JP6539945B2 - Laminated sheet and foam laminated sheet - Google Patents

Description

  The present invention relates to a laminated sheet and a foam laminated sheet. The foam laminate sheet has a foam resin layer, and is useful as foam wallpaper, various decorative materials, and the like. Further, the laminated sheet means a state before foaming of the foamed laminated sheet (so-called unfoamed raw fabric) or means a sheet useful as various decorative materials in a state where it does not have a foamed resin layer.

  Conventionally, a foam laminate sheet in which at least a foam resin layer is provided on a substrate is used as foam wallpaper, various decorative materials, and the like. The foamed resin layer is formed by foaming the foaming agent-containing resin layer, and the foaming agent-containing resin layer is formed by a coating method such as comma coating, a calendar method in which the resin composition is drawn into a sheet and laminated. It is known to form by extrusion film forming using an extruder such as

  Among the above methods for forming the foaming agent-containing resin layer, the extrusion film formation is excellent from the viewpoint of production efficiency, and from the viewpoint of improving the surface strength, the foaming agent-containing resin layer is sandwiched between non-foamed resin layers. The method etc. which three-layer coextrusion film forming is in the state are known. In addition, when performing the three-layer coextrusion film formation, ethylene (non-foamed resin layer A) is laminated on the surface of the foaming agent-containing resin layer opposite to the base, from the viewpoint of further improving the surface strength. It is known to use a (meth) acrylic acid copolymer (see, for example, Patent Document 1).

  However, when the foaming agent-containing resin layer is foamed to form the foamed resin layer, a nonpolar resin such as polyethylene is used for the foaming agent-containing resin layer in order to provide the followability necessary to form the bubbles. There is a problem that the adhesion between the foaming agent-containing resin layer and the non-foaming resin layer A containing an ethylene- (meth) acrylic acid copolymer which is a polar resin is lowered. Therefore, when the foaming agent-containing resin layer is foamed to form the foamed resin layer, air bubbles are generated between the foamed resin layer and the non-foamed resin layer A, and the non-foamed resin layer A partially floats. There is a problem of becoming a state.

  When the foamed laminate sheet formed as described above is embossed, the portion where the non-foamed resin layer A floats is stretched, and the surface of the foamed laminate sheet reflects light in a scaly shape. There is a problem that the designability is reduced. Furthermore, since the non-foamed resin layer A is easily detached from the part where the non-foamed resin layer A floats, there is a problem that it becomes a quality defect part.

  Moreover, the part in which the non-foamed resin layer A floated is easy to be damaged when it rubs, and there exists a problem that it is inferior to scratch resistance.

  Furthermore, in order to improve the adhesion between the foaming agent-containing resin layer and the non-foaming resin layer A, when the ethylene- (meth) acrylic acid copolymer is used for the foaming agent-containing resin layer, the foaming agent-containing resin layer is hard. And it is difficult to form bubbles.

  Therefore, scaly peeling between the foamed resin layer of the foamed laminate sheet and the non-foamed resin layer A is suppressed by the excellent adhesion between the foaming agent-containing resin layer of the laminated sheet and the non-foamed resin layer A. There is a demand for development of new laminated sheets and foamed laminated sheets excellent in scratch resistance.

JP 2007-55229 A

  An object of the present invention is to provide a laminated sheet and a foamed laminated sheet which are suppressed in scaly peeling between the foamed resin layer of the foamed laminated sheet and the non-foamed resin layer A and are also excellent in scratch resistance.

  As a result of intensive studies to achieve the above object, the present inventor has found that, in a laminate sheet in which at least a foaming agent-containing resin layer and a non-foamed resin layer A are laminated in this order on a substrate, the non-foamed resin layer It has been found that the above object can be achieved by the structure that A contains a polar resin and the foaming agent-containing resin layer contains a polyolefin resin and a specific resin and / or a specific wax. It came to complete.

