JP4597831B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet having a stable color pattern used for various furniture and building interior materials.

As decorative panels for furniture and kitchen product cabinets, decorative sheets are usually printed on wood-based materials, inorganic materials, synthetic resin-based materials, metal-based materials such as steel plates, etc. The thing of the structure which bonded together with the adhesive agent is used.
The decorative sheet used for such a surface decorative board is required to have a stable color tone, and is suitable for secondary processing such as laminating, wrapping, and V-cut processing, moderate flexibility, machinability, and resistance. Various characteristics such as workability such as breakability, weather resistance in use, light resistance, heat resistance, water resistance, solvent resistance, surface hardness, abrasion resistance, and scratch resistance are required.
In order to satisfy these requirements, a base material that sufficiently satisfies the processability is used, and a surface protective layer is applied to the surface of the base material, and the surface protective layer is an ionizing radiation curable resin composition. Is preferably used.
For example, Patent Document 1 has a surface protective layer in which a coating layer, a pattern layer, and an ionizing radiation curable resin composition are crosslinked and cured on the surface of the substrate, and the pattern layer is compared with the coating layer. A cosmetic material having high permeability of an ionizing radiation curable resin composition has been proposed (see Patent Document 1, Claims, FIGS. 1 and 2).

Conventionally, fluorescent whitening agents are blended in white polyester resin films for various printing materials and packaging materials for the purpose of highlighting the whiteness. For example, Patent Document 2 contains 4/100 (mass ratio) of polyester resin / fluorescent whitening agent = 99.5 / 0.5 (mass ratio), that is, 0.02 mass% of fluorescent whitening agent. A white polyester film roll containing is disclosed.
By the way, the white polyester resin film is used as the base material of the decorative sheet in order to enhance the color of the design pattern. As described above, the ionizing radiation curable resin composition is used as the surface protective layer of the decorative sheet. In some cases, the color tone of the decorative sheet is bluish due to the irradiation of ionizing radiation, particularly an electron beam, and color matching may be difficult.
Therefore, there has been a demand for a decorative sheet in which the color tone of the pattern is stable in the manufacturing process of the decorative sheet and color matching is easy.

JP 2001-199028 A JP 2004-050753 A

  An object of the present invention is to provide a decorative sheet in which the color tone of a pattern is stable and color matching is easy under such circumstances.

As a result of intensive studies to achieve the above object, the present inventor can solve the above problems by setting the blending amount of the optical brightener contained in the base material of the decorative sheet within an appropriate range. I found. The present invention has been completed based on such findings.
That is, the gist of the present invention is as follows.
1. A substrate made of a white polyester resin film, a pattern layer provided on a part or the entire surface of the substrate, and a surface protective layer covering a part or the entire surface including the pattern layer. a decorative sheet, wherein the surface protective layer is one obtained by crosslinking curing the electron beam curing resin composition, and that the base material has 0.001 to 0.01 wt% containing an optical brightener A decorative sheet.
2 . 2. The decorative sheet according to 1 above, wherein the electron beam curable resin composition comprises a (meth) acrylate monomer.
3 . The decorative sheet according to 2 above, wherein the (meth) acrylate monomer is a polyfunctional (meth) acrylate monomer.
4. 4. The decorative sheet according to 2 or 3 above, wherein the electron beam curable resin composition further contains a polymerizable oligomer.
5 . The decorative sheet according to any one of 1 to 4 above, wherein a primer layer is disposed between the substrate and the pattern layer.
6 . A step of forming a primer layer by applying a primer on a substrate made of a white polyester resin film containing 0.001 to 0.01% by mass of a fluorescent brightening agent, a pattern layer on a part or the entire surface of the primer layer A step of coating the electron beam curable resin composition on a part of or the entire surface including the pattern layer, and a surface protective layer by irradiating the electron beam curable resin composition with an electron beam The manufacturing method of the decorative sheet including the process of forming.

    ADVANTAGE OF THE INVENTION According to this invention, while the whiteness of a base material is ensured and the color of a design stands out, the color tone of a design can be stabilized and the decorative sheet which color matching is easy can be provided.

As described above, the decorative sheet of the present invention is composed of a base material made of a white polyester resin film, a design pattern layer, and a surface protective layer, and if necessary, a primer layer, a liquid repellent design layer, a transparent resin layer, etc. Further intermediate layers may be provided.
The primer layer is usually disposed between the substrate and the pattern layer, the liquid repellent pattern layer is on the pattern pattern layer, and the transparent resin layer that prevents penetration of the surface protective layer is on the liquid repellent pattern layer. A transparent resin layer that prevents penetration of the liquid repellent pattern layer is disposed on the pattern layer.

