JPH04239685A - Three-dimensional decorative printing method - Google Patents

Abstract

PURPOSE:To provide a three-dimensional decorative printing method which imparts stability for a long time to the adsorptive fixation of an ink containing a heat dispersive dye, permits the inked impression to be three-dimensionally dispersed in the thickness direction of a coating film so as to form a visually deep pattern and requires a small amount of the ink used, yet offering a clear printing. CONSTITUTION:A three-dimensional decorative printing method which comprises the steps of coating a base material with a transparent ionizing radiation curable coating material, a thermosetting coating material with the subsequent curing or semi-curing thereof or a coating material having the combined properties of the ionizing radiation curable coating material and the thermosetting coating material with the, subsequent semi-curing thereof, printing such a coat with an ink containing a heat dispersive dye, subsequently applying heat thereto to disperse the dye in the thickness direction of the coating film, thereby forming a three-dimensional pattern, and finally curing the coating film completely by applying ionizing radiation or heat thereto.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a three-dimensional decorative printing method in which a three-dimensional pattern is formed.

0002

[Prior Art] In order to print patterns on various base materials such as decorative boards, it is usual to print on the base material and then apply a paint that allows the printed area to be seen through, or to apply ink on the coating film. It was printed to form a pattern. However, such printing was visually flat, lacked depth, and lacked a sense of realism.

[0003] Conventionally, therefore, as a technique for obtaining a pattern with excellent transparency, depth, and abrasion resistance, for example, Japanese Patent Laid-Open No. 56
There was one described in the -166970 publication. This technology relates to a method for manufacturing decorative flooring materials, in which a white vinyl chloride resin is applied to a base material of glass fiber fabric, heated to gel, and then a clear vinyl chloride resin is applied on top of the white vinyl chloride resin and cured by heating. A base clear layer is formed, and the pattern of the print transfer sheet formed using sublimation ink is transferred to the clear coating layer, and then a clear vinyl chloride resin is applied. Thereafter, the clear layer is completely cured by heating, and at the same time, the printed portion of the clear ink formed by the transfer is allowed to penetrate into the base clear layer and the top clear layer.

[0004] Transfer sheets using sublimable dyes are generally used exclusively for textile products, especially fabric products, and when transferred to the fabric, the vapor of the dye reaches inside the spaces between the fibers. By penetrating the fabric, a vivid printing effect with depth in the thickness direction of the fabric was obtained.

[0005]

[Problem to be solved by the invention] Said Japanese Unexamined Patent Publication No. 56-16
In the technique described in Japanese Patent No. 6970, vinyl chloride resin is used as the thermoplastic resin of the clear layer. By the way, thermoplastic resin has an excellent ability to adsorb sublimated dyes, but as time passes, the adsorption ability gradually weakens, and the pattern becomes thinner and eventually disappears. There was a point.

On the other hand, printing an ink containing a sublimable dye on the surface of a thermosetting resin using a thermal transfer method is disclosed in Japanese Patent Publication No. 1-4.
It was known from Publication No. 1511. The method described in this publication involves coating a substrate to be printed with a crosslinkable thermosetting resin treated with polyisocyanate, then drying the coated substrate to crosslink at least a portion thereof, and further The dye is printed on the surface of the substrate by thermal sublimation.

However, what is described in the above publication is printed on the surface of the base material by a thermal transfer method, and no heat treatment is performed after printing, so that the sublimable dye diffuses into the interior of the coating film and develops. Because it was not printed, the printing was flat and lacked depth. Moreover, printing using the thermal transfer method uses a larger amount of printing ink than printing methods using general inks, resulting in a large amount of ink wasted. The reason for this is that when printing by thermal transfer, the amount of ink transferred to the printing surface is extremely small.

Therefore, the present invention provides long-term stability in adsorption and fixation of ink containing a heat-diffusible dye, and the printed ink is three-dimensionally diffused in the thickness direction of the coating film, giving it a visually deep appearance. To provide a three-dimensional decorative printing method in which a pattern is formed, the amount of ink used is small, and the pattern is clear.

