JP5929422B2 - Antiallergenic decorative sheet, decorative plate, and ionizing radiation curable resin composition - Google Patents

Description

  The present invention relates to a decorative sheet, a decorative plate, and an ionizing radiation curable resin composition having antiallergenic properties.

  In recent years, building materials for interior and exterior, such as building flooring and wall materials, are required to have antiallergenic properties that remove or inactivate allergens such as mites and pollen that cause allergic diseases. ing. As a building material having such antiallergenic properties, a building material is known in which an antiallergen agent composed of a zirconium salt is applied to the surface of a wood material such as a wood material or plywood (for example, see Patent Document 1). ). However, since such a building material is obtained by simply applying an anti-allergen agent, it easily peels off and has poor durability.

  In order to solve such problems, a photocurable resin composition in which a water-insoluble polymer antiallergen agent having a phenolic hydroxyl group is mixed with a photopolymerizable oligomer or the like is applied to a woody substrate, and light is applied. Cured flooring has been developed (see, for example, Patent Documents 2 and 3). However, like the flooring materials described in Patent Documents 2 and 3, simply adding an antiallergenic agent to the photocurable resin composition cannot provide sufficient antiallergenicity, and it is suitable for interior and exterior building materials. The demand for imparting excellent antiallergenicity was still unsatisfactory.

  With such a conventional technology as a background, development of a decorative sheet capable of effectively exhibiting the action of an anti-allergen agent in a decorative sheet used for interior and exterior building materials such as flooring is eagerly desired.

JP 2001-212806 A JP 2008-239721 A JP 2010-173115 A

  An object of the present invention is to provide a decorative sheet having high antiallergenicity, a decorative board using the same, and an ionizing radiation curable resin composition capable of imparting high antiallergenicity to an article to be coated. is there.

  As a result of intensive studies to achieve the above object, the present inventors have determined that a urethane (meth) acrylate oligomer obtained from a polyisocyanate having a molecular weight of 250 or less and a (meth) acrylate compound having a hydroxy group is a curable component It has high anti-allergenicity by laminating a cured product of an ionizing radiation curable resin composition containing the curable component and an anti-allergen agent having a phenolic hydroxyl group on the substrate as an anti-allergen functional layer. It has been found that a decorative sheet can be obtained. The present invention has been completed by further studies based on such knowledge.

That is, the present invention provides a decorative sheet, an ionizing radiation curable resin composition, and a decorative board of the following aspects.
Item 1. An anti-allergen functional layer on a substrate, the anti-allergen functional layer is a cured product of an ionizing radiation curable resin composition containing a curable component and an anti-allergen agent having a phenolic hydroxyl group, and the curable component A decorative sheet comprising a urethane (meth) acrylate oligomer obtained from a polyisocyanate having a molecular weight of 250 or less and a (meth) acrylate compound having a hydroxy group.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the polyisocyanate has a molecular weight of 150 to 225.
Item 3. Item 3. The decorative sheet according to Item 1 or 2, wherein the polyisocyanate is a monocyclic alicyclic polyisocyanate.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the urethane (meth) acrylate oligomer has 2 to 10 functional groups.
Item 5. The item according to any one of Items 1 to 4, wherein the ionizing radiation curable resin composition further comprises a urethane (meth) acrylate oligomer obtained from a polyisocyanate having a molecular weight of more than 250 and a (meth) acrylate compound having a hydroxy group as a curable component. The decorative sheet as described.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the antiallergen is a polyphenol compound supported on an inorganic solid acid.
Item 7. Item 7. The decorative sheet according to Item 6, wherein the polyphenol compound is at least one selected from catechin and tannic acid.
Item 8. Item 8. The decorative sheet according to Item 6 or 7, wherein the inorganic solid acid is a phosphate.
Item 9. Item 9. The decorative sheet according to any one of Items 1 to 8, wherein the compounding amount of the anti-allergen agent is 1 to 30 parts by mass with respect to 100 parts by mass of the curable component.
Item 10. An ionizing radiation curable resin composition comprising a urethane (meth) acrylate oligomer comprising a curable component and an antiallergen agent and obtained from a polyisocyanate having a molecular weight of 250 or less and a (meth) acrylate compound having a hydroxy group as the curable component .
Item 11. Item 11. The ionizing radiation curable resin composition according to Item 10, wherein the polyisocyanate has a molecular weight of 150 to 225.
Item 12. Item 12. The ionizing radiation curable resin composition according to Item 10 or 11, wherein the polyisocyanate is a monocyclic alicyclic polyisocyanate.
Item 13. Item 13. The ionizing radiation curable resin composition according to any one of Items 10 to 12, wherein the urethane (meth) acrylate oligomer has 2 to 10 functional groups.
Item 14. Item 10. The item according to any one of Items 10 to 13, wherein the ionizing radiation curable resin composition contains a urethane (meth) acrylate oligomer obtained from a polyisocyanate having a molecular weight of more than 250 and a (meth) acrylate compound having a hydroxy group as a curable component. The ionizing radiation curable resin composition described.
Item 15. Item 15. The ionizing radiation curable resin composition according to any one of Items 10 to 14, wherein the antiallergen is a polyphenol compound supported on an inorganic solid acid.
Item 16. Item 16. The ionizing radiation curable resin composition according to Item 15, wherein the polyphenol compound is at least one selected from catechin and tannic acid.
Item 17. Item 17. The ionizing radiation curable resin composition according to Item 15 or 16, wherein the inorganic solid acid is a phosphate.
Item 18. Item 10. A decorative board obtained by attaching the decorative sheet according to any one of Items 1 to 9 to a wooden substrate.

  The decorative sheet of the present invention has high anti-allergen properties and is effective for removing or reducing allergens in living spaces. Furthermore, the decorative sheet of the present invention also has various properties (weather resistance, solvent resistance, stain resistance, flexibility) required for practical use.

It is a schematic diagram which shows the cross section of the decorative sheet of this invention. It is a schematic diagram which shows the cross section of the decorative board of this invention.

