JP2019064082A - Foam laminated sheet and laminated sheet - Google Patents

Abstract

To provide a foam laminated sheet having good curl resistance, and a laminated sheet for forming the same.SOLUTION: A foam laminated sheet 10 has at least a fibrous base material 1 and a foam resin layer 2 arranged on one surface side of the fibrous base material 1, where the foam resin layer 2 contains a resin component and a water absorptive component, and the water absorptive component contains a nonion type crosslinked polyalkylene oxide as a main component. In the foam laminated sheet 10, the nonion type crosslinked polyalkylene oxide is a crosslinked object obtained by crosslinking the polyalkylene oxide, and accordingly has water absorption ability higher than that of a non-crosslinked object.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a foam laminate sheet used for wallpaper and the like, and a laminate sheet for forming the same.

  As a foam wallpaper and various decorative materials, a foam laminate sheet in which a foam resin layer is provided on a fibrous base material such as backing paper is used. The foam laminate sheet is obtained by foaming the foaming agent-containing resin layer using a laminate sheet provided with a foaming agent-containing resin layer containing a foaming agent on the fibrous base material. That is, the said lamination sheet is the state before foaming of the said foaming lamination sheet, and what is called a non-foaming original fabric is meant.

  As the foam laminate sheet, a PVC-based foam laminate sheet having a foam resin layer of vinyl chloride (PVC) resin is the mainstream. Further, in recent years, from the viewpoint of environmental consideration, development of a foam laminate sheet having a foamed resin layer of non-chlorine thermoplastic resin in place of PVC resin has also been promoted (Patent Documents 1 to 2 and the like).

JP 2005-120487 A JP 2012-213939 A JP 2005-82894 A

  By the way, when used as foam wallpaper, for example, a foam laminate sheet is pasted to a wall with water-based glue at the time of construction. At this time, the foamed laminate sheet to which the water-based paste is applied absorbs the moisture in the water-based paste, so that the entire sheet is rolled up and is easily curled largely, and there is a problem that the handling is difficult.

  One of the causes of the curling of the foam laminate sheet is an increase in the difference in volume expansion between the fibrous base material and the foam resin layer due to the hydrophobicity of the resin constituting the foam resin layer. When a water-based paste is applied to the fibrous base material surface of the foam laminate sheet, the fibrous base material absorbs the moisture in the paste and tends to swell. On the other hand, if the hydrophobicity of the resin constituting the foamed resin layer is high, the moisture absorbed by the fibrous base material is less likely to transfer to the foamed resin layer, and the foamed resin layer is less likely to swell due to water absorption. For this reason, when the foamed laminate sheet has a large difference in volumetric expansion between the fibrous base material and the foamed resin layer, it is likely to be largely curled by the stress generated inside due to the increase in the volumetric expansion difference. It is guessed.

  As a method of improving the curl resistance of a foaming lamination sheet, there is a method of reducing crystallinity of resin which constitutes a foaming resin layer, for example. However, depending on the type of resin, it is difficult to adopt the above method because it is difficult to increase the proportion of the copolymer component. Moreover, in general, a layer using a resin with low crystallinity is softened to reduce surface strength, so that even if the resistance to curling of the foam laminate sheet becomes good, scratch resistance decreases and other physical properties are affected. There is a problem that occurs.

  In addition, as another method for improving the curl resistance of the foam laminate sheet, for example, in Patent Document 3, measurement is made by (Wet tensile strength in the longitudinal direction) / (Wet tensile strength in the transverse direction) specified in JIS standards. The method of using the backing paper dried and printed using a Yankee dryer is disclosed. However, this method limits the applicable fibrous base material.

  The present invention has been made in view of the above situation, and provides a foam laminate sheet having good curl resistance, and a laminate sheet for forming the same.

  The present invention comprises at least a fibrous base material and a foamed resin layer disposed on one surface side of the fibrous base material, and the foamed resin layer contains a resin component and a water absorbing component, Provided is a foam laminate sheet, wherein the water absorbing component contains a nonionic cross-linked polyalkylene oxide as a main component.

  According to the present invention, since the nonionic crosslinked polyalkylene oxide is a crosslinked product obtained by crosslinking a polyalkylene oxide, it can have a higher water absorbing ability than a non-crosslinked product. In addition, since the polyalkylene oxide constituting the nonionic crosslinked polyalkylene oxide has thermoplasticity, it is easily compatible with the resin component contained in the foamed resin layer, and the nonionic crosslinked polyalkylene oxide is uniformly dispersed in the foamed resin layer. Can be dispersed and compounded. Therefore, for example, the moisture absorbed by the fibrous base material by the application of the aqueous paste is transferred to the foamed resin layer, and the moisture is absorbed by the nonionic crosslinked polyalkylene oxide, whereby the hydrophilicity or hydrophobicity of the resin is obtained. Regardless of this, it becomes possible to swell the entire foamed resin layer uniformly. As a result, the foamed resin layer can follow the swelling of the fibrous base material, and the difference in volumetric expansion coefficient between the fibrous base material and the foamed resin layer can be reduced, so that curling occurs. Can be suppressed, and a curling resistance can be made into a favorable foam lamination sheet.

  In the said invention, it is preferable that nonionic type bridge | crosslinking polyalkylene oxide is a compound which has a urethane bond in a molecule | numerator.

  In the said invention, it is preferable that content of the said water absorbing component is 5 mass parts or more and 30 mass parts or less with respect to 100 mass parts of said resin components. This is because the foamed resin layer is uniformly swollen, and the occurrence of curling can be sufficiently suppressed.

  In the said invention, it is preferable to have the non-foamed resin layer A in the surface on the opposite side to the surface at the side of the said fibrous base material of the said foamed resin layer. It is because the surface strength of the said foaming resin layer can be raised because the said non-foaming resin layer A has a surface protection function.

  In the said invention, it is preferable to have the non-foamed resin layer B in the surface at the side of the said fibrous base material of the said foamed resin layer. It is because the adhesiveness of the said foamed resin layer and the said fiber base material can be improved because the said non-foamed resin layer B has an adhesive function.

  Furthermore, the present invention comprises at least a fibrous base material and a foaming agent-containing resin layer disposed on one surface side of the fibrous base material, and the foaming agent-containing resin layer comprises a resin component and a water absorbing property. Provided is a laminated sheet comprising a component and a foaming agent, and the water absorbing component is mainly composed of a nonionic crosslinked polyalkylene oxide.

  According to the present invention, since the nonionic crosslinked polyalkylene oxide contained in the above-mentioned foaming agent-containing resin layer is a crosslinked product in which a polyalkylene oxide is crosslinked, it can have higher water absorbing ability than a non-crosslinked product. In addition, since the polyalkylene oxide constituting the nonionic crosslinked polyalkylene oxide has thermoplasticity, it is easily compatible with the resin component contained in the foaming agent-containing resin layer, and in the foaming agent-containing resin layer, nonionic crosslinked poly Alkylene oxide can be uniformly dispersed and complexed. For this reason, the laminate sheet of the present invention can be made to foam the above-mentioned foaming agent-containing resin layer to form a foam resin layer capable of swelling uniformly throughout the layer, and to form a foam laminate sheet having good curl resistance. Can.

  In the above invention, the nonionic crosslinked polyalkylene oxide is preferably a compound having a urethane bond in the molecule.

  In the said invention, it is preferable that content of the said water absorbing component is 5 mass parts or more and 30 mass parts or less with respect to 100 mass parts of said resin components. This is because the foaming agent-containing resin layer can be foamed to form a foamed resin layer that can swell uniformly and sufficiently due to water absorption.

  In the said invention, it is preferable to have the non-foaming resin layer A on the surface on the opposite side to the surface at the side of the said fibrous base material of the said foaming agent containing resin layer. It is because the surface strength of the foaming resin layer which foams a foaming agent containing resin layer and the above-mentioned foaming agent containing resin layer can be raised because the above-mentioned non-foaming resin layer A has a surface protection function.

