WO2020196767A1 - Foamed multilayer sheet, unfoamed multilayer sheet, fungicide, and resin composition - Google Patents

Abstract

The main purpose of the present disclosure is to provide a foamed multilayer sheet having a high fungicidal activity. This problem is solved by the provision in accordance with the present disclosure of a foamed multilayer sheet comprising a substrate and a foamed resin layer disposed on one surface side of the substrate, wherein the foamed resin layer contains a resin component and a fungicide, and the fungicide contains a first compound having a 2,4-dichlorophenethyl structure and an imidazole structure and a second compound having a 1H-pyrrole-3-carbonitrile structure and a 2,2-difluoro-1,3-benzodioxole structure.

Description

Foam laminated sheet, non-foamed laminated sheet, fungicide and resin composition

This disclosure relates to a foam laminated sheet.

For example, as wallpaper used for walls, ceilings, floors, etc., a foam laminated sheet in which a foamed resin layer is provided on a base material such as backing paper is known. Such a foamed laminated sheet is generally obtained by foaming a foaming agent-containing resin layer using a non-foamed laminated sheet having a base material and a foaming agent-containing resin layer containing a foaming agent.

It is known to add a fungicide to a foamed laminated sheet for the purpose of improving fungicide. For example, Patent Document 1 describes an antifungal agent for wallpaper containing 2-n-octyl-4-isothiazolin-3-one and methyl 2- (4-thiazolyl) -benzimidazole or 2-benzimidazole carbamate. The composition is disclosed.

Patent Document 2 discloses an antifungal resin composition containing an antibacterial antifungal agent composed of a benzimidazole compound, a phosphorus-based antioxidant, and a resin.

Japanese Unexamined Patent Publication No. 2003-192508 Japanese Unexamined Patent Publication No. 2004-18538

When a conventional fungicide is used, there is a problem that the fungicide is insufficient. The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a foamed laminated sheet having high antifungal properties.

In the present disclosure, it is a foamed laminated sheet having a base material and a foamed resin layer arranged on one surface side of the base material, and the foamed resin layer contains a resin component and a fungicide. However, the fungicide includes a first compound having a 2,4-dichlorophenethyl structure and an imidazole structure, a 1H-pyrrole-3-carbonitrile structure and a 2,2-difluoro-1,3-benzodioxole structure. Provided is a foamed laminated sheet containing the second compound having.

According to the present disclosure, a foamed laminated sheet having high antifungal properties can be obtained by using a combination of a first compound and a second compound as an antifungal agent.

In the above disclosure, the first compound may be a compound represented by the general formula (1), and R in the general formula (1) may be a carbon-containing group.

In the above disclosure, the first compound may be enilconazole.

In the above disclosure, the second compound is a compound represented by the general formula (2), R in the general formula (2) is a carbon-containing group, and n may be 0 or 1.

In the above disclosure, the second compound may be fludioxonyl.

In the above disclosure, the fungicide may further contain a third compound having a metal pyrithion structure.

In the above disclosure, the third compound is a compound represented by the general formula (3), M in the general formula (3) is Na, Zn, Fe, Cu or Ag, and n is 1 or It may be 2.

In the above disclosure, the foamed laminated sheet may have the non-foamed resin layer A at a position opposite to the base material with respect to the foamed resin layer.

In the above disclosure, the foamed laminated sheet may have a non-foamed resin layer B between the base material and the foamed resin layer.

In the above disclosure, the foamed resin layer may contain at least one of an olefin resin and a crosslinked product thereof as the resin component.

In the above disclosure, the olefin resin may be at least one of a polyolefin, an olefin vinyl ester copolymer, an olefin unsaturated carboxylic acid copolymer, and an olefin unsaturated carboxylic acid ester copolymer.

Further, in the present disclosure, the unfoamed laminated sheet having the base material and the foaming agent-containing resin layer arranged on one surface side of the base material, and the foaming agent-containing resin layer is a resin component. , A foaming agent and a fungicide, the fungicides include a first compound having a 2,4-dichlorophenethyl structure and an imidazole structure, and a 1H-pyrrole-3-carbonitrile structure and 2,2-. Provided is an unfoamed laminated sheet containing a second compound having a difluoro-1,3-benzodioxol structure.

According to the present disclosure, a non-foamed laminated sheet capable of forming a foamed laminated sheet having high antifungal properties can be obtained by using a combination of a first compound and a second compound as an antifungal agent.

Further, in the present disclosure, the fungicide used for the foamed laminated sheet, the first compound having a 2,4-dichlorophenethyl structure and an imidazole structure, the 1H-pyrrole-3-carbonitrile structure and the 2,2 Provided is an antifungal agent containing a second compound having a -difluoro-1,3-benzodioxole structure.

Further, in the present disclosure, the resin composition used for the foamed laminated sheet includes a resin component, a first compound having a 2,4-dichlorophenethyl structure and an imidazole structure, and 1H-pyrrole-3-carbonitrile. Provided is a resin composition comprising a fungicide containing a second compound having a structure and a 2,2-difluoro-1,3-benzodioxol structure.

The foamed laminated sheet in the present disclosure has the effect of having high antifungal properties.

It is the schematic sectional drawing which shows an example of the foam laminated sheet in this disclosure. It is the schematic sectional drawing which shows an example of the foam laminated sheet in this disclosure. It is the schematic sectional drawing which shows an example of the foam laminated sheet in this disclosure. It is the schematic sectional drawing which shows an example of the unfoamed laminated sheet in this disclosure.

Hereinafter, the foamed laminated sheet, the unfoamed laminated sheet, the fungicide, and the resin composition in the present disclosure will be described in detail.

A. Foam Laminated Sheet FIG. 1 is a schematic cross-sectional view showing an example of the foamed laminated sheet in the present disclosure. The foamed laminated sheet 10 shown in FIG. 1 has a base material 1 and a foamed resin layer 2 arranged on one surface side of the base material 1. The foamed resin layer 2 has a foamed cell S inside, and contains a resin component and a fungicide. One of the features of the present disclosure is that the first compound and the second compound are used in combination as the fungicide contained in the foamed resin layer 2.

