JP2012187922A - Decorative sheet having anti-allergenicity and decorative laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet that has a high anti-allergenicity and durability, and is excellent in weatherability, and to provide a decorative laminate using the same decorative sheet.SOLUTION: In the decorative sheet, the curable resin layer that has the anti-allergen function is formed on the thermoplastic resin base material. The decorative laminate uses the decorative sheet, wherein the curable resin layer is made by crosslinked curing of ionized radiation curable resin composition containing the ionized radiation curable resin and the anti allergen agent that is the polyphenol compound supported by inorganic solid acid; the ionized radiation curable resin contains 4-10 functional urethane (meth) acrylate oligomer; the content of the anti allergen agent is 5-30 pts.mass against 100 pts.mass of the ionized radiation curable resin in the ionized radiation curable resin composition.

Description

  The present invention relates to a decorative sheet and a decorative plate having antiallergenic properties.

  In recent years, building materials for interior and exterior, such as flooring and wall materials for buildings, have anti-allergenic properties such as removal and inactivation of allergens such as mites and pollen that cause allergic diseases. It is demanded. As a building material to which such anti-allergenicity is imparted, a building material obtained by coating an anti-allergen agent composed of a zirconium salt on the surface of a wood material such as a wood material or plywood is known (for example, a patent) Reference 1). In such a building material, since the anti-allergen agent was simply applied, it was easy to peel off and poor in 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. A cured flooring material has been developed (see, for example, Patent Document 2).

  However, the anti-allergen agent used in the flooring material described in Patent Document 2 is a phenolic polymer resin. In such an anti-allergen agent, the amount of the anti-allergen agent added to impart antiallergenicity When there is a large amount, there is a problem that the weather resistance of the resin layer containing the anti-allergen agent is lowered and the anti-allergen property cannot be exhibited for a long time.

  Thus, although it is required to impart antiallergenicity in a decorative sheet used for flooring or the like, a technology that combines high allergenicity and excellent weather resistance has not been developed yet. It is.

JP 2001-212806 A JP 2008-239721 A

  An object of the present invention is to provide a durable decorative sheet having high antiallergenicity and excellent weather resistance, and a decorative board using the same.

  As a result of intensive research to achieve the above object, the inventors of the present invention have provided an ionizing radiation curable resin in a decorative sheet in which a curable resin layer having an antiallergen function is formed on a thermoplastic resin substrate. And an ionizing radiation curable resin composition containing a polyphenol compound supported on an inorganic solid acid by crosslinking and curing to form the curable resin layer, and at least 4 as the ionizing radiation curable resin. 10 to 10 functional urethane (meth) acrylate oligomer, and in the ionizing radiation curable resin composition, the content of the antiallergen agent is in the range of 5 to 30 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. It has been found that by setting to, it can be provided with excellent weather resistance while having high antiallergenicity. The present invention has been completed by further studies based on such knowledge.

That is, the present invention provides a decorative sheet and a decorative plate having the following aspects.
Item 1. A decorative sheet in which a curable resin layer having an anti-allergen function is formed on a thermoplastic resin substrate,
The curable resin layer is obtained by crosslinking and curing an ionizing radiation curable resin composition containing an ionizing radiation curable resin and an antiallergen agent in which a polyphenol compound is supported on an inorganic solid acid,
The ionizing radiation curable resin contains a 4-10 functional urethane (meth) acrylate oligomer,
In the ionizing radiation curable resin composition, the content of the antiallergen agent is 5 to 30 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.
Item 2. Item 10. The decorative sheet according to Item 1, wherein the ionizing radiation curable resin composition contains 50 mass% or more of a 4 to 10 functional urethane (meth) acrylate oligomer per total amount of the ionizing radiation curable resin.
Item 3. Item 3. The decorative sheet according to Item 1 or 2, wherein the polyphenol compound is at least one selected from catechin and tannic acid.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the inorganic solid acid is a phosphate.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the thermoplastic resin substrate is a polyolefin-based resin sheet.
Item 6. Item 6. The decorative sheet according to Item 5, wherein the thermoplastic resin base material is a laminate of two or more different polyolefin resin sheets.
Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the curable resin layer contains at least one selected from an ultraviolet absorber, a light stabilizer, an antibacterial agent, an antiwear agent, and a matting agent.
Item 8. Item 8. A decorative board obtained by attaching the decorative sheet according to any one of Items 1 to 7 to a wooden substrate.

