JP2014069521A - Foamed laminated sheet, laminated sheet, and manufacturing method of these - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel foamed laminated sheet having excellent stain resistance and high designability, and a manufacturing method thereof capable of easily obtaining the foamed laminated sheet.SOLUTION: A foamed laminated sheet has a film layer 3 laminated on a resin foam layer 4. The foamed laminated sheet has voids 7 between the film layer and the resin foam layer.

Description

  The present invention relates to a foamed laminated sheet, a laminated sheet, and methods for producing them. The foamed laminated sheet has a foamed resin layer and is useful as foamed wallpaper, various decorative materials, and the like. Moreover, the said laminated sheet is a state before foaming of the said foaming laminated sheet, and means what is called an unfoamed original fabric.

  In recent years, as an interior material such as a wall covering material used in a house or the like, a material having excellent surface design is required. As an interior material excellent in surface design properties, for example, an interior material whose surface design properties vary depending on the viewing angle using light reflection characteristics is known. Examples of such an interior material include a foam that forms a design by reflecting light by forming a fine uneven shape on the surface (see, for example, Patent Document 1).

  However, the concavo-convex shape formed on the surface of such a foam needs to be fine for the purpose of utilizing the light reflection characteristics, and the dirt attached to the surface of the foam has a concavo-convex shape. When it enters, it becomes difficult to remove, so there is a problem that the contamination resistance of the surface is lowered.

  In addition, as an interior material using a material having a property of reflecting light, an interior material whose surface is coated with a composition to which a material such as a pearl pigment is added (for example, see Patent Document 2), a refractive index. There are known structures having a light reflection function including different structures and fine structures (see, for example, Patent Document 3).

  However, such interior materials and structures have problems that the manufacturing method becomes complicated and the manufacturing cost increases.

  Therefore, development of the foaming lamination sheet excellent in stain resistance and high designability and the manufacturing method which can obtain it simply are calculated | required.

JP-A-9-183162 JP 2001-303491 A JP 2004-151271 A

  An object of this invention is to provide the new foaming lamination sheet excellent in stain resistance and high designability, and the manufacturing method which can obtain it simply.

  As a result of intensive studies to achieve the above object, the present inventor is a foamed laminated sheet in which a film layer is laminated on a foamed resin layer, and a gap is formed between the film layer and the foamed resin layer. It has been found that the above-described object can be achieved by adopting a structure having the above, and the present invention has been completed.

That is, the present invention relates to the following foamed laminated sheet, laminated sheet, and methods for producing them.
1. A foamed laminated sheet in which a film layer is laminated on a foamed resin layer, wherein there is a gap between the film layer and the foamed resin layer.
2. Item 2. The foamed laminated sheet according to Item 1, wherein a cross-sectional shape of the void is a semicircular shape protruding toward the foamed resin layer.
3. Item 3. The foamed laminated sheet according to Item 1 or 2, further comprising a non-foamed resin layer A between the foamed resin layer and the film layer.
4). It is a lamination sheet for obtaining the foaming lamination sheet in any one of said claim | item 1-3, Comprising: The film layer is laminated | stacked on the foaming agent containing resin layer, The said film layer and the said foaming agent containing resin layer, A laminate sheet having a peel strength of 2.5 N / 25 mm or less.
5. It is a lamination sheet for obtaining the foaming lamination sheet in any one of said claim | item 1-3, Comprising: The film layer is laminated | stacked on the foaming agent containing resin layer, The said film layer and the said foaming agent containing resin layer, A laminate sheet characterized by having a weak adhesion region having a peel strength of 2.5 N / 25 mm or less and a strong adhesion region exceeding 2.5 N / 25 mm.
6). 6. The laminated sheet according to item 5, wherein the peel strength of the strong adhesion region is 3.0 N / 25 mm or more.
7). Item 7. The laminated sheet according to any one of Items 4 to 6, further comprising a non-foamed resin layer A between the foaming agent-containing resin layer and the film layer.
8). A laminated sheet obtained by laminating a film layer on a foaming agent-containing resin layer, and a laminated sheet having a peel strength between the film layer and the foaming agent-containing resin layer of 2.5 N / 25 mm or less was obtained. Thereafter, the foaming agent-containing resin layer of the laminated sheet is foamed to form a foamed resin layer, whereby a void is formed between the film layer and the foamed resin layer. Method.

Hereinafter, the foaming laminated sheet of this invention, a laminated sheet, and those manufacturing methods are demonstrated in detail, using a figure.
<< Foamed laminated sheet >>
FIG. 1 is an example of a cross-sectional side view when the foamed laminated sheet of the present invention is cut in a direction perpendicular to the surface thereof. The foamed laminated sheet 1 in FIG. 1 has at least a foamed resin layer 4 and a film layer 3 laminated on a substrate, and has a gap 7 between the film layer 3 and the foamed resin layer 4. Therefore, out of the reflected light reflected from the light incident from the upper part of the foamed laminated sheet, the reflection angle θ2 of the reflected light 12 reflected at the portion where the gap is formed and the reflected light reflected at the portion where the gap is not formed 11 is different from the reflection angle θ1, the surface gloss of the foamed laminated sheet 1 changes depending on the angle at which it is seen, and a unique design is formed. Further, when the surface of the foamed laminated sheet 1 is viewed from the front, since the portion where the voids are formed is observed in a crater shape, it is possible to simulate a block or a porous design of wood. Since the foamed laminated sheet of the present invention forms the high design as described above by forming the gap 7 between the foamed resin layer 4 and the film layer 3, there is no need to use a material such as a pearl pigment. In addition, since it is not necessary to form special fine irregularities on the surface, it is excellent in contamination resistance, and its manufacturing cost can be kept low.

