JP4006603B2 - Method for producing foam wallpaper - Google Patents

Description

  The present invention relates to a method for producing foamed wallpaper.

  Conventionally, a foamed wallpaper having a foamed resin layer using an ethylene-vinyl acetate copolymer (EVA) as a resin component on a paper base is known. For example, Patent Document 1 discloses a wallpaper in which a foamed resin layer containing a foaming agent, an inorganic component, a flame retardant, and a resin component (EVA) and a decorative layer are sequentially provided on a base material layer.

  When the foamed wallpaper is produced, when the foaming agent-containing resin layer (unfoamed resin layer) is laminated on the paper substrate using an extruder such as a T-die, abnormal foaming in the extruder is prevented. In order to ensure resin fluidity, it is necessary to use a resin component (EVA) having a high melt flow rate (MFR). A suitable MFR is usually about 40 to 120 g / 10 minutes.

  After lamination of the foaming agent-containing resin layer, the resin layer is generally irradiated with an electron beam to crosslink EVA, and after adjusting the melt tension (melt strength), the foaming agent-containing resin layer is made into a foamed resin layer by heating. Since the resin component having a high MFR has insufficient melt tension, foaming of the foaming agent-containing resin layer as it is tends to cause collapse of foamed cells, generation of coarse bubbles, and the like. Therefore, a resin component having a high MFR needs to increase the melt tension by resin crosslinking. Usually, in order to obtain a good foamed state, electron beam irradiation of 5 to 7 Mrad is required.

  However, when an electron beam of 5 to 7 Mrad is irradiated, a good foamed state is obtained, but there is a problem in that the paper-based substrate is burnt (discolored) and the design properties of the foamed wallpaper are impaired.

Therefore, the development of a foaming wallpaper manufacturing method including a step of forming a foaming agent-containing resin layer containing EVA by extrusion molding, which can simultaneously achieve a good foaming state and prevention of burning of a paper-based substrate has been developed. It is desired.
JP 2002-96433 A

  The present invention relates to a method for producing a foam wallpaper comprising a step of forming a foaming agent-containing resin layer containing EVA by extrusion molding, wherein the production method achieves both a good foamed state and prevention of burning of a paper-based substrate at the same time. The main purpose is to provide.

  As a result of intensive studies, the present inventor has found that the above object can be achieved by blending a specific component as an additive into the foaming agent-containing resin layer, and has completed the present invention.

  That is, this invention relates to the manufacturing method of the following foam wallpaper.

1. A foaming agent-containing resin layer containing a thermal decomposable foaming agent is laminated on the paper substrate by extrusion molding, then the resin contained in the foaming agent-containing resin layer is crosslinked by electron beam irradiation, and then heated to contain the foaming agent. A method for producing a foam wallpaper having a resin layer as a foam resin layer,
The foaming agent-containing resin layer contains an ethylene-vinyl acetate copolymer as a resin component, and further contains a diacrylate monomer having a tertiary carbon atom ,
The electron beam irradiation has an irradiation amount of 1 to 4 Mrad.
A method for producing a foam wallpaper.

  2. Item 2. The production method according to Item 1, wherein the resin component contained in the foaming agent-containing resin layer has a melt flow rate of 40 to 120 g / 10 min.

  3. The production according to Item 1 or 2, wherein the content of the diacrylate monomer having a tertiary carbon atom is 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin component contained in the foaming agent-containing resin layer. Method.

4 . Item 4. The method according to any one of Items 1 to 3 , wherein a pattern layer is further formed on the foaming agent-containing resin layer.

5 . Item 5. The production method according to Item 4 , wherein a surface protective layer further containing an ionizing radiation curable resin as a resin component is formed on the surface of the pattern layer.

6 . Item 6. The method according to Item 5 , wherein the resin contained in the foaming agent-containing resin layer is cross-linked by electron beam irradiation and the resin contained in the surface protective layer is cured.

7 . Item 7. The production method according to any one of Items 1 to 6 , wherein the extrusion molding is single layer or multilayer extrusion molding by a T-die extruder.

