JP2013063635A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having a function of reducing an aldehyde concentration in air, and to provide a decorative laminated sheet.SOLUTION: The decorative sheet including at least a surface protective layer on a base material sheet is characterized in that the surface protective layer is composed of a resin composition containing an ionizing radiation curable resin, an aldehyde adsorbent, and a non-photocatalyst.

Description

  The present invention relates to a decorative sheet having a function of reducing the aldehyde concentration in the air.

In response to the problem that volatile organic compounds (VOC) released from house members pollute indoor air and cause sick house syndrome, VOC is effectively reduced to reduce the concentration of VOC contained in the indoor air. There is an increasing need for building interior materials having a photocatalytic function for decomposition.
On the other hand, as a decorative sheet having a deodorizing performance using a photocatalyst, a decorative sheet having a diatomaceous earth layer on which a photocatalyst or the like is adsorbed on a base material has been proposed (see Patent Document 1). It can be considered to be applied as a decorative sheet having a function.

However, the decorative sheet that depends only on the photocatalytic decomposition action as in Patent Document 1 has a problem that the VOC concentration cannot be sufficiently reduced. Such a problem is particularly remarkable when used in a dark place such as a closet or a shelf board where sufficient irradiation of light necessary for exerting the catalytic action cannot be obtained.
Further, as a decorative sheet used for interior use for a house, improvement of surface properties represented by scratch resistance and contamination resistance is also demanded. However, in the decorative sheet described in Patent Document 1, these requirements are required. I was not satisfied.

JP 2005-324488 A

  The present invention has been made in view of the above problems in the prior art, has excellent scratch resistance and stain resistance, and has a function of adsorbing and decomposing aldehydes such as formaldehyde and acetaldehyde, which are typical VOCs. Thus, an object of the present invention is to provide a decorative sheet that can effectively reduce the indoor aldehyde concentration.

  As a result of intensive studies to achieve the above object, the present inventors provide a surface protective layer comprising a resin composition containing an ionizing radiation curable resin, an aldehyde adsorbent and a non-photocatalyst on a base sheet. Then, it discovered that the said subject could be solved. The present invention has been completed based on such findings.

That is, the present invention
[1] A decorative sheet having at least a surface protective layer on a substrate sheet,
The surface protective layer is a decorative sheet comprising a resin composition containing an ionizing radiation curable resin, an aldehyde adsorbent and a non-photocatalyst,
[2] The decorative sheet according to [1], wherein the ionizing radiation curable resin is an electron beam curable resin,
[3] The decorative sheet according to [1] or [2], wherein the aldehyde adsorbent is an inorganic aldehyde adsorbent and / or an organic-inorganic composite aldehyde adsorbent,
[4] Any of the above [1] to [3], wherein the resin composition contains 0.5 to 30 parts by mass of the aldehyde adsorbent with respect to 100 parts by mass of the ionizing radiation curable resin. Cosmetic sheet according to
[5] The non-photocatalyst contains at least one metal selected from the group consisting of titanium, iron, platinum, silver, palladium, zirconium, germanium, cerium, potassium, aluminum, gallium, cobalt, and nickel. The decorative sheet according to any one of [1] to [4] above,
[6] The decorative sheet according to [5], wherein the non-photocatalyst is a titanium phosphate compound.
[7] In any one of the above [1] to [6], the resin composition includes 0.5 to 10 parts by mass of the non-photocatalyst with respect to 100 parts by mass of the ionizing radiation curable resin. The decorative sheet,
[8] The decorative sheet according to any one of [1] to [7], further including a colored layer and / or a pattern layer on the base sheet.
[9] The decorative sheet according to any one of the above [1] to [8], which has a primer layer between the base sheet and the surface protective layer.
[10] The decorative sheet according to [9], wherein the primer layer includes an aldehyde adsorbent and / or a non-photocatalyst.
[11] A decorative board having an adherend on the back surface of the decorative sheet according to any one of [1] to [10],
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, while showing the reduction effect | action of the aldehyde density | concentration in air, the decorative sheet and decorative board which have the outstanding scratch resistance and stain | pollution resistance can be provided.

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

  The decorative sheet of the present invention has at least a surface protective layer on the substrate sheet, and may optionally have a colored layer and / or a pattern layer. Usually, it has the structure laminated | stacked in order of the base material sheet, the colored layer, the pattern layer, and the surface protective layer. Hereinafter, the decorative sheet of the present invention will be described in detail.

(Substrate sheet)
It does not specifically limit as a base material sheet, The thing generally used in the decorative sheet can be used. For example, paper, a nonwoven fabric, a thermoplastic resin sheet, or a laminate thereof is used.

