JP7632167B2 - Odor sealants for floors and floor coverings - Google Patents

Description

The present invention relates to an odor sealant for floors that is used together with flooring materials that are laid on the floor surfaces of indoor or outdoor buildings, or to flooring materials that include an odor sealant for floors.

In the past, strong odors and unpleasant smells could occur indoors due to the deterioration of buildings and the living conditions of residents. Such odors are caused, for example, by various chemical substances contained in building materials laid on the floors of buildings or indoor odors that have permeated the building materials and spread throughout the room. In such cases, the livability and comfort of the house are reduced.
In response to this, a flooring material has been proposed that is formed by providing a carbonized layer on the floor surface and that deodorizes the room by utilizing the surface activity of the carbonized material (Patent Document 1).

JP 2013-159941 A

The odors that adhere to typical flooring materials with high design properties can be difficult to eliminate through typical cleaning or repairs. However, when such flooring materials are used in place of typical flooring materials, it becomes difficult to impart a wide variety of design properties.
In recent years, in consideration of the environment, there has been progress in the development of gas barrier materials that use paper as a base material, without using synthetic resin films or the like.
The present invention has been made to solve these problems, and its object is to provide an odor sealing material for floors and a flooring material that are environmentally friendly and can suppress the adhesion of odors to buildings and the diffusion of odors from building materials to which odors have adhered.

In order to solve the above problems, an odor sealant for floors according to one embodiment of the present invention is characterized by comprising, in this order, a paper substrate, a layer containing a polyvinyl alcohol resin, a vapor deposition layer, a layer containing a polyolefin having a carboxyl group and at least one selected from a salt of a carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester, a primer layer, and an adhesive layer.

In order to solve the above problems, an odor sealant for floors according to one embodiment of the present invention is characterized by comprising, in this order, a layer containing a polyolefin having a carboxyl group and at least one selected from a salt of the carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester, a vapor deposition layer, a layer containing a polyvinyl alcohol-based resin, a paper substrate, a primer layer, and an adhesive layer.

In order to solve the above problems, a flooring material according to one aspect of the present invention is characterized by comprising the odor sealant for floors described above and a surface substrate attached to the surface of the odor sealant for floors.

According to the present invention, it is possible to obtain an odor-sealing material for floors and a flooring material that can suppress the adhesion of odors to buildings while being environmentally friendly.

1 is a cross-sectional view showing an example of the configuration of an odor sealant for floors according to a first embodiment of the present invention. FIG. FIG. 4 is a cross-sectional view showing an example of the configuration of an odor sealant for floors according to a second embodiment of the present invention. FIG. 4 is a cross-sectional view showing an example of the configuration of a flooring material according to a third embodiment of the present invention. FIG. 11 is a cross-sectional view showing an example of the configuration of a flooring material according to a fourth embodiment of the present invention.

The present invention will be described below through embodiments, but the following embodiments do not limit the invention according to the claims. In addition, not all of the combinations of features described in the embodiments are necessarily essential to the solution of the invention. In addition, the drawings are schematic diagrams of the invention according to the claims, and the dimensions of the width, thickness, etc. of each part are different from the actual ones, and the ratios between them are also different from the actual ones.
Hereinafter, each aspect of an embodiment of the present invention will be described with reference to the drawings.

The odor sealant for floors and flooring having the odor sealant for floors according to an embodiment of the present invention will be described below with reference to Figs. 1 to 4. The odor sealant for floors according to an embodiment of the present invention is laid, for example, in the lower layer of flooring to be laid on the floor surface of a building. In the following description, the side of the odor sealant for floors that faces the flooring will be referred to as the "top" of the odor sealant for floors, and the side of the odor sealant for floors that does not face the flooring (the lower side of the building) will be referred to as the "bottom".

1. First embodiment Fig. 1 is a cross-sectional view for explaining one configuration example of an odor sealing material for floors (first laminate 100A) according to a first embodiment of the present invention. The odor sealing material for floors according to this embodiment will be explained as the first laminate 100A. The first laminate 100A according to this embodiment is, for example, a deodorizing sheet for building materials that is laid on the lower layer of a floor material to be laid on the floor surface of a building.
The first laminate 100A comprises a first barrier layer 10A, a primer layer 20 provided on the lower surface (an example of the other surface) of the paper base material 11 formed on the first barrier layer 10A, and an adhesive layer 30 provided on the surface of the primer layer 20 opposite the first barrier layer 10A.

The first barrier layer 10A is a layer having a function of preventing indoor odors and odor-causing liquids from penetrating into the concrete or board of the building floor surface (hereinafter, sometimes referred to as the base) that is the underlying layer of the flooring material, and preventing various chemical substances from diffusing from the base into the room. The primer layer 20 is a layer provided to improve the adhesion between the first barrier layer 10A and the adhesive layer 30. The adhesive layer 30 is a layer provided to adhere the first laminate 100A to the base (concrete or board of the building floor surface). That is, the first laminate 100A is laid so that the first barrier layer 10A faces the flooring material (not shown) and the adhesive layer 30 faces the floor surface of the building, and is fixed to the floor surface of the building.
Hereinafter, each of the first barrier layer 10A, the primer layer 20 and the adhesive layer 30 will be described in detail.

(1.1) Basic composition of odor sealant for floors <First barrier layer>
The first barrier layer 10A has a laminated structure including, in this order, a paper base material 11, a layer 12 containing a polyvinyl alcohol-based resin, a vapor-deposited layer 13, and a layer 14 containing a polyolefin having at least one type selected from a carboxyl group, a salt of a carboxyl group, a carboxylic anhydride group, and a carboxylate ester.