[0009]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention applies a transparent or colored transparent ionizing radiation-curable paint to a base material, and irradiates the substrate with ionizing radiation-curable paint. is cured, printed with ink containing a heat-diffusible dye, and the coating film is heated to diffuse the dye in the thickness direction of the coating film.

[0010] Furthermore, the present invention involves coating a base material with a transparent or colored transparent ionizing radiation-curing paint, semi-curing the ionizing radiation-curing paint by irradiating it with ionizing radiation, and applying a heat-diffusible dye thereon. The coating film is completely cured by printing with an ink containing the dye, heating the coating film, and irradiating the dye with ionizing radiation while diffusing the dye in the thickness direction of the coating film. Furthermore, the present invention
A paint that has both ionizing radiation curability and thermosetting properties is applied to the base material, ionizing radiation is irradiated to semi-cure the coating that has both ionizing radiation curability and thermosetting properties, and then Furthermore, the present invention is a method in which the coating film is printed with an ink containing a heat-diffusible dye, and the coating film is heated to completely cure the coating film, and at the same time, the dye is diffused in the thickness direction of the coating film. A transparent or colored transparent thermosetting paint is applied to the material, an ink containing a heat-diffusible dye is printed on the material, and the thermosetting paint is cured by heating, at the same time the dye is diffused in the thickness direction of the coating film. This is what I did.

The ink containing a heat-diffusible dye used in the present invention may be a heat-diffusible type in which the heat-diffusible dye is contained in a binder, or a heat-diffusible ink containing a heat-diffusible dye or a heat-diffusible pigment in a wax. It is also possible to use a heat-melting type that is dispersed in the liquid. The heat-diffusible dye is preferably a disperse dye, and usually has a dye of 150 to
It is desirable to have a molecular weight of about 400. This dye is selected in consideration of thermal diffusion temperature, hue, weather resistance, stability in the binder resin, etc., and sublimable dyes are typically used. Specific examples of sublimable dyes include the following.

Miketone Polyester Yellow YL (C.I. Disperse Yellow 12) manufactured by Mitsui Toatsu Co., Ltd.
Kayaset Yellow C (C.I. Disperse Yellow 77) manufactured by Nippon Kayaku Co., Ltd., PTY manufactured by Mitsubishi Kasei Co., Ltd.
-52 (C.I. Solvent Yellow 14-1), Mitsui Toatsu Co., Ltd. Miketon Polyester Red BSF (C
．． I. Disperse Red 111), Nippon Kayaku Co., Ltd. Kayaset Red B (C.I. Disperse Red B)
), manufactured by Mitsubishi Kasei Co., Ltd., PTR-54 (C.I. Disperse Red 50), manufactured by Mitsui Toatsu Co., Ltd., Miketon Polyester Blue PBL (C.I. Disperse Blue 5)
6), PTB-67 (C.I. Disperse Blue 241) manufactured by Mitsubishi Kasei Co., Ltd., Kayaset Blue 906 (C.I. Solvent Blue 112) manufactured by Nippon Kayaku Co., Ltd.

[0013] The content of the dye in the ink depends on the sublimation temperature of the dye and the color rendering properties in the developed state, but it is usually 5.
It is present in an amount of the order of -70% by weight, preferably 10-60% by weight. Next, as the binder resin contained in the ink, one is usually selected that has high heat resistance and does not hinder dye transfer when heated, and for example, the following are used. As the cellulose resin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, etc. are used. As the vinyl resin, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinylpyrrolidone, polyester, polyacrylamide, etc. are used.

[0014] Next, the substrate to be printed can be applied to any material, but for example, wood, various metals, inorganic materials, fibers, plastic plates or sheets, or coatings applied to various substrates. Any board or sheet is fine.
It also includes various articles, building frames, vehicles, ships, and other structures. Examples of the base sheet material include paper such as tissue paper, parchment paper, and kraft paper, polyethylene film, polypropylene film, polyvinyl chloride film,
Plastic films such as polyvinylidene chloride film, polyvinyl alcohol film, polyethylene terephthalate film, polycarbonate film, nylon film, polystyrene film, ethylene vinyl acetate copolymer film, ethylene vinyl alcohol copolymer film, ionomer, or aluminum, copper,
A sheet of metal foil such as tin, iron, lead, etc., or a suitable composite of each of the above substrates, such as a sheet that is not completely hidden, such as transparent, translucent, or colored transparent, or an opaque sheet can be used. Furthermore, a release paper can be used as the base sheet.