  In the said invention, it is preferable to have the non-foamed resin layer B in the surface at the side of the said fibrous base material of the said foaming agent containing resin layer. Since the non-foamed resin layer B has an adhesive function, the adhesiveness between the fibrous base material and the foamed resin layer formed by foaming the foamed agent-containing resin layer and the foamed agent-containing resin layer can be enhanced. It is.

  The foam laminate sheet of the present invention has an effect that the curl resistance is good.

It is a schematic sectional drawing which shows an example of the foam lamination sheet of this invention. It is a schematic sectional drawing which shows an example of the foam lamination sheet of this invention. It is a schematic sectional drawing which shows an example of the foam lamination sheet of this invention. It is a schematic sectional drawing which shows an example of the lamination sheet of this invention.

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

A. Foamed Laminated Sheet The foamed laminated sheet of the present invention comprises at least a fibrous base material and a foamed resin layer disposed on one side of the fibrous base material, and the foamed resin layer comprises a resin component and A water absorbing component is contained, and the water absorbing component contains a nonionic crosslinked polyalkylene oxide as a main component.

  FIG. 1 is a schematic cross-sectional view showing an example of the foam laminate sheet of the present invention. The foam laminate sheet 10 of the present invention has at least a fibrous base material 1 and a foamed resin layer 2 disposed on one side of the fibrous base material 1. The foamed resin layer 2 contains a resin component and a water absorbing component, and the water absorbing component contains a nonionic crosslinked polyalkylene oxide as a main component. The foamed resin layer 2 has foamed cells S inside.

  Moreover, FIG. 2 and FIG. 3 is a schematic sectional drawing which shows the other example of the foaming laminated sheet of this invention. In FIG. 2, a non-foamed resin layer A (symbol 3 in FIG. 2) is provided on the surface of the foamed resin layer 2 opposite to the surface on the fibrous substrate 1 side, and the fibrous group of the foamed resin layer 2 is The example which has non-foaming resin layer B (code | symbol 4 in FIG. 2) in the surface by the side of the material 1 is shown. Further, in FIG. 3, in addition to the configuration illustrated in FIG. 2, the non-foamed resin layer A (symbol 3 in FIG. 2) has the pattern pattern layer 5 on the surface opposite to the surface on the fibrous substrate 1 side. Furthermore, the example which has the surface protective layer 6 in the surface on the opposite side to the surface by the side of the foamed resin layer 2 of the pattern layer 5 is shown.

  According to the present invention, since the nonionic crosslinked polyalkylene oxide is a crosslinked product obtained by crosslinking a polyalkylene oxide, it can have a higher water absorbing ability than a non-crosslinked product. In addition, since the polyalkylene oxide constituting the nonionic crosslinked polyalkylene oxide has thermoplasticity, it is easily compatible with the resin component contained in the foamed resin layer, and the nonionic crosslinked polyalkylene oxide is uniformly dispersed in the foamed resin layer. Can be dispersed and compounded. Therefore, for example, the moisture absorbed by the fibrous base material by the application of the aqueous paste is transferred to the foamed resin layer, and the moisture is absorbed by the nonionic crosslinked polyalkylene oxide, whereby the hydrophilicity or hydrophobicity of the resin is obtained. Regardless of this, it becomes possible to swell the entire foamed resin layer uniformly. As a result, the foamed resin layer can follow the swelling of the fibrous base material, and the difference in volumetric expansion coefficient between the fibrous base material and the foamed resin layer can be reduced, so that curling occurs. Can be suppressed, and a curling resistance can be made into a favorable foam lamination sheet.

  Hereinafter, the foam laminate sheet of the present invention will be described for each component.

1. Foamed Resin Layer The foamed resin layer in the present invention is disposed on one surface side of the fibrous base material, and contains a resin component and a water absorbing component.

(1) Composition The foamed resin layer contains a resin component and a water absorbing material, and the water absorbing component contains a nonionic crosslinked polyalkylene oxide as a main component.

(A) Water-Absorbing Component The water-absorbing component contained in the above-mentioned foamed resin layer is mainly composed of nonionic crosslinked polyalkylene oxide.

(i) Nonionic Cross-Linked Polyalkylene Oxide The above nonionic cross-linked polyalkylene oxide is a nonionic cross-linked product having a polyalkylene oxide main chain, is water insoluble, swells when it absorbs water, and forms a gel-like body can do. The nonionic crosslinked polyalkylene oxide may be a crosslinked product obtained by electron beam crosslinking of a polyalkylene oxide, or may be a compound having a urethane bond in the molecule. The nonionic cross-linked polyalkylene oxide being a compound having a urethane bond in the molecule means that the nonionic cross-linked polyalkylene oxide is a cross-linked product cross-linked by an isocyanate compound. The nonionic crosslinked polyalkylene oxide having a urethane bond in its molecule is referred to as a nonionic polyalkylene oxide modified product. Among them, the nonionic crosslinked polyalkylene oxide is preferably a compound having a urethane bond in the molecule, that is, a nonionic polyalkylene oxide modified product.

  The nonionic polyalkylene oxide modified product is a compound having a urethane bond in the molecule, and as such a nonionic polyalkylene oxide modified product, for example, a nonionic polyalkylene oxide obtained by crosslinking a polyalkylene oxide with an isocyanate compound. Examples thereof include modified products, and nonionic type polyalkylene oxide modified products obtained by crosslinking a polyalkylene oxide and a polyol with an isocyanate compound.

  Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer, polybutylene oxide, and mixtures thereof.

  The weight average molecular weight of the above polyalkylene oxide is not particularly limited as long as it is a molecular weight capable of forming a desired nonionic crosslinked polyalkylene oxide, and is appropriately selected according to the type of polyalkylene oxide, the type of nonionic crosslinked polyalkylene oxide, etc. It can be set. The weight average molecular weight of the polyalkylene oxide may be, for example, 500 or more, 1,000 or more, or 10,000 or more. The weight average molecular weight may be 6,000,000 or less, 500,000 or less, 100,000 or less, 50,000 or less, or 20,000 or less. It is also good. Although the measuring method in particular of a weight average molecular weight is not restrict | limited, For example, it can measure by GPC (gel permeation chromatography).

  As said isocyanate type compound, the aliphatic or aromatic diisocyanate which has an isocyanate group (-NCO) 1 or 2 or more in a molecule | numerator is mentioned. Here, alicyclic diisocyanate is also included. Specifically, 1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,8-dimethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate, 2,2'-dimethyl-4 4,4'-diphenylmethane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) benzene, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate Etc. These may be used alone or as a mixture of two or more.

  The polyol is preferably a low molecular weight diol having a molecular weight of 500 or less. Examples of the low molecular weight diol include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol and trimethylene glycol, 1,3-butanediol, 2,3-butanediol, Aliphatic or aromatic such as 1,4-butanediol, 1,5-pentanediol, glyceryl monobutyrate, 1,6-hexanediol, 1,9-nonanediol, hexylene glycol, octylene glycol, glyceryl monoacetate, etc. Family diols. These may be used alone or as a mixture of two or more.

  The nonionic polyalkylene oxide modified product can be synthesized, for example, by reacting a composition containing a polyalkylene oxide, a polyol and an isocyanate compound in a solution using a suitable solvent such as toluene, xylene, dimethylformamide or the like. Can. Alternatively, they can be synthesized by a method of reacting in a dispersed state, or a method of uniformly mixing both in powdery or solid state and then heating to a predetermined temperature for reaction.

  A commercially available product can be used as the nonionic crosslinked polyalkylene oxide. Examples of commercially available products include “Aqua Cork” (modified polyalkylene oxide) manufactured by Sumitomo Seika Chemicals Co., Ltd.

