such as a cock loft Walton type, a van de Graft type, a resonance transformer type, an insulated core transformer type, or a linear type, a dynamitron type, a high frequency type, etc. 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 surface protective 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 or the non-foamed resin layer 9 is low, for example, when an ethylene-vinyl alcohol copolymer resin film is used for the film layer 6, both layers are used as necessary. It is preferable to provide an adhesive layer 5 on the surface. 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. Specific examples of the thermoplastic resin include (meth) acrylic resin, polyurethane resin, polyester, polyamide resin, (meth) acrylic acid ester-olefin copolymer resin, vinyl acetate resin, ethylene-acetic acid. Thermoplastic which is the main component of easy-adhesive resins and copolymers, such as vinyl copolymer resins, ionomer resins, olefin-α olefin copolymer resins, or mixed resins thereof, and olefin resins and foamed resin compositions A blended product of a resin and a thermoplastic resin as a main component of the film layer can be mentioned.

The adhesive layer 5 is an interlayer between the foamed resin layer 3 or the non-foamed resin layer 9 and the film layer 6 as described above and as shown in FIG. 1, FIG. 2, or FIG. In addition, it can also be provided between the base material 2 and the foamed resin layer 3 as necessary. 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.

[Primer layer 7]
The foamed wallpaper of the present invention can be provided with a primer layer 7 between these layers as necessary for the purpose of improving the adhesion between the surface protective layer 8 and the film layer 6. The resin preferably used in the primer layer 7 is, for example, excellent in adhesion between the resin used in the film layer 6 and an ionizing radiation curable resin composition such as acrylic resin, polyurethane resin, and urethane-acrylic resin. Can be used. Further, for the purpose of strengthening the interlayer adhesion, a primer layer may be provided between the foamed resin layer 3 and the non-foamed resin layer 9 and between the foamed resin layer 3 or the non-foamed resin layer 9 and the film layer 6. it can.

[Non-foamed resin layer 9]
The non-foamed resin layer 9 improves the adhesive force between the foamed resin layer 3 and the substrate 2, and the ink composition used for the pattern layer 4 penetrates into the substrate 2 through the foamed resin layer 3. It is a layer provided for the purpose of suppression. There is no particular limitation on the stacking order of the non-foamed resin layer 9. For example, the non-foamed resin layer 9 and the foamed resin layer 3 may be stacked in this order on the substrate 2. The layers 9 may be stacked in this order. In particular, as shown in FIG. 2, the non-foamed resin layer 9 is provided between the base material 2 and the foamed resin layer 3, that is, the non-foamed resin layer 9 and the foamed resin layer 3 may be laminated in this order. This is preferable from the viewpoint of improving the adhesive force between the foamed resin layer and the substrate. For example, as shown in FIG. 3, a plurality of non-foamed resin layers 9 may be provided by laminating the non-foamed resin layer 9A, the foamed resin layer 3, and the non-foamed resin layer 9B in this order from the base material side. In this case, the plurality of non-foamed resin layers 9A and 9B may be the same or different. The same applies when a plurality of foamed resin layers 3 are present.
When an extrusion film forming method using a T die is employed for forming the foamed resin layer 3, the inorganic filler preferably contained in the foamed resin composition is likely to remain in the extrusion port (so-called die) of the extruder, Inorganic filler residues (so-called eyes and eyes) tend to become foreign matters on the sheet surface. In such a case, as described above, when the foamed resin layer 3 and the non-foamed resin layer 9 are laminated, the non-foamed resin layer 9A, the foamed resin layer 3, and the non-foamed resin layer 9B are laminated in this order from the base material side. It is particularly preferred that If the foamed resin layer 3 and the non-foamed resin layer 9 are configured as described above, the occurrence of eyes is suppressed by simultaneously forming the resin layer with the foamed resin layer sandwiched between two non-foamed resin layers. Therefore, excellent manufacturing stability can be obtained.