[Decorative sheet]
The anti-allergenic decorative sheet of the present invention has an anti-allergen functional layer on a substrate, and the anti-allergen functional layer includes an anti-allergen agent having a curable component and a phenolic hydroxyl group. A urethane (meth) acrylate oligomer (hereinafter referred to as “urethane (meth) acrylate oligomer A”) obtained from a polyisocyanate having a molecular weight of 250 or less and a (meth) acrylate compound having a hydroxy group as the curable component. In some cases).

  FIG. 1 is a schematic view showing an example of a preferred embodiment of the decorative sheet having antiallergenic properties of the present invention. The decorative sheet 10 of the present invention is provided with an anti-allergen functional layer 4 on a substrate 1, and the anti-allergen functional layer 4 has an embossed pattern 5. The substrate 1 is composed of a substrate 1A, The printing layer 2, the adhesive layer 3, and the base material 1B are laminated in order.

  Further, in the decorative sheet of the present invention, a backer layer 6 made of a resin layer is laminated on the back surface of the base material 1 (the surface opposite to the surface on which the anti-allergen functional layer 4 is laminated) as necessary. May be. Hereinafter, the configuration of the decorative sheet of the present invention will be described in detail.

≪Base material 1≫
The substrate 1 used in the present invention is not particularly limited as long as it is used for a conventionally known decorative sheet made of paper or thermoplastic resin. Examples of the paper substrate include backing paper, flame retardant paper, etc. Examples of the thermoplastic resin constituting the substrate include polyester resins, polyolefin resins such as polypropylene resins and polyethylene resins, ( A resin sheet made of a thermoplastic resin such as a (meth) acrylic resin, a polyurethane resin, a polyester resin, or a polyamide resin can be used. Among these, when used as a flooring, a polyolefin-based resin is preferable in terms of cost and sheet flexibility, and when a strength as a sheet such as scratch resistance is required, a polyester-based resin is preferable. It is used properly according to the.

Moreover, as the base material 1, the sheet | seat of the multilayer structure obtained by laminating | stacking two or more resin sheets can also be used. In this case, the resin used for two or more resin sheets may be the same or different. Of these, polyolefin resins can be preferably used. In the case of a two-layer structure, the combination of the resins is preferably polyethylene-polyethylene, polyethylene-polypropylene, or polypropylene-polypropylene.
In the case of a double-layered sheet, for example, in the case of a two-layer structure, an easy-adhesion layer is provided on the surface of the substrate 1A by providing a corona discharge treatment, and the resin substrate 1A is printed with a solid layer and / or a pattern layer. After the layer 2 is formed and then the adhesive layer 3 is provided as necessary, the substrate 1B is obtained by adhesion and pressure bonding by a method such as extrusion lamination, dry lamination, wet lamination, thermal lamination, or the like. The base materials 1A and 1B may be colored or non-colored, and are preferably colored from the viewpoint of improving design properties.

The thickness of the substrate 1 is usually 20 to 300 μm and is usually applied in terms of workability, flexibility and strength, and more preferably about 50 to 200 μm. When the base material 1 is a multi-layered sheet, the total thickness of the base materials constituting each layer may be within the above range, and the thicknesses of these base materials may be the same or different. The thickness of the base material constituting each layer (base materials 1A and 1B in the case of a two-layer structure) alone is preferably 20 to 150 μm, more preferably 40 to 100 μm.
The surface of the substrate 1 may be subjected to so-called easy adhesion treatment such as corona discharge treatment or plasma treatment, and an easy adhesion layer such as a primer layer or an anchor layer is formed on the surface of the substrate. It may be provided.

≪Print layer 2≫
The printed layer 2 is an arbitrary layer provided as desired for the purpose of improving the design of the decorative sheet, and is usually provided on the substrate 1. Moreover, when the base material 1 is a sheet having a multilayer structure described above, the printed layer 2 may be provided between the base materials constituting each layer as shown in FIG. It may be provided on the surface closest to the anti-allergen functional layer.

The printing layer 2 is composed of a pattern layer and / or a solid layer, and is formed by printing various patterns using ink and a printing machine. As the pattern of the pattern layer, a grain pattern simulating the surface of a rock such as a grain pattern, marble pattern (for example, travertine marble pattern), a fabric pattern simulating a texture or cloth pattern, a tiled pattern, a brickwork pattern, etc. There are also patterns such as parquet and patchwork that combine these. In addition, the solid layer is a layer that is uniformly and uniformly coated over the entire surface, and has the effect of concealing the substrate on which the base material or the decorative sheet is bonded in addition to the effect of improving the design. From the viewpoint of improving design properties, it is preferable to provide a pattern layer and a solid layer.
As a printing method, any of normal rotary printing such as gravure printing, flexographic printing, silk screen printing, and sheet-fed printing can be applied.
The ink used for printing the pattern layer is not particularly limited, and the binder includes inorganic pigments such as yellow lead, cadmium yellow, yellow iron oxide, titanium oxide, bitumen, carbon black, red pattern, disazo pigments, Mixing organic pigments such as indolinone, polyazo pigments, quinacridone, phthalocyanine blue, aluminum powder, copper powder, finely cut pieces of metal-deposited synthetic resin film, titanium dioxide-coated mica, and pigments with pearly luster such as fish scale foil Used.

≪Adhesive layer 3≫
As described above, the adhesive layer 3 is a layer provided as necessary when two or more base materials are laminated when the base material employs a sheet having a multilayer structure. Preferred examples of the adhesive include urethane, acrylic, acrylic / polyurethane, polyester, polyamide, polystyrene, and cellulose. These resins can be used singly or as a mixture of two or more.

<< Backer layer 6 >>
The backer layer 6 is a resin layer provided on the back surface of the substrate 1 (the surface opposite to the surface on which the anti-allergen functional layer 4 is laminated). By laminating such a backer layer 6, the effect of unevenness inevitably existing on the surface of the adherend is alleviated when the decorative sheet is attached to the adherend (especially woody plywood) as a decorative material. can do. In particular, when used as a decorative sheet for floors, the backer layer also serves as a layer that imparts cushioning properties to the decorative sheet.

  The resin for forming the backer layer 6 is not particularly limited, but a thermoplastic resin is preferable. For example, polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate , Polyethylene naphthalate-isophthalate copolymer, polyimide, polystyrene, polyamide, ABS and the like.

