JP6051538B2 - Laminated sheet with photocatalytic function - Google Patents

Description

  The present invention relates to a laminated sheet including a photocatalytic layer. More specifically, the present invention relates to a laminated sheet that can exhibit an excellent photocatalytic function and can suppress self-deterioration of the photocatalytic layer.

  With the recent increase in energy saving, building materials such as heat insulating materials and construction methods such as external heat insulating methods have been proposed in the housing field, and high heat insulation and high airtightness of houses are progressing. On the other hand, as indoor spaces become more airtight, allergens, cigarette smoke, odors from humans and pets, sick house syndrome caused by building materials, and harmful substances such as influenza viruses and other viruses and bacteria It has become a problem to stay in. It is considered effective to add functions such as allergen decomposition, deodorization, antibacterial, antiviral, etc. to the wall surface of the indoor space in order to remove the harmful substances that stay in the indoor space with high airtightness.

  Conventionally, it has been known that photocatalysts have functions such as allergen decomposition, deodorization, antibacterial, and antiviral, and are attached to the wall surface of an indoor space for the purpose of providing the photocatalytic function on the wall surface of the indoor space. A technique for binding a photocatalyst to a laminated sheet (wallpaper) with a resin has been proposed. For example, Patent Document 1 reports a decorative paper having a photocatalytic function, in which a foamable resin layer, a picture layer, an inorganic layer, and a photocatalyst layer are sequentially laminated on one side of a substrate. Patent Document 2 reports a building material in which a film containing a photocatalyst, an adsorbent such as zeolite, and a binder such as silicon dioxide is formed on the surface of the base. However, when the photocatalyst is bound with a resin as in Patent Document 1, the resin is inevitably decomposed with the development of the photocatalytic function, and the layer having the photocatalyst is self-degraded, so that the stain resistance is lowered. In addition, there is a problem that appearance characteristics are deteriorated due to discoloration. In addition, as in Patent Document 2, when a photocatalyst, an inorganic adsorbent, and an inorganic binder are combined, self-deterioration due to the development of the photocatalytic function can be suppressed. There is a problem that the adsorbed harmful substances remain without being decomposed.

  On the other hand, in the laminated sheet to which the photocatalyst is added, the expression of the photocatalytic function depends on the presence or absence of light irradiation. In order to compensate for the disadvantages of such a photocatalyst, a technique has been proposed in which a composite material in which a photocatalyst is coated with apatite and metal particles are supported is blended in a paint (see Patent Document 3). In such a composite material, the metal particles are included together with the photocatalyst, so that the antibacterial action based on the metal particles can be exhibited even in an environment without light irradiation. However, there is a drawback that the photocatalytic function cannot be sufficiently exhibited simply by providing such a composite material on the surface layer. Further, if the photocatalytic function is to be further improved, it is necessary to increase the content of the composite material in the surface layer. In this case, there is a problem that self-deterioration due to the development of the photocatalytic function is likely to occur again. .

  Conventionally, there is no known technique for efficiently expressing a photocatalytic function in a laminated sheet to which a photocatalyst is added. Further, as described above, even if the photocatalytic function can be efficiently expressed, the problem of self-deterioration due to the expression of the photocatalytic function is encountered. For this reason, in the laminated sheet to which the photocatalyst is added, it has been impossible to achieve both the expression of an excellent photocatalytic function and the suppression of self-deterioration by the photocatalytic function in the conventional technology.

Japanese Patent Laid-Open No. 10-180943 Japanese Patent Laid-Open No. 9-300515 JP 2008-50559 A

  It is an object of the present invention to provide a technique for expressing an excellent photocatalytic function and suppressing self-deterioration of the photocatalytic layer in a laminated sheet including a photocatalytic layer.

  The inventors of the present invention have intensively studied to solve the above-mentioned problems. As a result, a laminate in which a composite material obtained by coating a photocatalyst with an inorganic adsorbent and a photocatalyst layer containing an ionizing radiation curable resin is laminated on a substrate. The sheet has been found that the photocatalyst layer can exhibit a significantly superior photocatalytic function. Furthermore, it discovered that the said laminated sheet could suppress the self-deterioration of a photocatalyst layer. The present invention has been completed by further studies based on such knowledge.

That is, this invention provides the lamination sheet of the aspect hung up below, and its manufacturing method.
Item 1. A laminated sheet in which a composite material obtained by coating a photocatalyst with an inorganic adsorbent and a photocatalyst layer containing an ionizing radiation curable resin are laminated on a base material.
Item 2. Item 2. The laminated sheet according to Item 1, wherein the photocatalyst layer further contains at least one silicone compound selected from the group consisting of a silicone resin and a silicone-modified resin.
Item 3. Item 3. The laminated sheet according to Item 1 or 2, wherein the composite material is contained at a ratio of 3 to 15 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.
Item 4. Item 4. The laminated sheet according to any one of Items 1 to 3, wherein in the composite material, the inorganic adsorbent is apatite and the photocatalyst is titanium oxide.
Item 5. Item 5. The laminated sheet according to any one of Items 1 to 4, wherein the composite material further carries a metal.
Item 6. Item 6. The laminated sheet according to Item 5, wherein the metal is silver.
Item 7. Item 7. The laminated sheet according to any one of Items 1 to 6, wherein the ionizing radiation curable resin is a 2-6 functional urethane (meth) acrylate oligomer.
Item 8. Item 8. The laminated sheet according to any one of Items 1 to 7, wherein the photocatalyst layer has a thickness of 2 to 5 μm.
Item 7. Item 8. The laminated sheet according to any one of Items 1 to 7, wherein a foaming agent-containing resin layer containing a resin component and a foaming agent is provided between the substrate and the photocatalyst layer.
Item 8. Item 8. The laminated sheet according to any one of Items 1 to 7, wherein a foamed resin layer is provided between the substrate and the photocatalyst layer.
Item 9. A method for producing a laminated sheet, comprising a step of laminating a composite material obtained by coating a catalyst with an inorganic adsorbent and a photocatalyst layer containing an ionizing radiation curable resin on a substrate.

  The laminated sheet of the present invention is remarkably excellent in photocatalytic functions such as antiallergen, deodorant, antibacterial, antiviral, etc., and effectively removes harmful substances that stay in the indoor space even in a highly sealed indoor space. Can be disassembled. In addition, the laminated sheet of the present invention can suppress the self-degradation of the photocatalyst layer itself due to the development of the photocatalytic function, so that the function such as contamination resistance can be maintained over a long period of time, and the aging caused by the development of the photocatalytic function It is also possible to suppress the deterioration of appearance properties due to a general discoloration. Furthermore, the laminated sheet of the present invention has both good initial adhesion and weather resistance of the photocatalyst layer, and has sufficient desired physical properties required for a decorative sheet.

It is a figure which shows an example of laminated structure (sectional drawing) in the case of making the lamination sheet of this invention into a foaming lamination sheet. It is a figure which shows an example of laminated structure (sectional drawing) in the case of making the lamination sheet of this invention into a foaming lamination sheet. It is a figure which shows an example of laminated structure (sectional drawing) in the case of making the lamination sheet of this invention into a non-foaming lamination sheet. It is a figure which shows an example of laminated structure (sectional drawing) in the case of making the lamination sheet of this invention into a non-foaming lamination sheet.