[Non-foamed resin layer 9: resin]
The resin constituting the non-foamed resin layer 9 is not particularly limited, but is a polyolefin resin, a polyolefin resin coated with a urethane or acrylic coating agent, a methacrylic resin, a thermoplastic polyester resin, a polyvinyl alcohol resin. And thermoplastic resins such as fluororesins such as polyvinyl fluoride, polyvinylidene fluoride, and ethylene tetrafluoroethylene, and various copolymer resins, among which polyolefin resins are preferable.
Examples of the polyolefin-based resin include, for example, polyolefins such as polyethylene, polypropylene, polybutene, polybutadiene, and polyisoprene and various copolymers, copolymers of α-olefins having 4 or more carbon atoms (linear low density polyethylene), ethylene -Acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene- (meth) acrylic acid copolymer such as ethylene-methacrylic acid copolymer, ethylene-vinyl acetate Examples thereof include copolymers (EVA), ethylene-vinyl acetate copolymer saponified products or ionomers, or mixed resins composed of one or more of these. Among these, at least one of ethylene-vinyl acetate copolymer (EVA) and ethylene-methyl methacrylate copolymer (EMMA) is particularly preferable. The ethylene-vinyl acetate copolymer (EVA) and the tylene-methyl methacrylate copolymer (EMMA) are not particularly limited, and known or commercially available ones can be used. In particular, the ethylene-vinyl acetate copolymer (EVA) preferably has a vinyl acetate component (VA component) of 15 to 30% by mass. Moreover, as for a tylene-methyl methacrylate copolymer (EMMA), that whose methyl methacrylate component (EMA component) is 15-30 mass% is preferable. An ethylene-vinyl acetate copolymer (EVA) is preferable for the same reason as described in the explanation of the foamed resin layer 3.

[Non-foamed resin layer 9: other resin]
In this invention, other resin other than said resin may be contained as a resin component. For example, polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, polypropylene, propylene-butene-1 copolymer, polybutene-1, butene-1, propylene-ethylene-3 terpolymer, butene In addition to -1-hexene-1-octene-1-element copolymer and polymethylpentene, olefin-based elastomers described in JP-A-6-16832, JP-B-6-23278 and the like can also be used. . These resins can be used alone or in combination of two or more.

[Non-foamed resin layer 9: various additives]
Moreover, the non-foamed resin layer 9 can contain various additives as required. For example, an inorganic filler can be added to give an increase effect, or a flame retardant can be added to give flame retardancy. Moreover, when bridge | crosslinking, the crosslinking adjuvant used with a foamed resin layer can also be mix | blended.
Examples of the inorganic filler include powders (particles) such as calcium carbonate, barium sulfate, clay and talc, and inorganic hollow bodies such as mica, silica, alumina, diatomaceous earth, silica sand, and shirasu balloon.

  Suitable flame retardants include, for example, nitrogen compounds such as urea, hydroxides such as magnesium hydroxide and aluminum hydroxide (particularly compounds having crystal water), flame retardants containing self-extinguishing phosphorus or halogen elements, and the like. Yes. In particular, by blending a compound such as a hydroxide, flame retardancy can be achieved by the heat of vaporization of crystal water during combustion decomposition. Moreover, it is preferable when the mixed flame retardant compound which consists of a nitrogen compound and a phosphorus compound is mix | blended 25-100 mass parts with respect to 100 mass parts of polyolefin resin. This is because the compatibility with polyolefin is good and the thermal stability is also good.