FIG. 2 is a plan view of the surface of the foamed laminated sheet 1 of FIG. 1 as viewed from the front. In FIG. 2, voids 7 formed between the film layer 3 and the foamed resin layer 4 are observed on the surface of the foamed laminated sheet 1 in a crater shape through the surface protective layer 2 and the film layer 3. Moreover, as shown in FIG. 2, the area | region which has the space | gap 7 may be formed like a pattern in a part of foaming lamination sheet, and may be formed in the whole surface. It is preferable that the area | region which has the space | gap 7 is formed like a pattern pattern in a part of foaming lamination sheet by the point which is excellent in the high designability.
The shape of the void 7 is not particularly limited, but in FIG. 1, the cross-sectional shape is preferably a semicircular (substantially semicircular) shape protruding toward the foamed resin layer 4 side. When the gap has such a shape, the created design becomes a block or woody porous design, and the design is further improved.

  When the cross-sectional shape of the void is semicircular, the diameter R1 is preferably 100 to 500 μm. In addition, the said diameter can be measured with a microscope in the cross section cut | disconnected in the direction orthogonal to the surface of a foaming lamination sheet.

Moreover, it is preferable that the diameter R1 of a space | gap is 1.0 to 2.0 times with respect to the diameter 8L of the foam cell 8 which comprises a foamed resin layer. By setting the diameter R1 of the gap to such a diameter, it is possible to obtain a gap suitable for reflecting a light to form a design. The diameter 8L of the foam cell 8 is a length in a direction parallel to the sheet surface, and can be measured with a microscope in a cross section obtained by cutting the foam laminate sheet in a direction perpendicular to the surface of the foam laminate sheet. In addition, in the case where both the diameter when the cross-sectional shape of the void is a semicircular shape and the diameter of the foamed cell vary in size, in the cross section of the foamed laminated sheet, arbitrarily extract a region having a void, The diameter of three voids or foamed cells observed per 2 mm ^{2 in} the region may be measured and averaged.

≪Laminated sheet≫
FIG. 3 is a laminated sheet for obtaining the foamed laminated sheet of the present invention, and is a cross-sectional side view when an example thereof is cut in a direction perpendicular to the surface. In the laminated sheet 1 ′ of FIG. 3, at least a foaming agent-containing resin layer 4 ′ and a film layer 3 are laminated on a substrate. Moreover, since the laminated sheet of the present invention has a region where the adhesive strength between the foaming agent-containing resin layer and the film layer is 2.5 N / 25 mm or less, the foamed laminated sheet of the present invention is obtained by foaming the foaming agent-containing resin layer. be able to. That is, when the laminated sheet is heated, the foaming agent in the foaming agent-containing resin layer is decomposed to form a foamed resin layer. In the region where the adhesive strength is 2.5 N / 25 mm or less, the film layer and the foamed resin are formed. Gaps are formed because gaps are created between the layers, and the foaming gas easily intervenes therebetween. In addition, since a space | gap is formed with the gas which escapes from between resin, it is often formed scattered in one area | region.

  In the laminated sheet of the present invention, the peel strength between the film layer and the foaming agent-containing resin layer may be 2.5 N / 25 mm or less over the entire surface of the sheet. Moreover, even if it has the weak adhesion area | region whose peeling strength between the said film layer and the said foaming agent containing resin layer is 2.5 N / 25mm or less, and the strong adhesion area | region exceeding 2.5 N / 25mm. Good. In the strong adhesion region where the peel strength exceeds 2.5 N / 25 mm, even if the foaming agent-containing resin layer is foamed, it is difficult to cause peeling between the film layer and the foamed resin layer, so that formation of voids is suppressed. That is, by having regions with different adhesive strengths, it is possible to obtain a highly-designed foam laminated sheet having regions where voids are formed after foaming and regions where no voids are formed. As described above, a laminated sheet having a strong adhesion region is preferable because the interlayer adhesion is high, and thus processing in the manufacturing process is facilitated.

  In the laminated sheet of the present invention, the peel strength of a region where a void is generated when foamed (weakly bonded region) is more preferably 2.0 N / 25 mm or less. Furthermore, the peel strength of the weakly bonded region is preferably 1.0 N / 25 mm or more, and more preferably 1.5 N / 25 mm or more.

  On the other hand, the peel strength of a region where a void is not easily generated when foaming (strong adhesion region) is not limited as long as the peel strength between the foaming agent-containing resin layer and the film layer exceeds 2.5 N / 25 mm. 0.0N / 25 mm or more is preferable, and 3.5 N / 25 mm or more is more preferable. If the peel strength is too low, voids are formed and dispersed on the entire surface of the foamed laminate sheet, and the design created by the voids may not be noticeable.

  In this specification, the peel strength is a value (integral) measured by the following measuring method using a tensile tester RTF-1150-H (manufactured by A & D) in accordance with “JIS K 6854-3”. Average load). That is, the laminated sheet was cut into a size of 25 mm wide × 150 mm long to obtain a cut piece. The peeling speed: 100 mm / min, the peeling distance: 120 mm, the peeling angle: 180 °, and the base material and the foaming agent-containing resin layer side Then, a force is applied to the film layer side to separate. Depending on the resin type and thickness of the film layer, the film layer may extend during the peel test and accurate adhesive strength may not be measured. Therefore, Nichiban's “Cello Tape (registered trademark)” may be used on the surface of the film layer (the side opposite to the adhesive surface). ”Was pasted and the film layer side was reinforced and measured.