Further, as shown in FIG. 2, the foamed laminated sheet 10 has a non-foamed resin layer A (non-foamed resin layer 3) at a position opposite to the base material 1 with respect to the foamed resin layer 2. May be good. Similarly, the foamed laminated sheet 10 may have a non-foamed resin layer B (non-foamed resin layer 4) between the base material 1 and the foamed resin layer 2. Further, as shown in FIG. 3, the foamed laminated sheet 10 may have a pattern pattern layer 5 and a surface protection layer 6.

According to the present disclosure, a foamed laminated sheet having high antifungal properties can be obtained by using a combination of a first compound and a second compound as an antifungal agent.

As described above, it is known to add a fungicide to the foamed laminated sheet for the purpose of improving the fungicide. However, when a conventional fungicide is used, there is a problem that the fungicide is insufficient. On the other hand, according to the present disclosure, a foamed laminated sheet having high antifungal properties can be obtained by using the first compound and the second compound in combination. Further, as described in Examples described later, when the first compound and the second compound are used in combination, the antifungal property is remarkably improved as compared with the case where both are used alone. That is, it was confirmed that a synergistic effect can be obtained by combining the two. Further, by using the first compound and the second compound in combination, good foamability can be obtained.

1. 1. Foamed resin layer The foamed resin layer is a layer arranged on one surface side of the base material. Further, the foamed resin layer contains at least a resin component and a fungicide.

(1) Antifungal agents The antifungal agents in the present disclosure include the first compound having a 2,4-dichlorophenethyl structure and an imidazole structure, and 1H-pyrrole-3-carbonitrile structure and 2,2-difluoro-1,3. -Contains a second compound having a benzodioxole structure. The first compound and the second compound usually have a function as a fungicide, respectively. The fungicide may further contain a third compound described below.

(I) First compound The first compound in the present disclosure has a 2,4-dichlorophenethyl structure and an imidazole structure. The 2,4-dichlorophenethyl structure is a structure represented by the following (Ph (Cl) ₂ CH ₂ CH _2- ) or a structure in which hydrogen thereof is replaced with another element or group.

On the other hand, the imidazole structure is a structure having at least an imidazole ring. The imidazole structure may be a monocyclic structure (a structure containing only an imidazole ring) or a fused ring structure (a condensed structure of an imidazole ring and another aromatic ring). In particular, the imidazole structure has a structure represented by the following (A-1) (C ₃ H ₃ N _2- ) or a structure represented by the following (A-2) (C ₇ H ₅ N _2- ). Is preferable.

The structure represented by (A-1) corresponds to a monocyclic imidazole structure, and the first compound having a monocyclic imidazole structure has an advantage that the risk of discoloration can be reduced. Further, hydrogen in this structure may be substituted with another element or group. On the other hand, the structure represented by (A-2) corresponds to the benzimidazole structure, and many types of the first compound having the benzimidazole structure are known as fungicides, and the range of material selection is widened. There is an advantage. Further, hydrogen in this structure may be substituted with another element or group.

Above all, in the present disclosure, it is preferable that the first compound is a compound represented by the following general formula (1).

In the general formula (1), R is an arbitrary group, but it is preferably a carbon-containing group containing at least carbon. The carbon number of the carbon-containing group is, for example, 1 or more, and may be 2 or more. On the other hand, the carbon number of the carbon-containing group is, for example, 15 or less, and may be 10 or less. Examples of the carbon-containing group include ^one R group and ^one OR group. R ¹ is preferably an unsaturated hydrocarbon group or a saturated hydrocarbon group. The unsaturated hydrocarbon group preferably has a carbon-carbon double bond. Further, the unsaturated hydrocarbon group may be an aromatic hydrocarbon group. On the other hand, examples of the saturated hydrocarbon group include an alkyl group.

In particular, the first compound is preferably enilconazole (imazaryl). Imazalil is a compound represented by the following.

The content of the first compound is, for example, 0.01 part by mass or more, 0.05 parts by mass or more, or 0.1 parts by mass or more with respect to 100 parts by mass of the resin component. .. If the content of the first compound is too small, good antifungal properties may not be obtained. On the other hand, the content of the first compound is, for example, 10 parts by mass or less, 5 parts by mass or less, or 3 parts by mass or less with respect to 100 parts by mass of the resin component. Even if the content of the first compound is too large, there may be no difference in mold resistance.

(Ii) Second compound The second compound in the present disclosure has a 1H-pyrrole-3-carbonitrile structure and a 2,2-difluoro-1,3-benzodioxole structure. The 1H-pyrrole-3-carbonitrile structure is a structure represented by the following, or a structure in which hydrogen thereof is substituted with another element or group.

On the other hand, the 2,2-difluoro-1,3-benzodioxole structure is a structure represented by the following or a structure in which hydrogen thereof is replaced with another element or group.

Above all, in the present disclosure, it is preferable that the second compound is a compound represented by the following general formula (2).

In the general formula (2), R is an arbitrary group, but it is preferably a carbon-containing group containing at least carbon. Further, n may be 0 or 1. When n is 0, the carbon (C) in the 1H-pyrrole-3-carbonitrile structure and the carbon (C) in the 2,2-difluoro-1,3-benzodioxole structure form a CC bond. Is forming. The carbon number of the carbon-containing group is, for example, 1 or more, and may be 2 or more. On the other hand, the carbon number of the carbon-containing group is, for example, 15 or less, and may be 10 or less. Examples of carbon-containing groups include unsaturated hydrocarbon groups and saturated hydrocarbon groups. The unsaturated hydrocarbon group may be an aromatic hydrocarbon group. On the other hand, examples of the saturated hydrocarbon group include an alkenyl group.

In particular, the second compound is preferably fludioxonyl. Fludioxonyl is a compound represented by the following.

The content of the second compound is, for example, 0.01 part by mass or more, 0.05 parts by mass or more, or 0.1 parts by mass or more with respect to 100 parts by mass of the resin component. .. If the content of the second compound is too small, good antifungal properties may not be obtained. On the other hand, the content of the second compound is, for example, 10 parts by mass or less, 5 parts by mass or less, or 3 parts by mass or less with respect to 100 parts by mass of the resin component. Even if the content of the second compound is too large, there may be no difference in antifungal properties.