1. Laminated sheet The laminated sheet of the present invention is characterized in that a photocatalyst layer containing a composite material obtained by coating a photocatalyst with an inorganic adsorbent and an ionizing radiation curable resin is laminated on a substrate. Hereinafter, the laminated sheet of the present invention will be described in detail. In this specification, “self-degradation of the photocatalyst layer” means that the photocatalyst layer exhibits the photocatalyst function, thereby reducing the functions of the photocatalyst layer itself (photocatalyst function, contamination resistance, photocatalyst layer adhesion, etc.) Or the appearance properties deteriorate due to discoloration or the like resulting from the development of the photocatalytic function. In addition, “initial adhesion” refers to the property that the “photocatalyst layer” is difficult to peel off in the laminated sheet immediately after production, and “weather resistance” refers to the condition that the laminated sheet is irradiated with light continuously or intermittently. The “photocatalyst layer” exhibits the property that it is difficult to be peeled off after being exposed to.

Laminated structure The laminated sheet of the present invention has a laminated structure in which a photocatalyst layer is laminated on a substrate. In the laminated sheet of the present invention, one or two or more other layers may be provided between the substrate and the photocatalyst layer as long as the photocatalyst layer forms the outermost surface. For example, the laminated sheet of the present invention may be a foamed laminated sheet in which a foamed resin layer is provided between the base material and the photocatalyst layer layer, and a non-foamed resin layer is provided between the base material and the photocatalyst layer. Non-foamed laminated sheets may also be used. The laminated sheet of the present invention is preferably a foamed laminated sheet in which a foamed resin layer is provided between the substrate and the photocatalyst layer.

Composition of base material and photocatalyst layer Hereinafter, the composition and forming method of the base material and photocatalyst layer constituting the laminated sheet of the present invention will be described.

[Base material]
About the base material used for this invention, it does not restrict | limit in particular, According to the use etc. of a lamination sheet, it sets suitably.

For example, when the laminated sheet of the present invention is used as a decorative sheet for walls and ceilings, a fibrous base material that is usually used as wallpaper paper can be used as the base material. The fibrous base material may contain 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 as necessary. Specific examples of fiber base materials include general paper for wallpaper (pulp-based sheets sized with a sizing agent), flame-retardant paper (pulp-based sheets such as guanidine sulfamate and guanidine phosphate) Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper; fiber mixed paper (mixed synthetic fiber with pulp) and the like. The basis weight of the fibrous base material is not particularly limited, for example, 50 to 300 g / ^{m 2} approximately, and preferably about 50 to 120 / ^{m 2.}

  Further, for example, when the laminated sheet of the present invention is used as a decorative sheet for floors, a thermoplastic resin sheet (film) is suitably used as the base material. Specific examples of the thermoplastic resin constituting the thermoplastic resin sheet include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene / vinyl acetate copolymer, and ethylene. -(Meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, ionomer, (meth) acrylic acid ester and the like. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid. The thermoplastic resin sheet may be colored by adding a colorant (pigment or dye) as necessary. Examples of the colorant include inorganic pigments such as titanium dioxide, carbon black, and iron oxide; organic pigments such as phthalocyanine blue; and other various dyes. Furthermore, various additions such as a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, and a light stabilizer are added to the thermoplastic resin sheet as necessary. An agent may be included. In addition, in order to improve the adhesion with other layers, the thermoplastic resin sheet is oxidized on one or both sides as necessary (corona discharge treatment, chrome oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet ray). A physical or chemical surface treatment such as a treatment method or the like, or a concavo-convex method (a sand blast method, a solvent treatment method, or the like) may be applied. Although the thickness of a thermoplastic resin sheet can be suitably set with the use of the lamination sheet of this invention, a usage method, etc., generally 20-300 micrometers is preferable.

[Photocatalyst layer]
A photocatalyst layer is a layer which expresses a photocatalyst function, and is a layer located in the outermost surface in the lamination sheet of the present invention. The photocatalyst layer used in the present invention contains a composite material obtained by coating a photocatalyst with an inorganic adsorbent and an ionizing radiation curable resin.

  The composite material used for the photocatalyst layer is a substance in which the photocatalyst is coated with an inorganic adsorbent.

The photocatalyst constituting the composite material is not particularly limited as long as it can exhibit an oxidizing action or a superhydrophilic action by light irradiation. For example, titanium oxide (TiO ₂ ), sodium titanate (NaTiO ₃ , Na ₂₎ Ti ₆ O ₁₃ etc.), barium titanate (BaTiO ₃ ), strontium titanate (SrTiO ₃ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), cadmium sulfide (CdS), potassium niobate (K ₂ NbO ₃₎ , K ₄ Nb ₆ O _17, etc.), iron oxide (Fe ₂ O ₃ ), tantalum oxide (Ta ₂ O ₅ ), tin oxide (SnO ₂ ), bismuth oxide (Bi ₂ O ₃ ), nickel oxide (NiO), copper oxide _(Cu 2 O), silicon oxide _(SiO 2), molybdenum sulfide _(MoS 2), indium lead (InPb), oxidation Le Bromide _(RuO 2), and the like cerium oxide (CeO _2). Among these compounds, those in which the expression of the photocatalytic function depends on the crystal form is a crystalline compound capable of expressing the photocatalytic function. For example, in the case of titanium oxide, crystal types such as anatase type and brookite type are used. These photocatalysts may be used alone or in a combination of two or more.

  Among these photocatalysts, titanium oxide, particularly anatase-type titanium oxide, can exhibit an excellent photocatalytic function, and is therefore preferably used in the present invention.

  A porous inorganic compound is used as the inorganic adsorbent constituting the composite material. Specific examples of the inorganic adsorbent include apatites such as hydroxyapatite, fluoride apatite, nitride apatite, and carbonate apatite; silica; alumina; zeolite; activated carbon and the like. These inorganic adsorbents may be used alone or in combination of two or more. Among these inorganic adsorbents, apatite is preferable, and hydroxyapatite is more preferable from the viewpoint of being able to effectively adsorb harmful substances such as allergens and viruses and enabling more effective harmful substances.

  The composite material is preferably apatite-coated titanium oxide from the viewpoint of developing a more excellent photocatalytic function.

  In the composite material, the ratio of the photocatalyst to the inorganic adsorbent is not particularly limited as long as light can be transmitted to the photocatalyst through the gap between the coated inorganic adsorbents. For example, 100 parts by mass of the photocatalyst The inorganic adsorbent is 10 to 50 parts by mass, preferably 10 to 30 parts by mass.

  Although there is no restriction | limiting in particular about the average particle diameter of the said composite material, For example, 0.5-3 micrometers, Preferably 0.8-1.5 micrometers is mentioned.

  The composite material can be prepared according to a known method. For example, apatite-coated titanium oxide can be prepared according to the methods described in JP-A-2005-289778, JP-A-11-130612, JP-A-10-244166, and the like. Moreover, the said composite material is marketed, and a commercial item can also be used in this invention.

  The composite material may further carry a metal having antibacterial and deodorizing effects. By supporting such a metal, the decomposition action of harmful substances can be further improved in the laminated sheet of the present invention. Specific examples of the metal supported on the composite material include silver, zinc, gold, platinum, lead, magnesium, tin, iron, nickel, and sodium. These metals may be used individually by 1 type, and may be used in combination of 2 or more type. Among these metals, silver is preferably used as a metal supported on the composite material because it has a strong deodorizing and antibacterial action.

  When the metal is supported on the composite material, the amount of the metal supported is not particularly limited. For example, the metal is 1 to 50 parts by weight, preferably 10 to 30 parts by weight per 100 parts by weight of the photocatalyst. It is done.

  In order to support the metal on the composite material, for example, a method of ion exchange with ions of the metal to a portion capable of cation exchange in an inorganic adsorbent; the metal is physically adsorbed on the composite material Methods and the like. In addition, the said composite material with which the said metal was carry | supported is marketed, and a commercial item can also be used in this invention.

