JPS6255134A - Decorative sheet and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a decorative sheet that is applied as a decorative surface material to furniture, walls, etc. To provide a decorative sheet which has excellent properties, has an excellent sense of synchrony, and is highly designed.

[Conventional technology]

Decorative sheets, which are used as decorative surface materials for furniture, walls, etc., are made of thermosetting resins such as urethane resins and aminoalkyd resins, or two-component curing resins on a base sheet with a printed pattern layer formed on the surface. Apply a top coat of paint,
A common structure is a hardened version of this.

[Problem that the invention seeks to solve]

By the way, the above-mentioned conventional decorative sheet having a topcoat layer made of a curable resin does not have sufficient surface properties on the surface of the topcoat layer, and cannot be applied to horizontal surfaces where high scratch resistance, abrasion resistance, etc. are particularly required. At present, there are some difficulties with respect to this.

In contrast, the decorative sheet of the present invention is a novel decorative sheet that has excellent surface properties that allow it to be applied to horizontal surfaces that require a high degree of scratch resistance and abrasion resistance. The method for producing a decorative sheet of the present invention is a method for easily and reliably obtaining the decorative sheet of the present invention.

[Means for solving problems]

The decorative sheet of the present invention includes a base sheet made of paper or plastic film, a first printed pattern layer formed on the surface of the base sheet, and a top coat formed on the entire surface of the printed pattern layer. layer, and a second printed pattern layer formed on the surface of the top coat layer, wherein the top coat layer is a thermoplastic ionizing radiation curing type that exhibits a solid state at room temperature even in an uncured state. It is formed by the process of applying a top coat containing resin as the main component and the process of irradiating ionizing radiation. 1) The ionizing radiation-curable resin present at least on the surface of the base sheet has a crosslinked structure. Further, the top coating layer and the second printed pattern layer have different gloss states.

Further, the method for producing a decorative sheet of the present invention includes a printing step of forming a first printed pattern layer on the surface of a base sheet made of paper or a plastic film, and a printing step of forming a first printed pattern layer on the entire surface of the first printed pattern layer of the base sheet. , a step of applying a top coat mainly composed of a thermoplastic ionizing radiation curable resin that is solid at room temperature even in an uncured state to form a top coat layer, and a second printed pattern on the surface of the top coat layer. A printing step of forming a layer, and ionizing radiation is irradiated from the surface of the second printed pattern layer to eliminate ionization existing on at least the surface of the base sheet of the ionizing radiation-curable resin in the top coating layer. Introducing a crosslinked structure to radiation-curable resin,
The process consists of a step of forming a top coat layer in a cured state, and furthermore, the top coat layer and the second printed pattern layer are coated at room temperature even in the uncured state so that the top coat layer and the second printed pattern layer exhibit different gloss states. A top coat containing a solid thermoplastic ionizing radiation curable resin as a main component and a printing ink for forming the second printed pattern layer are selected.

In the decorative sheets of the present invention having the above-mentioned configurations and the manufacturing method thereof, the base sheet may include papers such as thin paper, titanium paper, and various processed papers, synthetic papers made of synthetic resins such as polypropylene and polyethylene, Synthetic resin mixed paper, cellophane, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyester.

Various synthetic resin films such as polystyrene, laminated sheets of these sheets, coated sheets coated with various resins, etc. are used.

Further, the first printed pattern layer and the second printed pattern layer are each formed by a known printing means using a known printing ink, but the printing ink forming the second printed pattern layer is
Since the second printed pattern layer and the top coating layer are formed to have different gloss states, a material containing a dissipating agent is used to give the second printed pattern layer a glossy matte feel. There are many things that are configured to appear.

In addition, the resin that is the main component of the top coat that makes up the top coat layer, that is, the thermoplastic ionizing radiation curable resin that is solid at room temperature even in its uncured state, has radically polymerizable unsaturated groups introduced into it. (1) having a glass transition temperature of 0 to 2 and having a radically polymerizable unsaturated group;
There are a polymer having a temperature of 50°C and (2) a monomer compound having a radically polymerizable unsaturated group and having a melting point of 20 to 250°C, as described below.