  Hereinafter, the material which comprises the lamination sheet of this invention is demonstrated.

Base Material The laminated sheet of the present invention preferably has a base material under the foaming agent-containing resin layer. Specific examples of the base material include general paper for wallpaper (pulp-based sheets sized with a sizing agent), flame-retardant paper (pulp-based sheets with flame retardants such as guanidine sulfamate and guanidine phosphate). Treated paper); inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; fibrous paper such as thin paper, fiber mixed paper (made by mixing synthetic fiber and pulp) Is mentioned. In addition, what corresponds to a nonwoven fabric on classification is included in these fibrous base materials.

The basis weight of the base material is not particularly limited, for example, 50 to 300 g / ^{m 2} approximately, and preferably about 50 to 120 / ^{m 2.}

Foaming agent-containing resin layer The foaming agent-containing resin layer is not limited as long as it contains a resin component and a foaming agent, and the foaming agent-containing resin layer is foamed by heating described later to become a foamed resin layer.

  The resin component contained in the foaming agent-containing resin layer is not particularly limited, but from polyethylene and an ethylene copolymer having monomers other than ethylene and α-olefin (hereinafter abbreviated as “ethylene copolymer”). It is preferable to contain at least one selected from the group consisting of In addition, polyethylene and ethylene copolymers are suitable for extrusion film formation from the viewpoints of melting point and melt flow rate (MFR), and have an advantage in terms of simplicity of forming a foaming agent-containing resin layer.

The polyethylene may be an ethylene homopolymer, or may be a copolymer of ethylene and an α-olefin. As an alpha olefin used as a comonomer of the said copolymer, C3-C20, Preferably a C3-C8 linear or branched alpha olefin is mentioned, for example. As the copolymer of ethylene and α-olefins, specifically, density 0.942 g / cm ³ or more high-density polyethylene (HDPE) and in a density of less than 0.93 g / cm ³ or more 0.942 g / cm ³ density polyethylene (MDPE), density of 0.91 g / cm ³ or more 0.93 g / cm ³ less than the low-density polyethylene (LDPE), density of 0.85 g / cm ³ or more 0.93 g / cm ³ less than the linear low density polyethylene , (LLDPE) and the like. These polyethylenes may be used individually by 1 type, and may be used in combination of 2 or more type. Among these polyethylenes, it is preferable to use polyethylene having a low density because curling of the foamed laminated sheet can be suppressed.

  Examples of the ethylene copolymer include an ethylene copolymer containing a carboxylic acid vinyl ester, an α, β unsaturated carboxylic acid, and an α, β unsaturated carboxylic acid ester as a constituent comonomer. Specific examples of the carboxylic acid vinyl ester include vinyl acetate. Specific examples of the α, β unsaturated carboxylic acid include acrylic acid and methacrylic acid. Specific examples of the α, β unsaturated carboxylic acid ester include methyl acrylate and methyl methacrylate. These comonomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the ethylene copolymer include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-acrylic. Examples include acid methyl copolymer (EMA) and ethylene- (meth) acrylic acid copolymer (EMAA). These ethylene copolymers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The copolymerization ratio of the comonomer in the ethylene copolymer is not particularly limited, but is preferably 5 to 35% by weight and more preferably 5 to 25% by weight based on the total weight of the ethylene copolymer. By adopting such a copolymerization ratio, the extrusion film forming property can be further improved. As a specific example, in the case of an ethylene-vinyl acetate copolymer, the copolymerization ratio (VA amount) of vinyl acetate is preferably 9 to 25% by weight, and 9 to 20% by weight based on the total weight of the copolymer. % Is more preferable. In the case of an ethylene-methyl methacrylate copolymer, the methyl methacrylate copolymerization ratio (MMA amount) is preferably 5 to 25% by weight, preferably 5 to 15% by weight, based on the total weight of the copolymer. Is more preferable.

  From the viewpoint of further improving the stain resistance and further providing excellent scratch resistance, the resin component of the foaming agent-containing resin layer is preferably polyethylene, ethylene-carboxylic acid vinyl ester copolymer, ethylene-α. , β unsaturated carboxylic acid ester copolymer; more preferably polyethylene, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer; particularly preferably ethylene- (meth) acrylic acid copolymer ( EMAA).

  When using the said ethylene and / or the said ethylene copolymer as a resin component of a foaming agent containing resin layer, 1 or more types of other resin components may be contained other than these resin components. When the ethylene and / or the ethylene copolymer and other resin components are used in combination, the ratio of these is not particularly limited, but per total amount of the ethylene and / or the ethylene copolymer and other resin components. The proportion of the ethylene and / or the ethylene copolymer is preferably 70% by weight or more, and more preferably 80% by weight or more.

  The MFR of the polyethylene or the ethylene copolymer is not particularly limited, but is preferably 7 to 500 g / 10 minutes and more preferably 9 to 130 g / 10 minutes from the viewpoint of further improving the extrusion film forming property. In the present invention, MFR is a value measured by a test method described in JIS K7210 (thermoplastic flow test method). The test conditions employ “190 ° C., 21.18N (2.16 kgf)” described in JIS K6760.