As the paper, for example, thin paper, craft paper, fine paper, linter paper, baryta paper, sulfate paper, Japanese paper, titanium paper, etc. can be used, and as the nonwoven fabric, for example, polyester resin, acrylic resin, nylon, vinylon, rayon Nonwoven fabric made of fibers such as glass can be used. The basis weight of paper or non-woven fabric is usually about ²⁰ to 100 g / m ² . In addition, for paper and nonwoven fabrics, resins such as acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin are added to strengthen the interlaminar strength between the fibers and other layers, and to prevent galling. It may be impregnated with resin after papermaking or embedded during papermaking, or it may be colored for the purpose of improving design properties.

  Examples of the thermoplastic resin sheet include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins, polyolefin resins, polyvinyl chloride resins, polystyrene resins, acrylonitrile-butadiene-styrene copolymer resins (ABS resins), and polycarbonates. Examples thereof include resins and polyamide resins, and polyolefin resins are particularly preferable.

  Polyolefin resins include polyethylene (high density, medium density, or low density), polypropylene (isotactic or syndiotactic), polybutene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer. And olefin-based thermoplastic elastomers. Examples of olefinic thermoplastic elastomers include hard segments made of crystalline polyolefin resin as described above and elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, atactic polypropylene, styrene-butadiene rubber, and hydrogenated styrene-butadiene rubber. What is obtained by mixing soft segments consisting of The mixing ratio of the hard segment and the soft segment is preferably about [soft segment / hard segment] = 5/95 to 40/60 (mass ratio). If necessary, the elastomer component may be crosslinked with a known crosslinking agent such as sulfur or hydrogen peroxide. Furthermore, the thermoplastic resin sheet may be colored for the purpose of improving design properties.

  Examples of the layer structure of the base sheet include those obtained by laminating the above-described paper, non-woven fabric, thermoplastic resin sheet and the like into a single layer or two or more layers by a known means such as an adhesive or heat fusion. The thickness of the base sheet (total thickness in the case of a laminate) is not particularly limited, but is usually about 25 to 500 μm.

(Colored layer)
The colored layer is also referred to as a concealing layer or an all-solid layer, and gives the intended color to the entire surface of the base sheet. Usually, it is formed with an opaque color, but it can also be formed with a colored transparent color and make use of the pattern of the base. When the color of the base sheet is utilized, or when the base sheet itself is appropriately colored, the formation of the colored layer may be omitted.

  As the ink used for forming the colored layer, a binder and a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent are appropriately mixed. The binder is not particularly limited, and examples thereof include polyurethane resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose (nitrified cotton) resins, cellulose acetate resins, and chlorides. Any one selected from vinyl-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated polypropylene resin, etc. is used alone or in combination of two or more. It is done.

  Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metal pigments made of scaly foil pieces such as aluminum and brass, pearlescent pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used. A so-called solid print layer having a thickness of about 1 to 20 μm is preferably used.

  The formation method in the case of providing a colored layer is not particularly limited, and a known method may be used depending on the application. The colored layer can be formed, for example, by using a printing method such as gravure printing, silk screen printing, offset printing, gravure offset printing, ink jet printing, or a coating method such as gravure coating or roll coating using ink or a coating liquid. .

(Picture layer)
The pattern layer is formed by printing various patterns using ink and a printing machine. As patterns, there are stone patterns imitating the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns imitating cloth and cloth patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done. As the pattern ink used for the pattern layer, the same ink as that used for the colored layer can be used. As for the formation method of the picture layer, a known method can be used as in the case of the colored layer.

(Surface protective layer)
The surface protective layer is a layer provided as the outermost surface layer of the decorative sheet, and is provided to protect layers between the base sheet and the surface protective layer, such as a colored layer and a pattern layer. In the present invention, the surface protective layer also has a role as a functional layer that takes in and adsorbs and decomposes aldehyde.
The surface protective layer in the decorative sheet of the present invention is made of a resin composition containing an ionizing radiation curable resin, an aldehyde adsorbent and a non-photocatalyst. When the surface protective layer contains an ionizing radiation curable resin, excellent scratch resistance can be obtained. Further, the ionizing radiation curable resin can suppress the aldehyde adsorbent and the non-photocatalyst from falling off, and can continuously exhibit the adsorption function of the aldehyde adsorbent and the decomposition function of the non-photocatalyst. Here, the surface protective layer, a coating amount is preferably in the range of usually 1 to 30 g / ^{m 2} (solids basis), more preferably a 1 to 15 g / ^{m 2.}

<Ionizing radiation curable resin>
The ionizing radiation curable resin used for the surface protective layer refers to a resin that is crosslinked and cured by irradiation with ionizing radiation such as ultraviolet rays and electron beams.
As the ionizing radiation curable resin, conventionally known compounds can be appropriately used. Specifically, polymerizable monomers or oligomers (including so-called prepolymers) commonly used as ionizing radiation curable resins can be appropriately selected or used in combination.

