JP5786560B2 - Method for producing foamed laminated sheet - Google Patents

Description

  The present invention relates to a foamed laminated sheet. The foamed laminated sheet has a foamed resin layer and is useful as foamed wallpaper, various decorative materials, and the like.

  Conventionally, various foamed laminated sheets (for example, foamed wallpaper) in which at least a foamed resin layer is laminated on a fibrous sheet and an embossed uneven pattern is formed from the outermost layer are known.

For example, in Patent Document 1, as a method for producing a foam decorative sheet, “at least a foaming agent-containing resin layer is formed on a substrate, and then the foaming agent-containing resin layer is resin-crosslinked, and then the foaming agent after resin crosslinking. A method for producing a foam decorative sheet for foaming a containing resin layer,
(1) The foaming agent-containing resin layer contains 70 parts by weight or more of inorganic particles with respect to 100 parts by weight of the resin component, and has a thickness of 60 to 200 μm.
(2) The method for producing a resin, wherein the resin crosslinking is performed by transmitting the base material from at least the base material side and irradiating the foaming agent-containing resin layer with an electron beam. Is described. The [0052] paragraph describes embossing the front surface.

  The main purpose of the resin crosslinking of the conventional foaming agent-containing resin layer as in Patent Document 1 is to control the foaming ratio by crosslinking the resin component by electron beam irradiation or to increase the uniformity of the foamed cells. (See paragraph [0003] of Patent Document 1). Many of such foamed laminated sheets satisfy the required performance with respect to the foaming ratio of the foamed resin layer and the uniformity of the foamed cells, but the surface strength of the foamed laminated sheet is insufficient and the durability of the embossed uneven pattern is not satisfactory. It has been pointed out that it may be sufficient. For example, regarding the durability of the embossed uneven pattern, it has been pointed out that the embossed uneven pattern disappears (so-called wrinkle return) when the foamed laminated sheet is heated.

  For the above problems, it can be proposed to increase the amount of electron beam irradiation to the foaming agent-containing resin layer, but if the amount of irradiation is increased, the foaming characteristics may be lowered or the discoloration of the fiber sheet may occur. It becomes a problem.

  Accordingly, there is a demand for the development of a new method for producing a foamed laminated sheet that can provide a foamed resin layer having good foaming characteristics and good durability of the embossed uneven pattern.

JP 2008-246792 JP

  An object of this invention is to provide the manufacturing method of the new foaming laminated sheet from which the foaming resin layer of a favorable foaming characteristic is obtained, and favorable durability of an embossing uneven | corrugated pattern is obtained.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by a specific production method in which the foaming agent-containing resin layer and the foamed resin layer are each irradiated with an electron beam, The present invention has been completed.

That is, this invention relates to the manufacturing method of the following foaming lamination sheet.
1. At least a foamed resin layer is laminated on the fibrous sheet, and an embossed concavo-convex pattern is formed from the outermost layer.
(1) Step 1 of laminating at least a foaming agent-containing resin layer on a fibrous sheet,
(2) Step 2 of forming the foamed resin layer by foaming the foaming agent-containing resin layer and (3) Step 3 of shaping an embossed uneven pattern from the outermost layer,
Prior to the step 2, the foaming agent-containing resin layer is subjected to electron beam irradiation A, and after the step 3, the foamed resin layer is subjected to electron beam irradiation B from the outermost layer side.
2. The said electron beam irradiation B is a manufacturing method of the said claim | item 1 performed on the conditions from which an electron beam does not reach | attain the said fiber sheet.
3. The foaming agent-containing resin layer contains at least one ethylene copolymer having 1) polyethylene and 2) ethylene and a component other than ethylene as a resin component, and the electron beam irradiation A has an acceleration voltage of 150. Item 3. The method according to Item 1 or 2, wherein the electron beam irradiation is irradiation of an electron beam of ˜250 kV, and the electron beam irradiation B is irradiation of an electron beam having an acceleration voltage of 100 to 150 kV.
4). Item 4. The production method according to any one of Items 1 to 3, further comprising a step of forming a pattern layer on the foaming agent-containing resin layer.
5. The said foaming agent containing resin layer is a manufacturing method in any one of said claim | item 1 -4 which has a non-foaming resin layer in the single side | surface or both surfaces.
6). The manufacturing method according to any one of Items 1 to 5, wherein the foaming agent-containing resin layer contains an ethylene-methacrylic acid copolymer as a resin component.

