JP4074209B2 - Decorative sheet - Google Patents

Decorative sheet Download PDF

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Publication number
JP4074209B2
JP4074209B2 JP2003077628A JP2003077628A JP4074209B2 JP 4074209 B2 JP4074209 B2 JP 4074209B2 JP 2003077628 A JP2003077628 A JP 2003077628A JP 2003077628 A JP2003077628 A JP 2003077628A JP 4074209 B2 JP4074209 B2 JP 4074209B2
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Japan
Prior art keywords
layer
surface protective
protective layer
decorative sheet
resin
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JP2003077628A
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JP2003340975A (en
Inventor
英一郎 横地
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大日本印刷株式会社
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Priority to JP2002-77925 priority Critical
Priority to JP2002077925 priority
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative sheet such as a decorative paper that can be used for building interior materials such as walls, furniture such as doors and surface materials such as furniture. In particular, the present invention relates to a decorative sheet excellent in marling resistance with less gloss change due to surface scratches.
[0002]
[Prior art]
Conventionally, decorative sheets using paper, resin sheets, etc., or plate-shaped decorative materials obtained by pasting the decorative sheet on an adherend substrate have been used for various applications such as building interior materials and fittings. . In addition, such a decorative sheet or a decorative material on which such a decorative sheet is applied is required to have a surface strength that is difficult to be damaged, is resistant to abrasion, and is usually required. Therefore, in applications where such surface strength is conventionally required, the decorative sheet has a surface protective layer provided on the entire surface thereof by a cross-linked cured product such as a two-component curable resin or an ionizing radiation curable resin. Often to do.
For example, a decorative sheet having a structure in which an unsaturated polyester resin paint is crosslinked and cured with an electron beam on a surface protective layer as a decorative paper whose base sheet is paper (see Patent Document 1).
As described above, when a coating film obtained by crosslinking and curing an ionizing radiation curable resin composed of a monomer, a prepolymer, or the like by ionizing radiation such as ultraviolet rays or electron beams is provided as a surface protective layer, the two-component curable urethane resin or the like is provided. Compared with its high crosslinkability, a decorative sheet with better surface strength can be obtained.
[0003]
[Patent Document 1]
Japanese Patent Publication No.49-31033
[0004]
[Problems to be solved by the invention]
However, even when a cross-linked cured product of ionizing radiation curable resin is used for the surface protective layer, it may not be sufficient for surface scratches. Therefore, such a case is usually dealt with by adding silica or the like as a filler to the surface protective layer to harden the surface protective layer. However, in particular, in the case of a decorative sheet whose surface gloss is adjusted by a surface protective layer as a design expression, the gloss may increase due to a collection of very fine scratches. For example, when a decorative sheet produced by sticking a decorative sheet to a base material of a wooden board is piled up and the surface of the decorative sheet (decorative sheet) is rubbed by vibration during transportation, or a decorative sheet manufacturing line It is in handling inside. And it is still good if the part where the fine scratches are given is uniform over the entire surface, but if a part of the surface is frequently rubbed, the gloss of the surface becomes noticeable and becomes a product defect. In particular, the product defect after sticking to the base material becomes a defect including the base material in addition to the decorative sheet, and there is a problem that the cost loss is large compared to the case of the decorative sheet alone. For this reason, there has been a demand for marling resistance so that the gloss change hardly occurs even when the surface is rubbed.
[0005]
That is, an object of the present invention is to improve the marring resistance in a decorative sheet such as a decorative paper.
[0006]
[Means for Solving the Problems]
  Then, in order to solve the said subject, in the decorative sheet of this invention, on a base material sheet,While providing all solid and / or handle layers,In a decorative sheet formed by laminating a surface protective layer made of a crosslinked cured product of an ionizing radiation curable resin, the surface protective layer isIt consists of a non-colored or colored transparent layerIt was set as the structure containing baking kaolin as a filler.The decorative sheet of the present invention is a decorative sheet in which a solid layer and / or a handle layer are provided on a base sheet, and a surface protective layer made of a crosslinked cured product of an ionizing radiation curable resin is laminated. The surface protective layer is composed of a non-colored or colored transparent layer and contains calcined kaolin as a filler, and the added amount of calcined kaolin is 5 to 50 parts per 100 parts by mass of the resin component forming the surface protective layer. The mass part is configured..The decorative sheet of the present invention is a decorative sheet in which a solid layer and / or a handle layer are provided on a base sheet, and a surface protective layer made of a crosslinked cured product of an ionizing radiation curable resin is laminated. The surface protective layer is composed of an uncolored or colored transparent layer, contains calcined kaolin as a filler, and has an average particle diameter of calcined kaolin of 0.5 to 2 μm. The decorative sheet of the present invention is a decorative sheet in which a solid layer and / or a handle layer are provided on a base sheet, and a surface protective layer made of a crosslinked cured product of an ionizing radiation curable resin is laminated. The surface protective layer is composed of a non-colored or colored transparent layer and contains calcined kaolin as a filler, and the added amount of calcined kaolin is 5 to 50 parts per 100 parts by mass of the resin component forming the surface protective layer. It is a mass part, Comprising: It was set as the structure whose average particle diameter of baking kaolin is 0.5-2 micrometers..