That is, the present invention relates to the following laminate sheet and foam laminate sheet.
1. It is a lamination sheet in which at least a foaming agent-containing resin layer and a non-foaming resin layer A are laminated in this order on a substrate,
(1) The non-foamed resin layer A contains a polar resin,
(2) The foaming agent-containing resin layer comprises a polyolefin resin and the following components (a) and / or (b):
(A) a resin having a carboxyl group and / or a carboxylic acid anhydride group;
(B) a wax having a carboxyl group and / or a carboxylic acid anhydride group;
And contains
Laminated sheet characterized by
2. The lamination according to claim 1, wherein the total content of the component (a) and the component (b) in the foaming agent-containing resin layer is 2 to 20 parts by mass with respect to 100 parts by mass of the polyolefin resin Sheet.
3. The component (a) is selected from copolymers containing an olefin and (meth) acrylic acid and / or maleic anhydride as monomer components, and a polyolefin resin modified with (meth) acrylic acid and / or maleic anhydride 3. The laminated sheet according to item 1 or 2, which is at least one selected from the group consisting of
4. The laminated sheet according to any one of Items 1 to 3, wherein the component (b) is a modified wax with (meth) acrylic acid and / or maleic anhydride.
5. The laminated sheet according to any one of Items 1 to 4, wherein the foaming agent-containing resin layer has a non-foamed resin layer B on the surface opposite to the surface on which the non-foamed resin layer A is formed.
6. The laminated sheet according to any one of Items 1 to 5, wherein the polar resin contained in the non-foamed resin layer A is an ethylene- (meth) acrylic acid copolymer.
7. 7. A foam laminate sheet obtained by foaming the foaming agent-containing resin layer of the laminate sheet according to any one of Items 1 to 6.
8. 8. The foam laminate sheet according to item 7 above, which is embossed from above the outermost surface layer.

  Hereinafter, the laminate sheet and the foam laminate sheet of the present invention will be described in detail.

«Laminated sheet»
The laminated sheet of the present invention is a laminated sheet in which at least a foaming agent-containing resin layer and a non-foaming resin layer A are laminated in this order on a substrate, and (1) the non-foaming resin layer A is a polar resin (2) The foaming agent-containing resin layer contains a polyolefin resin and the following (a) component and / or (b) component:
(A) a resin having a carboxyl group and / or a carboxylic acid anhydride group;
(B) a wax having a carboxyl group and / or a carboxylic acid anhydride group;
And containing.

  Since the non-foamed resin layer A contains a polar resin, the laminate sheet of the present invention having the above characteristics is excellent in scratch resistance. In addition, since the foaming agent-containing resin layer contains the polyolefin resin and the (a) component and / or the (b) component, the foaming agent-containing resin layer exhibits sufficient follow-up property to form bubbles. And excellent in adhesion to the non-foamed resin layer A. For this reason, in the foam laminate sheet obtained by foaming the laminate sheet of the present invention, the occurrence of scaly peeling between the non-foam resin layer A and the foam resin layer is suppressed, and excellent scratch resistance Can be shown.

  Hereinafter, the layer configuration of the laminated sheet and the foamed laminated sheet of the present invention will be described. In the following, the direction in which the foaming agent-containing resin layer and the non-foamed resin layer A are laminated is referred to as "upper" or It is referred to as "front side" and the opposite direction as viewed from the substrate is referred to as "bottom" or "back side".

The base material is not limited, and a known fibrous sheet (backing paper) can be used.
Specifically, general paper for wallpaper (sheet obtained by pulp-based sheet size treatment with known sizing agent); Flame-retardant sheet (paper sheet containing pulp-based sheet treated with flame retardant such as guanidine guanidine guanidine, phosphate guanidinium) Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; Fine paper; Thin paper and the like. The fibrous sheets used in the present invention also include those which fall under the category of nonwoven fabrics.

Although the basis weight of the substrate is not critical, preferably about 50 to 300 g / ^{m 2,} about 50~130g / ^{m 2} is more preferable.

Foaming Agent-Containing Resin Layer In the laminated sheet of the present invention, at least the foaming agent-containing resin layer is laminated on a substrate. The foaming agent-containing resin layer can be formed by a known film forming method such as a T-die film forming method or a calendar film forming method.

  The foaming agent-containing resin layer comprises a polyolefin resin and the following components (a) and / or (b): (a) a resin having a carboxyl group and / or a carboxylic acid anhydride group; (b) a carboxyl group and / or a carboxylic acid And a wax having an acid anhydride group. In the present specification, the polyolefin resin means a polymer using an olefin as a monomer.