  The water absorbing component contains a nonionic crosslinked polyalkylene oxide as a main component. Here, the fact that the water absorbing component contains the nonionic crosslinked polyalkylene oxide as the main component means that the ratio of the nonionic crosslinked polyalkylene oxide in the water absorbing component is the largest. That is, the water absorbing component may contain only the nonionic crosslinked polyalkylene oxide, and the water absorbing component includes the nonionic crosslinked polyalkylene oxide and one or more other types of water absorption other than the nonionic crosslinked polyalkylene oxide. The water-absorbent component may contain two or more kinds of the property material, and the ratio of the nonionic cross-linked polyalkylene oxide in the water-absorbing component may be the largest. In addition, other water-absorbing materials other than the nonionic crosslinked polyalkylene oxide will be described later. In the present invention, among them, it is preferable that the water absorbing component contains only nonionic crosslinked polyalkylene oxide, that is, the water absorbing component is nonionic crosslinked polyalkylene oxide. In addition, it is preferable that content of nonionic type | mold crosslinked polyalkylene oxide in 100 mass% of said water absorbing components is 70 mass% or more that using nonionic type crosslinked polyalkylene oxide as a main component specifically, Preferably it is 80 mass% or more, More preferably, it is 90 mass% or more, Especially preferably, it is 100 mass%. When the content of the nonionic crosslinked polyalkylene oxide in 100% by mass of the water absorbing component is 100% by mass, it means that the water absorbing component contains only the nonionic crosslinked polyalkylene oxide.

  When the water absorbing component contains a nonionic crosslinked polyalkylene oxide, the content of the nonionic crosslinked polyalkylene oxide can be appropriately set according to the composition of the water absorbing component with respect to 100 parts by mass of the resin component. For example, the content is preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the resin component, more preferably 5 parts by mass to 20 parts by mass, and particularly preferably 5 parts by mass to 10 parts by mass Is preferred. By setting the content of the nonionic crosslinked polyalkylene oxide with respect to 100 parts by mass of the resin component in the above range, the foamed resin layer is uniformly swollen, and the occurrence of curling can be sufficiently suppressed.

(ii) Other Water-Absorbing Material The water-absorbing component contains one or more water-absorbing materials other than the nonionic crosslinked polyalkylene oxide, provided that the nonionic crosslinked polyalkylene oxide is the main component. It is also good. As said other water absorbing material, the well-known water absorbing material which has a water absorption at least can be used, and the material which can be disperse | distributed uniformly to said resin component and compounded especially is preferable. The water-absorbing material may be a water-soluble material that absorbs and dissolves water, or may be a water-swellable material that does not dissolve in water and absorbs and swells water. As such a water absorbing material, an organic water absorbing material may be used, or an inorganic water absorbing material may be used.

  Examples of the organic water-absorbing material include hydrophilic polymers having thermoplasticity. The hydrophilic polymer may be a water-soluble polymer that absorbs and dissolves water, or may be a water-swellable polymer that does not dissolve in water and absorbs and swells water. Such a hydrophilic polymer can be, for example, at least one selected from the group consisting of a carboxyl group-containing polymer, a vinyl polymer, a water absorbing polymer, cellulose, a cellulose derivative, or a natural polymer. These may be contained singly or in combination of two or more.

  Examples of the carboxyl group-containing polymer include (meth) acrylic acid ester- (meth) acrylic acid copolymers such as carboxymethyl cellulose; polyacrylic acid; polymethacrylic acid; methyl methacrylate- (meth) acrylic acid copolymer and the like Styrene- (meth) acrylic acid copolymer; styrene-maleic anhydride copolymer; methyl vinyl ether-maleic anhydride copolymer, ethyl vinyl ether-maleic anhydride copolymer, isobutyl vinyl ether-maleic anhydride copolymer And vinyl ether-maleic anhydride copolymers; and salts thereof (for example, sodium polyacrylate cross-linked product) and the like.

  Examples of the vinyl polymer include polyvinyl alcohol; polyvinyl ethers such as polyvinyl methyl ether, polyvinyl ethyl ether and polyvinyl isobutyl ether; polyvinyl pyrrolidone; polyamylyl amide; or crosslinked polymers thereof.

  Examples of the water-absorbing polymer include crosslinked polyacrylic acid; saponified methyl acrylate-vinyl acetate copolymer; starch-acrylic acid graft copolymer; starch-acrylonitrile graft polymer; cellulose-acrylonitrile graft polymer; Cross-linked products of maleic anhydride copolymers; cross-linked polyethylene oxides or salts thereof.

  Examples of the cellulose include wood flour and cellulose powder. Moreover, as said cellulose derivative, methylcellulose; ethyl cellulose; hydroxyethyl cellulose etc. are mentioned, for example.

  Examples of the natural polymers include starches, dextrins, guar gum, gum arabic, gum tragacanth, sodium alginate, carrageenan, agar, gelatin, collagen (colloid), casein, chitose and the like.

  Examples of the inorganic water-absorbing material include zeolite, silica gel, alumina gel, silica alumina gel, activated carbon, activated clay, activated aluminum oxide, clay, kaolin, talc, bentonite, sepiolite, aluminum silicate and the like. These may be contained singly or in combination of two or more.

  The water-absorbing component may contain, as the other water-absorbing material, a hydrophilic polymer which is an organic water-absorbing material, or may contain an inorganic water-absorbing material, and the hydrophilic polymer and the inorganic material. Both of the water-absorbing materials may be included. Among them, the other water absorbing material is preferably a hydrophilic polymer. The hydrophilic polymer can be uniformly dispersed and compounded in the resin component, and the dispersed and complexed hydrophilic polymer can swell uniformly throughout the foamed resin layer by absorbing water. As a result, the curl resistance can be further improved.

  A commercial item can be used for the said other water-absorbing material. Commercially available products include, for example, "San Wet" manufactured by Sanyo Chemical Industries, Ltd., "Aqua Pearl", "Aquaric" manufactured by Nippon Shokuhin (acrylic acid polymer partial sodium salt cross-linked product), Sumitomo Seika Chemicals Co., Ltd. And “Aquakeep” (acrylic acid polymer partial sodium salt cross-linked product) and the like.

(Iii) Others In the foamed resin layer, the content of the water absorbing component is preferably 5 parts by mass or more and 30 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component. It is preferable that it is 5 to 10 mass parts especially. When the content of the water absorbing component is less than the above range, curling may not be sufficiently suppressed. On the other hand, when the content of the water absorbing component is more than the above range, the content of the resin component in the foamed resin layer decreases, and the physical properties such as surface strength exhibited by the resin component can not be obtained. There is a case.

  The water absorbing material contained in the water absorbing component may have water releasability in addition to the water absorbability. That is, the water absorbent material may have moisture absorbability. The moisture absorbing / releasing property refers to a function of absorbing moisture under high humidity conditions and releasing moisture (water separation) under dry conditions. When the foam laminate sheet of the present invention is used as foam wallpaper, for example, by the fact that the water-absorbent material has moisture absorption and release properties, it becomes a high humidity state by the application of water-based glue during gluing construction; The water absorbing material can absorb the transferred water to swell the foamed resin layer. On the other hand, after construction, since the water absorbing material releases moisture and the foamed resin layer does not contain water by drying, it is possible to suppress the occurrence of mold and deterioration of the adherend and the foam wallpaper due to moisture, etc. Can.

(B) Resin component The resin component contained in the said foamed resin layer can contain resin used for the foamed resin layer which comprises well-known foamed wallpaper etc. Examples of the resin include vinyl chloride resin, olefin resin, polystyrene resin, polyvinyl acetate, polyurethane, polytetrafluoroethylene, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylic resin, polyamide, polyacetal, Polycarbonate, polyester, polyphenylene sulfide, polyether ether ketone and the like can be mentioned. In the said foamed resin layer, these may be contained individually by 1 type, and 2 or more types may be contained.