  Typically, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable as the polymerizable monomer, 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. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphate di ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( (Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Examples include ethylene oxide-modified bisphenol A diacrylate. These polyfunctional (meth) acrylates may be used singly or in combination of two or more. (Meth) acrylate means acrylate or methacrylate, and similar terms have the same meaning.

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

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

When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 10 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin composition. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 − , 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, etc. Can be mentioned.
Examples of the polymerizable oligomer having a cationic polymerizable functional group in the molecule include aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

The surface protective layer preferably further contains silicone (meth) acrylate. Silicone (meth) acrylate mainly improves the stain resistance of the decorative sheet mainly due to a synergistic effect with the ionizing radiation curable resin. Silicone (meth) acrylate is one of silicone oils made of polysiloxane or modified silicone oil in which (meth) acrylic groups are introduced at one or both ends. As the silicone (meth) acrylate, conventionally known ones can be used, and the organic group is not particularly limited as long as the organic group is a (meth) acryl group, and a modified silicone oil having one or two organic groups is preferable. The structure of the modified silicone oil is roughly divided into a side chain type, a both-end type, a single-end type, and a side-chain both-end type depending on the bonding position of the organic group to be substituted. There is no particular limitation.
The content of the silicone (meth) acrylate is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin from the viewpoint of sufficiently improving the stain resistance and obtaining the effect of use. .1 to 5 parts by mass is more preferable. Moreover, as a functional group equivalent (molecular weight / functional group number) of silicone (meth) acrylate, what has the conditions of 100-20000 is mentioned, for example.

(Aldehyde adsorbent)
The aldehyde adsorbent used in the present invention (hereinafter sometimes simply referred to as an adsorbent) can be widely used as long as it has an adsorptive power to aldehydes such as formaldehyde and acetaldehyde and does not cause discoloration. In addition to compounds such as amines, ureas, amides, imides, hydrazides, azoles and azines, inorganic aldehyde adsorbents (inorganic adsorbents) and organic-inorganic composite aldehyde adsorbents (organic-inorganic composites) Adsorbents) can be used. These adsorbents can be used individually by 1 type or in combination of 2 or more types as appropriate.

  Examples of amines include hydroxylamine, ethanolamine, dimethylamine, diethylamine, isopropylamine, proline, hydroxyproline, dicyanodiamide, ethyleneimine, ethylenediamine, propylenediamine, diethylenetriamine, 2-diethylaminoethanol, 2-dimethylaminoethanol, 1, 2-diaminopropane, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, tetramethylenediamine, guanidine carbonate, glycine, alanine, sarcosine, glutamic acid, hexamethylenediamine, melamine, morpholine, 2-amino-4,5- Examples include dicyanoimidazole, 3-azahexane-1,6-diamine, and sodium aminobenzoate.

Examples of ureas include urea, thiourea, methylurea, ethyleneurea, acetylurea, azodicarbonamide, and the like.
Examples of amides include formamide, acetamide, succinic acid amide, dicyandiamide and the like.
Examples of imides include succinimide, hydantoin, and isocyanuric acid.

  Examples of hydrazides include lauric acid hydrazide, salicylic acid hydrazide, form hydrazide, acetohydrazide, propionic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy-2-naphthoic acid hydrazide, oxalic acid dihydrazide, and malonic acid dihydrazide. Succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecane-2 acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, diphthalide diacid dihydrazide, diphthalide diacid dihydrazide , Dimer acid dihydrazide, 2,6-naphthoic acid dihydrazide and the like.

  As azoles and azines, 3-methyl-5-pyrazolone, 1,3-dimethyl-5-pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 3-phenyl-6-pyrazolone, 3-methyl- Pyrazolones such as 1- (3-sulfophenyl) -5-pyrazolone, pyrazole, 3-methylpyrazole, 1,4-dimethylpyrazole, 3,5-dimethylpyrazole, 3,5-dimethyl-1-phenylpyrazole, 3 -Aminopyrazole, 5-amino-3-methylpyrazole, 3-methylpyrazole-5-carboxylic acid, 3-methylpyrazole-5-carboxylic acid methyl ester, 3-methylpyrazole-5-carboxylic acid ethyl ester, 1,2 , 3-triazole, 1,2,4-triazole, 3-n-butyl-3,5-dimethyl-1,2,4- Riazole, 3,5-di-n-butyl-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1, 2,4-triazole, 3,5-diamino-1,2,4-triazole, 5-amino-3-mercapto-1,2,4-triazole, 3-amino-5-phenyl-1,2,4- Triazole, 3,5-diphenyl-1,2,4-triazole, 1,2,4-triazol-3-one, urazole (3,5-dioxy-1,2,4-triazole), 1,2,4 -Triazole-3-carboxylic acid, 1-hydroxybenzotriazole, 5-hydroxy-7-methyl-1,3,8-triazaindolizine, 1H-benzotriazole, 4-methyl-1H-benzotria Lumpur, 5-methyl -1H- benzotriazole, 6-methyl-8-hydroxy-triazolopyridazine, 4,5-dichloro-3-pyridazine, maleic hydrazide, 6-methyl-3-pyridazone and the like.