  As said polyolefin resin, the polyolefin resin conventionally used for the lamination sheet as a wall covering material etc. can be widely adopted, and polyethylene, a polypropylene, a polybutylene, etc. are mentioned concretely. Among these, it is preferable to use polyethylene.

  As polyethylene, any of 1) homopolymers of ethylene and 2) copolymers of ethylene and α-olefins (ethylene-α-olefin copolymers) can be used. As the polyethylene, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and the like can be widely used. Among these, low density polyethylene is preferable.

  Component (a) is a resin having a carboxyl group and / or a carboxylic acid anhydride group. The component (a) is not particularly limited as long as it is a resin having at least one of a carboxyl group and a carboxylic acid anhydride group, and a monomer component having at least one of a carboxyl group and a carboxylic acid anhydride group as a functional group And resins modified with at least one of carboxylic acid and carboxylic acid anhydride. In the present invention, from the viewpoint of improving the compatibility with the polyolefin resin in the foaming agent-containing resin layer, the component (a) contains an olefin and (meth) acrylic acid and / or maleic anhydride as a monomer component. It is preferable to use a copolymer or a polyolefin resin modified with (meth) acrylic acid and / or maleic anhydride, and it is more preferable to use a copolymer containing an olefin and maleic anhydride as a monomer component. Moreover, ethylene, propylene, butylene etc. are mentioned as said olefin, Especially, ethylene is preferable. In the copolymer containing (meth) acrylic acid and / or maleic anhydride as a monomer component, the monomer component may constitute a main chain or may constitute a graft chain. In the present specification, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and other similar expressions are also the same.

  Specific examples of the component (a) include ethylene- (meth) acrylic acid copolymer, ethylene-maleic anhydride copolymer, propylene- (meth) acrylic acid copolymer, propylene-maleic anhydride copolymer, Ethylene- (meth) acrylic acid- (meth) acrylic acid methyl copolymer, ethylene-maleic anhydride- (meth) acrylic acid methyl copolymer, ethylene-propylene- (meth) acrylic acid copolymer, ethylene-propylene -Copolymers such as maleic anhydride copolymer, acid modified resins such as (meth) acrylic acid modified polyethylene, maleic anhydride modified polyethylene, (meth) acrylic acid modified polypropylene, and maleic anhydride modified polypropylene. As the component (a), these resins may be used alone or in combination of two or more.

  1-15 mass parts is preferable with respect to 100 mass parts of said polyolefin resin, and, as for content of (a) component in a foaming agent containing resin layer, 2-10 mass parts is more preferable.

  The component (a) preferably has a weight average molecular weight (Mw) of 10,000 to 200,000, and more preferably 10,000 to 100,000. The weight average molecular weight defined in the present invention is a value measured by GPC (gel permeation chromatography).

  The component (a) preferably has a MFR (melt flow rate) of 1 to 30 g / 10 min measured under the conditions of 190 ° C. and 21.18 N load described in JIS K 6922, and is 2 to 20. More preferable.

  The component (b) is a wax having a carboxyl group and / or a carboxylic acid anhydride group. The component (b) is not particularly limited as long as it is a wax having at least one of a carboxyl group and a carboxylic acid anhydride group, and a wax modified with at least one of a carboxylic acid and a carboxylic acid anhydride may be mentioned . In the present invention, as the component (b), it is preferable to use a modified wax with at least one of (meth) acrylic acid and / or maleic anhydride, and among them, using a modified wax with maleic anhydride has a melting point and extrusion It is more preferable because it is suitable for extrusion film formation from the viewpoint of torque reduction. The wax modified with at least one of carboxylic acid and carboxylic acid anhydride is not particularly limited, and paraffin wax, polyethylene wax, polypropylene wax and the like can be used. Among them, polyethylene wax is preferable.

  Specific examples of the component (b) include (meth) acrylic acid modified paraffin wax, maleic anhydride modified paraffin wax, (meth) acrylic acid modified polyethylene wax, maleic anhydride modified polyethylene wax, and (meth) acrylic acid modified polypropylene wax And maleic anhydride-modified polypropylene wax. As the component (b), these waxes may be used alone or in combination of two or more.