  Hereinafter, a typical structure of the decorative sheet of the present invention will be described with reference to FIG. 1 which is a schematic diagram showing one of the preferred embodiments of the present invention. In FIG. 1, the decorative sheet 1 of the present invention has a primer layer 5 disposed on the upper surface of a base material 2 made of a white polyester resin film, and a pattern layer 3 on a part or the entire upper surface of the elastic primer layer 5. Is disposed. However, when the primer layer 5 is not used, the pattern layer 3 may be disposed directly on the substrate 2. A surface protective layer 4 that covers a part of or the entire surface is disposed on the upper surface of the pattern layer 3. From the viewpoint of protecting the surface layer, it is important to use an ionizing radiation curable resin composition that has been crosslinked and cured in the surface protective layer 4.

  The white polyester resin film used for the base material 2 of the decorative sheet 1 of the present invention is a polyester resin film melt-extruded from a so-called extrusion die, and is usually unstretched or biaxially in the machine direction and the transverse direction. Although it is an oriented film, an unstretched film is preferred because it is easy to stick to various furniture, building interior materials, etc., and is also easy to be subjected to primer treatment. For this polyester resin film, a polymer obtained by condensation polymerization from dicarboxylic acid and glycol is used. Here, examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, and sebacic acid. Examples of the glycol include ethylene glycol, trimethylene glycol, and tetramethylene glycol. And cyclohexanedimethanol. Specific examples include polyethylene terephthalate, polytetramethylene terephthalate, polyethylene-p-oxybenzoate, poly-1,4-cyclohexylene dimethylene terephthalate, and polyethylene-2,6-naphthalenedicarboxylate. In the case of the present invention, polyethylene terephthalate is particularly preferable. The thickness of the polyester resin film is preferably 20 to 100 μm, and 40 to 50 μm in view of cost and good handling in use.

As the pigment of the white polyester resin film used for the substrate 2, titanium oxide white, zinc white, lead white, etc. are used, but titanium oxide white is preferable from the viewpoint of hiding power. And in order to increase the aesthetics of the pattern layer 3, it is preferable to contain a fluorescent whitening agent in the white polyester resin film. Examples of fluorescent brighteners include trade names “Ubitec” (Ciba Geigy), “OB-1” (Eastman), “TBO” (Sumitomo Seika Co., Ltd.), “Kay Coal” (Nippon Soda Co., Ltd.) )), “Kayalite” (Nippon Kayaku Co., Ltd.), “Lyukopua” EGM (Client Japan Co., Ltd.), Kyaphor NV liquid, a fluorescent whitening agent with a stilbene skeleton widely used in Japan. Medicinal Colors) is used.
Here, the fluorescent whitening agent is contained in the white polyester resin film in an amount of 0.01% by mass or less. Even if the fluorescent whitening agent is not contained in the white polyester resin film, the whiteness of the white polyester resin film is good. However, when 0.001 to 0.01% by mass is contained, the whiteness becomes even better, and the pattern This is preferable because the beauty of the layer 3 can be further increased. On the other hand, when the content exceeds 0.01% by mass, the substrate 2 becomes bluish by irradiation with ionizing radiation, particularly an electron beam, onto the surface protective layer 4 for crosslinking and curing the ionizing radiation curable resin composition, and the pattern layer Since the color tone of No. 3 is changed, it is difficult to match the color of the decorative sheet.

The pattern layer 3 is, for example, an oak, teak, walnut, or the like, a grained wood pattern, a marble pattern (for example, a travertine marble pattern), a stone pattern, a texture, or a cloth pattern Fabric patterns, tiled patterns, brickwork patterns, etc., and there are also patterns such as parquet 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. Gravure printing with normal ink is also used.
Here, as the normal ink for forming the pattern layer 3, those using conventional cellulose-based, salt-vinyl acetate-based, acrylic-based, and acrylic polyol-based binder resins are used. In order to be able to express well, what added luster pigments, such as a pearl pigment and metal powder, is preferable.

The ionizing radiation curable resin composition used for the surface protective layer 4 in the present invention has an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, irradiated with an electron beam or ultraviolet rays. It refers to a resin composition that crosslinks and cures.
In the present invention, the ionizing radiation curable resin composition preferably contains a polymerizable monomer having a radically polymerizable unsaturated group in the molecule, particularly a (meth) acrylate monomer, and ionizing radiation curing is suitably achieved. The From the viewpoint of curability, the content of the (meth) acrylate monomer is more preferably 50% by mass or more. Here, “(meth) acrylate” means “acrylate or methacrylate”.

  The (meth) acrylate monomer used in the present invention is preferably a polyfunctional (meth) acrylate. 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, etc. Is mentioned. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  The ionizing radiation curable resin composition may be mixed with a polymerizable oligomer together with the (meth) acrylate monomer within a range that does not impair the effects of the present invention. Examples of the polymerizable oligomer include epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates. 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 composition is used as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the 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, benzyldimethyl ketal, acetophenone dimethyl ketal It is done.
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.
In the present invention, it is preferable to use an electron beam curable resin composition as the ionizing radiation curable resin composition. This is because the electron beam curable resin composition can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator and can provide stable curing characteristics.