The ratio (M ₂ / M ₁ ) of the mass (M ₂ ) of the second compound to the mass (M ₁ ) of the first compound is, for example, 0.1 or more, may be 0.3 or more, and 0. It may be 5 or more, 0.7 or more, or 0.9 or more. On the other hand, M ₂ / M ₁ is, for example, 10 or less, may be 5 or less, may be 3 or less, may be 2 or less, or may be 1.5 or less. It may be less than or equal to 1.

(Iii) Third compound The fungicide in the present disclosure may further contain a third compound having a metal pyrithion structure. By using the third compound, better antifungal properties can be obtained.

In the present disclosure, it is preferable that the third compound is a compound represented by the following general formula (3).

In the general formula (3), M is Na, Zn, Fe, Cu or Ag, and Na or Zn is particularly preferable. Further, n may be 1 or 2.

Among them, the third compound is preferably sodium (2-pyridylthio-1-oxide) or bis (2-pyridylthio-1-oxide) zinc, and the latter is particularly preferable. Zinc bis (2-pyridylthio-1-oxide), also referred to as zinc pyrithione, is a compound represented below.

The content of the third compound is, for example, 0.01 part by mass or more, 0.02 part by mass or more, or 0.03 part by mass or more with respect to 100 parts by mass of the resin component. .. If the content of the third compound is too low, the antifungal property against Alternaria, for example, may be low. On the other hand, the content of the third compound is, for example, 5 parts by mass or less, 3 parts by mass or less, or 1 part by mass or less with respect to 100 parts by mass of the resin component. If the content of the third compound is too high, the discoloration resistance may be low.

Further, the mass of the third compound (M) relative to the total mass (M ₁ + M ₂ + M ₃ ) of the mass of the first compound (M ₁ ), the mass of the second compound (M ₂ ), and the mass of the third compound (M ₃ ). The ratio of ₃ ) (M ₃ / (M ₁ + M ₂ + M ₃ )) is 0.01 or more, may be 0.05 or more, or may be 0.07 or more. On the other hand, M ₃ / (M ₁ + M ₂ + M ₃ ) is, for example, 0.5 or less, 0.25 or less, or 0.15 or less.

(2) Resin component The foamed resin layer preferably contains at least one of a resin and a crosslinked product thereof as a resin component. The crosslinked product is a crosslinked product in which the molecular chains of the resin are crosslinked, and may be, for example, a crosslinked product crosslinked by electron beam irradiation or a crosslinked product crosslinked by a crosslinking agent.

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, and the like. Examples include polycarbonate, polyester, polyphenylene sulphide, and polyether ether ketone. In the foamed resin layer, these may be contained individually by 1 type, and may contain 2 or more types.

In the present disclosure, it is preferable that the foamed resin layer contains at least one of an olefin resin and a crosslinked product thereof as a resin component. Olefin-based resins and crosslinked products thereof tend to be less likely to exhibit antifungal properties than, for example, vinyl chloride resins. However, by using the antifungal agent in the present disclosure, the foamed resin layer becomes an olefin-based resin and its crosslinked Good antifungal properties can be obtained even when a substance is contained. Examples of the olefin resin include polyolefins, olefin vinyl ester copolymers, olefin unsaturated carboxylic acid copolymers, and olefin unsaturated carboxylic acid ester copolymers.

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

The olefin vinyl ester copolymer is a copolymer containing olefin and vinyl ester as a monomer component, and may be a binary or ternary or more copolymer. Examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and 1-dodecene. On the other hand, examples of the vinyl ester include vinyl acetate, vinyl caproate, vinyl propionate, vinyl caprylate, vinyl laurate, and vinyl stearate.

Specific examples of the olefin vinyl ester copolymer include ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl acetate copolymer, and the like. Examples thereof include ethylene-vinyl acetate copolymer and ethylene-vinyl stearate copolymer.

The olefin unsaturated carboxylic acid copolymer is a copolymer containing an olefin and an unsaturated carboxylic acid as a monomer component, and may be a binary or 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 and 1-dodecene. On the other hand, examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, and fumaric acid.

Specific examples of the olefin unsaturated carboxylic acid copolymer include an ethylene-acrylic acid copolymer (EAA) and an ethylene-methacrylic acid copolymer (EMAA).

Examples of the olefin unsaturated carboxylic acid ester copolymer include ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl methacrylate copolymer (EMMA), and ethylene-ethyl. Methacrylate copolymer (EEMA) can be mentioned.

The foamed resin layer preferably contains at least one of an olefin resin and a crosslinked product thereof as a main component as a resin component. In this case, the foamed resin layer may contain an olefin resin as a main component, or may contain a crosslinked product of the olefin resin as a main component, and may contain a mixture of the olefin resin and the crosslinked product thereof. It may be contained as a main component. The ratio of at least one of the olefin resin and the crosslinked product thereof to all the resin components of the foamed resin layer is, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more. You may. Further, the foamed resin layer may contain at least one of an olefin resin and a crosslinked product thereof as a resin component.

The melt flow rate (MFR) value of the resin used for the foamed resin layer is, for example, 5 g / 10 minutes or more, and may be 20 g / 10 minutes or more from the viewpoint of melt extrusion suitability. On the other hand, the MFR value of the resin is, for example, 200 g / 10 minutes or less, and may be 100 g / 10 minutes or less. If the MFR value is too large, the obtained foamed resin layer may be too soft and the scratch resistance may be poor.

The content of the resin component in the foamed resin layer is, for example, 30% by mass or more and 80% by mass or less, 40% by mass or more and 70% by mass or less, and 50% by mass or more and 60% by mass or less. There may be. If the content of the resin component is too large, a sufficient foaming ratio may not be obtained. On the other hand, if the content of the resin component is too small, the extrusion film forming property may be inferior.

(3) Inorganic Filler The foamed resin layer may contain an inorganic filler for the purpose of imparting flame retardancy, suppressing see-through, improving surface strength, and the like. The inorganic filler is not particularly limited, and examples thereof include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, molybdate compound, and titanium dioxide. 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 may be, for example, 0 parts by mass or more and 100 parts by mass or less, and 20 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the resin component. ..

