HK1235357A1 - Laminate sheet and foam laminate sheet, and production method and application method for same - Google Patents

Description

Laminated sheet, foamed laminated sheet, and methods for producing and applying them

Technical Field

The present invention relates to a laminated sheet and a foamed laminated sheet, and a method for producing and applying the same.

The foamed laminated sheet has a foamed resin layer and is useful as a foamed wallpaper, various decorative materials, and the like. The laminated sheet is a state before the foamed laminated sheet is foamed (i.e., a so-called unfoamed blank), or a sheet useful as various decorative materials in a state where the foamed resin layer is not provided.

Background

Conventionally, it has been known to apply a decorative material such as a wallpaper by combining a liner paper obtained by mixing and forming a pulp component and a synthetic resin component with a methyl cellulose adhesive, and for example, patent document 1 discloses a "wallpaper having a laminated structure of at least a liner paper and a decorative layer, wherein, when the wallpaper is applied to a wall surface using an adhesive, peeling of the wallpaper from the wall surface occurs at the adhesive layer, the adhesive is a methyl cellulose adhesive, the peeling strength of the wallpaper from the wall surface is 100 to 500g/3cm, the liner paper is formed by mixing and forming a pulp component and a synthetic resin component, and the interlayer peeling strength of the liner paper is greater than the peeling strength of the wallpaper from the wall surface.

The lining paper made by mixing the slurry component and the synthetic resin component can be applied to the wall surface as the surface to be applied with an adhesive by utilizing the characteristic of the synthetic fiber mixed paper that dimensional change is small when wet (characteristic of small elongation in water), and then the wallpaper with the lining paper is applied. The application of the adhesive to the surface to be worked has an advantage that it can be easily handled by ordinary consumers. Furthermore, by combining the methyl cellulose adhesive with the liner paper, there is an advantage that the liner paper can be peeled off between the liner paper and the adhesive when re-pasting an old wallpaper, the liner paper is less left on the surface to be worked and the surface to be worked is damaged, and the influence on the newly pasted wallpaper is small.

On the other hand, when another interleaving paper is used, the interleaving paper needs to be left for a while until its dimension is stabilized after the adhesive is applied to the interleaving paper, and then the interleaving paper needs to be attached to the surface to be worked, because the interleaving paper has a large elongation in water. In addition, since the wallpaper size may change after the wallpaper is pasted, cracks (slits) or bulges may occur in the joint portion of the wallpaper after the application. Further, when the adhesive is applied to the inner liner paper, not only a special adhesive applicator is required, but also the handling of the adhesive-applied wallpaper is not easy, and therefore, a professional person is forced to perform the work.

Further, as an adhesive used for wallpaper application, a starch-based adhesive (starch paste, a product in which a synthetic resin is added to starch paste) is generally used in addition to a methyl cellulose-based adhesive, but in the case of the starch-based adhesive, the adhesive strength between the lining paper and the adhesive is too strong, and when an old wallpaper is re-pasted, peeling between the papers may occur, leaving the lining paper on the surface to be applied, and the surface to be applied may be damaged.

Therefore, it is desired that the adhesive can be applied to the surface to be applied, and then the wallpaper and the like can be easily applied, in addition to the combination of the synthetic fiber mixed paper and the methyl cellulose adhesive, and that peeling occurs between the inner liner and the adhesive when re-pasting an old wallpaper.

Documents of the prior art

Patent document

Patent document 1: japanese patent publication No. 4205562

Disclosure of Invention

Problems to be solved by the invention

The present invention aims to provide a novel laminated sheet and a foamed laminated sheet (collectively referred to as "wallpaper and the like"), and specifically aims to provide a wallpaper which comprises: in addition to the combination of the synthetic fiber mixed paper and the methyl cellulose-based adhesive, the application can be easily performed even after the adhesive is applied to the surface to be applied, and peeling can occur between the inner liner paper and the adhesive when re-pasting.

Means for solving the problems

The inventors of the present invention have conducted extensive studies and, as a result, found that: the above object can be achieved when a fibrous substrate containing a crosslinked material of an ionizing radiation crosslinking type material is used as an inner liner paper of wallpaper or the like, and the present invention has been completed.

That is, the present invention relates to the following laminated sheet, foamed laminated sheet, and methods for producing them.

1. A laminated sheet characterized by having at least a resin layer laminated on a fibrous substrate containing a crosslinked material of an ionizing radiation crosslinking type.

2. The laminated sheet according to claim 1, wherein the resin layer is an olefin resin layer.

3. The laminated sheet according to claim 1 or 2, wherein the resin layer is a layer containing a foaming agent or a layer comprising a laminate of resin layers containing a foaming agent.

4. The laminated sheet according to claim 3, wherein the resin layer containing a foaming agent has a non-foamed resin layer on one surface or both surfaces.

5. The laminated sheet according to claim 3 or 4, wherein the resin layer containing a foaming agent is crosslinked with the resin by irradiation with an electron beam.

6. A foamed laminated sheet obtained by foaming a resin layer containing a foaming agent of the laminated sheet described in any one of items 3 to 5.

