JP5849574B2 - Method for producing foamed laminated sheet - Google Patents

Description

  The present invention relates to a method for producing a foam laminate sheet.

  Conventionally, foamed wallpaper in which a foamed resin layer is formed on a substrate is known. In recent years, foamed wallpaper has been developed in which holes are made in the foamed resin layer to provide air permeability. For example, a method of mechanically providing a large number of pores with a needle roll from the top of the foamed resin layer is known, but since the perforation processing is performed from the front side of the wallpaper after foaming, the vicinity of the perforation opening on the base material side In other words, there was a problem that the crepe was formed and the uniform coating property of the adhesive was impaired.

  Also, in embossing after drilling by needle embossing (Patent Document 1) and drilling before foaming, the resin is only primarily plastically deformed by the push needle, so that the holes are easily lost by foaming (holes are There was a tendency to block.

  On the other hand, there is also known a perforation method in which a hole is made in the foamed resin layer with heat using a laser or the like, but the heat generated at the time of perforation burns the resin on the inner surface of the hole, which decreases the design of the wallpaper. There was a problem.

  Therefore, development of the manufacturing method of the foam wallpaper excellent in air permeability without impairing the designability is desired.

Shoko 60-25262

  An object of this invention is to provide the manufacturing method of the foaming lamination sheet excellent in air permeability, without impairing the designability.

  As a result of intensive studies, the present inventor has found that the above object can be achieved by producing a foamed laminated sheet by a production method including a specific production process, and has completed the present invention.

That is, this invention relates to the manufacturing method of the following foaming lamination sheet.
1. The manufacturing method of a foaming lamination sheet including the following processes 1-4 in order:
(1) Step 1 of preparing a resin layer having a foaming agent-containing resin layer,
(2) Step 2 of laminating the resin layer on a substrate to form a laminated sheet,
(3) Step 3 of forming a hole in the resin layer by a thermal method, and (4) Step 4 of heating and foaming the foaming agent-containing resin layer.
2. The method for producing a foamed laminated sheet according to item 1, wherein the hole is formed through the substrate.
3. The method for producing a foamed laminated sheet according to Item 1 or 2, wherein the hole is formed by laser irradiation.
4. As the resin layer, a resin layer including a non-foamed resin layer A, the foaming agent-containing resin layer, and a non-foamed resin layer B is prepared, and the non-foamed resin layer B of the resin layer is adhered to the base material. The manufacturing method of the foaming lamination sheet in any one of said claim | item 1-3.
5. Before the said process 4, The manufacturing method of the foaming lamination sheet in any one of said claim | item 1-4 including the process of irradiating an electron beam with respect to the resin layer which has the said foaming agent containing resin layer.
6. After the said process 4, the manufacturing method of the foaming lamination sheet in any one of said claim | item 1-5 including the process of embossing the resin layer after foaming.
7. The manufacturing method of a foaming lamination sheet which contains the following processes 1-4 in order:
(1) Step 1 of preparing a resin layer having a foaming agent-containing resin layer,
(2) Step 2 of forming a hole in the resin layer having the foaming agent-containing resin layer by a thermal method,
(3) Step 3 of laminating the resin layer having the holes on the substrate to form a laminated sheet, and (4) Step 4 of heating and foaming the foaming agent-containing resin layer.
8. The method for producing a foamed laminated sheet according to Item 7, wherein the holes are formed by laser irradiation.
9. A resin layer comprising a non-foamed resin layer A, the foaming agent-containing resin layer, and a non-foamed resin layer B is prepared as the resin layer, and the non-foamed resin layer B of the resin layer is adhered to the substrate. Item 9. The method for producing a foamed laminated sheet according to Item 7 or 8.
10. The method for producing a foamed laminated sheet according to any one of Items 7 to 9, including a step of irradiating the resin layer having the foaming agent-containing resin layer with an electron beam before the step 4.
11. The method for producing a foamed laminated sheet according to any one of Items 7 to 10, further comprising a step of embossing the foamed resin layer after the step 4.

