JPH0549479B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is characterized in that the pattern itself is made of a resin that can be cross-linked and cured by irradiation with ionizing radiation (ultraviolet rays or electron beams), and is transferred to the surface coated with ionizing radiation-curable paint. The present invention also relates to a transfer sheet that can be cross-linked and cured by irradiation with ionizing radiation to provide a reinforced decorative surface in which the paint and pattern are solidified as one, and a patterning method using the same.

Prior Art Conventionally, patterning a painted surface requires both a painting process and a printing process, and a drying process is required for each process.

Or attach the decorative sheet using adhesive,
After that, there was a method to paint it, but it required both a laminating process and a painting process.

Furthermore, in any of the above methods, each step required a long drying time and was not efficient.

Problems to be Solved by the Invention Therefore, the present invention provides a transfer sheet that solves the above-mentioned drawbacks of the prior art, has a simple process, and enables efficient patterning, and a method using this transfer sheet. The purpose is to provide a patterning method.

Means for Solving the Problems The transfer sheet of the present invention includes a vehicle containing an ionizing radiation-curable resin that is solid at room temperature in an uncured state and is thermoplastic, on the release surface of the release sheet. Furthermore, the patterning method of the present invention involves overlaying this transfer sheet on the coated surface of the base material coated with the paint, and then irradiating it with ionizing radiation. After that, the releasable sheet is peeled off.

(Transfer Sheet) FIG. 1 is a cross-sectional view showing an example of the transfer sheet of the present invention, and shows the releasable surface (lower surface) of the releasable sheet 1.
2 shows a state in which a pattern layer 2 using an ionizing radiation-cured resin (described later) as a vehicle is shown.

The release sheet 1 is for holding each layer transferred by transfer until the time of transfer, and for example, a synthetic resin film; polyethylene terephthalate film, polyamide film, polypropylene film, polyethylene film, etc., or paper or synthetic paper is used. do. The release sheet 1 may be a laminate of each of the above materials.

The pattern layer 2 uses as a vehicle an ionizing radiation-curable resin, particularly an ionizing radiation-curable resin that is solid at room temperature in an uncured state and is thermoplastic. There are two types of such resins:

(1) A polymer having a radically polymerizable unsaturated group with a glass transition temperature of 0 to 250°C. More specifically, as a polymer, it is possible to use a polymer obtained by polymerizing or copolymerizing the following compounds ~ into which radically polymerizable unsaturated groups are introduced by methods (a) to (d) described below. .

Monomers having hydroxyl groups: N-methylolacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate, 2
-Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy, 3-phenoxypropyl methacrylate, 2-hydroxy, 3-phenoxypropyl acrylate, etc.

Monomers with carboxyl groups: acrylic acid, methacrylic acid, acryloyloxyethyl monosuccinate, etc.

Monomers with epoxy groups: glycidyl methacrylate, etc.

Monomers having an aziridinyl group: 2-aziridinylethyl methacrylate, allyl 2-aziridinylpropionate, etc.

Monomers with amino groups: acrylamide, methacrylamide, diacetone acrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc.

Monomer having a sulfon group: 2-acrylamido-2-methylpropanesulfonic acid, etc.

Monomer having isocyanate group: 2,4
- adducts of diisocyanates and radially polymerizable monomers having active hydrogen, such as 1 mol to 1 mol adducts of toluene diisocyanate and 2-hydroxyethyl acrylate;

Furthermore, in order to adjust the glass transition point of the above copolymer and the physical properties of the cured film, the above compound is copolymerized with the following monomers that can be copolymerized with this compound. You can also do it. Examples of such copolymerizable monomers include methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, and t-butyl acrylate. -Butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-
Examples include ethylhexyl methacrylate.

Next, the material according to the present invention is obtained by reacting the polymer obtained as described above by methods (a) to (d) described below to introduce a radically polymerizable unsaturated group. I can do it.

(a) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as acrylic acid or methacrylic acid is subjected to a condensation reaction.

(b) In the case of a polymer or copolymer of monomers having a carboxyl group or a sulfonate group, the aforementioned monomers having a hydroxyl group are subjected to a condensation reaction.

(c) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group, or an aziridinyl group, the above-mentioned monomer having a hydroxyl group or monomer having a carboxyl group is subjected to an addition reaction.

(d) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, a monomer having an epoxy group or a monomer having an aziridinyl group or a diisocyanate compound and a hydroxyl group-containing acrylic ester monomer A 1:1 molar ratio of the adducts is subjected to an addition reaction.

In order to carry out the above reaction, it is preferable to add a small amount of a polymerization inhibitor such as hydroquinone and carry out the reaction while blowing dry air.

(2) A compound having a melting point of 0 to 250°C and having a radically polymerizable unsaturated group. Specific examples include stearyl acrylate, stearyl methacrylate, triacryl isocyanurate, cyclohexanediol diacrylate, cyclohexanediol dimethacrylate, spiroglycol diacrylate, and spiroglycol dimethacrylate.