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

  The foaming agent used in the foaming agent-containing resin layer can be selected from known foaming agents. For example, azo type such as azodicarbonamide (ADCA) and azobisformamide; organic thermal decomposition type foaming agent such as hydrazide type such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide, microcapsule type foaming agent, Examples include inorganic foaming agents such as baking soda. These foaming agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  What is necessary is just to set suitably content of a foaming agent according to the kind of foaming agent, foaming magnification, etc. FIG. Specifically, the expansion ratio may be set to 7 times or more, preferably about 7 to 10 times, and the pyrolytic foaming agent is about 4 to 20 parts by mass with respect to 100 parts by mass of the resin component. It is preferable that If the amount of the foaming agent is too small, the foaming gas is retained in the foamed resin layer, and there is a possibility that a void cannot be formed between the foamed resin layer and the film layer.

  In addition to the above resin component and foaming agent, the foaming agent-containing resin layer contains additives such as inorganic fillers, pigments, foaming aids, crosslinking aids, stabilizers, and lubricants as necessary. Also good.

  Examples of the foaming aid include metal oxides such as zinc stearate, zinc oxide, and magnesium oxide and / or fatty acid metal salts. These foaming aids may be used alone or in combination of two or more. The content of these foaming aids is, for example, about 0.3 to 10 parts by mass, preferably about 1 to 5 parts by mass with respect to 100 parts by mass of the resin component. When these foaming aids, EMAA, and ADCA foaming agents are used in combination, the foamed resin layer and the base material may tend to turn yellow due to burning or chromophore formation in the foaming process. In such a case, as described in JP-A-2009-197219, it is preferable to use a carboxylic acid hydrazide compound as a foaming aid together with EMAA and ADCA foaming agent. At this time, it is preferable to use about 0.2-1 mass part of carboxylic acid hydrazide compounds 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. These inorganic fillers may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the inorganic filler is, for example, about 0 to 100 parts by mass, preferably about 20 to 70 parts by mass with respect to 100 parts by mass of the resin component.

  The pigment can be used regardless of whether it is an inorganic pigment or an organic pigment. 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). These pigments may be used alone or in combination of two or more. The content of the pigment is, for example, about 10 to 50 parts by mass, 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 appropriately set in consideration of the desired thickness of the foamed resin layer, the expansion ratio, and the like, and for example, about 40 to 100 μm can be mentioned.

  The foaming agent-containing layer is formed by applying a resin composition containing a resin component, a foaming agent, and other additives as necessary onto a substrate. The method for coating the resin composition on the substrate is not particularly limited, but extrusion film formation (extrusion lamination) with a T-die extruder is preferable. In addition, although the cylinder temperature and die temperature at the time of extrusion film formation should just be set suitably according to the kind of resin, generally it is about 100-140 degreeC.

Non-foamed resin layers A and B
In this invention, although a foaming agent containing resin layer may be formed independently on a base material, you may provide a non-foaming resin layer in the single side | surface or both surfaces of a foaming agent content layer.

  For example, a non-foamed resin layer B (adhesive resin layer) may be provided on the back surface of the foaming agent-containing resin layer (between the base material and the foaming agent-containing resin layer) for the purpose of improving the adhesive force with the base material. .

  The resin component of the non-foamed resin layer B 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 ethylene-vinyl acetate copolymer preferably has a vinyl acetate component (VA component) of 10 to 46% by mass and more preferably 15 to 41% by mass based on the total amount of the copolymer.

  Although it does not restrict | limit especially about the thickness of the non-foaming resin layer B, For example, about 5-50 micrometers is mentioned.

  In addition, for example, on the upper surface of the foaming agent-containing resin layer (the surface opposite to the substrate), the purpose of clarifying the pattern when forming the pattern layer or improving the scratch resistance of the foamed resin layer The non-foamed resin layer A may be provided.

  When the non-foamed resin layer A is provided, the foamed laminated sheet of the present invention is such that the foamed resin layer 4 and the non-foamed resin layer A9 are melted and integrated by heat during foaming, so that the foaming gas is not foamed resin. Through the layer A9, a gap 7 is formed between the film layer 3 and the non-foamed resin layer A9 as shown in FIG.

  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. Among these, polyolefin resins are preferable.

Examples of polyolefin resins include ethylene homopolymers, resins such as polypropylene, polybutene, polybutadiene, and polyisoprene, copolymers of ethylene and α-olefins having 4 or more carbon atoms (such as linear low density polyethylene), Ethylene (meth) acrylic copolymer resins such as ethylene-acrylic acid copolymer resins, ethylene-methyl acrylate copolymer resins, ethylene-ethyl acrylate copolymer resins, ethylene-methacrylic acid copolymer resins , Ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate copolymer resin saponified product, ionomer and the like.
Although it does not restrict | limit especially about the thickness of the non-foaming resin layer A, For example, about 5-10 micrometers is mentioned.

  In this invention, the aspect in which the said non-foaming resin layer B, the foaming agent containing resin layer, and the non-foaming resin layer A were formed in order is preferable.

  When the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides, a method of forming by coextrusion film formation with 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. In addition, a residue of inorganic filler (so-called eyes and eyes) tends to be generated, and this tends to become a foreign substance on the surface of the foaming agent-containing resin layer. In such a case, 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.

On the pattern pattern layer foaming agent-containing resin layer (or on the non-foamed resin layer A), a pattern pattern layer may be formed as necessary. The design pattern layer imparts design properties to the resin laminate. 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 using printing ink. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, and offset printing. As the printing ink, an ink composition containing a colorant, a binder resin, and a solvent can be used. These printing inks may be known or commercially available.