(Paper base material)
The paper base material 11 is not particularly limited and may be appropriately selected depending on the application of the flooring material to which the first laminate 100A is applied. There is no particular limitation as long as the paper is mainly composed of plant-derived pulp. Specific examples of the paper base material 11 include fine paper, special fine paper, coated paper, art paper, cast-coated paper, imitation paper, kraft paper, and glassine paper.

The thickness of the paper base material 11 is preferably, for example, 30 μm or more and 100 μm or less, and more preferably 30 μm or more and 70 μm or less. If the thickness of the paper base material 11 is 30 μm or more, the gas barrier properties can be further improved. Furthermore, if the thickness of the paper base material 11 is 100 μm or less, the diffusion of odors can be stably suppressed. Furthermore, the thickness of the paper base material 11 may be 70% or more of the total thickness of the laminate. If the thickness of the paper base material 11 is 70% or more of the total thickness of the laminate, it can be said to have excellent environmental suitability.

The paper substrate 11 may have a coating layer at least on the side in contact with the layer 12 containing a polyvinyl alcohol-based resin, which will be described later. The coating layer can prevent the layer 12 containing a polyvinyl alcohol-based resin from penetrating into the paper, and can also fill in the unevenness of the paper, allowing the layer containing the polyvinyl alcohol-based resin to be formed uniformly without defects. The coating layer may contain various copolymers such as styrene-butadiene, styrene-acrylic, and ethylene-vinyl acetate, polyvinyl alcohol-based resin, cellulose-based resin, paraffin (wax), etc. as binder resins, and may contain clay, kaolin, calcium carbonate, talc, mica, etc. as fillers.

The thickness of the coating layer is not particularly limited, but is preferably 1 μm to 10 μm, and more preferably 3 μm to 8 μm. If the coating layer is 1 μm or thicker, the layer containing the polyvinyl alcohol resin can be formed more uniformly. If the coating layer is 10 μm or thinner, each layer can be formed uniformly while keeping costs down.

The mass of the paper is preferably 50% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and even more preferably 80% by mass or more and 95% by mass or less, based on the entire laminate. If the mass of the paper is 50% by mass or more based on the entire laminate, the amount of plastic material used can be sufficiently reduced, the entire laminate can be said to be made of paper, and it has excellent recyclability.

(Layer Containing Polyvinyl Alcohol Resin)
The layer 12 containing a polyvinyl alcohol-based resin is provided on the surface of the paper substrate 11 to improve the adhesion between the paper substrate 11 and the deposition layer 13 described later, and to improve the gas barrier properties (particularly the oxygen barrier properties) of the laminate. Examples of polyvinyl alcohol-based resins include fully saponified polyvinyl alcohol resins, partially saponified polyvinyl alcohol resins, modified polyvinyl alcohol resins, and ethylene-vinyl alcohol copolymer resins. The degree of polymerization of the polyvinyl alcohol-based resin is preferably 300 or more and 1500 or less. If the degree of polymerization is 300 or more, the barrier properties and bending resistance of the gas barrier laminate become good, and if the degree of polymerization is 1500 or less, the viscosity of the coating liquid of the polyvinyl alcohol-based resin described later becomes low, and the coating property becomes good.

The layer 12 containing the polyvinyl alcohol resin can be provided by applying a coating liquid containing the above-mentioned polyvinyl alcohol resin and a solvent onto the paper substrate 11 and drying it. Examples of the solvent contained in the coating liquid include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide, and a mixed solvent of water and an alcohol such as methyl alcohol, ethyl alcohol, or isopropyl alcohol is particularly preferred. The coating liquid may also contain additives such as surfactants, preservatives, storage stabilizers, silane coupling agents, and organic titanates.

Such a layer 12 containing a polyvinyl alcohol-based resin has excellent flexibility, and can suppress cracking of the deposition layer 13 described below after bending (folding), thereby suppressing deterioration of the gas barrier properties, and can improve adhesion between the deposition layer 13 and the layer 12 containing a polyvinyl alcohol-based resin.

The content of the polyvinyl alcohol-based resin in the layer 12 containing the polyvinyl alcohol-based resin is, for example, 1% by mass or more and 100% by mass or less, preferably 20% by mass or more and 70% by mass or less, and more preferably 30% by mass or more and 50% by mass or more. If the content of the polyvinyl alcohol-based resin is 50% by mass or more, the gas barrier property can be improved and the diffusion of odors can be suppressed.

The thickness of the layer 12 containing polyvinyl alcohol-based resin is preferably, for example, 1 μm or more, and more preferably 2 μm or more and 5 μm or less. If the thickness of the layer 12 containing polyvinyl alcohol-based resin is 1 μm or more, the unevenness of the paper base material 11 described above can be efficiently filled, and the deposition layer 13 described below can be laminated uniformly. Furthermore, if the thickness of the layer 12 containing polyvinyl alcohol-based resin is 5 μm or less, the deposition layer 13 can be laminated uniformly while keeping costs down.

[Deposition layer]
The deposition layer 13 is a layer formed by depositing a metal or an inorganic compound. The deposition layer 13 may be a layer obtained by depositing aluminum, and may contain aluminum oxide (AlOx), silicon oxide (SiOx), or the like.