Further, in the present invention, the above (1) and (2) can be used as a mixture, and a radically polymerizable unsaturated monomer can also be added to them. This radically polymerizable unsaturated monomer improves crosslinking density and heat resistance when irradiated with ionizing radiation, and in addition to the above-mentioned monomers, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol methacrylate, trimethylolpropane triacrylate, 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 dimethacrylate, polyethylene glycol diglycidyl ether diacrylate, polyethylene glycol diglycidyl ether dimethacrylate, propylene glycol diglycidyl ether diacrylate Acrylate, Propylene Glycol Diglycidyl Ether Dimethacrylate, Polypropylene Glycol Diglycidyl Ether Diacrylate, Polypropylene Glycol Diglycidyl Ether Dimethacrylate, Sorbitol Tetraglycidyl Ether Tetraacrylate, Sorbitol Tetraglycidyl Ether Tetramethacrylate,
It is preferable to use 0.1 to 100 parts by weight based on 100 parts by weight of the solid content of the copolymer mixture described above. In addition, although the above-mentioned materials can be sufficiently cured by electron beam irradiation, when curing by ultraviolet irradiation, benzoin ethers such as benzoquinone, benzoin, benzoin methyl ether, halogenated acetophenones, and biacyl are used as sensitizers. It is also possible to use materials that generate radicals when irradiated with ultraviolet rays, such as the following.

The above resin is further kneaded with a pigment or dye colorant, a plasticizer, a stabilizer, other additives, a solvent or a diluent to form an ink. print on the surface,
It can be used as a transfer sheet.

In the above, since the coloring agent is irradiated through the pattern surface, care must be taken in selecting the coloring agent when irradiating ultraviolet rays with relatively low energy. In particular, it is best to avoid using phthalocyanine green, carbon black, diazo yellow, etc., which have low transmittance in the long wavelength range of ultraviolet rays. In addition, by adding silica, barium sulfate, clay, talc, shirasu balloon, barite, calcium carbonate, alumina, etc., the pigment content can be increased, the porosity of the pattern layer can be increased, and the penetration of the paint can be promoted.

(Patterning method) The above-mentioned transfer sheet can be transferred by various methods to pattern a base material, which is a transfer target.

For example, if ionizing radiation is applied after thermal transfer (hot stamping),
A crosslinked and cured pattern layer can be formed on a transfer target using a hot stamping method. According to this method, a pattern layer with excellent physical properties such as abrasion resistance and chemical properties can be formed not only on an unpainted base material but also on a coated base material.

The most effective patterning method using the transfer sheet of the present invention is to apply paint to the base material, overlap the transfer sheet on the surface of the paint that has not yet dried, and start from the transfer sheet side (if possible, from the base material) This method involves irradiating ionizing radiation (which may be done from the material side) and then peeling off the releasable sheet.

Figure 2 shows the state in which the transfer sheet is stacked so that the pattern layer 2 is in contact with the paint surface 4 applied to the base material 3 through the primer layer 5, and Figure 3 shows the state in which the release sheet is peeled off. It shows the condition.

As the base material 3, any material that is normally used as a base material for decorative materials (general term for decorative sheets and decorative laminates) can be used, but patterns with excellent physical and chemical properties can be used. As the base material that should have the layer, it is preferable to use a base material that has excellent physical and chemical properties, such as those in the following groups (a) to (c). Preferred examples include: (a) plates, sheets or foils made of metals such as iron, stainless steel, aluminum or copper, or metal molded products made from these plates, sheets or foils; (b) inorganic glass, marble; or an inorganic plate or molded product such as ceramics; (c) a thermosetting decorative board having at least on its surface a thermosetting resin such as unsaturated polyester resin, melamine resin, or diallyl phthalate resin;
A thermosetting resin sheet, a thermosetting resin molding, or a plate, sheet, or molded product made of a thermoplastic resin such as polyvinyl chloride resin or acrylic resin.

The paint applied to the base material 3 may be thermoplastic, but considering the adhesive strength with the pattern layer 2 to be transferred and the physical and chemical properties of the surface of the resulting coating film, thermosetting is preferable. It is preferable to use an ionizing radiation-curable coating material as in pattern layer 2.

The ionizing radiation-curable paint uses oligomers such as epoxy acrylate, urethane acrylate, acrylic acid-modified alkyd, and acrylic-modified polyester, and in addition, neopentyl glycol diacrylate, pentaerythritol acrylate, and trimethylol are used to adjust the crosslinked structure and viscosity. Blend monomers such as propane triacrylate. For UV-curable paints,
A benzoin-based, acetophenone-based, benzyl tar-based, or ketone/amine-based initiator is blended as a photoinitiator. In either case, if necessary, inorganic substances such as silica, calcium carbonate, precipitated barium carbonate, or organic substances such as PE particles may be used as gloss modifiers, and to increase scratch resistance, PE wax, fatty acid soap, etc. may be used. Added.

The coating can be applied by gravure coating, roll coating, reverse roll coating, flow coating, spray coating, or the like. Film thickness is 3μ
-1 mm, preferably about 5 μ to 100 μ.