  For the backer layer 6, for example, the resin component may be formed by a calendar method, an inflation method, a T-die extrusion method or the like, or a pre-molded resin film may be used.

  When the backer layer 6 is formed by extrusion molding of a molten resin, for example, extrusion molding using a T die can be suitably used. Moreover, when the backer layer 6 is a multilayer, for example, a multi-manifold type or feed block type T-die may be used to perform multilayer simultaneous extrusion. When making the backer layer 6 into a multilayer, it is preferable to make the layer nearest to the back surface of a base material sheet into an easily bonding resin layer, for example. Such an improvement can be achieved by, for example, blending a known thermoplastic elastomer into a layer that forms an easily adhesive resin layer. The type of the thermoplastic elastomer is not particularly limited, and can be widely selected from those that are highly compatible with the resin constituting the backer layer and can contribute to improvement in adhesion to the base sheet.

  In addition, when the backer layer 6 formed by extrusion molding is difficult to adhere to the back surface of the base material sheet by adhesion by thermal fusion, the backer layer 6 and the thermoplastic resin base material 1 are increased as necessary in order to enhance the adhesion. An adhesive layer may be provided on the well.

  Although the thickness of the backer layer 6 should just be 100 micrometers or more, about 150-600 micrometers is preferable and about 250-400 micrometers is more preferable. The backer layer 6 preferably has a tensile elastic modulus of 1000 MPa or more, and preferably 1500 MPa or more. The upper limit of the tensile elastic modulus is not particularly limited, but may be about 2500 MPa.

≪Anti-allergen functional layer 4≫
The anti-allergen functional layer 4 is a layer provided on the base material 1 through a primer layer as necessary, and is a layer that imparts anti-allergen properties to the decorative sheet of the present invention. The anti-allergen functional layer 4 is also superior in terms of properties such as weather resistance, solvent resistance, and contamination resistance, and is a layer that imparts other practical performance to the decorative sheet.

  The anti-allergen functional layer 4 includes a curable component and an anti-allergen agent, and is composed of a cured product obtained by curing an ionizing radiation curable resin composition including the urethane (meth) acrylate oligomer A as the curable component. Is a layer.

<Urethane (meth) acrylate oligomer A>
Urethane (meth) acrylate oligomer A is an oligomer obtained from a polyisocyanate having a molecular weight of 250 or less and a (meth) acrylate compound having a hydroxy group, and is a curable component exhibiting ionizing radiation curability. Here, ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays.

  The urethane (meth) acrylate oligomer A has a radically polymerizable unsaturated group, and in the present invention, this radically polymerizable unsaturated group has 2 to 10, that is, a 2 to 10 functional group is preferable. Preferably it is a 4-8 functional thing, More preferably, it is 4-6 functional, Most preferably, it is a 6 functional thing. When the number of functional groups is within the above range, excellent antiallergenicity can be obtained. In addition, the urethane (meth) acrylate oligomer A having the functional group number within the above range is effective in providing properties such as weather resistance, solvent resistance, and contamination resistance that are practically required.

  The number average molecular weight (number average molecular weight in terms of polystyrene measured by GPC method) of the urethane (meth) acrylate oligomer A is preferably about 500 to 5000, more preferably about 600 to 5000, and still more preferably. It is 600-3000, More preferably, it is 700-2500, Especially preferably, it is 800-1500, Most preferably, it is 850-1500. By using such urethane (meth) acrylate oligomer A together with the anti-allergen agent described later, a further excellent anti-allergenic property can be obtained. Moreover, since the ionizing radiation curable resin composition has an appropriate thixotropy, the formation of the antiallergen functional layer is facilitated.

(Polyisocyanate)
The molecular weight of the polyisocyanate may be an isocyanate compound having a molecular weight of 250 or less and having two or more isocyanate groups, and the molecular weight is preferably in the range of 100 to 250, more preferably 150 to 250, and particularly preferably 150 to 250. 225.
Such polyisocyanates include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene. Diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl- Aliphatic polyisocyanates such as 1,5-pentamethylene diisocyanate; 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate Monocyclic alicyclic rings such as nate, methyl-2,6-cyclohexane diisocyanate, 1,2-bis (isocyanate methyl) cyclohexane (hydrogenated XDI), 1,3-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate, norbornane diisocyanate Formula isocyanate: m-phenylene diisocyanate, p-phenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene Aromatic diisocyanates such as isocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate are preferred. Among these, aliphatic polyisocyanate and monocyclic alicyclic polyisocyanate are preferable, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated XDI are more preferable, and hexamethylene diisocyanate and isophorone are more preferable from the viewpoint of obtaining further excellent antiallergenicity. More preferred is diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

((Meth) acrylate compound having a hydroxy group)
Examples of (meth) acrylate compounds having a hydroxy group include hydroxy groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Alkylalkylates; polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; glycerol mono (meth) acrylate, glycerol di (meth) acrylate, glycerol methacrylate acrylate, 2- (Meth) acryloylethyl-2-hydroxyethyl phthalate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Meth) acrylate, cyclohexanedimethanol mono (meth) acrylate are preferably mentioned. Among these, 2-hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate from the viewpoint of obtaining excellent antiallergenicity and solvent resistance. Is preferred. These (meth) acrylate compounds may be used alone or in combination of two or more.

(Polyol)
In the present invention, a polyol can be used in obtaining the urethane (meth) acrylate oligomer A. As the polyol, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl- Aliphatic diols such as 1,3-hexanediol; alicyclic diols such as 1,4-cyclohexanedimethanol and tricyclodecane dimethanol; aromatic diols such as xylylenediol; diethylene glycol, triethylene glycol, polyethylene glycol, Preferred examples include polyether glycols such as polypropylene glycol and polytetramethylene glycol; trimethylolpropane, trimethylolethane, glycerin, hexanetriol, pentaerythritol and the like. These polyols may be used alone or in combination.