(1) Polymer having a radically polymerizable unsaturated group Compound 1 described below can be prepared by the method described below (in detail).
) to 7) homopolymers or copolymers into which radically polymerizable unsaturated groups have been introduced, or the above compound 1
) to 7) In order to adjust the glass transition point of the homopolymer or copolymer or to adjust the physical properties of the obtained cured film, a monomer copolymerizable with the homopolymer or copolymer described above is used. such as methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, brol acrylate, propyl methacrylate,
Butyl acrylate, butyl methacrylate, inbutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
There are copolymers obtained by copolymerizing the above-mentioned homopolymers or copolymers with 2-ethylhexyl acrylate), 2-ethylhexyl methacrylate, and the like.

Compounds 1) to Compounds 7) 1) Monomers having hydroxyl groups: N-methylol acrylamide, 2-hydroxyethyl acrylate, 2-human secidiptyl acrylate, 2-hydroxyprogyl acrylate, 2-hydroxyethyl acrylate, 2- Human secuidipyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-5-phenoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, etc. 2) Monomers having carboxyl groups: niacrylic acid, methacrylic acid, acryloyloxyethyl monomer Succinate, etc. 5) Monomers with epoxy groups such as nigericidyl methacrylate +) Monomers with aziridinyl groups: 2-azilyshel ethyl methacrylate, allyl 2-aziridinylpropionate, etc. 5) Amino7 groups Monomers having niacrylamide, methacrylamide, diaseptone acrylamide, dimethylaminoethyl methacrylate, diethylamide/ethyl methacrylate, etc. 6) Monomers having a sulfone group: 2
-acrylamide-2-methylpropanesulfonic acid, etc. 7) Monomer having isocyanate group = 2. Method for introducing a radically polymerizable unsaturated group such as an adduct of a diisocyanate such as an equimolar adduct of LL-toluene diisocyanate and 2-hydroxyethyl acrylate and a radically polymerizable monomer having active hydrogen (a) Having a hydroxyl group In the case of copolymers of monomers, monomers having carboxyl groups, such as acrylic acid and methacrylic acid, are condensed. In the case of a polymer or copolymer, the above-mentioned monomers having hydroxyl groups are subjected to a condensation reaction (c) In the case of a polymer or copolymer of monomers having epoxy groups, isocyanate groups, or aziridinyl groups, the above For addition reaction of monomers having hydroxyl groups or monomers having carboxyl groups) In the case of polymers or copolymers of monomers having hydroxyl groups or carboxyl groups, monomers having epoxy groups or aziridinyl groups. or diisocyanate) (addition reaction of a 1:1 molar adduct of a ζ compound and a hydroxyl group-containing acrylic ester monomer (2) Stearyl, a monomer compound having a radically polymerizable unsaturated group acrylate, stearyl methacrylate,
Triacrylisocyanurate, cyclohexanediol cyacrylate, cyclohexanediol dimethacrylate, spiroglycol dimethacrylate, etc.

1. In the above-mentioned top coating, it is of course possible to use the polymer having the radically polymerizable unsaturated group and the monomer compound having the radically polymerizable unsaturated group in combination. For the purpose of increasing the crosslinking density of the introduced crosslinked structure and improving heat resistance, for example, ethylene glycol cyacrylate, ethylene glycotyl dimethacrylate, polyethylene glycol cyacrylate, polyethylene glycol dimethacrylate, hexanezoolzoactrimethylol Pro/guntriacrylate, trimethylolpropane trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate , dipentaerythritol hexamethacrylate, ethylene glycol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether methacrylate, polyethylene glycol diglycysol ether diacrylate, polyethylene glycol diglycidyl ether methacrylate, propylene glycol diglycidyl ether ether Zoacrylate, propylene glycol digpylene glycol diglycidyl ether diacrylate, polypropylene glycol diglycidyl ether dimethacrylate,
A radically polymerizable unsaturated monomer such as sorbitol tetraglycidyl ether tetraacrylate or sorbitol tetraglycidyl ether tetramethacrylate is added to 0 of the polymer into which the radically polymerizable unsaturated group has been introduced.
It is also possible to add about 1 to 100% by weight.

