JP5794053B2 - Cosmetic sheet having anti-allergen function and mite repellent function - Google Patents

Description

  The present invention relates to a decorative sheet having an anti-allergen function and a tick repellent function.

  In recent years, building materials for interior and exterior, such as flooring and wall materials for buildings, have functionality such as antiallergen function that removes or inactivates allergens such as mites and pollen that cause allergic diseases. It is demanded. For example, like patent document 1, the flooring which provided the anti-allergen function to the topcoat (outermost layer) is proposed.

By the way, in addition to the anti-allergen function, interior and exterior building materials such as building floor materials and wall materials are also required to have functionality such as a tick repellent function. Examples of materials that exhibit a tick repellent function generally include insect repellents and mite repellents. Patent Document 2 discloses makeup using an insect repellent as an adhesive used when laminating a substrate and a decorative sheet. A board has been proposed.
However, the present situation is that the decorative sheet imparted with both the anti-allergen function and the tick repellent function has not been sufficiently studied. In addition, the original properties of the resin used to impart surface properties such as stain resistance, solvent resistance, and weather resistance to the decorative sheet are reduced by simply adding the anti-allergen agent as described above to the top coat of the decorative sheet. Resulting in. In other words, when both the anti-allergen agent and the mite repellent are added to the top coat, it is fully expected that the physical properties of the decorative sheet will be further lowered, and the makeup having the mite repellent function while maintaining the excellent anti-allergen function. The development of a sheet was desired.

JP 2001-212806 A Japanese Patent No. 4597831

  An object of the present invention is to provide a decorative sheet having a high anti-allergen function and a tick repellent function and having surface properties such as excellent stain resistance, solvent resistance, and weather resistance.

  The inventors of the present invention have made extensive studies in order to achieve the above object, and have found that the problem can be solved by a decorative sheet having the following configuration. The gist of the present invention is as follows.

1. A decorative sheet comprising a base sheet, a tick repellent functional layer containing a mite repellent having a vapor pressure at 25 ° C. of 0.1 × 10 ⁻⁶ kPa or more, and an anti-allergen functional layer containing an anti-allergen agent in this order. .
2. A decorative sheet comprising the decorative sheet according to 1 and a substrate in order.

  According to the present invention, it is possible to obtain a decorative sheet having a high antiallergen function and a mite repellent function and having surface properties such as excellent stain resistance, solvent resistance, and weather resistance.

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

[Decorative sheet]
The decorative sheet of the present invention has a base sheet, a tick repellent functional layer containing a mite repellent having a vapor pressure at 25 ° C. of 0.1 × 10 ⁻⁶ kPa or more, and an anti-allergen functional layer containing an anti-allergen agent in this order. It is characterized by.

  FIG. 1 is a schematic view showing an embodiment of the decorative sheet of the present invention. A decorative sheet 10 shown in FIG. 1 has a tick repellent functional layer 5 and an anti-allergen functional layer 6 in order on a base sheet 1. Hereinafter, each layer forming the decorative sheet 10 will be described.

Base sheet 1
As the base sheet, a resin sheet made of a thermoplastic resin is preferably exemplified. Examples of the thermoplastic resin include polyolefin resins such as polypropylene resins and polyethylene resins, polyethylene terephthalate (PET), and polyethylene naphthalate ( In addition to polyester resins such as PEN), (meth) acrylic resins, polyurethane resins, polyamide resins and the like are preferable.

Moreover, as a base material sheet, 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.
As for the thickness of a base material sheet, 20-300 micrometers is normally applied by the point of workability, a softness | flexibility, and an intensity | strength, and about 40-200 micrometers is more preferable. When the base sheet is a multi-layered sheet, the total thickness of the base sheets constituting each layer is preferably within the above range. In this case, the thickness of the base material sheet constituting each layer may be the same or different.

  When the base sheet has a multilayer structure, the embodiment of FIG. 2 will be described as an example. After the base sheet 1a has been subjected to corona discharge treatment on its surface, the printing layer 2 and the adhesive layer 3 are provided. The substrate sheet 1b is obtained by bonding and pressure bonding by a method such as extrusion lamination, dry lamination, wet lamination, thermal lamination or the like. These substrate sheets may be colored or non-colored.