As the printing method, commonly used printing methods such as gravure printing, offset gravure printing, planographic printing, electrostatic printing, jet printing, and other known printing methods can be applied. Next, the components of the ionizing radiation curable paint will be explained. Ionizing radiation-curable coatings include electron beam-curing coatings and ultraviolet-curing coatings, and the components of both are almost the same, except that the ultraviolet-curing coating contains a photopolymerization initiator and a sensitizer. Ionizing radiation-curable paints are
Generally, the film-forming component is mainly composed of polymers, oligomers, monomers, etc. having radically polymerizable double bonds in the solution, and other non-reactive polymers, organic solvents, waxes, etc. are used as necessary. It contains additives.

The film-forming component used in the ionizing radiation-curable paint of the present invention is preferably one having an acrylate functional group, such as a relatively low molecular weight polyester resin, polyether resin, acrylic resin, or epoxy resin. , urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, oligomers or prepolymers such as (meth)acrylates of polyfunctional compounds such as polyhydric alcohols, and ethyl (meth)acrylate, ethylhexyl as reactive diluents. (meth)acrylate, styrene, methylstyrene,
Monofunctional monomers such as N-vinylpyrrolidone as well as polyfunctional monomers, such as trimethylolpropane tri(meth)acrylate, hexanediol(meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol Tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-
It contains relatively large amounts of hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc.

In order to make the above-mentioned ionizing radiation curable paint into an ultraviolet curable paint, a photopolymerization initiator may be added thereto.
Acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthone, and a photosensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine, etc. may be mixed and used. I can do it. Particularly in the present invention, polyester acrylate with diallyl phthalate added is preferred.

These ionizing radiation-curable coatings can be cured by conventional curing methods, ie, by irradiation with electron beams or ultraviolet rays. For example, in the case of electron beam curing, 50~
An electron beam or the like having an energy of 1000 KeV, preferably 100 to 300 KeV is used, and in the case of ultraviolet curing, ultraviolet rays emitted from light beams of an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. are used. Available.

Next, the components of the thermosetting paint used in the present invention will be explained. Paint components include thermosetting resins such as phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine/urea cocondensation resin. , silicon resins, polysiloxane resins, etc., and if necessary, additives such as crosslinking agents, curing agents such as polymerization initiators, polymerization accelerators, solvents, viscosity modifiers, extender pigments, etc. are added. As the curing agent, isocyanates are commonly used for unsaturated polyester resins, polyurethane resins, peroxides such as methyl ethyl ketone peroxide, and radical initiators such as azobisisobutyronitrile are often used for unsaturated polyester resins. . Further, as the isocyanate as a curing agent, an aliphatic or aromatic isocyanate having a valence of two or more can be used, but an aliphatic isocyanate is preferable from the viewpoint of prevention of thermal discoloration and weather resistance. Specific examples include tolylene diisocyanate, xylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and the like.

[0020] In this method of curing the thermosetting resin, heating may be carried out after application, if necessary, in order to accelerate the reaction. For example, in the case of isocyanate-cured urethane-cured unsaturated polyester resin or polyester resin, it is usually 4
It is about 1 to 5 days at 0 to 60°C, and in the case of polysiloxane resin, it is usually about 1 to 300 minutes at 80 to 150°C.

Furthermore, the paint having both ionizing radiation curable and thermosetting properties used in the present invention is a blend of the ionizing radiation curable paint and the thermosetting paint. Next, the diffusion and fixation of the heat-diffusible dye within the coating film by further heating the cured coating film will be explained. The heating temperature for diffusing the heat-diffusible dye into the coating film varies depending on the type of dye, etc., but is preferably selected from a range of approximately 80 to 250°C.