Various rubbers may be added for the purpose of imparting flexibility, impact resistance, and easy adhesion to the polyolefin resin.
Examples of rubbers include diene rubbers, hydrogenated diene rubbers, and olefin elastomers. Among these, hydrogenated diene rubber is preferable. The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of a double bond of a diene rubber molecule, and is used as a modifier for a polyolefin resin in the present invention. There is a role to suppress the crystallization of the polyolefin resin and increase the flexibility and transparency. In general, when a diene rubber is added to a polyolefin resin, the weather resistance and heat resistance are lower than those of a polyolefin resin without the addition of a diene rubber due to the double bond of the diene rubber. Since the double bond is saturated with hydrogen, the weather resistance and heat resistance of the polyolefin resin are not deteriorated, and the double bond is satisfactory.

Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene / butadiene rubber. For the purpose of the present invention, styrene-butadiene rubber and the like are particularly preferable.
Although it does not specifically limit as addition amount of rubber | gum, Usually, what is necessary is just to be about 1-90 mass parts with respect to 100 mass parts of polyolefin resin.

  Moreover, the method of adding a pigment and performing transparent coloring or opaque coloring is mentioned. As the pigment, known or commercially available pigments can be used without limitation. For example, titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene Examples include organic pigments (including dyes) such as Brie RS and aniline black, metallic pigments such as aluminum and brass, pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate, and the like. These can select either a transparent colored pigment or an opaque colored pigment depending on the application. These pigments may be added and dispersed as powder or scaly foil pieces.

[Formation of non-foamed resin layer 9]
The non-foamed resin layer 9 can be formed by the same method as that for the foamed resin layer 3.
The non-foamed resin composition may be subjected to a crosslinking treatment for the purpose of improving the surface characteristics. The method for the crosslinking treatment is not limited, but crosslinking treatment (curing treatment) with ionizing radiation is preferable. Thereby, productivity is stabilized and the surface of the non-foamed resin layer 9 is hardened, and the surface characteristics are improved. When the non-foamed resin composition is subjected to a crosslinking treatment, the non-foamed resin composition can preferably contain a crosslinking agent.
When the foamed resin layer 3 and the non-foamed resin layer 9 are laminated, and when the extrusion film forming method using a T-die is adopted, the foamed resin layer 3 and the non-foamed resin layer 9 are formed separately. Or may be performed at the same time. In the case of simultaneous extrusion film formation, a multi-manifold type T die or the like that enables simultaneous formation of a plurality of layers by simultaneously forming a molten resin corresponding to each layer is used.
The thickness of the non-foamed resin layer 9 is preferably 5 to 25 μm, more preferably 20 to 40 μm, for the purpose of obtaining excellent surface characteristics and ensuring the unevenness followability of the wallpaper by embossing.