8 . Foam wallpaper produced by the method according to any one of items 1-7.

  The foamed wallpaper manufacturing method of the present invention is a method of crosslinking a resin contained in a foaming agent-containing resin layer by electron beam irradiation after laminating a foaming agent-containing resin layer containing a thermally decomposable foaming agent on a paper substrate by extrusion molding. The foaming agent-containing resin layer is then made into a foamed resin layer by heating, wherein the foaming agent-containing resin layer contains an ethylene-vinyl acetate copolymer (EVA) as a resin component, and It further comprises a diacrylate monomer having a tertiary carbon atom.

  In the production method of the present invention, the foaming agent-containing resin layer contains a diacrylate monomer having tertiary carbon atoms together with EVA. Since the diacrylate monomer acts as a crosslinking aid, it promotes EVA crosslinking by electron beam irradiation. Therefore, the amount of electron beam irradiation required to form a good foamed state can be reduced as compared with the conventional case. Specifically, since the electron beam irradiation amount can be reduced to about 1 to 4 Mrad (preferably about 1 to 3 Mrad), it is possible to prevent the paper-based substrate from being burned (discolored) while forming a good foamed state.

  Hereinafter, each process of the manufacturing method of this invention is demonstrated.

Formation of foaming agent-containing resin layer In the production method of the present invention, a foaming agent-containing resin layer containing a pyrolytic foaming agent is first laminated on a paper substrate by extrusion molding.

  The paper base is not particularly limited as long as it has mechanical strength, heat resistance and the like suitable as a wallpaper base, and a fibrous sheet can be generally used.

  Specifically, among fiber sheets, flame retardant paper (pulp-based sheets treated with flame retardants such as guanidine sulfamate and guanidine phosphate); inorganic additives such as aluminum hydroxide and magnesium hydroxide Inorganic paper including; fine paper; thin paper and the like.

The basis weight of the paper quality substrate is not limited, but preferably about 30~300g / ^{m 2,} about 50 to 80 g / ^{m 2} is more preferable.

  Specifically, the foaming agent-containing resin layer is laminated on a paper base by extruding a resin composition for forming the foaming agent-containing resin layer. The resin composition includes a resin component containing EVA, a pyrolytic foaming agent, and a diacrylate monomer having a tertiary carbon atom.

  The resin component may be substantially only EVA, but other resins may be mixed with EVA as a main component. For example, an alicyclic saturated hydrocarbon resin may be mixed. The content of EVA in the resin component is not limited, but is preferably about 50 to 100% by weight. Although it is not limited as an alicyclic saturated hydrocarbon resin, For example, (brand name "Arcon" Arakawa Chemical Industries make) can be used conveniently.

  The MFR of the resin component (including both alone or a mixture) is preferably about 40 to 120 g / 10 minutes, and more preferably about 50 to 75 g / 10 minutes. By using such a resin component, good resin fluidity can be secured during extrusion molding. When EVA is used alone as the resin component, EVA having the above MFR may be used. Further, when the resin component is composed of a mixture of a plurality of types of resins, the resin component is adjusted so as to be in the above MFR range. In addition, as MFR of the resin composition used for extrusion, it is desirable that it is about 30-120 g / 10min. By setting the MFR of the resin composition within such a range, generation of frictional heat during extrusion molding can be suppressed, and abnormal foaming of the pyrolytic foaming agent in the extrusion molding machine can be prevented.

  In addition, MFR of this specification is the value measured by the test method of JISK7210 (flow test method of thermoplastics). As test conditions, “190 ° C., 21.18 N (2.16 kgf)” described in JIS K 6760 is adopted.

  The pyrolytic foaming agent is not particularly limited, and examples thereof include azo series such as azodicarbonamide (ADCA) and azobisformamide; and hydrazide series such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide.

  The content of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. The expansion ratio is preferably 1.5 times or more, and more preferably about 3 to 7 times. From the viewpoint of expansion ratio, the content of the pyrolytic foaming agent is preferably about 1 to 20 parts by weight with respect to 100 parts by weight of the resin component in the resin composition.