  Each substrate sheet may be subjected to a so-called easy-adhesion treatment such as corona discharge treatment or plasma treatment on the surface thereof, and may be provided with an easy-adhesion layer such as an anchor layer. In addition, when the decorative sheet of the present invention is attached to a wooden substrate to form a decorative plate, a primer layer (back surface) using an acrylic resin having a thickness of about 1 to 5 μm on the back surface (wood substrate side) of the base sheet. A primer layer) may be provided.

Print layer 2
The printing layer may be provided with a solid layer under the pattern layer. 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. The solid layer has an effect of improving the design by giving uniform coloring over the entire surface.
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.
As FIG. 1 shows, what is necessary is just to provide a printing layer between a tick repellent function layer and a base material sheet, when a base material sheet is a single layer structure. As shown in FIG. 2, when the base sheet has a multilayer structure, the printing layer 2 may be provided between the base sheets 1a and 1b.

  Preferable examples of the adhesive forming the adhesive layer 3 include urethane-based, acrylic-based, acrylic / polyurethane-based, polyester-based, polyamide-based, polystyrene-based, and cellulose-based adhesives. These resins can be used singly or as a mixture of two or more.

Tick repellent functional layer 5
The tick repellent function layer is a layer containing a tick repellent having a vapor pressure of 0.1 × 10 ⁻⁶ kPa or more at 25 ° C. and imparting a tick repellent function to the decorative sheet of the present invention. The mite repellent used in the present invention is an agent having a relatively high vapor pressure, that is, an agent that is relatively easy to volatilize. Therefore, even if an anti-allergen functional layer is provided on the surface layer, the mite repellent function can be sufficiently exerted. it can.
The mite repellent used in the present invention has a vapor pressure at 25 ° C. of 0.1 × 10 ⁻⁶ kPa or more, more preferably 0.1 × 10 ^{−6 to} 0.1 × 10 ⁻⁴ kPa. If it is an agent which has a function, there will be no restriction | limiting in particular. Here, the vapor pressure at 25 ° C. is a value measured based on a usual method such as a gas flow method.

As such a mite repellent, a pyrethroid compound having a cyclopropanecarboxylic acid skeleton is preferably mentioned. As pyrethroid compounds, natural pyrethroid compounds such as pyrethrin (0.4 × 10 ⁻⁶ kPa), cineline and jasmolin; transfluthrin (0.4 × 10 ⁻⁶ kPa), teraretrin (0.5 × 10 ⁻⁶ kPa) 2,3,5,6-tetrafluoro-4-methoxybenzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (0.6 × 10 ⁻⁶ kPa), praretrin (0 .6 × 10 ⁻⁶ kPa), 2,3,5,6-tetrafluoro-4-methylbenzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (0.7 × 10 ^-6 kPa), 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 3-methoxy imino-2,2-dimethyl-cyclopropane Cal Kishirato (0.8 × 10 ^-6 kPa), allethrin ^{(0.8 × 10 -6 kPa),} 2,3,5,6- tetrafluoro-4-methoxymethylbenzyl 3- (2-methyl-1-propenyl ) -2,2-dimethylcyclopropanecarboxylate (0.9 × 10 ⁻⁶ kPa), 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 3- (1-propenyl) -2,2- Dimethylcyclopropanecarboxylate (0.2 × 10 ⁻⁵ kPa), furamethrin (0.3 × 10 ⁻⁵ kPa), 2,3,5,6-tetrafluoro-4-methylbenzyl 3- (2-methyl- 1-propenyl) -2,2-dimethylcyclopropanecarboxylate ^{(0.4 × 10 -5 kPa),} 2,3,5,6- tetrafluoro-4-methylbenzyl 3- (1-propenyl) -2 2-dimethylcyclopropane carboxylate (1.0 × 10 ^-5 kPa), empenthrin ^{(0.2 × 10 -4 kPa),} 5- propargyl-2-furfuryl 2,2,3,3-tetramethyl-cyclopropanecarboxylate Synthetic pyrethroid compounds such as lath (0.2 × 10 ⁻⁴ kPa) are preferred. Here, the value in parentheses after the compound name is the vapor pressure at 25 ° C. of the compound.
Among the above, as the pyrethroid compound, empentrin (0.2 × 10 ⁻⁴ kPa) is preferable from the viewpoint of obtaining a high mite repellent function and excellent surface properties.