  Moreover, in the said foaming resin, resin of the said resin component may be contained as a crosslinked material. The crosslinked product is a polymer in which the molecular chains of the above-described resin are crosslinked. The crosslinked product may be a crosslinked product crosslinked by electron beam irradiation or the like, or may be a crosslinked product crosslinked by a crosslinking agent.

  Among them, the resin component preferably contains at least one of an olefin resin and a crosslinked product thereof as a main component. The olefin resin is a non-halogen thermoplastic resin, and since it does not require the blending of a phthalic acid plasticizer, the environmental impact can be reduced compared to a halogen resin such as a vinyl chloride resin. It is.

  The resin component mainly contains at least one of an olefin resin and a crosslinked product thereof when the resin component contains an olefin resin as a main component and when the resin component contains a crosslinked product of an olefin resin as a main component And a mixture of an olefin resin and a crosslinked product thereof as the main component. Among them, a crosslinked product of an olefin resin or a mixture of an olefin resin and a crosslinked product thereof is preferably contained as a main component, and particularly preferably a crosslinked product of an olefin resin is contained as a main component. By the presence of the olefin resin as a crosslinked product in the foamed resin layer, the foamed resin layer can be made stronger and have excellent scratch resistance and abrasion resistance.

  In addition, when the resin component contains at least one of an olefin resin and a crosslinked product thereof as the main component, the resin component may contain only at least one of an olefin resin and a crosslinked product thereof; May contain at least one of an olefin resin and a crosslinked product thereof, and a resin other than these resins, and the ratio of the olefin resin and the crosslinked product in the resin component may be the largest. The resin component does not include the nonionic cross-linked polyalkylene oxide in the water absorbing component and other organic water absorbing materials. In the present invention, among the above, it is preferable that the resin component contains only at least one of an olefin resin and a crosslinked product thereof. Specifically, at least one of the olefin resin in 100% by mass of the resin component and the crosslinked product thereof is 70% by mass that at least one of the olefin resin and the crosslinked product thereof is the main component. The content is preferably at least 80% by mass, and particularly preferably at least 90% by mass. The content may be 100% by mass, that is, the resin component may be only at least one of an olefin resin and a crosslinked product thereof, may be 100% by mass or less, and 90% by mass or less. It may also be 80% by mass or less. Among them, the resin component is preferably at least one of an olefin resin and a crosslinked product thereof. The resin component does not include the nonionic cross-linked polyalkylene oxide in the water absorbing component and other organic water absorbing materials.

  Examples of the olefin resin include polyolefin, olefin-unsaturated carboxylic acid copolymer, olefin-unsaturated carboxylic acid ester copolymer, and olefin-vinyl ester copolymer.

  Examples of the polyolefin include polyethylene (PE), polypropylene (PP) and the like, among which PE is preferable. Examples of PE include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), and the like.

  The olefin-unsaturated carboxylic acid copolymer is a copolymer containing an olefin and an unsaturated carboxylic acid as monomer components, and may be a binary, ternary or higher copolymer. Examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like, among which ethylene Is particularly preferred. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid and the like, and among these, at least one selected from the group consisting of acrylic acid and methacrylic acid is particularly preferable. Specific examples of the olefin-unsaturated carboxylic acid copolymer include ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA).

  As the olefin-unsaturated carboxylic acid ester copolymer, for example, ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl methacrylate copolymer (EMMA), ethylene- Ethyl methacrylate copolymer (EEMA) etc. are mentioned.

  As the olefin-vinyl ester copolymer, for example, a copolymer of ethylene and vinyl acetate (ethylene-vinyl acetate copolymer), a copolymer of ethylene and vinyl caproate, a copolymer of ethylene and vinyl propionate A polymer, a copolymer of ethylene and vinyl caprylate, a copolymer of ethylene and vinyl laurate, a copolymer of ethylene and vinyl stearate, and the like can be mentioned.

  Among the above-mentioned olefin resins, an olefin-unsaturated carboxylic acid copolymer is preferable, and at least one selected from the group consisting of an ethylene-acrylic acid copolymer (EAA) and an ethylene-methacrylic acid copolymer (EMAA) It is more preferable that it is, and it is especially preferable that it is ethylene-methacrylic acid copolymer (EMAA). It is because the said foaming resin layer becomes a strong layer resulting from the hydrogen bond in resin, etc. by the carboxyl group which EAA and EMAA have, and it can be set as the foaming lamination sheet excellent in surface strength. Moreover, it is because the foaming state of the said foamed resin layer becomes favorable, and practical surface strength can be obtained.

  That is, it is preferable that the said resin component has as a main component at least one of the said olefin- unsaturated carboxylic acid copolymer and its crosslinked material. The olefin-unsaturated carboxylic acid copolymer may be contained singly or in combination of two or more.

  When the olefin resin is the olefin-unsaturated carboxylic acid copolymer, the content of the unsaturated carboxylic acid in the olefin-unsaturated carboxylic acid copolymer is not particularly limited, and for example, 5% by mass The above is preferable, and 10 mass% or more and 15 mass% or less is more preferable. This is because the foamed resin layer can have more excellent surface strength.

  When the olefin resin is the olefin-unsaturated carboxylic acid copolymer, the copolymerization ratio of the olefin-unsaturated carboxylic acid copolymer may vary depending on the type of the olefin-unsaturated carboxylic acid copolymer. When the saturated carboxylic acid copolymer is EAA or EMAA, the content of acrylic acid in EAA or methacrylic acid in EMAA is, for example, preferably 4% by mass or more and 20% by mass or less, and in particular 10% by mass or more and 15% by mass It is preferable that it is the following. By setting the content of acrylic acid in EAA or methacrylic acid in EMAA to the above range, the toughness derived from the interaction due to the polarity of acrylic acid or methacrylic acid, and the hardness derived from the degree of crystallinity formed by ethylene chains It is because it is excellent in the balance of.

  From the viewpoint of melt extrusion suitability, the melt flow rate (MFR) value of the resin component containing the above-mentioned olefin resin as a main component is preferably, for example, 5 g / 10 min or more and 200 g / 10 min or less, in particular 20 g / 10 min It is preferable that it is 100 g / 10 minutes or less. By setting the MFR value of the resin component to the above range, when forming the foaming agent-containing resin layer, which is the layer before foaming of the foamed resin layer, by extrusion film formation, the temperature rise is suppressed to produce in a non-foamed state. It can be a film. If the MFR value is too large, the resulting foamed resin layer may be too soft and may be inferior in scratch resistance. The above-mentioned MFR value is a temperature of 190 ° C. and a weight of 21.18 N (in accordance with the test method described in JIS K 7210: 2014 “Melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastics”). It can be measured under the condition of 2.16 kgf).

  The content of the resin component in 100% by mass (total solids) of the foamed resin layer can be 30% by mass or more and 80% by mass or less, preferably 40% by mass or more and 70% by mass or less, more preferably Can be 50% by mass or more and 60% by mass or less. When the content of the resin component in the foamed resin layer is larger than the above range, for example, when the foamed laminate sheet of the present invention is used as a foamed wallpaper, the concealing property may be inferior or a sufficient expansion ratio may be obtained. It may not be. On the other hand, when content of the said resin component in the said foamed resin layer is smaller than the said range, it may be inferior to extrusion film forming property. The resin component does not include the nonionic cross-linked polyalkylene oxide in the water absorbing component and other organic water absorbing materials.

(C) Inorganic filler In addition to the resin component and the water absorbing component described above, the foamed resin layer may contain an inorganic filler for the purpose of imparting flame retardancy, suppressing penetration, improving surface strength, etc. . The inorganic filler is not particularly limited, and examples thereof include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, a molybdenum compound, titanium dioxide and the like. In addition, these may be used individually by 1 type and may be used in combination of 2 or more types.

