JP2008081595A - Ionizing radiation-curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To impart a high design property, an excellent antimicrobial property, stain resistance, scratch resistance and executability to a building interior material such as wall paper using an ionizing radiation-curable resin composition as a surface-protecting layer by reducing discoloration of the ionizing radiation-curable resin composition imparted by a silver-based antimicrobial agent, imparting excellent stability and an antimicrobial property to the resin composition and further devising the resin composition so that Vickers hardness of a layer obtained by carrying out crosslinking and curing of the composition becomes a specific range. <P>SOLUTION: The ionizing radiation-curable resin composition comprises at least an ionizing radiation-curable resin and a silver-based antimicrobial agent in which at least silver ion is supported on an inorganic compound. In the ionizing radiation-curable resin composition, Vickers hardness of a layer obtained by carrying out crosslinking and curing of the composition is 0.45-1.3 and the amount of the supported silver ion is 0.1-30 mass%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ionizing radiation curable resin composition.

  Building interior materials such as wallpaper are required to be flame retardant from the standpoint of fire safety, and are often required to have a certain level of flame resistance by the Building Standards Act. In addition, architectural interior materials are required to have high designability in order to enhance comfort as an indoor living space. In particular, in order to have a three-dimensional design, a material that can be highly foamed as well as flexible. Is advantageous. As a material that meets these requirements, a material in which a pattern layer is provided on a vinyl chloride resin layer by printing, or a material in which an uneven pattern is formed by foaming and embossing the vinyl chloride resin layer is widely used. It has been. However, these wall papers have a problem that the stain resistance and the surface strength are not sufficient. This is because the wallpaper is made of a vinyl chloride resin having a problem of contamination and the like, and for the purpose of improving workability and design, it is applied to the surface of the wallpaper by forming a foam or a concavo-convex pattern. This is because fine irregularities and voids are generated.

  In order to solve the above problems, a surface protective layer is provided on the surface of the wallpaper to improve surface properties such as stain resistance. For example, urethane or acrylic resin is applied to the surface of the wallpaper to protect the surface. Layered methods are taken. However, the surface protective layer thus provided does not follow the foam or concavo-convex pattern when processed to form foam or concavo-convex pattern, resulting in uneven thickness of the surface protective layer, and the surface protective layer partially Cracks (cracks) occur in the film, causing problems in production stability such that the foam layer is exposed.

  A film having a foamed resin layer made of a thermoplastic resin containing a foaming agent and having excellent antifouling properties on the surface of the wallpaper, such as an acrylic resin film, a polyurethane resin film, a fluorine resin film, an ethylene-vinyl alcohol copolymer A method has been proposed in which a film or the like is bonded with an adhesive or the like to form a surface protective layer (for example, Patent Documents 1 and 2). However, only using these films as a surface protective layer has a problem of insufficient design and stain resistance. From the viewpoint of contamination resistance, it is desirable to use an ionizing radiation curable resin composition for the protective surface layer. However, conventional ionizing radiation curable resin compositions improve surface properties such as contamination resistance. There is also a problem that it is difficult to follow the process of forming foaming or uneven patterns.

  By the way, antibacterial property is mentioned as the performance required for wallpaper. Antibacterial properties were generally not required for high-design wallpaper that has been processed with foam or uneven patterns used for homes, etc., but wallpaper with high designability has been diversified. In addition, antibacterial properties are required. Conventionally, for wallpaper that does not process foam or uneven patterns, antibacterial particles are dispersed in a binder containing an isocyanate compound component on a vinyl chloride layer, a printed layer, etc. on the base material as having antibacterial properties An antibacterial wall covering material in which an antibacterial coating layer is laminated has been proposed (for example, Patent Document 3). However, the stain resistance is not sufficient, and the walls and ceilings of hospitals, food factories, etc. are assumed as application destinations. There was a problem of lack of sex.

JP 2001-260287 A JP 2001-260261 A Japanese Patent Laid-Open No. 8-113899

  Under such circumstances, the present invention reduces the discoloration of the ionizing radiation curable resin composition exerted by the silver-based antibacterial agent and imparts excellent stability and antibacterial properties to the ionizing radiation curable resin composition. Furthermore, by devising an ionizing radiation curable resin material so that the Vickers hardness of the layer formed by crosslinking and curing the ionizing radiation curable resin composition is in a specific range, wallpaper using this as a surface protective layer, etc. The purpose is to impart high designability and excellent antibacterial properties, contamination resistance, scratch resistance and workability to the interior materials of the building.

  As a result of intensive studies to achieve the above object, the present inventors have reduced discoloration of the ionizing radiation curable resin composition exerted by the silver-based antibacterial agent, and are excellent in the ionizing radiation curable resin composition. By devising the ionizing radiation curable resin material so as to give stability and antibacterial properties, and further to make the Vickers hardness of the layer formed by crosslinking and curing the ionizing radiation curable resin composition within a specific range, High designability, excellent antibacterial properties, stain resistance, scratch resistance and workability could be imparted to architectural interior materials such as wallpaper used as the surface protective layer.

That is, the present invention
(1) An ionizing radiation curable resin composition containing at least an ionizing radiation curable resin and a silver antibacterial agent having at least silver ions supported on an inorganic compound, wherein the ionizing radiation curable resin composition is crosslinked. An ionizing radiation curable resin composition characterized in that the cured layer has a Vickers hardness of 0.45 to 1.3 and a supported amount of the silver ions of 0.1 to 30% by mass of the inorganic compound. object,
(2) The ionizing radiation curable resin composition according to (1), further containing microsilica,
(3) The ionizing radiation curable resin composition according to (1) or (2), wherein the content of the antibacterial agent is 0.01 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. ,
(4) The ionizing radiation curable composition according to any one of (1) to (3), wherein the content of the microsilica is 0.1 to 5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. Resin composition,
(5) The ionizing radiation-curable resin composition according to any one of (1) to (4), wherein the inorganic compound is at least one selected from zeolite, hydroxide apatite, and zirconium phosphate, and (6 ) Foamed wallpaper using the ionizing radiation curable resin composition according to any one of (1) to (5) above,
Is to provide.