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

  Moreover, the binder resin used for printing ink can be set according to the kind of base material sheet. Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, and petroleum resins. Examples include resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like. These binder resins may be used alone or in combination of two or more.

Examples of the solvent (or dispersion medium) used for the printing ink include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, and acetic acid-2- Ester-based organic solvents such as methoxyethyl and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl Ketone organic solvents such as ketone and cyclohexanone; ether organic solvents such as diethyl ether, dioxane and tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, Chlorinated organic solvents such as tiger chloroethylene; and water. These solvents (or dispersion media) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The thickness of the design pattern layer is appropriately set according to the type of design pattern and the like, and generally about 0.1 to 10 μm.

An adhesive layer may be provided on the adhesive layer foaming agent-containing resin layer (or on the non-foamed resin layer A). Moreover, the adhesive bond layer may be provided on the design pattern layer, when the said design pattern layer is formed. The said adhesive bond layer is formed in order to improve the adhesive force of a foaming agent containing resin layer, the non-foaming resin layer A, or a design pattern layer, and a film layer.

  The adhesive layer is a foaming agent for the purpose of providing a weakly adhesive region and a strong adhesive region between the foaming agent-containing resin layer, the non-foamed resin layer A, or the pattern layer and the film layer in the laminated sheet. On the containing resin layer, the non-foamed resin layer A, or the pattern layer, it may be patterned and partially provided. In this case, a portion where the adhesive layer is provided becomes a strong adhesion region, and a portion where no adhesive layer is provided becomes a weak adhesion region.

  Resin used for an adhesive layer can be set according to the kind of layer adjacent to an adhesive layer. For example, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene -(Meth) acrylic acid copolymer (EMAA), 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.

  The said adhesive bond layer can be suitably formed by the method similar to the method of forming the above-mentioned pattern pattern layer, for example.

  Although the thickness of an adhesive bond layer is not limited, About 0.1-10 micrometers is preferable.

Film layer (transparent resin layer)
A film layer is laminated on the foaming agent-containing resin layer, the non-foamed resin layer A, the pattern layer, or the adhesive layer.

  The film layer (transparent resin layer) may be colored as long as it is transparent. When the film layer is formed on the front surface of the design pattern layer, it may be translucent as long as the design pattern layer is visible.

  The film layer is preferably in the form of a single layer or multiple layers, and at least one layer constituting the film layer is preferably a layer containing polyethylene and / or an ethylene copolymer.

  When the film layer is a multilayer, at least the layer disposed on the substrate side (that is, the lowermost layer disposed on the foaming agent-containing resin layer side of the multilayer) is polyethylene and / or ethylene copolymer. A layer containing a coalescence is preferable. The gas generated from the foamed layer during foaming is improved by laminating a film having a layer containing polyethylene and / or ethylene copolymer in the lowermost layer and then crosslinking with an electron beam to improve the melt tension of the resin layer. Can be efficiently suppressed. Therefore, even when a resin (polypropylene or the like) having a relatively low melt tension is disposed as the upper layer of the film layer, the contamination resistance of the film layer itself can be maintained.

  Although it does not specifically limit about the polyethylene and / or ethylene copolymer which are used for a film layer, Specifically, the thing similar to resin used for the said foaming agent containing resin layer is mentioned.

  When the film layer has a layer containing polyethylene and / or ethylene copolymer, among the polyethylene and ethylene copolymer, polyethylene and ethylene-α, β are preferable from the viewpoint of further improving the stain resistance. At least one unsaturated carboxylic acid ester copolymer, more preferably at least one of polyethylene and ethylene-methacrylic acid copolymer (EMAA), particularly preferably acid-modified polyethylene and ethylene-methacrylic acid copolymer (EMAA). At least one of them.

  Moreover, the layer containing the said polyethylene and / or an ethylene copolymer may contain the other resin component in the range which does not prevent the effect of this invention. The ratio of the polyethylene and / or ethylene copolymer to the other resin component is, for example, per the total amount of the polyethylene and / or ethylene copolymer and the other resin component, for example, the polyethylene and / or the ethylene copolymer. Is 50 to 100% by weight, preferably 60 to 100% by weight.

  When the film layer is a multilayer, two or more layers containing polyethylene and / or ethylene copolymer may be provided, and one resin layer other than the layer containing polyethylene and / or ethylene copolymer may be provided. More than one layer may be provided.

The MFR of the polyethylene and / or ethylene copolymer used for the film layer is not particularly limited, but is usually 1 to 100 g / 10 min, preferably 5 to 30 g / min from the viewpoint of further improving the extrusion film forming property. 10 minutes is mentioned.
When the film layer includes a resin layer other than the layer containing the polyethylene and / or ethylene copolymer, as a resin component of the resin layer, for example, a polyolefin resin other than polyethylene and / or ethylene copolymer, A methacryl resin, a polyvinyl alcohol resin, a fluororesin, etc. are mentioned. Among these, polyolefin resins other than polyethylene and / or ethylene copolymers are preferable, and examples of such polyolefin resins include single resins such as polypropylene, polybutene, polybutadiene, and polyisoprene.

  Although the thickness in particular of a film layer is not restrict | limited, For example, about 3-25 micrometers, Preferably about 5-20 micrometers is mentioned. When the film layer is a multilayer, the thickness of each layer is preferably about 5 to 15 μm.

  When the film layer is formed by extrusion film formation, extrusion film formation by a T-die extruder is suitable particularly when the film layer is a multilayer. For example, in the case of two layers, a multi-manifold type T die that can simultaneously form two layers by simultaneously extruding molten resin corresponding to the two layers can be used.