[0007]
In this way, by adding calcined kaolin as a filler to the surface protective layer made of a crosslinked cured product of ionizing radiation curable resin, the marling resistance is improved and improved.
[0008]
In the decorative sheet of the present invention, the fired kaolin is further surface-treated with a silane coupling agent in the above configuration.
[0009]
In this way, by using a calcined kaolin to be added whose surface is surface-treated with a silane coupling agent, the marling resistance is further improved and improved.
[0010]
In addition, the decorative sheet of the present invention has a configuration in which a primer layer is further provided between the base sheet and the surface protective layer in any of the above configurations.
[0011]
By providing the primer layer in this manner, the adhesion between the surface protective layer and the substrate sheet is improved, and the surface protective layer is not peeled off, dropped off or lost.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0013]
Overview:
First, FIG. 1 is a cross-sectional view illustrating a decorative sheet S according to the present invention. FIG. 1 (A) shows the case where the most basic layer structure is composed of two layers of a base sheet 1 and a surface protective layer 2, and FIG. 1 (B) shows the base sheet 1 and the surface as a decoration treatment. It is the structure which provided all the solid layers 3 and the handle layers 4 with respect to the base material sheet 1 in this order so that it might be between the protective layers 2. And in these, the surface protective layer 2 is comprised from the bridge | crosslinking hardened | cured material of ionizing-radiation-hardening resin, and baking kaolin is added in the surface protective layer as a filler. The present invention has found that the marring resistance is improved by using a calcined kaolin obtained by calcining not just ordinary kaolin as a filler.
[0014]
The decorative sheet of the present invention may have only two layers of the base sheet 1 and the surface protective layer 2 as shown in FIG. 1 (A). However, the decorative sheet usually has a higher design. For example, it is assumed that some decoration processing is performed as shown in FIG. A decoration process is normally performed with respect to a base material sheet. The base sheet may be a resin sheet, but in the case of paper or the like, the decorative sheet is also called decorative paper.
[0015]
Hereinafter, each layer will be described in detail.
[0016]
Base sheet:
As the base sheet 1, for example, paper, non-woven fabric, thermoplastic resin sheet, or a laminate thereof is used.
[0017]
As the paper, for example, thin paper, kraft paper, high quality paper, linter paper, baryta paper, sulfuric acid paper, Japanese paper and the like are used.
Moreover, as a nonwoven fabric, the nonwoven fabric which consists of fibers, such as a polyester resin, an acrylic resin, nylon, vinylon, glass, is used, for example. The basis weight of paper and non-woven fabric is usually 20-100 g / m2Degree. In addition, for paper and non-woven 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 flaking. The resin may be impregnated after resin impregnation or papermaking.
Note that a decorative sheet using paper (or non-woven fabric) as a base sheet is decorative paper.
[0018]
As the thermoplastic resin sheet, acrylic resin, polyester resin, polyolefin resin, polyvinyl chloride resin, polystyrene, ABS resin, polycarbonate resin, polyamide resin and the like are used.
[0019]
Specifically, for example, (1) polyethylene (high density, medium density, or low density), polypropylene (isotactic type or syndiotactic type), polybutene, ethylene-propylene copolymer, ethylene-propylene- Polyolefin resins such as butene copolymers and olefin thermoplastic elastomers. Examples of the olefinic thermoplastic elastomer include a hard segment made of a crystalline polyolefin resin as exemplified above, ethylene-propylene rubber, ethylene-propylene-diene rubber, atactic polypropylene, styrene-butadiene rubber, hydrogenated styrene-butadiene. A soft segment made of an elastomer such as rubber is mixed. The mixing ratio of the hard segment and the soft segment is about [soft segment / hard segment] = 5/95 to 40/60 (mass ratio). If necessary, the elastomer component is crosslinked by a known crosslinking agent such as sulfur or hydrogen peroxide.