  According to the present invention, the discoloration of the ionizing radiation curable resin composition exerted by the silver-based antibacterial agent is reduced, and the ionizing radiation curable resin composition is provided with excellent stability and antibacterial properties. By devising the ionizing radiation curable resin material so that the Vickers hardness of the layer formed by crosslinking and curing the curable resin composition is in a specific range, it is used as a building interior material such as a wallpaper using this as a surface protective layer. High designability and excellent antibacterial properties, stain resistance, scratch resistance and workability can be imparted.

  The ionizing radiation curable resin composition of the present invention has an energy quantum capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, crosslinked and cured by irradiation with ultraviolet rays or electron beams. An ionizing radiation curable resin and a silver-based antibacterial agent are essential components, and the composition is composed of these essential components and other desired components. For the formation of a surface protective layer for building interior materials such as wallpaper. It is preferably used.

[Ionizing radiation curable resin composition: ionizing radiation curable resin]
As the ionizing radiation curable resin used in the ionizing radiation curable resin composition of the present invention, a resin having a Vickers hardness of 0.45 to 1.3 obtained by crosslinking and curing it is appropriately selected. Can be used. When a layer obtained by crosslinking and curing the ionizing radiation curable resin composition is used as a surface protective layer of an architectural interior material such as the above-mentioned wallpaper, for example, the Vickers hardness is an important factor as a surface physical property. Here, the Vickers hardness means a value measured at a load of 20 mN / 20 s and a load time of 5 s using a Vickers hardness meter (Fischer Scope H100VP-HCU, manufactured by Fisher Instruments Co., Ltd.). Further, from the viewpoint of unevenness followability and crack resistance in embossing, it is preferable to use at least one selected from polymerizable monomers, oligomers and prepolymers conventionally used as ionizing radiation curable resins.

As the polymerizable monomer, a (meth) acrylate-based monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”.
The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( (Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Examples include ethylene oxide-modified bisphenol A diacrylate. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  Next, the polymerizable oligomer is preferably an oligomer having a radically polymerizable unsaturated group in the molecule, particularly an acrylate oligomer having a radically polymerizable unsaturated group, such as an epoxy (meth) acrylate or urethane (meth) acrylate. Type, polyester (meth) acrylate type, polyether (meth) acrylate type, and the like. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying, with (meth) acrylic acid, a polyurethane oligomer obtained by a reaction between polyether polyol or polyester polyol and polyisocyanate. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acids and polyhydric alcohols with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

When an ultraviolet curable resin composition is used as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin composition. . The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 - 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -Tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, etc. It is done.
Examples of the polymerizable oligomer having a cationic polymerizable functional group in the molecule include aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

It is preferable to further add silicone (meth) acrylate to the ionizing radiation curable resin composition of the present invention. Silicone (meth) acrylate mainly imparts stain resistance to wallpaper due to a synergistic effect with the ionizing radiation curable resin. Silicone (meth) acrylate is one of silicone oils made of polysiloxane or modified silicone oil in which (meth) acrylic groups are introduced at one or both ends. As the silicone (meth) acrylate, conventionally known ones can be used, and the organic group is not particularly limited as long as the organic group is a (meth) acryl group, and a modified silicone oil having one or two organic groups is preferable. The structure of the modified silicone oil is roughly divided into a side chain type, a both-end type, a single-end type, and a side-chain both-end type depending on the bonding position of the organic group to be substituted. There is no particular limitation.
The addition amount of the silicone (meth) acrylate is preferably 1 to 4 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition, from the viewpoint of sufficiently improving the stain resistance and obtaining the use effect. 2 parts by mass is more preferable. Moreover, as a functional group equivalent (molecular weight / functional group number) of silicone (meth) acrylate, what has the conditions of 1000-20000 is mentioned, for example.

As the ionizing radiation curable resin composition of the present invention, it is preferable to use an electron beam curable resin composition, among which at least one selected from acrylate monomers, oligomers and prepolymers having radically polymerizable unsaturated groups. Preferably there is. This is because the electron beam curable resin composition can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator and can provide stable curing characteristics.
From the viewpoint of the effects of the present invention, it is preferable to use a urethane acrylate oligomer having a radical polymerizable unsaturated group in combination of two types having different numbers of functional groups. Here, when two different types of functional groups are M and N, M and N satisfy M <N. The mass ratio of the urethane acrylate oligomer having M functional groups and the urethane acrylate oligomer having N functional groups is preferably 6/4 to 0.5 / 9.5, and more preferably 5/5 to 1/9. The number of functional groups M and N is preferably in the range of 2 to 4 and satisfies M <N. Therefore, such combinations of the number of functional groups M and N are 2, 3, 2, 4 and 3 and 4. is there.