  The content of the inorganic filler is not particularly limited, but can be, for example, about 0 parts by weight to 100 parts by weight with respect to 100 parts by weight of the resin component, and preferably about 20 parts by weight to 70 parts by weight. is there.

(D) Additives The above-mentioned foamed resin layer contains, if necessary, a pigment, an antioxidant, a crosslinking agent, a crosslinking aid, a surface treatment agent, an antifungal agent, an insect repellent, an antiseptic, an antibacterial agent, a diluent, a deodorant You may contain additives, such as an agent, a light stabilizer, and a plasticizer. In addition, an unfoamed foaming agent may be contained.

(2) Structure The foam resin layer has foam cells inside. The foam cell may be a closed cell or an open cell, or may be a mixture of a closed cell and an open cell. Further, the number, size, density, shape, and the like of the foam cells are not particularly limited, and can be appropriately designed according to the type, use, and the like of the foam laminate sheet of the present invention. The foam cell can be formed by foaming a foaming agent contained in the foaming agent-containing resin composition used for forming the foamed resin layer.

  The thickness of the foamed resin layer is not particularly limited, but can be, for example, 350 μm or more and 1500 μm or less, and preferably 500 μm or more and 1200 μm or less.

  The foamed resin layer is preferably crosslinked. That is, it is preferable that the resin component contained in the said foaming resin layer contains the crosslinked material of resin, and it is more preferable that the said resin component is a crosslinked material of resin.

2. Fibrous base material The fibrous base material in the present invention is a member which becomes one outermost layer in the laminating direction of the foamed laminate sheet of the present invention.

  As the above-mentioned fibrous base material, one having water-swelling property is suitably used. As such a fibrous base material, for example, known materials used for wallpaper application such as paper, non-woven fabric, woven fabric and the like can be mentioned. The paper may be ordinary paper or flame retardant paper.

  The above-mentioned flame retardant paper is a general paper in which a flame retardant is contained. Examples of the flame retardant include nitrogen compounds such as urea and ammonium compounds; hydroxides such as magnesium hydroxide and aluminum hydroxide (preferably hydrates); and flame retardants containing self-extinguishing phosphorus or halogen elements Can be mentioned. Above all, by blending a compound containing crystal water such as magnesium hydroxide etc., it is possible to preferably achieve flame retardancy by the heat of vaporization of the crystal water at the time of combustion and decomposition.

  The non-woven fabric may be a wet paper non-woven fabric, or may be a dry non-woven fabric such as an adhesive, mechanical bond (needle punch, stitch bond), or spun bond. Specific examples of the non-woven fabric include resin fiber non-woven fabrics such as rayon paper, pulp mixed with paper, Japanese paper, glass non-woven fabric, asbestos non-woven fabric, polyester non-woven fabric and polycarbonate non-woven fabric.

  The above-mentioned fibrous base material can contain optional materials such as a dry strength agent, a wet strength agent, a coloring agent, a sizing agent, a fixing agent and the like as needed.

  The thickness of the fibrous base material is not particularly limited, and can be appropriately set according to the application of the foam laminate sheet of the present invention.

3. Optional Configuration The foam laminate sheet of the present invention has at least the above-described fibrous base material and the foamed resin layer, but can include any configuration.

(1) Non-foamed resin layer A
In the present invention, the non-foamed resin layer A can be provided on the surface of the foamed resin layer opposite to the surface on the side of the fibrous base material. The non-foamed resin layer A disposed at the above position can enhance the surface strength of the foamed resin layer by having a surface protective function. That is, the non-foamed resin layer A can be used as a foamed resin layer protective layer.

  Examples of the resin component constituting the non-foamed resin layer A include polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, and fluorine resins. These resins can be used singly or in combination of two or more. Among them, polyolefin resins are preferable.

  Examples of the polyolefin-based resin include polyethylene (low density polyethylene (LDPE), high density polyethylene (HDPE)), single resins such as polypropylene, polybutene, polybutadiene, and polyisoprene, ethylene, and α-olefins having 4 or more carbon atoms. Copolymers (linear low density polyethylene (LLDPE)), ethylene-acrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid copolymers, etc. Examples thereof include (meth) acrylic acid copolymers, ethylene-vinyl acetate copolymers (EVA), saponified ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, and ionomers. In addition, "(meth) acrylic acid" means at least one of acrylic acid and methacrylic acid. The same applies to the portions described as other (meta).

  The non-foamed resin layer A may contain known additives such as a filler, a colorant, a light stabilizer, a foaming agent, other lubricants, and an antibacterial agent. The non-foamed resin layer A may be transparent, uncolored, or colored.

  The thickness of the non-foamed resin layer A is not particularly limited, and can be appropriately set to a size that can exhibit the above-described desired function. The thickness can be, for example, about 2 μm to 50 μm, and preferably about 5 μm to 20 μm.

(2) Non-foamed resin layer B
In the present invention, the non-foamed resin layer B can be provided on the surface on the fibrous base material side of the foamed resin layer. That is, the non-foamed resin layer B is disposed between the fibrous base material and the foamed resin layer. The non-foamed resin layer B disposed at the above-described position can improve the adhesion between the foamed resin layer and the fibrous base material by having an adhesive function. That is, the non-foamed resin layer B can be used as an adhesive layer.

  The resin component which comprises the said non-foaming resin layer B contains resin which has adhesiveness. It does not specifically limit as said resin, It can be made to be the same as that of the well-known resin used for a general adhesive agent. For example, thermoplastic resins, such as carboxylic acid modified | denatured olefin resin, ethylene-vinyl acetate copolymer (EVA), ionomer resin, etc. are mentioned. These resins can be used singly or in combination of two or more.

  Among them, ethylene-vinyl acetate copolymer (EVA) is preferable, and ethylene-vinyl acetate copolymer (EVA) having a vinyl acetate component (VA component) content (copolymerization ratio) of 10% by mass to 46% by mass is preferable. The ethylene-vinyl acetate copolymer (EVA) of 15% by mass or more and 41% by mass or less is more preferable.

  The thickness of the non-foamed resin layer B is not particularly limited, and can be appropriately set to a size that can exhibit the above-described desired function. The thickness can be, for example, about 5 μm to 50 μm.

(3) Pattern-patterned layer The foam laminate sheet of the present invention can have a pattern-patterned layer on the surface of the foamed resin layer opposite to the surface on the side of the fibrous base material. It is because a designability can be given to the foaming lamination sheet of the present invention.

  The picture pattern layer may be in direct contact with the surface of the foamed resin layer opposite to the surface on the side of the fibrous base material, or may be in contact via a primer layer or an adhesive layer. If the non-foamed resin layer A is provided on the surface of the foamed resin layer opposite to the surface on the side of the fibrous base material, the design pattern layer is the foamed resin of the non-foamed resin layer A It can have on the side opposite to the side on the layer side. In the above case, the pattern layer may be in direct contact with the non-foamed resin layer A, or may be in contact via a primer layer or an adhesive layer.

  The pattern layer may at least have a pattern portion, and may have a support layer supporting the pattern portion according to the method of forming the pattern layer.

  The design pattern which the above-mentioned design pattern part shows is not specifically limited, According to the purpose, it can choose suitably. Examples of the pattern include wood grain patterns, stone patterns, grain patterns, tile patterns, brick pile patterns, grain patterns, skin patterns, geometric figures, characters, symbols, abstract patterns, flower patterns, etc. .

  The pattern-patterned layer can be formed, for example, by printing a pattern-patterned portion on one surface of a support layer using a printing ink. Further, instead of the support layer, the printing resin is applied to the surface of the foamed resin layer opposite to the surface on the side of the fibrous substrate, or the surface of the non-foamed resin layer A opposite to the foamed resin layer. The pattern may be printed by direct printing using ink.