(4) Additives The foamed resin layer contains pigments, antioxidants, light stabilizers, cross-linking agents, cross-linking aids, foaming aids, insect repellents, preservatives, antibacterial agents, diluents, and deodorants, if necessary. It may contain additives such as agents and plasticizers. Further, a non-foaming foaming agent may be contained.

(5) Structure of foamed resin layer The foamed resin layer has a foamed cell inside. The foam cell may be a closed cell or an open cell, and the closed cell and the open cell may be mixed. Further, the number, size, density, shape, etc. of the foamed cells are not particularly limited, and can be appropriately designed according to the type, application, etc. of the foamed laminated sheet in the present disclosure. The foam cell can be formed by foaming the 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 may be, for example, 350 μm or more and 1500 μm or less, and 500 μm or more and 1200 μm or less.

2. 2. Base material The base material in the present disclosure is a member that holds the foamed resin layer. Examples of such a base material include a fibrous base material. Examples of the fibrous base material include known materials used for wallpaper applications such as paper, non-woven fabric, and woven fabric. The above-mentioned paper may be general paper or flame-retardant paper.

Flame retardant paper is paper that contains a flame retardant in general paper. Examples of the flame retardant include nitrogen compounds such as urea and ammonium compounds; hydroxides (preferably hydrates) such as magnesium hydroxide and aluminum hydroxide; and flame retardants containing self-extinguishing phosphorus or halogen elements. Be done. Among them, compounds containing water of crystallization, such as magnesium hydroxide, can be made flame-retardant by the heat of vaporization of water of crystallization during combustion decomposition.

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

The base material can contain any material such as a dry paper strength enhancer, a wet paper strength enhancer, a colorant, a sizing agent, and a fixing agent, if necessary.

The thickness of the base material is not particularly limited, and can be appropriately set according to the use of the foamed laminated sheet in the present disclosure. The basis weight of the base material is, for example, 30 g / m ² or more and 100 g / m ² or less, and may be 50 g / m ² or more and 70 g / m ² or less.

3. 3. Arbitrary Configuration The foamed laminated sheet in the present disclosure has a base material and a foamed resin layer arranged on one surface side of the base material. Further, the foam laminated sheet may have an arbitrary configuration.

(1) Non-foamed resin layer A
The foamed laminated sheet in the present disclosure may have the non-foamed resin layer A at a position opposite to the base material with respect to the foamed resin layer. By providing the non-foamed resin layer A, for example, the surface strength of the foamed resin layer can be increased. That is, the non-foamed resin layer A preferably functions as a protective layer for the foamed resin layer.

The non-foamed resin layer A preferably contains at least one of a resin and a crosslinked product thereof as a resin component. The crosslinked product is a crosslinked product in which the molecular chains of the resin are crosslinked, and may be, for example, a crosslinked product crosslinked by electron beam irradiation or a crosslinked product crosslinked by a crosslinking agent.

Examples of the above-mentioned resin include olefin-based resin, methacrylic-based resin, thermoplastic polyester-based resin, polyvinyl alcohol-based resin, and fluorine-based resin. In the non-foamed resin layer A, these may be contained individually by 1 type, and may contain 2 or more types.

Examples of the olefin resin include the same materials as those in the foamed resin layer described above. Preferred olefin-based resins used for the non-foamed resin layer A include, for example, polyethylene (low density polyethylene (LDPE), high density polyethylene (HDPE)), polypropylene, polybutene, polybutadiene, polyisoprene and other resin units, and ethylene. Copolymer of α-olefin having 4 or more carbon atoms (linear low density polyethylene (LLDPE)), ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene -Ethylene (meth) acrylic acid-based copolymer such as methacrylic acid copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate copolymer saponified product, ethylene-vinyl alcohol copolymer, ionomer Can be mentioned. In addition, "(meth) acrylic acid" means at least one of acrylic acid and methacrylic acid. The same applies to the parts described as other (meta).

The non-foaming resin layer A may contain known additives such as fillers, colorants, light stabilizers, foaming agents, and other lubricants and antibacterial agents. 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, but is, for example, 2 μm or more and 50 μm or less.

(2) Non-foamed resin layer B
The foamed laminated sheet in the present disclosure may have a non-foamed resin layer B between the base material and the foamed resin layer. The non-foamed resin layer B has, for example, an adhesive function, so that the adhesiveness between the foamed resin layer and the base material can be enhanced.

The non-foamed resin layer B preferably contains at least one of a resin and a crosslinked product thereof as a resin component. The crosslinked product is a crosslinked product in which the molecular chains of the resin are crosslinked, and may be, for example, a crosslinked product crosslinked by electron beam irradiation or a crosslinked product crosslinked by a crosslinking agent.

Examples of the above resin include olefin resins. Examples of the olefin resin include the same materials as those in the foamed resin layer described above. Preferred olefin-based resins used for the non-foamed resin layer B include, for example, ethylene-vinyl acetate copolymer (EVA). The content (copolymerization ratio) of the vinyl acetate component (VA component) in the ethylene-vinyl acetate copolymer (EVA) is, for example, 10% by mass or more and 46% by mass or less, and 15% by mass or more and 41% by mass. It may be as follows. The thickness of the non-foamed resin layer B is not particularly limited, but is, for example, 5 μm or more and 50 μm or less.

(3) Pattern pattern layer The foamed laminated sheet in the present disclosure may have a pattern pattern layer at a position opposite to the base material with respect to the foamed resin layer. By providing the pattern pattern layer, the foam laminated sheet can be easily imparted with design. The foamed laminated sheet in the present disclosure does not have to have a pattern layer.

The pattern pattern layer may be in direct contact with the foamed resin layer, or may be in contact with the primer layer or the adhesive layer. When the foamed laminated sheet has the non-foamed resin layer A, the foamed laminated sheet may have the foamed resin layer, the non-foamed resin layer A, and the pattern layer in this order. In this case, the pattern layer may be in direct contact with the non-foamed resin layer A, or may be in contact with the primer layer or the adhesive layer.