  Hereinafter, the manufacturing method of the foaming lamination sheet of this invention is demonstrated in detail.

The method for producing a foamed laminated sheet of the present invention is a method for producing a foamed laminated sheet in which at least a foamed resin layer is laminated on a fibrous sheet, and an embossed uneven pattern is formed from the outermost layer,
(1) Step 1 of laminating at least a foaming agent-containing resin layer on a fibrous sheet,
(2) Step 2 of forming the foamed resin layer by foaming the foaming agent-containing resin layer and (3) Step 3 of forming an embossed uneven pattern from the outermost layer,
Prior to the step 2, the foaming agent-containing resin layer is subjected to electron beam irradiation A, and after the step 3, the foamed resin layer is subjected to electron beam irradiation B from the outermost layer side.

  The method for producing a foamed laminated sheet of the present invention having the above characteristics can adjust the melt tension of the foaming agent-containing resin layer, particularly by performing electron beam irradiation A on the foaming agent-containing resin layer prior to step 2. Therefore, the foaming ratio and the uniformity of the foamed cells when forming the foamed resin layer can be ensured. Moreover, since the surface strength can be ensured by performing electron beam irradiation B on the foamed resin layer from the outermost layer side after Step 3, even when heat is applied to the foamed laminated sheet, the disappearance of the embossed uneven pattern ( Wrinkle return) is suppressed.

Hereinafter, each process of the manufacturing method of this invention is demonstrated.
≪First process≫
In the first step, at least a foaming agent-containing resin layer is laminated on the fibrous sheet.

  It is not limited as a lamination mode, in addition to a mode in which a foaming agent-containing resin layer is laminated on a fibrous sheet, a mode in which a pattern layer or a surface protective layer is laminated on a foaming agent-containing resin layer, foaming The aspect etc. which laminate | stack a non-foaming resin layer on the single side | surface or both surfaces of an agent containing resin layer are mentioned.

Each of these layers can be laminated by combining printing, coating and other coatings, extrusion film formation, and the like. Printing, coating, etc. can be performed according to conventional methods.
(Fiber sheet)
Fiber sheets (so-called backing paper) include general paper for wallpaper (pulp-based sheets sized with a known sizing agent); flame-retardant paper (pulp-based sheets such as guanidine sulfamate and guanidine phosphate) Treated with a flame retardant); inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper.

Although the basis weight of the substrate is not critical, preferably about 50 to 300 g / m ^2, more preferably about 50~120 g / m ^2.
(Foaming agent-containing resin layer)
In the present invention, the foaming agent-containing resin layer comprises at least one of 1) polyethylene as a resin component and 2) an ethylene copolymer having monomers other than ethylene and ethylene (hereinafter abbreviated as “ethylene copolymer”). It is preferable to contain 1 type.

  As the polyethylene, low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), and the like can be widely used. Among these, low-density polyethylene is preferable.

  Ethylene copolymers are suitable for extrusion film formation in terms of melting point and MFR. Examples of the ethylene copolymer include an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene-ethyl acrylate copolymer (EEA), and an ethylene-methyl acrylate copolymer ( EMA), ethylene-methacrylic acid copolymer (EMAA), ethylene-α olefin copolymer, and the like. These ethylene copolymers can be used alone or in admixture of two or more. Among these ethylene copolymers, at least one of ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer and ethylene-methacrylic acid copolymer is preferable, and when these are used in combination with other resins The content of at least one of ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-methacrylic acid copolymer is preferably 70% by mass or more, and more preferably 80% by mass or more.

  In the ethylene copolymer, the content of monomers other than ethylene is preferably 5 to 25% by mass, more preferably 9 to 20% by mass. By adopting such a copolymerization ratio, the extrusion film forming property is further enhanced. As a specific example, the ethylene-vinyl acetate copolymer has a vinyl acetate copolymerization ratio (VA amount) of preferably 9 to 25% by mass, and more preferably 9 to 20% by mass. The ethylene-methyl methacrylate copolymer has a methyl methacrylate copolymerization ratio (MMA amount) of preferably 5 to 25% by mass, more preferably 5 to 15% by mass. Further, the ethylene-methacrylic acid copolymer is preferably 2 to 15% by mass, more preferably 5 to 11% by mass as the copolymerization ratio (MAA amount) of acrylic acid.