  Inorganic adsorbents include, but are not limited to, zeolite, aluminum phosphate, hydroxyapatite, and the like. From the viewpoint of adsorption performance, mordenite type, Y type, and ZSM-5 type zeolite are preferable, and hydrogen ion exchanged ZSM-5 type zeolite (for example, “HSZ-800” manufactured by Tosoh Corporation) is more preferable.

  Examples of the organic / inorganic composite adsorbent include composite materials in which compounds such as the amines, ureas, amides, imides, hydrazides, azoles and azines mentioned above are supported on an inorganic compound. Examples of the inorganic compound that can be used as the carrier include silicon dioxide, activated carbon, sepiolite, and mica from the viewpoint of heat resistance. Among these inorganic compounds, it is particularly preferable to use a porous body of silicon dioxide from the viewpoint of adsorption performance.

More specifically, as the organic-inorganic composite adsorbent, as described in paragraph [0016] of JP-A-2003-52800, an amine compound having a primary amino group is supported on the above-described inorganic compound. And composite materials. As compounds of amines having a primary amino group, as described in paragraph [0020] of the same publication, aliphatic compounds include “H ₂ N— (CH ₂ CH ₂ —NH) _n —CH ₂ CH”. ₂ NH ₂ (n is an integer of 0 or more and 3 or less) ”is preferable, and aniline is preferable as the aromatic compound.

  In the present invention, among these, it is preferable to use an inorganic adsorbent or an organic-inorganic composite adsorbent as a material that is unlikely to cause discoloration or bleed-out of the surface protective layer. More preferably, an adsorbent is used.

  The addition amount of the adsorbent is not particularly limited, but considering the suitability for applying the composition for forming the surface protective layer by printing, 0.5 to 30 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin Is preferably added, and more preferably 1 to 20 parts by mass.

(No photocatalyst)
The non-photocatalyst used in the present invention refers to a substance that exhibits a catalytic function for decomposing an aldehyde without being irradiated with ultraviolet rays or visible light, and can be used without particular limitation as long as it satisfies the above conditions. By including a substance having such a function in the surface protective layer, the aldehyde adsorbed on the adsorbent can be decomposed, and the function of the adsorbent can be exhibited efficiently and in the long term. In addition, since it does not require light irradiation, it can exhibit an aldehyde decomposition action at night, and can provide a decorative sheet suitable for use in a dark place such as a closet or a shelf board. Further, since the non-photocatalyst exhibits a relatively gradual catalytic action, there is a low possibility that the organic component will be decomposed even when combined with an organic binder or the like, so that a decorative sheet having excellent long-term durability can be provided.

As the non-photocatalyst, for example, an inorganic material containing a metal such as titanium, iron, platinum, silver, palladium, zirconium, germanium, cerium, potassium, aluminum, gallium, cobalt, or nickel can be used. Specific examples include titanium phosphate compounds, iron oxide, and the like, and materials known as charge transfer catalysts (CT catalysts) as described in, for example, JP-A No. 2002-1121 can be used. Said non-photocatalyst can be used individually by 1 type or in combination of 2 or more types.
Of these, a titanium phosphate compound is most preferable from the viewpoint of effects. Examples of the titanium phosphate compound include Ti (OH) (H ₂ PO ₄ ) ₂ (OR), Ti (OH) (PO ₄ ), Ti (OH) ₂ (H ₂ PO ₄ ) (OR), Ti (OH) (HPO ₄ ) (OR), Ti (OH) (HPO ₄ ) (H ₂ PO ₄ ), Ti (OH) ₂ (H ₂ PO ₄ ) ₂ , Ti (OH) ₃ (H ₂ PO ₄ ) Or these condensates etc. can be used. Here, R is an alkyl group having 1 to 4 carbon atoms.

  The addition amount of the non-photocatalyst is not particularly limited, but considering the suitability for applying the composition for forming the surface protective layer by printing, 0.5 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin Is preferably added, and more preferably 0.5 to 5 parts by mass.