  In addition, the film layer may be formed by laminating a film formed in advance on an adjacent layer, and even when there are a plurality of film layers, a film layer composed of a plurality of layers may be formed in advance. You may form by shape | molding and laminating this to the adjacent layer.

  The surface of the film layer on which the surface protective layer to be described later is formed is subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment as necessary. Also good. The surface treatment may be performed according to a conventional method for each treatment.

  When the film layer contains polyethylene and / or an ethylene copolymer as a resin component, the film layer is irradiated with an electron beam from the film layer side of the laminated sheet, so that the polyethylene and / or ethylene in the film layer is irradiated. The copolymer is preferably crosslinked. Thus, by cross-linking by electron beam irradiation, the heat resistance of the layer containing polyethylene and / or ethylene copolymer is improved, and the finally obtained foamed laminated sheet has excellent stain resistance and scratch resistance. It becomes possible to make it.

Surface protective layer A surface protective layer may be formed on the film layer for the purpose of adjusting the gloss and / or protecting the film layer.

  The surface protective layer may contain a curable resin such as a room temperature curable resin, a heat curable resin, an ionizing radiation curable resin, a one-component reactive curable resin, a two-component reactive curable resin, or an ionizing radiation curable resin. preferable.

  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 film 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 film layer.

  When forming a surface protective layer for the purpose of surface strength (scratch resistance, etc.), contamination resistance, film layer protection, etc. of foamed laminated sheets, 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.

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

≪Method for producing laminated sheet and foam laminated sheet≫
<Method for producing laminated sheet>
As a manufacturing method of the lamination sheet of this invention, the manufacturing method of the lamination sheet which has the following processes 1 and 2 is mentioned, for example.
(1) Step 1 of forming at least a foaming agent-containing resin layer on a substrate,
(2) Step 2 of laminating the film layer on the foaming agent-containing resin layer so as to have a region where the peel strength is 2.5 N / 25 mm or less.

  In Step 1 above, the components used for forming the foaming agent-containing resin layer, the specific conditions of the forming method, and the like are as described in the section of the composition of each layer.

  Moreover, the said process 1 may perform electron beam irradiation after forming a foaming agent containing resin layer. Thereby, the resin component can be cross-linked to adjust the surface strength, foaming characteristics, etc. of the foamed resin layer. 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 50 kGy. A known electron beam irradiation apparatus can be used as the electron beam source.

  The step 1 may further include a step of forming a pattern layer on the foaming agent-containing resin base layer (on the non-foamed resin layer when a non-foamed resin layer is provided).

  Further, an adhesive layer may be formed between these layers forming the laminated sheet as needed for the purpose of adjusting interlayer adhesion.

  In the step 2, the film layer is formed on the foaming agent-containing resin layer (on the non-foamed resin layer, the pattern layer, or the adhesive layer, on the outermost layer among these layers), This is a step of laminating so that the peel strength varies depending on the region.

  In the above step 2, as a method of laminating the film layer on the foaming agent-containing resin layer so as to have at least a region where the peel strength is 2.5 N / 25 mm or less, for example, the foaming agent-containing resin layer and the film layer Examples thereof include a method of adjusting the laminate strength and a method of locally applying a weight difference to the foaming agent-containing resin layer and the film layer by using a metal or rubber roll having an uneven surface on the surface during lamination.

  Moreover, as another method of laminating | stacking, the method of apply | coating the adhesive layer entirely or partially on a foaming agent containing resin layer, and laminating | stacking a film layer is mentioned. Also, a plurality of adhesive layers having different adhesive strengths are used, and a weak adhesive region where the peeling strength between the foaming agent-containing resin layer and the film layer is 2.5 N / 25 mm or less and a strong adhesive region exceeding 2.5 N / 25 mm. It can also be formed. By dividing the region in this way, designs with various patterns can be formed.

  The peel strength of the weakly bonded region is more preferably 2.0 N / 25 mm or less. If the peel strength is too high, the surface of the foamed resin layer and the film layer are difficult to peel off, and there is a possibility that voids are hardly formed between the film layer and the foamed resin layer. Moreover, the peel strength of the weakly bonded region is preferably 1.0 N / 25 mm or more, and more preferably 1.5 N / 25 mm or more.

  Further, the peel strength of the strong adhesion region is more preferably more than 3.0 N / 25 mm, and further preferably 3.5 N / 25 mm or more. If the peel strength is too low, the surface of the foamed resin layer in the strong adhesion region and the film layer are easily peeled off, and voids are formed and dispersed all over the foamed laminated sheet, and the design created by the voids is conspicuous. There is a risk of not.

  The manufacturing method of the said laminated sheet may have the process 3 which bridge | crosslinks a film layer further by irradiating an electron beam from the said film layer side (3).

  When the film layer is a layer containing polyethylene and / or ethylene copolymer by crosslinking by electron beam irradiation in this way, the heat resistance of the film layer is improved and the foamed laminated sheet finally obtained is excellent. It is possible to provide anti-contamination and scratch resistance.

  The energy of the irradiated electron beam is, for example, about 150 to 250 kV, preferably about 175 to 200 kV. The irradiation dose is, for example, about 10 to 100 kGy, preferably about 10 to 50 kGy. A known electron beam irradiation apparatus can be used as the electron beam source. The effect of improving heat resistance is obtained by such electron beam irradiation.