  In the present invention, the resin component contained in the foaming agent-containing resin layer has an MFR (melt flow rate) of 10 to 25 g / 10 min measured under the conditions of 190 ° C. and a load of 21.18 N described in JIS K 6922. preferable. When the MFR is within the above range, there is little increase in temperature when the foaming agent-containing resin layer is formed by extrusion film formation, and the film can be formed in a non-foamed state. It can be printed on any surface and there are few patterns missing. If the MFR is too large, the resin is too soft and the resulting foamed resin layer may have insufficient scratch resistance.

  As the resin composition for forming the foaming agent-containing resin layer, for example, a resin composition containing the above resin component, inorganic filler, pigment, pyrolytic foaming agent, foaming aid, crosslinking aid and the like can be suitably used. . In addition, stabilizers, lubricants and the like can be used as additives.

  Examples of the thermally decomposable foaming agent include azo series such as azodicarbonamide (ADCA) and azobisformamide; hydrazide series such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide. The content of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. From the viewpoint of the expansion ratio, it is 7 times or more, preferably about 7 to 10 times, and the pyrolytic foaming agent is preferably about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

  The foaming aid is preferably a metal oxide and / or a fatty acid metal salt. For example, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, laurin Magnesium acid, zinc oxide, magnesium oxide and the like can be used. About 0.3-10 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of these foaming adjuvants, about 1-5 mass parts is more preferable.

  When these foaming aids are used in combination with EMAA and ADCA foaming agents, the effect of the original foaming aid is impaired by the reaction of the acrylic acid part of EMAA with the foaming aid in the foaming process. There is a problem. Therefore, when EMAA and ADCA foaming agent are used in combination, it is preferable to use a carboxylic acid hydrazide compound as a foaming aid as described in JP-A-2009-197219. At this time, the carboxylic acid hydrazide compound is preferably used in an amount of about 0.2 to 1 part by mass with respect to 1 part by mass of the ADCA foaming agent.

  Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including an inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained. The content of the inorganic filler is preferably about 0 to 100 parts by mass and more preferably about 20 to 70 parts by mass with respect to 100 parts by mass of the resin component.

  For pigments, 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) ), Cadmium red, ultramarine, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide. Examples of organic pigments include aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone. Perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine). The content of the pigment is preferably about 10 to 50 parts by mass, more preferably about 15 to 30 parts by mass with respect to 100 parts by mass of the resin component.

The thickness of the foaming agent-containing resin layer is preferably about 40 to 100 μm, and the thickness of the foamed resin layer after foaming is preferably about 300 to 700 μm.
(Non-foamed resin layers A and B)
The foaming agent-containing resin layer may have a non-foamed resin layer on one side or both sides.

  For example, the back surface (surface on which the fibrous sheet is laminated) of the foaming agent-containing resin layer may have a non-foamed resin layer B (adhesive resin layer) for the purpose of improving the adhesive force with the fibrous sheet. .

  The resin component of the adhesive resin layer is not particularly limited, but an ethylene-vinyl acetate copolymer (EVA) is preferable. As the EVA, a known or commercially available EVA can be used. In particular, the vinyl acetate component (VA component) is preferably 10 to 46% by mass, more preferably 15 to 41% by mass.

  The thickness of the adhesive resin layer is not limited, but is preferably about 5 to 50 μm.

  On the upper surface of the foaming agent-containing resin layer, a non-foamed resin layer A may be provided for the purpose of clarifying the design pattern when forming the design pattern layer or improving the scratch resistance of the foamed resin layer.

  Examples of the resin component of the non-foamed resin layer A include polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, and fluorine resins. Of these, polyolefin resins are preferred.

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

  The thickness of the non-foamed resin layer A is not limited, but is preferably about 5 to 50 μm.

  When the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides, simultaneous extrusion film formation by a T-die extruder is suitable. For example, in the case of having non-foamed resin layers on both sides, a multi-manifold type T die capable of simultaneously forming three layers by simultaneously extruding molten resins corresponding to the three layers can be used.