7. A method of manufacturing a laminated sheet, comprising:

(1) a step of forming at least a resin layer on a fibrous substrate, and

(2) a step of immersing the ionizing radiation crosslinking material in the above fibrous substrate,

after the two steps, at least the fibrous base material is irradiated with ionizing radiation to crosslink the ionizing radiation crosslinking material to form a crosslinked body.

8. The method for producing a laminated sheet according to claim 7, wherein at least the resin layer is formed on the fibrous substrate by extrusion film formation.

9. The method of producing a laminated sheet according to claim 7 or 8, wherein the resin layer is a foaming agent-containing resin layer or a laminate comprising foaming agent-containing resin layers, and the ionizing radiation is an electron beam, and the crosslinking of the ionizing radiation-crosslinkable material and the crosslinking of the foaming agent-containing resin layer are simultaneously performed by irradiating the electron beam with the ionizing radiation.

10. A method for producing a foamed laminated sheet, wherein the foaming agent-containing resin layer of the laminated sheet produced by the production method according to any one of the above 7 to 9 is foamed by heating, and the resin layer is a foaming agent-containing resin layer or a layer composed of a laminate including a foaming agent-containing resin layer.

11. A construction method comprising applying the laminated sheet or foamed laminated sheet described in any one of items 1 to 6 to a construction surface to which an adhesive is applied.

12. A method of applying an adhesive to the back surface of the laminated sheet or foamed laminated sheet described in any one of items 1 to 6, and then attaching the sheet or foamed laminated sheet to a surface to be applied.

13. The construction method according to claim 11 or 12, wherein the surface to be constructed is a wall surface and/or a ceiling.

ADVANTAGEOUS EFFECTS OF INVENTION

The laminated sheet of the present invention contains a crosslinked material of an ionizing radiation crosslinking type material in a fibrous substrate, and can suppress elongation (dimensional change) in water to a low level by containing the crosslinked material regardless of the type of the fibrous material of the fibrous substrate. Therefore, the application of the adhesive to the surface to be applied can be easily performed, and peeling between the fibrous substrate and the adhesive can be caused at the time of re-mounting regardless of the type of the adhesive. This effect can be achieved in both of the laminated sheet and the foamed laminated sheet of the present invention. Such laminated sheets and foamed laminated sheets of the present invention have great advantages in that ordinary consumers can easily perform construction (pasting) and remounting.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of the layer structure of the laminated sheet of the present invention.

Detailed Description

The laminated sheet and foamed laminated sheet of the present invention, and their production methods and application methods will be described in detail below.

Laminated sheet

The laminated sheet of the present invention is characterized in that at least a resin layer is laminated on a fibrous substrate containing a crosslinked material of an ionizing radiation crosslinking type.

The laminated sheet of the present invention having the above-described features can suppress elongation (dimensional change) in water to a low level by containing the crosslinked material regardless of the type of the fiber material of the fibrous substrate, by containing the crosslinked material in the fibrous substrate containing the crosslinked material of the ionizing radiation crosslinking type material. Therefore, the application of the adhesive to the surface to be applied can be easily performed, and peeling between the fibrous substrate and the adhesive can be caused at the time of re-mounting regardless of the type of the adhesive. This effect can be achieved in both of the laminated sheet and the foamed laminated sheet of the present invention. Such laminated sheets and foamed laminated sheets of the present invention have great advantages in that ordinary consumers can easily perform construction (pasting) and remounting.

Hereinafter, each layer constituting the laminated sheet will be described. In the present specification, the direction in which the resin layer is laminated as viewed from the fibrous substrate is referred to as "upper" or "front surface", and the direction opposite to the direction in which the resin layer is laminated as viewed from the fibrous substrate is referred to as "lower" or "back surface".

Fibrous substrates

As the fibrous substrate, a fibrous substrate containing a crosslinked material of an ionizing radiation crosslinking type material is used. Here, the crosslinked material of the ionizing radiation-crosslinkable material is formed by impregnating (various means including impregnation, coating, spraying, and the like) a fibrous substrate (a substrate in a fibrous sheet state) with the ionizing radiation-crosslinkable material and then irradiating the fibrous substrate with ionizing radiation.

Specific examples of the fibrous sheet include plain paper for wallpaper (paper obtained by sizing a sheet mainly containing a sizing agent with a known sizing agent); flame-retardant paper (paper in which a sheet of a pulp main body is treated with a flame retardant such as guanidine sulfamate or guanidine phosphate); inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; high-quality paper; tissue paper; synthetic fiber mixed paper (paper made by mixing pulp and synthetic fiber), and the like.

The fibrous sheet used in the present invention includes, in terms of classification, sheets belonging to nonwoven fabrics. In the present invention, from the viewpoint of improving the adhesion to the resin layer, among the above exemplified fibrous sheets, plain paper for wallpaper and flame-retardant paper are preferably used.

The grammage of the fibrous sheet is not limitedPreferably 50 to 300g/m²About, more preferably 50 to 130g/m²Left and right.

