JP6308243B2 - Coating agent - Google Patents

Description

  The present invention relates to a structure installed indoors, a decorative sheet suitable for matte decoration on a floor surface, and a decorative material using the decorative sheet.

  Conventionally, as a decorative sheet suitable for matte decoration, for example, a decorative sheet in which matte silica is added to the outermost surface layer is known (Patent Documents 1, 2, etc.). As the matte silica, those having a pore volume of around 1.0 ml / g are generally used.

  However, although it is possible to reduce the gloss by using matte silica, a large amount of matte silica must be added as the luster is reduced, and the cloudiness of the outermost surface layer increases and weather resistance, There is a problem that physical properties such as contamination resistance and sliding resistance are deteriorated. In addition, since the fluidity of the coating agent containing matte silica is remarkably lowered, spotted irregularities and streaky irregularities are likely to occur on the coating surface, which makes coating difficult. On the other hand, if the outermost surface layer is made thick in order to improve the above physical properties, there is a problem that it is difficult to reduce the gloss.

  Further, it has been proposed to make the outermost surface layer uneven, thereby reducing the gloss without causing cloudiness and deterioration of physical properties. However, it is difficult to sufficiently reduce the gloss with this method.

  Therefore, there is a demand for the development of a decorative sheet in which a sufficiently low gloss is achieved without causing a cloudiness and a decrease in physical properties regardless of the thickness of the outermost surface layer.

Japanese Patent Laid-Open No. 2004-167779 JP 2004-148632 A

  An object of the present invention is to provide a decorative sheet in which a sufficiently low gloss is achieved without causing white turbidity and deterioration of physical properties regardless of the thickness of the outermost surface layer.

  As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved when the outermost surface layer of the decorative sheet is formed from a cured coating film of a specific coating agent. It came to complete.

That is, this invention relates to the following coating agent.
1. A coating agent used for producing a decorative sheet having a surface protective layer as an outermost surface layer on a base sheet,
(1) The surface protective layer is a cured coating film of the coating agent,
(2) The coating agent contains a filler and an ionizing radiation curable resin,
(3) The filler is
The pore volume is 1.8 ml / g or more and 3.0 ml / g or less,
The apparent specific gravity is 0.05 g / ml or more and 0.18 g / ml or less,
An oil absorption of Ri Der more than 300ml / 100g,
The average particle size is 3-50 μm,
A coating agent characterized by that.
2. Content of the said filler is a coating agent of the said claim | item 1 which is 1-30 weight part with respect to 100 weight part of said ionizing radiation curable resins.
3. Item 3. The coating agent according to Item 1 or 2, wherein the thixotropic property of the coating agent is 0.18 or more (rotation ratio: 60 rpm / 6 rpm).
4). The coating agent according to any one of Items 1 to 3, wherein the ionizing radiation curable resin is an ionizing radiation curable resin containing a urethane (meth) acrylate prepolymer.
5. The said decorative sheet is a coating agent in any one of said claim | item 1-4 by which the pattern pattern layer, the transparent resin layer, and the surface protective layer are laminated | stacked in order on the said base material sheet.

  Hereinafter, the present invention will be described in detail.

Coating Agent The coating agent used in the present invention has a pore volume of 1.8 to 3.0 ml / g, an apparent specific gravity of 0.05 to 0.22 g / ml, and an oil absorption of 300 ml / 100 g or more. It contains a matte filler and an ionizing radiation curable resin. By using the cured coating film of this coating agent as the outermost surface layer of the decorative sheet, sufficient gloss reduction can be achieved without causing white turbidity and deterioration of physical properties regardless of the thickness of the outermost surface layer. Can do. The reason for this is that by using a specific matting filler, the matting filler is less likely to settle and convection in the coating agent and the coating film of the coating agent, and the effect of the matting filler is impaired compared to conventional products. It can be difficult.

  The matte filler is not limited as long as the pore volume is 1.8 to 3.0 ml / g, the apparent specific gravity is 0.05 to 0.22 g / ml, and the oil absorption is 300 ml / 100 g or more. Particularly preferred are those having a pore volume of 1.9 to 2.5 ml / g, an apparent specific gravity of 0.10 to 0.20 g / ml, and an oil absorption of 300 to 400 ml / 100 g. In the present invention, since the effect of irregular reflection of light can be obtained efficiently by having a pore volume of 1.8 to 3.0 ml / g in particular, a good matting effect can be obtained.