[Ionizing radiation curable resin composition: Silver antibacterial agent]
The antibacterial agent contained in the ionizing radiation curable resin composition of the present invention is a silver antibacterial agent.
In the silver-based antibacterial agent, the carrier is an inorganic compound, and the carrier carries at least silver ions in combination with silver ions or silver ions in addition to copper ions and zinc ions. Any inorganic compound can be used. For example, inorganic ions such as activated carbon, activated alumina, silica gel, etc., zeolite, hydroxide apatite, zirconium phosphate, calcium phosphate, titanium phosphate, potassium titanate, hydrous bismuth, hydrous zirconium oxide, hydrotalcide, etc. An exchanger etc. are mentioned. These inorganic compounds can be used alone or in combination of two or more.
Among the above inorganic compounds, the inorganic ion exchanger is preferable because it can firmly support silver ions, and at least one selected from zeolite, hydroxide apatite, and zirconium phosphate can be suitably used, and zirconium phosphate alone More preferably it is used. In addition, a silver antibacterial agent having silver ions supported on a three-dimensional network structure of zirconium phosphate is particularly preferable in terms of discoloration and elution of silver components. The particle shape of the silver-based antibacterial agent includes a sphere, an ellipsoid, a polyhedron, a scale shape, and the like, and is not particularly limited. However, a spherical shape is preferable, and an average particle size is preferably 0.1 to 3.0 μm, 0 More preferably, the thickness is 5 to 2.5 μm. If it is within this range, sufficient antibacterial properties and ink stability can be obtained, and the anti-contamination property is not lowered by the protrusion of the silver antibacterial agent particles, and the abrasion of the coating roll or doctor does not occur. . The supported amount of silver ions is required to be 0.1 to 30% by mass of the inorganic compound as the carrier, and preferably 0.1 to 20% by mass. Within this range, sufficient antibacterial properties can be obtained, and the problem that the surface protective layer is discolored due to the release of silver ions from the carrier does not occur. Further, the content of the silver antibacterial agent is 100 masses of ionizing radiation curable resin from the viewpoint of obtaining sufficient antibacterial properties, surface properties such as ink stability, stain resistance, unevenness followability by embossing, and design properties. 0.01-10 mass parts is preferable with respect to part, and 0.5-3.5 mass parts is more preferable.

As a method for supporting silver ions on these inorganic compounds, a known supporting method can be appropriately employed. For example, a method of supporting by physical adsorption or chemical adsorption, a method of supporting by an ion exchange reaction, a method of supporting by a binder, a method of supporting by injecting a silver compound into an inorganic compound, thin film formation such as vapor deposition, dissolution precipitation reaction, sputtering, etc. The method of carrying | supporting by forming the thin layer of a silver compound on the surface of an inorganic compound by a method etc. is mentioned.
Silver antibacterial agents include, for example, “Novalon AG-300” (manufactured by Toa Gosei Chemical Co., Ltd., silver ion-carrying zirconium phosphate), “antibacterial ceramics” (manufactured by Shinto V Serax Co., Ltd., silver ion-carrying apatite), “Zeomic” Commercial products such as “AJ-10D” (manufactured by Sinanen New Ceramic, silver ion-supported zeolite) can also be used.

[Ionizing radiation curable resin composition: Microsilica]
For the purpose of improving the dispersion and sedimentation stability of the silver antibacterial agent contained in the ionizing radiation curable resin composition of the present invention, ionizing radiation curing is performed for the purpose of improving the leveling property of the coating film of the surface protective layer 6 to be obtained. The conductive resin composition preferably further contains microsilica. The particle shape of the microsilica includes a sphere, an ellipsoid, a polyhedron, a scale shape and the like, and is not particularly limited, but a spherical shape is preferable. The average particle size of the microsilica is preferably 3 μm or less, and more preferably 2 μm or less. The lower limit of the average particle size is not particularly limited, but is 0.03 μm for manufacturing reasons. The content of microsilica is 0.1 with respect to 100 parts by mass of the ionizing radiation curable resin from the viewpoint of improving the stability of the silver antibacterial agent in the ionizing radiation curable resin composition and making the coating property appropriate. -5.0 mass parts, More preferably, it is 0.5-3.0 mass parts.

[Ionizing radiation curable resin composition: other additives]
Moreover, various additives can be mix | blended with the ionizing radiation-curable resin composition of this invention according to the desired physical property of the surface protective layer obtained. Examples of the additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a coupling agent, a plasticizer, and an antifoaming agent. Agents, fillers, solvents, colorants and the like.
Here, as the weather resistance improving agent, an ultraviolet absorber or a light stabilizer can be used. The ultraviolet absorber may be either inorganic or organic. As the inorganic ultraviolet absorber, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle size of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, benzotriazole type, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-) is specifically mentioned. Amylphenyl) benzotriazole, 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of polyethylene glycol, and the like. On the other hand, examples of the light stabilizer include hindered amines, specifically 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1,2,2). , 6,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate and the like. In addition, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

Examples of the wear resistance improver include, for inorganic substances, spherical particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable. Organic materials include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is usually about 10 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles.
Examples of the polymerization inhibitor include hydroquinone, p-benzoquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol and the like, and examples of the crosslinking agent include a polyisocyanate compound, an epoxy compound, a metal chelate compound, an aziridine compound, and an oxazoline compound. Used.
As the filler, for example, barium sulfate, talc, clay, calcium carbonate, aluminum hydroxide and the like are used.
Examples of the colorant include known coloring pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue, phthalocyanine green, titanium oxide, and carbon black.
As the infrared absorber, for example, a dithiol metal complex, a phthalocyanine compound, a diimmonium compound, or the like is used.

[Foam wallpaper]
The ionizing radiation curable resin composition of the present invention is preferably used as a surface protective layer for foamed wallpaper. A typical structure of a foam wallpaper using the ionizing radiation curable resin composition of the present invention will be described with reference to FIG. FIG. 1 is a schematic view showing a cross section of a foamed wallpaper 1 of the present invention. In the example shown in FIG. 1, the foamed wallpaper 1 of the present invention includes a foamed resin layer 3, a non-foamed resin layer 4 provided as necessary, a pattern layer 5, and an ionizing radiation curable resin of the present invention. A surface protective layer 6 formed by crosslinking and curing the composition is sequentially laminated.