The ionizing radiation-crosslinkable material is not particularly limited, and a compound containing a prepolymer (including an oligomer) and/or a monomer as a main component, the prepolymer having a radically polymerizable unsaturated group and/or a cationically polymerizable functional group in a molecule, which can be crosslinked (crosslinked) by irradiation with ionizing radiation such as ultraviolet rays or electron beams, can be used. These prepolymers or monomers can be used alone or in combination of two or more. In view of permeability into a fibrous substrate, a monomer having a low viscosity is preferable.

Specifically, examples of the prepolymer or monomer include compounds having a (meth) acryloyl group, a radical polymerizable unsaturated group such as a (meth) acryloyloxy group, and a cation polymerizable functional group such as an epoxy group in the molecule. Also, a polyene/thiol based prepolymer obtained by combining a polyene and a polythiol is also preferable. Here, (meth) acryloyl means acryloyl or methacryloyl.

Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. The molecular weight of these compounds is preferably about 250 to 100000.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol dimethacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Examples of the prepolymer having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol epoxy resins and novolak epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polyhydric thiols such as trimethylolpropane trimercaptoacetate and pentaerythritol tetramercaptoacetate. Examples of the polyene include polyenes obtained by adding allyl alcohol to both ends of polyurethane formed from a diol and a diisocyanate.

As the ionizing radiation crosslinking material, in order to promote the crosslinking reaction, it is preferable to use a polyfunctional prepolymer or a polyfunctional monomer having two or more polymerizable functional groups in 1 molecule as the prepolymer or monomer.

As the ionizing radiation crosslinking material, a material obtained by combining these prepolymers or monomers with another material may be used. Examples of the material used in combination with these prepolymers or monomers include resins such as acrylic resins, urethane resins, epoxy resins, and polyester resins, which are commonly used as general coating materials. When these prepolymers or monomers are used in combination with these resins, the prepolymers or monomers may also be compounds that function as crosslinking agents for crosslinking these resins.

As ionizing radiation for crosslinking the ionizing radiation crosslinking-type material, electromagnetic waves or charged particles having energy capable of causing a crosslinking reaction of molecules in the ionizing radiation crosslinking-type material are used. Generally, ultraviolet rays or electron beams may be used, and visible light, X-rays, ion rays, and the like may be used.

Examples of the ultraviolet source include a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light lamp, and a metal halide lamp. The wavelength of the ultraviolet light is preferably 190 to 380 nm.

As the electron beam source, for example, various electron beam accelerators of a cockcroft-walton type, a van der graff type, a resonance transformer type, an insulation core transformer type, a linear type, a high-frequency high-voltage accelerator type, a high-frequency type, and the like can be used. Among them, an electron beam source capable of irradiating electrons having an energy of 100 to 1000keV, preferably 100 to 300keV is particularly preferable.

The density of the fibrous substrate containing the crosslinked material of the ionizing radiation crosslinking type material varies depending on the kind of the fibrous substrate before containing the crosslinked material, the content of the crosslinked material, and the like, and the basis weight of the fibrous substrate used is 65g/m²In the case of the left and right fibrous sheets, the density of the fibrous substrate containing the crosslinked material is 0.60 to 0.65g/cm³Left and right; when an inorganic paper containing an inorganic additive such as aluminum hydroxide is used, the concentration is 1.0g/cm³Left and right. In addition, the gram weight of the product is 65g/m²In the case of the left and right fibrous sheets, the strength between sheets of the crosslinked fibrous substrate is about 0.25 to 3.8N/(3cm width).

Resin layer

In the laminated sheet of the present invention, at least a resin layer is laminated on a fibrous substrate. The resin layer can be formed by a known film forming method such as a T-mold film forming method or a calender film forming method.

As the resin component contained in the resin layer, vinyl chloride resins, olefin resins, and the like that have been conventionally used as wall surface finishing materials can be widely used, and since vinyl chloride resins are concerned with bleeding of plasticizers over time, olefin resins are more preferable than vinyl chloride resins in terms of improving the durability of the laminate sheet, and specifically, vinyl resins are preferably contained.

The ethylene resin may be not only Polyethylene (PE), but also an ethylene copolymer (hereinafter simply referred to as "ethylene copolymer") containing ethylene and a component other than ethylene as monomers.

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.

From the viewpoint of melting point and MFR, the ethylene copolymer is suitable for extrusion film formation. Examples of the ethylene copolymer include an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene-acrylic acid copolymer (EAA), an ethylene-ethyl acrylate copolymer (EEA), an ethylene-methyl acrylate copolymer (EMA), an ethylene-methacrylic acid copolymer (EMAA), and an ethylene- α -olefin copolymer. These ethylene copolymers can be used alone or in combination of two or more. Among these ethylene copolymers, an ethylene-vinyl acetate copolymer and an ethylene-methyl methacrylate copolymer are particularly preferable, and when one or more of these ethylene copolymers and another resin are used in combination, the content of each of the ethylene-vinyl acetate copolymer and the ethylene-methyl methacrylate copolymer is preferably 70% by weight or more, and more preferably 80% by weight or more.