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

The manufacturing method of the foam lamination sheet of Embodiment 1 of this invention is the following processes 1-4:
(1) Step 1 of preparing a resin layer having a foaming agent-containing resin layer,
(2) Step 2 of laminating the resin layer on a substrate to form a laminated sheet,
(3) Step 3 of forming holes in the resin layer by a thermal method, and (4) Step 4 of heating and foaming the foaming agent-containing resin layer.
In order.

Moreover, the manufacturing method of the foaming lamination sheet of Embodiment 2 of this invention is the following processes 1-4:
(1) Step 1 of preparing a resin layer having a foaming agent-containing resin layer,
(2) Step 2 of forming a hole in the resin layer having the foaming agent-containing resin layer by a thermal method,
(3) Step 3 of laminating the resin layer having the holes on the substrate to form a laminated sheet, and (4) Step 4 of heating and foaming the foaming agent-containing resin layer.
In order.

  In the manufacturing method of the foamed laminated sheet of Embodiments 1 and 2, the hole is formed in the resin layer having the foaming agent-containing resin layer by a thermal method before the foaming agent-containing resin layer is heated and foamed. Since the resin is removed, the pores are not completely closed after foaming by heating, and air permeability can be imparted to the foamed laminated sheet. Further, even if the resin on the inner surface of the hole is burned by heat at the time of drilling, since the resin is deformed by subsequent foaming, the resin burn becomes inconspicuous. In addition, according to this method, since the crease cannot be punched on the base material side (back side of the foam laminate sheet) of the foam laminate sheet, it is possible to uniformly apply the adhesive to the substrate. In addition, since the thickness of the product as a foam is not reduced by the push needle, there is no reduction in design and unevenness (performance for covering the unevenness of the base).

  Thus, according to the manufacturing method of the foaming laminated sheet of this invention, the foaming laminated sheet excellent in air permeability can be obtained, without impairing design property.

  Hereinafter, the manufacturing method of Embodiment 1 and 2 of this invention is demonstrated in detail.

(1) Embodiment 1
Process 1
In step 1 of Embodiment 1, a resin layer having a foaming agent-containing resin layer is prepared. That is, in step 1, the foaming agent-containing resin layer may be formed as a single layer, or a resin layer composed of a plurality of layers having a foaming agent-containing resin layer (for example, the non-foaming resin layer A, the foaming agent-containing resin layer, and the like) A resin layer made of non-foamed resin layer B) may be formed. In the following description, these are collectively referred to as “resin layer” for convenience, and the resin layer is described as including a foaming agent-containing resin layer single layer.

(I) Foaming agent-containing resin layer After forming the foaming agent-containing resin layer, the foaming resin layer is formed by foaming the foaming agent-containing resin layer.

  The foaming agent-containing resin layer used in the present invention preferably contains an olefin-based resin as a resin component. 1) Polyethylene (PE) and 2) An ethylene copolymer having monomers other than ethylene and ethylene (hereinafter referred to as “ethylene copolymer”) And abbreviated as “ethylene copolymer”).

  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.

  The ethylene copolymer is suitable for extrusion film formation from the viewpoint of melting point and MFR. Examples of the ethylene copolymer include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer ( EMA), ethylene-methacrylic acid copolymer (EMAA), and ethylene-α olefin copolymer.

  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.

  Moreover, 5-25 mass% is preferable as content of monomers other than ethylene, and, as for ethylene copolymer, 9-20 mass% is more preferable. 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, 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. Moreover, 2-15 mass% is preferable as a copolymerization ratio (MAA amount) of methacrylic acid, and, as for an ethylene-methacrylic acid copolymer, 5-11 mass% is more preferable.