In the present invention, the mite repellent is preferably carried on an inorganic solid acid, and more specifically, the above-described pyrethroid compound is preferably carried on an inorganic solid acid. When the mite repellent is carried on an inorganic solid acid, the mite repellent is less likely to volatilize, and the durability of the mite repellent function is improved.
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-type zeolite and H-substituted ZSM-5 type zeolite, phosphate compounds such as zirconium phosphate, aluminum phosphate, tin phosphate, cerium phosphate, titanium phosphate, antimonic acid, etc. Preferred 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, particularly zirconium phosphate having strong acid strength is preferable, and layered zirconium phosphate having a crystal system having a layered structure is preferable. .

  The shape of the inorganic solid acid is preferably a 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, it is preferable from the viewpoint of easy handling and obtaining an excellent mite repellent function.

  As a method for supporting the mite repellent on the inorganic solid acid, a conventionally known method can be adopted without any particular limitation. For example, an inorganic solid acid molded into a predetermined shape is impregnated with a desired mite repellent aqueous solution, excess water is removed by filtration or evaporation, dried, and then fired as necessary. Preferably, an aqueous solution of a desired mite repellent is added to the hydrosol or slurry, kneaded, dried, and fired as necessary.

  In the present invention, when a pyrethroid compound supported on an inorganic solid acid is used as a mite repellent, the weight ratio of the pyrethroid compound to the inorganic solid acid is preferably 50:50 to 0.1: 99.9, more Preferably it is 30: 70-0.5: 99.5. When the weight ratio is within the above range, a particularly excellent tick repellent function can be obtained. Such a tick repellent is also available as a commercial product, for example, organic / inorganic hybrid type “Nine Sect (trade name)” (manufactured by Toagosei Co., Ltd.), and the like.

  The tick repellent functional layer is preferably formed of a resin composition containing a tick repellent and a curable resin. As the curable resin, a curable resin usually used for forming a decorative sheet, for example, an acrylic resin, a polyester resin, a polyurethane resin, a polyurethane-acrylic copolymer, a vinyl chloride-vinyl acetate copolymer resin, a chlorinated polypropylene. A known material such as a resin, a chlorinated polyethylene resin, a two-component curable resin, or an ionizing radiation curable resin can be used. Although there is no particular limitation, a two-component curable type containing a main agent and a curing agent such as an isocyanate compound. Preferred examples include resin compositions and ionizing radiation curable resins.

  The main component contained in the two-component curable resin composition is not particularly limited as long as it is cured by the presence of a curing agent such as an isocyanate compound. Examples of the main agent include (meth) acrylic acid esters such as methyl (meth) acrylate and hydroxyl groups such as (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. Acrylic polyols obtained by addition polymerization with monomers having a diol, known diols such as glycols such as ethylene glycol and propylene glycol and dibasic acids such as adipic acid, maleic acid, phthalic acid and terephthalic acid, and these acids Functional groups such as polyester polyols obtained by polycondensation reaction with at least one selected from esters, etc., or polyether polyols obtained by addition polymerization of the above diols with ethylene oxide, propylene oxide, tetrahydrofuran, etc. Polyol having a hydroxyl group preferred. These can be used individually or in mixture of multiple types. Among the above, acrylic polyol is particularly preferable from the viewpoint of interlayer adhesion between the tick repellent functional layer and the anti-allergen functional layer.

  Examples of the curing agent include aromatic polyisocyanates such as methylenebis (4,1-phenylene) = diisocyanate, 2,4-tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate; 1,6 Preferred are isocyanate compounds such as aliphatic (or alicyclic) polyisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate.

In addition, so-called modified polyisocyanates such as adduct-modified products, burette-modified products, isocyanurate-modified products, uretonimine-modified products, uretdione-modified products, carbodiimide-modified products, and elastic-modified polyisocyanates of the above isocyanate compounds can also be used as curing agents.
In this invention, a hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the present invention, the use ratio of the main agent and the curing agent is usually selected in a mass ratio of 100: 1 to 100: 15, preferably 100: 2 to 100: 10, and more preferably 100. : 2 to 100: 8. When the mass ratio of the main agent and the curing agent is within the above range, excellent interlayer adhesion can be obtained. In addition, when an anti-allergen agent having a phenolic hydroxyl group is added to the anti-allergen functional layer described later, the anti-allergen function may be lowered if an excessive curing agent is included in the adjacent mite repellent functional layer, which will be described later. By providing the blocking layer, a high antiallergen function can be maintained.

