JP2022101282A - Composition for self-adsorbable foamed sheets, self-adsorbable foamed sheet, self-adsorbable laminate, and method for producing self-adsorbable laminate - Google Patents

Abstract

To provide a self-adsorbable foamed sheet having excellent deodorizing and adsorbing properties, and a composition for self-adsorbable foamed sheets that can provide the self-adsorbable foamed sheet.SOLUTION: A composition for self-adsorbable foamed sheets contains a polymer, and a metal-containing oxycellulose nanofiber containing a metal other than sodium in the form of salt, the content of the metal-containing oxycellulose nanofiber being 0.1 pt.mass or more and 1.00 pt.mass or less relative to 100 pts.mass of the polymer.SELECTED DRAWING: None

Description

The present invention relates to a composition for a self-adsorptive foam sheet, a self-adsorptive foam sheet, a self-adsorptive laminate, and a method for producing a self-adsorbent laminate.

Conventionally, as a sticking sheet used by sticking to a smooth adherend such as a window glass, it is made of a foam material having a large number of fine pores and has a self-adsorptive sheet-like member, that is, a self-adsorptive foam sheet. (Hereinafter, it may be simply referred to as "foam sheet".) Is used. The adhesive mode of the self-adsorptive foam sheet is not adhesive adhesion but adsorption to an adherend using fine pores. Therefore, the self-adsorptive foam sheet is easier to reattach than the conventional adhesive sheet that employs adhesive adhesion, and is suitably used for applications such as wallpaper, posters, and stickers. When used in these applications, the self-adsorptive foam sheet is usually used in the form of a self-adsorptive laminate (hereinafter, may be simply referred to as "laminated sheet") laminated with a base material. By decorating the surface of the self-adsorptive laminate on the substrate side with printing or the like, it can be advantageously used for the above-mentioned applications.

By the way, in recent years, it has been studied to add modified cellulose nanofibers to a resin foam for the purpose of imparting adsorption performance and strength to odorous gas and the like. For example, Patent Document 1 states that a composition for a foam resin containing cellulose nanofibers having a sodium salt-type or acid-type carboxy group introduced on the surface thereof and a resin emulsion is foamed to have excellent strength. Moreover, it is described that a foam capable of adsorbing an odor such as ammonia can be obtained.

International Publication No. 2013/146847

Therefore, the present inventor has attempted to add the modified cellulose nanofibers of the above-mentioned prior art to the composition for a self-adsorptive foamed sheet in order to impart deodorant properties to the self-adsorptive foamed sheet which is a resin foam. rice field. However, according to the study of the present inventor, the self-adsorptive foamed sheet containing modified cellulose nanofibers having sodium salt-type or acid-type carboxy groups introduced on its surface did not have sufficient deodorizing properties. .. Further, when the modified cellulose nanofibers are contained in the self-adsorptive foamed sheet, the adsorptivity (self-adhesive force) of the self-adsorptive foamed sheet to the adherend may decrease. Therefore, there is still room for improvement in the self-adsorptive foam sheet in terms of achieving both deodorant property and adsorptive property.

Therefore, an object of the present invention is to provide a self-adsorptive foam sheet having excellent deodorant property and adsorptive property, and a composition for a self-adsorptive foam sheet capable of providing the self-adsorptive foam sheet.
Another object of the present invention is to provide a self-adsorptive laminate having excellent deodorant and adsorptive properties, and a method for producing the self-adsorptive laminate.

The present inventor has made diligent studies for the purpose of solving the above problems. As a result, the present inventor includes the polymer and the metal-containing cellulose oxide nanofibers containing a metal other than sodium in the form of a salt, and the content of the metal-containing cellulose oxide nanofibers is controlled within a predetermined range. We have found that the self-adhesive foamed sheet produced by using the self-adsorbing foamed sheet composition is excellent in adsorptivity and deodorant property, and completed the present invention.

That is, the present invention aims to advantageously solve the above-mentioned problems, and the self-adsorbing foamed sheet composition of the present invention contains a polymer and a metal other than sodium in the form of a salt. It contains metal-containing cellulose oxide nanofibers, and the content of the metal-containing cellulose oxide nanofibers is 0.1 parts by mass or more and 1.00 parts by mass or less with respect to 100 parts by mass of the polymer. .. As described above, if the composition for self-adsorptive foamed sheet contains metal-containing oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt and the content ratio thereof is within the above range, the foamed sheet can be obtained. Deodorant and adsorptive properties can be achieved at a high level.

In the composition for a self-adsorptive foam sheet of the present invention, it is preferable that the polymer contains a (meth) acrylate monomer unit. The polymer containing the (meth) acrylate monomer unit has excellent flexibility and can impart good adsorptivity to the foamed sheet.
In addition, in this invention, "the polymer contains a monomer unit" means "the polymer obtained by using the monomer contains a repeating unit derived from a monomer". do. Further, in the present invention, "(meth) acrylate" means acrylate and / or methacrylate.

In the composition for self-adsorbing foam sheet of the present invention, it is preferable that the number average fiber diameter of the metal-containing cellulose oxide nanofibers is 100 nm or less. Metal-containing cellulose oxide nanofibers having a number average fiber diameter of 100 nm or less are excellent in dispersibility, and even if the amount is small, the obtained foamed sheet is satisfactorily imparted with desired properties such as deodorization. be able to.
In the present invention, the "number average fiber diameter" of the metal-containing cellulose oxide nanofibers is the fiber diameter measured by measuring the fiber diameters of five or more metal-containing cellulose oxide nanofibers using an interatomic force microscope. It can be obtained by calculating the number average.

In the composition for self-adsorbing foam sheet of the present invention, it is preferable that the metal-containing cellulose oxide nanofibers are metal-containing carboxylated cellulose nanofibers. The carboxylated cellulose nanofibers are excellent in dispersibility, and even if the amount is small, the obtained foamed sheet can be satisfactorily imparted with desired properties such as deodorant properties.

In the composition for a self-adsorptive foam sheet of the present invention, it is preferable that the metal other than sodium is at least one selected from the group consisting of silver, zinc, and copper. Metal-containing cellulose oxide nanofibers containing at least one selected from the group consisting of silver, zinc, and copper have excellent deodorizing properties, and can satisfactorily impart deodorizing properties to the obtained foamed sheet.

Further, the present invention is intended to advantageously solve the above-mentioned problems, and the self-adsorptive foamed sheet of the present invention is obtained by foaming and sheet-like any of the above-mentioned self-adsorptive foamed sheet compositions. It is characterized by being molded into. As described above, the self-adsorptive foam sheet obtained by foaming and molding the above-mentioned composition for self-adsorptive foam sheet into a sheet shape is excellent in deodorant property and adsorptive property.

The self-adsorbing foam sheet of the present invention preferably has a density of 0.3 g / cm ³ or more. When the density is 0.3 g / cm ³ or more, the strength of the self-adsorbing foamed sheet can be sufficiently increased.
In the present invention, the density of the self-adsorptive foam sheet can be measured by the method described in Examples.

Further, the present invention is intended to advantageously solve the above-mentioned problems, and the self-adsorptive laminate of the present invention comprises a base material and one of the above-mentioned self-adsorptive foam sheets. It is characterized by. As described above, the self-adsorptive laminate provided with the self-adsorptive foam sheet described above is excellent in deodorant property and adsorptive property.

Further, the present invention is intended to advantageously solve the above-mentioned problems, and the method for producing a self-adsorptive laminate of the present invention prepares any of the above-mentioned self-adsorptive foam sheet compositions. It is characterized by including a step of foaming the self-adsorptive foamed sheet composition to obtain a foamed composition, and a step of molding the foamed composition into a sheet on a substrate. As described above, by foaming the above-mentioned composition for self-adsorptive foam sheet and molding the obtained foamed composition into a sheet on the substrate, a self-adsorptive laminate having excellent deodorant property and adsorptive property can be obtained. Obtainable.

According to the present invention, it is possible to provide a self-adsorptive foamed sheet having excellent deodorant property and adsorptive property, and a composition for a self-adsorptive foamed sheet capable of providing the self-adsorptive foamed sheet.
Further, according to the present invention, it is possible to provide a self-adsorptive laminate having excellent deodorant property and adsorptive property, and a method for producing the self-adsorptive laminate.

It is a flowchart explaining an example of the method of manufacturing the self-adsorptive laminate which concerns on this invention. It is explanatory drawing which shows the schematic structure of the evaluation apparatus used for the evaluation of the air bleeding property of a self-adsorptive laminated body in an Example and a comparative example.

Hereinafter, embodiments of the present invention will be described in detail.

(Composition for self-adsorptive foam sheet)
The self-adsorbing foamed sheet composition of the present invention (hereinafter, also simply referred to as “foamed sheet composition”) comprises a polymer and metal-containing oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt. Includes and optionally further comprises solvents and other additives.
The composition for a foamed sheet of the present invention contains metal-containing oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt in an amount of 0.1 part by mass or more and 1.00 part by mass with respect to 100 parts by mass of the polymer. It is characterized by including in the range of less than a part. The composition for a foamed sheet of the present invention can be suitably used for producing the self-adsorptive foamed sheet of the present invention and the self-adsorptive laminate of the present invention, which are excellent in adsorptivity and deodorant property.
The odor to be deodorized in the present invention is not particularly limited, and examples thereof include an ammonia odor, a methyl mercaptan odor, and a hydrogen sulfide odor.

<Polymer>
The polymer used in the self-adsorptive foamed sheet composition of the present invention forms a resin matrix in a foamed sheet obtained by foaming and molding the composition into a sheet.

As the polymer, any polymer capable of forming a foamed sheet can be used. The polymer is not particularly limited, but is, for example, a group consisting of a (meth) acrylate monomer unit, an unsaturated carboxylic acid monomer unit, a vinyl cyanide monomer unit, and an alkenyl aromatic monomer unit. Can include at least one monomeric unit selected from.
The polymer preferably contains a (meth) acrylate monomer unit. This is because the obtained foamed sheet is imparted with flexibility, and the foamed sheet can exhibit a good adsorption force (self-adhesive force).
The polymer is a monomer unit other than the (meth) acrylate monomer unit, the unsaturated carboxylic acid monomer unit, the vinyl cyanide monomer unit, and the alkenyl aromatic monomer unit (hereinafter, “others”). It is referred to as "monomer unit of").

<< (meth) acrylate monomer unit >>
The (meth) acrylate monomer unit is a repeating unit derived from the (meth) acrylate monomer. The (meth) acrylate monomer is not particularly limited, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (. Meta) sec-butyl acrylate, (meth) n-heptyl acrylate, (meth) n-hexyl acrylate, (meth) n-octyl acrylate, 2-ethyl hexyl (meth) acrylate, n (meth) acrylate -(Meta) acrylic acid alkyl ester monomers such as dodecyl; (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 3-methoxypropyl, (meth) acrylic acid 3-methoxybutyl, (meth) acrylic acid Examples include (meth) acrylic acid alkoxyalkyl ester monomers such as ethoxymethyl; and the like.
The (meth) acrylate monomer may be used alone or in combination of two or more. Further, in the present invention, "(meth) acrylic" means acrylic and / or methacrylic.