  The decorative sheet of the present invention and the decorative board using the same have high anti-allergenic properties and excellent durability with weather resistance, and can suppress a decrease in anti-allergenic properties with the passage of use period. it can. In addition, the decorative sheet of the present invention and the decorative board using the same have stain resistance required for practical use, and also have practical performance required for a decorative sheet and a decorative plate.

  Furthermore, in the decorative sheet of the present invention and the decorative board using the same, it is provided with excellent processability by using 4 to 10 functional urethane (meth) acrylate oligomer to be blended in the curable resin layer. For example, even if the cross-sectional V-shaped groove is cut and bent into an L-shape so as to close the cross-sectional V-shaped groove (hereinafter also referred to as “V-shaped cut processing”), Generation of cracks in the processed portion can be suppressed.

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 is a decorative sheet in which a curable resin layer having an anti-allergen function is formed on a thermoplastic resin substrate, and the curable resin layer is ionizing radiation curable. An ionizing radiation curable resin composition containing a resin and an antiallergen agent in which a polyphenol compound is supported on an inorganic solid acid is crosslinked and cured. The ionizing radiation curable resin is a 4 to 10 functional urethane (meth). In the ionizing radiation curable resin composition containing an acrylate oligomer, the content of the anti-allergen agent is 5 to 30 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

  FIG. 1 is a schematic view showing an example of a preferred embodiment of the decorative sheet having antiallergenic properties of the present invention. A decorative sheet 10 that is one embodiment of the present invention shown in FIG. 1 is provided with a curable resin layer 4 on a thermoplastic resin substrate 1, and the curable resin layer 4 has an embossed pattern 5. The thermoplastic resin substrate 1 is obtained by laminating a thermoplastic resin substrate A, a printing layer 2, an adhesive layer 3 and a thermoplastic resin substrate B in this order.

  In addition, the decorative sheet of the present invention has a backer layer 6 made of a resin layer on the back surface of the thermoplastic resin substrate 1 (the surface opposite to the surface on which the curable resin layer 4 is laminated) as necessary. May be laminated. Hereinafter, the configuration of the decorative sheet of the present invention will be described in detail.

<< Thermoplastic resin substrate 1 >>
The thermoplastic resin substrate 1 used in the present invention is not particularly limited as long as it is composed of a thermoplastic resin and is usually used for a decorative sheet. Examples of the thermoplastic resin constituting the base material include thermoplastic resins such as polyester resins, polyolefin resins such as polypropylene resins and polyethylene resins, (meth) acrylic resins, polyurethane resins, polyester resins, and polyamide resins. The resin sheet which consists of 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 thermoplastic resin 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-layered structure, an easy-adhesion layer is provided on the surface of the thermoplastic resin substrate 1A by providing a corona discharge treatment, and a solid layer and / or a pattern layer is provided on the resin substrate 1A. After forming the printing layer 2 comprising the above, and then providing the adhesive layer 3 as necessary, the thermoplastic resin substrate 1B is bonded and pressed by a method such as extrusion lamination, dry lamination, wet lamination, or thermal lamination. can get. The thermoplastic resin substrates 1A and 1B may be colored or non-colored, and from the viewpoint of improving the design properties, it is preferable that either one is colored.

As for the thickness of the thermoplastic resin base material 1, 20-300 micrometers is normally applied by the point of workability, a softness | flexibility, and an intensity | strength, and about 50-200 micrometers is more preferable. When the thermoplastic resin substrate 1 is a multi-layered sheet, the total thickness of the substrates constituting each layer may be in the above range, and the thicknesses of these substrates 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.
Further, the surface of the thermoplastic resin substrate 1 may be subjected to a so-called easy adhesion treatment such as corona discharge treatment or plasma treatment, and a primer layer or anchor layer on the surface of the thermoplastic resin substrate. It may be provided with an easy-adhesion layer.