(Other additives)
The surface protective layer can contain various additives depending on the physical properties required depending on the purpose and application. The additive includes a wear resistance improver such as inorganic particles such as alumina and silica and resin particles such as acrylic, and a wax obtained by dissolving or dispersing resins such as polypropylene and polyethylene in an organic solvent such as an ester. , Weather resistance improver, polymerization inhibitor, crosslinking agent, infrared absorber, antistatic agent, adhesion improver, leveling agent, thixotropic agent, coupling agent, plasticizer, antifoaming agent, filler, colorant And antibacterial agents. In addition, the compounding quantity of these various additives is set suitably in the range which does not impair the effect of this invention, acquiring the effect of various additives fully.

  The surface protective layer may contain a photocatalyst as long as the effects of the present invention are not impaired. A known substance can be used as the photocatalyst, and it is not particularly limited as long as it is a substance that exhibits a function of decomposing aldehyde with visible light.

(Method for forming surface protective layer)
The surface protective layer of the present invention is prepared, for example, by a resin composition prepared by appropriately mixing the above-mentioned ionizing radiation curable resin, aldehyde adsorbent, non-photocatalyst, and other additives (hereinafter also referred to as ionizing radiation curable resin composition). ) Is coated on the base material sheet, and then cured by irradiation with ionizing radiation. Examples of coating methods for ionizing radiation curable resin compositions include gravure coating, bar coating, roll coating, reverse roll coating, comma coating, and other printing methods, gravure printing, gravure offset printing, screen printing, etc. A known method can be used.
In addition, in order to improve the adhesion between the base sheet, the surface protective layer, and other layers, a primer layer described in detail later can be provided between the respective layers.

As the ionizing radiation used for crosslinking and curing the ionizing radiation curable resin composition, an electron beam or an ultraviolet ray is usually used, but a visible ray, an X-ray, an ion beam or the like may be used.
When an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but is usually about 70 to 300 kV. In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base sheet that deteriorates due to the electron beam, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal, it is possible to suppress the irradiation of the extra electron beam to the base sheet, and to minimize the deterioration of the base sheet due to the excess electron beam.
The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
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 the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are usually 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)
A primer layer may be provided between the base sheet and the surface protective layer (interlayer) as necessary. By providing the primer layer, interlayer adhesion can be enhanced.
The primer layer may be in contact with the surface protective layer, and a colored layer, a pattern layer, or the like may be interposed between the surface protective layer and the primer layer. The primer layer may be in contact with the base material sheet, and a colored layer, a pattern layer, or the like may be interposed between the base material sheet and the primer layer.
As a specific example of the position where the primer layer is provided, for example, in the case where a colored layer and a picture layer are provided on the base sheet, it is between the picture layer and the surface protective layer.
Examples of materials for forming the primer layer include resins such as polyester resin, polyurethane resin, acrylic resin, polycarbonate resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral resin, nitrocellulose resin (nitrified cotton), Compounds such as alkyl titanates and ethyleneimines can also be used. Among these, it is preferable to use an acrylic urethane resin, urethane nitrified cotton, a two-component curable urethane resin, or the like as a binder resin. The material for forming the primer layer can be used alone or in combination of two or more.
As the two-component curable urethane-based resin, a fatty acid isocyanate such as hexamethylene diisocyanate (HMDI) is preferable as an isocyanate that is a curing agent, and an acrylic polyol is preferably used as a polyol that is a main agent. It is preferable in terms of obtaining properties and adhesion.

  Further, the primer layer may contain the aldehyde adsorbent, non-photocatalyst, and other additives as necessary. The non-photocatalyst generates radicals having an oxidizing action from water in the air, and the radicals decompose organic substances such as aldehydes. Therefore, in particular, if the primer layer contains a non-photocatalyst and the base sheet has water absorption properties, the non-photocatalyst is in the vicinity of the base sheet, so that the decomposition function is further improved. As a result, the indoor aldehyde concentration is reduced. It can be reduced efficiently.

  Examples of the base sheet having water absorption include thin paper, kraft paper, and titanium paper.

  The content of the aldehyde adsorbent in the primer layer is preferably 0.5 to 50 parts by mass and more preferably 1 to 25 parts by mass with respect to 100 parts by mass of the material forming the primer layer.

  The content of the non-photocatalyst in the primer layer is preferably 0.01 to 10 parts by mass and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the material forming the primer layer.

The primer layer is formed in the state in which the material for forming the primer layer is used as it is or dissolved or dispersed in a solvent, or mixed with an aldehyde adsorbent, a non-photocatalyst, and other additives as desired. It can be formed according to known printing methods such as gravure printing, coating methods, and the like. Moreover, the coating amount of a primer layer is about 0.5-5 g / m < ² > normally.