The thickness of the deposition layer 13 may be set appropriately depending on the intended use, but is preferably 30 nm to 100 nm, and more preferably 50 nm to 80 nm. By setting the thickness of the deposition layer 13 to 30 nm or more, it becomes easier to ensure sufficient continuity of the deposition layer 13. Furthermore, by setting the thickness of the deposition layer 13 to 100 nm or less, it becomes easier to sufficiently suppress the occurrence of curling and cracking, and to easily achieve sufficient gas barrier performance and flexibility.

The deposition layer 13 is preferably formed by a vacuum deposition method from the viewpoint of oxygen gas barrier performance and film uniformity. There are known methods for forming the deposition layer, such as vacuum deposition, sputtering, and chemical vapor deposition (CVD), but vacuum deposition is preferred because of its high deposition rate and high productivity. As a heating means in the vacuum deposition method, it is preferable to use any of the electron beam heating method, resistance heating method, and induction heating method. Considering that the deposition rate can be easily controlled by the irradiation area and electron beam current, and that the temperature of the deposition material can be increased and decreased in a short time, it is more preferable to use the electron beam heating method. In addition, in order to improve the adhesion between the deposition layer 13 and the paper substrate 11 and the density of the deposition layer 13, it is also possible to perform deposition using a plasma assist method or an ion beam assist method. In addition, in order to improve the transparency of the deposition film that constitutes the deposition layer 13, reactive deposition in which various gases such as oxygen are blown in during deposition may be used.

[Polyolefin-containing layer]
The polyolefin-containing layer 14 is a layer provided on the surface of the vapor-deposited layer 13 so as to be in contact with the vapor-deposited layer 13, and contains a polyolefin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester.
In the first embodiment, the polyolefin-containing layer 14 is provided on the top of the first laminate 100A, that is, on the side of the laminate facing the flooring material. This configuration improves the water resistance of the first laminate 100A, and prevents the sheet from being damaged even if a large amount of water seeps in from the floor side.

Such a layer 14 containing polyolefin has excellent flexibility, can suppress cracking of the deposition layer 13 after bending (folding), and has excellent adhesion to the deposition layer 13. Furthermore, by including the above-mentioned polyolefin, a laminate with excellent water vapor barrier properties can be obtained. Furthermore, by providing a layer containing polyolefin, it can also function as a heat seal layer, so there is no need to provide a separate heat seal layer.

The polyolefin-containing layer 14 may contain other components in addition to the polyolefins described above. Examples of other components include silane coupling agents, organic titanates, polyacrylics, polyesters, polyurethanes, polycarbonates, polyureas, polyamides, polyolefin-based emulsions, polyimides, melamines, and phenols.

The polyolefin content in the polyolefin-containing layer 14 is, for example, preferably 50% by mass or more, and more preferably 70% by mass or more. If the polyolefin content in the polyolefin-containing layer 14 is 50% by mass or more, the gas barrier properties can be improved and the diffusion of odors can be suppressed.

The thickness of the polyolefin-containing layer 14 is preferably, for example, 2 μm to 10 μm, and more preferably 3 μm to 8 μm. If the thickness of the polyolefin-containing layer 14 is 2 μm or more, it can fully fulfill the role of the heat seal layer described above. Furthermore, if the thickness of the polyolefin-containing layer 14 is 10 μm or less, it can fully fulfill the adhesion and barrier properties to the deposition layer while keeping costs down.

The polyolefin-containing layer 14 can be provided by applying a coating liquid containing the above-mentioned polyolefin and a solvent onto the deposition layer 13 and drying it. Examples of the solvent contained in the coating liquid include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, and butyl acetate. These solvents may be used alone or in combination of two or more. Among these, from the viewpoint of characteristics, methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water are preferred. Furthermore, from the viewpoint of the environment, methyl alcohol, ethyl alcohol, isopropyl alcohol, and water are more preferred.

The first barrier layer 10A is permeable to odors through the layer 12 containing a polyvinyl alcohol resin and the vapor deposition layer 13, and can prevent the diffusion of odors into the room. The layer 14 containing a polyolefin can protect the vapor deposition layer 13 and improve the gas barrier properties of the vapor deposition layer 13, making it easier to maintain the odor prevention function of the first barrier layer 10A when the first laminate 100A is laid or when the first laminate 100A is in use (when a tenant lives in the residence in which the first laminate 100A is laid).

<Primer layer>
The primer layer 20 is provided in close contact with the surface of the first barrier layer 10A facing the paper substrate 11, and is provided to improve the adhesion between the first barrier layer 10A and the adhesive layer 30.
As the primer constituting the primer layer 20, for example, resin materials such as ester-based resins, urethane-based resins, acrylic-based resins, polycarbonate-based resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral-based resins, nitrocellulose-based resins, etc. can be used alone or in combination. The primer layer 20 is formed by applying these resin materials to the first barrier layer 10A by an appropriate application method such as roll coating or gravure printing.

It is particularly preferable that the primer constituting the primer layer 20 is formed from a resin containing a copolymer of an acrylic resin and a urethane resin and an isocyanate. The copolymer of an acrylic resin and a urethane resin is obtained by blending and reacting an acrylic polymer component (component A) having a hydroxyl group at the end, a polyester polyol component (component B) having hydroxyl groups at both ends, and a diisocyanate component (component C) to form a prepolymer, and then adding a chain extender (component D) such as a diamine to this prepolymer to extend the chain. This reaction forms a polyester urethane, and the acrylic polymer component is introduced into the molecule to form an acrylic-polyester urethane copolymer having a hydroxyl group at the end. The primer constituting the primer layer 20 is formed by reacting the hydroxyl groups at the ends of this acrylic-polyester urethane copolymer with isocyanate and curing it.