In addition, when an inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer and the foaming agent-containing resin layer is formed by extrusion film formation, an extrusion port (so-called die) of the extruder is used. Inorganic filler residues (so-called eyes and eyes) are easily generated, and this tends to be a foreign matter on the surface of the foaming agent-containing resin layer. Therefore, when an inorganic filler is included in the resin composition forming the foaming agent-containing resin layer, it is preferable to form a three-layer coextrusion film as described above. That is, it is possible to suppress the occurrence of the above-mentioned corners by co-extrusion film formation in a mode in which the foaming agent-containing resin layer is sandwiched between non-foamed resin layers.
(Pattern pattern layer)
A pattern layer may be formed on the foaming agent-containing resin layer (or on the non-foamed resin layer A) as necessary. That is, the manufacturing method of this invention may have the process of forming a pattern pattern layer.

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

  The pattern pattern layer can be formed, for example, by printing a pattern pattern. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, offset printing, and the like. As the printing ink, a printing ink containing a colorant, a binder resin, and a solvent can be used. These inks may be known or commercially available.

  As the colorant, for example, a pigment used in the above-described foaming agent-containing resin layer can be appropriately used.

  Binder resin can be set according to the kind of lower layer resin which forms a pattern layer. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy Resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, 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, etc. Chlorinated organic solvents; and water. These solvents (or dispersion media) can be used alone or in the form of a mixture.

The thickness of the design pattern layer is different from the type of design pattern, but is generally preferably about 0.1 to 10 μm.
(Surface protective layer)
In the present invention, a surface protective layer may be provided on the surface of the foaming agent-containing resin layer or the design pattern layer for the purpose of adjusting the gloss and / or protecting the design 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 pattern pattern layer and a surface protective layer is not fully acquired, a surface protective layer can also be provided after carrying out the adhesion process (primer process) of the surface of a pattern pattern layer.

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

  The thickness of the surface protective layer is not limited, but is preferably about 0.1 to 15 μm.

  In the present invention, electron beam irradiation A is performed on the foaming agent-containing resin layer prior to step 2 described later. The purpose of the electron beam irradiation A is to ensure the expansion ratio and the uniformity of the foamed cells when the foamed resin layer is formed by adjusting the melt tension of the foaming agent-containing resin layer.

  Electron beam irradiation A is performed from the fiber sheet side or the outermost layer side after laminating the foaming agent-containing resin layer on the fiber sheet (after laminating the pattern layer and surface protective layer as necessary). The mode which irradiates a line may be sufficient, or the mode which irradiates an electron beam to a foaming agent content resin layer before making only a foaming agent content resin layer beforehand, and laminating | stacking on a fibrous sheet may be sufficient. A known electron beam irradiation apparatus can be used as the electron beam source.

As for the conditions of electron beam irradiation A, the acceleration voltage is preferably 150 to 250 kV, and more preferably 175 to 200 kV. Further, the irradiation dose is preferably 10 to 70 kGy, more preferably 20 to 60 kGy.
≪Process 2≫
In step 2, the foamed resin layer is formed by foaming the foaming agent-containing resin layer.

  The heating conditions at the time of foaming are not limited as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds. In the present invention, since the melt tension of the foaming agent-containing resin layer is adjusted by electron beam irradiation A, the foaming ratio and the uniformity of the foamed cells can be ensured.

The thickness of the foamed resin layer after foaming is about 300 to 700 μm.
≪Process 3≫
In step 3, an embossed concavo-convex pattern is formed from the outermost layer.

  The embossed concavo-convex pattern is formed by embossing (unevenness forming using an embossed plate). 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 present invention, after the step 3, the electron beam irradiation B is performed on the foamed resin layer from the outermost surface layer side. The purpose of the electron beam irradiation B is to ensure the surface strength of the foamed laminated sheet. By performing electron beam irradiation B, disappearance of the embossed uneven pattern is suppressed when heat is applied to the foamed laminated sheet. A known electron beam irradiation apparatus can be used as the electron beam source.

  The electron beam irradiation B is preferably performed under conditions where the electron beam does not reach the fibrous sheet. By satisfying such a condition, it is possible to prevent burning of the fibrous sheet due to electron beam irradiation. Specifically, the acceleration voltage is preferably 100 to 150 kV, more preferably 100 to 140 kV. Further, the irradiation dose is preferably 10 to 70 kGy, more preferably 20 to 60 kGy.