Moreover, various additives can be mix | blended with the ionizing radiation-curable resin composition in this invention according to the desired physical property of the cured resin layer obtained. Examples of the additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, a matting agent, a surface reinforcing agent, an antistatic agent, an adhesion improver, a leveling agent, a thixotrope. Examples include a property-imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, and a solvent.
Here, as the weather resistance improving agent, an ultraviolet absorber or a light stabilizer can be used. The ultraviolet absorber may be either inorganic or organic, and as the inorganic ultraviolet absorber, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle diameter of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, benzotriazole type, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-) is specifically mentioned. Amylphenyl) benzotriazole, 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of polyethylene glycol, and the like. On the other hand, examples of the light stabilizer include hindered amines, specifically 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1,2,2). , 6,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate and the like. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

Examples of the wear resistance improver include, for inorganic substances, spherical particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape and the like, and are not particularly limited, but a spherical shape is preferable. Organic materials include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is usually about 30 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles.
Examples of the polymerization inhibitor include hydroquinone, p-benzoquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. Examples of the crosslinking agent include a polyisocyanate compound, an epoxy compound, a metal chelate compound, an aziridine compound, and an oxazoline compound. Used.
As the filler, for example, barium sulfate, talc, clay, calcium carbonate, aluminum hydroxide and the like are used.
As the infrared absorber, for example, a dithiol metal complex, a phthalocyanine compound, a diimmonium compound, or the like is used.
As the matting agent and the surface reinforcing agent, inorganic and / or organic fine particles such as silica and plastic beads may be added.

In the present invention, a polymerizable monomer, a polymerizable oligomer and various additives, which are the ionizing radiation curable components, are uniformly mixed at predetermined ratios to prepare a coating liquid composed of an ionizing radiation curable resin composition. To do. The viscosity of the coating solution is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the substrate by a coating method described later.
In the present invention, the coating liquid prepared in this way is applied to the surface of the substrate 2 or the primer layer 5 and the pattern layer 3 so that the thickness after curing is 1 to 20 μm, Coating is performed by a known method such as bar coating, roll coating, reverse roll coating, or comma coating, preferably gravure coating, to form an uncured resin layer. When the thickness after curing is 1 μm or more, a cured resin layer having a desired function is obtained. The thickness of the surface protective layer after curing is preferably about 2 to 20 μm.

In the present invention, the uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer. Here, the ionizing radiation is preferably an electron beam. And when using an electron beam, although the acceleration voltage can be suitably selected according to the resin to be used or the thickness of the layer, it is preferable to cure the uncured resin layer at an acceleration voltage of about 70 to 300 kV.
In addition, in electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material 2 or a primer layer 5 and a base material that deteriorates due to an electron beam as the pattern layer 3, an electron beam is used. By selecting an accelerating voltage so that the penetration depth of the resin and the thickness of the resin layer are substantially equal, it is possible to suppress irradiation of the electron beam to the base material 2 or the primer layer 5 and the pattern layer 3. preferable.
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).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft 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. Can be used.
When ultraviolet rays are used as the 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.
The cured resin layer thus formed has various functions by adding various additives, for example, a so-called hard coat function, anti-fogging coat function, and anti-fouling coat having high hardness and scratch resistance. A function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can be imparted.

By the way, it is preferable to perform primer treatment on the base material 2 to form the primer layer 5 because the adhesion between the base material 2 and the pattern layer 3 can be improved.
As a primer used for the decorative sheet of the present invention, for example, a urethane resin-based paint, a water-based acrylic urethane resin-based paint, a water-based chlorinated polyolefin resin-based paint, or the like is preferably used. In particular, by using a urethane resin-based paint or a water-based acrylic urethane resin-based paint, stable rubber-like elasticity can be maintained over a wide temperature range.
The urethane resin can be obtained, for example, by a polycondensation reaction between glycols such as ethylene glycol, propylene glycol, neopentyl glycol, and 1,6 hexane glycol and dibasic acids such as adipic acid, isophthalic acid, and terephthalic acid. A resin made of a linear block copolymer obtained by a reaction of a polyester polyol and an isocyanate such as tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or the like is used.

  The decorative sheet of the present invention is adhered to various substrates via an adhesive, and the substrate on which the decorative sheet is adhered is adhered to a cold press, hot press, roll press, laminator, wrapping, edge pasting machine, vacuum press, etc. It is pressed using an apparatus and processed into a decorative board or the like.