[0020]
(2) Acrylic resins such as polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer [however, (meth) Acrylate means acrylate or methacrylate].
[0021]
(3) Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, ethylene-terephthalate-isophthalate copolymer, polyethylene naphthalate, polyester thermoplastic elastomer, and amorphous polyester. Examples of the polyester-based thermoplastic elastomer include a highly crystalline and high melting point aromatic polyester for the hard segment, and a block polymer using amorphous polyether having a glass transition temperature of −70 ° C. or less for the soft segment. For example, polybutylene terephthalate is used as the highly crystalline and high melting point aromatic polyester, and polytetramethylene glycol or the like is used as the amorphous polyether. The amorphous polyester typically includes ethylene glycol-1,4-cyclohexanedimethanol-terephthalic acid copolymer.
[0022]
(4) Other resins such as polycarbonate resin, polyvinyl chloride resin, polyamide resin, polyphenylene sulfide, polyether ether ketone and the like can be mentioned.
[0023]
As the layer structure of the base sheet, the above-mentioned paper, nonwoven fabric, thermoplastic resin sheet or the like is used as a single layer, or two or more different types are laminated. The thickness (total thickness in the case of a laminated body) of a base material sheet is about 25-500 micrometers normally.
[0024]
Surface protective layer:
The surface protective layer 2 is a layer provided as the outermost surface layer of the decorative sheet, and is formed as a cross-linked cured product obtained by cross-linking and curing this resin using an ionizing radiation curable resin. As a surface protective layer, first of all, by using an ionizing radiation curable resin as the resin, compared with the case where a two-component curable urethane resin or the like is used, its high cross-linkability, anti-marling resistance and the like. It becomes easy to impart surface properties such as wear or contamination resistance. Second, the surface protective layer contains calcined kaolin as a filler. Thereby, the marring resistance is improved.
[0025]
The surface protective layer is usually formed as a non-colored transparent layer. Alternatively, it is formed as a colored transparent layer. This is to make it possible to see through the handle layer that is usually provided under the surface protective layer. However, if there is no need for the handle layer or the like, it may be non-colored opaque or colored opaque.
[0026]
The surface protective layer is made of a liquid ionizing radiation curable resin (composition) containing calcined kaolin, a coating method such as gravure coating or roll coating, or a printing method such as gravure printing, gravure offset printing, screen printing, etc. The film can be formed on the substrate sheet by the known film formation method, and then crosslinked and cured by ionizing radiation irradiation. The thickness of the surface protective layer is usually 1 to 30 g / m in terms of coating amount.2(Based on solid content). In addition, the ionizing radiation curable resin (composition) is obtained by appropriately adding a solvent for adjusting coating suitability and printing suitability.
[0027]
As ionizing radiation curable resin, specifically, ionizing radiation in which prepolymers (including so-called oligomers) and / or monomers having radically polymerizable unsaturated bonds or cationically polymerizable functional groups in the molecule are appropriately mixed. A composition that can be cross-linked and cured is preferably used. Here, the ionizing radiation means electromagnetic waves or charged particles having energy capable of crosslinking by polymerizing molecules, and usually electron beam (EB) or ultraviolet ray (UV).
[0028]
Specifically, the prepolymer or monomer is a compound having a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, a cationically polymerizable functional group such as an epoxy group in the molecule. Become. These prepolymers and monomers are used alone or in combination. Here, for example, the (meth) acryloyl group means an acryloyl group or a methacryloyl group. Further, as the ionizing radiation curable resin, a polyene / thiol-based prepolymer based on a combination of polyene and polythiol is also preferably used.
[0029]
Examples of prepolymers having radically polymerizable unsaturated groups in the molecule include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate. it can. The molecular weight is usually about 250 to 100,000. In addition, the description (meth) acrylate in this specification means an acrylate or a methacrylate. In addition, the acrylate compound and the methacrylate compound are collectively referred to simply as an acrylate (compound).
[0030]
Examples of the monomer having a radical polymerizable unsaturated group in the molecule include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like as monofunctional monomers. In addition, among polyfunctional monomers, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
[0031]
Examples of prepolymers having a cationically polymerizable functional group in the molecule include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolak type epoxy compounds, and vinyl ether type resins such as fatty acid vinyl ethers and aromatic vinyl ethers. .
Examples of thiols include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those obtained by adding allyl alcohol to both ends of polyurethane by diol and diisocyanate.
