JP2756595B2 - Method for producing laminated decorative sheet having raised print layer between layers - Google Patents

Description

The present invention relates to a method for producing a laminated decorative sheet having a printed layer between layers.

[Problems to be solved by conventional technology and invention]

At present, ionizing radiation curable resins are attracting attention in various fields and are widely used. For example, in the field of building materials, it has been applied as a coating material suitable for performing emboss printing on a non-heat-resistant base material such as vinyl chloride. That is, since the ionizing radiation-curable resin is quickly cured by irradiating with ionizing radiation after printing, it is suitable for forming a thick print layer (build-up printing). In addition, the above resin is generally suitable for applications such as heat resistance and surface protection because it becomes a cured film having a high crosslinking density and excellent heat resistance upon curing.

However, although the cured ionizing radiation-curable resin film quickly cures and has a high crosslink density and excellent heat resistance, it has poor adhesion to other synthetic resin layers after curing, and as a result, In the case where another synthetic resin layer is bonded and laminated on the above-mentioned cured film, conventionally, it has been necessary to bond the synthetic resin layer as an object to be bonded with an adhesive. However, the method of adhering another synthetic resin layer via an adhesive as described above complicates the working process and is disadvantageous in terms of cost. In addition, the bonding method using an adhesive sometimes has insufficient bonding strength between the cured ionizing radiation-curable resin film and another synthetic resin layer, and for example, there has been a problem that both are separated during processing or use after bonding. .

The present invention has been made in view of the above points, and manufactures a laminated decorative sheet having a raised printing layer between layers capable of easily and firmly adhering another synthetic resin layer on a raised printing layer made of an ionizing radiation-curable resin. The aim is to provide a method.

[Means for solving the problem]

The present invention provides (1) a base film which is at least one of which is transparent and a synthetic resin to be bonded, and then, on the base film, a raised printing layer which forms a partial pattern made of an ionizing radiation-curable resin. Is formed by printing, the embossed printing layer is semi-cured by irradiating ionizing radiation, and then the synthetic resin layer to be adhered is formed on the entire surface of the base film over the formed portion and the non-formed portion of the embossed printing layer. Formed and then irradiated with ionizing radiation to completely cure the raised print layer, having a raised print layer between the layers characterized by adhering the raised print layer and the synthetic resin layer to be bonded A method for producing a laminated decorative sheet, (2) using, as the ionizing radiation-curable resin, a resin containing an organic polymer material that is non-reactive to ionizing radiation; Have A method of manufacturing a laminated decorative sheet,
(3) Production of a laminated decorative sheet having a raised printing layer between layers according to (1) or (2), wherein the semi-cured ionizing radiation-curable resin film is a film having no tackiness and an apparently dry cured state. Method.

The manufacturing method of the present invention is an ionizing radiation-curable resin formed by printing on a base film. The manufacturing method of the present invention is a partial pattern comprising an ionizing radiation-curable resin formed by printing on a basic film. Is semi-cured by irradiating ionizing radiation to the raised printing layer. As a method of semi-curing, there are a method by selecting a material and a composition of the ionizing radiation-curable resin composition, a method by selecting irradiation conditions of ionizing radiation, and the like.

By forming a semi-cured ionizing radiation-curable resin film having a chemical adhesive property while having no tackiness and an apparently dry cured state by the semi-curing step, once wound up in a roll shape, There is an advantage that a resin or the like can be applied thereon. In order to obtain a semi-cured film having the above characteristics, an organic polymer material containing an electron beam or an ultraviolet curable resin as a main component, and inactive to ionizing radiation, is added from 0 to 99 parts, and ionized radiation is applied. It may be cured until it apparently hardens.

Examples of the ionizing radiation curable resin used in the present invention include an electron beam or ultraviolet curable resin, and these resins are used in a paint or the like depending on the application. The coating material composed of an electron beam or ultraviolet curable resin contains, as a film-forming component, a polymer, an oligomer, a monomer, etc. having a radical polymerizable double bond in its structure as a main component, and if necessary, an organic solvent, a wax. It contains other additives. The electron beam curable paint and the ultraviolet curable paint are similar in composition except that the latter contains a photopolymerization initiator and a sensitizer.

Particularly preferred for the purpose of the present invention are those in which the film-forming component has an acrylate-based functional group, such as a polyester resin, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, a spiro resin having a relatively low molecular weight. Acetal resin, polybutadiene resin, polythiol polyene resin, oligomer or prepolymer such as (meth) acrylate of polyfunctional compound such as polyhydric alcohol, and ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene as reactive diluent Monofunctional monomers such as methylstyrene and N-vinylprolidone, and trimethylolpropane tri (meth)
Acrylate, hexadiol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexadiol di ( It contains relatively large amounts of polyfunctional monomers such as (meth) acrylate and neopentyl glycol (meth) acrylate.