In step 3, the foaming agent-containing resin layer may be cross-linked together with the film layer. By crosslinking the foaming agent-containing resin layer, the surface strength, foaming characteristics, etc. of the foamed resin layer can be adjusted.
Here, when only the film layer is cross-linked, it is not necessary to cross-link the lower foaming agent-containing resin layer, so that it is not necessary to deeply penetrate the electron beam, and the acceleration voltage can be lowered.

Moreover, you may form a surface protective layer in the outermost surface of a lamination sheet for the purpose of improving scratch resistance, a surface state, etc. as needed.
<Method for producing foam laminated sheet>
As a manufacturing method of the foaming lamination sheet of this invention, it is a lamination sheet which laminated | stacked the film layer on the foaming agent containing resin layer, for example, Comprising: The peeling strength between the said film layer and the said foaming agent containing resin layer is 2 After obtaining a laminated sheet having a region of .5 N / 25 mm or less, the foaming agent-containing resin layer of the laminated sheet is foamed to form a foamed resin layer, whereby the film layer and the foamed resin layer are interposed. The manufacturing method of the foaming lamination sheet which forms a space | gap is mentioned.

  As a method for producing such a foamed laminated sheet, specifically, for example, in addition to Steps 1 to 3 above, (4) Step 4 in which the foaming agent-containing resin layer is made into a foamed resin layer by heating the laminated sheet. The manufacturing method which has is mentioned.

  The heating conditions in the step 4 are not limited as long as the foaming agent-containing resin layer becomes a foamed resin layer by decomposition of the foaming agent. An example of the heating temperature is about 210 to 240 ° C., and an example of the heating time is about 20 to 80 seconds. Heating can be performed using a known heating furnace or gear oven.

  The thickness of the foamed resin layer after foaming is not particularly limited, but examples include about 300 to 700 μm.

  Moreover, in the manufacturing method of the said foaming lamination sheet, after the process 4, you may perform the process 5 which embosses from on an outermost surface layer as needed.

  Embossing can be performed by known means such as an embossed plate. Specifically, a desired embossed pattern can be formed by pressing the embossed plate after heat-softening the surface 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, a hairline, and a multiline groove.

  The foamed laminated sheet of the present invention can be obtained through the above steps 1 to 4 and step 5 as necessary.

  The foamed laminated sheet of the present invention is excellent in stain resistance and high design properties. Moreover, the laminated sheet of this invention can obtain the foamed laminated sheet of this invention simply by foaming the foaming agent containing resin layer.

  Moreover, according to the manufacturing method of the foaming lamination sheet of this invention, the said foaming lamination sheet can be manufactured simply.

It is side surface sectional drawing of an example of the foaming lamination sheet which concerns on this invention. It is the top view which looked at the surface of an example of the foaming lamination sheet which concerns on this invention from the front. It is a side view sectional view of an example of a lamination sheet concerning the present invention. It is side surface sectional drawing of an example of the foaming lamination sheet which concerns on this invention. It is a photograph of the section which cut an example of the foam lamination sheet concerning the present invention in the direction which intersects perpendicularly with the surface of a foam lamination sheet. The magnification is 300 times. It is a figure which shows the designability evaluation method of a foaming lamination sheet.

  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, the non-foamed resin layer A / the foaming agent-containing resin layer / the non-foamed resin layer B are extruded onto the fibrous sheet so as to have a thickness of 5 μm / 50 μm / 5 μm. A film was formed, and the surface temperature of the non-foamed resin layer B was set to 120 ° C. and laminated on the fibrous sheet. Thereby, the laminated body which consists of a fibrous sheet / non-foamed resin layer B / foaming agent containing resin layer / non-foamed resin layer A / fibrous sheet was obtained. As the fiber sheet, wallpaper paper “WK-665, manufactured by Kojin” (thickness: 100 μm) was used.

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 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 from an ethylene-methacrylic acid copolymer (EMAA) “N1560, manufactured by Mitsui DuPont Polychemical Co., Ltd.” (MFR = 60 g / 10 min, MAA amount: 15 mass%).

  The foaming agent-containing resin layer is composed of 100 parts by mass of an ethylene-methacrylic acid copolymer (EMAA) “Nucleel N1110H, manufactured by Mitsui DuPont Polychemical Co., Ltd.” (MFR = 100 g / 10 min, MMA amount: 11% by mass), calcium carbonate. (Inorganic filler) “Whiteon H, manufactured by Shiraishi Kogyo Co., Ltd.” 30 parts by mass, Titanium dioxide (inorganic filler) “Taypure R350, manufactured by DuPont” 20 parts by mass, Foaming agent “Vinihole AC # 3, manufactured by Eiwa Kasei Kogyo Co., Ltd.” 6 It was formed by 6 parts by mass of a foaming aid “ADHS, manufactured by Otsuka Chemical Co., Ltd.”.

  The non-foamed resin layer B was formed of an ethylene-vinyl acetate copolymer (EVA) “Evaflex EV150, manufactured by Mitsui DuPont Polychemical Co., Ltd.” (vinyl acetate content 33% by mass).

  Next, on the non-foamed resin layer A, using a multi-manifold T-die extruder, the lower layer of the film layer is acid-modified polyethylene “Modic M545, manufactured by Mitsubishi Chemical Corporation” (5 μm), and the upper layer is polyethylene “HC170, Japan Polyethylene (MFR: 10 g / 10 min) ”(10 μm) is co-extruded to form a film, heat-laminated using a roll having a concavo-convex shape formed on the surface, locally applied, A film layer was laminated on the foaming agent-containing resin layer via the non-foamed resin layer A to obtain a laminated sheet having a weak adhesion region and a strong adhesion region.