The coating layer of the above-mentioned topcoat paint, that is, the coating layer of the topcoat paint whose main component is a thermoplastic ionizing radiation-curable resin that solidifies at room temperature even in an uncured state, can be sufficiently cured with an electron beam. However, when curing this by UV irradiation, bendine ethers such as benzoquinone, benzoin, benzoin methyl ether, /,
It is preferable to mix sensitizers such as rhodanized acetophenones and piacetyls.

Examples of methods for applying the top coating paint to the entire surface of the first printed pattern layer of the base sheet include natural roll coating, reverse roll coating, gray coating, barcode coating, spray coating, mesh roll coating, and 70- Methods such as coat, knife coat, screen foot, photom coat, etc. may be used.

In addition, the ionizing radiation applied after the above-mentioned top coating layer is formed includes, for example, Kotscroft-Solton type, Punchgraph type, resonant transformer type, insulated core transformer type, linear type, Dynamidron type, etc. Electron beams emitted from various types of electron accelerators such as type and high frequency type electron accelerators with energy in the range of 50 to 1 OOOKeV, preferably 100 to 300 KeV, ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs. , ultraviolet light using a light source such as a metal halide lamp is used.

〔Example〕

The specific configurations of the decorative sheet and the manufacturing method thereof of the present invention will be explained below with reference to manufacturing examples.0 Example 1゜Basic weight 659/, r? Resin mixed paper [manufactured by Tamakoshi Paper Co., Ltd.]
Acrylic ink [Morohoshi Ink Co., Ltd.: KL-HA] was applied to the surface of a base sheet made of CB-FIX-65S].
After applying peta printing using T), on top of this peta printing, a first printed pattern layer corresponding to the wood grain pattern excluding the conduit portion is applied using nitrocellulose ink (manufactured by Showa Ink Co., Ltd.: SAM). Then, a top coat [Yupimer, manufactured by Mitsubishi Yuka Fine Co., Ltd.] whose main component is triazine-based acrylate [ultraviolet curable resin: melting point 120°C] is applied to the entire surface of the first printed pattern layer. coating layer,
Urethane ink formed by peta printing using a gravure printing machine, and further containing 25% by weight of a matting agent on the surface coated with the top coat (Showa Ink Co., Ltd. AS 06M)
Accordingly, a second printed pattern layer corresponding to the conduit portion of the wood grain pattern was formed so that the wood grain pattern appeared by the combination of the first printed pattern layer and the second printed pattern layer.

After that, the obtained sheet was passed under an ozone-containing high-pressure mercury lamp (160 WAR lamp) for 10 m/min.
A crosslinked structure was introduced into the ultraviolet curable resin in the top coat layer to form a top coat layer, thereby obtaining an example product of the present invention.

The obtained decorative sheet, which is an example of the present invention, has a glossy matte feel between the conduit portion and the non-conduit portion in the wood grain pattern, and has a high design quality with excellent synchronicity. Needless to say, it had extremely excellent physical properties such as scratch resistance, abrasion resistance, and solvent resistance.

[Actions and effects of the present invention]

In the decorative sheet of the present invention, the top coat layer is formed so as to cover the entire surface of the first printed pattern layer in the base sheet on which the first printed pattern layer is formed, and the top coat layer is Among the ionizing radiation-curable resins in the paint layer, at least the resin present on the surface of the base sheet is crosslinked and cured by irradiation with ionizing radiation, so the solvent resistance on the surface of the decorative sheet is Scratch resistance,
It has extremely excellent abrasion resistance and can be used particularly for horizontal surfaces that require excellent surface properties such as scratch resistance and abrasion resistance.