(Manufacturing method of decorative sheet)
The decorative sheet of the present invention is manufactured by, for example, the following manufacturing method, but is not limited thereto.
A colored layer and a pattern layer are sequentially formed on the substrate sheet by a gravure printing method, and then a primer layer is applied by gravure printing. Next, an ionizing radiation curable resin composition prepared by mixing an ionizing radiation curable resin, an adsorbent and a non-photocatalyst is applied by a gravure offset method, and an electron beam is irradiated to form a surface protective layer. The desired decorative sheet is obtained.

  Moreover, the uneven | corrugated pattern by embossing may be formed in the decorative sheet of this invention for the purpose of improving the designability. The uneven pattern can be formed by heating and pressing with an embossing plate from the upper surface of the surface protective layer, that is, the outermost layer side, when the decorative sheet in the manufacturing process is at a temperature that can be embossed by any means. it can. A well-known single wafer or a rotary embossing machine is used to form the uneven pattern. As the shape of the uneven pattern, there are a wood grain pipe groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain, a hairline, a striated groove, and the like.

(Decorative board)
The decorative sheet of the present invention can be made into a decorative plate by bonding with various adherends. The material of the adherend is not particularly limited, and examples thereof include inorganic non-metallic materials, metallic materials, wood materials, and plastic materials.

Specifically, in inorganic non-metallic systems, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium oxalate, Non-ceramic ceramic materials such as gypsum and gypsum slag, ceramic materials such as earthenware, ceramics, porcelain, setware, glass, and glazing.

  In a metal system, metal materials (metal steel plate), such as iron, aluminum, and copper, are mentioned, for example.

  In the wood system, for example, a single board, plywood, particle board, fiber board, laminated board made of cedar, straw, firewood, lauan, teak and the like can be mentioned.

  In the plastic system, for example, resin materials such as polypropylene, ABS resin, and phenol resin can be used.

  The decorative plate can be arbitrarily cut by cutting the decorative plate and using a cutting machine such as a router or a cutter on the surface or the end of the decorative plate to give an optional decoration such as grooving or chamfering. And various uses, for example, interior or exterior materials of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, margins, surface decorative boards for fittings such as malls, kitchens, furniture or light electrical appliances, It can be suitably used for a surface decorative plate of a cabinet such as an OA device, an interior or exterior of a vehicle.

  When bonding an adherend and a decorative sheet, for example, polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural An adhesive containing rubber or the like as an active ingredient can be used. In the present invention, it is preferable to use at least one selected from the group consisting of non-formaldehyde adhesives and low formaldehyde adhesives defined in JAS and JIS emission formaldehyde standards “F ☆☆☆☆”. .

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this Example.
In addition, about the decorative sheet and the decorative board produced by each Example and the comparative example, the performance was evaluated with the following method.

(Performance evaluation)
(I) Contamination resistance test Contamination resistance was evaluated according to the JAS contamination A test. Specifically, a decorative sheet and a decorative plate cut into a 10 cm square were used as test pieces, and these were placed horizontally, and then the commercially available blue ink or black ink (JIS) on the surface protective layer surface of the test piece. Draw a straight line with a width of 10 mm and a length of 10 cm with red crayon (as defined in S6037 marking pen) and red crayon (as defined in JIS S6026), leave it for 4 hours, wipe dry with a cloth, and if there is something that cannot be wiped off with ethanol A cloth impregnated with was wiped off. What was wiped off by dry wiping was evaluated as ◯, what was wiped off by ethanol wiping was △, and what was not wiped by ethanol wiping was rated as x.

(Ii) Scratch resistance test A steel wool (made by Nippon Steel Wool Co., Ltd., trade name “Bonster”) is attached to a weight to which a load of 21 kPa (1.5 kgf / 7 cm ² ) is applied, and the surfaces of the decorative sheet and the decorative board After carrying out a rubbing test (steel wool resistance test) for rubbing 20 times, the scratch resistance on the surface of the decorative sheet was visually observed to evaluate the scratch resistance. The case where there was no scratch was marked with ◯, and the case where the scratch was confirmed was marked with ×.