[Foaming wallpaper: Base material 2]
Hereinafter, it demonstrates in detail based on FIG. 1 which showed one of the preferable embodiment of the foam wallpaper of this invention.
The base material 2 according to the present invention is not particularly limited as long as it is usually used as wallpaper. For example, a backing paper, a flame retardant paper, a synthetic resin sheet, a woven fabric, a nonwoven fabric, a knitted fabric and the like are appropriately used depending on the application. You can choose. Each of these materials may be used alone, but may be a laminate of any combination such as a composite of paper. In addition, a flame retardant, an inorganic agent, a dry paper strength enhancer, a wet paper strength enhancer, a colorant, a sizing agent, a fixing agent, and the like may be appropriately added as necessary. Above all, for regular wallpaper such as pulp-based flame retardant paper impregnated with water-soluble flame retardant such as guanazine sulfanilate and guanazine phosphate, inorganic paper mixed with inorganic agent such as calcium carbonate, aluminum hydroxide, magnesium hydroxide, etc. It is said to be a backing paper, and from the viewpoint of curling prevention, the underwater elongation is preferably 1% or less. Incidentally, the elongation in water is determined by the JAPAN TAPPI paper pulp test method No. It is a value measured according to 27: 2000.
Although there is no restriction | limiting in particular about the thickness of the base material 2, Basic weight is about 50-300 g / m < ² > normally, Preferably it is the range of 60-160 g / m < ² >.

[Foamed wallpaper: foamed resin layer 3]
The foamed resin layer 3 shown in FIG. 1 is provided to give a wallpaper a three-dimensional design feeling and flame retardancy. The foamed resin composition that forms the foamed resin layer 3 is preferably composed of a resin, a foaming agent, and an inorganic filler.
The resin constituting the foamed resin layer 3 is preferably a thermoplastic resin, and examples of the thermoplastic resin include polyvinyl chloride resins, polyethylene resins, polypropylene resins, polybutene resins, and other polyolefin resins, and ethylene-vinyl acetate copolymers. Resin, polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-styrene copolymer resin, nylon, polyacetal resin, acrylic resin, polycarbonate resin, polyester resin, poly Examples thereof include thermoplastic resin simple substances and copolymers such as vinyl acetate resin, polyvinyl alcohol resin, and polyurethane resin, or a mixed resin thereof. Among them, polyvinyl chloride resin is preferable because it has film formability, flexibility, processability at low temperature, and can be used as a relatively low cost wallpaper, and from the viewpoint of environmental protection, polyolefin resin, ethylene -Vinyl acetate copolymer resin is preferred.

The foamed resin layer 3 is formed by a method such as a comma coater method, an extrusion film forming method, a calender film forming method, or the like, which is obtained by emulsifying a foamed resin composition into an emulsion composition or pelletized. can do. Here, the emulsification can be carried out by a usual method. For example, the emulsion composition is obtained by emulsifying the thermoplastic resin in the foamed resin composition by an emulsion polymerization method or the like, and then a foaming agent or an inorganic filler described later. Can be obtained by adding a predetermined amount.
Further, the thickness of the foamed resin layer 3 is preferably 50 to 300 μm in the film-formed state, and the thickness after foaming is preferably 500 to 1200 μm.

[Foaming wallpaper: Foamed resin layer 3 Foaming agent]
Examples of the foaming agent used in the foamed resin layer 3 include inorganic foaming agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, and ammonium nitrite, N, N′-dimethyl-N, N′-dinitrosotephthalamide Nitroso compounds such as N, N′-dinitrosopentamethylenetetramine, azodicarbonamide, azobisformamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate and other azo compounds, Sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3'-disulfonyl hydrazide, calcium azide, 4,4'-diph Sulfonyl di azide, azide compounds such as p- toluenesulfonyl azide and the like. Low cost, low heat of decomposition, excellent flame retardancy and self-extinguishing properties, stable in water, non-toxic, and capable of processing heat decomposition chemical foaming agent below decomposition temperature Therefore, a thermally decomposable foaming agent of an azo compound such as azodicarbonamide or azobisformamide is preferable.

  The addition amount of the foaming agent may be appropriately determined depending on the required design properties, but is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic resin of the foamed resin layer 3. If necessary, a foaming aid that promotes the decomposition of the foaming agent can be used in combination in order to improve the foaming effect. For example, when azodicarbonamide is used as the foaming agent, zinc oxide, lead sulfate, urea, zinc stearate, or the like is used as the foaming aid.

[Foamed wallpaper: foamed resin layer 3 inorganic filler]
There is no restriction | limiting in particular as the inorganic filler used for the foamed resin layer 3 concerning this invention, A various thing can be used.
Examples of inorganic fillers include calcium carbonate, magnesium carbonate, fly ash, dehydrated sludge, natural silica, synthetic silica, kaolin, clay, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, barium sulfate, calcium hydroxide, and water. Aluminum oxide, alumina, magnesium hydroxide, talc, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite , Aluminum borate, silica balloon, glass flake, glass balloon, silica, iron slag, copper, iron, iron oxide, carbon black, sendust, alnico magnet, magnetic powder such as various ferrites, cement Glass powder, diatomaceous earth, antimony trioxide, magnesium oxysulfate, hydrated aluminum, hydrated gypsum, alum, and the like. Among these, aluminum hydroxide is preferable because it has a low decomposition temperature, a large endothermic amount, and low cost. In addition, although these inorganic fillers may be used independently, 2 or more types may be used together.

  These inorganic fillers have the effect of imparting flame retardancy to the foamed wallpaper of the present invention, and the effect is further increased when incorporated in a large amount. In order to sufficiently obtain the flame retardancy of the wallpaper, it is preferable to add 100 parts by mass or more of an inorganic additive to 100 parts by mass of the thermoplastic resin of the foamed resin layer 3. 5-25 micrometers is preferable and, as for the average particle diameter of an inorganic filler, 5-15 micrometers is more preferable.