Here, as the (meth) acrylate monomer, a (meth) acrylic acid alkyl ester monomer is preferable from the viewpoint of further increasing the flexibility of the foamed sheet and ensuring better self-adhesion of the laminated sheet. A (meth) acrylic acid alkyl ester monomer (hereinafter, "C1-14 (meth) acrylic acid alkyl ester monomer") having an alkyl group (bonded to a non-carbonyl oxygen atom) having 1 or more and 14 or less carbon atoms. It may be abbreviated.) Is more preferable.

Examples of the C1-14 (meth) acrylic acid alkyl ester monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, and n-butyl acrylate. Heptyl, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, n-methacrylate Dodecyl is mentioned. Among these, n-butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate are preferable from the viewpoint of self-adhesiveness and cost.

The ratio of the (meth) acrylate monomer unit in the polymer is preferably 60% by mass or more, with 100% by mass of all the repeating units (all monomer units) contained in the polymer. It is more preferably mass% or more, further preferably 80% by mass or more, particularly preferably 85% by mass or more, preferably 99% by mass or less, and preferably 95% by mass or less. It is more preferably 92% by mass or less, and further preferably 92% by mass or less. When the ratio of the (meth) acrylate monomer unit in the polymer is 60% by mass or more, the self-adhesive force of the foamed sheet and the laminated sheet can be sufficiently secured. On the other hand, when the ratio of the (meth) acrylate monomer unit in the polymer is 99% by mass or less, the self-adhesive force of the foamed sheet and the laminated sheet does not excessively increase. Therefore, it is possible to suppress the resin remaining on the adherend of the foamed sheet and the laminated sheet.

<< Unsaturated carboxylic acid monomer unit >>
The unsaturated carboxylic acid monomer unit is a repeating unit derived from the unsaturated carboxylic acid monomer.
Specific examples of the unsaturated carboxylic acid monomer include α, β-ethylenic unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; α and β such as itaconic acid, maleic acid and fumaric acid. -Ethionic unsaturated polycarboxylic acid; α, β-ethylenically unsaturated polycarboxylic acid partial ester such as monomethyl itaconate, monobutyl maleate, monopropyl fumarate; and the like can be mentioned. Further, those having a group that can be induced to a carboxylic acid group by hydrolysis or the like, such as maleic anhydride and itaconic anhydride, can also be used in the same manner. Among these, itaconic acid, acrylic acid, and methacrylic acid are preferable, and acrylic acid is more preferable, from the viewpoint of reactivity with a cross-linking agent described later, stability of the polymer latex, and cost.
The unsaturated carboxylic acid monomer may be used alone or in combination of two or more.

The ratio of unsaturated carboxylic acid monomer units in the polymer is preferably 0.1% by mass or more, with 100% by mass of all repeating units (all monomer units) contained in the polymer. , 0.5% by mass or more, more preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2.5% by mass or less. When the ratio of the unsaturated carboxylic acid monomer unit in the polymer is 0.1% by mass or more, the cross-linking reaction by the cross-linking agent described later can be sufficiently proceeded. As a result, it is possible to suppress resin residue on the adherend of the foamed sheet and the laminated sheet while imparting sufficient strength to the obtained foamed sheet. On the other hand, when the proportion of the unsaturated carboxylic acid monomer unit in the polymer is 10% by mass or less, it becomes easy to keep the viscosity of the polymerization system at the time of polymerization in an appropriate range, and the polymer The cross-linking does not proceed excessively and the self-adhesive force of the foamed sheet and the laminated sheet is not impaired.

<< Vinyl cyanide monomer unit >>
The vinyl cyanide monomer unit is a repeating unit derived from the vinyl cyanide monomer.
Specific examples of the vinyl cyanide monomer include α, β-ethylenically unsaturated nitrile monomer. The α, β-ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an α, β-ethylenically unsaturated compound having a nitrile group, but for example, acrylonitrile; α-chloroacrylonitrile, α-bromo. Examples thereof include α-halogenoacrylonitrile such as acrylonitrile; α-alkylacrylonitrile such as methacrylonitrile and α-ethylacrylonitrile; Among these, acrylonitrile is preferable from the viewpoint of improving the cohesive force of the foamed sheet composition and increasing the breaking strength of the foamed sheet.
The vinyl cyanide monomer may be used alone or in combination of two or more.

The ratio of vinyl cyanide monomer units in the polymer is preferably 1% by mass or more, with 100% by mass of all repeating units (all monomer units) contained in the polymer. % Or more, more preferably 5% by mass or more, more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less. preferable. When the ratio of the vinyl cyanide monomer unit in the polymer is 1% by mass or more, it is possible to impart sufficient strength to the obtained foamed sheet and suppress resin residue on the adherend of the laminated sheet. can. On the other hand, when the ratio of the vinyl cyanide monomer unit in the polymer is 30% by mass or less, the foamed sheet and the laminated sheet having good self-adhesive force can be obtained by sufficiently ensuring the flexibility of the obtained foamed sheet. Obtainable.

<< Alkenyl aromatic monomer unit >>
The alkenyl aromatic monomer unit is a repeating unit derived from the alkenyl aromatic monomer.
Specific examples of the alkenyl aromatic monomer include styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene, and the like. Among these, styrene is preferable from the viewpoint of polymerizability and cost.
The alkenyl aromatic monomer may be used alone or in combination of two or more.

The ratio of the alkenyl aromatic monomer unit in the polymer is preferably 0.5% by mass or more, with 100% by mass of all the repeating units (all monomer units) contained in the polymer. It is more preferably 1% by mass or more, further preferably 1.5% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and 5% by mass or less. It is more preferable to have. When the ratio of the alkenyl aromatic monomer unit in the polymer is 0.5% by mass or more, it is possible to prevent water from entering the foam sheet based on the hydrophobicity of the alkenyl aromatic monomer unit. The water resistance of the foamed sheet and the laminated sheet can be improved. On the other hand, when the ratio of the alkenyl aromatic monomer unit in the polymer is 20% by mass or less, it is possible to sufficiently secure the flexibility of the obtained foamed sheet and obtain a laminated sheet having good self-adhesiveness. can.

<< Other monomer units >>
The other monomer unit is a repeating unit derived from another monomer copolymerizable with the above-mentioned monomer.
Examples of other monomers include conjugated diene monomers, α, β-ethylenic unsaturated polyvalent carboxylic acid complete ester monomers, vinyl cyanide monomers, and carboxylic acid unsaturated alcohol ester monomers. , Olefin-based monomers, crosslinkable monomers and the like. These monomers may be used alone or in combination of two or more.

Specific examples of the conjugated diene monomer include butadiene, isoprene, 1,3-pentadiene, cyclopentadiene, and the like.

Specific examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid complete ester monomer include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, and dimethyl itaconic acid. ..

Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, and the like.

Specific examples of the carboxylic acid unsaturated alcohol ester monomer include vinyl acetate.

Specific examples of the olefin-based monomer include ethylene, propylene, butene, and pentene.

The crosslinkable monomer is a monomer capable of efficiently cross-linking inside the polymer molecule and / or between the polymer molecules. The crosslinkable monomer is not particularly limited as long as the polymer can be crosslinked, but is a polyfunctional monomer having a plurality of polymerizable unsaturated bonds (excluding the above-mentioned conjugated diene monomer), and a crosslinkable functional group. Examples thereof include monomers having.
When a crosslinkable monomer is used, the ratio of the crosslinkable monomer unit in the polymer is 0.1% by mass, where 100% by mass is the total repeating unit (all monomer units) contained in the polymer. It is preferably 10% by mass or less. When the ratio of the crosslinkable monomer unit in the polymer is within the above range, it becomes easy to keep the viscosity of the polymerization system at the time of polymerization in an appropriate range, and the crosslinking of the polymer proceeds excessively. This makes it easier to prevent the self-adhesiveness of the foamed sheet and the laminated sheet from being impaired.

[Polyfunctional monomer]
Examples of the polyfunctional monomer include bifunctional monomers such as divinylbenzene, ethylene diacrylate, ethylene dimethacrylate, and allyl methacrylate; and trifunctional monomers such as trimethylolpropane trimethacrylate. ; Etc. can be used. The polyfunctional monomer preferably has an unsaturated bond at the end. As the polyfunctional monomer, one kind may be used alone, or two or more kinds may be used in combination.

[Monomer with crosslinkable functional group]
Examples of the monomer having a crosslinkable functional group include a monomer having a functional group such as an organic acid group other than a carboxy group, a hydroxyl group, an amino group, an amide group, a mercapto group and an epoxy group.

The monomer having an organic acid group is not particularly limited, and typical examples thereof include a monomer having an organic acid group such as a sulfonic acid group. In addition to these, monomers containing a sulfenic acid group, a sulfinic acid group, a phosphoric acid group and the like can also be used.

Specific examples of the monomer having a sulfonic acid group include α, β-unsaturated sulfonic acid such as allyl sulfonic acid, metharyl sulfonic acid, vinyl sulfonic acid, acrylamide-2-methylpropane sulfonic acid, and these. Salt can be mentioned.

When the monomer having an organic acid group is used, the content of the monomer unit derived from the monomer having an organic acid group in the polymer is 0.1% by mass or more and 10% by mass or less. It is preferably 0.5% by mass or more and 5% by mass or less. When the content of the monomer unit derived from the monomer having an organic acid group in the polymer is within the above range, it becomes easy to keep the viscosity of the polymerization system at the time of polymerization in an appropriate range. In addition, it becomes easy to prevent the cross-linking of the polymer from progressing excessively and impairing the self-adhesiveness of the foamed sheet and the laminated sheet.

The monomer unit having an organic acid group is convenient and preferable to be introduced into the polymer by polymerizing the monomer having an organic acid group, but it is preferable that the monomer unit has a known polymer after the polymer is formed. An organic acid group may be introduced by the reaction.

When a monomer having a functional group other than the organic acid group (hydroxyl group, amino group, amide group, epoxy group) is used, a single amount derived from the monomer of the functional group other than the organic acid group in the polymer. The content of the body unit is preferably 10% by mass or less. When the content of the monomer unit derived from the monomer of the functional group other than the organic acid group in the polymer is 10% by mass or less, the viscosity of the polymerization system at the time of polymerization can be kept in an appropriate range. In addition, it becomes easy to prevent the cross-linking of the polymer from progressing excessively and impairing the self-adhesiveness of the foamed sheet and the laminated sheet.

The polymer preferably does not have an N-methylol group from the viewpoint of sufficiently suppressing the formation of formaldehyde when foaming and curing the foamed sheet composition. More specifically, it is preferable that the polymer does not contain a monomer unit having an N-methylol group.
Here, examples of the monomer having an N-methylol group include N-methylolacrylamide and N-methylolmethacrylamide.