<< Printing 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 thermoplastic resin substrate 1. In the case where the thermoplastic resin substrate 1 is a sheet having a multilayer structure as described above, the printing layer 2 may be provided between the substrates constituting each layer as shown in FIG. The sheet may be provided on the surface closest to the curable resin 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 >>
The adhesive layer 3 is a layer provided as necessary when laminating two or more thermoplastic resin substrates when the thermoplastic resin substrate employs a sheet having a multilayer structure as described above. . 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 thermoplastic resin substrate 1 (the surface opposite to the surface on which the curable resin 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.

<< Curable resin layer 4 >>
The curable resin layer 4 is a layer provided on the thermoplastic resin substrate 1 through a primer layer as necessary, and imparts antiallergenicity to the decorative sheet of the present invention, as well as weather resistance and contamination resistance. It is a layer that imparts excellent properties such as properties.

  The curable resin layer 4 includes an ionizing radiation curable resin and an antiallergen agent in which a polyphenol compound is supported on an inorganic solid acid, and the ionizing radiation curable resin is a 4 to 10 functional urethane (meth) acrylate. It is a layer formed by crosslinking and curing an ionizing radiation curable resin composition containing an oligomer and having an antiallergen agent content of 5 to 30 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

(Ionizing radiation curable resin)
The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid, and is a radically polymerizable unsaturated group. It is what has. The urethane (meth) acrylate oligomer used in the present invention needs to have 4 to 10 radical polymerizable unsaturated groups, that is, a 4 to 10 functional group. From the viewpoint of improving workability such as V-cut processing while providing further excellent antiallergenicity and weather resistance, the urethane (meth) acrylate oligomer is preferably 4 to 8 functional, more preferably 4 to 4 Hexafunctional is mentioned. Further, the more functional groups of the urethane (meth) acrylate oligomer, the higher the antifouling property of the cured resin layer 4 can be improved.

  The number average molecular weight (number average molecular weight in terms of polystyrene measured by GPC method) of the 4-10 functional urethane (meth) acrylate oligomer is preferably about 600 to 5000, more preferably 600 to 3000, and still more preferably. Is 600-2200. By using such a urethane (meth) acrylate oligomer together with an anti-allergen agent to be described later, it is possible to obtain an anti-allergenic property and a further excellent weather resistance. Moreover, since the ionizing radiation curable resin composition has an appropriate thixotropy, the curable resin layer can be easily formed.

As the ionizing radiation curable resin, the above-described 4 to 10 functional urethane (meth) acrylate oligomer is essential, but it is a polymerizable monomer commonly used as an ionizing radiation curable resin as long as the effects of the present invention are not impaired. In addition, it can be appropriately selected from polymerizable oligomers or prepolymers.
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.

  The content of the 4 to 10 functional urethane (meth) acrylate oligomer in the ionizing radiation curable resin composition is not particularly limited. For example, it is 50% by mass or more per total amount of the ionizing radiation curable resin, preferably 50-95 mass%, More preferably, 60-95 mass% is mentioned. When the content of the 4- to 10-functional urethane (meth) acrylate oligomer is within the above range, excellent weather resistance can be obtained, and at the same time, excellent workability capable of handling various processes including V-cut processing. In addition, an even better antiallergenicity can be obtained.

(Anti-allergen)
The anti-allergen agent used in the present invention is a polyphenol compound supported on an inorganic solid acid, and can impart not only excellent anti-allergenic properties but also excellent weather resistance to the decorative sheet of the present invention. .

  The polyphenol compound is an organic compound having a plurality of phenolic hydroxy groups in the molecule, that is, hydroxy groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring. For example, low molecular weight polyphenols and high molecular weight tannic acids called catechins such as epicatechin, gallotannin, epigallocatechin, epicatechin gallate, epigallocatechin gallate and the like have excellent antiallergenic properties and industrially. It is preferably mentioned from the viewpoint that it can be easily obtained at low cost. 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, phosphates, and complex oxides are preferable. Particularly, zirconium phosphate having strong acid strength is preferable, and the crystal system has a layered structure. Zirconium phosphate is preferred.