  Further, by using the matte filler having the pore volume, the apparent specific gravity, and the oil absorption amount, it is possible to obtain an effect that the matte filler is less likely to settle and convection in the coating agent and the coating film of the coating agent. Therefore, it is suppressed that the dispersibility of the matte filler is uneven during the drying of the coating film. Specifically, by using the matte filler, the thixotropy of the coating agent can be improved to 0.18 or more, preferably 0.19 to 0.23. The thixotropy value in this specification was measured using a B-type viscometer (JIS Z 8803) at a rotation ratio (60 rpm / 6 rpm) when the solid content concentration of the coating agent was 50% by weight. Value (JIS K 6901).

  As the matte filler, those having the above physical properties can be selected from known inorganic particles such as silica and organic pigments.

The average particle size of the matte filler is preferably about 1 to 50 μm. With such an average particle size, the storage property of the coating agent is good, and when the average particle size is equal to or less than the thickness of the coating film, the coating workability is also preferred. The average particle diameter is a value measured by a laser diffraction method, and means a particle diameter (D ₅₀ ) corresponding to a cumulative frequency of 50%.

  The content of the matte filler is preferably about 1 to 30 parts by weight and more preferably about 5 to 20 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin described later.

  The ionizing radiation curable resin is not particularly limited, and prepolymers (including oligomers) and / or monomers containing radically polymerizable double bonds capable of undergoing a crosslinking reaction upon irradiation with ionizing radiation such as ultraviolet rays and electron beams. A transparent resin containing as a main component can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a cross-linking curing reaction.

  Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. Among these prepolymers, at least one of polyester (meth) acrylate and urethane (meth) acrylate is preferable. These molecular weights are usually preferably about 250 to 100,000.

  As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  Examples of the prepolymer having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.

  In addition to the matting filler and the ionizing radiation curable resin, the coating agent can be blended with known additives as necessary.

  Examples of additives include weathering agents such as ultraviolet absorbers and light stabilizers, and scratch-resistant fillers.

  Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and triazine ultraviolet absorbers. As the light stabilizer, for example, a hindered amine light stabilizer is suitable. The content of these weathering agents is not limited, but both the ultraviolet absorber and the light stabilizer may be about 1000 to 100000 ppm by weight. In particular, in the present invention, it is preferable to use a triazine ultraviolet absorber and / or a hindered amine light stabilizer.

Examples of the scratch-resistant filler include silica and alumina. The average particle diameter is preferably about 1 to 50 μm. With such an average particle size, the storage property of the coating agent is good, and when the average particle size is equal to or less than the thickness of the coating film, the coating workability is also preferred. The pore volume of the scratch-resistant filler is less than 1.0 ml / g, preferably 0 ml / g or more and less than 1.0 ml / g. Moreover, the apparent specific gravity of the case scuff filler is silica is less 0.4 g / cm ² exceeds 2.2 g / cm ^2.

  The content of the scratch-resistant filler is preferably about 3 to 30 parts by weight, and more preferably about 3 to 20 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.

  The coating agent of this invention can be prepared by mixing the said component. For example, mixing is performed using a known kneader such as a Banbury mixer, a kneader blender, a Brabender plastograph, a small batch mixer, a continuous mixer, or a mixing roll.

  In addition, a solvent (or dispersion medium) can be used as needed. For example, petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate Alcohol alcohol solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol and propylene glycol; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, dioxane, Ether-based organic solvents such as tetrahydrofuran; Chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichlorethylene, and tetrachloroethylene; Solvents, and the like. These solvents (or dispersion media) can be used alone or in admixture of two or more.

Cured coating film of coating agent The coating agent of the present invention forms a cured coating film by forming a film-like coating film by a known coating method such as gravure coating or roll coating, and then curing the coating film. The coating film may be directly formed on the outermost surface layer of the decorative sheet, or may be formed by laminating on a peelable transfer sheet substrate. In order to cure the coating film, for example, ionizing radiation may be irradiated.

  As the ionizing radiation used for curing the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion rays, or the like may be used.

  As the ultraviolet light source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used. As a wavelength of ultraviolet rays, 190 to 380 nm is usually preferable.

  As the electron beam source, for example, various electron beam accelerators such as a cockcroft 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. Among them, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.