[0032]
In the case of crosslinking and curing with ultraviolet rays, a photopolymerization initiator is added to the ionizing radiation curable resin. In the case of a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, and benzoin methyl ethers can be used alone or in combination as a photopolymerization initiator. In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture as a photopolymerization initiator. be able to.
In addition, as addition amount of these photoinitiators, it is about 0.1-10 mass parts with respect to 100 mass parts of ionizing radiation curable resin.
[0033]
In addition, the ionizing radiation curable resin may further include an ionizing radiation non-curable resin such as a vinyl chloride-vinyl acetate copolymer, a vinyl acetate resin, an acrylic resin, or a cellulose resin, if necessary. These thermoplastic resins may be added.
[0034]
And calcined kaolin is a kaolin obtained by calcining general (hydrous) kaolin, but by adding calcined kaolin as a filler, marring resistance that could not be realized with silica or hydrous kaolin before firing. Improved. The particle size of the calcined kaolin powder may be appropriately selected according to the application, required physical properties, and the like. For example, the average particle size is about 0.5 to 2 μm. Further, the amount of calcined kaolin may be appropriately selected according to the use and required physical properties. For example, ionizing radiation curable resin (however, when the surface protective layer contains other resins, ionizing radiation is used. The total of curable resin and other resin) is about 5 to 50 parts by mass with respect to 100 parts by mass.
In addition, the calcined kaolin has a refractive index in the range of 1.6 to 1.7, particularly at its central value of 1.65 (the hydrous kaolin has a refractive index of 1.56), depending on the refractive index of the resin of the surface protective layer. In order to approach, there is an advantage also in terms of transparency of the surface protective layer. In addition, calcined kaolin is superior in paint stability to hydrous kaolin.
[0035]
In addition, as the calcined kaolin, a surface-treated one may be used. By using this surface-treated calcined kaolin, the effect of improving marring resistance can be further increased. As the surface treatment, there is a surface treatment with a silane coupling agent.
[0036]
In addition, as said silane coupling agent, the well-known silane coupling agent which has an alkoxy group, an amino group, a vinyl group, an epoxy group, a mercapto group, a chloro group etc. is mentioned.
For example, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxy Propyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane , Γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysila Etc.
[0037]
In the surface protective layer, other known additives such as a lubricant such as silicone resin and wax, a colorant, a stabilizer, an antifungal agent and the like may be appropriately added as necessary.
[0038]
As an electron beam source of ionizing radiation, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, or a linear type, a dynamitron type, a high frequency type, etc. Those that irradiate with electrons having an energy of 100 to 1000 keV, preferably 200 to 300 keV are used. As the ultraviolet light source, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp is used.
[0039]
Decoration processing:
As a decorative sheet, there are only two layers of a base sheet and a surface protective layer, or only a configuration through a primer layer made of a two-component curable urethane resin or the like in order to strengthen the adhesion between both layers. However, in general, the decorative sheet has a configuration in which some decoration processing is performed in order to improve design properties. Of course, even if the base sheet and the surface protective layer are mainly decorative sheets, for example, when the base sheet is a resin sheet, addition of a colorant to the resin sheet, colored paper, Or the decoration process as addition of the coloring agent in a surface protective layer, etc. is possible. However, since a high-design expression by a printed pattern or the like cannot be performed, a pattern layer or the like is usually provided for high-design. The contents of such a decoration process are not particularly limited, and various conventionally known decoration processes in the field of decorative sheets may be appropriately employed. Hereinafter, the pattern layer, all the solid layers, and surface unevenness shaping will be described as examples.
[0040]
[Pattern layer]
First, the pattern layer 4 is a layer for partially printing and forming a pattern to express a pattern. The pattern layer is preferably provided as a layer inside the decorative sheet from the viewpoint of the durability of the pattern. Therefore, the handle layer is positioned so as to be between the base sheet and the surface protective layer, and is usually provided on the front side surface of the base sheet.
[0041]
When the pattern layer is provided, the contents of the pattern layer, such as the pattern layer forming method, the material, and the pattern thereof, are not particularly limited and may be set according to the intended use. The pattern layer is usually formed using ink by a conventionally known printing method such as gravure printing, silk screen printing, offset printing, gravure offset printing, and ink jet printing.
Pattern patterns include, for example, wood grain pattern, stone pattern, sand grain pattern, cloth pattern, tile tone pattern, brick tone pattern, leather pattern, letters, symbols, geometric patterns, or combinations of two or more of these It is.