  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. Further, from the viewpoint of enhancing the coating suitability of the curable resin layer and eliminating the adverse effects on its gloss and stain resistance, the inorganic solid acid preferably has a particle size smaller than the thickness of the curable resin layer. . The particle size of the inorganic solid acid is substantially the same as the particle size of the anti-allergen agent.

  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. .

  Content of an antiallergen agent is 5-30 mass parts with respect to 100 mass parts of ionizing radiation-curable resins, Preferably it is 8-25 mass parts. In the present invention, even when the content of the anti-allergen agent is small, excellent antiallergenicity can be obtained, and excellent weather resistance can be provided. Furthermore, in addition to excellent antiallergenicity and weather resistance, more preferably, an antiallergen agent is used with respect to 100 parts by mass of the ionizing radiation curable resin from the viewpoint of improving workability such as V-cut processing. 8-15 mass parts is mentioned.

(Other additives)
In addition, the ionizing radiation curable resin composition further includes an ultraviolet absorber, a light stabilizer, an antibacterial agent, and an antiwear agent in order to satisfy the characteristics required for those to which the decorative sheet of the present invention is applied. , And additives such as matting agents or anti-settling agents can be included.

  The ultraviolet absorber (UVA) absorbs harmful ultraviolet rays and improves the long-term weather resistance and stability of the hard coat film provided with the surface protective layer of the present invention. In addition, the light stabilizer itself absorbs little ultraviolet light, but stabilizes by efficiently capturing harmful free radicals generated by the ultraviolet light.

  The ultraviolet absorber that can be used in the present invention may be either inorganic or organic. Examples of the inorganic ultraviolet absorber include titanium oxide, cerium oxide, and zinc oxide having an average particle size of about 5 to 120 nm. It can be preferably used. Moreover, as an organic type ultraviolet absorber, a benzotriazole type, a triazine type, a benzophenone type, a salicylate type, an acrylonitrile type etc. can be mentioned preferably, for example. Of these, triazines are preferred because they have a high ability to absorb ultraviolet rays and do not easily deteriorate even with high energy such as ultraviolet rays. Moreover, in order to suppress bleed-out, an ionizing radiation reaction type ultraviolet absorber may be used as necessary.

  Among these, as the triazine ultraviolet absorber, for example, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3, 5-triazine, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3 -Tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- 2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like are preferred, and these may be used alone or in combination. A combination of species can be used.

  The content of the ultraviolet absorber is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

  The light stabilizer used in the present invention is preferably a hindered amine light stabilizer, and is preferably an ionizing radiation reaction type hindered amine light stabilizer.

  Examples of hindered amine light stabilizers include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and methyl. (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4 -Yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine) and the like.

  The content of the light stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

  The ionizing radiation reaction type hindered amine light stabilizer is not particularly limited as long as it has reactivity with a 4-8 functional urethane (meth) acrylate oligomer employed as an ionizing radiation curable resin. Preferable examples include a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and at least one selected from these is preferable. Of these, a (meth) acryloyl group is preferable. Examples of such a light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate.

  The blending amount of such an ionizing radiation reaction type hindered amine light stabilizer is 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. .

An antibacterial agent can be blended with the ionizing radiation curable resin composition used in the present invention in order to impart antibacterial properties. As such an antibacterial agent, the carrier is an inorganic compound, and the carrier carries at least silver ions using silver ions or silver ions in combination with copper ions and zinc ions. Any inorganic compound can be used. For example, inorganic ions such as activated carbon, activated alumina, silica gel, etc., zeolite, hydroxide apatite, zirconium phosphate, calcium phosphate, titanium phosphate, potassium titanate, hydrous bismuth, hydrous zirconium oxide, hydrotalcide, etc. An exchanger etc. are mentioned. These inorganic compounds can be used alone or in combination of two or more.
Among the above inorganic compounds, the inorganic ion exchanger is preferable because it can firmly support silver ions, and at least one selected from zeolite, hydroxide apatite, and zirconium phosphate can be suitably used, and zirconium phosphate alone More preferably it is used. In addition, a silver antibacterial agent having silver ions supported on a three-dimensional network structure of zirconium phosphate is particularly preferable in terms of discoloration and elution of silver components.