  The printing ink which forms the said pattern part can be set as the composition which contains a coloring agent, binder resin, and a solvent at least, for example. The details of the composition of the printing ink may be the same as the composition of the printing ink used for forming the pattern layer disclosed in, for example, JP-A-2017-43009 and JP-A-2011-179161. it can. Moreover, the said printing ink can use a well-known or commercially available thing. The printing method is not particularly limited, and known printing methods can be used. Moreover, when the said pattern-pattern part is formed in the whole surface solid form, you may use a well-known coating method.

  The thickness of the pattern layer is not particularly limited, and can be appropriately set according to the type of pattern. The thickness can be, for example, about 0.1 μm to 10 μm.

(4) Primer layer The foam laminate sheet of the present invention can have a primer layer on the surface of the above-mentioned foamed resin layer opposite to the surface on the side of the above-mentioned fibrous base material.

  Examples of the resin contained in the primer layer include acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, polyurethane resin, chlorinated polypropylene resin, chlorinated polyethylene resin and the like. Among them, acrylic resin, chlorinated polypropylene resin and the like are preferable.

  The thickness of the primer layer is not particularly limited, and can be set as appropriate. The thickness can be, for example, about 0.1 μm or more and 10 μm or less, and preferably about 0.1 μm or more and 5 μm or less.

  According to the layer configuration of the foam laminate sheet of the present invention, the primer layer is disposed between layers of a plurality of layers disposed on the surface of the foam resin layer opposite to the surface on the fibrous base material side. Can. As the arrangement position of the primer layer, for example, an interlayer between the foamed resin layer and the non-foamed resin layer A, an interlayer between the non-foamed resin layer A and the design pattern layer, an interlayer between the non-foamed resin layer A and the surface protective layer And an interlayer between the pattern layer and the surface protective layer, but not limited thereto.

(5) Surface Protective Layer The foam laminate sheet of the present invention can have a surface protective layer on the outermost side of the above-mentioned foamed resin layer on the opposite side to the above-mentioned fibrous base material side. This is because the surface strength of the foam laminate sheet of the present invention can be enhanced.

  The type of the surface protective layer is not particularly limited, and can be appropriately selected depending on the purpose of providing the surface protective layer, such as gloss adjustment and protection of the pattern layer. For example, if the purpose is to adjust gloss, the surface protective layer may include, for example, a known matting agent such as silica. In the case of the purpose of the surface strength (scratch resistance etc.), stain resistance, protection of a picture pattern layer, etc. of the foamed laminate sheet of the present invention, the surface protective layer may be, for example, an ionizing radiation curable type. A cured product of the resin can be contained as a resin component.

  The thickness of the surface protective layer is not particularly limited, and can be set as appropriate. The thickness can be, for example, about 0.5 μm to 10 μm.

  The surface protective layer may be in direct contact with the surface of the foamed resin layer opposite to the surface on the side of the fibrous base material, or may be in contact via a primer layer or an adhesive layer.

  In the case where the non-foamed resin layer A is provided on the surface of the foamed resin layer opposite to the surface on the fibrous base material side, the surface protective layer is the foamed resin layer side of the non-foamed resin layer A It can have on the side opposite to the side of. In the above case, the surface protective layer may be in direct contact with the non-foamed resin layer A, or may be in contact via a primer layer or an adhesive layer.

  If it is a case where it has a design pattern layer on the surface on the opposite side to the surface by the side of the above-mentioned fibrous base material of the above-mentioned foaming resin layer, the above-mentioned surface protection layer will be the surface by the side of the above-mentioned foaming resin layer of the above-mentioned design pattern layer It can be on the opposite side. In the above case, the surface protective layer may be in direct contact with the pattern-patterned layer, or may be in contact via a primer layer or an adhesive layer.

(6) Embossed Pattern An embossed pattern may be provided on the outermost surface of the foam laminate sheet of the present invention opposite to the fibrous base material. Examples of the emboss pattern include wood grain conduit grooves, stone plate surface irregularities, cloth surface texture, satin, grain, hair lines, line grooves, and the like, and a combination thereof may be used.

4. Production Method As a method for producing the foam laminate sheet of the present invention, for example, the above-mentioned fibrous base material and one side of the above-mentioned fibrous base material are disposed, and a resin component and nonionic crosslinked polyalkylene oxide are main components. And a foaming agent-containing resin layer containing a foaming agent, by heating the laminate sheet, and foaming the foaming agent-containing resin layer to form a foamed resin layer. . In addition, the manufacturing method of a lamination sheet is mentioned later. The heating temperature and heating time in the foaming step are not particularly limited as long as foam cells can be formed in the layer by decomposition of the foaming agent contained in the foaming agent-containing resin layer, and the composition of the foaming agent-containing resin layer It can be set appropriately according to

5. Applications The foam laminate sheet of the present invention can be used as an interior material for foam wallpaper, various decorative materials, and the like. Above all, it is useful as foam wallpaper.

B. Laminated Sheet The laminated sheet of the present invention has at least a fibrous base material and a foaming agent-containing resin layer disposed on one side of the fibrous base material, and the foaming agent-containing resin layer is a resin The water absorbing component contains a component, a water absorbing component, and a foaming agent, and the water absorbing component contains a nonionic crosslinked polyalkylene oxide as a main component.

  FIG. 4 is a schematic cross-sectional view showing an example of the laminated sheet of the present invention. The laminated sheet 100 of the present invention has at least a fibrous base material 1 and a foaming agent-containing resin layer 20 disposed on one side of the fibrous base material 1. The foaming agent-containing resin layer 20 contains a resin component, a water absorbing component, and a foaming agent, and the water absorbing component contains a nonionic crosslinked polyalkylene oxide as a main component. Since the foaming agent-containing resin layer 20 is unfoamed, unlike the foamed resin layer 2 illustrated in FIG. 1, the foamed cell S is not contained inside the layer.

  In the laminated sheet of the present invention, the foaming agent is foamed in the foaming agent-containing resin layer by heating or the like to form a foamed resin layer. Thereby, the foam lamination sheet demonstrated by the term of said "A. foam lamination sheet" can be formed.

  According to the present invention, since the nonionic crosslinked polyalkylene oxide contained in the above-mentioned foaming agent-containing resin layer is a crosslinked product in which a polyalkylene oxide is crosslinked, it can have higher water absorbing ability than a non-crosslinked product. In addition, since the polyalkylene oxide constituting the nonionic crosslinked polyalkylene oxide has thermoplasticity, it is easily compatible with the resin component contained in the foaming agent-containing resin layer, and in the foaming agent-containing resin layer, nonionic crosslinked poly Alkylene oxide can be uniformly dispersed and complexed. For this reason, the laminate sheet of the present invention can be made to foam the above-mentioned foaming agent-containing resin layer to form a foam resin layer capable of swelling uniformly throughout the layer, and to form a foam laminate sheet having good curl resistance. Can.

  Hereinafter, the lamination sheet of this invention is demonstrated for every structural member.

1. Foaming agent-containing resin layer The foaming agent-containing resin layer in the present invention is disposed on one surface side of the fibrous base material, and contains a resin component, a water absorbing component, and a foaming agent. The said foaming agent containing resin layer does not have a foaming cell inside.

(1) Composition The foaming agent-containing resin layer contains a resin component, a water absorbing component, and a foaming agent, and the water absorbing component contains a nonionic crosslinked polyalkylene oxide as a main component.

(A) Resin Component The resin component contained in the foaming agent-containing resin layer has been described in detail in the section “A. Foamed laminated sheet”, and therefore the description thereof is omitted here.

(B) Water-Absorbing Component The water-absorbing component contained in the foaming agent-containing resin layer has been described in detail in the section “A. Foamed Laminated Sheet”, and therefore the description thereof is omitted here. The nonionic crosslinked polyalkylene oxide which is the main component of the water absorbing component is not particularly limited, but is preferably a compound having a urethane bond in the molecule.