[0042]
The ink used for forming the pattern layer is composed of a vehicle composed of a binder and the like, a colorant such as a pigment and a dye, and various additives such as extender pigments, stabilizers, plasticizers, catalysts, and curing agents that are appropriately added thereto. The binder resin may be appropriately selected from thermoplastic resins, thermosetting resins, ionizing radiation curable resins, and the like according to required physical properties, printability, and the like. For example, cellulose resins such as nitrocellulose, cellulose acetate, cellulose acetate propionate, poly (meth) methyl acrylate, poly (meth) butyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate- ( An acrylic resin such as a (meth) acrylic acid 2-hydroxyethyl copolymer, a urethane resin, a vinyl chloride-vinyl acetate copolymer, a polyester resin, an alkyd resin, or a mixture containing these is used as the binder resin.
In addition, as coloring agents, inorganic pigments such as titanium white, carbon black, iron black, petal, yellow lead and ultramarine, organic pigments such as aniline black, quinacridone red, isoindolinone yellow and phthalocyanine blue, titanium dioxide coated mica Bright pigments such as foil powder such as aluminum, or other dyes are used.
[0043]
[All solid layers]
The entire solid layer 3 is a layer formed on the entire surface between the base sheet and the surface protective layer, and may be provided alone without being combined with the pattern layer 4 described above, but is usually combined with the pattern layer 4. In many cases, a solid layer is used as the base of the pattern layer 4.
[0044]
When all solid layers are provided, there are no particular restrictions on the formation method, materials, and the like of all solid layers, and the solid layers may be made according to the intended use. All solid layers are ink or coating liquid, conventionally known printing methods such as gravure printing, silk screen printing, offset printing, gravure offset printing, and ink jet printing, or conventionally known printing methods such as gravure coating and roll coating. It is formed by a coating method or the like. The thickness of all solid layers is usually 1 to 10 g / m in terms of coating amount.2(Based on solid content).
[0045]
There are various purposes for providing the whole solid layer 3, for example, to realize one or more functions such as (1) basic color expression, (2) concealment, and (3) permeability control. In the basic color expression of (1), the base color is usually produced for the pattern coloring by the pattern layer. In the provision of concealment in (2), with respect to a base sheet made of paper or a colored resin sheet, the variation in color tone between lots is concealed to stabilize the color of the decorative sheet, and the resin sheet having transparency is used. For the base sheet, the coated base is concealed to stabilize the coloring and pattern expression of the decorative sheet. In the suppression of permeability in (3), the penetration of the ink or coating liquid into the base sheet when forming the pattern layer or the surface protective layer on the permeable base sheet such as paper is suppressed. It prevents the surface protective layer from appearing as uneven gloss on the surface. Of these functions, the decoration processing is (1) and (2), but the solid layer referred to in the present invention includes a form used only for purposes other than the decoration processing of (3).
[0046]
The whole solid layer has various functions as described above depending on the application, and the same material as the ink material as described in the pattern layer can be used. Therefore, further explanation about the resin of the binder is omitted. In addition, various colorants such as titanium white listed in the pattern layer are added for basic color expression and concealment, but it is of course unnecessary to add a colorant for coloring purposes in terms of suppressing permeability. .
[0047]
[Surface unevenness shaping]
Surface irregularity shaping is a decorative treatment for shaping irregularities on the surface of the surface protective layer. The effect of improving the marling resistance according to the present invention can be obtained even when the decorative sheet surface has an uneven pattern. For example, it is a concavo-convex pattern in which convex portions other than the concave portions form a flat surface and become a gloss adjustment surface, such as a concavo-convex pattern of a grain conduit groove. In this case, the marling resistance is microscopically resistant to the gloss change of the flat surface (convex portion).
Note that the surface gloss change targeted for marling resistance is usually an increase in the gloss when the surface gloss is moderately reduced by design (also referred to as semi-gloss). It is a change in gloss that gives off gloss with a reduced erasing feeling. However, the gloss change targeted by the marring resistance includes gloss reduction as well as gloss increase.
As the uneven pattern, those according to the application are adopted, for example, wood grain conduit grooves, tiled or brick joint grooves, relief patterns, letters, figures, geometric patterns, satin, or cleavage of granite. It is an uneven pattern on the surface. Further, the uneven pattern may be a combination thereof.