  Although there is no restriction | limiting in particular about content of the said composite material in a photocatalyst layer, For example, the said composite material is about 3-30 mass parts per 100 mass parts of ionizing radiation curable resin mentioned later, Preferably it is about 5-20 mass parts. Is mentioned. According to the present invention, since a high photocatalytic function can be expressed by combining the composite material and the ionizing radiation curable resin, the content of the composite material is 100 parts by mass of the ionizing radiation curable resin. Even with a small amount of about 5 to 20 parts by mass, the photocatalytic function can be effectively expressed.

  In addition, as the ionizing radiation curable resin used in the photocatalyst layer, one or more kinds of monomers, oligomers and prepolymers having a polymerizable unsaturated bond or an epoxy group in the molecule can be appropriately selected and used. . Here, ionizing radiation refers to electromagnetic waves or charged particle beams having energy quanta that can polymerize or crosslink molecules, and usually ultraviolet rays or electron beams are used. The ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation.

  Preferable examples of the monomer used as the ionizing radiation curable resin include a (meth) acrylate monomer having a polymerizable unsaturated bond. Especially, the polyfunctional (meth) acrylate monomer which has 2 or more of ethylenically unsaturated bonds in a molecule | numerator is preferable. In such a polyfunctional (meth) acrylate monomer, the number of ethylenically unsaturated bonds is, for example, 2 to 8, preferably 2 to 6, and more preferably 3 to 4. In the present specification, “(meth) acrylate” means “acrylate or methacrylate”.

  Specific examples of the (meth) acrylate monomer having a polymerizable unsaturated bond include 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 phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylol propylene Tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified tri Methylolpropane 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 Examples thereof include modified dipentaerythritol hexa (meth) acrylate. One of these (meth) acrylates may be used alone, or two or more may be used in combination.

  Moreover, as a suitable example of the oligomer used as ionizing radiation curable resin, an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, a polyether (meth) acrylate oligomer, etc. are mentioned. . Among these, a polyfunctional oligomer having two or more ethylenically unsaturated bonds in the molecule, particularly a polyfunctional urethane (meth) acrylate oligomer is preferable. In such a polyfunctional oligomer, the number of ethylenically unsaturated bonds is, for example, 2 to 16, preferably 2 to 8, and more preferably 2 to 6.

  Furthermore, as the oligomer used as the ionizing radiation curable resin, in addition to those exemplified above, a highly hydrophobic polybutadiene (meth) acrylate oligomer having a (meth) acrylate group in the side chain of the polybutadiene oligomer; main chain Silicone (meth) acrylate oligomers with polysiloxane bonds in them; Aminoplast resin (meth) acrylate oligomers modified with aminoplast resins with many reactive groups in small molecules; Novolac epoxy resins, bisphenol epoxy resins And oligomers having a cationically polymerizable functional group in the molecule such as aliphatic vinyl ether and aromatic vinyl ether.

  These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type. Among these oligomers, preferred are polyfunctional oligomers, more preferred are polyfunctional urethane (meth) acrylate oligomers, and particularly preferred are 2 to 6 functional urethane (meth) acrylate oligomers.

  The content of the ionizing radiation curable resin in the photocatalyst layer is not particularly limited. For example, the ionizing radiation curable resin is about 50 to 90 parts by mass, preferably 60 to 85 parts by mass per 100 parts by mass of the total amount of the photocatalyst layer. Degree.

  The photocatalyst layer may contain a monofunctional (meth) acrylate together with the ionizing radiation curable resin for the purpose of imparting surface physical properties such as contamination resistance and controlling the surface tension. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  Further, in order to provide the photocatalyst layer with excellent contamination resistance, the photocatalyst layer may contain at least one silicone compound selected from the group consisting of a silicone resin and a silicone-modified resin. . The silicone resin blended in the photocatalyst layer is not particularly limited as long as it has a Si—O—Si bond (siloxane bond) as a skeleton. For example, polysiloxane; polydimethylsiloxane, polymethylphenylsiloxane, methyl Modified silicone resins such as styrene modified silicone, olefin modified silicone, fluorine modified silicone, polyether modified silicone, alcohol modified silicone, amino modified silicone, mercapto modified silicone, epoxy modified silicone, carboxyl modified silicone, amino-polyether co-modified silicone, etc. Is mentioned. In addition, the silicone-modified resin blended in the photocatalyst layer may include any of silicone graft polymer and silicone block polymer, for example; silicone modified acrylic resin, silicone modified urethane resin, silicone modified Examples include polyester resins, silicone-modified polycarbonate resins, and silicone-modified polyimide resins. These silicone compounds may be used alone or in combination of two or more.

  The content of the silicone compound in the photocatalyst layer is not particularly limited. For example, the silicone compound is about 0.5 to 10 parts by mass, preferably about 100 parts by mass of the total amount of the ionizing radiation curable resin. Is about 1 to 7 parts by mass.

  Moreover, when using an ultraviolet curable resin composition as ionizing radiation curable resin, it is desirable that the photocatalyst layer contains a photopolymerization initiator. What is necessary is just to select suitably as an initiator for photopolymerization according to polymerization modes, such as a monomer and an oligomer to be used.

  Furthermore, the photocatalyst layer has a matting agent, a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an ultraviolet absorber, an antioxidant, an antistatic agent depending on the desired physical properties to be provided. In addition, various additives such as an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a coloring agent may be included.

Although it does not restrict | limit especially about the coating amount of a photocatalyst layer, For example, 2-5 g / m < ² >, Preferably 2.5-3.5 g / m < ² > is mentioned.

  The thickness of the photocatalyst layer is not particularly limited and is determined according to the coating amount of the photocatalyst layer described above, and for example, 1 to 5 μm, preferably 2 to 4 μm. According to the present invention, since the high photocatalytic function can be expressed by combining the composite material and the ionizing radiation curable resin, even if the photocatalytic layer is a thin layer having a thickness of 2 to 4 μm, The photocatalytic function can be expressed effectively.

  The formation of the photocatalyst layer is a gravure coat, bar coat, roll coat, reverse roll coat, comma coat, composition obtained by mixing the composite material, ionizing radiation curable resin, and other components contained as necessary. After coating by a method such as extrusion formation, ionizing radiation is irradiated to cure the ionizing radiation curable resin composition. When the ionizing radiation curable resin is cured using an electron beam, examples of the electron beam irradiation condition include an acceleration voltage of about 70 to 300 kV and an irradiation dose of about 5 to 250 kGy.

Foamed laminated sheet When the laminated sheet of the present invention is made into a foamed laminated sheet, it is non-foamed between the base material and the foamed resin layer as necessary for the purpose of improving the adhesive force between the base material and the foamed resin layer. A resin layer (non-foamed resin layer B) may be formed. In addition, when making a foamed laminated sheet, the top surface of the foamed resin layer (the surface on which the photocatalyst layer is laminated) is made clearer when the pattern layer is formed and the foamed resin layer has improved scratch resistance. The non-foamed resin layer (non-foamed resin layer A) may be formed as needed for the purpose of making it happen. Furthermore, when making it into a foaming laminated sheet, the pattern layer may be formed as needed on the upper surface of the foamed resin layer and the lower surface of the photocatalyst layer for the purpose of imparting design properties to the laminate sheet.

  That is, as an example of a suitable laminated structure when the laminated sheet of the present invention is a foamed laminated sheet, as shown in FIG. 1, substrate 1 / non-foamed resin layer B2 / foamed resin layer 3 / non-foamed resin layer A4 Laminated structure in which / pattern pattern layer 5 / photocatalyst layer 6 is laminated in order; as shown in FIG. 2, a laminated structure in which base material 1 / foamed resin layer 3 / patterned pattern layer 5 / photocatalyst layer 6 are laminated in order It is done. 1 and 2 are suitable for use as a decorative sheet for walls and ceilings using a fibrous base material as a base material.