  In the foaming agent-containing resin layer, the content of the water absorbing component is preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin component. This is because the foaming agent-containing resin layer can be foamed to form a foamed resin layer that can swell uniformly and sufficiently due to water absorption. About the more preferable range of content of the said water absorbing component, it can be made to be the same as content of the water absorbing component in the foamed resin layer demonstrated by the term of said "A. foam laminated sheet".

(C) Foaming agent The foaming agent contained in the above-mentioned foaming agent containing resin layer can be chosen from publicly known foaming agents. Examples of the foaming agent include: azo-based compounds such as azodicarbonamide (ADCA) and azobisformamide; organic thermally decomposing-type foaming agents such as hydrazide-based compounds such as oxybenzenesulfonyl hydrazide (OBSH) and para-toluenesulfonyl hydrazide; Microcapsule type foaming agents, inorganic foaming agents such as baking soda, etc. may be mentioned. These may be contained singly in the above-mentioned foaming agent-containing resin layer, or may be contained in two or more kinds. Among them, the foaming agent-containing resin layer preferably contains azodicarbonamide (ADCA) as a foaming agent.

  The content of the foaming agent can be appropriately set according to the type of the foaming agent, the foaming ratio, and the like. The expansion ratio can be, for example, 1.5 times or more, preferably 3 times or more and 7 times or less. The content of the foaming agent can be about 1 to 20 parts by mass, preferably 3 to 10 parts by mass, with respect to 100 parts by mass of the resin component contained in the foaming agent-containing resin layer. It can be less than or equal to parts by weight. The resin component does not include the nonionic cross-linked polyalkylene oxide in the water absorbing component and other organic water absorbing materials.

(D) Foaming auxiliary agent The said foaming agent containing resin layer can contain a foaming auxiliary. Examples of the foaming aid include known materials used as a foaming aid such as metal oxides and fatty acid metal salts, and can be appropriately selected according to the type of the foaming agent. Specifically as the above-mentioned foaming aid, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, calcium laurate, magnesium oxide, zinc oxide, magnesium oxide, Carboxylic acid hydrazide compounds and the like can be mentioned. These may be contained singly in the above-mentioned foaming agent-containing resin layer, or may be contained in two or more kinds.

  When the resin component of the above-mentioned foaming agent-containing resin layer contains an olefin-unsaturated carboxylic acid copolymer, it is preferable to contain a carboxylic acid hydrazide compound as a foaming aid. Even when the carboxylic acid hydrazide compound is used in combination with an olefin-unsaturated carboxylic acid copolymer having a carboxyl group, it is hard to deactivate the effect of the foaming aid by a chemical reaction. For this reason, it is because it can suppress that a foaming resin layer, a fibrous base material, etc. yellow by yellowing which arises in the case of foaming of the said foaming agent containing resin layer, or formation of a chromophore. As the carboxylic acid hydrazide compound, for example, a monohydrazide compound having one hydrazide group in the molecule, a dihydrazide compound having two hydrazide groups in the molecule, and a polyhydrazide compound having three or more hydrazide groups in the molecule Can be mentioned. Specific monohydrazide compounds, dihydrazide compounds and polyhydrazide compounds can be, for example, compounds disclosed in JP-A-2009-197219. These may be contained singly in the above-mentioned foaming agent-containing resin layer, or may be contained in two or more kinds.

  Although content of the said foaming adjuvant is not specifically limited, For example, It shall be 0.3 mass part or more and about 10 mass parts or less with respect to 100 mass parts of resin components contained in the said foaming agent containing resin layer, for example Preferably, it can be 1 part by mass or more and 5 parts by mass or less. The resin component does not include the nonionic cross-linked polyalkylene oxide in the water absorbing component and other organic water absorbing materials.

  The foaming agent-containing resin layer preferably contains azodicarbonamide (ADCA) as a foaming agent, and preferably contains a carboxylic acid hydrazide compound as the foaming aid. The content of the carboxylic acid hydrazide compound in this case can be, for example, about 0.2 parts by mass or more and 1 part by mass or less with respect to 1 part by mass of azodicarbonamide (ADCA).

(E) Others The above-mentioned foaming agent-containing resin layer may contain an inorganic filler and optional additives. The inorganic filler and optional additives are described in detail in the section “A. Foamed Laminated Sheet” above, and thus the description thereof is omitted here.

(2) Structure The thickness of the foaming agent-containing resin layer is not particularly limited as long as the thickness of the foamed resin layer after foaming can be made into a desired range, but for example, it can be 30 μm to 300 μm, preferably 50 μm. It is 150 μm or less.

  The blowing agent-containing resin layer is preferably crosslinked. That is, it is preferable that the resin component contained in the said foaming agent containing resin layer contains a crosslinked material, and it is more preferable that the said resin component is a crosslinked material.

2. Fibrous base material The fibrous base material in the present invention has been described in detail in the section "A. Foamed laminated sheet", and thus the description thereof is omitted here.

3. Optional Configuration The laminated sheet of the present invention has at least the above-described fibrous base material and the foaming agent-containing resin layer, but may further include any configuration. For example, the laminated sheet of the present invention can have the non-foamed resin layer A on the surface opposite to the surface on the side of the fibrous base material of the foaming agent-containing resin layer. It is because the surface strength of the foaming resin layer which foams a foaming agent containing resin layer and the above-mentioned foaming agent containing resin layer can be raised more because the above-mentioned non-foaming resin layer A has a surface protection function.

  Moreover, the laminated sheet of this invention can have the non-foamed resin layer B in the surface at the side of the said fibrous base material of the said foaming agent containing resin layer. By the non-foamed resin layer B having an adhesive function, the adhesiveness between the fibrous base material and the foamed resin layer formed by foaming the foaming agent-containing resin layer and the foaming agent-containing resin layer can be enhanced. is there.

  About the said non-foaming resin layer A and the non-foaming resin layer B, since it demonstrated in detail of the term of said "A. foam laminated sheet", description here is abbreviate | omitted.

  Moreover, the lamination sheet of this invention can have a pattern pattern layer, a primer layer, a surface protection layer etc. on the surface on the opposite side to the surface at the side of the said fibrous base material of the said foaming agent containing resin layer. Furthermore, an embossed pattern may be provided on the outermost surface of the foam laminate sheet of the present invention opposite to the fibrous base material. The pattern pattern layer, the primer layer, the surface protective layer, and the embossed pattern have been described in detail in the section “A. Foam laminated sheet”, and thus the description thereof is omitted here.

4. Production Method As a method for producing the laminated sheet of the present invention, for example, a fiber containing a resin component, a water absorbing component containing a nonionic cross-linked polyalkylene oxide as a main component, and a foaming agent at least is used. The method which has a foaming agent containing resin layer formation process which forms a foaming agent containing resin layer on a quality base material is mentioned.

  The resin component, the foaming agent, and the water absorbing component contained in the above-mentioned foaming agent-containing resin composition are the same as the respective materials described in the section of "1. foaming agent-containing resin layer".

  The method for forming the foaming agent-containing resin layer on the fibrous base material using the above-mentioned foaming agent-containing resin composition is not particularly limited. An extrusion laminating method of extruding a resin composition to form a film can be used. In addition, after the foaming agent-containing resin composition is extruded to form a sheet of the foaming agent-containing resin layer, the sheet of the foaming agent-containing resin layer may be laminated to the fibrous base material in a separate step. The cylinder temperature and die temperature at the time of extrusion film formation can be appropriately adjusted.

  The manufacturing method of the lamination sheet of the present invention may have an electron beam irradiation process of irradiating an electron beam to the above-mentioned foaming agent content resin layer, and crosslinking a resin component after a foaming agent content resin layer formation process. It is because the resin component contained in the said foaming agent containing resin layer can bridge | crosslink and form a crosslinked material, and it can adjust the surface strength, foaming characteristic, etc. of the foaming resin layer finally obtained. The energy intensity of the electron beam is not particularly limited, but may be, for example, about 150 kV to about 250 kV, and preferably about 175 kV to about 200 kV. Further, the irradiation dose is not particularly limited, but can be, for example, about 10 kGy or more and 100 kGy or less, and preferably about 10 kGy or more and 50 kGy or less. A well-known electron beam irradiation apparatus can be used as an electron beam source.