[Uneven pattern 10]
The foamed wallpaper of the present invention is preferably provided with a concavo-convex pattern 10 by embossing in order to impart excellent design properties. The concavo-convex pattern 10 is formed by heating and pressing with an embossing 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 that can be embossed by any means. Can do. 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 foamed wallpaper of the present invention is manufactured, for example, by the following manufacturing method, but is not limited thereto.
The foamed wallpaper shown in FIGS. 1, 2 and 3 is manufactured as follows. The resin constituting the primer layer 7 and the ionizing radiation curable resin composition are sequentially coated on one surface of the film layer 6 made of a thermoplastic resin film, and the adhesive layer 5 and the primer are coated on the other surface as necessary. The surface protective sheet is obtained by coating the resin constituting the layer 7 and further irradiating predetermined ionizing radiation to crosslink and cure the ionizing radiation curable resin composition. Further, a foamed resin obtained by forming a foamed resin composition comprising a thermoplastic resin containing a foaming agent, an inorganic filler, and other additives as necessary on the substrate 2 by an extrusion film forming method alone. Non-foamed resin obtained by laminating layer 3 or forming the foamed resin composition and a non-foamed resin composition containing a resin constituting the non-foamed resin layer simultaneously by an extrusion film forming method using a T-die Layer 9 and foamed resin layer 3 are laminated (if necessary, non-foamed resin layer 9A, foamed resin layer 3 and non-foamed resin layer 9B are laminated in this order), and ink composition constituting pattern layer 4 thereon After the product is coated by gravure printing, the foamed resin layer 3 and the non-foamed resin layer 9 are cross-linked and cured by irradiating an electron beam or the like as necessary, and the foamed resin is further heated at about 250 ° C. using a heating foaming furnace. The composition is foamed to form a foamed resin layer 3 to obtain a base sheet. Next, after the substrate sheet is cooled, it is reheated to about 150 ° C. and then between the cooling roll (surface protective sheet side) and the pressure roll on which the embossed plate is formed from the outermost layer side of the surface protective layer sheet. Both the sheets are thermocompression-bonded by passing them through, and after forming the concavo-convex pattern 10, the foamed resin layer 3 or the non-foamed resin layer 9 adjacent to the substrate 2 from the outermost layer side of the surface protective layer 8 is cooled. Thus, the foamed wallpaper 1 of the present invention in which the uneven pattern 10 is formed can be obtained. As described above, the primer layer 7 and the adhesive layer 5 can be further 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 water absorption of each film used for the film layer and the sum of the elongation in the flow direction (%) and the elongation in the width direction (%) after 10 minutes of water immersion (23 ° C.) were obtained in each Example. Evaluation of the workability of the foamed wallpaper (curling property, opening and peelability), evaluation of the uneven pattern of the foamed wallpaper and stain resistance (electric burn) were evaluated by the following methods.
(1) Water absorption rate In accordance with JIS K7209 A method, the immersion temperature was changed to 30 ° C. and measured.
(2) Sum of elongation rate (%) in flow direction and width direction (%) of film after 10 minutes of water immersion (23 ° C.) Water immersion (23 ° C.) 10 of each film used for film layer 6 Using a test piece (12 cm × 12 cm) with a scale of 10 cm × 10 cm in the center, the elongation of the film after the minute was measured in both the flow direction (MD) and the width direction (CD), and the flow The sum of the elongation (%) in the direction and the elongation (%) in the width direction was evaluated.
(3) Evaluation of workability (curling)
The foamed wallpaper produced in each example was applied using wallpaper paste coating machine with wallpaper paste (Yaoi Chemical Co., Ltd., trade name: Rua Mild) at a coating amount of 130 g / m ^2. Then, under the condition of 20 ° C. (relative humidity: 65%), the curling property (floating property) of the wallpaper edge after 1 hour was evaluated according to the following criteria.
Good: Float width 5 mm or less Defect: Float width 5 mm or more (4) Evaluation of workability (opening)
The wallpaper produced in each example was coated with a wallpaper paste (Yaoi Chemical Co., Ltd., trade name “Loa Mild”) at a coating amount of 130 g / m ² using a wallpaper paste coating machine. The wallpaper was cut in half in the width direction and stuck on a semi-incombustible gypsum board with a thickness of 9 mm so that the ears overlapped. After construction and leaving at 20 ° C. (relative humidity: 65%) for 1 week, the width of the opening of the part where the ears overlap (joint part) is measured using a microscope. Evaluated by criteria.
Good: Opening width less than 0.08 mm Poor: Opening width 0.08 mm or more (5) Evaluation of workability (peelability)
The wallpaper produced in each example was applied at a coating amount of 120 g / m ² using a wallpaper paste coating machine with a wallpaper construction paste (manufactured by Yayoi Chemical Industry Co., Ltd., trade name “Loua Mild”). Then, it was attached to a gypsum board (manufactured by Yoshino Gypsum Co., Ltd., trade name: non-combustible tiger board, size: 1800 mm × 900 mm, thickness: 12.5 mm). Under an environment of 20 ° C. (relative humidity: 30%), it was left for one week, and the wallpaper was gently peeled off from the upper corner. At this time, whether or not the wallpaper peels between the layers of the backing material, and if it peels between the layers of the backing material, the peelability is evaluated according to how many times it is peeled off, and the operation is performed three times or less. The case where it peeled cleanly was considered good.
(6) Evaluation of uneven pattern (embossing moldability)
Evaluation of the uneven pattern of the foamed wallpaper obtained in each Example was performed visually. Judgment criteria were evaluated as follows.
Good: Uneven pattern is sharp and has excellent designability Almost good: Uneven pattern is not found in the uneven pattern, but there is no problem. Defect: Uneven unevenness in uneven pattern (7) Evaluation of stain resistance (electric burn )
Electric dust was reproduced by attaching carbon black on the surface of the foamed wallpaper obtained in Examples and Comparative Examples. This was wiped off with a sponge containing a neutral detergent, and the wiping property of the electric burn was evaluated visually.
Good: No carbon black blown residue Almost good: Carbon black blown residue remained slightly, but no problem in practical use. Bad: Carbon black blown residue was remarkable.