The diacrylate monomer having a tertiary carbon atom, specifically, dicyclopentenyl diacrylate, dicyclopentenyl oxyethyl diacrylate can be used. About 0.5-10 weight part is preferable with respect to 100 weight part of resin components in a resin composition, and, as for content of the said diacrylate monomer, about 1-2 weight part is more preferable.

  The resin composition may contain additives such as inorganic fillers, pigments, flame retardants, and heat stabilizers as necessary. About these addition amount, it can set suitably according to the kind of foam wallpaper.

  Among these, examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including an inorganic filler, an effect of enhancing surface characteristics such as scratch resistance can be obtained in addition to the effect of suppressing see-through. The content of the inorganic filler is preferably about 0 to 100 parts by weight and more preferably about 20 to 70 parts by weight with respect to 100 parts by weight of the resin component in the resin composition.

  The pigment is as follows. Inorganic pigments include, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), and cadmium. Examples thereof include red, ultramarine blue, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide. Examples of organic pigments include aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone, Perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine) and the like. The content of the pigment is set according to the desired degree of coloring of the foamed resin layer.

  The resin composition can be extruded by, for example, a T-die extruder.

  Since the foaming agent-containing resin layer immediately after extrusion has adhesiveness due to heat of fusion, it can be in close contact with the paper-based substrate without an adhesive. In addition, prior to laminating with a paper-based substrate, a foaming agent-containing resin layer is prepared in advance by extrusion molding, and the foaming agent-containing resin layer is placed on the paper-based substrate, and both are adhered to each other by thermal lamination. Good. In this case, for example, there is a method in which a paper base is heated in advance and the foaming agent-containing resin layer is brought into close contact therewith. In addition, when making it adhere | attach by heat | fever lamination, it is necessary to carry out at the temperature which a thermal decomposition type foaming agent does not foam.

  Although the thickness of a foaming agent containing resin layer is not limited, About 50-200 micrometers is preferable and about 80-150 micrometers is more preferable.

  Although the aspect which laminated | stacked the foaming agent containing resin layer independently on a paper-like base material was demonstrated above, you may laminate | stack the foaming agent containing resin layer in the aspect which formed the non-foaming resin layer in the single side | surface or both surfaces. For example, the non-foamed resin layer A may be further provided between the paper-based substrate and the foaming agent-containing resin layer. The non-foamed resin layer A is preferably one that enhances the adhesion between the foaming agent-containing resin layer and the paper-based substrate. Moreover, you may further provide the non-foaming resin layer B on the upper surface of a foaming agent containing resin layer. The non-foamed resin layer B is preferably one that can enhance the surface strength of the foamed wallpaper while protecting the foaming agent-containing resin layer. In addition, when an inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer, an inorganic filler residue (so-called eyes) is easily generated at the extrusion port (so-called die) of the extrusion molding machine. It tends to be a foreign material on the surface of foam wallpaper. Therefore, when the inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer, the non-foaming resin layer A and the non-foaming resin layer B can be coextruded together with the foaming agent-containing resin layer. preferable. The coextrusion molding can be performed, for example, by using a multi-manifold type T die. Thus, by simultaneously extruding and molding the foaming agent-containing resin layer between the non-foamed resin layers, it is possible to suppress the occurrence of the eyes.

  The resin component contained in the non-foamed resin layer A is not limited, but EVA is preferable from the viewpoint of improving the adhesion. The non-foamed resin layer A may contain known additives in addition to the resin component, but is preferably blended so that the content of the resin component is 70 to 100% by weight.

  The thickness of the non-foamed resin layer A is not limited, but is preferably about 10 to 50 μm.

  The resin component contained in the non-foamed resin layer B is not limited, but it is preferable to contain at least one of EVA and an ethylene-unsaturated carboxylic acid copolymer from the viewpoint of improving surface characteristics. In particular, when an ethylene-unsaturated carboxylic acid copolymer is contained, a strong layer resulting from hydrogen bonding in the resin can be formed, which is advantageous in improving surface characteristics. The non-foamed resin layer B may contain known additives in addition to the resin component, but is preferably blended so that the content of the resin component is 70 to 100% by weight.