  Although the thickness of a cured coating film is not specifically limited, Although it can set suitably according to the kind of decorative sheet, it is 0.1-50 micrometers normally, Preferably it is about 1-20 micrometers.

The decorative sheet of the present invention uses the cured coating film of the coating agent as a surface protective layer located on the outermost surface of the decorative sheet. That is, the cured coating film of the coating agent is used as the outermost surface layer (surface protective layer) of the decorative sheet in which one or more layers are laminated on the base sheet.

Although the specific layer structure of the decorative sheet is not limited, for example,
(1) The structure which laminated | stacked the surface protection layer on the base material sheet,
(2) The structure which laminated | stacked the primer layer and the surface protective layer in order on the base material sheet,
(3) A configuration in which a pattern layer, a primer layer, and a surface protective layer are sequentially laminated on a base sheet,
(4) A configuration in which a pattern layer and a surface protective layer are sequentially laminated on a base sheet,
(5) A configuration in which a transparent resin layer, a primer layer, and a surface protective layer are sequentially laminated on a base sheet,
(6) (Transparency) A configuration in which a pattern layer is laminated on the back surface of the base sheet, and a (transparency) surface protective layer is laminated on the front surface of the base sheet.
(7) (Transparency) A structure in which a pattern layer is laminated on the back surface of the base sheet, and a primer layer and a surface protective layer are laminated in order on the front face of the (transparency) base sheet.
(8) A configuration in which an adhesive layer, a transparent resin layer, a primer layer, and a surface protective layer are sequentially laminated on a base sheet,
(9) A configuration in which a pattern layer, an adhesive layer, a transparent resin layer, a primer layer, and a surface protective layer are sequentially laminated on a base sheet,
(10) In the above (1) to (9), the backer layer (in the case where there is a pattern layer on the back side of the substrate sheet, the back side of the pattern layer) or the backer layer Synthetic resin layer) to reduce the influence of the dressing
Etc.

Hereinafter, as a specific description of the layer configuration, the layer configuration of the above (9) is illustrated, and layers other than the surface protective layer will be described. The backer layer will also be described.
(Substrate sheet)
Although it does not limit as a base material sheet, the base material sheet which contains polyolefin resin as a resin component is preferable. Essentially, a sheet made of polyolefin resin is used.

  It does not specifically limit as polyolefin resin, What is normally used in the field | area of a decorative sheet can be used. For example, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, polyolefin-based thermoplastic elastomer, etc. Is mentioned. Among these, polypropylene, polyolefin-based thermoplastic elastomers and the like are particularly preferable.

  A homopolymer or copolymer having polypropylene as a main component is also preferable, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part and having 2 to 20 carbon atoms other than propylene. -Olefins. In addition, a propylene-α-olefin copolymer containing 15 mol% or more of a comonomer of ethylene, butene-1,4-methylpentene-1, hexene-1, or octene-1 is also preferable.

  The polyolefin-based thermoplastic elastomer is preferably a mixture of isotactic polypropylene in the hard segment and atactic polypropylene in the soft segment in a weight ratio of 80:20.

  The polyolefin resin may be formed into a film by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.

  The thickness of the base sheet is not particularly limited and can be set according to the product characteristics, but is usually 40 to 150 μm, preferably about 50 to 100 μm.

  An additive may be mix | blended with a base material sheet as needed. Examples of the additive include a filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, and a colorant (see below). The blending amount of the additive can be appropriately set according to the product characteristics.

  It does not specifically limit as a coloring agent, Well-known coloring agents, such as a pigment and dye, can be used. For example, inorganic pigments such as titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black; isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene Organic pigments (including dyes) such as blue RS and aniline black; metal pigments such as aluminum and brass; pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. The coloring mode of the base sheet includes transparent coloring and opaque coloring (hiding coloring), and these can be arbitrarily selected. For example, when the ground color of an adherend (a base material on which a decorative sheet is pasted, such as a wooden base material) is concealed, opaque coloring may be selected. On the other hand, in order to make the ground pattern of the adherend visible, transparent coloring may be selected.

  One or both surfaces of the base sheet may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., as necessary. For example, when the corona discharge treatment is performed, the surface tension of the substrate sheet surface may be 30 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.

  A primer layer may be provided on one side or both sides of the base sheet as necessary.

  A primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a base material sheet. Examples of the primer agent include a urethane resin primer agent made of acrylic modified urethane resin, a primer agent made of urethane-cellulose resin (for example, a resin made by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton), and the like. Is mentioned.