  The ionizing radiation curable resin preferably used as the curable resin is a resin that is cured by irradiation with ionizing radiation. 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 ionizing radiation curable resin can be appropriately selected from conventionally used polymerizable monomers and polymerizable oligomers or prepolymers.
As the polymerizable monomer, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate monomer is preferable. The polyfunctional (meth) acrylate monomer is not particularly limited as long as it is a (meth) acrylate monomer having two or more ethylenically unsaturated bonds in the molecule. These (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, a polyether (meth) acrylate. Preferred are (meth) acrylate oligomers such as oligomers and acrylic (meth) acrylate oligomers, and these oligomers can be used singly or in combination of two or more.

Here, the urethane (meth) acrylate oligomer can be obtained, for example, by esterifying, with (meth) acrylic acid, a polyurethane prepolymer obtained by a reaction between polyether polyol or polyester polyol and polyisocyanate.
The epoxy (meth) acrylate oligomer can be obtained, for example, by esterifying the oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin with (meth) acrylic acid. Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used.
Examples of the polyester (meth) acrylate oligomer include esterification of a hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to carboxylic acid with (meth) acrylic acid.
The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.
In addition, acrylic (meth) acrylate oligomers can be copolymerized with (meth) acrylic acid alkyl esters, glycidyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, hydroxyalkyl (meth) acrylate, etc. These functional group-containing (meth) acrylic compounds or oligomers formed by copolymerization with (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and other carboxylic acids.

  The polymerizable oligomer is preferably a (meth) acrylate oligomer having a reactive functional group such as a hydroxyl group, an amino group, or a thiol group, particularly an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer having a hydroxyl group, a hydroxyl group. Polyester (meth) acrylate oligomers having are preferred.

  These polymerizable oligomers preferably used as the ionizing radiation curable resin preferably have 2 to 10 radical polymerizable unsaturated groups. When the number of functional groups is within the above range, since excellent flexibility is obtained, excellent processability capable of dealing with various processes including V-cut is obtained.

  The weight average molecular weight of these polymerizable oligomers (polystyrene equivalent weight average molecular weight measured by GPC method) is preferably about 600 to 5,000. When the weight average molecular weight is within the above range, weather resistance and contamination resistance can be obtained together with excellent antiallergen function. Moreover, since the ionizing radiation curable resin has an appropriate thixotropy, the formation of the tick repellent functional layer is facilitated.

  Moreover, when using the above-mentioned polymerizable oligomer, a monofunctional or polyfunctional urethane (meth) acrylate monomer may be used in combination as appropriate within the range not impairing the object of the present invention, for the purpose of reducing the viscosity. it can. These (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the mite repellent in the resin composition is preferably 0.01 to 20 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the curable resin (main component in the two-part curable resin composition). Is 0.05 to 15 parts by mass. When the content of the mite repellent is within the above range, the resin composition is excellent in applicability and has a high mite repellent function, a function of improving the adhesion between the base sheet and the anti-allergen layer, and excellent Workability is obtained.

  The thickness of the tick repellent functional layer is preferably 0.5 to 50 μm, more preferably 0.5 to 25 μm. When the thickness is within the above range, a high mite repellent function and excellent processability can be obtained.

Anti-allergen functional layer 6
The anti-allergen functional layer is a layer that imparts an anti-allergen function to the decorative sheet of the present invention. The anti-allergen functional layer is preferably formed of a resin composition for an anti-allergen functional layer containing a curable resin and an anti-allergen agent.

  The curable resin used for forming the anti-allergen functional layer is not particularly limited as long as it is a resin that is cured by irradiation with heat or ionizing radiation. In the present invention, a resin that is cured by irradiation with ionizing radiation, that is, an ionizing radiation curable resin is preferable. By using an ionizing radiation curable resin, high surface properties can be obtained.