  Examples of the particle shape of such an antibacterial agent include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like, and a spherical shape is preferable, and an average particle diameter thereof is 0.1 to 3.0 μm, and more preferably 0. It is about 5 to 2.5 μm. As such antibacterial agents, for example, “Novalon AG-300” (trade name, manufactured by Toagosei Co., Ltd.) which is a silver phosphate carrying zirconium phosphate, “Antimicrobial ceramics” (Shinto V ceramics) which is a silver ion carrying apatite. Commercially available products such as “Zeomic AJ-10D” (manufactured by Sinanen New Ceramic Co., Ltd., trade name), which is a silver ion-supported zeolite, can be used. The compounding quantity of these antibacterial agents is 0.1-10 mass parts with respect to 100 mass parts of ionizing radiation curable resin, Preferably, it is about 0.5-5 mass parts.

  The ionizing radiation curable resin composition used in the present invention can be blended with an antiwear agent in order to increase the hardness of the surface of the curable resin layer and improve the scratch resistance. Examples of such antiwear agents include inorganic and organic fillers. Examples of inorganic materials include spherical particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable.

  Of these inorganic antiwear agents, silica is a preferred one. Silica improves friction resistance and does not hinder the transparency of the surface protective layer. As the silica, it is possible to appropriately select and use conventionally known silica, and for example, colloidal silica can be preferably mentioned. Colloidal silica is preferable because it hardly affects the transparency even when the amount added is increased. As the particle diameter of silica, those having a primary particle diameter of 5 to 1000 nm are preferably used, more preferably 10 to 50 nm, and particularly preferably 10 to 30 nm. When silica having a primary particle diameter of 1000 nm or less is used, transparency is secured. Moreover, the primary particle diameter of the silica used does not need to be one kind, and it is also possible to mix and use silica having different primary particle diameters. As a compounding quantity of a silica, it is preferable that it is a ratio of 1-20 weight part with respect to 100 mass parts of ionizing radiation curable resin. Spherical α-alumina or colloidal alumina is also preferable because of its high hardness, a large effect on improving wear resistance, and relatively easy to obtain spherical particles.

  Examples of organic fillers include synthetic resin beads such as crosslinked acrylic resins and polycarbonate resins. The particle diameter is preferably about 30 to 100% of the normal film thickness from the viewpoint of maintaining transparency. The blending amount is preferably about 1 to 20 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.

  The ionizing radiation curable resin composition used in the present invention can be blended with a so-called matting agent (matting agent) for matting the surface of the curable resin layer. Various kinds of matting agents are used, and inorganic fine powders, organic fillers, and the like can be used. As inorganic fine powder, silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, fine powder of silicate, etc. can be used, and acrylic, urethane, Examples include fillers made of nylon, polypropylene, urea resins, styrene crosslinked fillers, benzoguanamine crosslinked fillers, and the like.

Among these matting agents, inorganic fine powders, particularly silica, are preferable because they are easily available and exhibit a sufficient matting effect even when added in a small amount. Such silica particles preferably have a particle size of about 1 to 40 μm, particularly preferably 2 to 20 μm. About the kind of such a silica particle, a conventionally well-known thing can be used regardless of a process / unprocessed, These can be used individually or in mixture of 2 or more types. In the present invention, amorphous silica is also preferred from the viewpoint of matting effect.
As a compounding quantity of a silica particle, it is 4-30 mass parts with respect to 100 mass parts of ionizing radiation curable resin, and it is more preferable that it is 10-20 mass parts.

  In addition, the ionizing radiation curable resin composition used in the present invention can contain various additives as long as the performance is not impaired. Examples of the various additives include polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, antifoaming agents. Examples include odorants and solvents.

  When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the curable resin. The initiator for use can be appropriately selected from those conventionally used.