As component A, a linear acrylic acid ester polymer having a hydroxyl group at the end is used. In particular, it is preferable to use linear polymethyl methacrylate (PMMA) having a hydroxyl group at the end as component A, because it has excellent weather resistance (especially properties against photodegradation) and is easy to copolymerize with urethane to make it compatible. Component A is an acrylic resin component in the copolymer, and it is more preferable that the molecular weight is 5000 to 7000 (weight average molecular weight) from the viewpoint of weather resistance and adhesiveness. In addition, as component A, only a polymer having hydroxyl groups at both ends may be used, but a mixture of a polymer having a conjugated double bond remaining at one end and a polymer having hydroxyl groups at both ends may also be used.

Component B is a material that reacts with component C (diisocyanate component) to form a polyester urethane and constitutes a urethane resin component in the copolymer. Component B is a polyester diol having hydroxyl groups at both ends. Examples of polyester diols include an addition reaction product of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or its derivative, or an epoxy compound, a condensation product of a dibasic acid and a diol, and a polyester compound derived from a cyclic ester compound. Examples of diols include short-chain diols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanediol, and methylpentenediol, and alicyclic short-chain diols such as 1,4-cyclohexanedimethanol. Examples of basic acids include adipic acid, phthalic acid, isophthalic acid, and terephthalic acid. A preferred polyester polyol is an adipate-based polyester that uses adipic acid or a mixture of adipic acid and terephthalic acid as the acid component and 3-methylpentene diol and 1,4-cyclohexane dimethanol as the diol component.

The urethane resin component formed by the reaction of component B and component C gives flexibility to the primer layer 20 and contributes to improving adhesion. In addition, the acrylic resin component containing an acrylic polymer contributes to the weather resistance and blocking resistance of the primer layer 20. The molecular weight of component B in the urethane resin may be within a range that can provide a urethane resin that can fully exhibit flexibility in the primer layer 20. For example, when component B is a polyester diol containing adipic acid or a mixture of adipic acid and terephthalic acid, 3-methylpentene diol, and 1,4-cyclohexane dimethanol, it is preferable that the molecular weight of component B is 500 or more and 5,000 or less (weight average molecular weight).

Component C is an aliphatic or alicyclic diisocyanate compound having two isocyanate groups per molecule. Examples of this diisocyanate compound include tetramethylene diisocyanate, 2,2,4 (2,4,4)-1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,4'-cyclohexyl diisocyanate. As the diisocyanate component, isophorone diisocyanate is preferred because of its excellent physical properties and cost. When components A to C are reacted, the equivalent ratio of the total hydroxyl groups (or amino groups) of the acrylic polymer, polyester polyol, and chain extender described below to the isocyanate groups is adjusted so that there is an excess of isocyanate groups.

The three components A, B, and C are reacted for about 2 to 10 hours in an environment of 60°C to 120°C. The isocyanate groups of the diisocyanate react with the hydroxyl groups at the ends of the polyester polyol to form a polyester urethane resin component, and a compound in which diisocyanate is added to the hydroxyl groups at the ends of the acrylic polymer is also mixed in. This forms a prepolymer in which excess isocyanate groups and hydroxyl groups remain. A diamine such as isophorone diamine or hexamethylene diamine is added as a chain extender to the formed prepolymer, and the isocyanate groups react with the chain extender to extend the chain. This introduces the acrylic polymer component into the polyester urethane molecule, and an acrylic-polyester urethane copolymer with hydroxyl groups at the ends can be obtained.

The coating solution is prepared by adding isocyanate to the acrylic-polyester urethane copolymer and adjusting the viscosity to a required level, taking into consideration the coating method and the amount of coating after drying. The adjusted coating solution is applied to the first barrier layer 10A by a well-known coating method such as gravure coating or roll coating, thereby forming the primer layer 20.
The isocyanate may be any isocyanate capable of reacting with the hydroxyl group of the acrylic-polyester urethane copolymer to crosslink and harden it, and for example, a divalent or higher aliphatic or aromatic isocyanate is used. In particular, it is desirable to use an aliphatic isocyanate from the viewpoints of preventing thermal discoloration and weather resistance. Specific examples of the aliphatic isocyanate include monomers of tolylene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate, or polymers such as dimers and trimers thereof, or polyisocyanates such as derivatives (adducts) in which these isocyanates are added to polyols.

The coating amount of the primer layer 20 after drying is preferably 1 g/m ² or more and 20 g/m ² or less, and more preferably 1 g/m ² or more and 5 g/m ² or less. Furthermore, the primer layer 20 may contain additives such as a filler such as silica powder, a light stabilizer, and a colorant, as necessary.

<Adhesive Layer>
The adhesive layer 30 includes, for example, an adhesive base material 31 and a pressure-sensitive adhesive layer 32 provided on the adhesive base material 31, and is, for example, a sheet-like adhesive layer (i.e., an adhesive sheet).
The adhesive substrate 31 is preferably a laminate cloth in which a support made of a mesh sheet material or the like is laminated with, for example, a resin film, or a coating cloth in which the surface of a support is covered with a resin material. For example, a nonwoven fabric or a woven fabric is used as the support.