  The content of the component (b) in the foaming agent-containing resin layer is preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, with respect to 100 parts by mass of the polyolefin resin.

  The component (b) preferably has a weight average molecular weight (Mw) of 1,000 to 10,000, and more preferably 1,500 to 5,000.

  The wax having a carboxyl group and / or a carboxylic acid anhydride group which is the component (b) is a resin having a carboxyl group and / or a carboxylic acid anhydride group which is the component (a) and has a MFR and a weight average It is distinguished by molecular weight. That is, the wax having a carboxyl group and / or a carboxylic acid anhydride group which is the component (b) has an extremely low molecular weight, and the component (b) has such a high fluidity that the MFR can not be measured. For this reason, the resin having a carboxyl group and / or a carboxylic acid anhydride group used as the component (a) and a wax having a carboxyl group and / or a carboxylic acid anhydride group used as the component (b) are different from each other Is shown.

  In the present invention, the resin component (a resin component obtained by mixing the polyolefin resin and the (a) component and / or the (b) component) contained in the foaming agent-containing resin layer resin layer depends on the film forming method, but the JIS It is preferable that MFR (melt flow rate) measured on the conditions of 190 degreeC of K 6922 and load 21.18N is 10-25 g / 10min. When the MFR is within the above range, the temperature rise upon forming the foaming agent-containing resin layer by extrusion film formation is small, and film formation can be performed in a non-foamed state, so when forming a patterned layer later Print processing can be performed on a flat surface and there is little pattern omission and the like. If the MFR is too large, the resin may be too soft, which may result in insufficient scratch resistance of the formed foaming agent-containing resin layer.

  The laminated sheet of the present invention is a so-called unfoamed original fabric having a foaming agent-containing resin layer. The foamed laminate sheet of the present invention is obtained by foaming the foaming agent-containing resin layer.

  As a resin composition which forms a foaming agent containing resin layer, the resin composition which contains the above-mentioned resin ingredient, an inorganic filler, a pigment, a thermal decomposition type foaming agent, a foaming auxiliary agent, a crosslinking auxiliary agent etc. can be used conveniently, for example . In addition, stabilizers, lubricants and the like can be used as additives.

  Examples of the thermal decomposition type foaming agent include azo-based compounds such as azodicarbonamide (ADCA) and azobisformamide; and hydrazide-based compounds such as oxybenzene sulfonyl hydrazide (OBSH) and para-toluenesulfonyl hydrazide. The content of the thermal decomposition-type foaming agent can be appropriately set according to the type of the foaming agent, the expansion ratio and the like. From the viewpoint of the expansion ratio, it is about 6 times or more, preferably about 7 to 10 times, and the thermal decomposition type foaming agent is preferably about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

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

  In addition, when using these (meth) acrylic-acid containing resin and the ADCA foaming agent in combination with these foaming adjuvants and (a) resin, in the foaming process, (meth) acrylic of (meth) acrylic-acid containing resin There is a possibility that the effect as a foaming auxiliary may be impaired by reaction of an acid part and a metal type foaming auxiliary. Therefore, when using a (meth) acrylic acid-containing resin and an ADCA foaming agent in combination, it is preferable to use a carboxylic acid hydrazide compound as a foaming aid, as described in JP-A-2009-197219. At this time, 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 agents.

  Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including the inorganic filler, the effect of suppressing the blindness, the effect of improving the surface characteristics, the effect of suppressing heat generation during combustion and the like can be obtained. The content of the inorganic filler is preferably about 0 to 100 parts by mass, and more preferably about 5 to 70 parts by mass with respect to 100 parts by mass of the resin component.

  As the inorganic pigment, for example, titanium oxide, zinc flower, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chromium titanium yellow, iron oxide Cadmium red, ultramarine blue, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, mica titanium, zinc sulfide and the like. In addition, as organic pigments, for example, aniline black, perylene black, azo type (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavanthrone, anthrapyrimidine, anthraquinone, quinacridone) And perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine) and the like. The content of the pigment is preferably about 10 to 50 parts by mass, and more preferably about 15 to 30 parts by mass with respect to 100 parts by mass of the resin component, although it depends on the required color tone concentration.

