JP3082950B2 - 3D makeup printing method - Google Patents

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 pattern is formed three-dimensionally.

[0002]

2. Description of the Related Art To print a pattern on various base materials such as decorative boards, usually, printing is applied to the base material and a paint that allows the printed portion to be seen through is applied to the base material, or ink is applied onto the coating film. The pattern was formed by printing. However, such printing is visually flat, poor in depth, and lacks realism.

[0003] Conventionally, as a technique for obtaining a pattern excellent in transparency, depth and abrasion resistance, for example, Japanese Patent Application Laid-Open No.
There was one described in JP-166970. This technology relates to a method of manufacturing a decorative flooring material, in which a white vinyl chloride resin is applied to a base material of a glass fibrous fabric, gelled by heating, a clear vinyl chloride resin is applied thereon, and then heated and cured. To form a base clear layer, and then transfer the pattern of the printing transfer sheet formed using the sublimable ink to the clear coating layer,
Further, a clear vinyl chloride resin is applied, and 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 penetrated into the base clear layer and the top clear layer.

[0004] A transfer sheet using the sublimable dye is generally used exclusively for textile products, especially for fabric products, and when transferred to the fabric, the vapor of the dye reaches the inside of the space between the fibers. By penetration, a vivid printing effect having a depth in the thickness direction of the fabric was obtained.

[0005]

The above-mentioned JP-A-56-16
In the technique described in Japanese Patent No. 6970, a vinyl chloride resin is used as the thermoplastic resin of the clear layer. By the way, thermoplastic resins have a good ability to adsorb sublimed dyes, but as time goes on, the ability to absorb the dye 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 by a thermal transfer method is disclosed in
No. 1511 was known. The publication describes that a substrate to be printed is coated with a crosslinkable thermosetting resin treated with a polyisocyanate, and then the coated substrate is dried to at least partially crosslink, A dye is printed on the surface of the substrate by a thermal sublimation method.

However, what is described in the above publication is printed on the surface of a substrate by a thermal transfer method, and no heat treatment is performed after printing, and the sublimable dye is diffused into the coating film and developed. The printing was flat and of poor depth. In addition, printing by the thermal transfer method requires a larger amount of printing ink and more waste of ink than a printing method using a general ink. The reason for this is that in the printing by the thermal transfer method, the amount of the ink transferred to the printing surface is extremely small.

Therefore, the present invention has a long-term stability in the adsorption and fixing of an ink containing a heat-diffusible dye, and the printed ink diffuses three-dimensionally in the thickness direction of the coating film to have a visually deep depth. It is an object of the present invention to provide a three-dimensional decorative printing method in which a pattern is formed and the amount of ink used is small and clear.

[0009]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a base material having an ionizing radiation curable property and a thermosetting property.
Paint with both properties and irradiate it with ionizing radiation.
Semi-hard paint with both radiation-curing and thermosetting properties
And printed on it with an ink containing a heat-diffusible dye,
At the same time as heating the coating film to completely cure the coating film,
The material is diffused in the thickness direction of the coating film.

[0010]

The ink containing a heat-diffusible dye used in the present invention may be a heat-diffusion type in which the heat-diffusible dye is contained in a binder, or may be a wax containing a heat-diffusible dye or a heat-diffusible pigment. A hot-melt type dispersed therein can also be used. The heat-diffusible dye is preferably a disperse dye, and is usually 150 to
It is desirable to have a molecular weight of about 400. This dye is selected in consideration of heat diffusion temperature, hue, weather resistance, stability in a binder resin, and the like, and a sublimable dye is typically used. Specific examples of the sublimable dye include the following.