The application amount of the primer agent is not particularly limited, but is usually 0.1 to 20 g / m ² , preferably about 0.5 to 10 g / m ² .
(Pattern pattern layer)
A pattern layer is formed on the base sheet.

  The design pattern layer imparts design properties with a desired design to the decorative sheet, and the type of design is not particularly limited. Examples thereof include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern.

  The method for forming the pattern layer is not particularly limited. For example, a colored ink or coating obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. What is necessary is just to form by the printing method etc. which used the agent etc.

  Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may further contain fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  Examples of the binder resin include acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum Resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like. These resins can be used alone or in admixture of two or more.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Inorganic solvents and the like, such as water; chlorinated organic solvents. These solvents (or dispersion media) can be used alone or in admixture of two or more.

  Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When forming a solid pattern pattern layer, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating Various coating methods such as a coating method may be mentioned. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used or combined with other forming methods. Good.

The thickness of the pattern layer is not particularly limited and can be set as appropriate according to the product characteristics, but the layer thickness after drying is about 0.1 to 20 μm.
(Colored hiding layer)
A colored concealment layer may be formed as a base for the pattern pattern layer or instead of the pattern pattern layer. The colored masking layer is provided when it is desired to mask the ground color of the adherend from the front surface of the decorative sheet. Of course, when the base sheet is transparent, even when the base sheet is concealed, it may be formed to stabilize the concealment.

  As the ink for forming the colored masking layer, an ink for forming a pattern layer and capable of masking coloring can be used.

  The method for forming the colored concealment layer is preferably a method that can be formed so as to cover the entire base sheet (entirely solid). For example, the roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method and the like described above are preferable.

The thickness of the colored concealing layer is not particularly limited and can be set as appropriate according to product characteristics, but the layer thickness after drying is about 0.1 to 20 μm.
(Transparent adhesive layer)
A transparent adhesive layer is formed on the pattern layer. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of transparent and colorless, colored and translucent. The transparent adhesive layer is formed in order to bond the pattern layer and the transparent resin layer.

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet.

  Examples of the adhesive known in the field of decorative sheets include thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and curable resins such as thermosetting urethane resin. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  For example, the adhesive layer is applied on the pattern layer (strictly, on the base sheet so as to cover the pattern layer), dried, laminated with a transparent resin layer, and then cured. Can be formed. Conditions such as drying temperature and drying time are not particularly limited, and may be set as appropriate according to the type of adhesive. The method of applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, and comma coating. The method can be adopted.

Although the thickness of an adhesive bond layer is not specifically limited, The thickness after drying is 0.1-30 micrometers, Preferably it is about 1-20 micrometers.
(Transparent resin layer)
The transparent resin layer may be colored as long as it is transparent, and may be translucent as long as the pattern layer is visible.

  Examples of the resin include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, and ionomer. , Polymethylpentene, acrylic acid ester, methacrylic acid ester, polycarbonate, cellulose triacetate and the like. Among the above, polyolefin resins such as polypropylene are preferable. More preferably, it is a polyolefin resin having stereoregularity. When using a polyolefin resin, it is desirable to form a transparent resin layer by extruding a molten polyolefin resin.

  For the transparent resin layer, if necessary, a filler, matting agent, foaming agent, flame retardant, lubricant, antistatic agent, antioxidant, ultraviolet absorber, light stabilizer, radical scavenger, soft component Various additives such as rubber (for example, rubber) may be included.

  The thickness of the transparent resin layer is not particularly limited, but is generally about 10 to 150 μm.

The surface of the transparent resin layer on which the surface protective layer is formed is subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment as necessary. Also good. The surface treatment may be performed according to a conventional method for each treatment. (Primer layer)
A primer layer for facilitating the formation of the surface protective layer is provided on the transparent resin layer.

  The primer layer can be formed by applying a known primer agent to the transparent resin layer. Examples of the primer agent include a urethane resin-based primer agent composed of an acrylic-modified urethane resin and the like, and a resin-based primer agent composed of a block copolymer of acrylic and urethane.

The application amount of the primer agent is not particularly limited, but is usually 0.1 to 20 g / m ² , preferably about 0.5 to 10 g / m ² .
(Embossing)
After laminating a cured coating film of a coating agent as a surface protective layer (outermost surface layer) on the transparent resin layer, the front surface of the surface protective layer may be embossed.