  These inorganic fillers may be blended as they are, but the inorganic fillers are previously silane-based, titanate-based, aluminate-based, zircoaluminum-based coupling agents, phosphoric acid-based, fatty acid-based surfactants, etc. , Oils and fats, waxes, stearic acid, silane coupling agents and the like.

  Moreover, the foamed resin layer 3 can mix | blend various additives according to the physical property requested | required. Examples of the additive include a fungicide, an insecticide, an antiseptic, an antibacterial agent, a diluent, a deodorant, a light stabilizer, a plasticizer, and the like.

[Foamed wallpaper: non-foamed resin layer 4]
The non-foamed resin layer 4 shown in FIG. 1 improves the scratch resistance, wear resistance, etc. of the resulting foamed wallpaper by using a tough resin that cannot be used for the foamed resin layer from the viewpoint of inhibiting foaming. In addition, it is provided for the purpose of suppressing the penetration of the ink composition used in the pattern layer 5 described later into the substrate 2. Since especially an effect is exhibited when the base material 2 is permeable base materials, such as paper and a nonwoven fabric, providing is preferable.
The non-foamed resin layer 4 is preferably a uniform and uniform layer obtained by crosslinking and curing a curable resin having adhesiveness with the resin constituting the ink composition used for the pattern layer 5, as shown in FIG. It is preferable to provide between the layer 5 and the foamed resin layer 3. By having the non-foamed resin layer 4, the surface of the pattern layer 5 laminated on the base material 2 is smoothed, and the adhesion between the base material 2 and the pattern layer 5 can be enhanced.

Although there is no restriction | limiting in particular as resin which comprises the non-foaming resin layer 4, It is preferable to use the tough resin which could not be used for a foaming resin layer from a viewpoint of foaming inhibition as mentioned above. For example, polyolefin resins such as polyethylene resins, polypropylene resins, polybutene resins, acrylic resins, methacryl resins, thermoplastic polyester resins, polyvinyl alcohol resins, fluorine resins, and other thermoplastic resins alone and various And more specifically, an ethylene-acrylic acid copolymer resin, an ethylene-methacrylic acid copolymer resin, an ethylene-ethyl acrylate copolymer resin, an ethylene-methacrylic resin. Examples thereof include an acid methyl copolymer resin, an ethylene-methyl acrylate copolymer resin, and an ethylene-vinyl alcohol copolymer resin. Among these, ethylene-methacrylic acid copolymer resins and ethylene-vinyl alcohol copolymer resins can be particularly preferably used from the viewpoint of film forming characteristics.
The non-foamed resin layer 4 can be formed by a method such as a comma coater method, an extrusion film forming method, or a calender film forming method. 5-20 micrometers is preferable and, as for the thickness of the non-foaming resin layer 4, 10-15 micrometers is more preferable.

[Foaming wallpaper: picture layer 5]
The pattern layer 5 shown in FIG. 1 gives decorativeness to the base material 2, and is formed by printing various patterns using an ink composition and a printing machine. In general, it can be formed with ink by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, or the like. As patterns, there are stone patterns imitating the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns imitating cloth or cloth patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done.

As the ink composition used for forming the pattern layer 5, a binder and a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed. The binder is not particularly limited. For example, polyurethane resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated polyethylene resin, Any one of chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc. may be used alone or in combination A mixture of seeds or more is used. Among these, from the viewpoint of the effect of the present invention, a polyurethane resin, a vinyl acetate resin, an acrylic resin, a polyester resin, a cellulose resin, a polyamide resin or the like is used alone or in combination of two or more. Is preferred.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metallic pigments composed of scaly foil pieces such as aluminum and brass, pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.
The pattern layer 5 preferably has a thickness of about 1 to 20 μm.

[Foaming wallpaper: surface protective layer 6]
The surface protective layer 6 according to the present invention has a Vickers hardness of 0.45 to 1.3 and is obtained by crosslinking and curing the ionizing radiation curable resin composition, and the ionizing radiation curable resin composition is at least an inorganic compound. It contains a silver-based antibacterial agent carrying silver ions, and is laminated on the upper surface of the pattern layer 5 to impart antibacterial properties to the foamed wallpaper of the present invention, stain resistance, scratch resistance, etc. It is provided for the purpose of improving the surface physical properties.

[Foaming wallpaper: surface protection layer 6 coating method]
In the formation of the surface protective layer 6 of the present invention, first, an ionizing radiation curable resin such as a polymerizable monomer or a polymerizable oligomer, a silver-based antibacterial agent, and if necessary, microsilica and various additives are respectively added at a predetermined ratio. To prepare an ionizing radiation curable resin composition. The viscosity of the ionizing radiation curable resin composition is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the base material by a coating method described later. It may be added.
Gravure coating, bar coating, roll coating, reverse roll coating, comma so that the ionizing radiation curable resin composition thus prepared on the surface of the substrate has a thickness after curing of 1 to 20 μm. It coats by well-known systems, such as a coat, preferably a gravure coat, and forms an uncured resin layer. When the thickness after curing is 1 μm or more, a cured resin layer having a desired function is obtained. The thickness of the layer after curing is preferably about 2 to 20 μm.

Next, the uncured resin layer is cured by irradiating the uncured resin layer with ionizing radiation such as an electron beam or ultraviolet rays. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excess electron beam.
The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. Can be used.
When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp etc. are used.
The surface protective layer thus formed has various functions by adding various additives, for example, a so-called hard coat function, anti-fogging coat function, and anti-fouling coat having high hardness and scratch resistance. A function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can also be imparted.