In addition, the decorative sheet of the present invention is one in which an ionizing radiation-curable resin that is solid at room temperature even in an uncured state is coated on the surface of a base sheet, and this is crosslinked and cured by irradiation with ionizing radiation. Even if the resin impregnated inside the base sheet remains uncured without being irradiated with ionizing radiation, the uncured resin will not become sticky; Since there is no possibility of poor adhesion, the decorative sheet is of high quality. Incidentally, when an ionizing radiation-curable resin that is liquid at room temperature in an uncured state is coated and cured by irradiation with contact ionizing radiation, the ionizing radiation does not reach the resin that has penetrated into the base sheet. However, the above-described functions and effects of the decorative sheet of the present invention are noteworthy, compared to the disadvantages of remaining in an uncured state, causing stickiness and poor adhesion.

Furthermore, in the decorative sheet of the present invention, since a crosslinked structure is introduced into the ionizing radiation-curable resin in the top coat layer after the second printed pattern layer is formed, the crosslinked structure is introduced into the top coat layer and the surface of the top coat layer. The adhesion between the formed second printed pattern layer is good, and it is necessary that the first printed pattern layer and the second printed pattern layer have good adhesion.
Since the gloss conditions between the printed pattern layer and the printed pattern layer are different from each other, functions and effects such as a high level of design with excellent synchronicity and a high level of synchronicity can also be achieved. Note that if an overcoat layer is not formed using an ionizing radiation-curable resin that is liquid at room temperature in an uncured state, it is difficult to form a second printed pattern layer because the surface is sticky before curing. In contrast, the above-mentioned top coat in the decorative sheet of the present invention The high adhesion between the layer and the second printed image layer is also noteworthy.

Further, the method for manufacturing a decorative sheet of the present invention has the effect that a decorative sheet having the above-mentioned special functions and effects can be easily and reliably obtained.

Furthermore, in the method for producing a decorative sheet of the present invention, a paint whose main component is a thermoplastic ionizing radiation-curable resin that is solid at room temperature even in an uncured state must be used as the top coat. Even after the top coat is applied to the base sheet and before the sheet is irradiated with ionizing radiation, there is no sticky resin on the surface and it is possible to wind it up into a roll. It also has the effect of being easy to handle during the manufacturing process.

Claims (5)

[Claims] (1) A base sheet made of paper or plastic film, a first printed pattern layer formed on the surface of the base sheet, and a first printed pattern layer formed on the entire surface of the first printed pattern layer of the base sheet. and a second printed pattern layer formed on the surface of the top coat layer, and the top coat layer is made of thermoplastic material that is solid at room temperature even in an uncured state. A coating layer of a paint containing an ionizing radiation-curable resin as a main component, wherein at least the ionizing radiation-curable resin in the coating layer is present on the surface of the base sheet. A decorative sheet, which is crosslinked and cured by irradiation with ionizing radiation, and further characterized in that the top coating layer and the second printed pattern layer have different gloss states. (2) The decorative sheet according to claim 1, wherein the second printed pattern layer is a printed pattern layer using printing ink using a solvent-volatile resin as a vehicle. (3) The decorative sheet according to claim 1, wherein the second printed pattern layer is a printed pattern layer using printing ink using a two-component curing resin as a vehicle. (4) The second printed pattern layer is a printed pattern layer formed by printing ink using a thermoplastic ionizing radiation-curable resin as a vehicle that is solid at room temperature even in an uncured state, and is present on at least the surface of the base sheet. 2. The decorative sheet according to claim 1, wherein the ionizing radiation-curable resin is crosslinked and cured by irradiation with ionizing radiation. (5) A step of printing on the surface of a base sheet made of paper or plastic film to form a first printed pattern layer, and solidifying the entire surface of the first printed pattern layer at room temperature even in an uncured state. a step of applying a top coat mainly composed of a thermoplastic ionizing radiation-curable resin exhibiting a shape;
A step of printing on the surface coated with the top coat to form a second printed pattern layer, and irradiating ionizing radiation from the surface of the second printed pattern layer to eliminate ionization existing on at least the surface of the base sheet. and curing the radiation-curable resin to form a top coat layer, and further, the top coat and the second printed pattern layer are mixed so that the top coat layer and the second printed pattern layer have different gloss states. A method for producing a decorative sheet, comprising selecting an ink for forming a printed pattern layer.