The embossing method is not particularly limited. For example, a preferable method is to heat soften the front surface of the transparent acrylic resin layer, pressurize and shape with an embossing plate, and then cool. For embossing, a known single-wafer or rotary embossing machine is used. Examples of the concavo-convex shape include a wood grain plate conduit groove, a stone plate surface unevenness (such as granite cleaved surface), a cloth surface texture, a satin texture, a grain, a hairline, a ridge line, and the like.
(Backer layer)
Backer layer on the back side of the base sheet (if the back side of the base sheet has a pattern layer), a backer layer (synthesizing to increase the scratch resistance and reduce the influence of the substrate) (Resin layer) may be provided. In addition, the above scratch resistance refers to a dent scratch when a load is applied partially, and the decorative sheet of the present invention has sufficient scratch resistance without providing a backer layer, but a backer layer is provided. Thus, various performances such as scratch resistance can be further enhanced.

  As a method for forming the backer layer, extrusion molding of a molten resin is suitable, for example, extrusion molding using a T die is suitable.

  As a method of adhering the back surface of the base material sheet and the backer layer, a method of adhering the base material sheet and the backer layer obtained by extruding the molten resin by heat fusion, the base material sheet and the backer layer For example, a method of bonding by providing an adhesive layer (further, if necessary, a primer layer) between them may be used.

  The resin constituting the backer layer is not limited, but a thermoplastic resin such as polyethylene, polypropylene (PP), polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, amorphous polyethylene terephthalate. (A-PET), highly heat-resistant polyalkylene terephthalate [for example, polyethylene terephthalate in which a part of ethylene glycol is substituted with 1,4-cyclohexanedimethanol, diethylene glycol or the like, so-called trade name PET-G (Eastman Chemical) Company)), polybutylene terephthalate (PBT), polycarbonate, polyarylate, polyethylene naphthalate, polyethylene naphthalate-isophthalate Coalescence, polyimide, polystyrene, polyamide, ABS (acrylonitrile - butadiene - styrene copolymer) and the like. These resins can be used alone or in combination of two or more.

  The thickness of the backer layer can be set as appropriate depending on the use of the final product, the method of use, etc., but is generally preferably 100 to 800 μm. Among these, 400-600 micrometers is more preferable.

  If necessary, the backer layer may be subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, degreasing treatment, surface roughening treatment, and the like on the adhesion surface. Further, a primer layer may be further provided on the back surface in consideration of adhesiveness with the adherend.

  In the present invention, by providing the backer layer, the scratch resistance can be enhanced and the influence of the adherend can be reduced. For example, the effect of unevenness existing on the surface of the adherend can be alleviated, and especially when the adherend is made of wood, the unevenness of polishing formed on the surface during sanding or the knots on the wood (so-called ducts) ) Can be mitigated. In particular, in the case of a decorative sheet having a low gloss, it is easy to be affected by the duck of the wood-based adherend. Therefore, it is preferable to reduce the influence of the duck by providing a backer layer.

Cosmetic Material The decorative sheet of the present invention can be made into a cosmetic material 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 timber and the like 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 shape of such an adherend is not particularly limited, and may be a flat plate in consideration of installation on a flooring or the like.

  After joining with the adherend, for example, according to the characteristics of the final product, cutting, use of a tenor, sag processing, provision of V-shaped grooves, chamfering on four sides, etc. may be performed.

  The matting agent used in the present invention has a pore volume of 1.8 to 3.0 ml / g, an apparent specific gravity of 0.05 to 0.22 g / ml, and an oil absorption of 300 ml / 100 g or more. It contains a filler and an ionizing radiation curable resin. By using the cured coating film of this coating agent as the outermost surface layer of the decorative sheet, sufficient gloss reduction can be achieved without causing white turbidity and deterioration of physical properties regardless of the thickness of the outermost surface layer. Can do. The reason for this is that by using a specific matting filler, the matting filler is less likely to settle and convection in the coating agent and the coating film of the coating agent, and the effect of the matting filler is impaired compared to conventional products. It can be difficult.

It is a schematic diagram which shows the layer structure of the decorative sheet produced in the Example and the comparative example.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Examples 1-7 and Comparative Examples 1-6 (no backer layer)
(Production of decorative sheet)
A colored polypropylene sheet (thickness 60 μm) was prepared as a base sheet.