(Iii) Aldehyde adsorption performance test A decorative sheet and a test piece cut into a 10 cm square were inserted into a 5 liter Tedlar bag. A gas having a formaldehyde concentration of 50 ppm was prepared using a 28% aqueous formaldehyde solution and synthetic air ((nitrogen: oxygen) volume ratio 4: 1, relative humidity 50%), and 1 liter was fed into the Tedlar bag. Thereafter, the change with time of the formaldehyde concentration in the Tedlar bag was measured by gas chromatography, and the formaldehyde removal rate after 6 hours was calculated by the following formula (1).
(Formaldehyde removal rate) [%] = [{(initial concentration) − (concentration after 6 hours)} / (initial concentration)] × 100 (1)

Example 1
On a base material sheet made of building material thin paper (general paper grade, basis weight 30 g / m ² ), the binder resin is an acrylic resin and a white concealing all-solid layer containing titanium oxide as a colorant, and the binder resin is nitrified A wood pattern layer (pattern layer) which is a cotton resin and contains a colorant was sequentially formed by gravure printing. Next, on the obtained laminate, an electron beam curable resin composition having the following composition was applied at a coating amount of 4 g / m ² by a gravure offset method, and then irradiated with an electron beam (acceleration voltage 175 kV, irradiation amount). 50 kGy), the coating film was crosslinked and cured to form a colorless and transparent surface protective layer, and a decorative sheet was prepared. The results evaluated by the above method are shown in Table 1.
Electron beam curable resin composition:
-Trifunctional acrylate monomer 60 parts by mass-Bifunctional acrylate monomer 40 parts by mass-Silicone methacrylate 0.6 parts by mass-Silica particles (average particle size 4-5 μm) 15 parts by mass-Aldehyde adsorbent (organic-inorganic composite adsorbent, Toa 15 parts by mass, manufactured by Gosei Co., Ltd., product number: NS-103, 1 part by mass of titanium phosphate compound (product name: Ecochimera, manufactured by YOO Corporation)

Example 2
A decorative sheet was prepared in the same manner as in Example 1 except that the aldehyde adsorbent added to the electron beam curable resin composition was 5 parts by mass. The results evaluated in the same manner as in Example 1 are shown in Table 1.

Example 3
A decorative sheet was prepared in the same manner as in Example 1 except that the amount of the aldehyde adsorbent added to the electron beam curable resin composition was 3 parts by mass. The results evaluated in the same manner as in Example 1 are shown in Table 1.

Example 4
In Example 1, a decorative sheet was produced in the same manner as in Example 1 except that no silicone methacrylate was added to the electron beam curable resin composition. The results evaluated in the same manner as in Example 1 are shown in Table 1.

Example 5
On a base material sheet made of building material thin paper (general paper grade, basis weight 30 g / m ² ), the binder resin is an acrylic resin and a white concealing all-solid layer containing titanium oxide as a colorant, and the binder resin is nitrified A wood pattern layer (pattern layer) which is a cotton resin and contains a colorant was sequentially formed by gravure printing. Next, a primer layer forming composition having the following composition was applied on the obtained laminate by gravure printing at a coating amount of 2 g / m ² to form a primer layer. Next, an electron beam curable resin composition having the following composition was applied by a gravure offset method at a coating amount of 4 g / m ² , and then irradiated with an electron beam (acceleration voltage 175 kV, irradiation amount 50 kGy) to crosslink the coating film. It was cured to form a colorless and transparent surface protective layer, and a decorative sheet was produced. The results evaluated by the above method are shown in Table 1.
Primer layer forming composition:
-Acrylic polyol 85 parts by mass-Isocyanate curing agent (hexamethylene diisocyanate (HDMI)) 15 parts by mass-Aldehyde adsorbent (organic-inorganic composite adsorbent, manufactured by Toa Gosei Co., Ltd., product number: NS-103) 15 parts by mass-Phosphoric acid 1 part by mass of titanium compound (trade name: Ecochimera, manufactured by YOO Corporation) Electron beam curable resin composition:
-Trifunctional acrylate monomer 60 parts by mass-Bifunctional acrylate monomer 40 parts by mass-Silicone methacrylate 0.6 parts by mass-Silica particles (average particle size 4-5 μm) 15 parts by mass-Aldehyde adsorbent (organic-inorganic composite adsorbent, Toa 15 parts by mass, manufactured by Gosei Co., Ltd., product number: NS-103, 1 part by mass of titanium phosphate compound (product name: Ecochimera, manufactured by YOO Corporation)

Example 6
A decorative sheet was produced in the same manner as in Example 1. After applying vinyl acetate resin emulsion adhesive (manufactured by Aika Kogyo Co., Ltd., Aika Ivon A-593T) to the particle board as a decorative board substrate (adhering material), the decorative sheets are laminated and integrated to obtain a decorative board It was.

Comparative Example 1
In Example 1, a decorative sheet was prepared in the same manner as in Example 1 except that the aldehyde adsorbent and the titanium phosphate compound were not added to the electron beam curable resin composition. The results evaluated in the same manner as in Example 1 are shown in Table 1.