[0048]
As a specific example of the decoration treatment for shaping the concave and convex pattern such as the wood grain conduit groove on the surface, a pattern having a high and low permeability is provided as a base for the coating liquid (or ink) for forming the surface protective layer. There is a technique for forming a concavo-convex pattern by forming a surface protective layer (see FIG. 2 and JP-A-2001-328228). For example, the solid sheet 3 and the handle layer 4 are appropriately provided on the base material sheet 1, and the resin solution is applied to the entire surface to form the permeation suppression layer 5. In order to do this, an ink to which a filler such as silica is added is printed to form the patterned permeable pattern layer 6. The permeable pattern layer is, for example, a layer expressing an appropriately uneven pattern such as a conduit groove pattern. And if the coating liquid used as the surface protective layer is applied over the entire surface, the coating liquid in the portion on the permeable pattern layer 6 penetrates into the permeable pattern layer. Since the coating liquid of the part does not permeate, a concavo-convex pattern 7 having a concave portion on the permeable pattern layer 6 is formed on the surface of the surface protective layer 2. Moreover, according to this uneven | corrugated pattern shaping technique, since the inside of the recessed part of the shaped uneven | corrugated pattern 7 can also be made into a rough surface, the design of the glossiness difference between a convex part and a recessed part can also be expressed (FIG. 2).
[0049]
Primer layer:
The primer layer is preferably provided between the surface protective layer and the substrate sheet when it is necessary to enhance the interlayer adhesion between the surface protective layer and the substrate sheet. As a specific example of the position where the primer layer is provided, for example, when the pattern layer is provided between the base sheet and the surface protective layer, it is between the pattern layer and the surface protective layer.
For the primer layer, for example, a resin such as a urethane resin, an acrylic resin, and polyvinyl butyral may be used alone or in combination. The primer layer is formed from a coating liquid (or ink) made of these resins by a known coating method such as gravure coating or roll coating, or a known printing method such as gravure printing. The coating amount of the primer layer is usually 0.5 to 5 g / m.2(Based on solid content).
[0050]
Substrate:
By the way, the decorative sheet of the present invention can be used as a decorative material such as a decorative board by sticking to the surface of various adherend substrates.
[0051]
There is no restriction | limiting in particular as said adherence base material. For example, the material of the adherend substrate is inorganic non-metallic, metallic, woody, plastic or the like. Specifically, in inorganic non-metallic systems, for example, paper-making cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium oxalate, There are non-ceramic ceramic materials such as gypsum and gypsum slag, inorganic materials such as earthenware, ceramics, porcelain, setware, glass, and ceramics. Moreover, in a metal system, there exist metal materials, such as iron, aluminum, copper, for example. In the wood system, there are, for example, veneer, plywood, particle board, fiber board, laminated timber made of cedar, straw, firewood, lawan, teak and the like. In the plastic system, for example, there are resin materials such as polypropylene, ABS resin, and phenol resin.
The shape of the adherend substrate is arbitrary such as a flat plate, a curved plate, and a polygonal column.
[0052]
Application:
Further, the use of the decorative sheet of the present invention is not particularly limited, but it is adhered to the surface of the substrate to be adhered as described above, and it is a building interior material such as a wall or a ceiling, a door, a door frame, a window frame. It is used as a surface material for furniture such as a surface material for furniture such as a surface material for furniture such as a surface material for furniture such as a folding edge and a baseboard.
[0053]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
[0054]
[Example 1: calcined kaolin]
Building material thin paper (general paper grade, basis weight 30g / m2A white concealing all-solid layer 3 in which the binder resin is an acrylic resin and titanium oxide is used as a colorant on the base sheet 1, and a wood grain design pattern layer in which the binder resin is a nitrified cotton resin and contains a colorant 4 were sequentially formed by gravure printing. Next, an electron beam curable resin coating solution having the following composition was applied on the obtained laminate by a gravure offset method, and then the coating film was crosslinked and cured by irradiation with an electron beam to obtain a thickness of 4 g / m.2Then, a non-colored transparent surface protective layer 2 was formed, and a decorative sheet S as shown in the sectional view of FIG.
[0055]
Composition of electron beam curable resin coating solution:
50 parts by mass of acrylate trifunctional monomer
30 parts by mass of acrylate bifunctional monomer
Silicone methacrylate 0.6 parts by mass
Firing kaolin (average particle size 0.8 μm) 30 parts by mass
[0056]
[Example 2: calcined kaolin (surface treatment type)]
In Example 1, except that the electron beam curable resin coating solution used for forming the surface protective layer was changed to the one added with the surface-treated calcined kaolin as shown below, the same as in Example 1. A decorative sheet was prepared.