The pattern pattern layer has at least a pattern pattern portion, and may have a support portion that supports the pattern pattern portion depending on the method of forming the pattern pattern layer.

The pattern in the pattern part is not particularly limited and can be appropriately selected according to the purpose. Examples of the pattern include a wood grain pattern, a stone grain pattern, a sand grain pattern, a tiled pattern, a brickwork pattern, a cloth grain pattern, a squeezed pattern, a geometric figure, a character, a symbol, an abstract pattern, and a flower pattern.

The pattern pattern layer can be formed by printing the pattern pattern portion on one surface of the support portion using printing ink, for example. Further, instead of the support portion, the pattern portion may be directly printed on the surface of the foamed resin layer or the non-foamed resin layer A using printing ink.

The printing ink contains, for example, a colorant, a binder resin, and a solvent at least. Regarding the details of the composition of the printing ink, for example, the same composition as that of the printing ink used for forming the pattern layer disclosed in JP-A-2017-43009 and JP-A-2011-179161 can be adopted. Further, as the printing ink, a known or commercially available ink can be used. The printing method is not particularly limited, and a known printing method can be used. Further, when the pattern portion is formed in a solid shape on the entire surface, a known coating method can also be used.

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

(4) Surface Protective Layer The foamed laminated sheet in the present disclosure may have a surface protective layer at a position opposite to the base material with respect to the foamed resin layer. By providing the surface protective layer, the surface strength of the foamed laminated sheet can be increased.

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. For example, for the purpose of gloss adjustment, the surface protective layer may contain a known matting agent such as silica. Further, when the purpose is to protect the pattern layer, or when the purpose is to improve scratch resistance or stain resistance, the surface protection layer contains, for example, a cured product of an ionizing radiation curable resin as a resin component. You may be doing it.

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

The surface protective layer may be in direct contact with the foamed resin layer, or may be in contact with the primer layer or the adhesive layer.

When the foamed laminated sheet has the non-foamed resin layer A, the foamed laminated sheet preferably has the foamed resin layer, the non-foamed resin layer A, and the surface protective layer in this order. In this case, the surface protective layer may be in direct contact with the non-foamed resin layer A, or may be in contact with the primer layer or the adhesive layer.

When the foamed laminated sheet has a pattern layer, the foamed laminated sheet preferably has a foamed resin layer, a pattern layer, and a surface protection layer in this order. In this case, the surface protective layer may be in direct contact with the pattern layer, or may be in contact with the primer layer or the adhesive layer. When the foamed laminated sheet has the non-foamed resin layer A and the pattern layer, the foamed laminated sheet preferably has the foamed resin layer, the non-foamed resin layer A, the pattern layer, and the surface protection layer in this order.

(5) Primer Layer The foamed laminated sheet in the present disclosure may have a primer layer between the layers constituting the foamed laminated sheet.

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

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

The primer layer is arranged, for example, between the base material and the non-foaming resin layer B, between the non-foaming resin layer B and the foaming resin layer, between the foaming resin layer and the non-foaming resin layer A, and non-foaming. Examples thereof include an layer between the resin layer A and the pattern layer, an layer between the non-foamed resin layer A and the surface protective layer, and an layer between the pattern layer and the surface protective layer.

(6) Embossed pattern The foamed laminated sheet in the present disclosure may have an embossed pattern on the outermost surface on the opposite side of the base material with respect to the foamed resin layer. Examples of the embossed pattern include a wood grain conduit groove, a stone plate surface unevenness, a cloth surface texturer, a satin finish, a grain, a hairline, and a perforated groove, and a combination thereof may be used.

4. Applications The foamed laminated sheet in the present disclosure can be used as an interior material such as foam wallpaper and various decorative materials. Above all, it is useful as a foam wallpaper.

5. Manufacturing Method The manufacturing method of the foamed laminated sheet in the present disclosure is not particularly limited, but for example, a method having a foaming step of heating a foaming agent-containing resin layer of a non-foamed laminated sheet to be described later and foaming to form a foamed resin layer. Can be mentioned. The heating temperature and heating time in the foaming step are not particularly limited as long as the foaming cell can be formed in the layer by decomposing the foaming agent contained in the foaming agent-containing resin layer, and the composition of the foaming agent-containing resin layer is not limited. It can be set as appropriate according to the situation.

B. Non-foamed laminated sheet FIG. 4 is a schematic cross-sectional view showing an example of the unfoamed laminated sheet in the present disclosure. The unfoamed laminated sheet 11 shown in FIG. 4 has a base material 1 and a foaming agent-containing resin layer 2a arranged on one surface side of the base material 1. The foaming agent-containing resin layer 2a contains a resin component, a foaming agent, and a fungicide. One of the features of the present disclosure is the use of two specific compounds as the fungicide contained in the foaming agent-containing resin layer 2a.

According to the present disclosure, a non-foamed laminated sheet capable of forming a foamed laminated sheet having high antifungal properties can be obtained by using a combination of a first compound and a second compound as an antifungal agent.

1. 1. Foaming Agent-Containing Resin Layer The foaming agent-containing resin layer contains at least a resin component, a foaming agent, and a fungicide. Since the resin component and the fungicide are the same as those described in "A. Foamed Laminated Sheet" above, the description here is omitted.

The foaming agent contained in the foaming agent-containing resin layer can be selected from known foaming agents. Examples of the foaming agent include azo-based foaming agents such as azodicarbonamide (ADCA) and azobisformamide; organic thermal-decomposable foaming agents such as hydrazide-based oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide, and microcapsules. Examples include mold foaming agents and inorganic foaming agents such as baking soda. These may be contained alone in the foaming agent-containing resin layer, or may be contained in two or more types.

The content of the foaming agent can be appropriately set according to the type of foaming agent, the foaming ratio, and the like. The foaming ratio is, for example, 1.5 times or more, and may be 3 times or more and 7 times or less. The content of the foaming agent is, for example, 1 part by mass or more and 20 parts by mass or less, and 3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component contained in the foaming agent-containing resin composition. It may be.