Preferable examples of the thermosetting resin include phenol resin, phenol / formalin resin, urea resin, urea / formalin resin, melamine resin, melamine / formalin resin, alkyd resin, epoxy resin, and unsaturated polyester resin.
Moreover, as ionizing radiation curable resin, what was described as ionizing radiation curable resin preferably for formation of a tick repellent functional layer is mentioned preferably.

  The anti-allergen agent is not particularly limited as long as it is an agent that exhibits an anti-allergen function. Preferable anti-allergen agents include those having a phenolic hydroxyl group, that is, a phenol compound, which functions to adsorb and inactivate allergenic substances. 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 agent, “Marcalinker M (trade name)” (Maruzen Petrochemical Co., Ltd.) can be used, and this anti-allergen agent 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. 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. Preferred from the viewpoint of having an excellent antiallergen function 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 the antiallergen function.
As an inorganic solid acid, the inorganic solid acid described as a support | carrier of the above-mentioned mite repellent is mentioned preferably. Moreover, the carrying | supporting to the inorganic solid acid of an antiallergen agent can be performed by the method similar to the carrying | support to the inorganic solid acid of a tick repellent.

  In the present invention, when a polyphenol compound supported on an inorganic solid acid is used as an anti-allergen agent, the weight ratio of the polyphenol compound to the inorganic solid acid is preferably 10:90 to 95: 5, more preferably 20: It is 80-80: 20, More preferably, it is 20: 80-40: 60. When the weight ratio is within the above range, a particularly excellent antiallergen function can be obtained due to the synergistic effect of the polyphenol compound and the inorganic solid acid. Such an anti-allergen agent can also be obtained 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, can be mentioned as a commercial product.

  The compounding quantity of an antiallergen agent is 1-30 mass parts with respect to 100 mass parts of ionizing radiation-curable resins, Preferably it is 3-25 mass parts, More preferably, it is 8-15 mass parts. In the present invention, even in such a small amount, by combining with the above 2 to 10 functional urethane (meth) acrylate oligomer, an excellent antiallergen function can be obtained, and excellent weather resistance and contamination resistance can be obtained. Sex is also obtained.

  In addition, the anti-allergen functional layer 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 the application of the decorative sheet of the present invention. , And additives such as matting agents or anti-settling agents can be included. Moreover, a tick repellent can also be added in the range which does not impair the effect of this invention.

Preferred examples of the UV absorber include organic UV absorbers such as benzotriazole, triazine, and benzophenone, and triazines that have high UV-absorbing ability and are less susceptible to deterioration due to high energy such as UV rays. preferable. Also, when ionizing radiation curable resin is used as the curable resin, ionizing radiation having an ethylenic double bond-containing functional group such as (meth) acryloyl group or vinyl group as necessary to suppress bleed out. A reactive ultraviolet absorber may 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 curable resin.

As the light stabilizer, a hindered amine-based light stabilizer is preferable. When an ionizing radiation curable resin is used as the curable resin, an ionization having an ethylenic double bond-containing functional group such as a (meth) acryloyl group or a vinyl group. A radiation-responsive hindered amine light stabilizer is preferred. Examples of such a light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate.
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 curable resin.

  As the antibacterial agent, the carrier is an inorganic adsorbent such as activated carbon, activated alumina or silica gel, or an inorganic compound such as zeolite or zirconium phosphate. In addition to silver ions or silver ions, the carrier contains copper ions or zinc ions. A combination of at least silver ions used in combination is preferred.

  As the antiwear agent, the inorganic filler preferably includes spherical particles such as α-alumina and silica, and the organic filler preferably includes a synthetic resin bead such as a crosslinked acrylic resin and a polycarbonate resin. The particle size is usually about 30 to 100% of the film thickness, and the blending amount is about 1 to 20 parts by weight with respect to 100 parts by weight of the curable resin.

Preferred examples of the matting agent include inorganic fine powders such as silica and calcium silicate, organic fillers made of acrylic resin and urethane resin, and the like.
As a compounding quantity of a matting agent, it is 4-30 mass parts with respect to 100 mass parts of curable resin, and it is more preferable that it is 10-20 mass parts.

  Moreover, when using ultraviolet curable resin as curable resin, it is desirable to add about 0.1-5 mass parts of photoinitiators with respect to 100 mass parts of curable resin.