  The foamed laminated sheet manufacturing method of the present invention is capable of adjusting the melt tension of the foaming agent-containing resin layer, particularly by performing electron beam irradiation A on the foaming agent-containing resin layer prior to step 2, so that the foaming resin layer can be adjusted. It is possible to ensure the expansion ratio and the uniformity of the expanded cells when forming the film. Moreover, since the surface strength can be ensured by performing electron beam irradiation B on the foamed resin layer from the outermost layer side after Step 3, even when heat is applied to the foamed laminated sheet, the disappearance of the embossed uneven pattern ( Wrinkle return) is suppressed.

Explanation of friction elements (Fig. 1 in Fig. 1) and holders (Fig. 2 in Fig. 1) used in "Testing by the method described in the Surface Strengthening Performance Regulation Established by Wallpaper Product Standards Council" in Test Example 1 FIG.

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

Example 1
Using a three-type three-layer T-die extruder, the film is extruded onto a fibrous sheet so that the thickness is 8 μm / 70 μm / 8 μm in the order of non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B did. Thereby, the laminated body which consists of non-foaming resin layer A / foaming agent containing resin layer / non-foaming resin layer B / fibrous sheet was obtained. As the fibrous sheet, wallpaper paper “WK-665, manufactured by Kojin” was used.

  The extrusion conditions were such that the cylinder temperature containing the resin for forming the non-foamed resin layer A was 130 ° C., the cylinder temperature containing the resin composition for forming the foaming agent-containing resin layer was 120 ° C., and non-foamed The temperature of the cylinder containing the resin for forming the resin layer B was 120 ° C. The die temperature was 120 ° C. for all.

  Each layer was formed using the following components.

  The non-foamed resin layer A was formed by EMAA “Nucleel N1560, manufactured by Mitsui DuPont Polychemical”.

  The foaming agent-containing resin layer is 100 parts by mass of EMAA "Nucleel N1110H, made by Mitsui & DuPont Polychemical", 30 parts by mass of calcium carbonate "Whiteon H, made by Shiraishi Kogyo", and 20 parts by mass of the colorant "Typure R350, made by DuPont" , 5 parts by mass of the foaming agent “Vinihole AC # 3, made by Eiwa Kasei Kogyo” and 5 parts by mass of the foaming aid “ADHS, made by Otsuka Chemical”.

  The non-foamed resin layer B was formed by EVA “Ultrasen 750, manufactured by Tosoh”.

  Electron beam irradiation A (195 kV, 50 kGy) was performed from the non-foamed resin layer A side of the laminate.

  Next, after corona discharge treatment of the non-foamed resin layer A, a textile pattern was printed using a water-based ink ("Hydric", manufactured by Dainichi Seika Kogyo Co., Ltd.) as a pattern print by a gravure printing machine, and further water-based A surface protective layer was formed by coating ink ("ALTOP", manufactured by Dainichi Seika Kogyo).

  Next, after heating at 220 ° C. for 35 seconds to make the foaming agent-containing resin layer into a foamed resin layer, a metal roll (embossed plate) having a fabric-like uneven pattern was pressed to form an embossed uneven pattern.

  Next, electron beam irradiation B (125 kV, 50 kGy) was performed from the surface protective layer side. The electron beam irradiation B does not reach the fibrous sheet. This obtained the foaming lamination sheet.

Example 2
100 parts by weight of EVA “Ultrasen 633, manufactured by Tosoh”, 30 parts by weight of calcium carbonate “Whiteon H, manufactured by Shiroishi Kogyo”, 20 parts by weight of colorant “Typure R350, manufactured by DuPont”, foaming agent Example except that it was formed with 5 parts by weight of “Vinihole AC # 3, made by Eiwa Kasei Kogyo”, 5 parts by weight of foaming aid “Adeka Stub OF-010, made by ADEKA”, and 1 part by weight of crosslinking aid “made by OPSTAR JUA702 JSR” In the same manner as in Example 1, a foamed laminated sheet was produced.