Miketone Polyester Yellow YL (CI Disperse Yellow 12) manufactured by Mitsui Toatsu Co., Ltd.
Kayaset Yellow C (CI Disperse Yellow 77) manufactured by Nippon Kayaku Co., Ltd., PTY manufactured by Mitsubishi Kasei Corporation
-52 (CI Solvent Yellow 14-1), Miketone Polyester Red BSF, manufactured by Mitsui Toatsu Co., Ltd.
(CI Disperse Red 111), Kayaset Red B (CI Disperse Red B) manufactured by Nippon Kayaku Co., Ltd., PTR-54 (C.I.
I. Disperse Red 50), Miketone Polyester Blue PBL (CI Disperse Blue 56), manufactured by Mitsui Toatsu Co., Ltd., PTB-67, manufactured by Mitsubishi Kasei Corporation
(CI Disperse Blue 241), Kayaset Blue 906 (CI 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 property in the state of color development.
It is present in an amount of up to 70% by weight, preferably of the order of 10 to 60% by weight. Next, as the binder resin contained in the ink, one having high heat resistance and not hindering the transfer of the dye when heated is usually selected. For example, the following resins are used. Ethyl cellulose, hydroxyethyl cellulose,
Hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate and the like are used. As the vinyl resin, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl pyrrolidone,
Polyester, polyacrylamide and the like are used.

The substrate to be printed can be applied to anything, for example, a plate or sheet of wood, various metals, minerals, fibers, plastics, etc., or a coating applied to various substrates. It may be anything, such as a plate or a sheet, and further includes various articles, structures of buildings, structures such as vehicles and ships. As the sheet material of the base material, for example,
Paper such as thin paper, parchment paper, kraft paper, polyethylene film, polypropylene film, polyvinyl chloride film, 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, plastic film such as ionomer or aluminum,
Sheets such as metal foils of copper, tin, iron, lead or the like, or sheets that are not completely concealed, such as transparent, translucent, colored transparent, etc., or opaque sheets made of an appropriate composite of the above substrates can be used. Further, release paper can be used as the base sheet.

As the printing method, a commonly used printing method, for example, a known printing method such as a gravure printing method, an offset gravure printing method, a lithographic printing method, an electrostatic printing method, or a jet printing method can be applied. Ionization used in the present invention
For paints that have both radiation-curing and thermosetting properties
Blends ionizing radiation curable paint with thermosetting paint
Can be used. First ionizing radiation curing
The sex component will be described. The said ionizing radiation curable coating material has an electron beam curing paint and ultraviolet curing paint, the components of both, except that ultraviolet curable coating material contains a photopolymerization initiator or sensitizer is substantially the same. Ionizing radiation-curable paints are
Generally, as a film-forming component, a polymer, an oligomer, a monomer, etc. having a radical polymerizable double bond in the solution as a main component, and, if necessary, a non-reactive polymer, an organic solvent, a wax or the like. It contains additives.

[0016] The ionizing radiation curable paint film forming component used preferably include those having a functional group of acrylate, e.g., a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin,
Urethane resin, alkyd resin, spiro acetal resin, polybutadiene resin, polythiol polyene resin,
Oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as polyhydric alcohols and ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N
Monofunctional monomers such as vinylpyrrolidone and polyfunctional monomers, for example, 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 and the like.

In order to make the above-mentioned ionizing radiation-curable paint into an ultraviolet-curable paint, a photopolymerization initiator may be used therein.
Using a mixture of acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthone, and n-butylamine, triethylamine, tri-n-butylphosphine, etc. as a photosensitizer Can be. Particularly, in the present invention, polyester acrylate to which diallyl phthalate is added is preferable.

These ionizing radiation-curable paints can be cured by a usual curing method, that is, by irradiation with an electron beam or ultraviolet rays. For example, in the case of electron beam curing, 50 is emitted from various electron beam accelerators such as Cockloft-Walton type, Bande graph type, Resonant transformation type, Insulating core transformer type, Linear type, Dynamitron type, High frequency type.
An electron beam or the like having an energy of 1000 to 1000 KeV, preferably 100 to 300 KeV is used. In the case of ultraviolet curing, an ultraviolet ray emitted from a light beam 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. Is available.