The foaming agent-containing resin layer may contain a foaming aid. Examples of the foaming aid include known materials used as the foaming aid, such as metal oxides and fatty acid metal salts, which can be appropriately selected depending on the type of foaming agent. Specifically, as a foaming aid, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, magnesium laurate, zinc oxide, magnesium oxide, carboxylic acid. Examples thereof include acid hydrazide compounds. These may be contained alone in the foaming agent-containing resin layer, or may be contained in two or more types.

When the 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, the efficacy of the foaming aid is not easily deactivated by a chemical reaction. Therefore, it is possible to suppress yellowing of the foamed resin layer, the base material, and the like due to burning and formation of chromophores that occur when the foaming agent-containing resin layer is foamed. Examples of the carboxylic acid hydrazide compound include 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 alone in the foaming agent-containing resin composition, or may be contained in two or more types.

The content of the foaming aid is not particularly limited, but is, for example, 0.3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component contained in the foaming agent-containing resin layer, and 1 part by mass. The above may be 5 parts by mass or less.

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

The foaming agent-containing resin layer may contain the above-mentioned inorganic filler and various additives. The thickness of the foaming agent-containing resin layer may be, for example, 30 μm or more and 300 μm or less, and may be 50 μm or more and 150 μm or less.

2. 2. Base material The base material in the non-foamed laminated sheet in the present disclosure is the same as that described in "A. Foamed laminated sheet" above, and thus the description thereof is omitted here.

3. 3. Optional Configuration The unfoamed laminated sheet in the present disclosure has a base material and a foaming agent-containing resin layer arranged on one surface side of the base material. Further, the non-foamed laminated sheet may have an arbitrary configuration such as a non-foaming resin layer A, a non-foaming resin layer B, a pattern pattern layer, a surface protection layer, a primer layer, and an embossed pattern. Since these configurations are the same as those described in the above "A. Foam laminated sheet", the description here is omitted. Further, the unfoamed laminated sheet in the present disclosure is usually a sheet used for manufacturing the above-mentioned foamed laminated sheet.

4. Manufacturing Method The manufacturing method of the unfoamed laminated sheet in the present disclosure is not particularly limited, but for example, a foaming agent-containing resin composition containing a resin component, a foaming agent, and a fungicide is used on a substrate. A method having a foaming agent-containing resin layer forming step for forming a foaming agent-containing resin layer can be mentioned.

As a method for forming the foaming agent-containing resin layer, for example, an extrusion laminating method in which the foaming agent-containing resin composition is extruded onto a base material by a T-die extruder to form a film can be used. Alternatively, the foaming agent-containing resin composition may be extruded to form a sheet of the foaming agent-containing resin layer, and then the sheet of the foaming agent-containing resin layer may be laminated on the base material in a separate step. The cylinder temperature and die temperature during extrusion film formation can be adjusted as appropriate.

Further, after the foaming agent-containing resin layer forming step, an electron beam irradiation step of irradiating the foaming agent-containing resin layer with an electron beam to crosslink the resin component may be performed. The resin component contained in the foaming agent-containing resin layer can be crosslinked to form a crosslinked product, and the surface strength, foaming characteristics, etc. of the finally obtained foamed resin layer can be adjusted. The energy intensity of the electron beam is, for example, 150 kV or more and 250 kV or less, and may be 175 kV or more and 200 kV or less. The irradiation amount may be, for example, 10 kGy or more and 100 kGy or less, and may be 10 kGy or more and 50 kGy or less. A known electron beam irradiation device can be used as the electron beam source.

Further, a non-foaming resin layer forming step of forming a non-foaming resin layer on one side or both sides of the foaming agent-containing resin layer may be performed. The non-foamed resin layer may be formed by extrusion film formation, or may be formed by heat laminating each film. Of these, simultaneous extrusion film formation using a T-die extruder is preferable. For example, when both the non-foaming resin layer A and the non-foaming resin layer B are provided, the foaming agent-containing resin composition and each non-foaming are used by using a multi-manifold type T-die capable of simultaneously forming three layers. By simultaneously extruding the resin composition for forming the resin layer, that is, by simultaneously performing the foaming agent-containing resin layer forming step and the non-foaming resin layer forming step, the non-foaming resin layer A, the foaming agent-containing resin layer, and the non-foaming resin layer are formed. A three-layer laminate in which the foamed resin layers B are laminated in this order can be formed.

When the foaming agent-containing resin composition contains an inorganic substance such as a pigment, it is preferable to use a method using a three-layer simultaneous extrusion film forming method. When the foaming agent-containing resin layer is formed by extrusion film formation, inorganic residue (rheumatism) is likely to be generated at the extrusion port of the extruder, and this is likely to become a foreign substance on the surface of the foaming agent-containing resin layer. On the other hand, using the method of three-layer simultaneous extrusion film formation, the foaming agent-containing resin layer and the non-foaming resin layer are simultaneously formed by sandwiching the foaming agent-containing resin layer between the non-foaming resin layers containing no inorganic substances. As a result, it is possible to suppress the occurrence of eyes and eyes.

Further, if necessary, each step of forming the pattern pattern layer, the primer layer and the surface protection layer may be performed. The method for forming each layer of the pattern layer, the primer layer and the surface protection layer is not particularly limited, and examples thereof include a conventional coating method such as printing and coating, and an extrusion film forming method.

C. Antifungal agent The antifungal agent used in the present disclosure is a fungicide used for a foamed laminated sheet, and is a first compound having a 2,4-dichlorophenethyl structure and an imidazole structure, and a 1H-pyrrole-3-carbonitrile structure. And a second compound having a 2,2-difluoro-1,3-benzodioxol structure. Since the fungicide is the same as the above-mentioned contents, the description here is omitted.

Further, the fungicide in the present disclosure may contain only the first compound and the second compound, and may further contain other compounds. Examples of other compounds include the above-mentioned third compound. In addition, examples of other compounds include inorganic fillers. Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, molybdate compound, and titanium dioxide. Further, the inorganic filler preferably functions as a carrier for supporting the first compound and the second compound. This is because the dispersibility of the first compound and the second compound is improved. Similarly, the inorganic filler preferably functions as a carrier carrying a tertiary compound.