<< Properties >>
[Glass-transition temperature]
The glass transition temperature of the polymer is preferably −10 ° C. or lower, more preferably −13 ° C. or lower, further preferably −17 ° C. or lower, and particularly preferably −20 ° C. or lower. .. When the glass transition temperature of the polymer is −10 ° C. or lower, the foamed sheet and the laminated sheet can be satisfactorily adhered to the adherend while sufficiently ensuring the self-adhesive force of the foamed sheet and the laminated sheet. This makes it possible to prevent moisture from entering between the layers between the adherend and the foamed sheet and between the layers between the adherend and the laminated sheet. Therefore, the water resistance of the foamed sheet and the laminated sheet can be improved.
The lower limit of the glass transition temperature of the polymer is not particularly limited, but is preferably −40 ° C. or higher from the viewpoint of sufficiently suppressing resin residue on the adherend of the foamed sheet and the laminated sheet.
As for the glass transition temperature of the polymer, for example, the glass transition temperature of the film obtained by drying the polymer latex containing the polymer is measured by using a differential scanning calorimeter according to JIS K 7121. Can be obtained by As the differential scanning calorimeter, for example, DSC7000X (manufactured by Hitachi High-Tech Science Corporation) can be used.

[Gel fraction]
The gel fraction of the polymer is preferably 95% by mass or less, more preferably 93% by mass or less. When the gel fraction is 95% by mass or less, a foamed sheet and a laminated sheet having an appropriate self-adhesive force and excellent smoothness can be produced. The lower limit of the gel fraction of the polymer is not particularly limited, but can be, for example, 50% by mass or more, and 70% by mass or more.
The gel fraction of the polymer can be measured by, for example, the following method. First, the polymer is applied on a polyethylene terephthalate (PET) film having a thickness of 50 μm with a 250 μm applicator and dried at room temperature for 24 hours to obtain a resin film. Using this film as a sample, a predetermined amount (X) (about 500 mg) is precisely weighed, immersed in 100 ml of ethyl acetate at room temperature for 3 days, and then the insoluble matter is filtered through a 200 mesh wire mesh and kept at room temperature for 15 hours. The sample is air-dried at 100 ° C. for 2 hours, cooled at room temperature, and then the weight (Y) of the sample is measured. Then, by substituting X and Y into the following equation, the gel fraction is calculated.
Gel fraction (%) = (Y) / (X) x 100

<< Preparation method of polymer >>
The polymerization method for obtaining the polymer is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like, and any method other than these may be used. There is no particular limitation on the type and amount of the polymerization initiator, emulsifier, dispersant and the like used for the polymerization. At the time of polymerization, there is no particular limitation on the method of adding a monomer, a polymerization initiator, an emulsifier, a dispersant and the like. Further, there are no restrictions on the polymerization temperature, pressure, stirring conditions, and the like.
Although the polymer can be used as a solid, it should be used in the state of latex containing a polymer (polymer latex) such as latex obtained by emulsion polymerization or latex obtained by post-emulsification of the polymer. Is preferable. The polymer is easy to operate in mixing with oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt, an optional solvent and other additives, and the composition for a foamed sheet obtained. This is because it is convenient for foaming things.
Here, as described above, when the polymer is used in the preparation of a composition for a foamed sheet in the form of a polymer latex, the solid mass concentration of the polymer latex is from the viewpoint of maintaining the density of the obtained foamed sheet. , 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, particularly preferably 52% by mass or more, and 70% by mass or less. It is preferably 58% by mass or less, and more preferably 58% by mass or less.

<Metal-containing oxidized cellulose nanofibers containing metals other than sodium in the form of salts>
The metal-containing oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt used in the self-adsorptive foamed sheet composition of the present invention are foamed sheets produced by using the foamed sheet composition of the present invention. It is a component that imparts deodorant properties to the product. The metal-containing cellulose oxide nanofibers are not particularly limited as long as they have deodorant properties.
Further, the metal-containing cellulose oxide nanofibers can impart strength to the obtained foamed sheet. Therefore, the density of the foamed sheet can be reduced while maintaining the strength of the foamed sheet. If the density of the foamed sheet is reduced (that is, if more bubbles are formed in the foamed sheet), the contact area between the metal-containing cellulose oxide nanofibers and the outside air is increased, so that the deodorizing power of the foamed sheet is improved. .. Therefore, by including the metal-containing cellulose oxide nanofibers in the composition for a foamed sheet, it is possible to improve the deodorizing property of the foamed sheet while maintaining the strength of the foamed sheet.

The composition for a foamed sheet of the present invention contains metal-containing oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt in an amount of 0.1 part by mass or more and 1.00 part by mass with respect to 100 parts by mass of the polymer. It is necessary to include in the range of less than a part. This makes it possible to achieve both adsorptivity and deodorant properties at a high level in the foamed sheet produced by using the foamed sheet composition.

The composition for a foamed sheet contains metal-containing cellulose oxide nanofibers containing a metal other than sodium in the form of a salt in an amount within the above range, thereby achieving both the adsorptivity and the deodorizing property of the foamed sheet at a high level. The reason for this is not always clear, but it is presumed to be as follows. That is, if the content of the metal-containing cellulose oxide nanofibers containing a metal other than sodium in the form of a salt is less than 0.1 parts by mass, the amount of the metal-containing cellulose oxide nanofibers exhibiting deodorizing performance is too small. , It is considered that the deodorizing property of the foamed sheet is lowered. On the other hand, when the content exceeds 1.00 parts by mass, the elasticity of the foamed sheet composition is improved and the viscosity is reduced, and the amount of the resin in contact with the adherend is reduced. It is considered that the adsorptivity of the obtained foamed sheet to the adherend is lowered.

From the viewpoint of achieving both adsorptivity and deodorizing properties at a higher level in the obtained foamed sheet, the content of the metal-containing cellulose oxide nanofibers in the foamed sheet composition is 0 with respect to 100 parts by mass of the polymer. It is preferably 3 parts by mass or more, more preferably 0.4 parts by mass or more, preferably 0.9 parts by mass or less, and more preferably 0.8 parts by mass or less.

<< Properties >>
The metal-containing oxidized cellulose nanofibers are preferably metal-containing carboxylated cellulose nanofibers. The metal-containing carboxylated cellulose nanofibers have excellent dispersibility, and even if the blending amount in the composition for a foamed sheet is small, the obtained foamed sheet can be satisfactorily imparted with desired properties such as deodorant properties. Because it can be done.

Here, in the carboxylated cellulose nanofibers constituting the metal-containing carboxylated cellulose nanofibers, the primary hydroxyl group at the 6-position of the β-glucose unit of the raw material cellulose is oxidized to the carboxy group via the aldehyde group. .. From the viewpoint of sufficiently imparting desired properties to the metal-containing carboxycellulose nanofibers, in the carboxylated cellulose nanofibers, the primary hydroxyl group is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 70 mol% or more. It is preferable that 90 mol% or more is oxidized to the carboxy group.

The amount of carboxy group of the metal-containing carboxylated cellulose nanofiber can be measured according to the method described in JP-A-2016-141777 or JP-A-2019-199622.

[Metal other than sodium]
The metal other than sodium contained in the metal-containing cellulose oxide nanofibers can be a metal according to the characteristics desired to be imparted to the metal-containing cellulose oxide nanofibers. The metal other than sodium is, for example, at least one selected from the metals of Group 2 to 14 and Periods 3 to 6 in the Long Periodic Table; more preferably magnesium, aluminum, calcium, titanium, chromium, etc. At least one selected from the group consisting of manganese, iron, cobalt, nickel, copper, zinc, silver, tin, barium, and lead; more preferably composed of aluminum, calcium, iron, cobalt, copper, zinc, and silver. At least one selected from the group; particularly preferably at least one selected from the group consisting of silver, zinc, and copper.
The metal-containing cellulose oxide nanofibers containing copper and silver (copper-containing cellulose oxide nanofibers, silver-containing cellulose oxide nanofibers) are particularly excellent in deodorizing sulfur-based malodorous gases such as hydrogen sulfide and methyl mercaptan. ..

The amount of the metal other than sodium in the metal-containing oxidized cellulose nanofiber is not limited as long as it can impart the desired properties to the obtained foamed sheet. For example, in the metal-containing carboxylated cellulose nanofibers, metals other than sodium are preferably present in a proportion of 1/3 or more of the molar amount of the carboxy group of the carboxylated cellulose nanofibers, and more than 1/2. It is more preferable that it is present in proportion. The larger the content ratio of the metal other than sodium in the metal-containing oxidized cellulose nanofiber, the better the deodorizing property of the obtained foamed sheet can be improved.

The metal in the metal-containing cellulose nanofibers can be qualitatively and quantified by the ICP-AES method according to the method described in, for example, JP-A-2016-141777 or JP-A-2019-199622.

[Number average fiber diameter]
The number average fiber diameter of the metal-containing cellulose oxide nanofibers is preferably 100 nm or less, more preferably 50 nm or less, further preferably 30 nm or less, and particularly preferably 10 nm or less. Metal-containing cellulose oxide nanofibers having a number average fiber diameter of 100 nm or less are excellent in dispersibility, and even if the amount of the foamed sheet composition is small, the obtained foamed sheet is desired to have deodorant properties. This is because the characteristics of the above can be satisfactorily imparted.

[Number average fiber length]
Further, the metal-containing cellulose oxide nanofibers preferably have a number average fiber length of 50 nm or more and 2000 nm or less, more preferably 70 nm or more and 1500 nm or less, further preferably 100 nm or more and 1000 nm or less, and further preferably 400 nm or more. It is particularly preferably 600 nm or less. When the number average fiber length is 50 nm or more, sufficiently high mechanical strength can be imparted to the obtained foamed sheet. Further, when the number average fiber length is 2000 nm or less, the dispersibility of the metal-containing cellulose oxide nanofibers can be ensured, and the concentration of the dispersion can be sufficiently increased.

The number average fiber length of the metal-containing oxidized cellulose nanofibers includes, for example, the number average fiber length of natural cellulose used as a raw material, oxidation treatment conditions, conditions for dispersing (defibrating) the carboxylated cellulose nanofibers after the oxidation treatment, and the like. It can be adjusted by changing the conditions for dispersion (defibration) after the metal replacement step. Specifically, if the time of the dispersion treatment (defibration treatment) is lengthened, the number average fiber length can be shortened.

For the number average fiber length of the metal-containing cellulose oxide nanofibers, for example, the fiber length of five or more metal-containing cellulose oxide nanofibers is measured using an atomic force microscope, and the average value of the obtained measured values is calculated. It can be measured by doing so. As the atomic force microscope, for example, a Dimension FastScan AFM (Tapping mode manufactured by BRUKER) can be used.

[Average degree of polymerization]
Further, the metal-containing oxidized cellulose nanofibers preferably have an average degree of polymerization (average value of the number of glucose units contained in the cellulose molecule) of 100 or more and 2000 or less, and more preferably 300 or more and 1500 or less. , 500 or more and 1000 or less, and particularly preferably 500 or more and 700 or less. When the average degree of polymerization is 100 or more, a sufficiently high mechanical strength can be imparted to the foamed sheet. Further, when the average degree of polymerization is 2000 or less, the dispersibility of the metal-containing cellulose oxide nanofibers can be ensured, and when the dispersion liquid is used, the concentration of the dispersion liquid can be sufficiently increased.

The average degree of polymerization of the metal-containing oxidized cellulose nanofibers is the average degree of polymerization of natural cellulose used as a raw material, the conditions for oxidation treatment, the conditions for dispersing (defibrating) the carboxylated cellulose nanofibers after the oxidation treatment, and after the metal replacement step. It can be adjusted by changing the conditions for dispersion (defibration).

