JPS6311947B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a decorative material having recesses.

To manufacture decorative materials industrially, patterns of natural rock, wood grain, artificial textiles, etc. or abstract patterns are imitated on base materials such as plywood, gypsum board, iron plates, valve cement boards, etc. using methods such as photolithography. A common method for manufacturing is to attach a decorative sheet printed using a printing plate or to print directly onto a base material.

For such decorative materials, when using photolithographic technology as described above, it is easy to obtain decorative materials that can be mistaken for the real thing from the perspective of just patterns and colors, but the texture and texture of the surface It is difficult to reproduce the degree of light reflection, depth, etc. using mere printing technology.

The same applicant as the present invention first provided a heat-sensitive pattern on a heat-shrinkable plastic film, and then irradiated it with heat rays to melt the plastic film in the portion corresponding to the heat-sensitive pattern and form holes. Alternatively, they invented a method for manufacturing decorative materials that utilizes the phenomenon of creating dents, but although this manufacturing method allows for the industrial production of decorative materials with recesses, the color of the recesses is limited to black, and other colors cannot be produced. It has almost no dents, or only slight dents, so it is suitable for reproducing the simulated grain of wood such as walnut and rosewood, which are usually finished in dark tones even in natural products. However, it is somewhat unsuitable for teak, unsuitable for plain wood and light-colored patterns other than wood grain, and has the disadvantage that its range of applications is limited.

As a result of repeated research in view of the above-mentioned drawbacks, the present inventor found that when a heat-shrinkable plastic film is provided with a pattern made of an electron beam curable composition that emits heat during polymerization and irradiated with an electron beam, the above-mentioned polymerization occurs. In a pattern made of an electron beam curable composition that sometimes emits heat, the heat generated when the electron beam curable composition polymerizes causes the adjacent heat-shrinkable plastic film to melt.
The present invention was completed based on the discovery of a phenomenon in which the material softens and contracts, resulting in concave portions.

The present invention will be explained in detail below.

The heat-shrinkable plastic film used in the present invention includes polyethylene crosslinked film, modified polyethylene film, polypropylene film, modified polypropylene film, polystyrene film, polyvinyl chloride film, polymethyl methacrylate film, polyester film, polyvinylidene chloride film, and hydrochloric acid film. A film such as a rubber film that is stretched during film formation or a film that is stretched after film formation can be used, but is not limited thereto. Further, the stretching direction may be either vertical (film forming direction), horizontal (direction perpendicular to the film forming direction), or both. The thickness of these heat-shrinkable plastic films can be selected arbitrarily, but if it is too thin, the depth of the recess cannot be obtained beyond the thickness, which is undesirable, and if it is too thick, there are, of course, economic problems. Considering that the performance as a decorative material, such as ease of bending, flammability, and handling suitability, will deteriorate, the thickness of 10 μm
~0.5 mm is considered preferable.

The heat-shrinkable plastic film described above may be used alone or in combination with other suitable substrates, such as paper or paperboard, synthetic paper, plastic film or sheet, cloth, rubber, Metal foil or plate of iron or aluminum,
Substrates such as plywood, particle board, gypsum board, pulp cement board, etc. can be used;
Known methods such as dry lamination, wet lamination, semi-wet lamination, lamination using extrusion coating, and heat fusion may be used to combine these substrates and the heat-shrinkable plastic film. Furthermore, it may be made into two layers or multiple layers.

Next, in the present invention, the electron beam curable composition that generates heat during polymerization for forming a pattern made of an electron beam curable composition that generates heat during polymerization is an electron beam curable compound that generates heat during polymerization. A material obtained by kneading a coloring agent such as a dye or a pigment, a surfactant, a plasticizer, an inorganic filler, a stabilizer, etc. can be used. Examples of electron beam-curable compounds that emit heat during polymerization include prepolymers or oligomers having ethylenically unsaturated bonds in the molecule, such as unsaturated polyesters, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, and melamine. One or more of various acrylates such as acrylate, various methacrylates such as polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate, and a monomer having an ethylenically unsaturated bond in the molecule. , for example, styrenic monomers such as styrene and α-methylstyrene; methyl acrylate,
Acrylic acid esters such as 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxy methacrylate Methacrylic acid esters such as ethyl, ethoxytityl methacrylate, phenyl methacrylate, lauryl methacrylate; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; acrylic acid 2-(N,
N-dimethylamino)ethyl, methacrylic acid 2-
(N,N-dimethylamino)ethyl, 2-(N,N-dibenzylamino)ethyl acrylate, (N,N-dimethylamino)methyl methacrylate, 2-(N,N-diethylamino)propyl acrylate, etc. Substituted amino alcohol esters of unsaturated acids of acrylate,
Polyfunctional compounds such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and/or polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithio Propionate, pentaerythritol tetrathioglycolate, etc. can be used alone or in combination.

Furthermore, since the above-mentioned electron beam curable compounds that emit heat during polymerization usually do not necessarily have good printability, in such cases, a soluble compound is added to the electron beam curable compounds that emit heat during polymerization. Such compounds may include ethylcellulose, ethylhydroxyethylcellulose,
Cellulose derivatives such as cellulose acetate propionate and cellulose acetate, styrene resins and styrene copolymer resins such as polystyrene and polyα-methylstyrene, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, etc. , acrylic or methacrylic resin alone or copolymer resin, rosin, rosin-modified maleic acid resin, rosin-modified phenolic resin, rosin ester resin such as polymerized rosin, polyvinyl acetate resin, coumaron resin, vinyl toluene resin, vinyl chloride resin, polyester It is preferable to appropriately select and use resins, polyurethane resins, butyral resins, and mixtures of several types of these resins.