  Hereinafter, the composition and forming method of each layer (other than the base material and the photocatalyst layer) provided when the laminated sheet of the present invention is made into a foamed laminated sheet will be described.

[Foamed resin layer]
A foamed resin layer is a layer provided between a base material and a photocatalyst layer as needed. The foamed resin layer is formed by forming a foaming agent-containing resin layer comprising a resin composition containing a resin component and a foaming agent, and then foaming the foaming agent-containing resin layer.

  The resin component used in the foamed resin layer is not particularly limited as long as it can form a foamed shape by the action of a foaming agent. For example, 1) polyethylene, and 2) ethylene and components other than ethylene are monomers. And those containing at least one ethylene copolymer (hereinafter abbreviated as “ethylene copolymer”).

The polyethylene used in the present invention is not particularly limited, for example, density 0.942 g / cm ³ or more high-density polyethylene (HDPE) and density 0.93 g / cm ³ or more 0.942 g / cm ³ less than in Examples thereof include density polyethylene (MDPE), low density polyethylene (LDPE) having a density of 0.91 g / cm ³ or more and less than 0.93 g / cm ³ , and linear low density polyethylene (LLDPE). Among these, low density polyethylene is preferable.

  Examples of the ethylene copolymer used in the present invention include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-methyl. Examples thereof include acrylate copolymers (EMA), ethylene- (meth) acrylic acid copolymers (EMAA), ionomers of ethylene- (meth) acrylic acid copolymers, and ethylene-α olefin copolymers. These ethylene copolymers may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the ethylene copolymer, the ratio of monomers other than ethylene and ethylene is not particularly limited. For example, the content of monomers other than ethylene is usually 5 to 25% by mass, preferably 5 to 20% by mass. Can be mentioned. Specifically, the copolymerization ratio (VA amount) of vinyl acetate in the ethylene-vinyl acetate copolymer is, for example, 9 to 25% by mass, preferably 9 to 20% by mass. The copolymerization ratio (MMA amount) of methyl methacrylate in the ethylene-methyl methacrylate copolymer is, for example, 5 to 25% by mass, preferably 5 to 15% by mass. The copolymerization ratio (MAA amount) of (meth) acrylic acid in the ethylene- (meth) acrylic acid copolymer is, for example, 2 to 15% by mass, preferably 5 to 11% by mass.

  The resin component used for the foamed resin layer is preferably polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene- (meth) acrylic acid copolymer, and polyethylene and ethylene-α-olefin. Examples thereof include a mixture of copolymers and a vinyl chloride resin. These resin components may be used individually by 1 type, and may be used in combination of 2 or more type.

  When a mixture of polyethylene and ethylene-α-olefin copolymer is used as the resin component, these ratios are not particularly limited. For example, per 100 parts by mass of polyethylene and ethylene-α-olefin copolymer, ethylene- Examples of the α-olefin copolymer include 50 parts by mass or more and less than 100 parts by mass.

  Although it does not restrict | limit especially about the melt flow rate value of the resin component contained in a foamed resin layer, For example, about 10-100 g / 10min is mentioned. The melt flow rate value in the present specification is “190 ° C., 21.18 N (2.16 kgf)” described in JIS K 6760 as test conditions in accordance with the test method described in JIS K 7210 (thermoplastic flow test method). It is a value measured by adopting it.

  It does not restrict | limit especially as a foaming agent used for a foamed resin layer, It can select from a well-known foaming agent. For example, azo type such as azodicarbonamide (ADCA) and azobisformamide; organic thermal decomposition type blowing agent such as hydrazide type such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide; microcapsule type blowing agent; baking soda Inorganic foaming agents such as

  The content of the foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. From the viewpoint of the expansion ratio, it is 3 times or more, preferably about 7 to 10 times, and the foaming agent may be, for example, about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

  In order to improve the foaming effect of the foaming agent, a foaming aid may be included in the foamed resin layer as necessary. Although it does not restrict | limit especially as a foaming adjuvant, For example, a metal oxide, a fatty-acid metal salt, etc. are mentioned. More specifically, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, magnesium laurate, zinc oxide, magnesium oxide, lauric hydrazide, Salicylic acid hydrazide, form hydrazide, acetohydrazide, propionic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy-2-naphthoic acid hydrazide, lauric acid hydrazide, salicylic acid hydrazide, form hydrazide, acetohydrazide, propionic acid P-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy-2-naphthoic acid hydrazide and the like. These foaming aids may be used alone or in combination of two or more. Although content of these foaming adjuvants is suitably set according to the kind of foaming adjuvant, the kind of foaming agent, content, etc., for example, 0.3-10 mass with respect to 100 mass parts of resin components About 1 part, Preferably about 1-7 mass parts is mentioned.

  The foamed resin layer may contain an inorganic filler as necessary for imparting flame retardancy, suppressing see-through, improving surface characteristics, and the like. The inorganic filler is not particularly limited, and examples thereof include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. These inorganic fillers may be used individually by 1 type, and may be used in combination of 2 or more type. Although content in particular of these inorganic fillers is not restrict | limited, For example, about 0-100 mass parts with respect to 100 mass parts of resin components, Preferably about 20-70 mass parts is mentioned.

  The foamed resin layer may contain a pigment as necessary. The pigment is not particularly limited and may be either an inorganic pigment or an organic pigment. Inorganic pigments include, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), and cadmium. Examples thereof include red, ultramarine blue, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide. Examples of organic pigments include aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone, Perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine) and the like. These pigments may be used alone or in combination of two or more. Although content in particular of these pigments is not restrict | limited, For example, about 10-50 mass parts with respect to 100 mass parts of resin components, Preferably about 15-30 mass parts is mentioned.

  Furthermore, the foamed resin layer may contain additives such as an antioxidant, a cross-linking agent, and a surface treatment agent as necessary as long as the effects of the present invention are not hindered.

  The foamed resin layer may be cross-linked as necessary. The method for crosslinking the foamed resin layer is not particularly limited. For example, there is a method of previously crosslinking the foaming agent-containing resin layer before foaming by irradiating the foaming agent-containing resin layer before foaming with an electron beam. Can be mentioned. Specifically, with respect to the foaming agent-containing resin layer, the acceleration voltage is 100 to 200 kV, preferably 100 to 140 kV, the irradiation amount is set to 2 to 200 kGy, preferably 2.5 to 100 kGy, and the electron beam irradiation is performed. The method of performing is illustrated.

  Although it does not restrict | limit especially about the thickness of a foamed resin layer, For example, 300-700 micrometers is mentioned. As thickness before foaming of a foamed resin layer (namely, thickness of a foaming agent containing resin layer), 40-100 micrometers is mentioned, for example.

  The foamed resin layer is formed by a calendering method, an inflation method, a T-die extrusion method, etc. after forming a foaming agent-containing resin layer composed of a resin composition containing a resin component, a foaming agent, and other additives as required. It is formed by foaming the foaming agent-containing resin layer.

[Non-foamed resin layer B (adhesive resin layer)]
The non-foamed resin layer B is an adhesive resin layer formed between the base material and the foamed resin layer as necessary for the purpose of improving the adhesive force between the base material and the foamed resin layer.

  The resin component of the non-foamed resin layer B is not particularly limited, but an ethylene-vinyl acetate copolymer (EVA) is preferable. EVA can be a known or commercially available one. In the EVA used for the non-foamed resin layer B, the ratio of the vinyl acetate component (VA component) is not particularly limited, but may be, for example, 10 to 46 mass%, preferably 15 to 41 mass%.