  The urethane (meth) acrylate oligomer A obtained by using a polyol is improved in flexibility, but the stain resistance and solvent resistance may be lowered. Therefore, in consideration of flexibility, contamination resistance, solvent resistance, and the like that should be provided in the decorative sheet of the present invention, the necessity and amount of use of the polyol may be appropriately determined. From the viewpoint of obtaining excellent solvent resistance, among the above-mentioned polyols, polyols having a molecular weight of 100 to 250, particularly 1,6-hexanediol and 3-methyl-1,5-pentanediol are used. Is preferred.

(Oligomer synthesis)
The urethane acrylate oligomer A used in the present invention can be obtained by reacting the above-described polyisocyanate having a molecular weight of 250 or less with a (meth) acrylate having a hydroxy group and, if necessary, a polyol.
For example, the urethane acrylate oligomer A is prepared by reacting the above polyisocyanate and (meth) acrylate, and if necessary, the polyol at the same time, or reacting the polyisocyanate and (meth) acrylate, It can be obtained by a method of reacting a polyol. In the case of using a polyol, for example, a polyisocyanate and a polyol are reacted under conditions such that the isocyanate group is excessive with respect to the hydroxyl group derived from the polyol to obtain a urethane oligomer having an isocyanate group at the terminal. Then, it can also be obtained by a method of reacting the isocyanate group with the hydroxy group of (meth) acrylate.

The compounding ratio of the polyisocyanate and the (meth) acrylate having a hydroxy group is usually about 1: 1 to 1: 2, and preferably 1: 1 to 1: 1.6. is there.
Moreover, when using a polyol, the usage-amount of polyisocyanate, (meth) acrylate, and a polyol is the molar ratio of an isocyanate group: hydroxyl group as for the compounding ratio of polyisocyanate and a polyol, Preferably it is 1.3: 1-3: 1. More preferably, the ratio of the terminal isocyanate group of the urethane oligomer obtained by the reaction of polyisocyanate and polyol and the hydroxy group of (meth) acrylate is such that the ratio is 1.5: 1 to 2: 1. The amount is preferably set to a ratio of about 1: 1 to 1: 1.5.

The reaction may be performed at a temperature at which the urethanization reaction is performed, usually about 30 to 90 ° C. It is also possible to use urethanation catalysts such as naphthenic acid metal catalysts such as cobalt naphthenate, tin catalysts such as dibutyltin dilaurate, and amine catalysts such as triethylamine.
Further, a polymerization inhibitor can be added to control the thermal polymerization reaction of the (meth) acryloyl group. Preferred examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether. The usage-amount of a polymerization inhibitor is about 50-5000 ppm normally with respect to (meth) acrylate.

<Urethane (meth) acrylate oligomer B>
The ionizing radiation curable resin composition used in the present invention has, in addition to the urethane acrylate oligomer A, a polyisocyanate having a molecular weight of more than 250 and a hydroxy group as a curable component for the purpose of improving the flexibility of the decorative sheet. It is preferable to contain an oligomer (hereinafter, also referred to as “urethane (meth) acrylate oligomer B”) obtained from the (meth) acrylate compound it has. As the urethane (meth) acrylate oligomer B, for example, the number of functional groups is 2 to 4, and the number average molecular weight is preferably 900 to 5000, more preferably 900 to 3000, and still more preferably 900 to 2000. .

  The polyisocyanate used for the production of the urethane (meth) acrylate oligomer B is not particularly limited as long as the molecular weight is larger than 250, but examples thereof include dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI). A bialicyclic polyisocyanate is mentioned.

  Moreover, the (meth) acrylate compound which has a hydroxyl group used for manufacture of the urethane (meth) acrylate oligomer B is the same as that used in the urethane (meth) acrylate oligomer A.

  Furthermore, the urethane (meth) acrylate oligomer B may contain a polyol as a constituent component. The polyol used for the urethane (meth) acrylate oligomer B is the same as that used for the urethane (meth) acrylate oligomer A.

  The urethane (meth) acrylate oligomer B can be obtained by reacting a polyisocyanate having a larger molecular weight of 250, a (meth) acrylate having a hydroxy group, and a polyol as required, according to a conventional method. Specific reaction conditions are the same as those of the urethane (meth) acrylate oligomer A except for the types of components used.

  The content of the urethane (meth) acrylate oligomer B is preferably 1 to 60% by mass, more preferably 5 to 55% by mass, and more preferably 5 to 45% with respect to the total amount with the urethane (meth) acrylate oligomer A. More preferred is mass%. When the content is within the above range, the flexibility can be improved while maintaining the high antiallergenicity of the decorative sheet of the present invention.

<Other curable components>
The ionizing radiation curable resin composition used in the present invention can contain curable components other than the urethane (meth) acrylate oligomers A and B described above as long as the effects of the present invention are not inhibited.
Preferred examples of such a curable component include polymerizable monomers, polymerizable oligomers and prepolymers commonly used as ionizing radiation curable compounds.

  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. 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. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

Next, examples of the polymerizable oligomer include oligomers having radically polymerizable unsaturated groups in the molecule, such as epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
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 type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

  In the present invention, a monofunctional (meth) acrylate can be appropriately used in combination with the polyfunctional (meth) acrylate and the like within a range that does not impair the object of the present invention, for the purpose of reducing the viscosity. . These monofunctional (meth) acrylates may be used alone or in combination of two or more.

<Anti-allergen>
The anti-allergen agent used in the present invention has a phenolic hydroxyl group, that is, a water-insoluble polymer having a phenolic hydroxyl group, and the phenolic hydroxyl group adsorbs an allergenic substance and inactivates it. There is no particular limitation as long as it functions. Such anti-allergen agents include those composed of polyphenol compounds, which are organic compounds having a plurality of phenolic hydroxyl groups in the molecule, that is, hydroxyl groups bonded to aromatic rings such as benzene rings and naphthalene rings, for example, poly ( Preferred examples include polyphenol-based polymers such as 4-vinylphenol) and poly (vinyl 3,4,5-hydroxybenzoate). As a commercially available anti-allergen, “Marcalinker M (trade name)” (Maruzen Petrochemical Co., Ltd.) can be used, and this anti-allergen is effective against various allergens such as mites and pollen. It works.