The adhesive layer 32 can be formed from a conventionally known resin material. Examples of resin materials constituting the adhesive layer 32 include styrene resins such as polystyrene and poly-α-methylstyrene, acrylic resins such as polymethyl methacrylate and polyethyl acrylate, vinyl resins such as polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and polyvinyl acetal, polyester resins, polyamide resins, epoxy resins, polyurethane resins, petroleum resins, synthetic resins such as ionomers, ethylene-acrylic acid copolymers, and ethylene-acrylic acid ester copolymers, cellulose derivatives such as nitrocellulose, ethylcellulose, cellulose acetate propionate, and cellulose acetate butyrate, rosin, rosin-modified maleic acid resin, ester gum, polyisobutylene rubber, butyl rubber, styrene-butadiene rubber, butadiene-acrylonitrile rubber, and polychlorinated olefins. These resins may be used alone or in a mixture of two or more.

The amount of the adhesive layer 32 formed (the amount of solids remaining after the coating liquid is applied and dried) is preferably 0.1 g/m ² or more and 2.0 g/m ² or less.
In addition, known additives other than resins can be used in the adhesive layer 32 within the scope that does not impair the above-mentioned performance. Examples of additives that can be used include inorganic pigment fine particles, isocyanate compounds, silane coupling agents, dispersants, viscosity modifiers, release agents, slipping agents such as wax and resin fillers, ultraviolet absorbers, light stabilizers, antioxidants, fluorescent brightening agents, and antistatic agents.

By providing the adhesive layer 30, the first laminate 100A becomes a so-called tucked odor-preventing sheet for building materials. Therefore, when laying the first laminate 100A, it can be easily attached to the base, improving the workability of the first laminate 100A.

(1.2) Effects of First Embodiment The first stack 100A as described above has the following effects.
(1) The first laminate 100A is permeable to odors and can prevent the odors from diffusing into the room through the polyvinyl alcohol-based resin-containing layer 12, the vapor deposition layer 13, and the polyolefin-containing layer 14. Therefore, the first laminate 100A can exhibit a high odor prevention function.
(2) In the first laminate 100A, the layer 12 containing the polyvinyl alcohol-based resin has a thickness of 1 μm or more and 5 μm or less. With this configuration, the first laminate 100A can efficiently fill in the unevenness of the paper base material 11, and the vapor deposition layer 13 can be laminated uniformly.
(3) In the first laminate 100A, the thickness of the vapor deposition layer 13 is 30 nm or more and 100 nm or less. With this configuration, the first laminate 100A has sufficient gas barrier performance and improved flexibility while suppressing the occurrence of curling and cracking.
(4) In the first laminate 100A, the thickness of the polyolefin-containing layer 14 is 2 μm or more and 10 μm or less. With this configuration, the first laminate 100A can improve the adhesion to the deposition layer 13 while suppressing costs, and can enhance the barrier property.
(5) The first laminate 100A becomes a so-called tucked deodorizing sheet for building materials by providing the adhesive layer 30. Therefore, the first laminate 100A can be easily laid and has high workability.

2. Second Embodiment Next, an odor sealant for floors according to a second embodiment of the present invention will be described with reference to FIG.
Fig. 2 is a cross-sectional view for explaining one configuration example of the odor sealant for floors (second laminate 100B) according to the second embodiment of the present invention. The odor sealant for floors according to this embodiment will be explained as the second laminate 100B. As shown in Fig. 2, the second laminate 100B includes a second barrier layer 10B, a primer layer 20 provided on the lower surface (an example of the other surface) of the layer 14 containing polyolefin formed on the second barrier layer 10B, and an adhesive layer 30 provided on the surface of the primer layer 20 opposite to the first barrier layer 10A.
That is, the second laminate 100B differs from the first laminate 100A according to the first embodiment in that it has a second barrier layer 10B instead of the first barrier layer 10A, and a primer layer 20 is formed on the lower surface of the layer 14 containing polyolefin instead of the paper base material 11.

The second barrier layer 10B will be described below. Note that the layers other than the second barrier layer 10B (primer layer 20 and adhesive layer 30) have the same configuration as the layers of the first laminate 100A, so their description will be omitted.

(2.1) Basic composition of odor sealant for floors <Second barrier layer>
The second barrier layer 10B has a laminated structure including, in this order, a layer 14 containing a polyolefin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic anhydride group, and a carboxylic ester, a vapor deposition layer 13, a layer 12 containing a polyvinyl alcohol resin, and a paper base material 11. In the first laminate 100A according to the first embodiment, the paper base material 11 is formed on the side of the laminate that does not face the flooring material (the lower side of the laminate). On the other hand, in the second laminate 100B according to the second embodiment, the paper base material 11 is formed on the side of the laminate that faces the flooring material (the upper side of the laminate) to form the second barrier layer 10B, which has high flexibility, can protect the vapor deposition layer 13, and can improve gas barrier properties.

(2.2) Advantages of Second Embodiment The second stack 100B as described above has the following advantages in addition to the advantages of the first embodiment.
(6) The second laminate 100B has a paper base material 11 formed on the side of the laminate facing the flooring material (the upper side of the laminate). With this configuration, the deposition layer 13 is protected by the paper base material 11, making it easier to maintain the odor prevention function of the second barrier layer 10B.

3. Third embodiment Next, a configuration example of a flooring material having an odor-preventing sheet, which is a first laminate 100A according to a third embodiment, will be described with reference to Fig. 3. Fig. 3 is a cross-sectional view showing the configuration of a first flooring material 200A having the first laminate 100A.

The first flooring material 200A includes a first laminate 100A and a surface substrate 210 laminated on the surface of the first laminate 100A (i.e., the first barrier layer 10A). The first laminate 100A has a similar configuration to the first laminate 100A described above, and therefore a description thereof will be omitted.
The surface substrate 210 may be, for example, a decorative material in which a decorative sheet is laminated on the surface of a substrate, or may be a floor board or a tatami mat. The first laminate 100A and the surface substrate 210 are preferably bonded together.