[Primer layer 7]
For the purpose of improving the adhesion between the ionizing radiation curable resin composition used for the surface resin layer 6 and the pattern layer 5, a primer layer 7 may be provided between these layers as necessary. As the resin preferably used here, for example, a resin having good adhesion between the pattern binder layer such as acrylic resin, urethane resin, urethane-acrylic resin and the ionizing radiation curable resin composition can be used.

[Foaming wallpaper: uneven pattern 8]
The foamed wallpaper of the present invention is preferably provided with a concavo-convex pattern by embossing in order to make the wallpaper excellent in design. The concavo-convex pattern 8 shown in FIG. 1 is heated and pressed with an embossed plate from the upper surface of the surface protective layer 6, that is, the outermost layer side, when the wallpaper in the manufacturing process is at a temperature that can be embossed by any means. Can be formed. The deepest part of the unevenness formed by heating and pressurizing with the embossed plate reaches the upper surface of the foamed resin layer 3. A well-known sheet or rotary embossing machine is used to form the concavo-convex pattern 8, and the concavo-convex pattern 8 has the following shapes: wood grain conduit groove, stone plate surface unevenness, cloth surface texture, satin texture, sand texture, hairline , There are many strips. The embossing may be mechanical embossing by heating and pressurization with the above-mentioned embossing plate, for example, foaming as described in Japanese Patent Publication No. 43-28636 and Japanese Patent Publication No. 47-2918. An uneven shape in which a pattern layer is provided on a base material impregnated with an agent, and a foaming inhibitor is printed in synchronization with the pattern of the pattern layer, and then foamed by heating to synchronize with the pattern of the pattern layer. Chemical embossing may be used.

[Foamed wallpaper: manufacturing method]
The foamed wallpaper of the present invention is manufactured, for example, by the following manufacturing method, but is not limited thereto.
A foamed resin layer 3 is formed by coating an emulsion composition of a foamed resin composition made of a thermoplastic resin containing a foaming agent, an inorganic filler, and other additives as necessary on the substrate 2 by a comma coater method. Furthermore, the resin composition which forms the non-foamed resin layer 4 provided as needed is coated by the comma coater method, and the ink composition which forms the pattern layer 5 on it is applied by gravure printing. Next, the resin composition for forming the primer layer 7 provided if necessary is applied by gravure printing, and then ionizing radiation curable with a silver-based antibacterial agent and, if necessary, microsilica and various additives added. The surface protection layer 6 is formed by coating the resin composition and irradiating an electron beam to crosslink and cure the ionizing radiation curable resin composition. The sheet thus obtained was foamed with the foamed resin composition at about 230 ° C. using a heating foaming furnace to form the foamed resin layer 3, cooled, and then reheated to about 150 ° C. From the surface protective layer side, the foamed resin layer 3 is formed from the outermost layer side of the surface protective layer 6 by forming a concavo-convex pattern by passing between a cooling roll on which an embossed plate is formed and a pressure roll. Thus, the foamed wallpaper of the present invention having a concavo-convex pattern can be obtained. As described above, the non-foamed resin layer and the primer layer can be provided between desired layers as necessary.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation methods)
The ionizing radiation curable resin composition of each Example and the foamed wallpaper produced using the ionizing radiation curable resin composition were evaluated by the following methods.
(1) Evaluation of discoloration of ionizing radiation curable resin composition About 25 ml of the ionizing radiation curable resin composition used in Examples and Comparative Examples is poured into a glass sample bottle having a capacity of 30 ml, and a plastic screw is used. Sealed with a type lid and left at room temperature under an illuminance of 300 lux. The change in color of the ionizing radiation curable resin composition in the sample bottle before and 48 hours after standing was visually confirmed. Evaluation was made based on the following criteria.
○ No change at all △ Although there was a slight discoloration to brown, there was no problem in design at the time of coating, and there was no problem in practical use. × Significant discoloration occurred, and the design feeling was impaired (2) Stability of coating solution (Evaluation of sedimentation of silver antibacterial agents)
The ionizing radiation curable resin composition (coating liquid) used in Examples and Comparative Examples was allowed to stand on a pan, and the state of the coating liquid was visually evaluated after 24 hours. Judgment criteria were evaluated as follows.
○ No change △ Antibacterial agent slightly settled on the bottom of bread, but no problem in practical use × Antibacterial agent significantly settled on bottom of bread (3) Evaluation of antibacterial properties Foam obtained in Examples and Comparative Examples After the wallpaper was treated with hot water (95 ° C., 30 minutes), 1 ml of a bacterial solution of Staphylococcus aureus and Escherichia coli was dropped and cultured at 37 ° C. for 24 hours. Thereafter, the bacteria were washed out with a sterilized phosphate buffer. The number of viable bacteria in the washed buffer solution was measured by a pour plate method using a medium for measuring the number of bacteria. The culture conditions were 37 ° C. and 24 hours. As a control, a test using only the bacterial solution was performed at the same time. The greater the number of viable bacteria, the worse the antibacterial properties.
(4) Evaluation of stain resistance In accordance with JIS K-6902, water pen (black), water pen (red), red crayon, lipstick, whiteboard marker, oily magic as pollutants, each example and comparison It was made to adhere to the foam wallpaper obtained in the example, and after 24 hours, it was wiped dry with a soft cloth (gauze), and the remaining concrete residue was visually evaluated. Judgment criteria were evaluated as follows.
○ Pollutants can be completely wiped out △ Contaminants remain slightly, but they are minor and have no practical problems × Contaminant remains remarkably (5) Workability Wallpaper obtained in each example and comparative example A test piece (90 cm × 150 cm) is taken from After applying the adhesive to the backside of the collected test piece with a gluing machine at an application amount of 50 to 300 g / m2, and leaving it for 180 minutes in a combined state so that air does not touch the surface where the adhesive is applied The test piece was laminated on the gypsum board, and the whole was crimped with a brush, and the joint was crimped with a roller. The state of the surface of the test piece was visually evaluated according to the following evaluation criteria.
○ The surface is not damaged △ The surface is slightly scratched, but there is no problem as a product × The surface is markedly damaged and the product is defective (6) Scratch resistance Surface enhanced product performance indication by the Japan Vinyl Industry (1997) The scratch resistance was evaluated in accordance with the method described on January 1, 1980.
Five pieces of test pieces (25 mm × 250 mm) are collected from a standard location from the inside 10 cm from each end of the wallpaper obtained in each example and comparative example. The collected test piece is left for 24 hours or more under the conditions of a temperature of 15 to 30 ° C. and a relative humidity of 65 ± 20%, and using a friction tester II (load 200 g) defined in JIS L 0823, the transition distance is 120 mm. The gap was moved 5 times with 30 reciprocations per minute, and the degree of damage was visually evaluated according to the following evaluation criteria.
○ Grade 5 (no change)
△ Grade 4 (Slight changes on the surface)
× 3rd grade (The surface is broken and the vinyl layer is visible)
(7) Evaluation of concavo-convex pattern (embossing formability) Evaluation of the concavo-convex pattern of the wallpaper obtained in each Example and the comparative example was performed visually. Judgment criteria were evaluated as follows.
○ Uneven pattern is sharp and has excellent design properties. △ Uneven pattern is not found in the uneven pattern, but there is no problem. × Uneven unevenness in the uneven pattern. (8) Evaluation of occurrence of cracks Obtained in each example and comparative example The evaluation of the occurrence of cracks in the wallpaper was performed visually. Judgment criteria were evaluated as follows.
○ Cracks do not occur △ Some cracks occur, but there is no practical problem. × Cracks remarkably occur.