Example 1
As the base material 2, a glossy backing paper (thickness: 100 μm) having a rice weighing of 60 g / m ² , which was made with a Yankee dryer, was used. The surface smoothness was 34 seconds and the underwater elongation was 1.11%.
A foamed resin composition having the following composition was formed into a film using an extruder, and a foamed resin layer was laminated so as to have a thickness of 100 μm. The extrusion conditions at this time were a cylinder temperature of 120 ° C. and a die temperature of 120 ° C. A pattern layer 4 was formed by gravure printing with an application amount of 3 g / m ² using an ink containing an acrylic resin as a binder and carbon black and a stem as a colorant. Next, the foamed resin layer was irradiated with an electron beam having a pressurization voltage of 175 kV and an irradiation dose of 50 kGy (5 Mrad) to perform a crosslinking treatment.
Separately from the above, an ethylene-vinyl alcohol copolymer resin film coated with an adhesive in advance as the film layer 6 {manufactured by Kuraray Co., Ltd., trade name “EVAL FILM HF-ME” (film thickness: 12 μm, ethylene content 44 mol%)} and a gravure printing of urethane-acrylic copolymer resin at a coating amount of 2.0 g / m ² on the upper surface of the film layer 6 (the side where the adhesive is not applied). Then, an ionizing radiation curable resin having the following composition was applied thereon by a gravure offset coater method at a coating amount of 2.0 g / m ² . After coating, the surface protective layer 8 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.
After obtaining the base material which formed the foamed resin layer 3 by foaming the foamed resin composition at 230 ° C. using a heating foaming furnace, after applying the pattern layer 4 and laminating the foamed resin composition. The foamed wallpaper having a concavo-convex pattern on the surface is obtained by passing between the cooling roll and the pressure roll formed with the embossing mold at the same time as the surface protection sheet obtained above, and thermocompression bonding while embossing. It was. The surface tension of the surface protective layer was lower than 30 dyne / cm.
The water absorption rate of the film used for the film layer and the sum of the elongation rate in the flow direction (%) and the elongation rate in the width direction (%) after 10 minutes of water immersion (23 ° C.), and the construction of the resulting foamed wallpaper Evaluation of the property (curling property, opening and peelability), evaluation of the uneven pattern of the foamed wallpaper, and evaluation of the stain resistance (electric burn) were evaluated. The results are shown in Table 1.

Foamed resin composition composition Vinyl chloride resin (manufactured by Tosoh Corporation, trade name: R-720): 100 parts by mass Titanium dioxide (pigment) (manufactured by DuPont, trade name: Taipure R-108): 17 parts by weight Calcium carbonate ( Shiraishi Kogyo Co., Ltd., trade name: Whiten H): 100 parts by weight Plasticizer (Sanken Chemical Co., DOP): 55 parts by weight Foaming agent (manufactured by Eiwa Kasei, trade name: ADCA # 3): 4 parts by weight Light stabilizer (Product name: OF-101): 1 part by mass Cell regulator (manufactured by Kyodo Pharmaceutical, KF-110A-6): 1 part by mass