(3.1) Composition of flooring <Surface material>
Hereinafter, a case where the surface base material 210 is a decorative material 210a will be described.
3, the decorative material 210a is provided on the surface of the first laminate 100A facing the first barrier layer 10A. The decorative material 210a has a decorative base material 220 that serves as the base material of the decorative material, and a decorative sheet 230 laminated on the upper surface of the decorative base material 220. The decorative sheet 230 is a sheet member that has a pattern or is colored.

(Decorative substrate)
The decorative base material 220 can be made of any material similar to the base material (layer) in conventional flooring materials, such as wood, metal, or synthetic resin.
An example of the decorative base material 220 made of a wood-based material is laminated wood. An example of the decorative base material 220 made of a metal-based material is an aluminum plate. An example of the decorative base material 220 made of a synthetic resin-based material is a resin sheet formed of a thermoplastic resin including a polyolefin-based resin such as polyethylene or polypropylene, which has excellent so-called hinge properties such as deformation property, crack resistance, and recovery property.

(decorative sheet)
The decorative sheet 230 is formed, for example, by printing a picture pattern layer on the front surface of a polyolefin resin sheet, and laminating a transparent resin layer and a surface protection layer in this order on the front surface of the picture pattern layer.
The polyolefin resin sheet is a sheet body of polyolefin resin formed by a calendar method, an inflation method, a T-die extrusion method, etc. Examples of polyolefin resins include polypropylene (PP), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), etc.

The picture pattern layer is a layer that imparts design to the decorative sheet 230 with a desired pattern. The type of pattern is not particularly limited, but examples include wood grain, stone grain, sand grain, tiled patterns, brickwork patterns, fabric patterns, leather-stained patterns, geometric figures, letters, symbols, and abstract patterns. The picture pattern layer may also be a single-color decorative sheet 230 without a picture pattern. A known decorative sheet may also be used as the decorative sheet 230.

The first floor material 200A as described above may have a buffer layer provided, for example, on the surface of the decorative base material 220 opposite the decorative sheet 230.
The first flooring material 200A having the first laminate 100A as described above is preferable because it makes it possible to lay the first laminate 100A at the same time as laying the first flooring material 200A.

(3.2) Advantages of the Third Embodiment The first floor material 200A as described above has the following advantages in addition to the advantages of the first embodiment.
(7) The first flooring material 200A having the first laminate 100A can be laid simultaneously with the laying of the first flooring material 200A. This makes it possible to lay the first laminate 100A without increasing the number of work steps.

4. Fourth embodiment Next, a configuration example of a flooring material having an odor-preventing sheet, which is the second laminate 100B according to the fourth embodiment, will be described with reference to Fig. 4. Fig. 4 is a cross-sectional view showing the configuration of a second flooring material 200B having the second laminate 100B.

(4.1) Basic structure of flooring The second flooring 200B comprises a second laminate 100B and a surface substrate 210 laminated on the surface of the second laminate 100B (i.e., the second barrier layer 10B). In other words, the second flooring 200B differs from the first flooring 200A according to the third embodiment in that the second laminate 100B is provided instead of the first laminate 100A. The second laminate 100B has the same structure as the second laminate 100B described above, and therefore will not be described.

The second flooring material 200B as described above may have a buffer layer provided, for example, on the surface of the decorative base material 220 opposite the decorative sheet 230, similar to the first flooring material 200A.
The second floor material 200B having the second laminate 100B as described above is preferable because it makes it possible to lay the second laminate 100B at the same time as laying the second floor material 200B.

(4.2) Advantages of the Fourth Embodiment The second floor material 200B as described above has the following advantages in addition to the advantages of the first and second embodiments.
(8) The second floor material 200B having the second laminate 100B can be laid simultaneously with the laying of the second floor material 200B. This makes it possible to lay the second laminate 100B without increasing the number of work steps.

The laminate according to this embodiment will be described below with reference to examples. In the examples, odors were evaluated in a room where flooring was laid using the laminate according to this embodiment, and in a room where flooring was laid without using the laminate according to this embodiment.

Example 1
A coating liquid in which a polyvinyl alcohol resin having a degree of saponification of 98% and a degree of polymerization of 500 was dissolved in a water/IPA=8/2 solution at a solid content concentration of 10% by mass was applied to the clay-coated surface of a paper substrate (clay-coated paper, paper thickness: 28 μm, clay-coated layer thickness: 5 μm) with a bar coater, and dried in an oven to form a layer containing polyvinyl alcohol resin. The thickness of the layer containing polyvinyl alcohol resin was set to 0.8 μm. Subsequently, AL deposition was performed on the layer containing polyvinyl alcohol resin by vacuum deposition to form a deposition layer. The thickness of the deposition layer was set to 28 nm. Then, a coating liquid containing a salt of a carboxyl group (manufactured by Mitsui Chemicals, Inc., Chemipearl S500) was applied to the deposition layer with a bar coater, and dried in an oven to form a layer containing polyolefin. The thickness of the layer containing polyolefin was set to 1.8 μm. As a result, a barrier layer was formed.
Next, a two-component curing resin, which is a urethane resin/nitrocellulose resin as a main agent and an isocyanate as a curing agent, was applied to the other side of the paper substrate by gravure printing so that the coating amount as a solid content was 1 g/m2. Next, an adhesive sheet (Konishi Co., Ltd., WF435) was attached to the surface of the two-component curing resin, which was an adhesive layer formed by applying an acrylic resin to the surface of the laminate cloth, which was an adhesive substrate, and drying the acrylic resin to form an adhesive layer. Finally, a primer layer was formed between the paper substrate and the adhesive layer by drying the two-component curing resin.
In this manner, a laminate was formed in Example 1. The mass of the paper in the entire laminate was 79 mass %.