(Formation of curable resin layer)
The curable resin layer 4 of the decorative sheet of the present invention is composed of the above-mentioned ionizing radiation curable resin composition, that is, an antiallergen agent in which a 4 to 10 functional urethane (meth) acrylate oligomer and a polyphenol compound are supported on an inorganic solid acid. And an ionizing radiation curable resin composition containing other optional components are applied onto a thermoplastic resin substrate via an easy-adhesion layer such as a primer layer, if necessary, and ionized. It is formed by crosslinking and curing by irradiation with radiation. The formation of the curable resin layer 4 is specifically performed as follows.

  The ionizing radiation curable resin composition for forming the curable resin layer is coated with a gravure coat, bar coat, roll coat, reverse roll coat, comma coat so that the thickness after curing is usually about 5 to 30 μm. Or the like, preferably by gravure coating. Moreover, it is preferably 10 to 20 μm from the viewpoint of stain resistance and scratch resistance. In the case where 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 uncured resin layer formed by application of the ionizing radiation curable resin composition is irradiated with ionizing radiation or the like to be crosslinked and cured, whereby the curable resin layer 3 is formed. Here, when an electron beam is used for curing, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but it is preferable to cure the uncured resin layer at an acceleration 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 the curable resin layer 3 is provided on the thermoplastic resin base material 1, a primer layer is used as an easy-adhesion layer in order to ensure adhesion between the thermoplastic resin base material 1 and the curable resin layer 3. (Not shown) can be provided between the thermoplastic resin substrate 1 and the curable resin layer 3.

  As a resin for forming such a primer layer, urethane resin, (meth) acrylic resin, (meth) acrylic-urethane copolymer resin, urethane-based resin mainly composed of acrylic polyol, vinyl chloride-vinyl acetate copolymer Copolymers, polyester resins, butyral resins, chlorinated polypropylene, chlorinated polyethylene, etc. are used. If necessary, these resins are mixed with a constitutional content, solvent, stabilizer, plasticizer, curing agent, etc. Can be used as

  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 thermoplastic resin substrate by a known printing method, coating method, etc., dried, This can be done by curing. 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 thermoplastic resin substrate, the thermoplastic resin substrate sheet 1 is subjected to corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment. It is also possible to increase the adhesion to the thermoplastic resin substrate by performing an easy adhesion treatment such as.

  Moreover, when laminating the curable resin layer 3 on the primer layer, in order to ensure the adhesiveness between the curable resin layer 3 and the primer layer, the curable resin layer is applied to the surface of the primer layer by the above-described easy adhesion treatment. The primer layer can be kept in a semi-cured state, after which the curable resin layer is applied, and then irradiated with ionizing radiation, By curing, the curable resin layer and the primer layer 2 can be integrated to improve the adhesion between them.

(Embossed pattern)
In this way, the decorative sheet of the present invention in which the curable resin layer is laminated on the thermoplastic resin base material is embossed on the decorative sheet surface in consideration of application to flooring or wall materials or design properties. The embossed pattern 5 can also be applied. Embossing can be formed from the surface of the curable resin layer by various methods in addition to heating and pressing with an emboss plate. 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)
The decorative sheet of the present invention can also be provided with a separator on the surface of the thermoplastic resin base sheet side through 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 affixing to interior materials such as floor materials and wall materials, and has excellent antiallergenic properties and excellent weather resistance. 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 wooden boards, as wooden boards, there are veneers made of various materials such as cedar, cocoon, firewood, pine, lawan, teak, melapie, wood veneer, wood plywood, particle board, medium density fiber board (MD
And wood materials such as F). 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 400 μl of an aqueous solution of mite allergen (“purified mite antigen Der f II (trade name)”, manufactured by Shiba Goat Co., Ltd.) was dropped onto the decorative sheet obtained in each of the examples and comparative examples. After standing for a period of time, mite allergens on the decorative sheet are collected, and the amount of mite allergens is determined using the tania allergen simple measurement kit (“Daniscan (trade name)”, manufactured by Asahi Breweries) according to the following criteria. Allergenicity was evaluated.
○: Anti-allergenicity is recognized ×: Anti-allergenicity is not recognized

(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. △: The surface of the decorative sheet slightly yellows. X: The surface of the decorative sheet remarkably yellows.