  Also preferred are those in which a polyphenol compound is supported on an inorganic solid acid. An anti-allergen agent in which a polyphenol compound is supported on an inorganic solid acid can be provided with excellent anti-allergenic properties, and further can be provided with further excellent weather resistance, solvent resistance, and contamination resistance. Examples of the polyphenol compound used in such an embodiment include low molecular weight polyphenols called catechins such as epicatechin, gallotannin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, and high molecular weight tannic acid. It is preferably mentioned from the viewpoint of having excellent antiallergenicity and being easily and inexpensively available industrially. As the polyphenol compound, those described above can be used alone or in combination. Among these, tannic acid is preferable from the viewpoint of antiallergenicity.

  The inorganic solid acid is an inorganic substance, and has an acid site or an active site that releases hydrogen ions on its surface and develops acidity. For example, zeolites such as H-substituted Y zeolite, H-substituted ZSM-5 zeolite, zirconium phosphate, aluminum phosphate, tin phosphate, cerium phosphate, titanium phosphate and other phosphates, antimonic acid, Preferable examples include composite oxides such as silica alumina, silica titania, silica zirconia, titania alumina, and titania zirconia. Among these, from the viewpoint of excellent heat resistance and high solid acidity, zeolites and composite oxides are preferable, zirconium phosphate having particularly strong acid strength is preferable, and layered zirconium phosphate having a crystal system having a layered structure is preferable. preferable.

  Examples of the shape of the inorganic solid acid include powder, lump, plate, and fiber, but it is preferably powder from the viewpoint of handling. In the case of powder, the average particle size is preferably 0.01 to 50 μm, and more preferably 0.02 to 20 μm. When the average particle size is within the above range, handling is easy and it is preferable from the viewpoint of obtaining excellent antiallergenicity.

  In the present invention, the weight ratio of the polyphenol compound and the inorganic solid acid is preferably 10:90 to 95: 5, more preferably 20:80 to 80:20, and still more preferably 20:80 to 40:60. is there. When the weight ratio is within the above range, particularly excellent antiallergenicity can be obtained due to the synergistic effect of the polyphenol compound and the inorganic solid acid.

  The above-mentioned anti-allergen agent is also available as a commercial product, for example, “Allelimbu (trade name)” (manufactured by Toagosei Co., Ltd.), which is a combination of a polyphenol compound and a zirconium compound, is mentioned as a commercial product. .

  The compounding amount of the anti-allergen agent is preferably 1 to 30 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total amount of the curable components in the ionizing radiation curable resin composition. Preferably it is 8-25 mass parts, Most preferably, it is 8-15 mass parts. In this invention, even if it is such a small compounding quantity, the outstanding antiallergenicity is obtained by using said urethane (meth) acrylate oligomer A as a sclerosing | hardenable component. Further, in the present invention, since it is not necessary to use a large amount of the anti-allergen agent in this way, it is possible to suppress a decrease in the weather resistance and contamination resistance of the anti-allergen functional layer containing the anti-allergen agent, and an excellent anti-allergenic agent. Allergenicity can also be expressed over a long period of time.

<Various additives>
Additives such as UV absorbers, light stabilizers, antibacterial agents, antiwear agents, matting agents, or anti-settling agents for the anti-allergen functional layer composition to meet various requirements depending on the application Can be contained.
The anti-allergen functional layer composition used in the present invention may contain various additives as long as the performance is not impaired. Examples of various additives include polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, and solvents. Etc.
When an ultraviolet curable resin is used as the curable resin, it is desirable to add about 0.1 to 5 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the curable resin. The agent can be appropriately selected from those conventionally used.

(Formation of anti-allergen functional layer)
The anti-allergen functional layer 4 of the decorative sheet of the present invention includes the ionizing radiation curable resin composition described above, that is, the ionizing radiation curable resin containing the urethane (meth) acrylate oligomer A and the anti-allergen agent having a phenolic hydroxyl group as essential components. A resin composition is applied on a substrate via an easy-adhesion layer such as a primer layer as necessary, and cured by irradiation with ionizing radiation or the like. Specifically, the anti-allergen functional layer 4 is formed as follows.

  Application of the ionizing radiation curable resin composition forming the anti-allergen functional layer, gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., so that the thickness after curing is usually about 5 to 30 μm Of known methods, preferably by gravure coating. Moreover, it is preferably 10 to 20 μm from the viewpoint of stain resistance and scratch resistance. When the ionizing radiation curable resin composition contains a solvent, it is preferable to irradiate the ionizing radiation after the coating layer is preheated and dried with a hot air dryer or the like after coating.

The anti-allergen functional layer 4 is formed by curing the uncured layer formed by applying the ionizing radiation curable resin composition by irradiation with ionizing radiation. Here, when an electron beam is used for curing, the accelerating voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but it is preferable to cure the uncured layer usually at an accelerating voltage of about 70 to 300 kV.
The irradiation dose is preferably such that the crosslinking density of the ionizing radiation curable resin 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).

The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.

  When ultraviolet rays are used as 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.

≪Primer layer≫
When providing the anti-allergen functional layer 4 on the base material 1, in order to ensure adhesiveness, a primer layer (not shown) is provided between the base material 1 and the anti-allergen functional layer 4 as an easy adhesion layer. Can be provided.

  As the resin for forming the primer layer, urethane resin, (meth) acrylic resin, (meth) acrylic-urethane copolymer resin, urethane resin mainly composed of acrylic polyol, vinyl chloride-vinyl acetate copolymer, polyester Resin, butyral resin, chlorinated polypropylene, chlorinated polyethylene, etc. are used, and if necessary, those containing a constitutional content, solvent, stabilizer, plasticizer, curing agent etc. in these resins should be used as a primer. Can do.

  For the formation of the primer layer, the primer resin composition described above is used as it is or dissolved or dispersed in a solvent, and is applied to a substrate by a known printing method, coating method, etc., dried and cured. Can be done by. The thickness of the primer layer is usually in the range of 0.1 to 5 μm, and particularly preferably in the range of 0.5 to 3 μm. When forming this primer layer on the substrate, the substrate 1 is subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment. Further, the adhesiveness with the substrate can be enhanced.