  When the laminate sheet of the present invention has a non-foamed resin layer on one side or both sides of the foaming agent-containing resin layer, a non-foamed resin layer forming a non-foamed resin layer on one side or both sides of the foaming agent-containing resin layer It can have a forming step. The non-foamed resin layer may be formed by extrusion film formation, or may be formed by heat laminating each film. Among them, coextrusion film formation by a T-die extruder is preferable. For example, in the case of providing both the non-foamed resin layer A and the non-foamed resin layer B, a foaming agent-containing resin composition and each non-foamed using a multi-manifold type T die capable of simultaneously forming three layers. The non-foamed resin layer A, the foaming agent-containing resin layer, and the non-foaming resin layer are obtained by simultaneously extruding the resin composition for forming the resin layer, that is, by simultaneously performing the foaming agent-containing resin layer formation step and the non-foamed resin layer formation step. It is possible to form a three-layer laminate in which the foamed resin layer B is laminated in this order.

  In addition, when inorganic substances, such as a pigment, are contained in the said foaming agent containing resin composition, it is preferable to use the method by three-layer simultaneous extrusion film forming. When the foaming agent-containing resin layer is formed by extrusion film formation, the residue (in the eyes) of the inorganic substance is easily generated at the extrusion port of the extruder, and this tends to be foreign matter on the surface of the foaming agent-containing resin layer. On the other hand, the foaming agent-containing resin layer and the non-foaming resin layer are sandwiched by the non-foaming resin layer containing no inorganic substance at the same time using the method of three-layer coextrusion film formation. By forming it, generation of eyes can be suppressed.

  In the method of producing a laminated sheet according to the present invention, a step of forming a design pattern or a primer layer in an arbitrary order on the surface opposite to the surface on the fibrous base side of the foaming agent-containing resin layer It is possible to have a step of providing a surface protective layer on the outermost side of the foaming agent-containing resin layer on the opposite side to the fibrous base material side, and a step of embossing on the outermost surface layer. These steps are preferably performed after the electron beam irradiation step. The formation method of each layer of a pattern, a primer layer, and a surface protective layer is not specifically limited, For example, the coating method of the conventional method, such as printing and application | coating, the extrusion film forming method, etc. are mentioned. Further, as a method of forming the embossed pattern, for example, there is a method of pressing an embossed plate having a desired embossed pattern after heat softening the outermost surface layer of the laminated sheet on the opposite side to the fibrous base material side.

5. Applications The laminate sheet of the present invention is useful for forming the foam laminate sheet described in the section "A. Foam laminate sheet" above.

  The present invention is not limited to the above embodiment. The above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples.

[Examples 1 to 8 and Comparative Examples 1 to 2]
The foaming agent-containing resin composition was prepared by melt-kneading with the composition shown in Table 1 below.

  The foaming agent-containing resin composition was extruded to a thickness of 100 μm using a T-die extruder to form a foaming agent-containing resin layer, and a backing paper was laminated on one side to form a laminated sheet. The extrusion conditions were a cylinder temperature of 110 ° C. and a die temperature of 120 ° C.

  An electron beam (200 kV, 35 kGy) was irradiated to the laminated sheet from the side of the foaming agent-containing resin layer. Next, an acrylic aqueous ink (manufactured by Showa Ink) was coated on the foaming agent-containing resin layer using a gravure printer to form a patterned layer. Thereafter, the laminated sheet was heated in a gear oven at 220 ° C. for 30 seconds to 40 seconds to foam the foaming agent-containing resin layer to form a foamed resin layer, thereby obtaining a foamed laminate sheet.

[Evaluation: Curl resistance]
The foamed laminate sheets obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were immersed in water, and the degree of curl was visually confirmed, and evaluated based on the following evaluation criteria. The results are shown in Table 2 below.
(Evaluation criteria)
· ○: no curling at all, sheet hanging down △: slightly curled, half of the sheet rolls up · ×: curled, the entire sheet rolls up

[Discussion]
The foamed laminate sheet obtained in Examples 1 to 8 can suppress large curling in the entire sheet because the foamed resin layer contains the nonionic type polyalkylene oxide modified product as a water absorbing component, and the curling resistance can be suppressed. The sex was good. On the other hand, the foamed laminate sheets obtained in Comparative Examples 1 and 2 did not contain the nonionic type polyalkylene oxide modified product in the foamed resin layer, and therefore, the entire sheet largely curled and the curl resistance was poor.

[Reference evaluation: Scratch resistance]
The load of 200 g is applied to the surface on the patterned layer side of the foam laminate sheet obtained in Examples 1 to 8 and Comparative Examples 1 and 2 in accordance with the "surface reinforced wallpaper performance specification" established by the Japan Vinyl Industry Association vinyl construction group. The scratch resistance test was performed for 5 cycles, and the scratch resistance was evaluated based on the following evaluation criteria. The results are shown in Table 3 below.
(Evaluation criteria)
· ○: no change in scratch marks (fuzziness) · Δ: slight change in scratch marks (fuzziness)
· :: Scratch marks greatly change (fuzzy)
· ×: The scratch mark resin was broken, and the backing paper was exposed

[Discussion]
From the results of Table 3, it is possible to contain ethylene-methacrylic acid copolymer (EMAA), which is an olefin-unsaturated carboxylic acid copolymer among olefin resins, and a crosslinked product thereof as the resin component of the foamed resin layer as a main component And the scratch resistance of the foam laminate sheet became better.

1 ... fibrous base material 2 ... foamed resin layer 3 ... non-foamed resin layer A
4 ... Non-foamed resin layer B
10 ... Foamed laminated sheet 20 ... Foaming agent-containing resin layer 100 ... Laminated sheet

Claims (10)

At least a fibrous base material, and a foamed resin layer disposed on one side of the fibrous base material,
The foamed resin layer contains a resin component and a water absorbing component,
A foam laminate sheet, wherein the water absorbing component contains as a main component nonionic cross-linked polyalkylene oxide.   The foamed laminate sheet according to claim 1, wherein the nonionic crosslinked polyalkylene oxide is a compound having a urethane bond in the molecule.   The foam laminated sheet of Claim 1 or Claim 2 whose content of the said water absorbing component is 5 mass parts or more and 30 mass parts or less with respect to 100 mass parts of said resin components.   The foam laminated sheet according to any one of claims 1 to 3, wherein a non-foamed resin layer A is provided on the surface of the foamed resin layer opposite to the surface on the side of the fibrous base material.   The foam laminated sheet according to any one of claims 1 to 4, wherein a non-foamed resin layer B is provided on the surface on the fibrous base material side of the foamed resin layer. At least a fibrous base material and a foaming agent-containing resin layer disposed on one side of the fibrous base material,
The foaming agent-containing resin layer contains a resin component, a water absorbing component, and a foaming agent,
A laminated sheet, wherein the water absorbing component is mainly composed of nonionic crosslinked polyalkylene oxide.   The laminated sheet according to claim 6, wherein the nonionic crosslinked polyalkylene oxide is a compound having a urethane bond in the molecule.   The laminated sheet according to claim 6 or 7, wherein a content of the water absorbing component is 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin component.   The laminated sheet according to any one of claims 6 to 8, wherein a non-foamed resin layer A is provided on the surface opposite to the surface on the side of the fibrous base material of the foaming agent-containing resin layer. .   The laminated sheet according to any one of claims 6 to 9, wherein a non-foamed resin layer B is provided on the surface on the fibrous base material side of the foaming agent-containing resin layer.