  The thickness of the non-foamed resin layer B is not limited, but is preferably about 10 to 50 μm.

After laminating the foaming agent-containing resin layer on the resin-crosslinked paper base material by electron beam irradiation, the resin (particularly EVA) contained in the foaming agent-containing resin layer is crosslinked by electron beam irradiation. Since EVA is a resin that is crosslinked by electron beam irradiation, the melt tension of the foaming agent-containing resin layer can be adjusted depending on the degree of crosslinking.

  As the electron beam irradiation device, for example, a Cockcroft-Walton type, a bandegraft type, a resonant transformer type, an insulating core transformer type, or a linear type, a dynamitron type, a high frequency type, or the like can be used.

  The energy of the electron beam is preferably about 150 to 250 kV, and more preferably about 160 to 200 kV.

  The amount of electron beam irradiation takes into consideration the content of the crosslinking aid and the degree of adjustment of the melt tension by resin crosslinking (adjustment for obtaining a good foamed state) to prevent the paper-based substrate from being burnt in the subsequent foaming process. What is necessary is just to set suitably from a viewpoint, However, About 1-4 Mrad is enough, About 1-3 Mrad is more preferable. In the production method of the present invention, the resin component (EVA) can be sufficiently crosslinked even at such an irradiation amount, and the melt tension can be adjusted to a desired range. And since an electron beam irradiation amount can be reduced, the burning (discoloration) of a paper-like base material can be prevented in the foaming process mentioned later.

Formation of foamed resin layer (heat treatment)
After adjusting the melt tension of the foaming agent-containing resin layer, the foaming resin layer is formed by heating the foaming agent-containing resin layer. That is, by thermally decomposing the thermally decomposable foaming agent contained in the foaming agent-containing resin layer, the foaming agent-containing resin layer is foamed (expanded) to become a foamed resin layer.

  The heating conditions are not limited as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 180 to 240 ° C, more preferably about 210 to 230 ° C. The heating time is preferably about 20 to 60 seconds, and more preferably about 25 to 40 seconds.

  Although the thickness of the foamed resin layer obtained by foaming is not limited, about 300-1000 micrometers is preferable and about 500-800 micrometers is more preferable.

Formation of Pattern Pattern Layer In the production method of the present invention, a pattern pattern layer may be further formed on the foaming agent-containing resin layer. In addition, a surface protective layer described later may be formed on the surface of the pattern layer for the purpose of adjusting the gloss and / or protecting the pattern layer. In addition, when the non-foamed resin layer B is formed on the foaming agent-containing resin layer, the pattern layer is formed on the surface of the non-foamed resin layer B. The formation time of the pattern layer is not limited, but it is preferably performed before the heat treatment.

  The pattern layer imparts design properties to the foamed wallpaper. Examples of the design pattern include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern. The pattern can be selected according to the type of foam wallpaper.

  The pattern pattern layer can be formed, for example, by printing a pattern pattern on the front surface of the foaming agent-containing resin layer. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, and offset printing. As the printing ink, a known printing ink containing a colorant, a binder resin, and a solvent can be used.

  The pigment can be used as the colorant.

  The binder resin can be set according to the type of paper base material. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer system Examples include resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Chlorinated organic solvents; and water.

  The thickness of the pattern layer is different from the type of pattern, but is preferably about 0.1 to 15 μm.

Surface protective layer (overcoat layer)
In the production method of the present invention, a surface protective layer may be formed on the surface of the pattern layer for the purpose of adjusting the gloss and / or protecting the pattern layer. The kind of surface protective layer is not limited. If it is a surface protective layer aiming at gloss adjustment, there exists a surface protective layer containing known fillers, such as a silica, for example. As a method for forming the surface protective layer, a known method such as gravure printing can be employed. In addition, when the adhesiveness of a design pattern layer and a surface protection layer is not fully acquired, a surface protection layer can also be provided after carrying out the adhesion process (primer process) of the surface of a design pattern layer.