Methods of forming patterns on the heat-shrinkable plastic film using the electron beam curable composition that generates heat during polymerization include known printing methods such as gravure printing, offset gravure printing, and offset printing. method, screen printing method, letterpress printing method, etc. can be used.

Furthermore, in addition to the above pattern made of an electron beam curable composition that generates heat during polymerization, a pattern made of a normal ink composition may be provided. As the vehicle, the compounds listed above as soluble in the electron beam curable compound that generates heat during polymerization are appropriately selected and used. , an inorganic filler, a stabilizer, a solvent, etc. may be appropriately kneaded.Also, as a method for printing a pattern made of the above-mentioned ordinary ink composition on a heat-shrinkable plastic film, the above-mentioned polymerization method can be used. A method similar to the method used to provide a heat-shrinkable plastic film with a pattern made of an electron beam curable composition that sometimes generates heat can be used.

Note that when providing a pattern made of an electron beam curable composition that emits heat during polymerization and a pattern made of ordinary ink on a heat-shrinkable plastic film, either pattern may be provided first, or These patterns may be printed on the same side of the heat-shrinkable film or may be printed on the front and back sides.

Furthermore, as mentioned above, when using the heat-shrinkable film in combination with the other suitable substrate mentioned above,
Either or both of a pattern made of an electron beam curable composition that emits heat during polymerization and a pattern made of ordinary ink is provided on the other substrate described above in advance, and then a heat-shrinkable film is closely attached onto the pattern. There is no problem.

After producing a printed matter by providing a heat-shrinkable plastic film with a pattern made of an electron beam curable composition that emits heat during polymerization as described above, the printed matter is irradiated with an electron beam. It is emitted from various electron beam accelerators such as Kotscroft-Walton type, Van de Graaff type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type, and is 50 to 1000 KeV, preferably 100 to An electron beam with an energy in the range of 300 KeV is used. While the printing paper is running continuously, it is usually sufficient to irradiate a continuous curtain-shaped electron beam from a linear filament. By irradiating the electron beam in this way, the electrons that generate heat during polymerization on the printed matter An electron beam curable compound that emits heat during polymerization in a pattern made of a radiation curable composition is polymerized and cured, and the heat generated at that time melts, softens, and shrinks the heat-shrinkable plastic film in the portion adjacent to the pattern. and create a recess. Incidentally, when the base material of the printed matter is a heat-shrinkable plastic film alone, the electron beam irradiation can be carried out as it is, or when it is composited with another base material as described above, it can be performed before the composite. In addition, any method may be used to carry out the irradiation after compositing, and furthermore, it may be irradiated by any of the above methods and then compositing with another substrate. It is possible to use an appropriate selection from among the substrates.

Further, although a protective layer is usually provided on the surface of decorative materials for the purpose of finishing, such a protective layer may also be provided in the present invention, and synthetic resin etc. diluted with an appropriate solvent may be used. Alternatively, a coating material made of an electron beam curable composition may be used and cured by electron beam irradiation.

According to the method for manufacturing a decorative material having recesses of the present invention, recesses that are in sync with printing can be easily provided, and the color of the recesses is not limited to black as in the case of heat rays, but can be freely selected. Of course, it is possible to form recesses that match the printing of any type of wood grain, and it is also possible to form recesses that match the printing of patterns other than wood grain, especially light-colored patterns.
It can be used for building materials such as flooring and ceiling materials, surface decoration for furniture and TV cabinets, packaging materials, miscellaneous goods, etc.

Hereinafter, the present invention will be explained in more detail using Examples.

Example 1 Oak wood grain pattern was printed on a semi-rigid transparent heat-shrinkable polyvinyl chloride film with a thickness of 50 μm using the gravure printing method using each color of gravure ink containing vinyl chloride/vinyl acetate copolymer resin as a binder. After that, a pattern of the conduit portion was printed using the following white ink using a gravure printing method in synchronization with the wood grain pattern.

1,6-hexanediol diacrylate
100 parts by weight polyvinyl acetate (Sekisui Chemical Ethnyl C-2)
20 〃 Titanium oxide 30 〃 Thereafter, O ₂
Accelerating voltage in a nitrogen stream with a concentration of 300PPm or less
When irradiated with an electron beam of 150 KV, irradiation current of 10 mA, and irradiation dose of 10 Mrad, a decorative sheet with conduit portions was obtained. This decorative sheet was then adhered to plywood using a PVC/acrylic emulsion type adhesive to create a decorative sheet. Got the board.

Example 2 After printing on the back side of the film using the same film and ink as used in Example 1, the thickness was
After bonding and curing using a 100 μm oak skin-colored colored semi-rigid polyvinyl chloride sheet and a urethane dry laminating adhesive, an electron beam was irradiated from the film side under the same conditions as in Example 1.
A sheet with a recessed conduit portion was obtained and adhered to plywood in the same manner as in Example 1 to obtain a decorative board.

Example 3 The same film used in Example 1 was used at 30 g/m ²
A composite sheet made by wet-laminating thin paper with PVC/acrylic emulsion was used in the same manner as in Example 1 to obtain a decorative sheet with recessed conduit portions, and was attached to plywood in the same manner as in Example 1 to form a decorative sheet. I got it.

Claims (1)

[Claims] 1. A decorative material having recesses, which comprises at least the steps of preparing a heat-shrinkable plastic film with a pattern made of an electron beam curable composition that emits heat during polymerization to produce a printed matter, and irradiating the printed matter with an electron beam. manufacturing method.