Further, the fungicide in the present disclosure can be added to any layer in the foamed laminated sheet, but it is preferably added to the foamed resin layer. Further, the fungicide used in the present disclosure may be a fungicide used for a non-foamed laminated sheet. In this case, it can be added to any layer in the unfoamed laminated sheet, but it is preferably added to the foaming agent-containing resin layer.

D. Resin Composition The resin composition in the present disclosure is a resin composition used for a foamed laminated sheet, which is a resin component, a first compound having a 2,4-dichlorophenethyl structure and an imidazole structure, and 1H-pyrrole-. Includes a fungicide containing a second compound having a 3-carbonitrile structure and a 2,2-difluoro-1,3-benzodioxol structure. Since the fungicide and the resin component are the same as those described above, the description thereof is omitted here. Furthermore, the resin composition may further contain at least one of the above-mentioned inorganic fillers and additives.

Further, the resin composition in the present disclosure can be used for producing an arbitrary layer containing a resin in the foamed laminated sheet, but it is preferably used for producing a foamed resin layer. Further, the resin composition in the present disclosure may be a resin composition used for a non-foamed laminated sheet. In this case, it can be used to prepare an arbitrary layer containing a resin, but it is preferably used to prepare a foaming agent-containing resin layer.

Note that the present disclosure is not limited to the above embodiment. The above embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present disclosure and exhibiting the same action and effect is described in this invention. Included in the technical scope of the disclosure.

[Example 1]
A foaming agent-containing resin composition was prepared by melt-kneading with the formulation shown below.
-Resin: EVA "EV450: Mitsui-Dupont Polychemical Co., Ltd." 100 parts by mass-Inorganic filler: Titanium dioxide "CR58-2: Ishihara Sangyo Co., Ltd." 20 parts by mass-Foamant: Azo-based foaming agent "Vinihole AC # 3: manufactured by Eiwa Kasei Kogyo Co., Ltd." 4 parts by mass, foaming aid: hydrazide-based foaming aid "ADH: manufactured by Otsuka Chemical Co., Ltd." 2 parts by mass, fungicide 1: "Imazaril" 0 .2 parts by mass, fungicide 2: "fludioxonyl" 0.2 parts by mass

The following resins were prepared as the resins used for the non-foamed resin layers A and B.
-Non-foamed resin layer A: Resin LDPE "LC604: Made by Japan Polyethylene Corporation"
-Non-foamed resin layer B: Resin EVA "EV40W: Mitsui / Dupont Polychemical Co., Ltd."

The foaming agent-containing resin composition and the resins for the non-foaming resin layers A and B were extruded at the same time using a multi-manifold type T-die capable of simultaneously forming three layers. As a result, a three-layer laminate in which the non-foaming resin layer A (10 μm), the foaming agent-containing resin layer (100 μm), and the non-foaming resin layer B (10 μm) were laminated in this order was formed. Then, a backing paper (fibrous base material) was laminated on the surface of the non-foamed resin layer B to obtain an unfoamed laminated sheet. The extrusion conditions were a cylinder temperature of 110 ° C. and a die temperature of 120 ° C.

The obtained unfoamed laminated sheet was irradiated with an electron beam (200 kV, 35 kGy) from the non-foamed resin layer A side. Next, an acrylic water-based ink (manufactured by Showa Ink) was coated on the non-foamed resin layer A using a gravure printing machine to form a pattern layer. Then, it 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, and a foamed laminated sheet was obtained.

[Example 2]
A foam laminated sheet was obtained in the same manner as in Example 1 except that the proportions of the fungicides 1 and 2 were changed to 0.1 parts by mass, respectively.

[Example 3]
A foam laminated sheet was obtained in the same manner as in Example 1 except that the type of resin was changed to EMAA "N1110H: manufactured by Mitsui-Dupont Polychemical Co., Ltd."

[Example 4]
A foaming agent-containing resin composition was prepared by melt-kneading with the formulation shown below. A foam laminated sheet was obtained in the same manner as in Example 1 except that the obtained foaming agent-containing resin composition was used.
-Resin: EVA "EV450: Mitsui-Dupont Polychemical Co., Ltd." 100 parts by mass-Inorganic filler: Titanium dioxide "CR58-2: Ishihara Sangyo Co., Ltd." 20 parts by mass-Foamant: Azo-based foaming agent "Vinihole AC # 3: manufactured by Eiwa Kasei Kogyo Co., Ltd." 4 parts by mass, foaming aid: hydrazide-based foaming aid "ADH: manufactured by Otsuka Chemical Co., Ltd." 2 parts by mass, fungicide 1: "Imazaril" 0 .18 parts by mass, fungicide 2: "fludioxonyl" 0.18 parts by mass, fungicide 3: "zincpyrythion" 0.04 parts by mass

[Example 5]
A foamed laminated sheet was obtained in the same manner as in Example 4 except that the proportions of the fungicides 1, 2 and 3 were changed to 0.36 parts by mass, 0.36 parts by mass and 0.08 parts by mass, respectively. It was.

[Example 6]
A foamed laminated sheet was obtained in the same manner as in Example 4 except that the type of resin was changed to EMAA "N1110H: manufactured by Mitsui-Dupont Polychemical Co., Ltd."

[Comparative Example 1]
A foam laminated sheet was obtained in the same manner as in Example 1 except that the fungicides 1 and 2 were not used.

[Comparative Example 2]
A foamed laminated sheet was obtained in the same manner as in Example 1 except that the fungicide 2 (fludioxonyl) was not used and the proportion of the fungicide 1 (imazaryl) was changed to 0.4 parts by mass.

[Comparative Example 3]
A foamed laminated sheet was obtained in the same manner as in Example 1 except that the ratio of the fungicide 2 (fludioxonyl) was changed to 0.4 parts by mass without using the fungicide 1 (imazaryl).

[Comparative Example 4]
Foam lamination in the same manner as in Example 1 except that 2-n-octyl-4-isothiazolin-3-one "Bioside 7663: manufactured by Taisho Technos Co., Ltd." was used instead of the fungicides 1 and 2. I got a sheet.