The average degree of polymerization of the metal-containing oxidized cellulose nanofibers is, for example, Isogai, A. et al. , Mutoh, N. et al. , Onabe, F.I. , Usuda, M. et al. , "Viscosity measurement of cellulose / SO ^2- amine-dimethyl sulfoxide solution", Sen'i Gakkaishi, 45, 299-306 (1989). Can be measured according to.

<< Usage >>
The metal-containing cellulose oxide nanofibers can be used in the state of a dispersion liquid dispersed in a dispersion medium such as water. In this dispersion, the metal-containing cellulose oxide nanofibers preferably have a number average fiber diameter of 100 nm or less, more preferably 2 nm or more and 50 nm or less, still more preferably 2 nm or more and 10 nm or less, and particularly preferably 2 nm or more and 5 nm or less. Highly dispersed at the level.
Therefore, if the dispersion liquid is used, a foamed sheet composition capable of obtaining a foamed sheet having an excellent deodorizing effect can be satisfactorily obtained. Specifically, the dispersion liquid containing the metal-containing cellulose oxide nanofibers is added to the above-mentioned polymer or polymer latex as it is, and the obtained mixed liquid is stirred to obtain the metal-containing cellulose oxide nanofibers. It is possible to satisfactorily obtain a composition for a foamed sheet in which is sufficiently dispersed. Further, it is preferable to add the dispersion liquid containing the metal-containing cellulose oxide nanofibers to the stirred polymer or polymer latex little by little using a pipette or the like because the aggregation of the metal-containing cellulose oxide nanofibers can be prevented.
Here, the solid content concentration of the metal-containing cellulose nanofibers in the dispersion is preferably 0.1% or more and 2.0% or less. When the solid content concentration is 0.1% or more, the content of the dispersion medium such as water in the obtained composition for foamed sheet is prevented from increasing and the viscosity of the composition is prevented from decreasing, and the composition is smoother and more uniform. Sheet can be molded. On the other hand, when the solid content concentration is 2.0% or less, it is possible to prevent the dispersion liquid from forming a jelly-like pseudogel, and further improve the dispersibility of the metal-containing cellulose nanofibers in the obtained composition for foamed sheets. Can be made to.
When solid metal-containing cellulose oxide nanofibers are used, the dispersion may be dried by a known means.

<< Manufacturing method >>
The metal-containing oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt used in the composition for a foamed sheet of the present invention are, for example, JP-A-2016-141777 and JP-A-2019-199622. It can be manufactured according to the method described in.
The metal-containing oxidized cellulose nanofibers containing a metal other than sodium produced as described above in the form of a salt are usually obtained as a dispersion liquid dispersed in a dispersion medium such as water.

<Solvent>
The solvent that can be arbitrarily contained in the composition for foamed sheet of the present invention is not particularly limited, but water is preferable. Here, when water is used as the solvent, the water contained in the foamed sheet composition is, for example, water derived from a polymer latex and / or a metal-containing oxidized cellulose nanofiber containing a metal other than sodium in the form of a salt. It can be water derived from the aqueous dispersion of the above and / or water derived from other additives.

<Other additives>
The composition for a foamed sheet of the present invention can optionally contain various additives in order to improve the processability in the manufacturing process of the foamed sheet and the laminated sheet and to improve the performance of the obtained foamed sheet and the laminated sheet. .. Examples of such additives include cross-linking agents, foam stabilizers such as higher fatty acid salts and surfactants, foaming aids, thickeners, fillers, preservatives, fungicides, gelling agents, and flame-retardant agents. , Anti-aging agents, antioxidants, pigments, dyes, tackifiers, conductive compounds, water-resistant agents, oil-resistant agents and the like. As specific examples of the above-mentioned other additives, known additives, for example, those described in International Publication No. 2016/147679 can be used without particular limitation.

<< Crosslinking agent >>
The cross-linking agent arbitrarily contained in the composition for foamed sheet of the present invention may be any that can form a cross-linked structure with the above-mentioned polymer (particularly, the unsaturated carboxylic acid monomer unit of the above-mentioned polymer). There is no particular limitation. Examples of such a cross-linking agent include a carbodiimide-based cross-linking agent; an epoxy-based cross-linking agent; an oxazoline-based cross-linking agent; Examples thereof include salt-based cross-linking agents; metal chelate-based cross-linking agents; peroxide-based cross-linking agents; and the like. Among them, an epoxy-based cross-linking agent is preferably used, and a compound having two or more epoxy groups in one molecule is more preferably used. As the epoxy-based cross-linking agent, fatty acid polyglycidyl ether, glycerol polyglycidyl ether, and ethylene glycol diglycidyl ether are preferable.

Here, the epoxy-based cross-linking agent may be synthesized by a known method, or a commercially available product may be used. Examples of commercially available epoxy-based cross-linking agents include "Ricabond (registered trademark)" manufactured by Japan Coating Resin Co., Ltd.
The epoxy-based cross-linking agent has an epoxy group thereof and a functional group or the like in the polymer (for example, a carboxylic acid group derived from an unsaturated carboxylic acid monomer unit), so that the polymer can be contained in a molecule or a molecule. A crosslinked structure is formed between them. If an epoxy-based cross-linking agent is used, it is possible to form a foamed sheet having an appropriate self-adhesive force and excellent strength. Therefore, if a composition for a foamed sheet containing an epoxy-based crosslinking agent is used as the cross-linking agent, it is possible to suppress resin residue on the adherend of the foamed sheet and the laminated sheet.

In the present invention, it is preferable not to use a cross-linking agent that causes formaldehyde such as melamine-formaldehyde resin, urea-formaldehyde resin, and phenol formaldehyde resin.

Here, the blending amount of the cross-linking agent in the composition for foamed sheet is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, 3 parts by mass, per 100 parts by mass of the above-mentioned polymer. It is more preferably more than parts by mass, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. When the blending amount of the cross-linking agent is within the above-mentioned range, a foamed sheet having appropriate strength and elasticity can be obtained. Therefore, when the pressure applied to the foamed sheet is released, the foamed cells in the crushed foamed sheet can be restored to their original shape. Then, the self-adhesive force of the foamed sheet and the laminated sheet can be ensured, and the resin residue on the adherend of the foamed sheet and the laminated sheet can be sufficiently suppressed.

<< Foaming agent >>
As the foam stabilizer, fatty acid ammonium such as ammonium stearate; sulfonic acid type anionic surfactant such as alkylsulfosuccinate; quaternary alkylammonium chloride; alkylbetaine amphoteric; and fatty acid alkanolamine can be used.

<< Thickener >>
As the thickener, an acrylic polymer such as sodium polyacrylate; fine particles of an inorganic compound such as fine silica; and a reactive inorganic compound such as magnesium oxide can be used.

<Characteristics of composition for foam sheet>
When the foamed sheet composition contains a solvent (in the form of a dispersion in which metal-containing cellulose oxide nanofibers are dispersed), the viscosity of the foamed sheet composition is 800 mPa · s or more and 10,000 mPa · s or less. It is preferably 900 mPa · s or more and 8,000 mPa · s or less, and more preferably 1,000 mPa · s or more and 7,500 mPa · s or less. If the viscosity of the foamed sheet composition is 1,000 mPa · s or more, liquid dripping occurs when the foamed composition formed from the foamed sheet composition is applied onto the substrate to form the foamed sheet. It is possible to prevent the thickness from becoming difficult to control. On the other hand, if the viscosity of the foamed sheet composition is 10,000 mPa · s or less, it does not become difficult to control the foaming ratio by mechanical foaming when forming the foamed sheet.
The viscosity of the foamed sheet composition can be measured by the method described in Examples.

The pH of the foamed sheet composition is preferably 5 or more, more preferably 7 or more, further preferably 8 or more, and preferably 10 or less, 9.7. It is more preferably less than or equal to, and even more preferably 9.5 or less. When the pH of the foam sheet composition is 5 or more, the metal of the metal-containing cellulose nanofibers containing a metal other than sodium in the form of a salt is disengaged to become a carboxylic acid, resulting in precipitation and aggregation of the nanofibers. Further, it is possible to satisfactorily prevent sedimentation due to aggregation of detached metal ions. On the other hand, when the pH of the foamed sheet composition is 10 or less, it is possible to satisfactorily prevent a decrease in the strength of the foamed layer due to the difficulty in proceeding with the cross-linking reaction when a cross-linking agent is used.
The pH of the foamed sheet composition can be measured by the method described in Examples.

<Manufacturing method of composition for foam sheet>
In the composition for foamed sheet of the present invention, metal-containing oxidized cellulose nanofibers containing a polymer and a metal other than sodium in the form of a salt are mixed with a solvent and other additives used as desired by an arbitrary method. Can be manufactured by

For example, when a polymer latex is used in preparing a composition for a foamed sheet, the polymer latex may be optionally used as a metal-containing cellulose oxide nanofiber containing a metal other than sodium in the form of a salt. The additive of the above may be added and mixed by a known method.

Further, for example, when a dispersion liquid of metal-containing oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt is used when preparing a composition for a foamed sheet, a solid polymer or a weight is used in this dispersion liquid. The coalesced latex and other optional additives may be added and mixed by known methods.

Further, for example, when a solvent is not used in preparing the composition for a foamed sheet, a solid polymer and metal-containing oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt are optionally used. Other solid additives may be mixed using known methods, such as known rolls, Henchel mixers, kneaders and the like.

From the viewpoint of satisfactorily dispersing the metal-containing oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt in the composition for a foamed sheet, a metal other than sodium is added to the polymer latex under stirring. A dispersion of metal-containing cellulose oxide nanofibers contained in the form (for example, an aqueous dispersion) is added to obtain a mixed solution, and then other additives are optionally added to the mixed solution by a known method. Further mixing is preferred. As for other additives, those that increase the viscosity in the system, such as a cross-linking agent and a thickener, are preferably added later to maintain a uniform composition in the system.

(Self-adsorbing foam sheet)
The self-adsorptive foamed sheet of the present invention is obtained by foaming and molding the above-mentioned composition for a foamed sheet of the present invention into a foamed sheet.

<Characteristics>
The density of the self-adsorbing foam sheet is not particularly limited, but is preferably 0.3 g / cm ³ or more, more preferably 0.4 g / cm ³ or more, and 0.7 g / cm ³ or less. It is preferably 0.6 g / cm ³ or less, and more preferably 0.6 g / cm 3. When the density of the foamed sheet is 0.3 g / cm ³ or more, the strength of the foamed sheet can be ensured. On the other hand, when the density of the foamed sheet is 0.7 g / cm ³ or less, the deodorizing property of the foamed sheet is ensured and the air bleeding property (the air pool remaining between the foamed sheet and the adherend is easily formed). The ability to remove) can be sufficiently enhanced.

The thickness of the foamed sheet is preferably 30 μm or more, more preferably 50 μm or more, further preferably 100 μm or more, preferably 3 mm or less, and more preferably 1 mm or less. , 500 μm or less, more preferably 400 μm or less. When the thickness of the foamed sheet is 30 μm or more, the deodorant property and the mechanical strength of the foamed sheet and the laminated sheet can be sufficiently ensured. On the other hand, when the thickness of the foamed sheet is 3 mm or less, a laminated sheet having excellent repetitive stickability (rework performance) can be obtained.