By using such a polyfunctional (meth) acrylate-based ionizing radiation-curable paint, a cured resin layer having excellent surface hardness, transparency, abrasion resistance, scratch resistance, and the like can be obtained. Further, when high flexibility and shrinkage resistance are required for such a cured resin layer, an appropriate amount of a thermoplastic resin, such as a non-reactive acrylic resin or various waxes, is added to the above-mentioned curable paint. By doing so, we can meet those demands.

Further, in order to make the above-mentioned curable paint a UV-curable paint, an acetophenone agent, a benzophenone agent, Michler benzoyl benzoate, α
-Amiloxime ester, tetramethylthiuram monosulfide, thioxanthone, and n- as a photosensitizer
Butylamine, triethylamine, tri-n-butylphosphine and the like can be used as a mixture.

In the case of electron beam irradiation, ionizing radiation is emitted from various electron beam accelerating groups such as Cockloft-Walton type, Pandegraph type, Resonant transformation type, Insulation core transformation type, Linear type, Dynamitron type, High frequency type, etc. An electron beam having an energy of 50 to 1000 keV, preferably 100 to 300 keV is used. In the case of ultraviolet irradiation, ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc,
Ultraviolet rays emitted from a light source such as a metal halide lamp are used.

In order to semi-cure the ionizing radiation-curable resin by irradiation of these ionizing radiations, usually, the irradiation time and / or the intensity of the ionizing radiation is appropriately adjusted, and the irradiation amount of the ionizing radiation is 0.003 MJ / m ² or more. It is preferably 0.15 MJ / m ² or less.

In addition, in order to make the ionizing radiation-curable resin more semi-cured in the present invention, non-reactive organic polymer materials contained in the resin include ethyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, cellulose acetate and the like. A cellulose derivative of
Styrene resins such as polystyrene and poly-α-methylstyrene, and poly (methyl) methacrylate (ethyl, butyl)
(Meth) acrylic resin, rosin, rosin modified maleic resin, rosin modified phenol resin, rosin ester resin such as polymerized rosin, polyvinyl acetate, chroman resin, vinyl toluene resin, polyvinyl chloride, polyvinyl chloride, vinyl acetate copolymer Coalescing, polyester, polyurethane, butyral resin, etc.
Or a mixture of two or more of these.

The mixing ratio of the ionizing radiation-curable resin and the non-reactive organic polymer material is 99: 1 to 1:99 to achieve the object of the present invention, but semi-cured while maintaining the characteristics of the ionizing radiation-curable paint. In order to make the state, it is preferably about 40: 6 to 99: 1.

Next, the production method of the present invention is to directly form a synthetic resin layer to be adhered on the raised printing layer made of semi-cured ionizing radiation curable resin, over the entire surface of the formed portion and the non-formed portion of the raised printing layer. And filling and enclosing the raised printing layer between the layers.

The material of the resin for the layer to be bonded can be selected according to the intended use.For example, cellulosic resins, cellulose resins such as acetate, polyethylene, polypropylene, polyolefin resins such as polymethylpentene, and polyesters such as polyethylene terephthalate. Resin, polyvinyl chloride, polyvinylidene chloride, vinyl polymer such as polyvinyl chloride-vinyl acetate copolymer, polystyrene, styrene resin such as AS resin, polycarbonate, polyvinyl alcohol, or polyamide such as nylon 6, nylon 66, Polyarylate, polyimide, polyetheretherketone and the like are used. Above all, polyvinyl chloride is preferred for applications such as floor tiles and decorative sheets in view of workability, flame retardancy, and price. In addition, as the resin material, an ionizing radiation curable resin or the like can be used.

The resin layer to be bonded may be obtained by dissolving the above resin material with a solvent to form a coating. The resin material preferably has a configuration that allows ionizing radiation to pass therethrough.

Extrusion coating, doubling with hot pressure, gravure coating, roll coating, reverse roll coating, flow coating, comma coating, spray coating,
Means such as a known coating method such as a bar coat can be applied.

According to the present invention, the ionizing radiation-curable resin is finally cured again by completely re-irradiating the ionizing radiation with the ionizing radiation, whereby the ionizing radiation-curable resin film and the synthetic resin layer to be bonded can be bonded. Irradiation with ionizing radiation at this time can employ the same means as described above, and the irradiation conditions include energy for completely curing the ionizing radiation-curable resin,
In other words, in the electron beam 0.04MJ / m ² or more, the UV 0.1 mJ / m ²
That is all.

The bonding method of the present invention having the above-described configuration can be applied to applications such as floor tiles and decorative sheets having a raised printing layer made of an ionizing radiation-curable resin inside.