If necessary, the base material may be subjected to primer treatment (the layer indicated by reference numeral 5 in FIGS. 2 and 3) in order to improve the adhesion between the base material and the paint. For this purpose, a baking primer such as a two-component epoxy type, acrylic type, or urethane type primer can be used.

The electron beams used to crosslink and cure the paint layer and pattern layer on the substrate after the transfer sheet is superimposed on the paint surface include Kotscroft-Walton type, Van de Graaff type, resonant transformer type, and insulated core transformer. It is emitted from various electron beam accelerators such as type, linear type, dynamitron type, and high frequency type.
Preferably, an electron beam with an energy in the range of 100 to 300 KeV is used, and the ultraviolet rays are emitted from an ultraviolet source using a light source such as 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. use something

By irradiating with ionizing radiation, the pattern layer 2 and the paint layer 4 are crosslinked and cured individually and with each other to become integrated. Thereafter, the patterning on the base material 3 is completed by peeling off the releasable sheet 1.

Effects/Effects According to the present invention, it is possible to provide a transfer sheet that can be handled in the same way as a transfer sheet made using a normal thermoplastic vehicle in a printed and dried state, and also allows the transfer sheet to be used on a painted surface. A pattern layer with excellent physical and chemical properties can be obtained by transferring the transfer sheet to a paint surface and cross-linking and curing it. Moreover, the process is simple as it only requires placing the transfer sheet on the paint surface and irradiating it with ionizing radiation. There are also advantages.

Applications Patterned plates, sheets, foils, or molded products thereof obtained by transfer using the transfer sheet of the present invention have excellent physical and chemical properties on the surface, so they can be used for various types of weak electric current. Product chassis, bathtubs (especially aprons), kitchen equipment exteriors,
It is particularly suitable for the interior of building lobbies, around escalators and elevators, etc.

Example 1 Polyethylene terephthalate film (manufactured by Toray Industries, Lumirror T-60, thickness
25 μm), an abstract pattern was printed by the gravure printing method using ink having the following composition to obtain a transfer sheet.

Ink composition Triazine acrylate 50 parts by weight (Mitsubishi Yuka Fine, LZ-065) Micro silica 10 〃 Yellow colorant (polyazo yellow) 10 〃 Solvent 30 〃 (MIBK/Vinegar butylene/Troll=2/6/2) A stainless steel plate is used as the base material for transfer.
This was degreased, coated with a two-component baking epoxy paint to a thickness of 5 μm, and heated to 170°C.
A primer layer was obtained by performing a curing treatment for 1 minute.

On this primer layer, urethane acrylate type UV paint (Nippon Paint, Ubicoat) is coated to a thickness of 20 μm using a roll coater, and the above transfer sheet is degassed by placing the printed side in contact with the coated side of the paint. Laminated through rolls.

The laminate was irradiated from the release film side through a UV irradiation line equipped with five 80 W/cm ozone-less UV lamps at a speed of 20 m/min to cure the paint.

After curing, the release film was peeled off to obtain a stainless steel decorative board with excellent physical and chemical properties, in which the pattern and paint were crosslinked and cured together.

Example 2 Polyethylene terephthalate film (manufactured by Toray Industries, F-60, thickness 25 μm) was used as a release film.
An abstract pattern was printed using the gravure printing method using ink having the composition shown below to obtain a transfer sheet.

Ink composition Polymethyl methacrylate resin 10 parts by weight Hexanediol diacrylate 1 〃 Toluene 40 parts by weight Methyl ethyl ketone 40 〃 Pigment 10 〃 A hairline-treated stainless steel plate was used as the transfer object, and was treated with a primer in the same manner as in Example 1. The coating was applied in the same manner as in Example 1, except that the sensitizer was removed, and the transfer sheet was laminated.

The release film side of the laminate is irradiated with 3 Mrad of electron beam accelerated at 200 KeV to cross-link and cure the pattern and paint.Then, the release film is peeled off and the physical and chemical properties are determined. In both cases, an excellent stainless steel decorative board was obtained.

[Brief explanation of drawings]

1 to 3 are sectional views showing the present invention. DESCRIPTION OF SYMBOLS 1... Release sheet, 2... Pattern layer, 3... Base material, 4... Paint surface, 5... Primer layer.

Claims (1)

[Scope of Claims] 1. The releasable surface of the releasable sheet has a pattern layer containing, as a vehicle, an ionizing radiation-curable resin that is solid at room temperature in an uncured state and is thermoplastic. A transfer sheet characterized by: 2. A transfer sheet having a pattern layer containing a thermoplastic ionizing radiation-curable resin, which is solid at room temperature in an uncured state and as a vehicle, is coated with paint on the release surface of the release sheet. A patterning method characterized by overlapping the coated surface of the coated base material, then irradiating ionizing radiation, and then peeling off the release sheet. 3. The patterning method according to claim 2, which uses an ionizing radiation-cured paint as the paint.