  In addition, formation of the said weak adhesion area | region and a strong adhesion area | region consists of a metal roll of Ra = 1.20 μm, an impression cylinder made of silicon rubber having a width of 150 mm in the center portion being 1.0 mm smaller than the circumference of the other portion, The non-foamed resin layer A and the film layer were pressed and adhered by rolling the laminated sheet with a force of 2.0 MPa. In the laminated sheet, the portion that has passed through the central part of the silicon rubber impression cylinder during pressure contact becomes a weakly bonded region after pressure contact, and a void is formed when the foaming agent-containing resin layer is heated and foamed. .

  Next, an ionizing radiation curable resin (manufactured by Dainichi Seika Kogyo Co., Ltd.) containing silica, silicone, and an ionic conductive agent is applied on the film layer and irradiated with an electron beam (irradiation conditions: 195 kV, 60 kGy). A surface protective layer having a thickness of 2 μm was formed.

Finally, after heating at 220 ° C. for 40 seconds to make the foaming agent-containing resin layer a foamed resin layer, a metal roll (embossed plate) having a fabric-like uneven pattern was pressed to form an embossed uneven pattern.
<Evaluation results>
(Peel strength)
The peel strength of the weakly bonded region of the obtained laminated sheet was 1.9 N / 25 mm, and the peel strength of the strongly bonded region was 3.1 N / 25 mm. The peel strength was measured by the following method.
(Peel strength)
First, the laminated sheet was cut into a size of 25 mm wide × 150 mm long to obtain a cut piece, and measured at a peeling speed: 100 mm / min, a peeling distance: 120 mm, and a peeling angle: 180 °. The peel strength is measured in accordance with “JIS K 6854-3”, but the extension was confirmed on the film layer side, so Nichiban's “Cello Tape (registered trademark)” was placed on the film layer side (the side opposite to the adhesive surface). ) And reinforced and measured. Moreover, the tensile tester RTF-1150-H (made by A & D company) was used for the measurement of peeling strength.

  In addition, about the foaming lamination sheet produced in the Example, the gross measurement test was done and the design property and stain resistance were evaluated. Each test method and evaluation method were as follows.

≪Gloss measurement≫
Using a gloss meter, the 60 ° gloss value was measured in accordance with JIS K 7105. The measurement was performed on a portion where no void was formed and a portion where a void was formed.

≪Design evaluation≫
As shown in FIG. 6, the foamed laminated sheet is placed under light-shielded conditions (a weak light source is applied in a dim room), from the direction perpendicular to the surface of the foamed laminated sheet (arrow 1), and in the direction of about 45 ° (arrowed). Visual observation was performed from 2). The part where the void was formed was confirmed.

≪Contamination resistance≫
The measurement was performed in accordance with the anti-smudge wallpaper performance regulations of the Wallpaper Product Standards Council (SV standard).
The evaluation results of each test are shown in Table 1 below.

Results Since the foamed laminated sheet of Example 1 has a gap between the film layer and the foamed resin layer, when looking at the surface of the foamed laminated sheet, a unique design has been created in which the luster changes depending on the viewing angle, The design property evaluation was good. It was. In addition, since a design is created by forming a gap between the foamed resin layer and the film layer, it is not necessary to form a fine uneven shape for reflecting light on the surface, and the stain resistance is also improved. It was excellent.

1. Foamed laminated sheet 1 ′. Laminated sheet 2. 2. Surface protective layer Film layer4. Foamed resin layer 4 ′. 4. Foaming agent-containing resin layer Non-foamed resin layer B
6). Base material 7. Air gap 8 Foam cell 9. Non-foamed resin layer A
10. Incident light 11. Reflected light reflected on the surface of the foamed resin layer 12. Reflected light reflected from the surface of the air gap

Claims (8)

  A foamed laminated sheet in which a film layer is laminated on a foamed resin layer, wherein there is a gap between the film layer and the foamed resin layer.   2. The foamed laminated sheet according to claim 1, wherein a cross-sectional shape of the void is a semicircular shape protruding toward the foamed resin layer.   The foamed laminated sheet according to claim 1, further comprising a non-foamed resin layer A between the foamed resin layer and the film layer.   It is a lamination sheet for obtaining the foaming lamination sheet in any one of Claims 1-3, Comprising: The film layer is laminated | stacked on the foaming agent containing resin layer, The said film layer and the said foaming agent containing resin layer, A laminate sheet having a peel strength of 2.5 N / 25 mm or less.   It is a lamination sheet for obtaining the foaming lamination sheet in any one of Claims 1-3, Comprising: The film layer is laminated | stacked on the foaming agent containing resin layer, The said film layer and the said foaming agent containing resin layer, A laminate sheet characterized by having a weak adhesion region having a peel strength of 2.5 N / 25 mm or less and a strong adhesion region exceeding 2.5 N / 25 mm.   The laminate sheet according to claim 5, wherein the peel strength of the strong adhesion region is 3.0 N / 25 mm or more.   The laminated sheet according to any one of claims 4 to 6, further comprising a non-foamed resin layer A between the foaming agent-containing resin layer and the film layer.   A laminated sheet obtained by laminating a film layer on a foaming agent-containing resin layer, and a laminated sheet having a peel strength between the film layer and the foaming agent-containing resin layer of 2.5 N / 25 mm or less was obtained. Thereafter, the foaming agent-containing resin layer of the laminated sheet is foamed to form a foamed resin layer, whereby a void is formed between the film layer and the foamed resin layer. Method.

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