(3) Contamination resistance According to 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.

(4) V-cutting suitability (items related to sheet flexibility)
After the base sheet side of the decorative sheet manufactured in each Example and Comparative Example was adhered and laminated to an MDF having a thickness of 10 mm using an adhesive, the MDF and the adhesive were provided on the opposite side of the decorative sheet side. Cut the V-shaped groove that reaches the interface with the layer, test the plywood by bending it into an L-shape (cross section) so that the groove is closed, and visually observe the processed part. evaluated. 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 thermoplastic resin 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 an adhesion primer (“EBR primer”, Showa Ink Industries, Ltd.) 1 The anti-allergen agent A (“Alleluve”) was prepared by supporting 100 parts by mass of a tetrafunctional urethane acrylate oligomer (number average molecular weight: 1200) on a surface of a base material coated at 0.5 g / m ² and a polyphenol compound supported on a zirconium compound. (Product Name) ", manufactured by Toagosei Co., Ltd., and an ionizing radiation curable resin composition containing 10 parts by mass and a matting agent (amorphous silica, particle size: 5 μm) 16 parts by mass (15 g / m ² ) did. After coating 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 kG (3 Mrad) to form a curable resin layer (15 μm). Obtained. Each characteristic was evaluated about the obtained decorative sheet, and the evaluation results are shown in Table 1 together with the blending amount of the ionizing radiation curable resin composition.

Example 2
In Example 1, a decorative sheet was prepared in the same manner as in Example 1 except that the tetrafunctional urethane (meth) acrylate oligomer was changed to a hexafunctional urethane (meth) acrylate oligomer (number average molecular weight: 1400). ) To (4) were evaluated. The results are shown in Table 1.

Example 3
In Example 1, a decorative sheet was prepared in the same manner as in Example 1 except that the amount of the anti-allergen agent was 20 parts by mass, and evaluations on the above (1) to (4) were performed. The results are shown in Table 1.

Example 4
In Example 2, a decorative sheet was prepared in the same manner as in Example 1 except that the amount of the anti-allergen agent was 20 parts by mass, and evaluations on the above (1) to (4) were performed. The results are shown in Table 1.

Example 5
In Example 1, a decorative sheet was prepared in the same manner as in Example 1 except that the tetrafunctional urethane (meth) acrylate oligomer was changed to a 10 functional urethane (meth) acrylate oligomer (number average molecular weight: 1800), and the above (1 ) To (4) were evaluated. The results are shown in Table 1.

Example 6
In Example 5, a decorative sheet was prepared in the same manner as in Example 5 except that the amount of the anti-allergen agent was 20 parts by mass, and evaluations on the above (1) to (4) were performed. The results are shown in Table 1.

Example 7
In Example 1, instead of the tetrafunctional urethane (meth) acrylate oligomer, 80 parts by mass of a hexafunctional urethane (meth) acrylate oligomer (number average molecular weight: 1400) and a bifunctional glycol (meth) acrylate monomer (number average molecular weight: 300) ) A decorative sheet was prepared in the same manner as in Example 1 except that 20 parts by mass was used, and evaluations on the above (1) and (2) were performed. The results are shown in Table 1.

Example 8
In Example 1, instead of the tetrafunctional urethane (meth) acrylate oligomer, 70 parts by mass of a hexafunctional urethane (meth) acrylate oligomer (number average molecular weight: 1400) and a bifunctional glycol (meth) acrylate monomer (number average molecular weight: 300) ) A decorative sheet was prepared in the same manner as in Example 1 except that 30 parts by mass were used, and the evaluations regarding (1) and (2) were performed. The results are shown in Table 1.

Example 9
In Example 1, instead of the tetrafunctional urethane (meth) acrylate oligomer, 70 parts by mass of a hexafunctional urethane (meth) acrylate oligomer (number average molecular weight: 1400) and a bifunctional urethane (meth) acrylate oligomer (number average molecular weight: 1000) ) A decorative sheet was prepared in the same manner as in Example 1 except that 30 parts by mass was used, and evaluations on the above (1) to (4) were performed. The results are shown in Table 1.