  In the present invention, the resin component contained in the foaming agent-containing resin layer has an MFR (melt flow rate) measured at 190 ° C. and a load of 21.18 N described in JIS K 6922 of 10 to 100 g / 10 min. Is preferred. When MFR is within the above range, there is little increase in temperature due to shearing heat generation when the foaming agent-containing resin layer is formed by extrusion film formation, and the film can be formed in a non-foamed state. Can be printed on a smooth surface and there is little pattern loss or the like. If the MFR is too large, the resin is too soft, so that a sufficient melt tension suitable for film formation cannot be obtained, 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 appropriately selected depending on the resin to be used, but in general, metal oxides and / or fatty acid metal salts are preferable. For example, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, octylic acid Calcium, magnesium octylate, zinc laurate, calcium laurate, magnesium laurate, 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.

  In addition, when the resin used is EMAA and / or EAA, when used in combination with an ADCA foaming agent, in the foaming process, as a foaming aid by the acrylic foamed part of EMAA and / or EAA and a metal-based foaming aid There is a problem that the effect of. Therefore, when EMAA and / or EAA and ADCA foaming agent are used in combination, as described in JP-A-2009-197219, carboxylic acid hydrazide compound or adipic acid dihydrazide (ADHS) is used as a foaming aid. It is preferable to use it. At this time, it is preferable to use about 0.2-1 mass part of carboxylic acid hydrazide compound or adipic acid dihydrazide with respect to 1 mass part of 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. About 0-100 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of an inorganic filler, about 20-70 mass parts is more preferable.

  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). About 10-50 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of a pigment, about 15-30 mass parts is more preferable.

  In the present invention, the foaming agent-containing resin layer may be resin-crosslinked by electron beam irradiation. What is necessary is just to implement according to the method described in the postscript manufacturing method as a method of irradiating an electron beam to a foaming agent containing resin layer, and the method of making it foam. 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.

(Ii) 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 resin layer having the foaming agent-containing resin layer is preferably a resin layer composed of the non-foaming resin layer A, the foaming agent-containing resin layer, and the non-foaming resin layer B.

  The back surface (surface on which the base material 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 base material.

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

  The thickness of the non-foamed resin layer B (adhesive resin layer) is not limited, but can be about 3 to 50 μm, preferably about 3 to 20 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, fluorine resins, and the like, among which polyolefin resins are preferable.

  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 such as (EAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA) -(Meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate copolymer resin saponified product, ionomer, and the like. These resin components can be used alone or in admixture of two or more.

In order to obtain particularly excellent scratch resistance and abrasion resistance, the resin component is at least one of acrylic acid (CH ₂ ═CHCOOH) and methacrylic acid (CH ₂ ═C (CH ₃ ) COOH). A copolymer obtained by a combination of a monomer and ethylene can be suitably used as a resin component. More specifically, it is desirable to use at least one of an ethylene- (meth) acrylic acid copolymer and an ionomer resin. As the ionomer resin, a resin having a structure in which the molecules of the ethylene- (meth) acrylic acid copolymer are intermolecularly bonded with metal ions such as sodium and zinc can be used. When such a resin component is used, it is possible to form a strong layer caused by hydrogen bonds in the resin. The content of acrylic acid or methacrylic acid in the copolymer is not limited, but is preferably 15% by mass or less, and more preferably about 4 to 15% by mass. As these resins, commercially available products can be used.

  A known additive can also be blended in the resin composition. In that case, although content of the said resin component in a resin composition is not limited, Usually, it is preferable to set suitably in the range of 70-100 mass%.

  The thickness of the non-foamed resin layer A is not limited, but can be about 3 to 50 μm, preferably about 3 to 20 μm.

  In the present invention, an embodiment in which the non-foamed resin layer B, the foaming agent-containing resin layer, and the non-foamed resin layer A are sequentially formed on the substrate is also preferable from the viewpoint of manufacturing described later.

  The melt flow rate value of the resin component of the non-foamed resin layer A depends on the type of the resin component used and the like, but generally may be appropriately set within a range of 10 g / 10 minutes or more. Usually, it is preferably 10 to 100 g / 10 minutes, particularly preferably 10 to 95 g / 10 minutes, and more preferably 20 to 80 g / 10 minutes. By using a material having such a numerical range, more excellent scratch resistance, wear resistance and the like can be obtained.