Primer layer 4
The decorative sheet of the present invention can be provided with a primer layer as shown in FIGS. 2 and 3 from the viewpoint of improving the adhesion between the base sheet and the tick repellent functional layer. The primer layer is formed of a resin composition containing a curable resin. Examples of the curable resin include acrylic resin, polyester resin, polyurethane resin, polyurethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, and chlorinated polypropylene. Known materials such as resins and chlorinated polyethylene resins can be used, and there is no particular limitation, but from the viewpoint of improving adhesion, the main agent and isocyanate as described as a curable resin forming a tick repellent functional layer A two-component curable resin composition containing a curing agent such as a compound is preferred. When a two-component curable resin composition is used for forming the primer layer, it is preferable to employ an ionizing radiation curable resin as the curable resin for forming the tick repellent functional layer. By such a combination, excellent adhesion between the base material sheet and the tick repellent functional layer can be obtained, and a decrease in the anti-allergen function due to the curing agent contained in the primer layer can be suppressed. .

The primer layer has a thickness of about 0.5 to 10 μm, preferably 0.5 to 5 μm. When the thickness of the primer layer is within the above range, excellent adhesion between the base sheet and the tick repellent functional layer can be obtained.
Moreover, you may add a tick repellent to a primer layer, if it is a range which does not inhibit the function of a primer layer.

Block layer The decorative sheet of the present invention has a tick repellent functional layer and an antiallergenic function from the viewpoint of maintaining a high antiallergen function when a two-component curable resin composition is used as a curable resin for forming the tick repellent functional layer. A block layer is preferably provided between the layers (not shown). This is because an excellent inhibitory effect on the deactivation of the curing agent contained in the primer layer, particularly the anti-allergen agent due to the isocyanate compound, is obtained, and an excellent anti-allergen function is obtained. The block layer is formed of a resin composition containing a curable resin, and preferred examples of the curable resin include the ionizing radiation curable resin described as the curable resin for forming the mite repellent layer. Among ionizing radiation curable resins, from the viewpoint of maintaining a high antiallergen function, (meth) acrylate oligomers having a reactive functional group such as a hydroxyl group or an amino group or a thiol group, such as an epoxy (meth) acrylate oligomer, A urethane (meth) acrylate oligomer having a hydroxyl group and a polyester (meth) acrylate oligomer having a hydroxyl group are preferred. When a two-part curable resin composition is used as a curable resin for the formation of a tick repellent functional layer or a primer layer, excellent deactivation of a curing agent contained in the resin composition, particularly an anti-allergen agent caused by an isocyanate compound This is because an excellent anti-allergen function is obtained.

When the ionizing radiation curable resin having a hydroxyl group is used as the curable resin, the thickness of the block layer is usually about 1 to 45 μm, preferably 3 to 35 μm, more preferably 5 to 25 μm. Moreover, when the ionizing radiation curable resin used as curable resin does not have a hydroxyl group, it is about 1-30 micrometers normally, 5-27 micrometers is preferable, More preferably, it is 10-25 micrometers. When the block layer is within the above range, the coating property of the resin composition is excellent and a high antiallergen function can be maintained.
Moreover, you may add a tick repellent to a block layer, if it is a range which does not inhibit the function of a block layer.

  The decorative sheet of the present invention can be provided with an embossed pattern (not shown) by embossing on the surface. 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 in the shape of an embossed pattern, It forms according to the characteristic of the building material to which the decorative sheet of this invention is applied.

[Method for producing decorative sheet]
The decorative sheet of the present invention is, for example, an anti-allergen functional layer containing a curable resin and an anti-allergen agent after applying and curing a resin composition containing a mite repellent and a curable resin on a base sheet. It can manufacture by apply | coating and hardening the resin composition for water.

  Application of each resin composition is gravure coating, bar coating, roll coating, reverse roll coating, comma coating, flow coater, spraying method, airless spray method, air spray method, brush coating, trowel coating, dipping method, pulling method , A known method such as a nozzle method, a winding method, a sink method, a piling method, and a patching method, preferably a gravure coating.

  In addition, when an ionizing radiation curable resin is used as the curable resin, the resin is preferably cured by irradiating with ionizing radiation. When an electron beam is used, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer. Usually, the acceleration voltage is about 70 to 300 kV, and the irradiation dose is 5 to 300 kGy (0.5 to 30 Mrad), preferably Is selected in the range of 5 to 100 kGy (0.5 to 10 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.