The content of the monomer other than ethylene in the ethylene copolymer is preferably 5 to 25% by weight, more preferably 9 to 20% by weight. By adopting such a copolymerization ratio, the extrusion film formability can be further improved. Specifically, in the ethylene-vinyl acetate copolymer, the copolymerization ratio (VA amount) of vinyl acetate is preferably 9 to 25% by weight, more preferably 9 to 20% by weight. In the ethylene-methyl methacrylate copolymer, the copolymerization rate (MMA content) of methyl methacrylate is preferably 5 to 25% by weight, more preferably 5 to 15% by weight. In the ethylene-methacrylic acid copolymer, the copolymerization ratio (MAA amount) of acrylic acid is preferably 2 to 15% by mass, and more preferably 5 to 11% by mass.

In the present invention, the resin component contained in the resin layer varies depending on the film-forming method, and preferably has an MFR (melt flow rate) of 10 to 40g/10 min as measured under the conditions of 190 ℃ and 21.18N load as described in JIS K6922. When the MFR is within the above range, the film can be formed in a non-foamed state with little temperature rise at the time of forming the resin layer by extrusion film formation, and therefore, when a pattern layer is formed later, printing treatment can be performed on a smooth surface, and a pattern is rarely missed. If the MFR is too large, the resin is too soft, and there is a fear that the scratch resistance of the formed resin layer may be insufficient.

In the present invention, the resin layer may be a layer containing a foaming agent, or may be a layer composed of a laminate including a foaming agent-containing resin layer. In these cases, the obtained laminated sheet is a so-called preform having a resin layer containing a foaming agent. Then, the resin layer containing a foaming agent is foamed to obtain the foamed laminated sheet of the present invention.

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

Examples of the thermal decomposition type foaming agent include azo type foaming agents such as azodicarbonamide (ADCA) and azodicarbonamide; and hydrazide-based foaming agents such as oxybis (benzenesulfonyl) hydrazide (OBSH) and p-toluenesulfonyl hydrazide. The content of the thermal decomposition type foaming agent can be appropriately set depending on the kind of the foaming agent, the expansion ratio, and the like. From the viewpoint of expansion ratio, the amount is 7 times or more, preferably about 7 to 10 times, and the amount of the thermal decomposition type foaming agent is preferably about 1 to 20 parts by mass per 100 parts by mass of the resin component.

The foaming aid is preferably a metal oxide and/or a fatty acid metal salt, and examples thereof include zinc stearate, calcium stearate, magnesium stearate, zinc caprylate, calcium caprylate, magnesium caprylate, zinc laurate, calcium laurate, magnesium laurate, zinc oxide, and magnesium oxide. The content of these foaming aids is preferably about 0.3 to 10 parts by mass, more preferably about 1 to 5 parts by mass, per 100 parts by mass of the resin component.

When these foaming aids, EMAA and ADCA foaming agents are used in combination, there is a problem that the effect as a foaming aid is impaired by the reaction between the acrylic acid moiety of EMAA and the metallic foaming aid in the foaming step. Therefore, when EMAA and ADCA blowing agents are used in combination, a carboxylic acid hydrazide compound is preferably used as a blowing aid as described in Japanese patent laid-open No. 2009-197219. In this case, the carboxylic acid hydrazide compound is preferably used in an amount of about 0.2 to 1 part by mass based on 1 part by mass of the ADCA blowing agent.

Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and molybdenum compounds. The inclusion of the inorganic filler can achieve a crack-inhibiting effect, a surface property-improving effect, an effect of inhibiting heat generation during combustion, and the like. The content of the inorganic filler is preferably about 0 to 100 parts by mass, and more preferably about 20 to 70 parts by mass, per 100 parts by mass of the resin component.

Examples of the inorganic pigment include titanium oxide, zinc white, carbon black, iron oxide yellow, chrome yellow, molybdate orange, cadmium yellow, titanium nickel yellow, chrome titanium yellow, iron oxide (iron oxide red), cadmium red, ultramarine, iron blue, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, mica titanium, and zinc sulfide. Examples of the organic pigment include aniline black, perylene black, azo compounds (azo lakes, insoluble azo compounds, condensed azo compounds), polycyclic compounds (isoindolinone, isoindoline, quinophthalone, perinone, xanthone, anthrapyrimidine, anthraquinone, quinacridone, perylene, pyrrolopyrrole dione, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, standard vat blue, and halogenated phthalocyanine). The content of the pigment is preferably about 10 to 50 parts by mass, and more preferably about 15 to 30 parts by mass, per 100 parts by mass of the resin component.

In the present invention, the resin layer containing a foaming agent may be crosslinked by the resin by electron beam irradiation. The method of irradiating the resin layer containing the foaming agent with an electron beam and the method of foaming the resin layer may be performed by the method described in the production method described later. In the present invention, particularly in the case where the ionizing radiation irradiated to the fibrous substrate is an electron beam, the crosslinking of the ionizing radiation crosslinking-type material and the resin crosslinking of the resin layer containing the foaming agent can be simultaneously performed.

In the present invention, the resin layer may be a resin layer having a pattern different from that of a pattern layer described later. The pigment and resin used are the same as those used for the pattern layer described later. The resin layer may be a resin layer containing an ionizing radiation curable resin, a thermosetting resin (including a room temperature curable resin, a two-liquid reaction curable resin), or the like.