Although it does not restrict | limit especially about the thickness of the non-foaming resin layer B, For example, 3-50 micrometers, Preferably about 3-20 micrometers is mentioned.
The method for forming the non-foamed resin layer B is not particularly limited, and examples thereof include a calendar method, an inflation method, and a T-die extrusion method. As a preferred example of the method for forming the non-foamed resin layer B, the foamed resin layer and the non-foamed resin layer B are formed by using a multi-manifold type T-die capable of simultaneously forming two or more layers by extruding molten resin simultaneously. Can be formed by coextrusion.

[Non-foamed resin layer A]
The non-foamed resin layer A is a layer formed on the upper surface of the foamed resin layer as necessary for the purpose of clarifying the pattern when forming the pattern layer or improving the scratch resistance of the foamed resin layer. It is.

  The resin component of the non-foamed resin layer A is not particularly limited, and examples thereof include polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, and fluorine resins. These resin components may be used individually by 1 type, and may be used in combination of 2 or more type. Among these resin components, a polyolefin resin is preferable.

  Specific examples of polyolefin resins include polyethylene, polypropylene, polybutene, polybutadiene, polyisoprene, and other resins, copolymers of α-olefins having 4 or more carbon atoms (linear low density polyethylene), and ethylene-acrylic acid. Examples thereof include a methyl copolymer, an ethylene-ethyl acrylate copolymer, an ethylene- (meth) acrylic acid copolymer, an ethylene-vinyl acetate copolymer, a saponified ethylene-vinyl acetate copolymer, and an ionomer.

  Although it does not restrict | limit especially about the thickness of the non-foaming resin layer A, For example, 3-50 micrometers, Preferably about 3-20 micrometers is mentioned.

  A method for forming the non-foamed resin layer A is not particularly limited, and examples thereof include a calendar method, an inflation method, and a T-die extrusion method. A preferred example of the method for forming the non-foamed resin layer A is a method in which a foamed resin layer and a non-foamed resin layer B are simultaneously extruded using a multi-manifold type T die. When three layers of the non-foamed resin layer A, the foamed resin layer, and the non-foamed resin layer B are provided, these three layers are formed using a multi-manifold type T-die capable of forming three layers simultaneously. It is desirable to form by coextrusion.

[Pattern pattern layer]
The pattern layer is a layer formed on the top surface of the foamed resin layer (or non-foamed resin layer A) as necessary for the purpose of imparting design properties to the laminate sheet.

  Examples of the design pattern include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern. A design pattern can be suitably selected according to the use of a foaming lamination sheet.

  The pattern pattern layer can be formed, for example, by printing a pattern pattern. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, offset printing, and the like. As the printing ink, a printing ink containing a colorant, a binder resin, a solvent (or a dispersion medium), and the like can be used. These inks may be known or commercially available.

  Although it does not restrict | limit especially as a coloring agent, For example, the pigment used with the said foamed resin layer can be used suitably.

  The binder resin may be set as appropriate according to the type of the base sheet. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate. Examples include copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like. These binder resins may be used alone or in combination of two or more.

  Although it does not restrict | limit especially as a solvent (or dispersion medium), For example, petroleum-type organic solvents, such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, methylcyclohexane; Ethyl acetate, butyl acetate, 2-methoxyacetate Ester-based organic solvents such as ethyl and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketone organic solvents such as cyclohexanone; ether organic solvents such as diethyl ether, dioxane and tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, Chlorinated organic solvents such as tiger chloroethylene; and water. These solvents (or dispersion media) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The thickness of the design pattern layer is appropriately set according to the type of design pattern and the like, and may be about 0.1 to 10 μm, for example.

Non-foamed laminated sheet When the laminated sheet of the present invention is made into a non-foamed laminated sheet, a non-foamed resin layer may be formed between the substrate and the photocatalyst layer. Further, when making a non-foamed laminate sheet, it is necessary between the base material and the non-foamed resin layer or between the non-foamed resin layer and the photocatalyst layer for the purpose of imparting design properties to the non-foamed laminate sheet. Accordingly, a pattern layer may be formed. In addition, when a pattern layer is provided between the base material and the non-foamed resin layer, an adhesive layer is formed between the non-foamed resin layer and the pattern layer as necessary for the purpose of improving the adhesive strength between the non-foamed resin layer and the pattern layer. May be.

  As an example of a suitable laminated structure when the laminated sheet of the present invention is a non-foamed laminated sheet, as shown in FIG. 3, a base material 1 / non-foamed resin layer 7 / pattern pattern layer 5 / photocatalyst layer 6 are laminated in order. And a laminated structure in which a substrate 1 / pattern layer 5 / adhesive layer 8 / non-foamed resin layer 7 / photocatalyst layer 6 are laminated in order, as shown in FIG. The laminated sheet having the structure shown in FIG. 3 is suitable for use as a decorative sheet for walls and ceilings using a fibrous base material as a base material. Moreover, the laminated sheet having the structure shown in FIG. 4 is suitable for use as a decorative sheet for a floor using a thermoplastic resin sheet (film) as a base material.

  Hereinafter, the composition and formation method of each layer (other than the base material and the photocatalyst layer) provided when the laminated sheet of the present invention is made into a non-foamed laminated sheet will be described.

[Non-foamed resin layer]
In the non-foamed laminated sheet, the non-foamed resin layer is a layer formed from a non-foamed resin and provided between the substrate and the photocatalyst layer.

  The non-foamed resin layer may be either transparent or opaque, but transparent when a pattern layer is provided on the substrate (that is, when the pattern layer is provided between the base and the non-foamed resin). It is desirable that When the resin layer is made transparent, it may be any of colorless and transparent, colored and transparent, translucent and the like.

  Examples of the resin component that can form a transparent non-foamed resin layer include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, and ethylene / (meth) acrylic acid copolymer. Examples thereof include polymers, ethylene / (meth) acrylic acid ester copolymers, ionomers, polymethylpentene, (meth) acrylic acid esters, polycarbonates, and cellulose triacetates. These resin components may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although the thickness of a non-foaming resin layer is suitably set according to the use etc. of the laminated sheet of this invention, about 20-200 micrometers is mentioned, for example.

  The non-foamed resin layer may be formed by gravure coating, bar coating, roll coating, reverse roll coating, comma coating, extrusion forming, etc., or after laminating the resin component into a sheet or film in advance. Also good.

[Pattern pattern layer]
In the non-foamed laminated sheet, the pattern layer is formed between the base material and the non-foamed resin layer or between the non-foamed resin and the photocatalyst layer as necessary for the purpose of imparting design properties to the laminate sheet. Layer. About the composition of a pattern pattern layer used for a non-foaming laminated sheet, a formation method, etc., it is the same as that of the pattern pattern layer used with the said foaming lamination sheet.

[Adhesive layer]
In the case where the pattern layer is provided between the base material and the non-foamed resin layer, the adhesive layer is provided with a non-foamed resin layer as necessary for the purpose of improving the adhesive force between the non-foamed resin layer and the pattern layer. It is a layer formed between picture pattern layers.

  The adhesive layer is preferably composed of a transparent resin that functions as an adhesive so as not to impair the design effect of the pattern layer on the substrate. Examples of such transparent resins include thermoplastic resins such as polyamide resins, acrylic resins and vinyl acetate resins; thermosetting resins such as urethane resins.

  Although the thickness in particular of an adhesive layer is not restrict | limited, For example, about 0.1-30 micrometers, Preferably about 1-20 micrometers is mentioned.

  The adhesive layer can be formed by a printing technique such as gravure printing, flexographic printing, silk screen printing, or offset printing.

In the laminated sheet of the uneven pattern invention, an uneven pattern by embossing may be applied to the surface (surface opposite to the fibrous base material) as necessary in order to impart design properties. Embossing can be performed by known means such as pressing of an embossed plate. The concavo-convex pattern is not particularly limited, and examples thereof include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain, a hairline, and a striated groove.