  In addition, when the anti-allergen functional layer 4 is laminated on the primer layer, in order to ensure adhesion between the anti-allergen functional layer 4 and the primer layer, the anti-allergen functional layer is applied to the surface of the primer layer by the above-described easy adhesion treatment. The primer layer can be kept semi-cured, and then the anti-allergen functional layer is applied and then ionized radiation is applied to cure the anti-allergen functional layer. By doing so, the anti-allergen functional layer and the primer layer 2 can be integrated, and the adhesiveness between both can also be improved.

≪Embossed pattern 5≫
In this way, the decorative sheet of the present invention in which the anti-allergen functional layer is laminated on the base material has an embossed pattern by embossing on the decorative sheet surface in consideration of application to flooring or wall materials or design properties. 5 can also be given. Embossing can be formed by various methods in addition to heat-pressing with an embossing plate from the anti-allergen functional layer surface. Although there is no restriction | limiting as a shape of the embossed pattern 5, It forms according to the characteristic of the building material to which the decorative sheet of this invention is applied.

≪Separator≫
In the decorative sheet of the present invention, a separator can also be provided on the substrate side surface (the surface when the backer layer 6 is provided) via an adhesive. By setting it as such a structure, the surface exposed by peeling a separator can be stuck to a to-be-adhered thing.
The decorative sheet thus obtained can be used, for example, by being attached to interior materials such as floor materials and wall materials, and interior materials or exterior materials having excellent antiallergenicity can be obtained.

[Decorative board]
The decorative board of the present invention is obtained by attaching the decorative sheet of the present invention to a wooden substrate. FIG. 2 is a schematic view showing an example of a preferred embodiment of the decorative board of the present invention. The decorative board 12 of the present invention is obtained by laminating a decorative sheet 10 and a wooden substrate 11 by using an adhesive.
As wood substrates, wood-based boards include veneer of various materials such as cedar, firewood, firewood, pine, lawan, teak, melapie, wood veneer, wood plywood, particle board, medium density fiber board (MDF), etc. Wood materials. These can be used alone or in a laminated manner. The wooden board includes not only a wooden board but also a plastic board containing paper powder and reinforced paper having strength.

In addition, as an adhesive used for adhering the decorative sheet and the wooden substrate, urea, vinyl acetate resin, urea resin, melamine resin, phenol resin, isocyanate, and the like can be used. , Used alone or as a mixed adhesive mixed arbitrarily. As needed, talc, calcium carbonate, clay, titanium white and other inorganic powders, wheat flour, wood flour, plastic powder, coloring agents, insect repellents, fungicides and the like can be added and mixed in the adhesive. .
The adhesive may be applied using an application device such as a spray, a spreader, or a bar coater. In general, the adhesive has a solid content of 35 to 80% by mass and is applied to the surface of the substrate in an application amount of 50 to 300 g / m <2>.

  Adhesion of the mirror surface decorative sheet on the substrate usually forms an adhesive layer on the back surface of the mirror surface decorative sheet, and the substrate is adhered, or the adhesive is applied on the substrate and the mirror surface decorative sheet is adhered. It depends on the method. For the sticking, a sticking apparatus such as a cold press, hot press, roll press, laminator, wrapping, edge sticking machine, vacuum press or the like can be used.

  The decorative board of the present invention thus obtained can be arbitrarily cut and subjected to optional decoration such as grooving and chamfering on the surface and the end of the mouth using a cutting machine such as a router or a cutter. it can. And it uses suitably for various uses, for example, a flooring, a wall material, etc.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.

(Evaluation method)
(1) Antiallergenicity The decorative sheet obtained in each of the Examples and Comparative Examples was prepared by adding an aqueous solution of mite allergen (“Derf1 (trade name)”, manufactured by Wako Pure Chemical Industries, Ltd.) (initial concentration of mite allergen: 100 ng / mg) was dripped, covered with a film so as not to dry naturally and allowed to stand for 24 hours, and then mite allergens on the decorative sheet were collected, and the inactivation rate of mite allergens was measured using an ELISA method. Antiallergenicity was evaluated according to the following criteria.
◎: Inactivation rate of mite allergen from initial concentration is 80% or more ○: Inactivation rate of mite allergen from initial concentration is more than 50% and less than 80% △: Mite allergen from initial concentration Inactivation rate of more than 30% and less than 50% x: Inactivation rate of mite allergen from initial concentration more than 10% and less than 30% XX: Inactivation rate of mite allergen from initial concentration Less than 10%

(2) Weather resistance The decorative sheets obtained in each of the examples and comparative examples were subjected to accelerated weathering tests with 20 hours of UV irradiation and 4 hours of fountain using an I-Super UV tester manufactured by Iwasaki Electric Co., Ltd. (Specifically, changes in the surface of the decorative sheet after 10 hours of UV irradiation, 4 hours of fountain, and 10 hours of UV irradiation were sequentially evaluated) were evaluated according to the following criteria.
○: The surface of the decorative sheet does not change or some yellowing is confirmed. △: The surface of the decorative sheet is yellowed. ×: The surface of the decorative sheet is markedly yellowed.

(3) Solvent resistance The decorative sheets produced in each of the examples and comparative examples were worn by reciprocating up to 500 times with a load of 1.5 kg using a gauze sufficiently containing methyl ethyl ketone. The appearance change at the time was evaluated according to the following criteria.
◯: No anti-allergen layer missing or exfoliation △: Anti-allergen layer exfoliation occurred 101 to 499 reciprocations ×: Anti-allergen layer exfoliation 100 or less reciprocations

(4) Contamination resistance In accordance with JIS-K-6902, after dripping office ink and blue black on the decorative sheet surface produced in each example and comparative example, the surface when wiped with water 24 hours later Changes were evaluated according to the following criteria.
○: The surface does not change. Δ: The surface is slightly contaminated, but the appearance is not impaired. ×: The surface is significantly contaminated.