Example 3
The non-foamed resin layer A is formed by LDPE “Petrocene 202, manufactured by Tosoh”, and the foaming agent-containing resin layer is formed by 100 parts by mass of LDPE “Petrocene 208, manufactured by Tosoh”, calcium carbonate “Whiteon H, manufactured by Shiroishi Kogyo”. "30 parts by weight, 20 parts by weight of the colorant" Taypure R350, made by DuPont ", 5 parts by weight of the foaming agent" Vinihole AC # 3, made by Eiwa Kasei Kogyo ", 5 parts by weight of the foaming aid" Adeka Stub OF-010, made by ADEKA " A foamed laminated sheet was prepared in the same manner as in Example 1 except that it was formed with 1 part by mass of the crosslinking aid “OPSTA JUA702 JSR”.

Example 4
A foamed laminated sheet was produced in the same manner as in Example 1 except that the electron beam irradiation A was performed from the fibrous sheet side.

Example 5
Example 1 except that after forming non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B, the film-formed resin sheet was subjected to electron beam irradiation A and then bonded to a fibrous sheet. In the same manner, a foamed laminated sheet was produced.

Comparative Example 1
A foamed laminated sheet was produced in the same manner as in Example 1 except that the electron beam irradiation B was not performed.

Comparative Example 2
A foamed laminated sheet was produced in the same manner as in Example 2 except that the electron beam irradiation B was not performed.

Comparative Example 3
A foamed laminated sheet was produced in the same manner as in Example 3 except that the electron beam irradiation B was not performed.

Test example 1
The foamed laminated sheets prepared in Examples and Comparative Examples were examined for 1) surface strength and 2) heat resistance of the uneven pattern.

Each test method and evaluation method were as follows.
≪Surface strength≫
The test was conducted by the method described in the Surface Strengthening Performance Rules established by the Wallpaper Product Standards Council.

  Specifically, the friction tester II type friction element specified in JIS L0849 is replaced with a predetermined one (see Fig. 1 in Fig. 1), and the tip surface of the claw of the friction element is level with the test piece base. Further, it was attached to a predetermined holder (see FIG. 2 in FIG. 1) so that the friction element does not move left and right. The test piece was affixed to the backing paper surface of the test piece using a double-sided tape so as to be parallel to the reciprocating direction of the friction element, and was firmly fixed to the test piece base so that the test piece did not move. In the test, a friction piece was gently placed on the test piece, and reciprocated 5 times at a reciprocating speed of 30 times per minute between a transition distance of 120 mm.

◎ when there is no change, ◯ when there is no change in surface shape but slight change in gloss, △ when there is a slight change in surface shape, and a tear of the resin layer is confirmed on the surface Things were rated as x.
≪Heat resistance of uneven pattern≫
The obtained foamed laminated sheet was placed in an oven at 200 ° C. for 2 minutes, and changes in the uneven pattern (such as the presence or absence of wrinkle return) were visually evaluated.

  A case where the wrinkle return was slight was evaluated as ◯, a case where the wrinkle return was clear was evaluated as Δ, and a case where the wrinkle return was obvious and surface roughness was generated was evaluated as ×.

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

Claims (6)

At least a foamed resin layer is laminated on the fibrous sheet, and an embossed concavo-convex pattern is formed from the outermost layer.
(1) Step 1 of laminating at least a foaming agent-containing resin layer on a fibrous sheet,
(2) Step 2 of forming the foamed resin layer by foaming the foaming agent-containing resin layer and (3) Step 3 of shaping an embossed uneven pattern from the outermost layer,
Prior to the step 2, the foaming agent-containing resin layer is subjected to electron beam irradiation A, and after the step 3, the foamed resin layer is subjected to electron beam irradiation B from the outermost layer side.   The said electron beam irradiation B is a manufacturing method of Claim 1 performed on the conditions from which an electron beam does not reach | attain the said fiber sheet.   The foaming agent-containing resin layer contains at least one ethylene copolymer having 1) polyethylene and 2) ethylene and a component other than ethylene as a resin component, and the electron beam irradiation A has an acceleration voltage of 150. The manufacturing method according to claim 1, wherein the electron beam irradiation is irradiation of an electron beam having an acceleration voltage of 100 to 150 kV.   The manufacturing method in any one of Claims 1-3 which has the process of forming a pattern pattern layer on the said foaming agent containing resin layer.   The said foaming agent containing resin layer is a manufacturing method in any one of Claims 1-4 which has a non-foaming resin layer in the single side | surface or both surfaces. The said foaming agent containing resin layer is a manufacturing method in any one of Claims 1-5 containing an ethylene-methacrylic acid copolymer as a resin component.

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