The foamed sheet preferably contains open cells in which a plurality of bubbles communicate with each other. If the foamed sheet contains such open cells, the air accumulated between the foamed sheet and the adherend can be easily removed to the outside of the foamed sheet via the open cells, so that the air in the foamed sheet can be easily removed. The pullability is further improved, and it can be attached to the adherend neatly and easily. Further, if the foamed sheet contains such open cells, the contact area with the outside air increases and more odorous components can be deodorized, so that the deodorizing property of the foamed sheet is further improved. When the foamed sheet is used as the foamed layer of the self-adsorbing laminate described later, the open cells in the foamed sheet extend in the plane direction of the foamed sheet from the viewpoint of further improving the air bleeding property and the deodorizing property. It is preferable to contain open cells.
The open cells in the foamed sheet can usually be confirmed by observing the cross section of the foamed sheet with, for example, a laser microscope, a digital microscope, a scanning electron microscope, or the like.
The open cells can also be confirmed at the stage of the foamed composition obtained by foaming the foamed sheet composition. Open cells can be confirmed, for example, by placing the foamed composition in a transparent container and observing it with X-ray CT.

The properties of the foamed sheet (density, thickness, open cells, hardness, etc.) are, for example, the mixing ratio of bubbles, the composition of the foamed sheet composition, the solid content concentration, the viscosity, and the drying and cross-linking in the method for producing the foamed sheet described later. It can be adjusted by changing the conditions and the like.

<Manufacturing method of self-adsorptive foam sheet>
The self-adsorbing foamed sheet can be produced by foaming and molding the above-mentioned composition for a foamed sheet on an arbitrary base material into a sheet shape.

Specifically, first, the foamed sheet composition is foamed to obtain an unsolidified foamed composition. Here, when the composition for a foamed sheet is in the form of a dispersion, a foamed dispersion can be obtained.

As the foaming method, mechanical foaming is usually adopted. The foaming ratio may be appropriately adjusted, but is usually 1.2 times or more and 5 times or less, preferably 1.5 times or more and 4 times or less. The method of mechanical foaming is not particularly limited, but can be carried out by mixing a certain amount of air into the dispersion of the composition for foam sheet and stirring it continuously or in a batch manner with an oak mixer, a whipper or the like. The foamed dispersion thus obtained becomes creamy.
By forming pores by the above mechanical foaming, a foamed sheet having excellent air bleeding property can be finally obtained. When the foaming ratio is 1.2 times or more, it is possible to prevent the air bleeding property from decreasing, and when it is 5 times or less, it is possible to prevent the strength of the foamed sheet from decreasing. ..

Next, the foaming composition is made into a sheet. The method for forming the foam composition into a sheet is not particularly limited. Suitable methods include, for example, a method of applying the foamed composition in the form of a sheet on an arbitrary substrate. The base material is not limited, but a base material exemplified in the section (self-adsorptive laminated sheet) described later and a process paper having peelability (hereinafter, referred to as “base material or the like”) can be used.
As a method of applying the foam composition onto a substrate or the like, a generally known coating device such as a roll coater, a reverse roll coater, a screen coater, a doctor knife coater, or a comma knife coater can be used.

Next, the foamed composition in the form of a sheet is solidified on a substrate or the like. The solidification of the foaming composition is carried out, for example, by cross-linking the polymer of the foaming composition. The method for cross-linking the polymer is not limited, but a method of heating and drying the foamed composition is preferable. The method of heat drying is not particularly limited as long as it is a method capable of drying the foamed composition on the substrate or the like and cross-linking the polymer, and a known drying oven (for example, a hot air circulation type) is used. Oven, hot oil circulation hot air chamber, far infrared heater chamber) can be used. The drying temperature can be, for example, 60 ° C. or higher and 180 ° C. or lower. Further, it is preferable to perform multi-step drying such that drying is performed from the inside at a low temperature in the early stage of drying and sufficiently dried at a higher temperature in the latter stage of drying, instead of performing drying at a constant temperature.

In this way, a self-adsorptive foamed sheet formed by solidifying the sheet-shaped foamed composition is formed on the base material or the like. At this time, if a process paper having peelability is used, the self-adsorptive foam sheet can be easily separated from the process paper, and the self-adsorbable foam sheet can be obtained as an independent film.

The self-adsorptive foam sheet thus obtained is not particularly limited, but is used, for example, after a separator film is attached to the surface thereof, the sheet is wound by a winder, cut by press cutting, a slitter, or the like. It can be processed to an easy size.

(Self-adsorptive laminate)
The self-adsorptive laminate of the present invention comprises a foamed layer made of a foamed sheet (self-adsorptive foamed sheet of the present invention) obtained by using the above-mentioned composition for a foamed sheet of the present invention, and a support for supporting the foamed layer. It comprises a base material as a body layer. The foamed sheet may be formed directly on the substrate or may be formed on the substrate via any layer.
Further, the self-adsorptive laminate of the present invention may be provided with foam sheets on both sides of the base material.

As the base material in the laminated sheet of the present invention, a paper base material, synthetic paper, a plastic base material, a fiber base material, a metal base material, a glass base material, or the like can be used. The thickness of the base material is not particularly limited, but can be, for example, 10 μm or more and 500 μm or less.

Examples of the paper base material include high-quality paper, art paper, coated paper, kraft paper, and those obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials.

The synthetic paper is not particularly limited, but the surface layer is made into paper by a combination of a thermoplastic resin and an inorganic filler.

Examples of the plastic base material include polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polystyrene resins; polyvinyl chloride resins; acrylic resins; polycarbonate resins; polyamide resins; fluororesins such as polytetrafluoroethylene. Examples thereof include a resin; a polyolefin resin such as polyethylene and polypropylene; a cyclic polyolefin resin, and a sheet-like base material composed of a mixture or laminate of these resins.

Examples of the fiber base material include natural fibers such as cotton and silk; polyamide-based synthetic fibers; polyester-based synthetic fibers; polypropylene-based synthetic fibers; polyvinyl chloride-based synthetic fibers; polyvinyl alcohol-based synthetic fibers; semi-synthetic fibers such as acetate. Examples include recycled artificial fibers such as rayon; and sheet-like substrates made of mixtures or laminates of these fibers.

The metal base material is not particularly limited, and examples thereof include a metal such as iron, copper, aluminum, gold, platinum, and silver, and a sheet-like base material made of an alloy or laminate thereof.

The glass base material is not particularly limited, and examples thereof include a sheet-like base material made of soda lime glass, borosilicate glass, non-alkali glass, quartz glass, and the like.

(Manufacturing method of self-adsorptive laminate)
In the self-adsorptive laminate of the present invention, for example, as described above, the foamed sheet composition is foamed and formed into a sheet on the substrate, and the sheet-shaped foamed composition is solidified on the substrate. It can be manufactured by forming a self-adsorbing foamed sheet. Alternatively, the self-adsorptive laminate of the present invention is produced by obtaining a self-adsorptive foam sheet as an independent film as described above and then laminating this on a substrate by a known means such as an arbitrary adhesive. You may.
Further, in the case of producing a self-adsorptive laminate having foam sheets on both sides of the base material, after forming the foam sheet on one surface of the base material as described above, the same applies to the other (opposite) surface. A foamed sheet may be formed on the surface of the substrate, or a foamed sheet as an independent film may be attached to both sides of the base material by a known means such as an adhesive.

Hereinafter, an example of a method for producing a self-adsorptive laminate by forming a self-adsorptive foam sheet on a substrate will be described with reference to the drawings.

FIG. 1 shows a flowchart illustrating an example of a method S10 for manufacturing a laminated sheet (hereinafter, may be abbreviated as “manufacturing method S10”). As shown in FIG. 1, the manufacturing method S10 includes a composition manufacturing step S1, a foaming step S2, and a sheeting step S3 in this order. Hereinafter, each step will be described.

<Composition preparation step S1>
The composition preparation step S1 is a step of preparing the composition for a self-adsorbing foamed sheet of the present invention. In the composition preparation step S1, the composition for a self-adsorptive foamed sheet of the present invention is produced by the method described in the above section <Method for producing a composition for a self-adsorbable foamed sheet>.

<Foam step S2>
The foaming step S2 is a step of foaming the foaming sheet composition obtained in the composition producing step S1 to obtain a foamed composition. In the foaming step S2, the foamed sheet composition is foamed by the method described in the above section <Method for producing a self-adsorbing foamed sheet> to produce a foamed composition.

<Sheet-making process S3>
The sheet forming step S3 is a step of forming the foamed composition obtained in the foaming step S2 into a sheet shape on the base material. In the foaming step S3, the foaming composition obtained in the foaming step S2 is applied and solidified on the substrate by the method described in the above section <Method for producing a self-adsorptive foam sheet> to form a substrate. A self-adsorptive foamed sheet in which a sheet-shaped foamed composition is solidified is produced. As a result, a self-adsorptive laminate having a foam layer made of a self-adsorptive foam sheet and a base material as a support layer for supporting the foam layer can be obtained.

The laminated sheet obtained through the above-mentioned steps S1 to S3 is not particularly limited, but is, for example, wound after the separator film is attached to the surface having self-adsorption property (that is, the surface on the foam sheet side). It can be wound up by a machine, cut by press cutting, slitter, etc., and processed into a size that is easy to use.

<Use of laminated sheet>
The laminated sheet of the present invention can be printed on the substrate surface thereof by, for example, offset printing, seal printing, flexographic printing, silk screen printing, gravure printing, laser printer, thermal transfer printer, inkjet printer or the like.
Laminated sheets printed on the base material surface are, for example, sales promotion cards, so-called POP cards (posters, stickers, displays, etc.), gardening POPs (insert labels, etc.), road signs (funeral, housing exhibition places, etc.). It can be advantageously used for outdoor applications such as display boards (no entry, forest road work, etc.) and indoor applications for adhering to wallpaper, floor materials, and wall materials.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. Further, in a polymer produced by polymerizing a plurality of types of monomers, the ratio of the monomer unit formed by polymerizing a certain monomer to the polymer is usually not specified unless otherwise specified. It is consistent with the ratio (preparation ratio) of the certain monomer to all the monomers used for the polymerization of the polymer. Then, various measurements and evaluations in Examples and Comparative Examples were carried out according to the following methods.

(Viscosity of composition for foam sheet)
The viscosity of the foamed sheet composition was measured at 23 ° C. using a B-type viscometer (“VISCOTESTER VT-06” manufactured by Rion Co., Ltd.).

(PH of composition for foam sheet)
The pH of the foamed sheet composition was measured at 23 ° C. using a pH meter (pH METER F-52 manufactured by HORIBA).

(Thickness and density of foam layer)
Cut eight laminated sheets into 50 mm x 50 mm squares, measure their weight (balance: BM-252 manufactured by A & D Co., Ltd.), measure the thickness (thickness meter: PEACOK MODEL H manufactured by Ozaki Seisakusho), and calculate the average value. Derived. Similarly, eight base materials (synthetic paper, film, etc.) were individually cut into squares of 50 mm × 50 mm, and their weights and thicknesses were measured to derive average values. The weight of the foam layer was calculated by subtracting the average weight of the base material from the average weight of the laminated sheet. Further, the thickness of the foamed layer was calculated by subtracting the average thickness of the base material from the average thickness of the laminated sheet. The value was divided by the volume (50 mm × 50 mm × average thickness) to calculate the density of the foam layer.