Use of laminated sheet The laminated sheet of the present invention is used as an interior sheet for buildings such as walls, ceilings and floors; surface decorative sheet for furniture such as window frames, doors and handrails; surface decorative sheet for furniture, OA equipment, etc. can do. In particular, when the laminate sheet of the present invention is a foam laminate sheet, it is suitable as a decorative sheet (wallpaper) for walls in indoor spaces or a decorative sheet for ceilings. Moreover, when the laminated sheet of the invention is a non-foamed laminated sheet having a laminated structure shown in FIG. 3, it is suitable as a decorative sheet (wallpaper) for walls in indoor spaces or a decorative sheet for ceiling, as shown in FIG. In the case of a non-foamed laminated sheet having a laminated structure, it is suitable as a decorative sheet for floors in indoor spaces.

2. Unfoamed laminated sheet (unfoamed raw fabric)
The present invention also provides a laminated sheet in which a foaming agent-containing resin layer and a photocatalyst layer are laminated in order on a substrate. In the laminated sheet, the foamed resin layer is in a state before foaming in the foamed laminated sheet, and is used as a production raw material (unfoamed raw material) of the foamed laminated sheet.

  The structure of the laminated sheet and the composition of each layer are the same as those described above except that the foamed resin layer of the foamed laminated sheet is in a state before foaming (that is, a foaming agent-containing resin layer containing a resin component and a foaming agent). It is the same.

3. Method for Producing Laminate Sheet The laminate sheet of the present invention is produced by laminating a photocatalyst layer on a substrate. Specifically, the method for producing a laminated sheet of the present invention is carried out by laminating a layer to be formed between a base material and a photocatalyst layer on a base material, if necessary, and then laminating the photocatalyst layer. Is called. The method for forming and laminating the photocatalyst layer is as described above.

  In order to further improve the adhesion of the photocatalyst layer, a primer layer may be provided between the photocatalyst layer and the layer located on the lower surface thereof. The primer layer can be formed by applying a known primer agent to the surface of the lower layer on which the photocatalytic layer is laminated. Examples of the primer agent include acrylic-modified urethane resins (acrylic urethane resins), urethane-cellulose resins (for example, resins in which hexamethylene diisocyanate is added to a mixture of urethane and nitrified cotton), and acrylic and urethane block copolymers. A polymer etc. are mentioned. Further, the primer layer may contain additives such as fillers such as calcium carbonate and clay; flame retardants such as magnesium hydroxide; antioxidants; ultraviolet absorbers; Good. When providing a primer layer, about the thickness, for example, 0.01-10 micrometers, Preferably about 0.1-1 micrometer is mentioned.

  Below, although the manufacturing process of the lamination sheet of this invention is divided and demonstrated to a foam lamination sheet and a non-foaming lamination sheet, it is not restrict | limited by this. In the following description of the manufacturing method, the contents already described in the above section “1. Laminated sheet” regarding the method of forming each layer constituting the foamed laminated sheet and the non-foamed laminated sheet, the method of forming the air holes, etc. Will be omitted.

Production process of foamed laminated sheet First, a foaming agent-containing resin layer is formed on a substrate (first process). When the non-foamed resin layer A and / or the non-foamed resin layer B is provided, the non-foamed resin layer A and / or the non-foamed resin layer is used together with the foaming agent-containing resin layer using a multi-manifold type T die. It is desirable to coextrude B.

  When the foaming agent-containing resin layer is melt-extruded with a T-die extruder, the cylinder temperature and the die temperature may be appropriately set according to the type of resin component used, etc. Can be mentioned.

  Next, after a pattern layer is formed on the foaming agent-containing resin layer (or non-foamed resin layer A) as necessary, a photocatalyst layer is formed (second step). The photocatalyst layer is formed by mixing the composite material, the ionizing radiation curable resin, and a composition mixed with other components as necessary on the foaming agent-containing resin layer (or the non-foamed resin layer A). After coating, the ionizing radiation curable resin composition is cured by irradiating with ionizing radiation.

  Thus, an unfoamed laminated sheet in which the foaming agent-containing resin layer and the photocatalyst layer are sequentially laminated on the substrate is prepared.

  After the second step, the foaming agent-containing resin layer is converted into a foamed resin layer by foaming the foaming agent-containing resin layer (third step). The conditions for foaming the foaming agent-containing resin layer are appropriately set according to the type of foaming agent, and examples include a method of heat treatment at a heating temperature of about 210 to 240 ° C. and a heating time of about 20 to 80 seconds.

  In addition, in order to adjust the melt tension of the foaming agent-containing resin layer and easily obtain a desired foaming ratio, after the first step or the second step, if necessary, with respect to the foaming agent-containing resin layer Crosslinking treatment can be performed.

  Next, a foamed laminated sheet is produced by embossing as necessary. Embossing can be performed according to a known method. For example, an embossed pattern can be shaped by pressing the surface of the photocatalyst layer from the surface of the photocatalyst layer to the transparent resin layer side at 120 to 160 ° C. using an embossed roll having a specific uneven pattern.

Method for producing non-foamed laminated sheet First, a pattern layer is formed on a substrate as necessary, and then a non-foamed resin layer is formed (first step). When providing a picture pattern layer between the base material and the non-foamed resin layer, an adhesive layer is formed between the picture pattern layer and the non-foamed resin layer as necessary.

  Next, after a pattern layer is formed on the non-foamed resin layer as necessary, a photocatalyst layer is formed (second step).

  Moreover, when forming a concavo-convex pattern on a non-foamed laminated sheet, embossing may be performed before laminating the photocatalyst layer, followed by formation of the photocatalyst layer, or embossing after laminating the photocatalyst layer. May be. The embossing conditions are as described above.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1
Fibrous sheet heated to 90 ° C. so as to have a thickness of 8 μm / 75 μm / 8 μm in the order of non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B using a three-type three-layer T-die extruder. An extrusion film was formed on the substrate. Thereby, the laminated sheet which consists of non-foaming resin layer A / foaming agent containing resin layer / non-foaming resin layer B / fibrous sheet was obtained. As the fibrous sheet, wallpaper paper “WK-665, manufactured by Kojin” was used.

  Extrusion conditions were such that the cylinder temperature containing the resin for forming the non-foamed resin layer A was 140 ° C., the cylinder temperature containing the resin composition for forming the foaming agent-containing resin layer was 120 ° C., and non-foamed The cylinder temperature in which the resin for forming the resin layer B was accommodated was 100 ° C. The die temperature was 120 ° C. for all.

Each layer was formed using the following components.
The non-foamed resin layer A was formed of polyethylene (“Petrocene 208”, manufactured by Tosoh Corporation).

  The foaming agent-containing resin layer is composed of 80 parts by mass of polyethylene (“Petrocene 208”, manufactured by Tosoh Corporation), 20 parts by weight of an ethylene-α-olefin copolymer (“LUMITAC 54-1”, manufactured by Tosoh Corporation), calcium carbonate (“Whiteon H”). ”, 30 parts by mass of Shiroishi Kogyo Co., Ltd., 30 parts by mass of coloring agent (“ Tai Pure R350 ”, DuPont), 5 parts by mass of foaming agent (“ Vinole AC # 3 ”, manufactured by Eiwa Kasei Kogyo Co., Ltd.), foaming aid (“ Adeka Stub ”) OF-101 ”(manufactured by ADEKA) and 4 parts by mass of a crosslinking aid (“ OBSTER JUA702 ”, manufactured by JSR) were kneaded.

  The non-foamed resin layer B was formed of an ethylene-vinyl acetate copolymer (“Ultrasen 750”, manufactured by Tosoh Corporation).