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 2
As the film layer 6, an ethylene-vinyl alcohol copolymer resin film coated with an adhesive in advance {manufactured by Kuraray Co., Ltd., trade name “EVAL FILM EF-F12” (film thickness: 15 μm, ethylene content 32 mol%)} A foamed wallpaper was obtained in the same manner as in Example except that was used.
The water absorption rate of the film used for the film layer and the sum of the elongation rate in the flow direction (%) and the elongation rate in the width direction (%) after 10 minutes of water immersion (23 ° C.), and the construction of the resulting foamed wallpaper Evaluation of the property (curling property, opening and peelability), evaluation of the uneven pattern of the foamed wallpaper, and evaluation of the stain resistance (electric burn) were evaluated. The results are shown in Table 1.

Example 3
As the film layer 6, an ethylene-vinyl alcohol copolymer resin film coated with an adhesive in advance {manufactured by Kuraray Co., Ltd., trade name “EVAL FILM EF-E” (film thickness: 20 μm, ethylene content 44 mol%)} A foamed wallpaper was obtained in the same manner as in Example except that was used.
The water absorption rate of the film used for the film layer and the sum of the elongation rate in the flow direction (%) and the elongation rate in the width direction (%) after 10 minutes of water immersion (23 ° C.), and the construction of the resulting foamed wallpaper Evaluation of the property (curling property, opening and peelability), evaluation of the uneven pattern of the foamed wallpaper, and evaluation of the stain resistance (electric burn) were evaluated. The results are shown in Table 1.

Example 4
As the film layer 6, an ethylene-vinyl alcohol copolymer resin film coated with an adhesive in advance {manufactured by Kuraray Co., Ltd., trade name “EVAL FILM EF-HS” (film thickness: 30 μm, ethylene content 47 mol%)} A foamed wallpaper was obtained in the same manner as in Example except that was used.
The water absorption rate of the film used for the film layer and the sum of the elongation rate in the flow direction (%) and the elongation rate in the width direction (%) after 10 minutes of water immersion (23 ° C.), and the construction of the resulting foamed wallpaper Evaluation of the property (curling property, opening and peelability), evaluation of the uneven pattern of the foamed wallpaper, and evaluation of the stain resistance (electric burn) were evaluated. The results are shown in Table 1.

Example 5
A wallpaper was obtained in the same manner as in Example 1 except for the configuration of the following foamed resin layer and non-foamed resin layer.
A non-foamed resin composition and a foamed resin composition having the following composition are simultaneously formed using an extruder with a T-die, and a non-foamed resin layer and a foamed resin layer are formed to have a thickness of 10 μm and 100 μm, respectively. A base material was laminated on the surface of the non-foamed resin layer. Extrusion conditions at this time were a cylinder temperature of 160 ° C. for the non-foamed resin layer, a cylinder temperature of 120 ° C. for the foamed resin layer, and a die temperature of 120 ° C. for both. The pattern layer 4 was formed on the foamed resin layer by gravure printing with an application amount of 3 g / m ² using an ink containing an acrylic resin as a binder and carbon black and a valve as a colorant. Next, the foamed resin layer was irradiated with an electron beam having a pressurization voltage of 175 kV and an irradiation dose of 50 kGy (5 Mrad) to perform a crosslinking treatment.
Evaluation of workability (curling property, opening and peelability) of the obtained foamed wallpaper, and evaluation of the uneven pattern of the foamed wallpaper and stain resistance (electric burn) were evaluated.

Non-foamed resin composition composition Ethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Smitate CV5053): 100 parts by mass

Foamed resin composition composition Ethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Smitate CV5053): 100 parts by weight Foaming agent (manufactured by Eiwa Kasei, trade name: ADCA # 3): 4 parts by weight calcium carbonate (Shiraishi Kogyo, trade name: Whiten H): 30 parts by mass Titanium dioxide (pigment) (DuPont, trade name: Taipure R-108): 20 parts by weight Light stabilizer (trade name: OF-101): 1 Mass part Crosslinking agent (manufactured by JSR Corporation, trade name: Obstar JVA-702): 1 part by mass

Ionizing radiation curable resin composition Same as Example 1.