[0057]
Composition of electron beam curable resin coating solution:
50 parts by mass of acrylate trifunctional monomer
30 parts by mass of acrylate bifunctional monomer
Silicone methacrylate 0.6 parts by mass
30 parts by mass of calcined kaolin
(Average particle size 0.8μm, silane coupling agent surface treated)
[0058]
[Example 3: calcined kaolin, uneven pattern]
Building material thin paper (general paper grade, basis weight 30g / m2A white concealing all-solid layer 3 in which the binder resin is an acrylic resin and titanium oxide is used as a colorant on the base sheet 1, and a wood grain design pattern layer in which the binder resin is a nitrified cotton resin and contains a colorant 4. Gravure printing of permeation suppression layer 5 made of a mixed resin of urethane resin and polyester resin, wood grain conduit pattern synchronized with the pattern conduit portion of the handle layer, binder resin is urethane resin and silica added permeable layer 6 Sequentially formed. Next, an electron beam curable resin coating solution having the following composition was applied on the obtained laminate by a gravure offset method, and then the electron beam was irradiated to crosslink and cure the coating to a thickness of 4 g / m.2Then, a non-colored transparent surface protective layer 2 was formed, and a desired decorative sheet S having a concavo-convex pattern 7 with a conduit groove pattern synchronized with the wood grain design of the handle layer as shown in the sectional view of FIG. 2 was obtained.
[0059]
Composition of electron beam curable resin coating solution:
50 parts by mass of acrylate trifunctional monomer
30 parts by mass of acrylate bifunctional monomer
Silicone methacrylate 0.6 parts by mass
Firing kaolin (average particle size 0.8 μm) 30 parts by mass
[0060]
[Comparative Example 1: Non-kaolin, silica]
In Example 1, the electron beam curable resin coating liquid used for forming the surface protective layer was changed to the one having silica added in place of the calcined kaolin as shown in the following composition. A decorative sheet was prepared.
[0061]
Composition of electron beam curable resin coating solution:
50 parts by mass of acrylate trifunctional monomer
30 parts by mass of acrylate bifunctional monomer
Silicone methacrylate 0.6 parts by mass
Silica (average particle size 6 μm) 30 parts by mass
[0062]
[Comparative Example 2: hydrous kaolin]
In Example 1, except that the electron beam curable resin coating solution used for the formation of the surface protective layer was changed to one having the usual water-containing kaolin added instead of calcined kaolin as shown in the following composition. A decorative sheet was prepared in the same manner as described above.
[0063]
Composition of electron beam curable resin coating solution:
50 parts by mass of acrylate trifunctional monomer
30 parts by mass of acrylate bifunctional monomer
Silicone methacrylate 0.6 parts by mass
Hydrous kaolin (average particle size 0.6μm) 30 parts by mass
[0064]
[Comparative Example 3: No filler]
In Example 1, except that the electron beam curable resin coating liquid used for forming the surface protective layer was changed to a composition having the following composition and containing no calcined kaolin and no filler. A decorative sheet was produced in the same manner.
[0065]
Composition of electron beam curable resin coating solution:
50 parts by mass of acrylate trifunctional monomer
30 parts by mass of acrylate bifunctional monomer
Silicone methacrylate 0.6 parts by mass
[0066]
[Example 4: Resin sheet / fired kaolin]
On the base material sheet 1 made of a white concealable polypropylene resin sheet having a thickness of 80 μm, the binder resin is urethane resin and the white concealing all solid layer 3 containing titanium oxide as a colorant, and the binder resin is urethane resin. The pattern layer 4 of the wood grain design containing a coloring agent was formed in order by gravure printing. Next, an electron beam curable resin coating solution having the following composition was applied on the obtained laminate by a gravure offset method, and then the coating film was crosslinked and cured by irradiation with an electron beam to obtain a thickness of 4 g / m.2A non-colored transparent surface protective layer 2 was formed, and a desired decorative sheet S was obtained as shown in the cross-sectional view of FIG.
[0067]
Composition of electron beam curable resin coating solution:
50 parts by mass of acrylate trifunctional monomer
30 parts by mass of acrylate bifunctional monomer
Silicone methacrylate 0.6 parts by mass
Firing kaolin (average particle size 0.8 μm) 30 parts by mass
[0068]
[Performance evaluation]
About each decorative sheet created in the Example and the comparative example, the marling resistance was evaluated. The marling resistance is 21 kPa (1.5 kgf / 7 cm2) A steel wool (made by Nippon Steel Wool Co., Ltd., trade name “Bonstar”) is attached to the weight to which the load is applied), and the surface of the decorative sheet is rubbed back and forth 20 times. The gloss change state of the sheet surface was evaluated by visual observation. The results are shown in Table 1. In the table, ◎ is excellent without gloss change, ◯ is fine with good gloss change, × is impossible with surface gloss change, and XX is not cut down to the lower pattern layer (outside problem).