The thickness of the resin layer (including a single layer or a plurality of layers) is preferably about 40 to 200 μm, and the thickness of the resin layer after foaming (including a single layer or a plurality of layers) is preferably about 300 to 1000 μm when the resin layer is a resin layer containing a foaming agent or a layer composed of a laminate including a resin layer containing a foaming agent.

Non-foamed resin layers A and B

The resin layer containing a foaming agent may have a non-foamed resin layer on one or both surfaces thereof.

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

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

The thickness of the adhesive resin layer is not limited, but is preferably about 3 to 50 μm, and more preferably about 5 to 20 μm.

The non-foamed resin layer a may be formed on the upper surface of the resin layer containing the foaming agent for the purpose of making the pattern clear when the pattern layer is formed 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, and among them, polyolefin resins are preferable.

Examples of the polyolefin-based resin include resin monomers such as polyethylene (low density polyethylene (LDPE) or High Density Polyethylene (HDPE)), polypropylene, polybutene, polybutadiene, and polyisoprene; ethylene (meth) acrylic acid copolymers such as copolymers of ethylene and an α -olefin having 4 or more carbon atoms (linear low density polyethylene (LLDPE)), ethylene-acrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, and ethylene-methacrylic acid copolymers; ethylene-vinyl acetate copolymer (EVA), saponified ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ionomer, and the like. In the present invention, when a polyvinyl chloride resin is used as the resin in the resin layer containing a foaming agent, it is preferable to form the non-foamed resin layer a (particularly, an ethylene-vinyl alcohol copolymer layer) in order to achieve durability of the laminated sheet. The term "(meth) acrylic acid" means acrylic acid or methacrylic acid, and the same applies to other portions described as (meth).

The thickness of the non-foamed resin layer A is not limited, but is preferably about 2 to 50 μm, and more preferably about 5 to 20 μm.

In the present invention, from the viewpoint of the production described below, a form in which the non-foamed resin layer B, the resin layer containing a foaming agent, and the non-foamed resin layer a are formed in this order is preferable.

Pattern layer

In the laminated sheet of the present invention, a patterned layer may be formed on a resin layer (a resin layer containing a foaming agent, a non-foamed resin layer a, etc.) or an undercoat layer described later, as necessary.

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

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

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

The binder resin may be set according to the type of the base material forming the pattern layer. Examples of the resin include acrylic resins, styrene resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, and rubber resins.

Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, and propylene glycol; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as methylene chloride, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; water, and the like. These solvents (or dispersion media) can be used alone or in a mixture state.

The thickness of the pattern layer varies depending on the type of pattern, and is preferably about 0.1 to 10 μm.

Base coat

An undercoat layer may be formed on the resin layer (the resin layer containing a foaming agent, the non-foamed resin layer a, etc.) or the pattern layer, if necessary.

As the resin contained in the undercoat layer, for example, acrylic acid, a vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, and the like can be used, and acrylic acid, chlorinated polypropylene, and the like are particularly preferable.

Examples of the acrylic acid include acrylic resins containing homopolymers or copolymers of (meth) acrylic esters such as polymethyl (meth) acrylate, polyethyl (meth) acrylate, polypropyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, and styrene-methyl (meth) acrylate copolymer.

The polyurethane is a composition containing a polyol (polyol) as a main component and isocyanate as a crosslinking agent (curing agent).

As the polyol, a compound having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, or the like can be used.

As the isocyanate, a polyisocyanate having two or more isocyanate groups in a molecule can be used. For example, aromatic isocyanates such as 2, 4-tolylene diisocyanate, xylylene diisocyanate, and 4, 4-diphenylmethane diisocyanate, or aliphatic (or alicyclic) isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate can be used.

The thickness of the undercoat layer is not limited, but is preferably about 0.1 to 10 μm, and more preferably about 0.1 to 5 μm.

Surface protective layer

The surface of the resin layer (the resin layer containing a foaming agent, the non-foamed resin layer a, etc.), the pattern layer, or the primer layer may have a surface protective layer for the purpose of gloss control and/or pattern layer protection.

The kind of the surface protective layer is not limited. For the surface protective layer for the purpose of adjusting gloss, for example, there is a surface protective layer containing a known filler such as silica. As a method for forming the surface protective layer, a known method such as gravure printing can be used.

When the surface protective layer is formed for the purpose of surface strength (scratch resistance, etc.) of the laminated sheet, stain resistance, protection of the pattern layer, and the like, the surface protective layer containing an ionizing radiation curable resin as a resin component is preferable. As the ionizing radiation curable resin, a resin that undergoes radical polymerization (curing) by irradiation of an electron beam is preferable.

Embossing

An embossed pattern may also be imparted to the surface of the laminated sheet or foamed laminated sheet. In this case, the embossing process may be performed from the outermost surface layer (the side opposite to the fibrous sheet). The embossing can be performed by a known method such as pressing an embossing plate. For example, in the case where the outermost surface layer is a surface protective layer, a desired embossed pattern can be provided by heating and softening the surface thereof and then pressing the embossing plate. Examples of the embossing pattern include a wood grain guide groove, a stone plate surface unevenness, a cloth surface texture, a coarse grain (pearskin grain), a sand grain, a fiber texture, a geometric pattern, a spline groove, and a contour pattern.