Comparative Example 1
In Example 1, a decorative sheet was prepared in the same manner as in Example 1 except that the tetrafunctional urethane (meth) acrylate oligomer was changed to a bifunctional urethane (meth) acrylate oligomer (number average molecular weight: 1000). ) To (4) were evaluated. The results are shown in Table 1.

Comparative Example 2
In Comparative Example 1, a decorative sheet was prepared in the same manner as in Comparative Example 1 except that the amount of the anti-allergen agent was 20 parts by mass, and the above evaluations (1) to (4) were performed. The results are shown in Table 1.

Comparative Example 3
In Example 2, a decorative sheet was prepared in the same manner as in Example 2 except that the antiallergen agent was a polyphenol compound-based antiallergen agent B ("Marcalinker M (trade name)" manufactured by Maruzen Petrochemical Co., Ltd.). Then, evaluations on the above (1) to (4) were performed. The results are shown in Table 1.

Comparative Example 4
In Comparative Example 3, a decorative sheet was prepared in the same manner as in Comparative Example 3 except that the amount of the anti-allergen agent was 20 parts by mass, and evaluations on the above (1) to (4) were performed. The results are shown in Table 1.

As is apparent from the results shown in Table 1, a 4- to 10-functional urethane (meth) acrylate oligomer and an antiallergen agent (antiallergen agent A) in which a polyphenol compound is supported on an inorganic solid acid are used in combination. When the anti-allergen agent per 5 parts by mass satisfied 5 to 30 parts by mass (Examples 1 to 9), it was confirmed that the anti-allergen had excellent anti-allergenicity and good weather resistance. On the other hand, when a bifunctional urethane (meth) acrylate oligomer is used (Comparative Examples 1-2) and when a polyphenol compound is used as an antiallergen agent without being supported on an inorganic solid acid (Comparative Examples 3-3). In 4), the antiallergenicity was inferior or the weatherability was inferior, and it was impossible to combine high antiallergenicity and excellent weatherability.
Furthermore, when a 4-8 functional compound was used as a urethane (meth) acrylate oligomer (Examples 1-4), it became clear that the workability in a V-shaped cut process became favorable.

1A. Thermoplastic resin substrate A
1B. Thermoplastic resin substrate B
2. Print layer 2. Adhesive layer 4. 4. Curable resin layer Embossed pattern 10. Cosmetic sheet 11. Wooden substrate 12. Veneer

Claims (8)

A decorative sheet in which a curable resin layer having an anti-allergen function is formed on a thermoplastic resin substrate,
The curable resin layer is obtained by crosslinking and curing an ionizing radiation curable resin composition containing an ionizing radiation curable resin and an antiallergen agent in which a polyphenol compound is supported on an inorganic solid acid,
The ionizing radiation curable resin contains a 4-10 functional urethane (meth) acrylate oligomer,
In the ionizing radiation curable resin composition, the content of the antiallergen agent is 5 to 30 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.   The decorative sheet according to claim 1, wherein the ionizing radiation curable resin composition contains 50% by mass or more of a 4-10 functional urethane (meth) acrylate oligomer per total amount of the ionizing radiation curable resin.   The decorative sheet according to claim 1 or 2, wherein the polyphenol compound is at least one selected from catechin and tannic acid.   The decorative sheet according to any one of claims 1 to 3, wherein the inorganic solid acid is a phosphate.   The decorative sheet according to any one of claims 1 to 4, wherein the thermoplastic resin substrate is a polyolefin resin sheet.   The decorative sheet according to claim 5, wherein the thermoplastic resin base material is a laminate of two or more different polyolefin resin sheets.   The decorative sheet according to any one of claims 1 to 6, wherein the curable resin layer contains at least one selected from an ultraviolet absorber, a light stabilizer, an antibacterial agent, an antiwear agent, and a matting agent.   A decorative board formed by attaching the decorative sheet according to any one of claims 1 to 7 to a wooden substrate.

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