[0022] The printed matter of various base materials obtained by such a decorative printing method can be used as a decorative printed product as it is. FIG. 1 is a conceptual diagram showing a cross section of a decorative sheet produced by the three-dimensional decorative printing method of the present invention adhered to plywood. For example, a wood pattern is printed on a transparent, translucent, or transparent plastic sheet substrate 1 such as a colored transparent sheet using an ink 2 containing a heat-diffusible dye, an ionizing radiation paint 3 is applied thereon, and the ionizing radiation is A decorative sheet is obtained by irradiating the ink to completely cure the coating film, and then heating to diffuse the heat-diffusible dye contained in the ink 2 into the coating film. Since the base sheet is transparent, for example, when it is attached onto plywood having a wood grain, the wood grain of the plywood can be seen through and a three-dimensional wood grain pattern is reproduced.

[0023]

[Example 1] Process 1 Electron beam curable paint, Aronix (registered trademark, manufactured by Toagosei Co., Ltd.) was applied to a thickness of 50 μm using a roll coater on a transparent polyvinyl chloride film with a thickness of 0.07 m/m. Thereafter, electron beam irradiation was performed under the conditions of 5 Mrad and 20 m/min to completely cure the coating film on the sheet.

Step 2 A wood grain pattern is created on the sheet using an ink containing a weather-resistant dye (brown, a mixture of Kayaset Yellow C, Kayaset Red B and Kayaset Blue 906 manufactured by Nippon Kayaku Co., Ltd.). Gravure printed. Step 3 The sheet was heated on a heating drum at 200° C. for 30 seconds to diffuse the heat-diffusible dye contained in the ink into the electron beam cured paint film.

Step 4 Next, the sheet obtained in Step 3 was laminated onto a Chinese plywood board using a vinyl chloride-vinyl acetate copolymer resin. In the decorative plate obtained in this way, the wood surface of the plywood can be seen through the coating film, and between the coating films, the printed wood grain patterns such as conduits are arranged three-dimensionally in the thickness direction of the coating film. So,
A deep and realistic wood grain pattern was formed.

[0026]

[Example 2] Step 1 An electron beam curable paint, Aronix (registered trademark, manufactured by Toagosei Co., Ltd.) was applied to a 50μ thick transparent polyvinyl chloride film with a thickness of 0.07m/m using a roll coater. Thereafter, electron beam irradiation was performed under the conditions of 1 Mrad and 20 m/min to semi-cure the coating film on the sheet without completely curing it.

Step 2 A wood grain pattern was gravure printed on the sheet using an ink containing a weather-resistant dye (same as in Example 1). Step 3 The sheet was heated on a heating drum at 200° C. for 30 seconds to diffuse the heat-diffusible dye contained in the ink into the electron beam cured paint film.

Step 4 The above sheet was irradiated with an electron beam at 4 Mrad and 20 m/min. Step 5 Next, the sheet obtained in Step 3 was laminated onto Chinese plywood using a vinyl chloride-vinyl acetate copolymer resin. In the decorative plate obtained in this way, the wood surface of the plywood can be seen through the coating film, and between the coating films, the printed wood grain patterns such as conduits are arranged three-dimensionally in the thickness direction of the coating film. So,
A deep and realistic wood grain pattern was formed.

[0029]

[Example 3] Step 1 100 parts of urethane acrylate (Aronix, registered trademark, manufactured by Toagosei Co., Ltd.) and 30 parts of acrylic monomer (Aronix, registered trademark, Toagosei Co., Ltd.) and 10 parts of isocyanate (Takenate, trade name, Takeda Pharmaceutical Co., Ltd.) were applied with a roll coater to a thickness of 50 μm, and then exposed to electron beams at 5 Mrad and 20 m/min. Irradiation was performed to completely cure the coating film on the sheet.

Step 2 A wood grain pattern was gravure printed on the sheet using an ink containing a weather-resistant dye (same as in Example 1). Step 3 The sheet was heated on a heating drum at 200° C. for 30 seconds to diffuse the heat-diffusible dye contained in the ink into the electron beam cured paint film.