  In the present invention, the foaming agent-containing resin layer may be resin-crosslinked by electron beam irradiation. As a method of irradiating an electron beam to a foaming agent containing resin layer, and a method of making it foam, it may carry out according to the method described in the manufacturing method of a postscript.

  In the present invention, the foaming agent-containing resin layer may be a layer which forms a pattern separately from the pattern layer to be described later. The pigment and resin to be used are the same as those which can be used for the picture pattern layer described later.

  The thickness of the foaming agent-containing resin layer is preferably about 40 to 200 μm, and the thickness of the foamed resin layer after foaming in the case of the foaming agent-containing resin layer is preferably about 300 to 1000 μm.

  2-20 mass parts is preferable with respect to 100 mass parts of polyolefin resin, and, as for the sum total of content of (a) component and (b) component in a foaming agent containing resin layer, 2.5-10 mass parts is more preferable. If the total content of the components (a) and (b) is too large, the foaming agent-containing resin layer may become hard and it may be difficult to form air bubbles, and if it is too small, the surface strength of the laminated sheet may be inferior There is.

Non-foamed resin layer A
A non-foamed resin layer A is formed on the upper surface of the foaming agent-containing resin layer for the purpose of sharpening the design pattern when forming the design pattern layer or improving the scratch resistance of the foamed resin layer.

  The non-foamed resin layer A contains a polar resin. Examples of the polar resin include polyolefin resins exhibiting a polarity, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, and fluorine resins. Among these, polyolefin resins showing polarity are preferable.

  Examples of polyolefin resins having polarity include ethylene-acrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid copolymers, etc. 2.) At least one of acrylic acid copolymer, ethylene-vinyl acetate copolymer (EVA), saponified ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ionomer and the like can be mentioned. Among these, ethylene- (meth) acrylic acid copolymers are preferable in that they are excellent in scratch resistance, excellent in adhesion to the above-mentioned foaming agent-containing resin layer, and excellent in suppression of scaly peeling.

  The content of the polar resin in the non-foamed resin layer A is preferably 70 to 100% by mass, and more preferably 80 to 100% by mass, based on 100% by mass of the non-foamed resin layer A. By setting the content of the polar resin in the above range, the non-foamed resin layer A can exhibit excellent scratch resistance.

  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.

Non-foamed resin layer B
The back surface of the foaming agent-containing resin layer (the surface on which the base material is laminated) may have a non-foaming resin layer B (adhesive resin layer) for the purpose of improving the adhesion to the base material.

  The resin component of the adhesive resin layer is not particularly limited, but ethylene-vinyl acetate copolymer (EVA) is preferable. EVA can use a well-known or commercially available thing. In particular, one having 10 to 46% by mass of the vinyl acetate component (VA component) is preferable, and one having 15 to 41% by mass is more preferable.

  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.

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

Pattern-patterned layer The laminate sheet of the present invention may have a pattern-patterned layer formed on the foaming agent-containing resin layer, the non-foamed resin layer A, or the primer layer or film layer described later, if necessary.

  A picture pattern layer gives design to a laminate sheet and a foam laminate sheet. Examples of the pattern include wood grain patterns, stone patterns, grain patterns, tile patterns, brickwork patterns, grain patterns, skin patterns, geometric figures, characters, symbols, abstract patterns, flower patterns, etc. It can be selected according to the purpose.

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

  As a coloring agent, a pigment which is used by the above-mentioned foaming agent containing resin layer can be used suitably, for example.

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

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

  The thickness of the pattern layer is different from that of the pattern, but in general, it is preferably about 0.1 to 10 μm.

Primer Layer The primer layer may be formed on the non-foamed resin layer A, the pattern pattern layer, or a film layer described later, if necessary. By forming the primer layer, the adhesion between each layer can be improved.

  As the resin contained in the primer layer, for example, acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, etc. can be used, but in particular, acrylic, chlorinated polypropylene, etc. Is desirable.