  After performing the corona discharge treatment on the front surface and the back surface of the base sheet, a primer agent was applied to each of the front surface and the back surface to form a primer layer (each thickness: 2 μm). The primer agent is a mixture of 100 parts by weight of a resin composition and 5 parts by weight of hexamethylene diisocyanate (curing agent). The resin composition contains an acrylic urethane copolymer, an acrylic polyol, and a triazine ultraviolet absorber (5 mass). %).

  Next, a woodgrain pattern layer (thickness 2 μm) was formed on the primer layer on the surface, and a transparent adhesive layer (thickness 3 μm) was formed thereon. A transparent thermoplastic polyolefin was heated and melt-extruded by a T-die extruder on the transparent adhesive layer to form a transparent resin layer (thickness 80 μm).

  Furthermore, a primer layer (2 μm) was formed on the transparent resin layer, and a coating agent having the composition shown in Table 1 below was applied on the primer layer by a gravure coating method (coating thickness 30 μm).

  Thereafter, in an atmosphere having an oxygen concentration of 100 ppm, the coating film of the coating agent was irradiated with an electron beam under the conditions of an acceleration voltage of 175 keV and 5 Mrad (50 kGy) to crosslink and cure the coating film to form a surface protective layer.

Scratch resistant filler: Silica (average particle size 3μm, pore volume 0.05ml / g, apparent specific gravity 0.65g / ml)
(Evaluation of decorative sheet)
Each decorative sheet was examined for design properties (matte properties), design properties (white turbidity), and scratch resistance. In addition, the storage stability of the coating agent was also examined during the production of each decorative sheet. Each test method and evaluation criteria were as follows. The evaluation results are shown in Table 1 above. «Designability (matte property)» Test method: The gloss value of the outermost surface was measured using a Murakami color gloss meter (60 °). The measurement was performed according to JIS Z 8471.

Evaluation criteria: ○: Gloss value of less than 8, Δ: Gloss value of 8 or more and less than 10, X: Gloss value of 10 or more << Designability (white turbidity) >>
Test method: The appearance of the sample was visually observed and evaluated.

Evaluation criteria: ○: Not cloudy, ×: Cloudy << Abrasion resistance >>
Test Method: The surface of the sample after 20 reciprocating rubbing tests was visually observed and evaluated using steel wool (# 0000) with a load of 300 g / cm ² .

Evaluation criteria ◎: No change in appearance, ○: No significant change in appearance, ×: Scratched << Storage stability of coating agent >>
Test method: The coating agent (solid content: 50% by weight) was allowed to stand at room temperature (23 ° C.) for 7 days in a sealed state, and then visually observed and evaluated. The evaluation was performed according to JIS K 5600.

Evaluation criteria: ○: No sediment, Δ: Precipitate exists but dissolves by stirring, ×: Precipitate exists, does not dissolve even by stirring
Examples 8 to 10 (with backer layer)
A colored polypropylene sheet (thickness 60 μm) was prepared as a base sheet.

  After the corona discharge treatment was applied to the surface of the base sheet, a primer agent (thickness 2 μm) was formed by applying a primer agent only to the surface. The primer agent is a mixture of 100 parts by weight of a resin composition and 5 parts by weight of hexamethylene diisocyanate (curing agent). The resin composition contains an acrylic urethane copolymer, an acrylic polyol, and a triazine ultraviolet absorber (5 mass). %).

  Next, a woodgrain pattern layer (thickness 2 μm) was formed on the primer layer on the surface, and a transparent adhesive layer (thickness 3 μm) was formed thereon. A transparent thermoplastic polyolefin was heated and melt-extruded by a T-die extruder on the transparent adhesive layer to form a transparent resin layer (thickness 80 μm).

  Furthermore, a primer layer (2 μm) was formed on the transparent resin layer, and a coating agent having the composition shown in Table 2 below was applied on the primer layer by a gravure coating method (coating thickness 30 μm).

  Thereafter, in an atmosphere having an oxygen concentration of 100 ppm, the coating film of the coating agent was irradiated with an electron beam under the conditions of an acceleration voltage of 175 keV and 5 Mrad (50 kGy) to crosslink and cure the coating film to form a surface protective layer.