  Next, a texture pattern was printed on the surface of the non-foamed resin layer A with a gravure printing machine using water-based ink ("Hydric", manufactured by Dainichi Seika Kogyo Co., Ltd.) to form a pattern pattern layer.

Thereafter, 5 parts by mass of apatite-coated anatase-type titanium oxide (hydroxyapatite: titanium oxide: silver = 15: 75: 10 (mass ratio)) supporting silver, 100 parts by mass of a bifunctional urethane acrylate oligomer, a matting agent ( An ionizing radiation curable resin composition containing 16 parts by mass of amorphous silica) and 2 parts by mass of a modified silicone resin (“KP-361”, manufactured by Shin-Etsu Silicone) is used with a gravure printing machine so as to be 3 g / m ^2. After coating, an electron beam with an acceleration voltage of 165 kV and an irradiation amount of 30 kG (3 Mrad) was irradiated to cure the ionizing radiation curable resin composition, thereby forming a photocatalyst layer (about 3 μm) on the outermost surface.

  Next, the obtained laminated sheet was heated in an oven (at 220 ° C. for 35 seconds) to foam the foaming agent-containing resin layer to form a foamed resin layer, and then a metal having a texture pattern on the photocatalyst layer Embossing was performed by pressing a roll and embossing to obtain a foamed laminated sheet.

Example 2
In the formation of the photocatalyst layer, 15 parts by mass of apatite-coated anatase-type titanium oxide (hydroxyapatite: titanium oxide: silver = 15: 75: 10 (mass ratio)) carrying silver is supported, 100 parts by mass of a bifunctional urethane acrylate oligomer, Example 1 except that an ionizing radiation curable resin composition containing 16 parts by mass of a matting agent (amorphous silica) and 2 parts by mass of a modified silicone resin (“KP-361”, manufactured by Shin-Etsu Silicone) was used. A foamed laminated sheet was obtained under the same conditions.

Example 3
In the formation of the photocatalyst layer, 3 parts by mass of apatite-coated anatase-type titanium oxide (hydroxyapatite: titanium oxide: silver = 15: 75: 10 (mass ratio)) on which silver is supported, 100 parts by mass of a bifunctional urethane acrylate oligomer, Example 1 except that an ionizing radiation curable resin composition containing 16 parts by mass of a matting agent (amorphous silica) and 2 parts by mass of a modified silicone resin (“KP-361”, manufactured by Shin-Etsu Silicone) was used. A foamed laminated sheet was obtained under the same conditions.

Example 4
A foamed resin composition comprising a polyvinyl chloride resin composition was coated on the surface of the fibrous sheet by a comma coating method to form an unfoamed resin layer having a thickness of 100 μm. This obtained the lamination sheet which consists of an unfoamed resin layer (polyvinyl chloride) / fibrous sheet. As the fibrous sheet, wallpaper paper “WK-665, manufactured by Kojin” was used. The polyvinyl chloride-containing resin composition is composed of 100 parts by mass of vinyl chloride resin (trade name: R-720, manufactured by Tosoh Corporation), 100 parts by mass of calcium carbonate (product name: Shiroishi Kogyo Co., Ltd., product name: Whiten H), and a foaming agent (manufactured by Otsuka Chemical). , Trade name: Uniform AZ Ultra) 3 parts by mass, antifungal agent (manufactured by Taisho Technos, trade name: Biosite 7663DS), 0.2 parts by weight, light stabilizer (manufactured by Adeka Argus Chemical, trade name: O-1305) 5 A material containing 20 parts by mass, 20 parts by mass of a diluent (manufactured by Shell Petroleum, trade name: Shellsol S) and 38 parts by mass of a plasticizer (diisononyl phthalate) was used.

  On the unfoamed resin layer of the resulting laminated sheet, a pattern layer and a photocatalyst layer were sequentially laminated under the same conditions as in Example 1. Next, the obtained laminated sheet is heated in an oven (at 220 ° C. for 35 seconds) to foam the foaming agent-containing resin layer to form a foamed resin layer, and then a metal roll having a textured pattern on the photocatalyst layer Was embossed by pressing and embossing to obtain a foamed laminated sheet.

Example 5
A foamed laminated sheet was obtained under the same conditions as in Example 1 except that the non-foamed resin layer A, the foaming agent-containing resin layer, and the non-foamed resin layer B were formed under the following conditions.

  The non-foamed resin layer A was formed by EMAA (“Nucleel N1560” (MMA content: 15 wt%), manufactured by Mitsui DuPont Polychemical Co., Ltd.).

  The foaming agent-containing resin layer is composed of 100 parts by mass of EVA (“Evaflex V406” (VA content: 20% by weight, MFR = 20), manufactured by Mitsui DuPont Polychemical Co., Ltd.), a flow modifier (“P-100”). 10 parts by mass, manufactured by Arakawa Chemical Co., Ltd., 20 parts by mass of titanium dioxide (pigment; “R103”, manufactured by DuPont), 5 parts by mass of foaming agent (“Uniform Ultra AZ3050I”, manufactured by Otsuka Chemical Co., Ltd.), and foaming assistant It was formed by 5 parts by mass of an agent (“ADK STAB OF-101”, manufactured by ADEKA Corporation).

  The non-foamed resin layer B was formed by EVA (“Evaflex EV150” (VA content: 33 wt%, melting point: 61 ° C.), manufactured by Mitsui DuPont Polychemical Co., Ltd.).

Comparative Example 1
In the formation of the photocatalyst layer, 6 parts by mass of hydroxyapatite, 12 parts by mass of anatase-type titanium oxide, 100 parts by mass of a bifunctional urethane acrylate oligomer, 16 parts by mass of a matting agent (amorphous silica), and a modified silicone resin (“KP- A foamed laminated sheet was obtained under the same conditions as in Example 1, except that an ionizing radiation curable resin composition containing 2 parts by weight of “361” (Shin-Etsu Silicone) was used.

Comparative Example 2
Silver-supported apatite-coated anatase-type titanium oxide (hydroxyapatite: titanium oxide: silver = 15: 75: 10 (mass ratio)) 5 parts by mass, urethane-acrylic resin 100 parts by mass, matting agent (amorphous silica) By applying and drying a resin composition containing 16 parts by mass and 2 parts by mass of a modified silicone resin (“KP-361”, manufactured by Shin-Etsu Silicone) using a gravure printing machine to 3 g / m ^2. A foamed laminated sheet was obtained under the same conditions as in Example 1 except that the photocatalyst layer was formed.

Comparative Example 3
Silver-supported apatite-coated anatase-type titanium oxide (hydroxyapatite: titanium oxide: silver = 15: 75: 10 (mass ratio)) 100 parts by mass, urethane-acrylic resin 100 parts by mass, matting agent (amorphous silica) By applying and drying a resin composition containing 16 parts by mass and 2 parts by mass of a modified silicone resin (“KP-361”, manufactured by Shin-Etsu Silicone) using a gravure printing machine to 3 g / m ^2. A foamed laminated sheet was obtained under the same conditions as in Example 1 except that the photocatalyst layer was formed.

Test example 1
In order to evaluate the functionality of the laminated sheets of Example 1-5 and Comparative Example 1-2, the stability of appearance properties, contamination resistance, initial adhesion, weather resistance, and antiallergen performance were measured.

Stability of appearance properties Each laminated sheet (2 × 5 cm) was placed in an indoor smoking space for 1 week, and the color tone change of the laminated sheet before and after the installation was visually confirmed. The results of visual observation were scored according to the following criteria, and the stability of appearance properties was evaluated. In addition, all the laminated sheets before installing in an indoor smoking space are white.