(Iii) Lamination of each layer It does not specifically limit as a method of preparing a resin layer, For example, the single layer extrusion by a T-die extruder, a multilayer simultaneous extrusion, etc. are mentioned. 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, if there are non-foamed resin layers on both sides, use a feed block system or multi-manifold type T-die that can simultaneously form three layers by simultaneously extruding molten resin corresponding to the three layers. Can do.

  In addition, when an inorganic filler is contained in the resin composition for forming the foaming agent-containing resin layer, and the foaming agent-containing resin layer is formed by extrusion film formation, the extrusion port of the extruder (so-called die slip) ), An inorganic filler residue (so-called eyes) is 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 contained in the resin composition forming the foaming agent-containing resin layer, it is preferable to form a three-layer coextrusion film as described above. In that case, it is preferable to co-extrusion the non-foamed resin layer A and the non-foamed resin layer B together with the foaming agent-containing resin layer as a layer not containing an inorganic filler. 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.

Process 2
In the process 2 of Embodiment 1, the resin layer which has the said foaming agent containing resin layer is laminated | stacked on a base material, and a lamination sheet is formed. For example, when the resin layer is obtained by laminating a foaming agent-containing resin layer and a non-foaming resin layer A by melt extrusion, a base material is laminated on the foaming agent-containing resin layer side of the resin layer. When the resin layer is laminated by melt extrusion so that the non-foamed resin layer B, the foaming agent-containing resin layer, and the non-foamed resin layer A are in this order, the non-foamed resin layer B side of the resin layer is Adhere to the substrate. In addition, in this invention, what laminated | stacked at least the resin layer on the base material is called a lamination sheet.

  It does not limit as a base material, A well-known fibrous base material (backing paper) etc. can be utilized.

  Specifically, wallpaper general paper (pulp-based sheet sized with a known sizing agent); flame-retardant paper (pulp-based sheet treated with a flame retardant such as guanidine sulfamate or guanidine phosphate) ); Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper; fiber mixed paper (paper made by mixing pulp and synthetic fiber).

Although the basis weight of the fibrous base material is not critical, preferably about 50 to 300 g / ^{m 2,} about 50 to 120 / ^{m 2} is more preferable.

  The method for laminating the resin layer on the substrate is not limited. For example, it is preferable to pressurize and laminate the base material and the resin layer. In particular, it is preferable to heat the substrate surface before pressurization and lamination. Although heating temperature is not limited, 80-160 degreeC is preferable. What is necessary is just to set a heating time suitably according to heating temperature etc. FIG.

Process 3
In step 3 of Embodiment 1, holes are formed in the resin layer of the laminated sheet by a thermal method.

  The hole may be formed from the front surface (resin side) of the laminated sheet, or from the back surface (base material side). In addition, when the air permeability of a base material is low, it is preferable to form the hole which penetrates a resin layer and a base material.

  By forming holes in the laminated sheet, the air permeability in the case of a foamed laminated sheet can be improved, and the moisture permeability can be adjusted. In addition, since the holes are formed by a thermal method, the resin in the perforated portion is removed, so that the holes are not blocked during foaming. Furthermore, since the hole is formed before the foaming step, the resin burn on the inner surface of the hole can be made inconspicuous.

  The thermal method of the present invention is not limited as long as it is a method of forming holes in a resin by thermal energy, and includes a method of irradiating various lasers. For example, in addition to a gas laser such as a carbon dioxide laser or an excimer laser, there is a solid laser such as a YAG laser. Laser drilling with carbon dioxide gas is preferred for the reason that through-holes can be more reliably and efficiently formed even during drilling by a thermal method, and the layer to be drilled does not remain in the drilled part. It can be processed by.

  By performing the tempering process by laser irradiation, the resin can be removed, and the blockage of the hole after foaming as seen in the embossing process by the needle roll can be suppressed.