  When forming a surface protective layer for the purpose of surface strength (such as scratch resistance) of foamed wallpaper, stain resistance, protection of the pattern layer, etc., those containing ionizing radiation curable resins as resin components are suitable. is there. The ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation.

  When a surface protective layer containing an ionizing radiation curable resin is formed, the surface protective layer can be cured by electron beam irradiation. Such electron beam irradiation can be performed simultaneously (same processing) as electron beam irradiation performed to crosslink the resin contained in the foaming agent-containing resin layer. That is, after forming a foaming agent-containing resin layer, a pattern layer and a surface protective layer containing an ionizing radiation curable resin in order, electron beam irradiation is performed to crosslink the resin contained in the foaming agent-containing resin layer and protect the surface. The resin contained in the layer can be cured.

  The thickness of the surface protective layer is different from the pattern type, but is preferably about 0.1 to 15 μm.

Embossing In the manufacturing method of the present invention, the outermost surface of the foam wallpaper may be embossed.

  Embossing can be performed by known means such as an embossed plate. For example, when the surface protective layer is the outermost surface layer, a desired embossed pattern can be formed by pressing the embossed plate after heat-softening the front surface. Examples of the embossed pattern include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain texture, a hairline, and a multiline groove.

  In the production method of the present invention, the foaming agent-containing resin layer contains a diacrylate monomer having tertiary carbon atoms together with EVA. Since the diacrylate monomer acts as a crosslinking aid, it promotes EVA crosslinking by electron beam irradiation. Therefore, the amount of electron beam irradiation required to form a good foamed state can be reduced as compared with the conventional case. Specifically, since the electron beam irradiation amount can be reduced to about 1 to 4 Mrad (preferably about 1 to 3 Mrad), it is possible to prevent the paper-based substrate from being burned (discolored) while forming a good foamed state.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
Using a three-type three-layer multi-manifold T-die extruder, films were formed in the order of i) non-foamed resin layer / ii) foaming agent-containing resin layer / iii) non-foamed resin layer in the order of 10 μm / 100 μm / 10 μm. The extrusion conditions were as follows: i) layer resin had a cylinder temperature of 90 ° C., ii) layer resin composition had a cylinder temperature of 100 ° C., and iii) layer resin had a cylinder temperature of 90 ° C. The die temperature was 100 ° C. for all.

  Next, a backing paper “HPT-65, made by Hokuetsu Paper” with a surface temperature of 90 ° C. was laminated on the surface of the layer iii) by thermal lamination. Thereby, the raw material for foam wallpaper was produced.

  Next, an electron beam (3MRad) was irradiated from above the i) layer of the raw material for foamed wallpaper to crosslink EVA contained in each layer, and then a corona discharge treatment was performed on the i) layer. Further, a pattern (texture pattern) layer was printed by a gravure printing machine using a water-based acrylic ink “Hydric, manufactured by Dainichi Seika Kogyo”. The pattern layer was formed by using a gravure plate in which a concave portion of a textured pattern was formed on a metal cylinder, and filling the concave portion with ink and pressing it against the sheet to copy the textured pattern. Next, a surface protective layer (gloss adjusting layer) was formed on the surface of the pattern layer. The surface protective layer was provided by gravure coating using a water-based acrylic ink “PLC, manufactured by Dainichi Seika Kogyo”.

  Next, the foaming agent contained in the foaming agent-containing resin layer was foamed by heating in a gear oven (220 ° C. × 30 seconds). Further, a foamed wallpaper was prepared by embossing the embossed pattern of the fabric pattern on the foam.

  Each layer was formed using the following components.

  The non-foamed resin layer i) was formed by EVA “Evaate CV5053, manufactured by Sumitomo Chemical”.