Next, the ionizing radiation curable coating used in the present invention is used.
It is described components of the thermosetting coating material in the postal. As thermosetting resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, unsaturated polyester resins, polyurethane resins, epoxy resins, amino alkyd resins, melamine / urea co-condensation resin, silicon resin, poly There is a siloxane resin, etc., if necessary, as an additive, a crosslinking agent, a curing agent such as a polymerization initiator,
A polymerization accelerator, a solvent, a viscosity modifier, an extender and the like are added. As the curing agent, isocyanates are generally used in unsaturated polyester resins. In polyurethane resins, peroxides such as methyl ethyl ketone peroxide, radical initiators such as azobisisobutyronitrile are often used in unsaturated polyester resins. . Further, as the isocyanate as a curing agent, divalent or higher valent aliphatic or aromatic isocyanates can be used, but aliphatic isocyanates are desirable from the viewpoint of preventing thermal discoloration and weather resistance. Specific examples include tolylene diisocyanate, xylene diisocyanate,
4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like.

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

Next, diffusion and fixation of the heat diffusible dye in the coating film by further heating the cured coating film will be described. The heating temperature for diffusing the heat diffusible dye into the coating film depends on the type of the dye and the like, but is preferably selected from the range of about 80 to 250 ° C.

The printed matter of various substrates obtained by such a decorative printing method can be directly used as a decorative printed product. 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 attached to a plywood. For example, a grain of a plastic sheet, such as a transparent, translucent, or colored transparent sheet, is printed with an ink 2 containing a heat-diffusible dye, and an ionizing radiation paint 3 is applied thereon. Is applied to completely cure the coating film, and then heat-diffusible dye contained in the ink 2 is diffused into the coating film by heating to form a decorative sheet. Since the base material sheet is transparent, for example, when it is pasted on a 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]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

Example 1 Step 1 On a transparent polyvinyl chloride film having a thickness of 0.07 m / m, 100 parts of urethane acrylate (Aronix, registered trademark, manufactured by Toagosei Co., Ltd.) and acrylic monomer 30
(Aronix, registered trademark, manufactured by Toagosei Co., Ltd.)
After applying a coating composition of 10 parts of isocyanate (Takenate, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) to a thickness of 50 μm with a roll coater, 5 Mrad · 20 m / min.
Irradiation was performed under the conditions described above 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 (the 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 electron beam-curable paint.

Step 4 Next, the sheet obtained in step 3 was bonded to a plywood of China using a vinyl chloride-vinyl acetate copolymer resin. In the decorative plate thus obtained, the wood surface of the plywood can be visually observed through the coating film, and between the coating films, a wood grain print such as a conduit is three-dimensionally arranged in the thickness direction of the coating film. So
A deep, realistic wood grain pattern was formed.

[0032]

[0033]

[0034]

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

[0036]

As described above in detail, according to the present invention, the heat diffusible dye of the printing ink printed on the substrate is heated to form a coating film of the ionizing radiation curable paint and / or the thermosetting paint. Since the ink is diffused in the direction, it has a long-term stability in fixing and fixing the ink containing the heat diffusible dye, and the printed ink spreads three-dimensionally in the thickness direction of the coating film and has a visually deep pattern. Were formed, and the amount of ink used was small, and a clear three-dimensional cosmetic printing method could be obtained.

[Brief description of the drawings]

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Ionizing radiation-curable paint 3 Ink

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) B41M 1/00-3/18 B05D 5/06

Claims (1)

(57) [Claims] 1. A coating material having both ionizing radiation curability and thermosetting properties is applied to a substrate, and a coating material having both ionizing radiation curing properties and thermosetting properties is applied by irradiating with ionizing radiation. Hardening, printing with an ink containing a heat-diffusible dye thereon, heating the coating to completely cure the coating, and simultaneously diffusing the dye in the thickness direction of the coating. Method.