[Evaluation]
[Antifungal]
(JIS test)
The mold resistance of the foamed laminated sheets obtained in Examples 1 to 6 and Comparative Examples 1 to 4 was evaluated. Specifically, the test was conducted in accordance with the "Antifungal Wallpaper Performance Regulations" (JIS Z 2911-2010 Mold Resistance Test A Method) established by the Wallpaper Industry Association. The evaluation criteria are as follows. The performance standard of "mold prevention" is to satisfy 0.

(Test for Alternaria)
The foam laminated sheets obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were tested against Alternaria. In the above JIS test, five common fungi such as black mold and blue mold were used, but instead of them, Alternaria was used as a single fungus. Alternaria is a type of fungus that is frequently detected in foamed laminated sheets (for example, wallpaper) in which mold is generated.

[Discoloration resistance]
The discoloration resistance of the foam laminated sheets obtained in Examples 1 to 6 and Comparative Examples 1 to 4 was evaluated. Specifically, using an ultraviolet fade meter (manufactured by Suga Test Instruments Co., Ltd .: "U48AU"), the temperature of the black panel is set to 63 ° C., and ultraviolet rays having a peak of spectral irradiance at a wavelength of 380 nm are emitted at a wavelength of 300 to 700 nm. Irradiation was performed at an irradiance of 500 W / m ² for 40 hours. The color difference ΔE of the same portion before and after irradiation with ultraviolet rays was determined, and the case where ΔE was 1.0 or less was evaluated as ◯, and the case where ΔE exceeded 1.0 was evaluated as ×.

As shown in Table 2, in Examples 1 to 6, high antifungal properties were obtained in the JIS test. In particular, in Examples 4 to 6, the antifungal property against Alternaria was also good. Since there is no standard for the performance of "mold prevention" against Alternaria, the performance standard used in the above JIS test was applied mutatis mutandis. In Examples 1 to 3, although the growth of hyphae of Alternaria was slightly confirmed under a microscope, the fungal property was relatively good. On the other hand, in Comparative Example 1, since the antifungal agent was not added, the antifungal property was remarkably low. Further, in Comparative Examples 2 and 3, the fungicide 1 (imazaryl) and the fungicide 2 (fludioxonyl) were used alone, but the fungicide was lower than that of Examples 1 to 6. From these results, it was confirmed that the results of Examples 1 to 6 were due to the synergistic effect of the fungicides 1 and 2. Further, the fungicide used in Comparative Example 4 is, for example, the fungicide described in Patent Document 1, but the fungicide was lower than that of Examples 1 to 6. In Examples 1 to 6 and Comparative Examples 1 to 4, good discoloration resistance was obtained.

1 ... Base material 2 ... Foamed resin layer 2a ... Foaming agent-containing resin layer 3 ... Non-foamed resin layer A
4 ... Non-foamed resin layer B
5 ... Pattern pattern layer 6 ... Surface protection layer 10 ... Foamed laminated sheet 11 ... Unfoamed laminated sheet

Claims (14)

1. A foamed laminated sheet having a base material and a foamed resin layer arranged on one surface side of the base material.
   The foamed resin layer contains a resin component and a fungicide, and contains
   The fungicide has a first compound having a 2,4-dichlorophenethyl structure and an imidazole structure, and a 1H-pyrrole-3-carbonitrile structure and a 2,2-difluoro-1,3-benzodioxol structure. A foamed laminated sheet containing a second compound.
2. The foamed laminated sheet according to claim 1, wherein the first compound is a compound represented by the general formula (1), and R in the general formula (1) is a carbon-containing group.
   

   
3. The foamed laminated sheet according to claim 1 or 2, wherein the first compound is enilconazole.
4. 1 to 3, wherein the second compound is a compound represented by the general formula (2), R in the general formula (2) is a carbon-containing group, and n is 0 or 1. The foamed laminated sheet according to any one of the claims.
   

   
5. The foamed laminated sheet according to any one of claims 1 to 4, wherein the second compound is fludioxonyl.
6. The foamed laminated sheet according to any one of claims 1 to 5, wherein the fungicide further contains a third compound having a metal pyrithion structure.
7. Claimed that the third compound is a compound represented by the general formula (3), M in the general formula (3) is Na, Zn, Fe, Cu or Ag, and n is 1 or 2. Item 6. The foamed laminated sheet according to Item 6.
   

   
8. The foam according to any one of claims 1 to 7, wherein the foamed laminated sheet has a non-foamed resin layer A at a position opposite to the base material with respect to the foamed resin layer. Laminated sheet.
9. The foamed laminated sheet according to any one of claims 1 to 8, wherein the foamed laminated sheet has a non-foamed resin layer B between the base material and the foamed resin layer.
10. The foamed laminated sheet according to any one of claims 1 to 9, wherein the foamed resin layer contains at least one of an olefin resin and a crosslinked product thereof as the resin component.
11. The foamed laminated sheet according to claim 10, wherein the olefin resin is at least one of a polyolefin, an olefin vinyl ester copolymer, an olefin unsaturated carboxylic acid copolymer, and an olefin unsaturated carboxylic acid ester copolymer.
12. An unexpanded laminated sheet having a base material and a foaming agent-containing resin layer arranged on one surface side of the base material.
    The foaming agent-containing resin layer contains a resin component, a foaming agent, and a fungicide.
    The fungicide has a first compound having a 2,4-dichlorophenethyl structure and an imidazole structure, and a 1H-pyrrole-3-carbonitrile structure and a 2,2-difluoro-1,3-benzodioxol structure. An unfoamed laminated sheet containing a second compound.
13. A fungicide used for foam laminated sheets
    Contains a first compound having a 2,4-dichlorophenethyl structure and an imidazole structure, and a second compound having a 1H-pyrrole-3-carbonitrile structure and a 2,2-difluoro-1,3-benzodioxole structure. Antifungal agent.
14. A resin composition used for a foam laminated sheet.
    With resin components
    Contains a first compound with a 2,4-dichlorophenethyl structure and an imidazole structure, and a second compound with a 1H-pyrrole-3-carbonitrile structure and a 2,2-difluoro-1,3-benzodioxol structure. Antifungal agent and
    A resin composition comprising.

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