The foaming agent-containing resin layer ii) is 100 parts by weight of EVA “Evaate CV5053, manufactured by Sumitomo Chemical”, 30 parts by weight of inorganic filler “Whiteon H, manufactured by Toyo Fine Chemical”, and titanium dioxide “Taypure R-108, manufactured by DuPont” 20 parts, blowing agents "VINYFOR AC # 3-K2, Eiwa Chemical industry Co., Ltd." 4 parts by weight, the cell controlling agent "STAB OF-101, manufactured by Asahi Denka Kogyo" 5 parts by weight, crosslinking aid "dicyclopentenyloxyethyl di It was formed by a resin composition containing 1 part by weight of “acrylate”.

  The non-foamed resin layer iii) was formed by EVA “Evaate CV5053, manufactured by Sumitomo Chemical”.

Example 2
Using a three-type three-layer multi-manifold T-die extruder, films were formed in the order of i) non-foamed resin layer / ii) foaming agent-containing resin layer / iii) non-foamed resin layer in the order of 10 μm / 100 μm / 10 μm. The extrusion conditions were as follows: i) layer resin had a cylinder temperature of 90 ° C., ii) layer resin composition had a cylinder temperature of 120 ° C., and iii) layer resin had a cylinder temperature of 90 ° C. The die temperature was 100 ° C. for all.

  Next, a backing paper “HPT-65, made by Hokuetsu Paper” with a surface temperature of 90 ° C. was laminated on the surface of the layer iii) by thermal lamination. Thereby, the raw material for foam wallpaper was produced.

  Next, an electron beam (3MRad) was irradiated from above the i) layer of the raw material for foamed wallpaper to crosslink EVA contained in each layer, and then a corona discharge treatment was performed on the i) layer. Further, a pattern (texture pattern) layer was printed by a gravure printing machine using a water-based acrylic ink “Hydric, manufactured by Dainichi Seika Kogyo”. The pattern layer was formed by using a gravure plate in which a concave portion of a textured pattern was formed on a metal cylinder, and filling the concave portion with ink and pressing it against the sheet to copy the textured pattern. Next, a surface protective layer (gloss adjusting layer) was formed on the surface of the pattern layer. The surface protective layer was provided by gravure coating using a water-based acrylic ink “PLC, manufactured by Dainichi Seika Kogyo”.

  Next, the foaming agent contained in the foaming agent-containing resin layer was foamed by heating in a gear oven (220 ° C. × 30 seconds). Further, a foamed wallpaper was prepared by embossing the embossed pattern of the fabric pattern on the foam.

  Each layer was formed using the following components.

  The non-foamed resin layer i) was formed by EVA “Evaate CV5053, manufactured by Sumitomo Chemical”.

The foaming agent-containing resin layer ii) is composed of 90 parts by weight of EVA “Evertate H4011, made by Sumitomo Chemical”, 10 parts by weight of alicyclic saturated hydrocarbon “Alcon P-100, made by Arakawa Chemical Industries”, and inorganic filler “Whiteon H”. , Manufactured by Toyo Fine Chemical Co., Ltd., 30 parts by weight, titanium dioxide, “Taypure R-108, manufactured by DuPont”, 20 parts by weight, foaming agent, “Vinihole AC # 3-K2, manufactured by Eiwa Kasei Kogyo”, cell regulator, “Adeka Stub OF- 101, made by Asahi Denka Kogyo "5 parts by weight, crosslinking aid" dicyclopentenyloxyethyl diacrylate "was formed of a resin composition comprising 1 part by weight.

  The non-foamed resin layer iii) was formed by EVA “Evaate CV5053, manufactured by Sumitomo Chemical”.

Example 3
Before forming the pattern (texture pattern) layer, the electron beam irradiation is not performed, and the surface of the pattern pattern layer is formed with a primer layer for ionizing radiation curable resin (2 μm), and the surface protective layer (ionizing radiation curing) is further formed on the surface. Mold resin layer) (10 μm) was formed. The primer layer was formed using EBR primer (manufactured by The Inktec). The surface protective layer was formed using Seika Beam EBL-200 (manufactured by Dainichi Seika Kogyo).