〔Example〕

 Next, the present invention will be described in more detail with reference to examples.

As shown in FIG. 1 (a), a 0.3 mm thick transparent polyvinyl chloride film 1 (manufactured by Riken Vinyl Industry: W-
500, 23phr), UV curable ink (DAINICHI SEIKA KOGYO: EXD) and vinyl chloride ink (DAINICHI SEIKA KOGYO: V-1)
2) The UV curable paint 2 mixed at a ratio of 95: 5 is patterned and printed with a gravure plate having a plate depth of 150μ.
Irradiation 3 was performed for 1 second at an intensity of 0 W / cm to semi-cure.

Next, as shown in FIG. 1 (b), a vinyl chloride ink (V-12 manufactured by Dainichi Seika Kogyo Co., Ltd.) for forming the synthetic resin layer 4 to be adhered on the pattern printing surface has a dry coating thickness of 2 μm. After solid printing, the sample was irradiated with ultraviolet rays at an intensity of 80 W / cm for 3 seconds 5.

By this second UV irradiation 5, the UV curable resin was completely cured, and the pattern printing layer 2 made of the UV curable resin and the vinyl chloride ink layer 4 were well bonded.

Next, as shown in FIG. 2 (c), a colored polyvinyl chloride sheet 6 having a thickness of 0.08 mm (10 ph
r) are laminated, and then press-pressed at a temperature of 150 ° C, a press pressure of 15 kg / cm ² , and a press time of 15 minutes. After cooling, the press plate was opened to obtain a laminated sheet 7 as shown in FIG.

The obtained laminated sheet was rich in adhesiveness and had a 180 ° peeling strength of 1500 g / cm.

〔The invention's effect〕

As described above, the method for producing a laminated decorative sheet having a raised printing layer between layers according to the present invention is a method for simply and firmly attaching another synthetic resin layer to a raised printing layer made of an ionizing radiation-curable resin without using an adhesive. Can be adhered to
A laminated decorative sheet having excellent interlayer adhesion can be obtained. For example, when a polyvinyl chloride resin layer was provided via an adhesive layer on a completely cured ionizing radiation-curable resin film as in the prior art, the 180 ° peeling strength was 100 g / cm. According to the method of the present invention, when the polyvinyl chloride resin layer is provided, the peeling strength is 1500 g / cm, and adhesion with excellent adhesive strength is achieved. Further, by applying the present invention, the bonding can be performed with a simple operation, and the cost can be reduced as compared with the conventional method.

Also, by using an ionizing radiation-curable resin containing an organic polymer material that is non-reactive to ionizing radiation, the allowable range of the minimum and maximum doses of ionizing radiation for semi-curing can be increased. Thus, there is an effect that the work becomes easy at the time of processing, and that the non-reactive organic polymer and the non-adhesive resin layer are chemically and physically well bonded.

Furthermore, by making the semi-cured ionizing radiation-curable resin film non-tacky and apparently in a dry-cured state, it can be wound and stored once, or can be coated on the ionizing radiation-curable resin film by a method such as coating. Thus, there is an effect that another resin layer can be laminated.

[Brief description of the drawings]

The drawings show an embodiment of the present invention. FIG. 1 is a cross-sectional view showing an example of a process of the method of the present invention, and FIG. 2 is a cross-sectional view showing a post-process in the present embodiment. 2 ... Ionizing radiation curable resin film 3 ... Ionizing radiation irradiation during semi-curing 4 ... Synthetic resin layer to be bonded 5 ... Ionizing radiation irradiation for complete curing

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-55-129472 (JP, A) JP-A-63-135207 (JP, A) JP-A-59-178251 (JP, A) 23856 (JP, B2) JP-B-56-46482 (JP, B2)

Claims (3)

(57) [Claims] 1. A substrate film which is transparent at least on one side and a synthetic resin to be adhered are prepared, and then a raised print layer forming a partial pattern made of an ionizing radiation curable resin is printed on the substrate film. After being formed by the above, the raised print layer is irradiated with ionizing radiation to be semi-cured, and then, over the formed portion and the non-formed portion of the raised print layer on the base film, a synthetic resin layer to be bonded is formed on the entire surface. And thereafter, irradiating with ionizing radiation to completely cure the raised print layer, and bond the raised print layer and the synthetic resin layer to be bonded. Sheet manufacturing method. 2. The laminated decorative sheet according to claim 1, wherein the ionizing radiation-curable resin contains an organic polymer material that is non-reactive to ionizing radiation. Production method. 3. The method of claim 1, wherein the semi-cured ionizing radiation-curable resin film is a film having no tackiness and an apparently dry-cured state. Method.