Example 1
As the substrate 2, rice wallpaper backing paper weighing 65 g / m ² (Nippon Paper Industries Co., NI-65A) using, to prepare a foamed resin composition in the following composition on the substrate, wherein A composition is formed into a film by an extrusion method to form a foamed resin layer, and further a gravure with an application amount of 3.0 g / m ² using an ink composition with an acrylic resin as a binder and an inorganic pigment as a colorant. The pattern layer 5 was formed by printing.
A primer layer 7 is formed on the pattern layer 5 by gravure printing with a coating amount of 2.0 g / m ² on a urethane-acrylic copolymer resin, and an ionizing radiation curable resin composition having the following composition is applied thereon. Coating was carried out by a gravure direct coater method at an amount of 2.0 g / m ² . After coating, the surface protective layer 6 was formed by irradiating an electron beam with an acceleration voltage of 175 kV and an irradiation dose of 30 kGy (3 Mrad) to cure the ionizing radiation curable resin.
The sheet thus obtained was foamed with a foamed resin composition at 230 ° C. using a heating foaming furnace to form the foamed resin layer 3, and then the cooling roll and the pressure roll of the embossed mold were formed. Through this, embossing was performed to obtain a foamed wallpaper having a concavo-convex pattern on the surface.
Foamed resin composition Composition Ethylene-vinyl acetate copolymer (Mitsui DuPont Chemical Co., Ltd., trade name: Everflex V406): 90 parts by mass Calcium carbonate (Shiraishi Kogyo, trade name: Whiten H): 40 masses Part Petroleum resin softening modifier (Arakawa Chemical Industries, Ltd., trade name: Archon R-100): 10 parts by weight Foaming agent (trade name: Uniform AZ Ultra): 4 parts by weight Titanium oxide ( Inorganic filler) (manufactured by DuPont, trade name: Taipure R-108): 20 parts by weight Light stabilizer (manufactured by Adeka Argus Chemical, trade name: O-1305): 5 parts by weight Dispersant (Daikyo Kasei Kogyo Co., Ltd.) Product name: MFX-50E): 3 parts by weight Crosslinking agent (manufactured by JSR Corporation, trade name: Obstar JVA-702): 1 part by weight Ionizing radiation curable resin composition Composition Trifunctional urethane Mer: 70 parts by mass Bifunctional urethane oligomer: 30 parts by mass Silica (average particle size of about 3 to 4 μm): 8 parts by mass Silicone methacrylate: 3 parts by mass Silver antibacterial agent (trade name: Novalon AG- 300, silver ion-supported phosphate-based carrier, silver ion support amount 2.5% by mass, average particle size 2 μm): 1 part by mass Weathering agent: 1 part by mass

Example 2
The antibacterial agent added to the ionizing radiation curable resin composition is a silver antibacterial agent (manufactured by Shinto V Serrax Co., Ltd., trade name: antibacterial ceramics, silver ion-carrying apatite carrier, silver ion carrying amount 3 mass%, average particle diameter A foamed wallpaper was obtained in the same manner as in Example 1 except that 3 parts by mass of 2.2 μm) was used.

Example 3
Antibacterial agent added to the ionizing radiation curable resin composition is silver antibacterial agent (manufactured by Sinanen New Ceramics, trade name: Zeomic AJ-10D, silver ion-carrying zeolite carrier, silver ion-carrying amount 2 mass%, average particle diameter A foamed wallpaper was obtained in the same manner as in Example 1 except that 3 parts by mass of 2.2 μm) was used.

Example 4
The antibacterial agent added to the ionizing radiation curable resin composition is a silver antibacterial agent (manufactured by Toa Gosei Chemical Co., Ltd., trade name: Novalon AG-300, a silver ion-carrying phosphate carrier, a silver ion carrying amount of 2.5 mass) %, An average particle size of 2.2 μm), and 1 part by mass of microsilica having an average particle size of 2 μm was further added to obtain a foamed wallpaper in the same manner as in Example 1.