Comparative Example 2
On a base material sheet made of building material thin paper (general paper grade, basis weight 30 g / m ² ), the binder resin is an acrylic resin and a white concealing all-solid layer containing titanium oxide as a colorant, and the binder resin is nitrified A wood pattern layer (pattern layer) which is a cotton resin and contains a colorant was sequentially formed by gravure printing. Next, on the obtained laminate, a thermosetting resin composition having the following composition was applied at a coating amount of 4 g / m ² by a gravure offset method to form a colorless and transparent surface protective layer. Further, a decorative sheet was prepared by curing at 70 ° C. for 24 hours. The results evaluated in the same manner as in Example 1 are shown in Table 1.
Thermosetting resin composition:
・ Acrylic polyol 85 mass parts ・ Isocyanate curing agent (hexamethylene diisocyanate (HDMI)) 15 mass parts ・ Silicone oil 4 mass parts ・ Silica particles (average particle size 4 to 5 μm) 15 mass parts ・ Aldehyde adsorbent (organic-inorganic composite adsorption) Agent, manufactured by Toa Gosei Co., Ltd., product number: NS-103) 15 parts by mass, titanium phosphate compound (manufactured by YOO Corporation, trade name: Ecochimera) 1 part by mass

Comparative Example 3
In Example 1, a decorative sheet was produced in the same manner as in Example 1 except that the aldehyde adsorbent was not added to the electron beam curable resin composition. The results evaluated in the same manner as in Example 1 are shown in Table 1.

  From Table 1 above, in Examples 1 to 6, since the surface protective layer contains an electron beam curable resin, performance superior in contamination resistance and scratch resistance compared to Comparative Example 2 using a thermosetting resin. It can be seen that Further, in comparison with Example 2 and Comparative Example 2, although the addition amount of the aldehyde adsorbent and the titanium phosphate compound is equal, Example 2 using an electron beam curable resin is more formaldehyde. It can be seen that an excellent result is shown in terms of the removal action of.

  It can be seen that the decorative sheets of Examples 1 and 5 both have excellent performance in stain resistance and scratch resistance, and show excellent results with a formaldehyde removal rate of 95%. In particular, in the decorative sheet of Example 5, the removal rate reached 95% earlier than Example 1, and it was possible to remove formaldehyde more efficiently.

  The decorative sheet of the present invention has a high removal rate of aldehydes such as formaldehyde, and has excellent stain resistance and scratch resistance. Therefore, the decorative sheet of the present invention is suitable for use as a building material such as wallpaper, flooring material, kitchenware, door material, etc., and effectively prevents indoor pollution caused by volatile organic compounds (VOC) released from housing members. It can be purified. The decorative board of the present invention has the same excellent effect as the decorative sheet, and is suitable for the same application as the decorative sheet.

1. Cosmetic sheet 2. 2. base material sheet 3. Colored layer Pattern layer5. 5. Surface protective layer 6. Adsorbent Photocatalyst

Claims (11)

A decorative sheet having at least a surface protective layer on a substrate sheet,
The surface protective layer is a decorative sheet comprising a resin composition containing an ionizing radiation curable resin, an aldehyde adsorbent and a non-photocatalyst.   The decorative sheet according to claim 1, wherein the ionizing radiation curable resin is an electron beam curable resin.   The decorative sheet according to claim 1 or 2, wherein the aldehyde adsorbent is an inorganic aldehyde adsorbent and / or an organic-inorganic composite aldehyde adsorbent.   The makeup according to any one of claims 1 to 3, wherein the resin composition contains 0.5 to 30 parts by mass of the aldehyde adsorbent with respect to 100 parts by mass of the ionizing radiation curable resin. Sheet.   The non-photocatalyst contains at least one metal selected from the group consisting of titanium, iron, platinum, silver, palladium, zirconium, germanium, cerium, potassium, aluminum, gallium, cobalt, and nickel. The decorative sheet according to any one of 1 to 4.   The decorative sheet according to claim 5, wherein the non-photocatalyst is a titanium phosphate compound.   The decorative sheet according to any one of claims 1 to 6, wherein the resin composition contains 0.5 to 10 parts by mass of the non-photocatalyst with respect to 100 parts by mass of the ionizing radiation curable resin. .   The decorative sheet according to any one of claims 1 to 7, further comprising a colored layer and / or a pattern layer on the base sheet. The decorative sheet according to any one of claims 1 to 8, comprising a primer layer between the base sheet and the surface protective layer.   The decorative sheet according to claim 9, wherein the primer layer includes an aldehyde adsorbent and / or a non-photocatalyst.   The decorative board which has an adherend on the back surface of the decorative sheet of any one of Claims 1-10.

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