  As the acrylic, for example, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate-(meth) acrylate (Meth) such as butyl copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-(meth) acrylic acid methyl copolymer, styrene-methyl (meth) acrylic acid copolymer The acrylic resin which consists of a homopolymer or copolymer containing acrylic ester is mentioned.

  The polyurethane is a composition containing a polyol (polyhydric alcohol) as a main ingredient and an isocyanate as a crosslinking agent (curing agent).

  As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.

  Further, as the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, an aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate, or an aliphatic (or alicyclic) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. ) Isocyanate is used.

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

A film layer may be formed on the film layer non-foamed resin layer A or the pattern layer as required. Although the position which forms a film layer is not limited, when forming a pattern layer, it is preferable to form in the upper surface of a pattern layer. By providing the film layer, the foaming agent-containing resin layer (foamed resin layer) and the pattern layer can be protected, and the surface physical properties of the laminated sheet can be further improved. Also, the adhesion between each layer can be improved.

  When a film layer is a transparency resin layer, as resin which can be used for a film layer, if transparent, it may be colored. When the transparent resin layer is formed on the front surface of the pattern layer, it may be translucent within the range in which the pattern layer can be visually recognized.

  The film layer is preferably a layer containing polyethylene and / or ethylene copolymer. As polyethylene and / or ethylene copolymer, copolymer of ethylene and α-olefin having 4 or more carbon atoms (linear low density polyethylene), ethylene- (meth) acrylic acid copolymer, ethylene-methyl (meth) acrylate Copolymer, ethylene (meth) acrylic acid copolymer such as ethylene-ethyl (meth) acrylate copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH), ethylene -A vinyl acetate copolymer saponified thing, an ionomer, etc. are mentioned, However, In this invention, it is preferable to use an ethylene-vinyl alcohol copolymer especially.

  Although the thickness of a film layer is not specifically limited, Generally, about 3-30 micrometers is preferable, and about 5-20 micrometers is more preferable.

Surface Protective Layer The surface of the non-foamed resin layer A, the pattern layer, the primer layer, or the film layer may have a surface protective layer for the purpose of gloss control and / or protection of the pattern layer.

  The type of surface protective layer is not limited. If it is a surface protection layer for the purpose of gloss adjustment, there is, for example, a surface protection layer containing a known filler such as silica. As a method of forming the surface protective layer, a known method such as gravure printing can be adopted.

  In the case of forming a surface protective layer for the purpose of surface strength (scratch resistance etc.) of the laminated sheet, stain resistance, protection of the pattern pattern layer, etc., one containing an ionizing radiation curable resin as a resin component is preferred. is there. As the ionizing radiation curable resin, those which undergo radical polymerization (curing) by electron beam irradiation are preferable. The thickness of the surface protective layer is not limited, but preferably about 0.1 to 15 μm.

The front surface of the embossed laminated sheet or the foam laminated sheet may be embossed. In this case, it may be embossed from the outermost surface layer (opposite to the substrate). Embossing can be carried out by a known means such as pressing of an embossing plate. For example, when the outermost surface layer is a surface protective layer, a desired embossed pattern can be shaped by pressing the embossed plate after heat softening the front surface. Examples of the emboss pattern include wood grain channel grooves, stone surface irregularities, cloth surface texture, satin, grain, hair lines, geometric patterns, cross streaks, contour patterns, and the like.

«Foamed laminated sheet»
The foam laminate sheet of the present invention is obtained by foaming the foaming agent-containing resin layer of the laminate sheet. The heating condition at the time of foaming is not limited as long as the foamed resin layer is formed by the decomposition of the thermal decomposition type foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds. The expansion ratio of the foamed resin layer is preferably 6 times or more, and more preferably about 7 to 10 times. By setting the expansion ratio in the above-mentioned range, the amount of resin used can be reduced, cost reduction can be achieved, and the non-combustibility of the foam laminate sheet can be enhanced.