Laminated foam sheet

The foamed laminated sheet of the present invention can be obtained by foaming the resin layer containing a foaming agent of the laminated sheet.

Laminated sheet and method for producing foamed laminated sheet

The method for producing the laminated sheet of the present invention is not limited, and for example, the laminated sheet is produced by a production method including

(1) A step of forming at least a resin layer on a fibrous substrate; and

(2) a step of immersing the ionizing radiation crosslinking material in the above fibrous substrate,

after the two steps, at least the fibrous base material is irradiated with ionizing radiation to crosslink the ionizing radiation crosslinking material to form a crosslinked body.

That is, the above-mentioned production method comprises a step of forming a resin layer on a fibrous substrate (including both a fibrous substrate containing a crosslinked material and a fibrous sheet) and a step of immersing an ionizing radiation crosslinking material in the fibrous substrate (the fibrous substrate not containing the crosslinked material), and after these two steps, the ionizing radiation crosslinking material is crosslinked by irradiating at least the fibrous substrate with ionizing radiation to form the crosslinked material. Here, the resin layer is preferably formed by extrusion film formation.

In the above-mentioned production method, the order of performing the steps (1) and (2) is not limited, and when the resin layer is formed by extrusion film formation, it is preferable to perform the step (2) after performing the step (1) from the viewpoint of laminating the resin layer on the fibrous substrate with good adhesion.

When a resin layer is formed by extrusion film formation and laminated on a fibrous substrate, in the case of using synthetic fiber mixed paper or nonwoven fabric as the fibrous substrate, it may be difficult to laminate the fibrous substrate and the resin layer with good adhesion. On the other hand, if the laminated sheet and the method for producing the same of the present invention are used, even in the case of using a fibrous substrate having good adhesion to a resin layer other than synthetic fiber mixed paper and nonwoven fabric, since the peeling between the fibrous substrate and the adhesive can be performed at the time of application and remounting of the adhesive to the surface to be applied, the adhesion between the fibrous substrate and the resin layer and the ease of application and remounting can be both satisfied.

In the step (2), the ionizing radiation crosslinking material is impregnated into the fibrous substrate by a method not particularly limited, and examples thereof include a method of coating the ionizing radiation crosslinking material on the fibrous substrate (in the case where the step (1) is performed, on the side opposite to the surface on which the resin layer is formed), a method of impregnating the fibrous substrate with the ionizing radiation crosslinking material, and the like. The ionizing radiation crosslinking type material may be diluted with a solvent as necessary and used.

When the resin layer is a layer formed of a laminate including a resin layer containing a foaming agent and the foaming agent-containing resin layer has a non-foamed resin layer on one surface or both surfaces thereof, the non-foamed resin layer B and/or the non-foamed resin layer a may be formed by extrusion film formation, or may be formed by thermally laminating the respective films, and preferably by simultaneous extrusion film formation using a T-die extruder. For example, when the non-foamed resin layers are provided on both surfaces, a multi-manifold type T die can be used in which 3 layers can be simultaneously formed by simultaneously extruding molten resins corresponding to 3 layers.

When the inorganic filler is contained in the resin composition for forming the resin layer containing the blowing agent, when the resin layer containing the blowing agent is extruded to form a laminate sheet, a residue of the inorganic filler (so-called build-up) (No. やに) is likely to be generated at an extrusion port (so-called fouling) of an extruder, and the residue is likely to form foreign matter on the surface of the resin layer containing the blowing agent. Therefore, when the inorganic filler is contained in the resin composition for forming the resin layer containing the foaming agent, the above-described 3-layer simultaneous extrusion film formation method is preferable. That is, the above-mentioned occurrence of the fouling can be suppressed by performing the simultaneous extrusion film formation with the resin layer containing the foaming agent sandwiched by the non-foamed resin layer.

After the resin layer containing the foaming agent is formed into a film, electron beam irradiation may be performed. This can crosslink the resin component, thereby adjusting the surface strength, foaming properties, and the like of the foamed resin layer. The energy of the electron beam is preferably about 150 to 250kV, more preferably about 175 to 200 kV. The irradiation dose is preferably about 10 to 100kGy, and more preferably about 10 to 50 kGy. As the electron beam source, a known electron beam irradiation device can be used. In particular, when the ionizing radiation irradiated to the fibrous substrate is an electron beam, the crosslinking of the ionizing radiation crosslinking-type material and the resin crosslinking of the foaming agent-containing resin layer can be simultaneously performed.

After a pattern layer and an undercoat layer are formed in an arbitrary order as required on a resin layer containing a foaming agent, a surface protective layer is formed as required to form a laminated sheet, and then a heat treatment is performed to convert the resin layer containing the foaming agent into a foamed resin layer, thereby obtaining a foamed laminated sheet. Fig. 1 illustrates a layer structure of a laminated sheet in which a non-foamed resin layer B, a resin layer containing a foaming agent, a non-foamed resin layer a, a pattern layer, an undercoat layer, and a surface protective layer are formed in this order on a fibrous substrate. These layers can be laminated by combining printing, coating such as coating, extrusion film formation, and the like, and coating such as printing, coating, and the like can be performed according to a conventional method.