  When the hole is formed in the resin layer, the pattern to be perforated can be selected as necessary, such as a lattice shape, a staggered shape, and an irregular shape, with respect to the resin layer.

  When the holes are formed by performing lattice-like perforation, the pitch is preferably 1 to 20 mm, more preferably 2 to 10 mm. The “pitch” is an interval between adjacent holes.

  Moreover, as a hole size, a hole with a diameter of 40 to 250 μm is preferable, a hole with a diameter of 45 to 200 μm is more preferable, and a hole with a diameter of 50 to 150 μm is still more preferable because it is difficult to stand out.

Process 4
In Step 4 of Embodiment 1, the foaming resin layer is formed by heating and foaming the foaming agent-containing 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 210 to 250 ° C, more preferably about 220 to 240 ° C. The heating time is preferably about 15 to 50 seconds, and more preferably about 20 to 45 seconds.

Other Step (i) Electron Beam Irradiation In the present invention, in the step before the step 4 of Embodiment 1, that is, the step before heating and foaming the foaming agent-containing resin layer, the resin layer having the foaming agent-containing resin layer is used. On the other hand, an electron beam can be irradiated.

  By irradiating the resin layer having the foaming agent-containing resin layer with an electron beam, the resin component is cross-linked to adjust the surface strength of the foamed resin layer, foaming characteristics (effect of improving foaming gas retention), and the like. can do. The energy of the electron beam is preferably about 150 to 250 kV, more preferably about 175 to 200 kV. The irradiation amount is preferably about 10 to 100 kGy, and more preferably about 10 to 60 kGy. A known electron beam irradiation apparatus can be used as the electron beam source.

  This electron beam irradiation may be performed after a pattern layer or a surface protective layer described later is formed. When a surface protective layer containing an ionizing radiation curable resin is laminated on the surface of the foaming agent-containing resin layer (or the surface of the non-foaming resin layer A), when the electron beam is irradiated, the foaming agent-containing resin layer is irradiated by electron beam irradiation. In addition, the surface protective layer can be cross-linked with the resin at the same time.

  The electron beam may be irradiated from the front surface side to the back surface side of the resin layer, or may be irradiated from the back surface side to the front surface side. In the present specification, the front surface side means the resin layer side, and the back surface side means the substrate side. In FIG. 1 described later, the upper side is the front surface side, and the lower side is the back surface side.

(Ii) Formation of Pattern Pattern Layer In Embodiment 1, a pattern pattern layer may be formed on the surface of the foaming agent-containing resin layer (or the surface of the non-foamed resin layer A) as necessary.

  The design pattern layer imparts design properties to the resin layer. 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 non-foamed resin layer A. 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.

  The binder resin can be set according to the type of the resin 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.

  When the pattern layer is difficult to adhere to the foaming agent-containing resin layer or the non-foamed resin layer A, a primer layer may be interposed between the layers as necessary.

  The surface of the foaming agent-containing resin layer (or the surface of the non-foamed resin layer A) is formed before the holes are formed in the resin layer or the laminated sheet because the printing ink can be prevented from bleeding or soaking into the formed holes. ) Is preferably formed with a pattern layer. For example, in Embodiment 1, it is preferable to form a pattern layer in Step 1 or 2. Moreover, in Embodiment 2 mentioned later, it is preferable to form a pattern layer in the process 1.

(Iii) Formation of surface protective layer In Embodiment 1, a surface protective layer can be further provided on the surface of the foaming agent-containing resin layer or the pattern layer for the purpose of adjusting the gloss and / or protecting the surface.

  The kind of surface protective layer is not limited. A one-component curable resin or a two-component curable resin using a binder resin or solvent equivalent to the pattern layer such as a thermoplastic resin such as an olefin resin, an acrylic resin, or a urethane resin can be used.

  In the case of forming a surface protective layer for the purpose of surface strength of foamed wallpaper (such as scratch resistance), stain resistance, and protection of the pattern layer, the one containing an ionizing radiation curable resin as a resin component Is preferred. The ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation.