(Strength of foam layer)
The obtained laminated sheet was cut into a size of 50 mm × 125 mm (width × length), and the gum tape cut out to a size of 50 mm × 150 mm (width × length) and the adhesive layer were bonded to each other from one end (gum tape). Has an extra 25 mm on the opposite side of the end bonded in the length direction). The remaining side of the gum tape in the portion where the laminated sheet and the gum tape were bonded was peeled off by 25 mm from the end, and the excess gum tape and the peeled gum tape 50 mm were folded around 25 mm and the adhesive layers of the gum tape were bonded to each other. Then, a force was applied to the entire surface of the sticking surface with a roller to bring the adhesive layer of the laminated sheet into close contact with the adhesive surface of the gum tape. The test piece was cut out in parallel in the length direction from a position having a width of 25 mm, and two sets of test pieces cut out into a size of 25 mm × 125 mm (width × length) were obtained. This test piece was allowed to stand in a constant temperature and humidity chamber at 60 ° C. and 80% RH for 1 hour, then taken out and adjusted for 1 hour in a constant temperature and humidity chamber at 23 ° C. and 50% RH. The laminated sheet of this test piece and the gum tape are attached to the opposite side of the end where the adhesive layers are attached to each other, that is, the adhesive layers of the gum tapes are attached to each other and not attached to the gum tape (25 mm from which the gum tape was peeled off first). (× 25 mm part) The upper and lower chucks (between chucks) of the tensile tester (Autograph AGS-20IS manufactured by Shimadzu Corporation) in the above constant temperature and humidity chamber, respectively, at the end where the adhesive layer of the gum tape is bonded to the end. It was sandwiched between 15 mm distances). Then, the test force when the T-type peeling test was carried out at a load cell of 50 N and a test speed of 300 mm / min was measured, and the test force per unit width was defined as the strength of the foam layer (N / cm). If the measurement result is 1 N / cm or more, it can be said that the foam layer has an appropriate strength.

(Self-adhesiveness (adsorption))
After preparing the self-adsorptive laminated sheet, a test piece cut into a size of 125 mm × 25 mm was prepared. The adsorption surface of the test piece was attached to the smooth glass surface, crimped from the top of the test piece with a load roller of 2 kgf, and left at 23 ° C. for 1 hour in a 50% RH environment. After that, the end of the test piece was fixed to the upper chuck of Autograph (AG-IS manufactured by Shimadzu Corporation), the glass plate was fixed to the lower chuck, and a 180 degree peeling test was performed at 23 ° C and 50% RH environment. Was carried out at a speed of 300 mm / min. The test force at this time was defined as the self-adhesive force (N / cm).

(Air release)
<Evaluation device>
The evaluation of the air bleeding property was performed using the evaluation device 100 shown in FIG. The evaluation device 100 shown in FIG. 2 is a device for evaluating the air bleeding property of the laminated sheet 50 in which the foamed sheet 51 and the base material 52 are laminated, and is a sample fixing plate 10 having a through hole 11 and a sample fixing plate 10. The gas pumping mechanism 40 for pumping air as a gas at a constant pressure from the other surface side (upper side in FIG. 2) to one surface side (lower side in FIG. 2) through the through hole 11 is provided. There is.
Here, the gas pumping mechanism 40 has a syringe 20 whose tip is connected to the through hole 11 of the sample fixing plate 10 on the other surface side of the sample fixing plate 10, and a weight 30. The syringe 20 is connected to the sample fixing plate 10 with its tip facing downward in the vertical direction (lower side in FIG. 2), and the needle 21 inserted and fixed in the through hole 11 of the sample fixing plate 10 A cylindrical outer cylinder 22 whose tip (lower end in FIG. 2) is connected to the through hole 11 via a needle 21, and a piston 23 inserted into the outer cylinder 22 from the rear end side of the outer cylinder 22. It is equipped with.
The weight 30 is mounted on a flange provided at the rear end (upper end in FIG. 2) of the piston 23.
Further, in the gas pressure feeding mechanism 40 having the above-described configuration, the piston 23 is pushed into the outer cylinder 22 by the own weight of the piston 23 and the weight 30, and the air in the outer cylinder 22 is sampled through the needle 21 and the through hole 11. It is pressure-fed to one surface side (foam sheet 51) of the fixing plate 10 with a constant pressure.
Then, in the evaluation device 100 having the above-described configuration, for example, the laminated sheet 50 covers the through hole 11 on the surface of one of the sample fixing plates 10 (the side opposite to the needle 21 side) to which the needle 21 is fixed. After pasting (step (A)), the outer cylinder 22 in which the piston 23 to which the weight 30 is attached is inserted to a position where the distance from the tip is L is connected to the needle 21, and the piston 23 and the weight 30 have their own weight. By measuring the time required for the 23 to travel the distance L (step (B)), the air bleeding property of the laminated sheet 50 can be evaluated. That is, where the air in the outer cylinder 22 is pushed out from the through hole 11 by the weight of the piston 23 and the weight 30 at a constant pressure, if the distance L is constant and the amount of air extruded from the inside of the outer cylinder 22 is constant. The laminated sheet 50 having a low air bleeding property has a longer time to travel the distance L, and the laminated sheet 50 having a high air bleeding property has a shorter time to travel the distance L. Therefore, the air bleeding property of the laminated sheet 50 can be quantitatively evaluated based on the time required for the piston 23 to travel the distance L. Further, since the amount and pressure of the air to be pumped can be evaluated under certain conditions, the air bleeding property can be evaluated with high repeatability. Further, since the laminated sheet 50 can be evaluated in a state of being attached to the sample fixing plate 10, it is possible to accurately evaluate the air bleeding property of the laminated sheet 50 in a state of being attached to the adherend.
As the sample fixing plate 10, a transparent polycarbonate plate (50 mm × 50 mm) having a thickness of 1 mm is used, and as the syringe 20, a glass syringe having a capacity of 2 mL having a metal syringe needle with a diameter of 2 mm is used, and a weight 30 is used. A weight having a weight of 30 g attached to the piston 23 with double-sided tape was used.

<Evaluation of air release>
After preparing the laminated sheet, it was cut into a size of 40 mm × 40 mm and used as a sample to be evaluated.
Then, the surface of the prepared sample on the foam sheet side is placed on the surface of one of the sample fixing plates 10 to which the needle 21 is fixed (the side opposite to the needle 21 side) so as to cover the through hole 11 and no air enters. After the pasting (step (A)), the outer cylinder 22 into which the piston 23 to which the weight 30 was attached was inserted to the position where the scale became 2 mL was connected to the needle 21. After that, the hands were released from the weight 30 and the piston 23, and the time required until the piston 23 and the weight 30 were completely dropped by their own weight (that is, until 2 mL of air was pumped) was measured (step (B)). This measurement operation was repeated three times, and the average value of the measured times was calculated. The smaller the average value, the better the air bleeding property of the laminated sheet.

(Evaluation of deodorant property)
After producing the laminated sheet, it was cut into 100 mm × 100 mm × thickness, and the foam layer side thereof was attached to 120 mm × 120 mm × 1 mm soda glass to prepare a sample. The sample was placed in a sampling pack (SMART BAG PA AA-5 manufactured by GL Sciences), and the mouth was heat-sealed and sealed. The sampling pack is degassed using a vacuum pump, 3 L of gas having a predetermined concentration (hydrogen sulfide gas: 80 mass ppm or ammonia gas: 70 mass ppm) is filled in the sampling pack, and then gas is detected at a predetermined time. The gas concentration (mass ppm) in the pack was measured using a tube (gas detector tube manufactured by Gastec). The lower the gas concentration in a short time, the better the deodorant property.

(Manufacturing Example 1)
<Preparation of polymer latex>
A monomer mixture consisting of 64 parts of ethyl acrylate, 12 parts of 2-ethylhexyl acrylate, 12 parts of n-butyl acrylate, 9 parts of acrylonitrile, 2 parts of styrene and 1 part of acrylic acid in 27.0 parts of deionized water. In addition, 0.4 part of polyoxyethylene alkyl sulfate sodium (manufactured by Kao Co., Ltd .: Latemul E-118B) was mixed and stirred to obtain a monomeric emulsion.
Next, separately from the above, a glass reaction vessel equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet, and a stirrer was prepared, and 43.0 parts of deionized water and 43.0 parts of deionized water were prepared in the glass reaction vessel. 0.2 part of polyoxyethylene alkyl sodium sulfate was added, and the temperature was raised to 80 ° C. with stirring. Then, while maintaining 80 ° C., 0.3 part of ammonium persulfate dissolved in 5.7 parts of deionized water was added, and then the monomer emulsion obtained above was added over 4 hours. Was added gradually. After the addition was completed, stirring was continued for another 4 hours, and then the mixture was cooled to terminate the reaction to obtain a reaction mixture. The polymerization conversion at this time was approximately 100% (98% or more), and the obtained reaction mixture was adjusted to pH 5.0 with 5% aqueous ammonia, and 2.5 parts of polyoxyethylene lauryl ether (Kao). After adding Emargen 120), the mixture was concentrated to obtain a polymer latex having a solid content concentration of 58%.

<Preparation of TEMPO Oxidized Cellulose Nanofiber Aqueous Dispersion>
1 g of coniferous bleached kraft pulp equivalent to dry weight, 5 mmol of sodium hypochlorite, 0.1 g (1 mmol) of sodium bromide and 0.016 g (1 mmol) of TEMPO were dispersed in 100 mL of water and 4 at room temperature. The pulp was gently stirred for a period of time and washed with distilled water to obtain TEMPO-catalyzed oxidized pulp (cellulose oxide). The amount of carboxy group in the obtained TEMPO-catalyzed oxidized pulp was 1.4 mmol / g.
Then, distilled water was added to the undried TEMPO-catalyzed oxidized pulp to prepare an aqueous dispersion having a solid content concentration of 0.1%. Then, use an ultrasonic homogenizer (nissei, Ultrasonic Generator) for 2 minutes at 7.5 x 1000 rpm using a homogenizer (Microtech Nithion, Hiscotron) as the aqueous dispersion, and use ice around the container. By defibrating with V-LEVEL4 and TIP26D for 4 minutes while cooling, an aqueous dispersion containing TEMPO-carboxylated cellulose nanofibers as TEMPO-oxidized cellulose nanofibers was obtained. Then, centrifugation from the TEMPO-carboxylated cellulose nanofiber aqueous dispersion using a centrifuge (SAKUMA, M201-1VD, angle rotor 50F-8AL) (12000 G (120 x 100 rpm / g), 10 minutes, 12 ° C. ) Was removed to obtain a transparent liquid TEMPO-carboxylated cellulose nanofiber aqueous dispersion having a concentration of 0.1%. The TEMPO-carboxylated cellulose nanofibers contained sodium (first metal) derived from an copolymer in the form of a salt.
<Preparation of hydrogen-substituted TEMPO oxidized cellulose nanofiber aqueous dispersion>
The pH of 100 mL of TEMPO-carboxylated cellulose nanofiber aqueous dispersion was adjusted to 1 by adding 1 mL of 1 M hydrochloric acid under stirring. Then, stirring was continued for 60 minutes (hydrogen replacement step).
Then, the TEMPO-carboxylated cellulose nanofibers gelled by the addition of hydrochloric acid were recovered by centrifugation (12000 G), and the recovered TEMPO-carboxylated cellulose nanofibers were sequentially washed with 1 M hydrochloric acid and a large amount of distilled water (first). Cleaning process).
Next, 100 mL of distilled water was added to obtain a hydrogen-substituted TEMPO-carboxylated cellulose nanofiber aqueous dispersion having a concentration of 0.1% in which hydrogen-substituted TEMPO-carboxylated cellulose nanofibers were dispersed (first dispersion step). .. The carboxy group on the surface of hydrogen-substituted TEMPO-carboxylated cellulose nanofibers is FT-IR (FT / IR-6100, manufactured by JASCO Corporation, FT / IR-6100) according to Biomacromolecules (2011, Vol. 12, pp. 518-522). As a result of measurement, 90% or more was replaced with the carboxylic acid type.