The heat treatment conditions are only required to be conditions under which the foamed resin layer can be formed by decomposition of the thermal decomposition type foaming agent, and the heating temperature is preferably about 210 to 240 ℃, and the heating time is preferably about 25 to 80 seconds. In addition, when the embossed pattern is provided, it is performed by a known technique such as pressing an embossing plate.

Laminated sheet and method of constructing foamed laminated sheet

The laminated sheet and the foamed laminated sheet of the present invention can be applied by applying an adhesive to the surface to be applied and then adhering the adhesive to the surface to be applied, as described above. The surface to be applied of the laminated sheet and the foamed laminated sheet to which the present invention is applied is not particularly limited, and can be applied to various applications required for decoration. That is, the laminated sheet and foamed laminated sheet of the present invention are particularly useful as a wallpaper and/or ceiling material.

The adhesive used for application of the laminated sheet and the foamed laminated sheet of the present invention is not particularly limited, and a common adhesive such as a starch-based adhesive (starch paste, a product in which a synthetic resin is added to starch paste, or the like), a methyl cellulose-based adhesive, or the like can be selected and used depending on the type of the application surface. As described above, the laminated sheet and the foamed laminated sheet of the present invention can be easily remounted by peeling the fibrous base material and the adhesive at the time of remounting even when they are constructed using an adhesive other than a methyl cellulose-based adhesive, for example, a starch-based adhesive which is commonly used in the construction of wall paper and ceiling material, and the fibrous base material is less likely to remain on the surface to be constructed.

The application method of the laminated sheet and the foamed laminated sheet of the present invention is not limited to the above application method, and the application can be performed by a conventional method in which an adhesive is applied to the back surfaces of the laminated sheet and the foamed laminated sheet (back surface of the fibrous substrate) and then the laminated sheet and the foamed laminated sheet are attached to the surface to be applied.

Examples

The present invention will be specifically described below by way of examples and comparative examples. However, the present invention is not limited to the examples.

Example 1

Using 3 kinds of 3-layer multi-manifold type T-die extruders, films were formed in the order of i) the non-foamed resin layer B, ii) the foaming agent-containing resin layer and iii) the non-foamed resin layer a to have thicknesses of 7 μm, 70 μm, and 7 μm. The extrusion conditions were: the cylinder temperature of the resin of the i) layer was 100 ℃, the cylinder temperature of the resin composition of the ii) layer was 120 ℃, and the cylinder temperature of the resin of the iii) layer was 130 ℃. The die temperature was all 120 ℃.

After the film formation, the sheet was impregnated with an ionizing radiation cross-linking material "NK Ester ADCP, manufactured by shinkamura chemical corporation" which was applied from the liner paper side immediately after the lamination of the surface of the layer i) on plain paper liner paper (manufactured by WK-665DO, KJ special paper).

Then, the impregnated ionizing radiation-crosslinkable material was crosslinked by irradiating the layer iii) with an electron beam (200KV, 30kGy) and the resin layer ii) containing at least a foaming agent was crosslinked to prepare a laminated sheet.

Next, a corona discharge treatment is performed on the iii) layer.

Next, an EVA aqueous emulsion was applied as a primer by a gravure printing machine at 2g/m²On the surface of the protective layer, a pattern layer was formed by printing a cloth pattern using an aqueous ink for patterning ("HYDRIC", manufactured by DAY HI KOKAI Co., Ltd.) and an aqueous ink for protective layer ("ALTOPP", manufactured by DAY HI KOKAI Co., Ltd.) by a gravure printing machine, and then the protective layer was continuously formed. Thus, a laminated sheet (unfoamed blank) was obtained, which successively had a fibrous substrate layer (plain paper liner), a non-foamed resin layer B, a resin layer containing a foaming agent, a non-foamed resin layer a, an undercoat layer, a pattern layer, and a protective layer.

Subsequently, the resin layer was heated in a Gill box (220 ℃ C. times.30 seconds) to foam the foaming agent contained in the resin layer containing the foaming agent. Then, a cloth-like uneven embossed pattern is applied to the outermost surface of the foam to produce a foamed laminated sheet (foamed wallpaper).

Each layer was formed using the following ingredients.

i) The non-foamed resin layer B was formed of EVA "EVAFLEX EV150(VA content: 33 wt%), manufactured by Du Pont-mitsui polychemics".

ii) the resin layer containing a foaming agent is formed of a resin composition containing 100 parts by weight of EVA "EVATATE H4011(VA content: 20 wt%), manufactured by sumitomo chemical, 100 parts by weight of calcium carbonate" white H, manufactured by eastern ocean fine chemical, "30 parts by weight of titanium dioxide" CR-63, manufactured by stone industry, "25 parts by weight of foaming agent" VINYFOR AC #3, "4 parts by weight of permanent chemical industry," foaming aid "Efco-ChemZNS-P ADEKA," 4 parts by weight, crosslinking aid "OPSTAR JUA-702, and" 1 part by weight "manufactured by JSR.

iii) the non-foamed resin layer A was formed of an ethylene-methacrylic acid copolymer resin "NUCREL N1560, manufactured by Du Pont-Mitsui Polychemicals".