Example 6
A wallpaper was obtained in the same manner as in Example 1 except for the configuration of the following foamed resin layer and non-foamed resin layer.
The non-foamed resin composition and the foamed resin composition used in Example 5 were simultaneously formed using a T-die extruder, and the non-foamed resin layer and the foamed resin were formed to have a thickness of 15 μm, 100 μm, and 10 μm, respectively. A layer and a non-foamed resin layer were formed in this order, and a substrate was laminated on the surface of the non-foamed resin layer having a thickness of 10 μm. Extrusion conditions at this time were as follows: the non-foamed resin layer (thickness 15 μm) had a cylinder temperature of 160 ° C., the foamed resin layer had a cylinder temperature of 120 ° C., and the non-foamed resin layer (thickness 10 μm) had a cylinder temperature of 100 ° C. The temperatures were all 120 ° C. On the non-foamed resin layer having a thickness of 15 μm, a pattern layer is formed by gravure printing with a coating amount of 3 g / m ² using an ink containing an acrylic resin as a binder and carbon black and a petrol as a colorant. 4 was formed. Next, the foamed resin layer was irradiated with an electron beam having a pressurization voltage of 175 kV and an irradiation dose of 50 kGy (5 Mrad) to perform a crosslinking treatment.
Evaluation of workability (curling property, opening and peelability) of the obtained foamed wallpaper, and evaluation of the uneven pattern of the foamed wallpaper and stain resistance (electric burn) were evaluated.
Evaluation of workability (curling property, opening and peelability) of the obtained foamed wallpaper, and evaluation of the uneven pattern of the foamed wallpaper and stain resistance (electric burn) were evaluated.

Comparative Example 1
Wallpaper as in Example 1 except that a vinyl chloride resin film (Okamoto Co., Ltd., film thickness: 23 μm) was used as the film layer 6 instead of the ethylene-vinyl alcohol copolymer resin film in Example 1. Got.
The water absorption rate of the film used for the film layer and the sum of the elongation rate in the flow direction (%) and the elongation rate in the width direction (%) after 10 minutes of water immersion (23 ° C.), and the construction of the resulting foamed wallpaper Evaluation of the property (curling property, opening and peelability), evaluation of the uneven pattern of the foamed wallpaper, and evaluation of the stain resistance (electric burn) were evaluated. The results are shown in Table 1.

Comparative Example 2
Example except that a polypropylene resin film (manufactured by Gunze Co., Ltd., trade name “ACB clear”, film thickness: 19 μm) was used as the film layer 6 instead of the ethylene-vinyl alcohol copolymer resin film of Example 1. The wallpaper was obtained in the same manner as in 1.
The water absorption rate of the film used for the film layer and the sum of the elongation rate in the flow direction (%) and the elongation rate in the width direction (%) after 10 minutes of water immersion (23 ° C.), and the construction of the resulting foamed wallpaper Evaluation of the property (curling property, opening and peelability), evaluation of the uneven pattern of the foamed wallpaper, and evaluation of the stain resistance (electric burn) were evaluated. The results are shown in Table 1.

As is clear from Table 1, all of the foamed wallpaper obtained in Examples 1 to 4 were evaluated for the curledness, openness and peelability of the foamed wallpaper, and the evaluation of the uneven pattern of the foamed wallpaper and the wiping property of electric burn. It was good in all the evaluations. In addition, Examples 5 and 6 were also good in all of the evaluation of the curling property of the foamed wallpaper, the opening and the peelability, the evaluation of the uneven pattern of the foamed wallpaper, and the wiping property of the electric burn.
On the other hand, the foamed wallpaper obtained in Comparative Examples 1 and 2 were all good in the evaluation of the uneven pattern and the evaluation of the wiping property of the electric burn, but in any of the curling property, the opening and the peelability. It was bad.