<Preparation of copper-containing TEMPO oxidized cellulose nanofiber aqueous dispersion>
50 g of the hydrogen-substituted TEMPO-carboxylated cellulose nanofiber aqueous dispersion having a concentration of 0.1% was stirred, 18 g of an aqueous solution of copper (II) acetate having a concentration of 0.1% was added thereto, and stirring was continued at room temperature for 3 hours (). Metal replacement step). After that, the carboxylated cellulose nanofiber gelled by the addition of an aqueous solution of copper (II) acetate was centrifuged (12000 G (120 x 100 rpm / 120 rpm /) using a centrifuge (SAKUMA, M201-1VD, angle rotor 50F-8AL). g) After recovery at 12 ° C. for 10 minutes, the recovered cellulose nanofibers were washed with a copper (II) acetate aqueous solution having a concentration of 0.1%, and then the recovered cellulose nanofibers were mixed with a large amount of distilled water. Washed with (washing process).
After that, 50 mL of distilled water is added, and ultrasonic treatment (2 minutes) is performed with V-LEVEL4 and TIP26D while cooling the circumference of the container with ice using an ultrasonic homogenizer (made by nissei, Ultrasonic Generator). TEMPO carboxylated cellulose nanofibers substituted with copper were dispersed. Then, centrifuge (12000 G (120 x 100 rpm / g)) using a centrifuge (SAKUMA, M201-1VD, angle rotor 50F-8AL) from the copper-substituted TEMPO-carboxylated cellulose nanofiber aqueous dispersion. The unfibered component was removed by 12 ° C. for 10 minutes). As a result, a copper-containing TEMPO-oxidized cellulose nanofiber (hereinafter, also simply referred to as “TOCN-Cu”) aqueous dispersion having a solid content concentration of 0.1% was obtained. Then, this aqueous dispersion was concentrated using an evaporator to obtain a TOCN-Cu aqueous dispersion having a solid content concentration of 0.5%.

<Preparation of foaming composition>
200 g of the above polymer latex (solid content concentration 58%) was weighed in a 500 ml disposable cup and stirred (1750 rpm) with a mixer (ROBOMICS manufactured by Tokushu Kagaku Kogyo). To the stirred polymer latex, gradually add 234 g of the above TOCN-Cu aqueous dispersion (solid content concentration: 0.5%) (TOCN-Cu content per 100 parts by mass of the polymer: 1 part by mass) little by little. After the addition, stirring was continued for 30 minutes. Then, while stirring the obtained mixture, 8 g of ammonium stearate (Nopco DC-100A concentration 30% manufactured by Sannopco Co., Ltd.) as a foam stabilizer and fatty acid polyglycidyl ether (manufactured by Japan Coating Resin Co., Ltd.) as an epoxy-based cross-linking agent. Ricabond EX-8 concentration 100%) 6 g and sodium polyacrylate (Aron A-20L concentration 15% manufactured by Toa Synthetic Co., Ltd.) 51 g as a thickener were added to the mixture in order, and then stirred for 30 minutes for foaming. A composition for a sheet was obtained. The concentration of the active ingredient in the composition for foam sheet was 27%, the viscosity was 1600 mPa · s, and the pH was 8.9. The composition for the foam sheet was foamed 1.5 times using a whisk (hand mixer THM272 manufactured by Tescom Co., Ltd.) to obtain a foam composition (foaming liquid) having a density of 0.67 g / cm ³ .

(Manufacturing Example 2)
In Production Example 1, 117 g of the TOCN-Cu aqueous dispersion (solid content concentration 0.5%) (TOCN-Cu content with respect to 100 parts by mass of the polymer: 0.5 parts by mass), polyacrylic acid as a thickener. A composition for a foamed sheet was obtained by the same treatment as in Production Example 1 except that 6 g of sodium acid was used. The concentration of the active ingredient in the composition for foam sheet was 38%, the viscosity was 1100 mPa · s, and the pH was 9.0. The composition for a foam sheet was foamed 1.9 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.50 g / cm ³ .

(Manufacturing Example 3)
In Production Example 1, 400 g of the polymer latex (solid content concentration 58%) and 135 g of the TOCN-Cu aqueous dispersion (solid content concentration 0.5%) (TOCN-Cu content with respect to 100 parts by mass of the polymer: Production Example 1 except that 16 g of ammonium stearate as a foam stabilizer, 12 g of fatty acid polyglycidyl ether as an epoxy-based cross-linking agent, and 12 g of sodium polyacrylate as a thickener were used. The same treatment as in the above was carried out to obtain a composition for a foamed sheet. The concentration of the active ingredient in the composition for foam sheet was 44%, the viscosity was 1100 mPa · s, and the pH was 8.9. The composition for a foam sheet was foamed 1.6 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.65 g / cm ³ .

(Manufacturing Example 4)
The foamed sheet composition of Production Example 3 was foamed 2.9 times using a whisk to obtain a foaming liquid having a density of 0.35 g / cm ³ , and a foamed composition was obtained in the same manner as in Production Example 3. rice field.

(Manufacturing Example 5)
In Production Example 1, a TOCN-Cu aqueous dispersion having a solid content concentration of 0.9% was prepared, and 300 g of the polymer latex (solid content concentration 58%) and 19 g (heavy) of the TOCN-Cu aqueous dispersion were prepared. TOCN-Cu content per 100 parts by mass of coalescence: 0.1 parts by mass), 12 g of ammonium stearate as a foam stabilizer, 9 g of fatty acid polyglycidyl ether as an epoxy-based cross-linking agent, and polyacrylic acid as a thickener. A composition for a foamed sheet was obtained by the same treatment as in Production Example 1 except that 9 g of sodium was used. The concentration of the active ingredient in the composition for foam sheet was 54%, the viscosity was 4300 mPa · s, and the pH was 8.7. The composition for a foam sheet was foamed 2.0 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.49 g / cm ³ .

(Manufacturing Example 6)
In Production Example 1, 200 g of the polymer latex (solid content concentration 58%) and 23 g of the TOCN-Cu aqueous dispersion (solid content concentration 0.5%) (TOCN-Cu content with respect to 100 parts by mass of the polymer: Production Example 1 except that 8 g of ammonium stearate as a foam stabilizer, 6 g of fatty acid polyglycidyl ether as an epoxy-based cross-linking agent, and 6 g of sodium polyacrylate as a thickener were used. The same treatment as in the above was carried out to obtain a composition for a foamed sheet. The concentration of the active ingredient in the foam composition was 52%, the viscosity was 2500 mPa · s, and the pH was 8.6. The composition for a foam sheet was foamed 2.8 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.34 g / cm ³ .

(Manufacturing Example 7)
In Production Example 1, a TOCN-Cu aqueous dispersion having a solid content concentration of 0.9% was prepared, and 161 g of the TOCN-Cu aqueous dispersion (TOCN-Cu content with respect to 100 parts by mass of the polymer: 1.3). (Parts by mass), 8 g of ammonium stearate as a foam stabilizer, 6 g of fatty acid polyglycidyl ether as an epoxy-based cross-linking agent, and 6 g of sodium polyacrylate as a thickener, as in Production Example 1. The treatment was performed to obtain a composition for a foamed sheet. The concentration of the active ingredient in the foam composition was 33%, the viscosity was 1100 mPa · s, and the pH was 9.2. The composition for a foam sheet was foamed 1.8 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.55 g / cm ³ .

(Manufacturing Example 8)
In Production Example 3, the treatment was carried out in the same manner as in Production Example 3 except that the TOCN-Cu aqueous dispersion was not added (TOCN-Cu content with respect to 100 parts by mass of the polymer: 0 parts by mass) to form a foamed sheet. I got something. The concentration of the active ingredient in the foam composition was 57%, the viscosity was 5200 mPa · s, and the pH was 8.4. The composition for foamed sheet was not foamed, but was defoamed using a defoaming machine to obtain an unfoamed liquid having a density of 1.01 g / cm ³ .

(Manufacturing Example 9)
In Production Example 1, 300 g of the polymer latex (solid content concentration 58%) was prepared without adding the TOCN-Cu aqueous dispersion (TOCN-Cu content to 100 parts by mass of the polymer: 0 parts by mass). Treatment was carried out in the same manner as in Production Example 1 except that 12 g of ammonium stearate as a foaming agent, 9 g of fatty acid polyglycidyl ether as an epoxy-based cross-linking agent, and 9 g of sodium polyacrylate as a thickener were used for foaming. A composition for a sheet was obtained. The concentration of the active ingredient in the composition for foam sheet was 57%, the viscosity was 7100 mPa · s, and the pH was 8.5. The composition for a foam sheet was foamed 1.2 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.84 g / cm ³ .

(Manufacturing Example 10)
The foaming sheet composition of Production Example 8 was foamed 1.6 times using a whisk to obtain a foaming composition (foaming liquid) having a density of 0.62 g / cm ³ .

(Manufacturing Example 11)
In Production Example 2, the same treatment as in Production Example 2 was performed except that the TOCN-Cu aqueous dispersion was not added (TOCN-Cu content with respect to 100 parts by mass of the polymer: 0 parts by mass) to form a foamed sheet. I got something. The concentration of the active ingredient in the composition for foam sheet was 57%, the viscosity was 6500 mPa · s, and the pH was 8.8. The composition for a foam sheet was foamed 2.5 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.40 g / cm ³ .

(Manufacturing Example 12)
In Production Example 1, a TOCN-Cu aqueous dispersion having a solid content concentration of 0.9% was prepared, and 200 g of the polymer latex (solid content concentration 58%) and 6.2 g of the TOCN-Cu aqueous dispersion were prepared. (TOCN-Cu content per 100 parts by mass of polymer: 0.05 parts by mass), 8 g of ammonium stearate as a foam stabilizer, 6 g of fatty acid polyglycidyl ether as an epoxy-based cross-linking agent, and poly as a thickener. A composition for a foamed sheet was obtained by the same treatment as in Production Example 1 except that 6 g of sodium acrylate was used. The concentration of the active ingredient in the composition for foam sheet was 55%, the viscosity was 3900 mPa · s, and the pH was 8.6. The composition for a foam sheet was foamed 2.3 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.43 g / cm ³ .