  The ionizing radiation curable resin is not particularly limited, and a prepolymer (including an oligomer) containing a radical polymerizable double bond capable of undergoing a polymerization and crosslinking reaction by irradiation of an electron beam in the molecule and / or a transparent mainly composed of a monomer. Resin can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a cross-linking curing reaction. Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  For gloss adjustment, it is desirable to form a surface protective layer containing a known filler such as silica. In addition, an additive such as silicone can be added in order to impart slipperiness and easy wiping of dirt. In addition, you may add functional materials, such as a deodorizer and an antibacterial agent, as needed.

  As a method for forming the surface protective layer, known methods such as gravure printing and melt molding 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.

  The thickness of the surface protective layer is not limited, but is preferably about 0.1 to 15 μm. The surface protective layer may be a single layer or may be a laminate of two or more layers. For example, a structure in which a cured resin layer is formed on the outermost surface and a thermoplastic resin is laminated thereunder may be employed.

  The pattern pattern layer and the surface protective layer may be formed after Step 1 or any of Steps 2 to 4.

(Iv) Embossing In the present invention, it is preferable to emboss the surface (front surface) of the resin layer after foaming after the step 4 of the first embodiment. An embossed pattern can be applied by embossing.

  Embossing can be performed by known means such as pressing an embossed plate. A desired embossed pattern can be shaped by pressing the embossed plate after heat-softening the foamed resin layer. 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.

(2) Embodiment 2
Step 1 and Step 4 of Embodiment 2 can be performed in the same manner as Embodiment 1 described above. Therefore, the description of the overlapping contents is omitted.

Process 2
In step 2 of Embodiment 2, holes are formed in the resin layer having the foaming agent-containing resin layer by a thermal method.

  The formation of the pores is performed when the resin layer having the foaming agent-containing resin layer is a resin layer composed of, for example, non-foaming resin layer A / foaming agent-containing resin layer / non-foaming resin layer B (adhesive layer). A hole may be formed from the foamed resin layer A side, or a hole may be formed from the non-foamed resin layer B side.

  In the second embodiment, by forming a hole in the resin layer, the air permeability in the case of a foamed wallpaper can be improved, and the moisture permeability can be adjusted. In addition, since the holes are formed by a thermal method, the holes are not blocked, and no sacra is formed on the base material side (the back side of the foamed laminated sheet) of the foamed laminated sheet. Furthermore, since the holes are formed before the heating and foaming step, it is possible to prevent the resin from being burnt on the inner surface of the holes and around the holes.

  In addition, according to this method, since holes are formed in the resin layer before laminating the resin layer on the base material in Step 3 described later, even when a breathable fibrous base material is used, There is no need to form holes, and the tensile strength of the foamed laminated sheet can be maintained. Further, the resin does not remain on the bottom surface of the perforation after the resin layer is laminated on the base material. Furthermore, since the through-hole is not through the entire layer so as to penetrate to the base material of the base, it is preferable that the adhesive does not ooze out from the perforated portion even when the adhesive is applied when the foam wallpaper is applied.

  The drilling process for forming holes in the resin layer is a drilling process using a thermal method. The details of the drilling process are as described above.

Process 3
In step 3 of Embodiment 2, the resin layer having the holes is laminated on the base material to form a laminated sheet. The method for laminating the resin layer on the substrate and the details of the substrate are as described above.

Other steps can be performed in the same manner as in the first embodiment.

  In addition, there exists air permeability as a parameter | index which shows the air permeability of a foaming lamination sheet. The air permeability depends on the pressure determined by the speed at which air escapes from one side of the paper to the other side (air permeation rate), and the following formula is used to calculate the ISO air permeability P [μm / (Pa · s )].

P = 127 / t _k
t _{k is} the average value (s) of the air resistance indication value by the Oken air permeability tester. As a measuring device, JIS P 8117: 2009 paper and paperboard—air permeability and air resistance test method (intermediate region) —Gurley method 6 Oken type tester method can be used.