<Criteria for stability of appearance properties>
1: There is no coloring and no discoloration is observed.
2: Almost no coloration and almost no discoloration.
3: Although slightly colored, discoloration is not so noticeable.
4: Clear coloring is recognized and discoloration is conspicuous.
5: Remarkable coloring is recognized and discoloration is conspicuous.

Contamination resistance Gauze (3 × 3 cm) was placed on the photocatalyst layer of each laminated sheet (10 × 5 cm), about 1 ml of coffee and about 1 ml of soy sauce were dropped on the gauze as contaminants and left for 24 hours. Moreover, a line was directly drawn on the photocatalyst layer of each laminated sheet (10 × 5 cm) with a crayon and an aqueous sign pen and left for 24 hours. Thereafter, each laminated sheet photocatalyst layer was washed with water and a neutral detergent. The degree of soiling of the laminated sheet after wiping was visually confirmed, and scored according to the following criteria to evaluate stain resistance.

<Criteria for contamination resistance>
1: No dirt remains.
2: Dirt remains only slightly, but there is no problem in practical use because the dirt does not stand out.
3: Slight dirt remains, but the dirt is hardly noticeable and has no practical problem.
4: Remaining dirt can be clearly recognized and dirt is conspicuous.
5: Remarkable residual dirt was observed and the dirt was outstanding.

Initial adhesion and weather resistance adhesion Each laminated sheet (2 x 5 cm) is allowed to stand in a weather resistance tester (ultraviolet carbon arc lamp type light resistance tester), and the photocatalyst layer is irradiated with ultraviolet rays for about 500 hours. It was. Before and after UV irradiation, cellophane tape ("CT24", manufactured by Nichiban Co., Ltd.) was adhered to the surface of the photocatalyst layer of each laminated sheet with the belly of the finger and then peeled off. The appearance of the laminated sheet after peeling was visually observed And observed. The results of visual observation were scored according to the following criteria to evaluate adhesion. In addition, the adhesiveness of the lamination sheet before ultraviolet irradiation was made into initial stage adhesiveness, and the adhesiveness of the laminated sheet after ultraviolet irradiation was made into weather resistance adhesion.

<Judgment criteria for adhesion>
1: The area of the photocatalyst layer peeled by the cellophane tape is less than 30%.
2: The area of the photocatalyst layer peeled off by the cellophane tape is 30% or more and less than 50%.
3: The area of the photocatalyst layer peeled off by the cellophane tape is 50% or more and less than 70%.
4: The area of the photocatalyst layer peeled off by the cellophane tape is 70% or more and less than 90%.
5: The area of the photocatalyst layer peeled by the cellophane tape is 90% or more.
In the determination of adhesion, when the rating is 1 or 2, it corresponds to a level having the adhesion required for practical use.

Anti-allergen performance Each laminated sheet was immersed in an aqueous solution containing mite allergen (Del f2) (hereinafter, allergen solution) and incubated at room temperature for 24 hours. Thereafter, the amount of mite allergen in each allergen solution after 24 hours was measured by ELISA. The ratio of the amount of mite allergen reduction after immersion of the laminated sheet to the amount of mite allergen before immersion of the laminated sheet was calculated as an allergen reduction rate and scored according to the following criteria to evaluate antiallergen performance.

<Criteria for anti-allergen performance>
1: Allergen reduction rate is 80% or more 2: Allergen reduction rate is 60% or more and less than 80% 3: Allergen reduction rate is 40% or more and less than 60% 4: Allergen reduction rate is less than 40%

  The obtained results are shown in Table 1. In the laminated sheet of Comparative Example 1-3, neither the appearance property stability nor the antiallergen performance was good. In particular, in the laminated sheets of Comparative Examples 1 and 3, since the amounts of the inorganic adsorbent and the photocatalyst were larger than those in Examples and Comparative Example 2, adsorption due to these materials occurred, and appearance properties and contamination resistance were reduced. Further, in the laminated sheet of Comparative Example 2, although the appearance property was relatively good, the allergen decomposition effect was low and the photocatalytic function was inferior. On the other hand, in the laminated sheet of Example 1-5, the stability of the appearance was good and the anti-allergen performance was excellent. Furthermore, all of the laminated sheets of Example 1-5 had good contamination resistance, initial adhesion, and weather resistance adhesion.

  Further, from the comparison of the evaluation results of the antiallergen performance of Example 1 and Comparative Example 2, it is also clear that the photocatalytic function is efficiently expressed by adopting an ionizing radiation curable resin as the resin used for the photocatalyst layer. It became. Although I do not want a limited interpretation regarding this effect, the reactive functional group derived from the ionizing radiation curable resin in the photocatalyst layer contributed to the improvement of the antiallergen performance and the like, and improved the photocatalytic function. It is presumed that the photocatalytic function was enhanced by the photocatalytic layer containing the ionizing radiation curable resin.

  From the above results, by forming a photocatalyst layer using an ionizing radiation curable resin together with a composite material in which a photocatalyst is coated with an inorganic adsorbent, an excellent photocatalytic function can be exhibited and self-degradation of the photocatalyst layer is suppressed. It became clear that we could do it.

1 Base material 2 Non-foamed resin layer B
3 Foamed resin layer 4 Non-foamed resin layer A
5 picture pattern layer 6 photocatalyst layer 7 non-foamed resin layer 8 adhesive layer

Claims (10)

On a base material, a photocatalyst layer containing a composite material of the photocatalyst formed by coating with an inorganic adsorbent ionizing radiation curing resin Ri Na are stacked,
The laminated sheet, wherein the photocatalyst layer further contains at least one silicone compound selected from the group consisting of a silicone resin and a silicone-modified resin . On the substrate, a photocatalyst layer containing a composite material obtained by coating a photocatalyst with an inorganic adsorbent and an ionizing radiation curable resin is laminated,
To ionizing radiation curable resin 100 parts by weight, the composite material is contained in a proportion of 3 to 15 parts by weight, the product layer sheet. On the substrate, a photocatalyst layer containing a composite material obtained by coating a photocatalyst with an inorganic adsorbent and an ionizing radiation curable resin is laminated,
Wherein the composite material, an inorganic adsorbent is hydroxyapatite, a photocatalyst is titanium oxide, the product layer sheet. On the substrate, a photocatalyst layer containing a composite material obtained by coating a photocatalyst with an inorganic adsorbent and an ionizing radiation curable resin is laminated,
It said composite material is further supporting a metal, the product layer sheet.   The laminated sheet according to claim 4, wherein the metal is silver. On the substrate, a photocatalyst layer containing a composite material obtained by coating a photocatalyst with an inorganic adsorbent and an ionizing radiation curable resin is laminated,
Ionizing radiation-curable resin is a 2-6 functional urethane (meth) acrylate oligomer, product layer sheet. On the substrate, a photocatalyst layer containing a composite material obtained by coating a photocatalyst with an inorganic adsorbent and an ionizing radiation curable resin is laminated,
The thickness of the photocatalyst layer is 2 to 5 [mu] m, product layer sheet. On the substrate, a photocatalyst layer containing a composite material obtained by coating a photocatalyst with an inorganic adsorbent and an ionizing radiation curable resin is laminated,
Between the photocatalyst layer and the substrate, the blowing agent-containing resin layer containing a resin component and a blowing agent is provided, the product layer sheet. On the substrate, a photocatalyst layer containing a composite material obtained by coating a photocatalyst with an inorganic adsorbent and an ionizing radiation curable resin is laminated,
Between the photocatalyst layer and the substrate, the foamed resin layer is provided, the product layer sheet. Including on a substrate, a composite photocatalyst formed by coating with an inorganic adsorbent, and ionizing radiation curable resin, and at least one silicone compound selected from the group consisting of silicone resin and silicone-modified resin The manufacturing method of a lamination sheet including the process of laminating | stacking a photocatalyst layer.