Example 2
In the barrier layer formed in Example 1, an adhesive layer and a primer layer were formed on the other surface side of the polyolefin-containing layer in the same manner as in Example 1. Except for this, a laminate of Example 2 was formed in the same manner as in Example 1. The mass of the paper in the entire laminate was 79 mass%.

Example 3
Except for changing the thickness of the layer containing the polyvinyl alcohol resin to 1 μm, a laminate of Example 3 was formed in the same manner as in Example 1. The mass of the paper in the entire laminate was 78 mass %.

Example 4
Except for changing the thickness of the layer containing the polyvinyl alcohol resin to 5 μm, a laminate of Example 4 was formed in the same manner as in Example 1. The mass of the paper in the entire laminate was 70 mass %.

(Example 5)
Except for changing the thickness of the vapor-deposited layer to 30 nm, a laminate of Example 5 was formed in the same manner as in Example 1. The mass of the paper in the entire laminate was 79 mass %.

Example 6
Except for changing the thickness of the vapor-deposited layer to 100 nm, a laminate of Example 6 was formed in the same manner as in Example 1. The mass of the paper in the entire laminate was 78 mass %.

(Example 7)
Except for changing the thickness of the polyolefin-containing layer to 2 μm, the laminate of Example 7 was formed in the same manner as in Example 1. The mass of the paper in the entire laminate was 78 mass %.

(Example 8)
Except for changing the thickness of the polyolefin-containing layer to 10 μm, a laminate of Example 8 was formed in the same manner as in Example 1. The mass of paper in the entire laminate was 64 mass %.

(Example 9)
A laminate of Example 9 was formed in the same manner as in Example 1, except that clay-coated paper with a paper thickness of 30 μm and a clay-coated layer thickness of 5 μm was used as the paper substrate. The mass of the paper in the entire laminate was 80 mass%.

(Example 10)
A laminate of Example 10 was formed in the same manner as in Example 1, except that clay-coated paper with a paper thickness of 100 μm and a clay-coated layer thickness of 5 μm was used as the paper substrate. The mass of the paper in the entire laminate was 93 mass%.

Example 11
Except for changing the thickness of the layer containing the polyvinyl alcohol resin to 3 μm and the thickness of the vapor deposition layer to 50 nm, a laminate of Example 11 was formed in the same manner as in Example 1. The mass of the paper in the entire laminate was 74 mass%.

Example 12
Except for changing the thickness of the polyolefin-containing layer to 3 μm, a laminate of Example 12 was formed in the same manner as in Example 11. The mass of the paper in the entire laminate was 72 mass %.

Example 13
As the paper substrate, clay-coated paper having a paper thickness of 50 μm and a clay-coated layer thickness of 5 μm was used. Except for this, the laminate of Example 13 was formed in the same manner as in Example 12. The mass of the paper in the entire laminate was 82 mass%.

(Example 14)
In the barrier layer formed in Example 13, an adhesive layer and a primer layer were formed on the other surface side of the polyolefin-containing layer in the same manner as in Example 13. Except for this, a laminate of Example 14 was formed in the same manner as in Example 13. The mass of the paper in the entire laminate was 82 mass%.

(Comparative Example 1)
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 50 μm was used as the substrate. In addition, a layer containing a polyvinyl alcohol resin, a vapor deposition layer, and a layer containing a polyolefin were not formed. A laminate of Comparative Example 1 was formed in the same manner as in Example 1 except for the above.

(Comparative Example 2)
A biaxially stretched ethylene vinyl alcohol (EVOH) film having a thickness of 50 μm was used as the substrate. In addition, a layer containing a polyvinyl alcohol resin, a vapor deposition layer, and a layer containing a polyolefin were not formed. A laminate of Comparative Example 2 was formed in the same manner as in Example 1.

<Evaluation>
The laminates obtained in the above-mentioned Examples 1 to 14 and Comparative Examples 1 and 2 were laid as the lower layer of flooring in different rooms, and the following evaluations were carried out for each room.

[Evaluation of odor suppression function]
Indoor air quality was measured in each room on multiple measurement days to confirm the odor suppression effect. To evaluate the odor suppression function, the first, second and third indoor air quality measurements were performed in each room on different measurement days. Each indoor air quality measurement was performed for about five hours.
Indoor air quality measurements included volatile organic compounds (VOCs), aldehydes, ammonia, formic acid, and acetic acid. Each substance was analyzed by the following methods.
Volatile organic compounds: solid phase collection - thermal desorption - gas chromatography mass spectrometry (GC/MS) method Aldehydes: DNPH collection - solvent extraction - high performance liquid chromatography (HPLC) method Ammonia, formic acid, acetic acid: liquid phase collection - ion chromatography (IC) method Each of the above analyses was evaluated on a four-point scale: ◎, ○, △, ×.
<Evaluation criteria>
◎: When the indoor concentration of each substance is equal to or less than the Ministry of Health, Labor and Welfare indoor concentration guideline value, and the concentration reduction effect of each substance is excellent. ○: When the indoor concentration of each substance is equal to or less than the Ministry of Health, Labor and Welfare indoor concentration guideline value, and the concentration reduction effect of each substance has been confirmed. △: When the indoor concentration of each substance is equal to or less than the Ministry of Health, Labor and Welfare indoor concentration guideline value, or the concentration reduction effect of each substance has been confirmed. ×: When the indoor concentration of each substance exceeds the Ministry of Health, Labor and Welfare indoor concentration guideline value, and the concentration reduction effect of each substance cannot be confirmed.