  The ISO air permeability of the foamed laminated sheet of the present invention is preferably 0.1 or more.

  FIG. 1 is a conceptual diagram illustrating a method for producing a foamed laminated sheet according to Embodiment 1 of the present invention. The manufacturing method of the foaming laminated sheet of FIG. 1 is (1) Step 1 of preparing a resin layer having a foaming agent-containing resin layer, (2) Step 2 of laminating the resin layer on a substrate to form a laminated sheet, (3) Step 3 of forming a hole in the resin layer in the laminated sheet by a thermal method, and (4) Step 4 of heating and foaming the foaming agent-containing resin layer are sequentially shown. In addition, in FIG. 1, the said hole has shown the aspect formed by penetrating a base material from the front surface of the said resin layer.

  FIG. 2 is a conceptual diagram showing a method for producing a foamed laminated sheet according to Embodiment 2 of the present invention. The manufacturing method of the foaming laminated sheet of FIG. 2 includes (1) Step 1 of preparing a resin layer having a foaming agent-containing resin layer, (2) A hole is formed in the resin layer having the foaming agent-containing resin layer by a thermal method. Step 2, forming step 3, (3) laminating the resin layer having the holes on the substrate, forming step 3 and (4) step 4 of heating and foaming the foaming agent-containing resin layer Yes.

  1 and 2, as the resin layer having the foaming agent-containing resin layer, Non-foamed resin layer A, 3. 1. a foaming agent-containing resin layer; The resin layer which consists of the non-foamed resin layer B is shown, 2 of the said resin layer. The non-foamed resin layer B is 1. An embodiment in which the substrate is bonded (laminated) is shown.

  In addition, a step of irradiating the resin layer having the foaming agent-containing resin layer with an electron beam may be included before the foaming agent-containing resin layer is heated and foamed. A step of embossing may be included.

  In the method for producing a foamed laminated sheet of the present invention, before the foaming agent-containing resin layer is heated and foamed, holes are formed in the resin layer having the foaming agent-containing resin layer by a thermal method. Therefore, the pores are not completely closed after foaming by heating, and air permeability can be imparted to the foamed laminated sheet. Further, even if the resin on the inner surface of the hole is burned by heat at the time of drilling, since the resin is deformed by subsequent foaming, the resin burn becomes inconspicuous. In addition, according to this method, since the crease cannot be punched on the base material side (back side of the foam laminate sheet) of the foam laminate sheet, it is possible to uniformly apply the adhesive to the substrate. In addition, since the thickness of the product as a foam is not reduced by the push needle, there is no reduction in design and unevenness (performance for covering the unevenness of the base).

  Thus, according to the manufacturing method of the foaming laminated sheet of this invention, the foaming laminated sheet excellent in air permeability can be obtained, without impairing design property.

It is a conceptual diagram showing the manufacturing method of the foaming lamination sheet of Embodiment 1 of this invention. It is a conceptual diagram showing the manufacturing method of the foaming lamination sheet of Embodiment 2 of this invention.

  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
Extruded using a three-type, three-layer, multi-manifold T-die extruder to a thickness of 5 μm / 70 μm / 5 μm in the order of non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B (adhesive resin layer) Filmed. Thereby, the resin layer which consists of non-foaming resin layer A / foaming agent containing resin layer / non-foaming resin layer B was obtained.

  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 cylinder temperature in which the resin for forming the resin layer B was accommodated was 100 ° C. The die temperature was 120 ° C. for all.

  Next, a fibrous base material (backing paper) (wallpaper paper WK-665 manufactured by Kojin Co., Ltd.) is prepared, and the non-foamed resin layer B side of the resin layer is overlapped with the fibrous base material. After heating the material to 120 ° C., the resin layer was adhered to the fibrous base material through a laminate roll.

  Next, the resin surface was irradiated with an electron beam (195 KV, 30 KGy) to crosslink the resin layer.