«Production method of laminated sheet and foam laminated sheet»
The method for producing the laminated sheet is not particularly limited, but for example, it is a method for producing a laminated sheet having a step of laminating at least a foaming agent-containing resin layer and a non-foamed resin layer A on a substrate,
(1) The non-foamed resin layer A contains a polar resin,
(2) The foaming agent-containing resin layer comprises a polyolefin resin and the following (a) component and / or (b) component:
(A) a resin having a carboxyl group and / or a carboxylic acid anhydride group;
(B) a wax having a carboxyl group and / or a carboxylic acid anhydride group;
And contains
The manufacturing method of the lamination sheet characterized by the above is mentioned.

  Although it does not specifically limit as a manufacturing method of a foaming lamination sheet, The foaming agent containing resin layer of the said lamination sheet is made to foam by heating, The manufacturing method of the foaming lamination sheet characterized by the above-mentioned is mentioned.

  When forming non-foamed resin layer A on one side of the foaming agent-containing resin layer, or when forming non-foamed resin layers A and B on both sides of the foaming agent-containing resin layer, coextrusion film formation by T-die extruder Is preferred. For example, in the case where non-foamed resin layers are formed on both sides, a multi-manifold type T-die capable of simultaneously forming three layers can be used by simultaneously extruding molten resins corresponding to the three layers.

  In addition, it is a case where an inorganic filler is contained in the resin composition which forms a foaming agent containing resin layer, Comprising: When forming a foaming agent containing resin layer by extrusion film forming, the extrusion port (so-called dice | dies) of an extruder Residues of the inorganic filler (so-called "eye marks") tend to be generated, which are likely to become foreign matter on the surface of the foaming agent-containing resin layer. Therefore, when an inorganic filler is contained in the resin composition which forms a foaming agent containing resin layer, it is preferable to carry out three-layer simultaneous extrusion film forming as mentioned above. That is, the coextrusion film formation is carried out in a mode in which the foaming agent-containing resin layer is sandwiched by the non-foaming resin layer, whereby the generation of the above-mentioned pores can be suppressed.

  After forming the foaming agent-containing resin layer, electron beam irradiation may be performed. Thereby, the resin component can be crosslinked to adjust the surface strength, the foaming property and the like of the foamed resin layer. The energy of the electron beam is preferably about 150 to 250 kV, and more preferably about 175 to 200 kV. The irradiation dose is preferably about 10 to 100 kGy, and more preferably about 10 to 50 kGy. A well-known electron beam irradiation apparatus can be used as an electron beam source.

  A pattern pattern layer, a film layer and a primer layer are formed in any order on the foaming agent-containing resin layer, if necessary, and a surface protection layer is formed as needed to form a laminated sheet, and then heat treatment is carried out. By forming the foaming agent-containing resin layer into a foamed resin layer, a foamed laminate sheet can be obtained. FIG. 1 illustrates the layer configuration of a laminated sheet in which a non-foamed resin layer B, a foaming agent-containing resin layer, a non-foamed resin layer A, a design pattern layer, a primer layer and a surface protective layer are sequentially stacked on a substrate. These layers can be laminated by combining coating such as printing and coating, extrusion film forming and the like, and coating such as printing and coating can be performed according to a conventional method.

  The heat treatment conditions may be such that the foamed resin layer is formed by the decomposition of the thermal decomposition type foaming agent, the heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds. Moreover, when attaching an embossing pattern, it implements by well-known means, such as a press of an embossing plate.

The laminate sheet of the present invention is scratch resistant because the non-foamed resin layer A contains a polar resin in a layer configuration in which at least a foaming agent-containing resin layer and a non-foamed resin layer A are laminated in this order on a substrate. Excellent. Further, the foaming agent-containing resin layer comprises a polyolefin resin and the following (a) component // or (b) component:
(A) a resin having a carboxyl group and / or a carboxylic acid anhydride group;
(B) a wax having a carboxyl group and / or a carboxylic acid anhydride group;
And. Therefore, the foaming agent-containing resin layer can exhibit sufficient followability to form air bubbles, and is excellent in adhesion to the non-foamed resin layer A. Thereby, in the foam laminate sheet obtained by foaming the laminate sheet of the present invention, the occurrence of scaly peeling between the non-foam resin layer A and the foam resin layer is suppressed, and excellent scratch resistance Can be shown.

It is a schematic diagram which shows an example of the laminated constitution of the lamination sheet of this invention.

  Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples. However, the present invention is not limited to the examples.