Example 5
The antibacterial agent added to the ionizing radiation curable resin composition is a silver antibacterial agent (manufactured by Toa Gosei Chemical Co., Ltd., trade name: Novalon AG-300, a silver ion-carrying phosphate carrier, a silver ion carrying amount of 2.5 mass) %, An average particle diameter of 2.2 μm), and a foamed wallpaper was obtained in the same manner as in Example 1 except that 2 parts by mass of microsilica having an average particle diameter of 2 μm was further added.

Comparative Example 1
The antibacterial agent added to the ionizing radiation curable resin composition was the same as in Example 1 except that the zinc oxide antibacterial agent having an average particle diameter of 1 μm (the amount of supported zinc oxide was 3% by mass) was changed to 5 parts by mass. Got foam wallpaper.

Comparative Example 2
1 part by weight of a silver-based antibacterial agent (manufactured by Toagosei Co., Ltd., trade name: Novalon AG-300, a silver ion-supported phosphate-based carrier, a silver ion support amount of 0.05% by mass, an average particle size of 2.2 μm) A foamed wallpaper was obtained in the same manner as in Example 1 except that the change was made.

Comparative Example 3
Silver antibacterial agent (manufactured by Toagosei Co., Ltd., trade name: Novalon AG-300, silver ion-carrying phosphate carrier, silver ion carrying amount 50% by mass, average particle size 2.2 μm) is changed to 1 part by mass Except for the above, a foamed wallpaper was obtained in the same manner as in Example 1.

Comparative Example 4
The composition of the ionizing radiation curable resin composition is trifunctional urethane oligomer: 0 part by mass, bifunctional urethane oligomer: 100 parts by mass, and a silver antibacterial agent (trade name: Novalon AG-300, manufactured by Toagosei Co., Ltd., silver ion) A foamed wallpaper was obtained in the same manner as in Example 1 except that the supported phosphate carrier, the amount of supported silver ions was 2.5% by mass, and the average particle size was 2.2 μm.

Comparative Example 5
The composition of the ionizing radiation curable resin composition is trifunctional urethane oligomer: 30 parts by mass, bifunctional urethane oligomer: 70 parts by mass, and silver-based antibacterial agent (trade name: Novalon AG-300, manufactured by Toagosei Co., Ltd., silver ion) A foamed wallpaper was obtained in the same manner as in Example 1 except that the supported phosphate carrier, the amount of supported silver ions was 2.5% by mass, and the average particle size was 2.2 μm.

Comparative Example 6
The composition of the ionizing radiation curable resin composition is trifunctional urethane oligomer: 100 parts by mass, bifunctional urethane oligomer: 0 part by mass, silver antibacterial agent (manufactured by Toagosei Co., Ltd., trade name: Novalon AG-300, silver ion) A foamed wallpaper was obtained in the same manner as in Example 1 except that the supported phosphate carrier, the amount of supported silver ions was 2.5% by mass, and the average particle size was 2.2 μm.

  Table 1 shows the results of the above evaluation on the foamed wallpaper obtained in Examples 1 to 5 and Comparative Examples 1 to 6. The foamed wallpaper obtained in each example showed high overall performance. Further, in Examples 4 and 5 to which microsilica was added, the dispersibility of the antibacterial agent in the obtained surface protective layer was further improved, and a uniform layer could be formed. showed that. On the other hand, although Comparative Example 1 used a zinc oxide antibacterial agent, it was insufficient in antibacterial properties, and Comparative Example 2 with a small amount of silver ions supported in the silver antibacterial agent was insufficient in antibacterial properties. In Comparative Example 3 in which the amount of silver ions supported is large, discoloration due to the liberation of silver ions is observed, and Comparative Examples 4 to 6 in which the Vickers hardness of the surface protective layer is outside the scope of the present invention, The antibacterial property was good, but the other characteristics were insufficient.

  According to the present invention, the discoloration of the ionizing radiation curable resin composition exerted by the silver-based antibacterial agent is reduced, and the ionizing radiation curable resin composition is provided with excellent stability and antibacterial properties. By devising the ionizing radiation curable resin material so that the Vickers hardness of the layer formed by crosslinking and curing the curable resin composition is in a specific range, it is used as a building interior material such as a wallpaper using this as a surface protective layer. High designability and excellent antibacterial properties, stain resistance, scratch resistance and workability can be imparted.

It is a schematic diagram which shows the cross section of the foam wallpaper of this invention.

Explanation of symbols

1. Wallpaper 2. Base material 3. Foamed resin layer 4. Non-foamed resin layer 5. Pattern layer 6. Surface protective layer 7. Primer layer 8. Uneven pattern

Claims (6)

  An ionizing radiation curable resin composition containing at least an ionizing radiation curable resin and a silver antibacterial agent having at least silver ions supported on an inorganic compound, wherein the ionizing radiation curable resin composition is crosslinked and cured. The ionizing radiation curable resin composition, wherein the layer has a Vickers hardness of 0.45 to 1.3 and the supported amount of silver ions is 0.1 to 30% by mass of the inorganic compound.   The ionizing radiation curable resin composition according to claim 1, further comprising microsilica.   3. The ionizing radiation curable resin composition according to claim 1, wherein the content of the antibacterial agent is 0.01 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.   4. The ionizing radiation curable resin composition according to claim 1, wherein the content of the microsilica is 0.1 to 5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.   The ionizing radiation curable resin composition according to claim 1, wherein the inorganic compound is at least one selected from zeolite, hydroxide apatite, and zirconium phosphate.   A foam wallpaper using the ionizing radiation curable resin composition according to claim 1.

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