(5) Sheet flexibility (items related to proper V-cut processing)
After the base material side of the decorative sheet manufactured in each example and comparative example was bonded and laminated to an MDF having a thickness of 10 mm using an adhesive, the MDF and the adhesive layer were opposite to the decorative sheet side. Cut the V-shaped cross section reaching the interface with the surface, test the plywood by bending it into an L shape (cross section) so that the groove is closed, visually observing the processed part, and evaluating according to the following criteria did. The processing temperature was normal temperature.
○: No crack is generated in the sheet processing part. △: A minute crack is generated in the sheet processing part, but there is no problem in appearance. ×: A crack is generated in the sheet processing part, and the sheet is whitened. A clear change is observed

Example 1
As a base material, a polyolefin resin sheet (formed by extruding colored polyethylene with a thickness of 80 μm with respect to 60 μm transparent polypropylene) and a primer for adhesion (“EBR primer”, manufactured by DIC Graphics Co., Ltd.) of 1.5 g / On the surface of the base material coated with m ² , the mixing ratio (molar ratio) of isophorone diisocyanate and 2-hydroxyethyl acrylate as urethane acrylate oligomer A (curable component) is isocyanate group: hydroxyl group = 1: 1. Anti-allergen A (“Alleluve (trade name)”, manufactured by Toagosei Co., Ltd.) having 100 parts by mass of the bifunctional urethane acrylate oligomer (number average molecular weight: 600) obtained as 5 and a polyphenol compound supported on a zirconium compound 10 parts by mass and matting agent , Particle size: 5 [mu] m) 16 parts by ionizing radiation curable resin composition coated comprising (15g / m ²⁾ was. After applying the ionizing radiation curable resin composition, the ionizing radiation curable resin composition is cured by irradiating an electron beam with an acceleration voltage of 165 kV and an irradiation amount of 30 kGy (3 Mrad) to form an antiallergen functional layer (thickness 15 μm). Obtained. Each characteristic was evaluated about the obtained decorative sheet, and is shown in Table 1.

Example 2
In Example 1, as a urethane acrylate oligomer A (curable component), a tetrafunctional urethane acrylate oligomer obtained by setting the mixing ratio (molar ratio) of isophorone diisocyanate and glycerol diacrylate to isocyanate group: hydroxyl group = 1: 1.5 A decorative sheet was prepared in the same manner as in Example 1 except that (number average molecular weight: 800) was used, and evaluations were made on each characteristic. The results are shown in Table 1.

Example 3
In Example 1, as urethane acrylate oligomer A (curable component), a hexafunctional urethane acrylate obtained by setting the mixing ratio (molar ratio) of isophorone diisocyanate and pentaerythritol triacrylate to isocyanate group: hydroxyl group = 1: 1.5 A decorative sheet was prepared in the same manner as in Example 1 except that the oligomer (number average molecular weight: 1000) was used, and evaluations were made on each characteristic. The results are shown in Table 1.

Example 4
In Example 1, as a urethane acrylate oligomer A (curable component), a 10-functional urethane obtained by setting the blending ratio (molar ratio) of isophorone diisocyanate and dipentaerythritol pentaacrylate to isocyanate group: hydroxyl group = 1: 1.5 A decorative sheet was prepared in the same manner as in Example 1 except that an acrylate oligomer (number average molecular weight: 2000) was used, and evaluations were made on each characteristic. The results are shown in Table 1.

Example 5
In Example 3, a decorative sheet was prepared in the same manner as in Example 3 except that the amount of the anti-allergen agent A used was 3 parts by mass, and evaluations were made on each characteristic. The results are shown in Table 1.

Example 6
In Example 3, a decorative sheet was prepared in the same manner as in Example 3 except that the amount of the anti-allergen agent A used was 30 parts by mass, and evaluations were made on each characteristic. The results are shown in Table 1.

Example 7
In Example 3, as urethane acrylate oligomer A (curable component), the blending ratio (molar ratio) of 1,6-hexamethylene diisocyanate and pentaerythritol triacrylate was obtained as isocyanate group: hydroxyl group = 1: 1.2. A decorative sheet was prepared in the same manner as in Example 3 except that (number average molecular weight: 1000) was used, and evaluations were made for each characteristic. The results are shown in Table 1.

Example 8
In Example 3, as urethane acrylate oligomer A (curing component), the blending ratio (molar ratio) of 1,2-bis (isocyanate methyl) cyclohexane (hydrogenated XDI) and pentaerythritol triacrylate was set to isocyanate group: hydroxyl group = A decorative sheet was prepared in the same manner as in Example 3 except that the 6-functional urethane acrylate oligomer (number average molecular weight: 1000) obtained as 1: 1.2 was used, and evaluations were performed on each characteristic. The results are shown in Table 1.

Example 9
In Example 6, instead of the anti-allergen A, an anti-allergen B which is a polyphenol compound (“Marcalinker M (trade name)” manufactured by Maruzen Petrochemical Co., Ltd.) was used. A decorative sheet was prepared and evaluated for each characteristic. The results are shown in Table 1.

Example 10
In Example 3, in place of the anti-allergen agent A, an anti-allergen agent B (“Marcalinker M (trade name)” manufactured by Maruzen Petrochemical Co., Ltd.), which is a polyphenol compound, was used in the same manner as in Example 3. A decorative sheet was prepared and evaluated for each characteristic. The results are shown in Table 1.

Example 11
In Example 3, as urethane acrylate oligomer A (curable component), isophorone diisocyanate and 1,6-hexanediol (molecular weight: 118.2) and 3-methyl-1,5-pentanediol (molecular weight: 118.2) The reaction product was obtained by setting the mixing ratio (molar ratio) to isocyanate group: hydroxyl group = 1.7: 1, and the mixing ratio (molar ratio) of the reaction product to pentaerythritol triacrylate was set to isocyanate group: hydroxyl group = 1: 1. A decorative sheet was prepared in the same manner as in Example 3 except that the hexafunctional urethane acrylate oligomer (number average molecular weight: 1300) obtained as 1.5 was used, and evaluations were made on each characteristic. The results are shown in Table 1.

Comparative Example 1
In Example 3, a decorative sheet was prepared in the same manner as in Example 3 except that the anti-allergen agent A was not used, and evaluations were performed on each characteristic. The results are shown in Table 1.

Comparative Example 2
In Example 3, instead of the urethane acrylate oligomer A, the mixing ratio (molar ratio) of dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) and pentaerythritol triacrylate was changed to isocyanate group: hydroxyl group = 1: 1. A decorative sheet was prepared in the same manner as in Example 3 except that the hexafunctional urethane acrylate oligomer (number average molecular weight: 1000) (urethane acrylate oligomer B) obtained as No. 3 was used, and evaluations were performed on each characteristic. The results are shown in Table 1.