Step 4 Next, the sheet obtained in Step 3 was laminated onto a Chinese plywood board using a vinyl chloride-vinyl acetate copolymer resin. In the decorative plate obtained in this way, the wood surface of the plywood can be seen through the coating film, and between the coating films, the printed wood grain patterns such as conduits are arranged three-dimensionally in the thickness direction of the coating film. So,
A deep and realistic wood grain pattern was formed.

[0032]

[Example 4] Process 1 Takerock (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) as a urethane-based thermosetting paint was coated with a roll coater to a thickness of 50μ on a transparent polyvinyl chloride film with a thickness of 0.07m/m. After application, heating was performed at 80° C. for 1 minute.

Step 2 A wood grain pattern was gravure printed on the sheet using an ink containing a weather-resistant dye (same as in Example 1). Step 3 The sheet was heated on a heating drum at 200° C. for 30 seconds to diffuse the heat-diffusible dye contained in the ink into the coating film of the thermosetting paint.

Step 4 Next, the sheet obtained in Step 3 was laminated onto a Chinese plywood board using a vinyl chloride-vinyl acetate copolymer resin. In the decorative plate obtained in this way, the wood surface of the plywood can be seen through the coating film, and between the coating films, the printed wood grain patterns such as conduits are arranged three-dimensionally in the thickness direction of the coating film. So,
A deep and realistic wood grain pattern was formed.

The method of the present invention is not limited to the above embodiments, and various modifications can be made based on the spirit of the present invention. For example, the transparent coating film is not limited to one layer, but a plurality of transparent coating films may be laminated, each layer may be printed, and then the heat-diffusible dye may be heated and diffused.

[0036]

Effects of the Invention As explained in detail above, according to the present invention, the heat-diffusible dye of the printing ink printed on the base material is heated to increase the thickness of the coating film of the ionizing radiation-curable paint and/or the thermosetting paint. Because the ink is diffused in the direction, the adsorption and fixation of ink containing heat-diffusible dyes is stable for a long period of time, and the printed ink develops three-dimensionally in the thickness direction of the coating film, creating a pattern with visual depth. was formed, and it was possible to obtain a three-dimensional decorative printing method that required only a small amount of ink and was clear.

[Brief explanation of the drawing]

FIG. 1 is a conceptual diagram of a cross section of a sheet printed by the three-dimensional decorative printing method of the present invention.

[Explanation of symbols]

1 Base material 2 Ionizing radiation curing paint 3 Ink

Claims (4)

[Claims] Claim 1: A transparent or colored transparent ionizing radiation-curable paint is coated on a base material, the ionizing radiation-curable paint is cured by irradiation with ionizing radiation, and then an ink containing a heat-diffusible dye is printed on the base material. A three-dimensional decorative printing method, characterized in that the dye is diffused in the thickness direction of the coating film by heating the coating film. [Claim 2] Painting a transparent or colored transparent ionizing radiation-curable paint on a substrate, semi-curing the ionizing radiation-curing paint by irradiating it with ionizing radiation, and printing on it with an ink containing a heat-diffusible dye. A three-dimensional decorative printing method characterized in that the paint film is heated to diffuse the dye in the thickness direction of the paint film, and then ionizing radiation is irradiated to completely cure the paint film. Claim 3: A paint having both ionizing radiation curability and thermosetting properties is coated on a base material, and ionizing radiation is irradiated to semi-coat the paint having both ionizing radiation curability and thermosetting properties. harden and print on it with ink containing heat diffusible dye,
A three-dimensional decorative printing method characterized in that the dye is diffused in the thickness direction of the coating film by heating the coating film to completely cure the coating film and simultaneously diffusing the dye in the thickness direction of the coating film. 4. A substrate is coated with a transparent or colored transparent thermosetting paint, an ink containing a heat-diffusible dye is printed on the base material, and the dye is applied at the same time as the thermosetting paint is cured by heating. A three-dimensional decorative printing method characterized by spreading in the thickness direction of the coating film.