  In this invention, it is preferable to form a primer layer from a viewpoint of improving the adhesiveness of a base material sheet and a tick repellent functional layer as mentioned above. The primer layer is preferably formed using a two-component curable resin composition as the curable resin, and the application of the resin composition is the application of a resin composition containing a curable resin that forms the above-described mite repellent functional layer. It can be performed by a method similar to the method. The same applies to the formation of the block layer.

[Decorative board]
The decorative board of the present invention is obtained by laminating the decorative sheet of the present invention on a substrate. A board | substrate is not limited, The thing similar to a well-known decorative board can be used, For example, a wooden material, a metal, ceramics, plastics, glass etc. are mentioned.
Examples of wood materials include veneers made of various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie, and wood materials such as wood veneer, wood plywood, particle board, and medium density fiberboard (MDF). . These can be used alone or in a laminated manner. The wooden board is not limited to a wooden board, but includes a plastic board containing paper powder and reinforced paper.

In addition, as an adhesive used for pasting the decorative sheet and the substrate, urea, vinyl acetate resin, urea resin, melamine resin, phenol resin, isocyanate, and the like can be used. It is used alone or as a mixed adhesive that is arbitrarily mixed. As needed, inorganic powders such as talc, calcium carbonate, clay and titanium white, 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 range of 50 to 300 g / m ² .

  Adhesion of a decorative sheet on a substrate usually forms an adhesive layer on the back side of the decorative sheet, and the substrate is adhered, or an adhesive is applied on the substrate, and a mirror surface decorative sheet is adhered. Depending on the method. For the sticking, a sticking device such as a cold press, hot press, roll press, laminator, wrapping, edge pasting 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 mouth using a cutting machine such as a router or a cutter. it can. And it is used suitably for various uses, for example, interior materials and exterior materials, such as a flooring and a wall material.

  Since the anti-allergen agent and the mite repellent are not actively used in the same layer, the decorative sheet of the present invention maintains excellent surface properties such as excellent stain resistance, solvent resistance, and weather resistance, and has excellent anti-resistance properties. Allergen function and mite repellent function can be exhibited. That is, the mite repellent functional layer does not attract ticks that cause allergens, and allergen substances brought in due to factors other than ticks can be inactivated by the anti-allergen functional layer. Therefore, the decorative sheet of the present invention can be suitably used as an interior material or exterior material such as a flooring material or a wall material, for example, by pasting it on a substrate to form a decorative board.

1. Base sheet 1a. Base sheet 1b. 1. Base sheet Print layer 2. Adhesive layer 4. Primer layer 5. 5. Tick repellent functional layer Anti-allergen functional layer 10. Decorative sheet

Claims (11)

A base sheet, a tick repellent functional layer containing a tick repellent having a vapor pressure at 25 ° C. of 0.1 × 10 ⁻⁶ kPa or more, and an anti-allergen functional layer containing an anti-allergen agent that removes or inactivates allergens in order A decorative sheet comprising the decorative sheet.   The decorative sheet according to claim 1, wherein the anti-allergen functional layer is a cured product of a resin composition for an anti-allergen functional layer containing a curable resin and an anti-allergen agent.   The decorative sheet according to claim 2, wherein the curable resin is an ionizing radiation curable resin.   The decorative sheet according to any one of claims 1 to 3, wherein the tick repellent functional layer is a cured product of a resin composition containing the mite repellent and a curable resin.   The decorative sheet according to any one of claims 1 to 4, wherein the anti-allergen agent has a phenolic hydroxyl group.   The decorative sheet according to any one of claims 1 to 5, wherein the anti-allergen agent is supported on an inorganic solid acid.   The decorative sheet according to any one of claims 1 to 6, wherein the mite repellent is a pyrethroid compound.   The decorative sheet according to any one of claims 1 to 7, wherein the mite repellent is supported on an inorganic solid acid.   The decorative sheet according to any one of claims 2 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 resin.   The cosmetic sheet according to any one of claims 4 to 9, wherein a compounding amount of the mite repellent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the curable resin.   A decorative sheet comprising the decorative sheet according to claim 1 and a substrate in order.

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