[0069]
[Table 1]
[0070]
As shown in Table 1, in each example in which calcined kaolin was added to the surface protective layer, the surface gloss change was slight and the performance was good or excellent. It was excellent with no gloss change. On the other hand, none of the comparative examples, such as silica addition, to which no calcined kaolin was added, including Comparative Example 2 to which hydrous kaolin was added, was impossible.
[0071]
【The invention's effect】
(1) According to the decorative sheet of the present invention, the marring resistance is good. For example, depending on the configuration of the decorative sheet, in the rubbing test as shown in the examples, 14 to 42 kPa (1 to 3 kgf / 7 cm2) A steel wool (made by Nippon Steel Wool Co., Ltd., trade name “Bonstar”) is attached to the weight to which the load is applied, and the decorative sheet surface is rubbed 20 times with this steel wool, and then the decorative sheet surface is visually observed. The marling resistance can be improved until the gloss change is slight or ideally no gloss change is seen at all.
(2) Further, if a surface-treated one is used as the calcined kaolin in the surface protective layer, the marling resistance is further improved and improved.
(3) If the primer layer is provided between the base sheet / surface protective layer, the adhesion between the surface protective layer / base sheet is improved, and the surface protective layer is not peeled off, dropped off, or lost.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of a decorative sheet according to the present invention.
FIG. 2 is a cross-sectional view illustrating another embodiment of the decorative sheet of the present invention.
[Explanation of symbols]
1 Base sheet
2 Surface protective layer
3 All solid layers
4 Pattern layers
5 Permeation suppression layer
6 Penetration pattern layer
7 Uneven pattern
S decorative sheet

Claims (6)

  1. In a decorative sheet formed by providing a solid layer and / or a handle layer on a base material sheet and laminating a surface protective layer made of a cross-linked cured product of an ionizing radiation curable resin, the surface protective layer is not colored. A decorative sheet comprising a colored transparent layer and containing calcined kaolin as a filler.
  2. In a decorative sheet formed by providing a solid layer and / or a handle layer on a base material sheet and laminating a surface protective layer made of a cross-linked cured product of an ionizing radiation curable resin, the surface protective layer is not colored. A decorative sheet comprising a colored transparent layer and containing calcined kaolin as a filler, and the amount of calcined kaolin added is 5 to 50 parts by mass with respect to 100 parts by mass of the resin component forming the surface protective layer .
  3. In a decorative sheet formed by providing a solid layer and / or a handle layer on a base material sheet and laminating a surface protective layer made of a cross-linked cured product of an ionizing radiation curable resin, the surface protective layer is not colored. A decorative sheet comprising a colored transparent layer, containing calcined kaolin as a filler, and having an average particle diameter of calcined kaolin of 0.5 to 2 μm .
  4. In a decorative sheet formed by providing a solid layer and / or a handle layer on a base material sheet and laminating a surface protective layer made of a cross-linked cured product of an ionizing radiation curable resin, the surface protective layer is not colored. It consists of a colored transparent layer and contains calcined kaolin as a filler, and the added amount of calcined kaolin is 5 to 50 parts by mass with respect to 100 parts by mass of the resin component forming the surface protective layer. A decorative sheet having an average particle size of 0.5 to 2 μm .
  5. The decorative sheet according to any one of claims 1 to 4, wherein the calcined kaolin is surface-treated with a silane coupling agent.
  6. The decorative sheet according to any one of claims 1 to 5 , comprising a primer layer between the base sheet and the surface protective layer.
JP2003077628A 2002-03-20 2003-03-20 Decorative sheet Active JP4074209B2 (en)

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JP2002077925 2002-03-20
JP2003077628A JP4074209B2 (en) 2002-03-20 2003-03-20 Decorative sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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JP4268486B2 (en) 2003-09-19 2009-05-27 大日本印刷株式会社 Coated paper
KR101189424B1 (en) * 2003-12-18 2012-10-10 다이니폰 인사츠 가부시키가이샤 Decorative material
US8187695B2 (en) * 2005-09-30 2012-05-29 Dai Nippon Printing Co., Ltd. Shaping sheet, resin decorative material and method of producing the same
JP6331576B2 (en) * 2014-03-28 2018-05-30 大日本印刷株式会社 Decorative sheet and decorative resin molded product

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