  According to the present invention, it is possible to prevent the occurrence of curling at the time of affixing to a wall surface and the opening at the time of affixing and sticking, and it is also excellent in releasability and wiping of electricity, and the uneven pattern of foamed wallpaper. It is possible to obtain a foam wallpaper having an excellent aesthetic feeling, and it is suitably used as a wallpaper for various buildings, general houses, and the like.

It is a schematic diagram which shows the cross section of one embodiment of the foam wallpaper of this invention. It is a schematic diagram which shows the cross section of the other embodiment of the foam wallpaper of this invention. It is a schematic diagram which shows the cross section of the other embodiment of the foam wallpaper of this invention.

Explanation of symbols

1. Foam wallpaper Base material 3. Foamed resin layer 4. Pattern layer 5. Adhesive layer 6. 6. Film layer Primer layer 8. Surface protective layer 9. Non-foamed resin layer 9A. Non-foamed resin layer 9B. Non-foamed resin layer 10. Uneven pattern

Claims (11)

  A foamed wallpaper in which at least a foamed resin layer, a pattern layer, a film layer, and a surface protective layer are sequentially laminated on a base material, and the base material has a surface smoothness of 40 seconds or less (measured in accordance with JIS P8119) And a film layer having a water absorption of 2 to 15% (measured by changing the immersion temperature to 30 ° C. according to JIS K7209 A method) wallpaper.   The foamed wallpaper according to claim 1, wherein the resin constituting the film layer is an ethylene-vinyl alcohol copolymer, polylactic acid and / or aliphatic polyamide.   The foamed wallpaper according to claim 1 or 2, wherein the base material has an underwater elongation (measured according to JAPAN TAPPI paper pulp test method No. 27: 2000) of 2.0% or less.   The sum of the elongation (%) in the flow direction and the elongation (%) in the width direction of the film layer after 10 minutes of water immersion (23 ° C) is 0.2% or more. Foam wallpaper according to any of the above.   The foamed wallpaper according to any one of claims 1 to 4, wherein the surface protective layer is obtained by crosslinking and curing an ionizing radiation curable resin composition.   The foamed wallpaper according to claim 5, wherein the ionizing radiation curable resin composition contains a polymerizable (meth) acrylate monomer and / or a polymerizable oligomer.   The foamed wallpaper according to claim 6, wherein the ionizing radiation curable resin composition further contains silicone (meth) acrylate.   The foamed wallpaper according to any one of claims 1 to 7, wherein the surface protective layer has a surface tension (measured in accordance with JIS K6768) of 30 dyne / cm or less.   The foamed wallpaper according to any one of claims 1 to 8, wherein the resin constituting the foamed resin layer contains at least one of a vinyl chloride resin, an ethylene-vinyl acetate copolymer, and an ethylene-methyl methacrylate copolymer. .   The foamed wallpaper according to any one of claims 1 to 9, which is mechanically embossed from the surface protective layer side. The manufacturing method of the foam wallpaper which has the following process (a)-(c), and a foamed resin layer, a pattern layer, a film layer, and a surface protective layer are laminated | stacked in order on a base material.
Step (a) A glossy backing paper having a surface smoothness (measured in accordance with JIS P8119) of 40 seconds or less is used as a base material, and at least a foamed resin layer and a pattern layer are provided on the base material. The process of obtaining a material sheet
Step (b) Step of forming a surface protective layer on a film layer having a water absorption of 2 to 15% (measured by changing the immersion temperature to 30 ° C. according to JIS K7209 A method) to obtain a surface protective sheet
Step (c) Step of thermocompression bonding the substrate sheet obtained in step (a) and the surface protective sheet obtained in step (b)

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