  Subsequently, a backer layer was formed by extruding and laminating a transparent resin on the back surface of the base sheet by a laminating method. The thickness of the backer layer was 250 μm, and the material was PP. In addition, after the corona discharge treatment was performed on the back surface of the backer layer, a primer layer was provided. Hereinafter, the thickness of the backer layer was changed to be Examples 9 and 10.

Examples 11-14 (with backer layer)
A surface protective layer was formed in the same manner as in Example 8 except that a primer layer was provided on the back surface of a colored polypropylene sheet (base material sheet) having a thickness of 60 μm.

  Subsequently, a backer layer was provided on the primer layer surface on the back surface of the base sheet via an adhesive. The thickness of the backer layer was 250 μm and the material was PET. Hereinafter, the thickness and material of the backer layer were varied to obtain Examples 12, 13, and 14.

Details of the material of the backer layer in Table 2 are as follows.
・ PP: Homopolypropylene, “PL500A” manufactured by Sun Allomer Co., Ltd.
・ A-PET: “A-PET sheet” manufactured by Echizen Polymer Co., Ltd.
・ PET (biaxial stretching): “Diafoil” made by Mitsubishi Plastics
・ PBT: “Duranex” manufactured by Polyplastics Co., Ltd.
(Evaluation of decorative sheet)
The decorative sheets of Examples 8 to 14 were examined for design properties (matte properties, cloudiness, adherend duck), static pressure load test, and scratch resistance. In addition, the storage stability of the coating agent was also examined during the production of each decorative sheet. Each test method and evaluation criteria were as follows (only new test methods and evaluation criteria will be explained). The evaluation results are shown in Table 2 above. Moreover, the evaluation result in the decorative sheet of Example 1 is also shown.
≪Adhesive material duck≫
Each decorative sheet was bonded to a wood-based adherend (Lawan plywood), and whether or not duck of the adherend was recognized with the naked eye was evaluated according to the following evaluation criteria.

◎: The wood base duck is completely invisible. ○: The wood base duck is visible, but it is slightly visible.
△: Slightly visible wood base material, but no problem in actual specifications (acceptable as a product)
X: Wood material duck is clearly visible (not acceptable as a product)
≪Static load test≫
Set a steel cylinder jig with a diameter of 20 mmφ on the surface of the test sample in a 45 ° tilted state, and push it in with a Tensilon universal testing machine (“RTC-1310A” manufactured by Orientec Co., Ltd.) until a load of 80 N is applied. The dent depth was measured and evaluated according to the following evaluation criteria.

A: Depth is less than 10 μm ○: Depth is 10 μm or more and less than 30 μm Δ: Depth depth is 30 μm or more and less than 50 μm (acceptable as a product)
X: Depth of 50 μm or more (not acceptable as a product)
As is clear from the results in Table 2, the decorative sheet of Example 1 has acceptable levels of the evaluation results of the adherend duck and the static pressure load test as a product. However, by providing a backer layer, both evaluation results can be improved. It can be seen that it can be increased. In particular, it can be seen that by setting the thickness of the backer layer to 400 to 600 μm, both evaluation results can be enhanced to ◎.

1. 1. Primer layer 2. base material sheet Wood grain pattern layer 4. 4. Transparent adhesive layer 5. Transparent resin layer Primer layer 7. Surface protective layer

Claims (5)

A coating agent used for producing a decorative sheet having a surface protective layer as an outermost surface layer on a base sheet,
(1) The surface protective layer is a cured coating film of the coating agent,
(2) The coating agent contains a filler and an ionizing radiation curable resin,
(3) The filler is
The pore volume is 1.8 ml / g or more and 3.0 ml / g or less,
The apparent specific gravity is 0.05 g / ml or more and 0.18 g / ml or less,
An oil absorption of Ri Der more than 300ml / 100g,
The average particle size is 3-50 μm,
A coating agent characterized by that.   The coating agent according to claim 1, wherein a content of the filler is 1 to 30 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.   The coating agent according to claim 1 or 2, wherein the thixotropy of the coating agent is 0.18 or more (rotation ratio: 60 rpm / 6 rpm).   The coating agent according to any one of claims 1 to 3, wherein the ionizing radiation curable resin is an ionizing radiation curable resin containing a urethane (meth) acrylate prepolymer.   The said decorative sheet is a coating agent in any one of Claims 1-4 in which the pattern layer, the transparent resin layer, and the surface protective layer are laminated | stacked in order on the said base material sheet.

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