  Next, after corona discharge treatment was performed on the non-foamed resin layer A, a water-based ink “Hydric (manufactured by Dainichi Seika Kogyo Co., Ltd.)” was used on the non-foamed resin layer A by a gravure printing machine. The fabric pattern was printed, and the surface protection layer was formed by coating water-based ink “ALTOP (manufactured by Dainichi Seika Kogyo)” as an overprint coat in the same apparatus. In this way, a laminated sheet composed of surface protective layer / pattern pattern layer / non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B / base material was obtained.

Next, using a laser drilling machine (scan type manufactured by MCT-600, Lofine Basel Japan) (using CO ₂ laser, output 100 W), drilling is performed on the resin layer in a 5 mm pitch grid pattern, A 200 μm diameter hole was formed.

  Next, the laminated sheet was heated at 220 ° C. for 30 seconds to foam the foaming agent-containing resin layer to obtain a foamed laminated sheet.

  Each layer was formed using the following components.

Comparative Example 1
A laminated sheet comprising a surface protective layer / pattern pattern layer / non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B / base material is obtained, and then the laminated sheet is heated at 220 ° C. for 30 seconds to obtain a foaming agent. After foaming the containing resin layer, a foamed laminated sheet was obtained in the same manner as in Example 1 except that the resin layer was perforated using a laser perforating machine to form holes.

Designability Evaluation About the foamed laminated sheets produced in Example 1 and Comparative Example 1, the designability was observed. The design property test method and evaluation criteria are as follows.

Using an optical microscope, 5 randomly selected perforations were observed 200 times from the front surface of the foamed laminated sheet, and the number of resin burns near the perforations was evaluated.
○: 1 point or less Δ: 2 to 3 points ×: 4 points or more The results are shown in Table 1 below.

1. Base material 2. Non-foamed resin layer B
3. Foaming agent-containing resin layer 3 ′. 3. Foamed resin layer Non-foamed resin layer A

Claims (9)

The manufacturing method of a foaming lamination sheet which contains the following processes 1-4 in order:
(1) Step 1 of preparing a resin layer having a foaming agent-containing resin layer,
(2) Step 2 of laminating the resin layer on a substrate to form a laminated sheet,
(3) Step 3 of forming a hole in the resin layer by laser irradiation , and (4) Step 4 of heating and foaming the foaming agent-containing resin layer.   The said hole is a manufacturing method of the foaming lamination sheet of Claim 1 formed through a base material. A resin layer comprising a non-foamed resin layer A, the foaming agent-containing resin layer, and a non-foamed resin layer B is prepared as the resin layer, and the non-foamed resin layer B of the resin layer is adhered to the base material. Item 3. A method for producing a foamed laminated sheet according to Item 1 or 2 . The manufacturing method of the foaming lamination sheet in any one of Claims 1-3 including the process of irradiating an electron beam with respect to the resin layer which has the said foaming agent containing resin layer before the said process 4. The manufacturing method of the foaming lamination sheet in any one of Claims 1-4 including the process of embossing the resin layer after foaming after the said process 4. The manufacturing method of a foaming lamination sheet which contains the following processes 1-4 in order:
(1) Step 1 of preparing a resin layer having a foaming agent-containing resin layer,
(2) Step 2 of forming a hole in the resin layer having the foaming agent-containing resin layer by laser irradiation ,
(3) Step 3 of laminating the resin layer having the holes on the substrate to form a laminated sheet, and (4) Step 4 of heating and foaming the foaming agent-containing resin layer. A resin layer comprising a non-foamed resin layer A, the foaming agent-containing resin layer, and a non-foamed resin layer B is prepared as the resin layer, and the non-foamed resin layer B of the resin layer is adhered to the base material. Item 7. A method for producing a foamed laminated sheet according to Item 6 . The manufacturing method of the foaming lamination sheet of Claim 6 or 7 including the process of irradiating an electron beam with respect to the resin layer which has the said foaming agent containing resin layer before the said process 4. FIG. The manufacturing method of the foaming lamination sheet in any one of Claims 6-8 including the process of embossing the resin layer after foaming after the said process 4.

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