[Evaluation of workability]
In each room, the laminates of Examples 1 to 14 and Comparative Examples 1 and 2 were laid on the floor surface, and then flooring materials were laid. The workability of the laminates of the Examples and Comparative Examples was evaluated.
In each of the above analyses, evaluation was performed using the following two-level scale of ○ or ×.
<Evaluation criteria>
○: When the laminate was laid, the laminate was easily laid. ×: When the laminate was laid, the laminate was not easily laid.

[Environmental suitability evaluation]
The resin usage rate in the entire laminate of the Examples and Comparative Examples was compared relative to each other to evaluate environmental suitability.
In each of the above analyses, evaluation was performed using the following two-level scale: ◎ or △.
<Evaluation criteria>
◎: When the resin usage rate in the entire laminate is low △: When the resin usage rate in the entire laminate is high compared to the evaluation "◎"

[Production cost evaluation]
The manufacturing costs of each of the laminates of Examples 1 to 14, Comparative Example 1 and Comparative Example 2 were evaluated.
In each of the above analyses, evaluation was performed using the following three-level scale: ◎, ○, ×.
<Evaluation criteria>
◎: The manufacturing cost of the laminate is cheaper than that of the evaluation "○". ○: The manufacturing cost of the laminate is cheaper. ×: The manufacturing cost of the laminate is more expensive than that of the evaluation "○".

(Evaluation Results)
Table 1 below shows the evaluation results of odor control function, ease of application, environmental compatibility and manufacturing costs.

As shown in Table 1, in the room where the laminates of Examples 1 to 14 were used, the concentrations of volatile organic compounds, aldehydes, ammonia, formic acid, and acetic acid were below the Ministry of Health, Labor, and Welfare indoor concentration guideline values, or the effect of reducing the concentration of each substance was confirmed. On the other hand, in the room where the laminates of Comparative Example 1 or Comparative Example 2 were used, it was not possible to confirm that the concentrations of nuclear materials were below the Ministry of Health, Labor, and Welfare indoor concentration guideline values, or that the effect of reducing the concentration of each substance was present.

In addition, as shown in Table 1, it was confirmed that the workability of the laminate was high when any of the laminates of Examples 1 to 14, Comparative Example 1, and Comparative Example 2 was used. In addition, as shown in Table 1, it was confirmed that when the laminate of the Examples was used, the environmental suitability was higher than when the laminate of the Comparative Example was used. Furthermore, the laminates of Examples 1 to 14 were inexpensive to manufacture, whereas the laminate of Comparative Example 2 was expensive to manufacture.
From the above evaluation results, it was confirmed that by laying the laminate of this embodiment as the lower layer of flooring material, it is possible to suppress the diffusion of odors without compromising workability, and that the laminate of this embodiment is highly environmentally friendly.

The scope of the present invention is not limited to the exemplary embodiments shown and described, but includes all embodiments that achieve the same effect as the object of the present invention. Furthermore, the scope of the present invention is not limited to the combination of the features of the invention defined by the claims, but can be defined by any desired combination of specific features among all the respective disclosed features.

10A: First barrier layer 10B: Second barrier layer 11: Paper substrate 12: Layer containing polyvinyl alcohol-based resin 13: Vapor deposition layer 14: Layer containing polyolefin 20: Primer layer 30: Adhesive layer 31: Adhesive substrate 32: Pressure-sensitive adhesive layer 100A: First laminate 100B: Second laminate 200A: First flooring material 200B: Second flooring material 220: Decorative substrate 230: Decorative sheet

Claims (9)

A paper substrate;
A layer containing a polyvinyl alcohol-based resin;
A deposition layer;
a layer containing a polyolefin having a carboxyl group and at least one selected from a salt of the carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester;
A primer layer;
An adhesive layer;
An odor sealant for floors comprising: a layer containing a polyolefin having a carboxyl group and at least one selected from a salt of the carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester;
A deposition layer;
A layer containing a polyvinyl alcohol-based resin;
A paper substrate;
A primer layer;
An adhesive layer;
An odor sealant for floors comprising: 3. The odor sealant for floors according to claim 1, wherein the layer containing the polyvinyl alcohol-based resin has a thickness of 1 μm or more and 5 μm or less. 4. The odor sealant for floors according to claim 1, wherein the thickness of the vapor deposition layer is 30 nm or more and 100 nm or less. The odor sealant for floors according to any one of claims 1 to 4, wherein the thickness of the layer containing the polyolefin is from 2 µm to 10 µm. An odor sealant for floors as described in any one of claims 1 to 5, wherein the thickness of the paper base material is 30 μm or more and 100 μm or less, and the thickness of the paper base material is 70% or more of the entire thickness of the odor sealant. 7. The odor sealant for floors according to claim 1, wherein the mass of the paper contained in the paper base material is 50 mass% or more based on the entire odor sealant. The adhesive layer includes an adhesive base layer and a pressure-sensitive adhesive layer provided on the adhesive base layer,
The adhesive base layer is a laminate cloth sheet,
The odor sealant for floors according to claim 1 , wherein the adhesive layer is an acrylic resin provided on the laminate cloth sheet. An odor sealant for floors according to any one of claims 1 to 8;
A surface substrate laminated on a surface of the odor sealant for floors;
A flooring material comprising:

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