Comparative example 1

A laminated sheet and a foamed laminated sheet were produced in the same manner as in example 1, except that the inner sheet was not impregnated with the ionizing radiation crosslinking material.

Comparative example 2

A laminated sheet and a foamed laminated sheet were produced in the same manner as in example 1, except that a woolen paper (manufactured by Ahlstrom) made by mixing a pulp with a synthetic fiber was used as the inner liner paper and the inner liner paper was not impregnated with an ionizing radiation crosslinking material.

Test example 1

The adhesion between the resin layer and the inner liner paper was evaluated by peeling the resin layer of the foamed laminated sheet from the inner liner paper in the width direction. The evaluation criteria are as follows.

O: the resin layer carries the fibers of the liner paper throughout the full width.

And (delta): the resin layer is partially provided with fibers of an inner liner paper.

X: the resin layer is completely free of fibers of the interleaf paper.

Test example 2

The foamed laminated sheet was evaluated for elongation in water. Specifically, the foamed laminated sheet was cut into 5cm in the MD and 11cm in the TD, a 10 cm-long mark line as the width in the TD was drawn from the center in the MD, and immersed in water for 1 hour, and the change rate was determined from the difference in mark line length between before and after immersion. The evaluation criteria for elongation in water are as follows.

O: less than 0.6 percent

X: is more than 0.6 percent.

Test example 3

A test piece was prepared by dissolving (1) a methyl cellulose adhesive (available from Methylan Special, Henkel) and (2) a starch adhesive (starch + synthetic resin) (available from Rua Mill, YAYOI Chemical Industry) in water in advance in a predetermined amount to prepare adhesives, applying the adhesives to a gypsum board surface, adhering the inner paper surface of each foamed laminate sheet to the board, and drying the inner paper surface. A25 mm wide cut was made in the test piece, and the cut was peeled off by hand, and the peeled surface was observed. The evaluation criteria are as follows.

O: the lining paper is not left on the plate surface, and peeling occurs between the lining paper and the adhesive.

And (delta): the liner paper remains partially on the adhesive side. The hand feeling is heavy when peeling.

×^※1: the liner paper is peeled off between the sheets, and remains on the base side of the gypsum board.

×^※2: the substrate of the gypsum board is peeled off.

[ Table 1]

Description of the symbols

1. Fibrous substrates

2. Non-foamed resin layer B

3. Resin layer containing foaming agent

4. Non-foamed resin layer A

5. Pattern layer

6. Base coat

7. Surface protective layer

Claims (13)

1. A laminated sheet characterized by:

at least a resin layer is laminated on a fibrous substrate,

the fibrous substrate contains a crosslinked body of an ionizing radiation crosslinking type material.

2. The laminated sheet of claim 1, wherein:

the resin layer is an olefin resin layer.

3. The laminated sheet according to claim 1 or 2, wherein:

the resin layer is a layer containing a foaming agent or a laminate comprising resin layers containing a foaming agent.

4. The laminated sheet of claim 3, wherein:

the resin layer containing a foaming agent has a non-foamed resin layer on one surface or both surfaces.

5. The laminated sheet according to claim 3 or 4, wherein:

the resin layer containing a foaming agent is crosslinked by the resin by electron beam irradiation.

6. A foamed laminated sheet characterized by:

the laminate sheet of any one of claims 3 to 5, which is obtained by foaming a resin layer containing a foaming agent.

7. A method of manufacturing a laminated sheet, comprising:

(1) a step of forming at least a resin layer on a fibrous substrate, and

(2) a step of immersing the ionizing radiation crosslinking material in the fibrous substrate,

after the two steps, at least the fibrous substrate is irradiated with ionizing radiation to crosslink the ionizing radiation crosslinking material to form a crosslinked body.

8. The method of manufacturing a laminated sheet according to claim 7, wherein:

at least the resin layer is formed on the fibrous substrate by extrusion film formation.

9. The method for manufacturing a laminated sheet according to claim 7 or 8, wherein:

the resin layer is a foaming agent-containing resin layer or a laminate comprising foaming agent-containing resin layers, and the ionizing radiation is an electron beam, and the crosslinking of the ionizing radiation-crosslinking material and the resin crosslinking of the foaming agent-containing resin layer are simultaneously performed by irradiating the electron beam.

10. A method for producing a foamed laminated sheet, characterized by comprising:

the foaming agent-containing resin layer of the laminated sheet obtained by the production method according to any one of claims 7 to 9 is foamed by heating the foaming agent-containing resin layer, wherein the resin layer is a foaming agent-containing resin layer or a layer composed of a laminate including a foaming agent-containing resin layer.

11. A construction method is characterized in that:

the laminated sheet or foamed laminated sheet according to any one of claims 1 to 6 is stuck to a surface to be coated with an adhesive.

12. A construction method is characterized in that:

the laminated sheet or foamed laminated sheet according to any one of claims 1 to 6, which is applied with an adhesive on the back side thereof and then adhered to a surface to be treated.

13. The construction method according to claim 11 or 12, wherein:

the constructed surface is a wall surface and/or a ceiling.