The above-mentioned adhesive is applied using an application device such as a spray, a spreader, or a bar coater. As the adhesive, vinyl acetate resin-based, urea resin-based, melamine resin-based, phenol resin-based, isocyanate-based adhesives, etc., are used alone or as a mixed adhesive obtained by arbitrarily mixing them. As needed, talc, calcium carbonate, clay, titanium white and other inorganic powders, wheat flour, wood flour, plastic powder, coloring agents, insect repellents, fungicides and the like can be added and mixed in the adhesive. . In general, the adhesive is applied to the substrate surface with a solid content of 35 to 80% by mass and an application amount of 50 to 300 g / m ² .

  The decorative board manufactured as described above is also optionally cut by cutting the decorative board, etc., and using a cutting machine such as a router or a cutter on the surface or the end of the groove, for optional processing such as grooving or chamfering. Can be decorated.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the stability of whiteness and color tone was measured according to the following method.
(1) Whiteness The whiteness is measured according to JIS Z8715 “When the sample group contains a fluorescent sample”, and the whiteness is significantly higher than that of a white polyester resin film that does not contain a fluorescent brightening agent. A sample having a high whiteness was evaluated as “very good” and a sample having the same whiteness was defined as “good”.
(2) Stability of color tone The color tone before and after electron beam irradiation on the decorative sheet of the sample was visually compared, and the color tone that did not change was judged as “no change” and the color tone that changed was judged as “changed”. .

Examples 1 and 2, Reference Example 1 and Comparative Example 1
Four thicknesses of Kyaphor NV liquid (manufactured by Nippon Kayaku Colors), which is an optical brightener, and 0.01 wt%, 0.001 wt%, 0.02 wt% and those that do not contain a fluorescent brightener A white polyester resin film having a thickness of 50 μm (same specification as polyethylene terephthalate Z-210 manufactured by Diafoil Co., Ltd.) is used as the base material 2, and a transparent polyester urethane resin is applied to the surface of the base material 2 at 3 to 5 g / m ^2. (Dry) After applying the primer to form the primer layer 5, the pattern layer 3 with a grain pattern is gravure-printed, and ethylene oxide-modified trimethylolpropane ethylene, which is a trifunctional acrylate monomer, is further formed thereon. 60 parts by mass of oxide triacrylate and difunctional acrylate monomer 40 parts by mass of pentaerythritol hexaacrylate, was applied by gravure offset coater method Average silica particles 2 parts by weight of the particle size 5μm and silicone acrylate prepolymer 1 part by weight electron beam-curable resin composition comprising at 5 g / m ² . After the coating, an electron beam with an acceleration voltage of 175 kV and an irradiation dose of 50 kGy (5 Mrad) was irradiated to cure the electron beam curable resin composition, whereby the surface protective layer 4 was obtained. Next, curing was performed at 70 ° C. for 24 hours to obtain a decorative sheet.
While evaluating about the stability of the color tone of these decorative sheets, the whiteness of each of the white polyester resin films was evaluated. The results are shown in Table 1.

  As is apparent from Table 1, if the content of the fluorescent whitening agent in the white polyester resin film as the base material is 0.01% by mass or less, the color tone of the decorative sheet pattern is stable and color matching is easy. It becomes.

  The decorative sheet of the present invention is suitably used as a decorative sheet for a surface decorative plate such as a cabinet for various furniture and kitchen products, and a building interior material.

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

Explanation of symbols

1. Cosmetic sheet Base material 3. Pattern pattern layer 4. 4. Surface protective layer Primer layer

Claims (6)

A substrate made of a white polyester resin film, a pattern layer provided on a part or the entire surface of the substrate, and a surface protective layer covering a part or the entire surface including the pattern layer. a decorative sheet, wherein the surface protective layer is one obtained by crosslinking curing the electron beam curing resin composition, and that the base material has 0.001 to 0.01 wt% containing an optical brightener A decorative sheet. The decorative sheet according to claim 1, wherein the electron beam curable resin composition contains a (meth) acrylate monomer. The decorative sheet according to claim 2 , wherein the (meth) acrylate monomer is a polyfunctional (meth) acrylate monomer. The decorative sheet according to claim 2 or 3 , wherein the electron beam curable resin composition further contains a polymerizable oligomer. The decorative sheet according to any one of claims 1 to 4 , wherein a primer layer is disposed between the substrate and the pattern layer.   A step of forming a primer layer by applying a primer on a substrate made of a white polyester resin film containing 0.001 to 0.01% by mass of a fluorescent brightening agent, a pattern layer on a part or the entire surface of the primer layer A step of coating the electron beam curable resin composition on a part of or the entire surface including the pattern layer, and a surface protective layer by irradiating the electron beam curable resin composition with an electron beam The manufacturing method of the decorative sheet including the process of forming.

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