(Manufacturing Example 13)
In Production Example 1, a TOCN-Cu aqueous dispersion having a solid content concentration of 0.9% was prepared, and 200 g of the polymer latex (solid content concentration 58%) and 1.3 g of the TOCN-Cu aqueous dispersion were prepared. (TOCN-Cu content per 100 parts by mass of polymer: 0.01 parts by mass), 8 g of ammonium stearate as a foam stabilizer, 6 g of fatty acid polyglycidyl ether as an epoxy-based cross-linking agent, and poly as a thickener. A composition for a foamed sheet was obtained by the same treatment as in Production Example 1 except that 6 g of sodium acrylate was used. The concentration of the active ingredient in the composition for foam sheet was 57%, the viscosity was 5000 mPa · s, and the pH was 8.6. The composition for a foam sheet was foamed 2.3 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.43 g / cm ³ .

(Manufacturing Example 14)
In Production Example 1, instead of the above TOCN-Cu aqueous dispersion, a sodium-containing TEMPO oxidized cellulose nanofiber (TOCN-Na) aqueous dispersion is used as the <Preparation of TEMPO Oxidized Cellulose Nanofiber Aqueous Dispersant> of Production Example 1. 24 g (TOCN-Na content per 100 parts by mass of polymer: 0.1 parts by mass) of TEMPO oxidized cellulose nanofiber aqueous dispersion (solid content concentration 0.5%) prepared in the above section, polyacrylic as a thickener. A composition for a foamed sheet was obtained by the same treatment as in Production Example 1 except that 6 g of sodium acid was used. The concentration of the active ingredient in the composition for foam sheet was 51%, the viscosity was 2600 mPa · s, and the pH was 8.8. The composition for a foam sheet was foamed 3.0 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.31 g / cm ³ .

(Manufacturing Example 15)
In Production Example 1, a TOCN-Cu aqueous dispersion having a solid content concentration of 0.9% was prepared, and 149 g of the TOCN-Cu aqueous dispersion was added (TOCN-Cu content per 100 parts by mass of the polymer: 1. Same as Production Example 1 except that 8 g of ammonium stearate as a foam stabilizer, 6 g of fatty acid polyglycidyl ether as an epoxy-based cross-linking agent, and 6 g of sodium polyacrylate as a thickener were used. To obtain a composition for a foamed sheet. The concentration of the active ingredient in the composition for foam sheet was 34%, the viscosity was 1300 mPa · s, and the pH was 9.1. The composition for a foam sheet was foamed 1.7 times using a whisk to obtain a foam composition (foaming liquid) having a density of 0.60 g / cm ³ .

(Example 1)
An automatic coating machine (main body: TQC shear AFA-Standard KT-AB4420, applicator: Cortec multi-applicator) on synthetic paper (SDI-80, thickness 80 μm) prepared in Production Example 1. It was applied using MA-250). The applied synthetic paper was placed in an oven at 80 ° C. (DNF400 manufactured by Yamato Scientific Co., Ltd.) for 80 seconds and then in an oven at 120 ° C. (DNF400 manufactured by Yamato Scientific Co., Ltd.) for 160 seconds to dry. A laminated sheet of 0.62 g / cm ³ was obtained. The strength of the foam layer of the laminated sheet, the self-adhesiveness to the glass, and the air bleeding property were evaluated. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Example 2)
An automatic coating machine (main body: TQC shear AFA-Standard KT-AB4420, applicator: Cortec multi-applicator) on synthetic paper (SDI-80, thickness 80 μm) prepared in Production Example 2. It was applied using MA-250). The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.55 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Example 3)
The effervescent liquid produced in Production Example 3 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.62 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Example 4)
The effervescent liquid produced in Production Example 4 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.44 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Example 5)
The effervescent liquid produced in Production Example 5 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.43 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Example 6)
The foaming liquid produced in Production Example 6 was applied onto a PET film (manufactured by Teijin Corporation, G2 double-sided easy-adhesive processing, thickness 50 μm) using an automatic coating machine. The applied PET film was placed in an oven at 80 ° C. for 80 seconds, then in an oven at 120 ° C. for 80 seconds, and then in an oven at 140 ° C. (DNF400 manufactured by Yamato Scientific Co., Ltd.) for 80 seconds to dry, and foamed to a foam layer thickness of 110 μm. A laminated sheet having a layer density of 0.35 g / cm ³ was obtained. The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Example 7)
The foaming liquid produced in Production Example 6 was applied onto a PET film (manufactured by Teijin Corporation, G2 double-sided easy-adhesive processing, thickness 50 μm) using an automatic coating machine. The applied PET film was placed in an oven at 80 ° C. for 80 seconds, then in an oven at 120 ° C. for 80 seconds, and then in an oven at 140 ° C. for 80 seconds to dry, and the foam layer thickness was 150 μm and the foam layer density was 0.35 g / cm. ³ laminated sheets were obtained. The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Example 8)
The foaming liquid produced in Production Example 6 was applied onto a PET film (manufactured by Teijin Corporation, G2 double-sided easy-adhesive processing, thickness 50 μm) using an automatic coating machine. The applied PET film was placed in an oven at 80 ° C. for 80 seconds, then in an oven at 120 ° C. for 80 seconds, and then in an oven at 140 ° C. for 80 seconds to dry, and the foam layer thickness was 170 μm and the foam layer density was 0.36 g / cm. ³ laminated sheets were obtained. The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Example 9)
The foaming liquid produced in Production Example 6 was applied onto a PET film (manufactured by Teijin Corporation, G2 double-sided easy-adhesive processing, thickness 50 μm) using an automatic coating machine. The applied PET film was placed in an oven at 80 ° C. for 80 seconds, then in an oven at 120 ° C. for 80 seconds, and then in an oven at 140 ° C. for 80 seconds to dry, and the foam layer thickness was 230 μm and the foam layer density was 0.37 g / cm. ³ laminated sheets were obtained. The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 1)
The effervescent liquid produced in Production Example 7 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.57 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 2)
The unfoamed liquid produced in Production Example 8 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having an unfoamed layer thickness of 120 μm and an unfoamed layer density of 1.06 g / cm ³ . .. The strength of the unfoamed layer of the laminated sheet, the self-adhesiveness to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 3)
The effervescent liquid produced in Production Example 9 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.78 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 4)
The effervescent liquid produced in Production Example 10 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.62 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 5)
The effervescent liquid produced in Production Example 11 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.43 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 6)
The effervescent liquid produced in Production Example 12 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.40 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 7)
The effervescent liquid produced in Production Example 13 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.39 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 8)
The effervescent liquid produced in Production Example 14 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.32 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

(Comparative Example 9)
The effervescent liquid produced in Production Example 15 was applied onto synthetic paper (manufactured by YUPO, SDI-80, thickness 80 μm) using an automatic coating machine. The applied synthetic paper was placed in an oven at 80 ° C. for 80 seconds and then in an oven at 120 ° C. for 160 seconds to dry, to obtain a laminated sheet having a foam layer thickness of 120 μm and a foam layer density of 0.60 g / cm ³ . The foam layer strength of the laminated sheet, the self-adhesive force to the glass, and the air bleeding property were measured. The results are shown in Table 1. In addition, the deodorant properties of the laminated sheet for hydrogen sulfide gas and ammonia gas were evaluated. The results are shown in Tables 2 and 3.

From the results of Tables 1 to 3, TOCN-Cu as a metal-containing oxidized cellulose nanofiber containing a polymer and a metal other than sodium in the form of a salt is contained, and the content of TOCN-Cu is 100 mass by mass of the polymer. In Examples 1 to 9 using the foamed sheet composition having 0.1 parts by mass or more and 1.00 parts by mass or less with respect to the portion, the self-adhesive force (adsorption) and deodorant property of the laminated body with respect to the substrate were obtained. It can be seen that can be compatible at a high level.
On the other hand, from the results of Tables 1 to 3, in Comparative Example 1 and Comparative Example 9 in which the contents of TOCN-Cu with respect to 100 parts by mass of the polymer were 1.30 parts by mass and 1.20 parts by mass, respectively, TOCN-Cu was used. It can be seen that the deodorizing property is excellent because it is contained in a large amount, but the self-adhesiveness is as low as 0.008 (N / cm) and 0.009 (N / cm), respectively.
Further, from the results of Tables 1 to 3, it can be seen that in Comparative Examples 2 to 5 in which TOCN-Cu is not used, the self-adhesiveness is excellent, but the deodorant property is poor because TOCN-Cu is not present.
Further, from the results of Tables 1 to 3, the self-adhesive force is excellent in Comparative Example 6 and Comparative Example 7 in which the contents of TOCN-Cu with respect to 100 parts by mass of the polymer are 0.05 part by mass and 0.01 part by mass, respectively. However, it can be seen that the deodorizing property is poor because the content of TOCN-Cu is low.
Furthermore, from the results in Tables 1 to 3, in Comparative Example 8 in which TOCN-Na was used as the metal-containing oxidized cellulose nanofiber, the self-adhesiveness was excellent, but the deodorizing property was not sufficient because TOCN-Cu was not used. You can see that.

According to the present invention, it is possible to provide a self-adsorptive foamed sheet having excellent deodorant property and adsorptive property, and a composition for a self-adsorptive foamed sheet capable of providing the self-adsorptive foamed sheet.
Further, according to the present invention, it is possible to provide a self-adsorptive laminate having excellent deodorant property and adsorptive property, and a method for producing the self-adsorptive laminate.

Claims (9)

It contains a polymer and metal-containing oxidized cellulose nanofibers containing a metal other than sodium in the form of a salt.
A composition for a self-adsorbing foamed sheet, wherein the content of the metal-containing cellulose oxide nanofibers is 0.1 part by mass or more and 1.00 parts by mass or less with respect to 100 parts by mass of the polymer. The self-adsorbing foamed sheet composition according to claim 1, wherein the polymer contains a (meth) acrylate monomer unit. The composition for a self-adsorptive foamed sheet according to claim 1 or 2, wherein the number average fiber diameter of the metal-containing cellulose oxide nanofibers is 100 nm or less. The composition for a self-adsorptive foamed sheet according to any one of claims 1 to 3, wherein the metal-containing oxidized cellulose nanofibers are metal-containing carboxylated cellulose nanofibers. The composition for a self-adsorptive foam sheet according to any one of claims 1 to 4, wherein the metal other than sodium is at least one selected from the group consisting of silver, zinc, and copper. A self-adsorptive foamed sheet obtained by foaming and molding the composition for a self-adsorptive foamed sheet according to any one of claims 1 to 5 into a foamed and sheet-like form. The self-adsorbing foam sheet according to claim 6, which has a density of 0.3 g / cm ³ or more. A self-adsorptive laminate comprising a base material and the self-adsorptive foam sheet according to claim 6 or 7. The step of preparing the composition for a self-adsorptive foam sheet according to any one of claims 1 to 5.
The step of foaming the composition for a self-adsorptive foam sheet to obtain a foamed composition, and
A method for producing a self-adsorptive laminate, which comprises a step of molding the foamed composition into a sheet on a substrate.

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