  Subsequently, electron beam irradiation (irradiation amount: 3 Mrad) was performed on the surface protective layer to cross-link EVA and to cure the resin contained in the surface protective layer.

  A foamed wallpaper was prepared in the same manner as in Example 1 except for the above conditions.

Comparative Example 1
A foam wallpaper was prepared in the same manner as in Example 1 except that the electron beam irradiation amount was 5 Mrad.

Comparative Example 2
A foamed wallpaper was prepared in the same manner as in Example 1 except that no crosslinking aid was used.

Comparative Example 3
A foamed wallpaper was prepared in the same manner as in Example 1 except that the crosslinking aid was not used and the electron beam irradiation amount was 5 Mrad.

Comparative Example 4
A foamed wallpaper was prepared in the same manner as in Example 1 except that the crosslinking aid was not used and the electron beam irradiation amount was set to 0 Mrad.

Comparative Example 5
A foamed wallpaper was prepared in the same manner as in Example 1 except that the crosslinking assistant was a functional group-free polymer having a tertiary carbon atom (trade name “Arcon P” manufactured by Arakawa Chemical Industries).

Comparative Example 6
The crosslinking aid, except for using diacrylate monomer having no tertiary carbon atoms (1,3-butanediol diacrylate), to produce a foam wallpaper in the same manner as in Example 1.

Comparative Example 7
A foamed wallpaper was prepared in the same manner as in Example 1 except that the crosslinking aid was a polyfunctional acrylate monomer having a tertiary carbon atom.

Test example 1
The foamed wallpaper produced in Examples and Comparative Examples was evaluated by visually observing the foamed wallpaper for the quality of the foamed state and the presence or absence of burning of the paper-based substrate.

  Regarding the foamed state, the case where the collapse of the foamed cell and the generation of the rough cell were not evaluated was evaluated as “◯”, the case where the cell was slightly recognized was evaluated as “Δ”, and the material which was clearly recognized was evaluated as “X”.

  Regarding the burning of the paper-based substrate, the case where the burning was not recognized was evaluated as “◯”, and the case where the burning was recognized was evaluated as “X”.

Test example 2
The foamed wallpaper produced in Examples and Comparative Examples was evaluated for surface contamination resistance.

  Contamination resistance is a test method written in the anti-smudge wallpaper performance regulations established by the Wallpaper Product Standards Council. The remaining one was evaluated as x.

  The results of each test example are shown in Table 1 below.

Claims (8)

A foaming agent-containing resin layer containing a thermal decomposable foaming agent is laminated on the paper substrate by extrusion molding, then the resin contained in the foaming agent-containing resin layer is crosslinked by electron beam irradiation, and then heated to contain the foaming agent. A method for producing a foam wallpaper having a resin layer as a foam resin layer,
The foaming agent-containing resin layer contains an ethylene-vinyl acetate copolymer as a resin component, and further contains a diacrylate monomer having a tertiary carbon atom ,
The electron beam irradiation has an irradiation amount of 1 to 4 Mrad.
A method for producing a foam wallpaper.   The manufacturing method according to claim 1, wherein the resin component contained in the foaming agent-containing resin layer has a melt flow rate of 40 to 120 g / 10 minutes.   The production according to claim 1 or 2, wherein the content of the diacrylate monomer having a tertiary carbon atom is 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin component contained in the foaming agent-containing resin layer. Method. The manufacturing method in any one of Claims 1-3 which forms a pattern pattern layer further on the foaming agent containing resin layer. The manufacturing method of Claim 4 which forms the surface protective layer which contains ionizing radiation curable resin as a resin component further on the surface of a design pattern layer. The manufacturing method according to claim 5 , wherein the resin contained in the foaming agent-containing resin layer is cross-linked by electron beam irradiation and the resin contained in the surface protective layer is cured. The manufacturing method according to any one of claims 1 to 6 , wherein the extrusion molding is single layer or multilayer extrusion molding by a T-die extruder. Claim 1-7 foamed wallpaper produced by the production method according to any one of.