As is clear from Table 1, when the anti-allergen functional layer was formed using urethane acrylate oligomer A as a curable component together with the anti-allergen agent, it had excellent anti-allergen properties. On the other hand, in Comparative Example 1 in which no anti-allergen agent was used, the anti-allergenicity was extremely inferior, and in Comparative Example 2 in which the urethane acrylate oligomer B was used alone, the anti-allergenicity was also shown to be extremely inferior.
In addition, as a comparison between Examples 3 and 10, as an antiallergen agent, a polyphenol compound supported on an inorganic solid acid expresses better antiallergenicity, and has excellent weather resistance, solvent resistance, In addition, it was confirmed that it could also have stain resistance.

Example 12
In Example 3, the urethane acrylate oligomer A is 80 parts by mass, and the urethane acrylate oligomer B is a blending ratio (moles) of dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) and polytetramethylene glycol (molecular weight: 300). Ratio) is isocyanate group: hydroxyl group = 1.5: 1, and a reaction product is obtained, and the blending ratio (molar ratio) of the reaction product to 2-hydroxyethyl acrylate is obtained as isocyanate group: hydroxyl group = 1: 1.3. A decorative sheet was prepared in the same manner as in Example 3 except that 20 parts by mass of the obtained bifunctional urethane acrylate oligomer (number average molecular weight: 1000) was used, and evaluations were performed on each characteristic. The results are shown in Table 2.

Examples 13 to 15 and Comparative Example 3
In Example 12, a decorative sheet was prepared in the same manner as in Example 12 except that the mixing ratio of urethane acrylate oligomer A and bifunctional urethane acrylate oligomer B was changed to the mixing ratio shown in Table 2. Was evaluated. The results are shown in Table 2.

  As is clear from Table 2, it was confirmed that the decorative sheet can be provided with good flexibility by using urethane acrylate oligomers A and B together as a curable component forming the anti-allergen functional layer.

  ADVANTAGE OF THE INVENTION According to this invention, the ionizing radiation-curable resin composition which can provide high anti-allergen property to the decorative sheet which has high anti-allergenic property, a decorative board using the same, and a to-be-coated article can be obtained. Furthermore, the decorative sheet, the decorative plate, and the ionizing radiation curable resin composition of the present invention also have various properties (weather resistance, solvent resistance, stain resistance, flexibility) required for practical use. Therefore, the decorative sheet, the decorative board, and the ionizing radiation curable resin composition of the present invention are suitably used as a building interior material, particularly a flooring material, taking advantage of such characteristics.

1A. Base material 1A
1B. Base material 1B
2. Print layer 2. Adhesive layer 4. 4. Anti-allergen functional layer Embossed pattern 10. Cosmetic sheet 11. Wooden substrate 12. Veneer

Claims (18)

An anti-allergen functional layer on a substrate, the anti-allergen functional layer is a cured product of an ionizing radiation curable resin composition containing an anti-allergen agent having a curable component and a phenolic hydroxyl group,
Look-containing urethane (meth) acrylate oligomer obtainable from a molecular weight of 250 or less of polyisocyanate and hydroxy group as the curable component (meth) acrylate compound,
Further comprising a molecular weight greater than 250 the polyisocyanate and hydroxyl groups as the curable component (meth) urethane obtainable from acrylate compound (meth) acrylate oligomer including decorative sheet. The decorative sheet according to claim 1, wherein the polyisocyanate having a molecular weight of 250 or less has a molecular weight of 150 to 225. The decorative sheet according to claim 1 or 2, wherein the polyisocyanate having a molecular weight of 250 or less is a monocyclic alicyclic polyisocyanate.   The decorative sheet according to any one of claims 1 to 3, wherein the number of functional groups of the urethane (meth) acrylate oligomer is 2 to 10. The decorative sheet according to any one of claims 1 to 4 , wherein the polyisocyanate having a molecular weight greater than 250 is a bialicyclic polyisocyanate .   The decorative sheet according to any one of claims 1 to 5, wherein the anti-allergen agent is a polyphenol compound supported on an inorganic solid acid.   The decorative sheet according to claim 6, wherein the polyphenol compound is at least one selected from catechin and tannic acid.   The decorative sheet according to claim 6 or 7, wherein the inorganic solid acid is a phosphate.   The cosmetic sheet according to any one of claims 1 to 8, wherein the compounding amount of the anti-allergen agent is 1 to 30 parts by mass with respect to 100 parts by mass of the curable component. Includes a curable component and an anti-allergen agent, see containing a urethane (meth) acrylate oligomer obtainable from a molecular weight of 250 or less of polyisocyanate and hydroxy group as the curable component (meth) acrylate compound,
Further molecular weight greater than 250 the polyisocyanate and having a hydroxy group (meth) acrylate compound urethane (meth) acrylate oligomer obtainable from a including ionizing radiation-curable resin composition as a curing component. The ionizing radiation curable resin composition according to claim 10, wherein the polyisocyanate having a molecular weight of 250 or less has a molecular weight of 150 to 250 . The ionizing radiation-curable resin composition according to claim 10 or 11, wherein the polyisocyanate having a molecular weight of 250 or less is a monocyclic alicyclic polyisocyanate.   The ionizing radiation-curable resin composition according to claim 10, wherein the urethane (meth) acrylate oligomer has 2 to 10 functional groups. The ionizing radiation-curable resin composition according to any one of claims 10 to 13 , wherein the polyisocyanate having a molecular weight greater than 250 is a bialicyclic polyisocyanate .   The ionizing radiation curable resin composition according to any one of claims 10 to 14, wherein the antiallergen is a polyphenol compound supported on an inorganic solid acid.   The ionizing radiation curable resin composition according to claim 15, wherein the polyphenol compound is at least one selected from catechin and tannic acid.   The ionizing radiation curable resin composition according to claim 15 or 16, wherein the inorganic solid acid is a phosphate. A decorative board formed by attaching the decorative sheet according to claim 1 to a wooden substrate.