(Preparation of blowing agent-containing resin layer)
The resin composition prepared according to the composition of Table 1 is kneaded using a laboplast mill (manufactured by HAAKE) at a temperature of 110 ° C., a rotor revolution number of 50 rpm, and a kneading time of 10 minutes to form a foaming agent-containing resin layer A resin composition was obtained.

  The resin composition for forming the obtained foaming agent-containing resin layer was press-molded to a thickness of 80 μm to prepare a foaming agent-containing resin layer.

(Preparation of non-foamed resin layers A and B)
The resin composition shown in Table 2 is laminated on the surface of the foaming agent-containing resin layer with a thickness of 5 μm, and the non-foaming resin layer A, the foaming agent-containing resin layer, and the non-foaming resin layer B are laminated in this order The obtained flat membrane resin sheet was obtained.

The obtained flat-film-like resin sheet was laminated on a 65 g / m ² backing paper (WK-665: made of KJ special paper). This state is referred to as a raw fabric α.

  Next, electron beam irradiation (195 KV 30 KGy) was performed from the non-foamed resin layer A side of the raw fabric α to prepare a laminated sheet.

  Finally, it was introduced into a gear oven heated to 220 ° C. for 35 seconds to foam the foaming agent-containing resin layer to form a foamed resin layer, thereby preparing a foam laminate sheet.

Test Example 1 (scale-like peeling evaluation test)
The state of the surface of the foam laminate sheet produced in Examples and Comparative Examples was visually observed to evaluate the presence or absence of scaly peeling.

Test Example 2 (Scratch Resistance Test)
About the foam lamination sheet produced by the Example and the comparative example, it tested according to the performance evaluation method of the surface-reinforced wallpaper established by the Wallpaper Industry Association, and was evaluated based on the following evaluation criteria.
○: There was no change in the surface.
Δ: Only the surface was damaged.
X: The scratch reached to the foamed resin layer.

  The results of Test Example 1 and Test Example 2 are shown in Table 3.

1. Base material 2. Non-foamed resin layer B
3. Foaming agent-containing resin layer4. Non-foamed resin layer A
5. Pattern layer 6. Primer layer7. Surface protection layer

Claims (7)

It is a lamination sheet in which at least a foaming agent-containing resin layer and a non-foaming resin layer A are laminated in this order on a substrate,
(1) The non-foamed resin layer A contains a polar resin,
(2) The foaming agent-containing resin layer comprises a polyolefin resin and the following (a) component and / or (b) component:
(A) a resin having a carboxyl group and / or a carboxylic acid anhydride group;
(B) a wax having a carboxyl group and / or a carboxylic acid anhydride group;
Contains and
The total of the blowing agent-containing resin layer (a) component and the content of the component (b), Ri 2-10 parts by der respect to the polyolefin resin 100 parts by weight,
The polar resin contained in the non-foamed resin layer A is ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate copolymer saponified product, ethylene- At least one member selected from the group consisting of vinyl alcohol copolymers and ionomers,
The content of the polar resin in the non-foamed resin layer A is 70 to 100% by mass, based on 100% by mass of the non-foamed resin layer A.
Laminated sheet characterized by The component (a) is selected from copolymers containing an olefin and (meth) acrylic acid and / or maleic anhydride as monomer components, and a polyolefin resin modified with (meth) acrylic acid and / or maleic anhydride The laminated sheet according to claim 1, which is at least one selected from the group consisting of Wherein component (b), (meth) modified wax by acrylic acid and / or maleic anhydride, the laminated sheet according to claim 1 or 2. The laminated sheet according to any one of claims 1 to 3 , wherein the foaming agent-containing resin layer has a non-foamed resin layer B on the surface opposite to the surface on which the non-foamed resin layer A is formed. The laminated sheet according to any one of claims 1 to 4 , wherein the polar resin contained in the non-foamed resin layer A is an ethylene- (meth) acrylic acid copolymer. A foamed laminated sheet obtained by foaming the foaming agent-containing resin layer of the laminated sheet according to any one of claims 1 to 5 . The foamed laminated sheet according to claim 6 , wherein the top surface layer is embossed.

Images