JPH0141505B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a decorative material, and more particularly to a method for manufacturing a decorative material having a convex pattern layer having pressure resistance and abrasion resistance.

Conventionally, methods for producing decorative materials having a convex pattern layer include mechanical embossing, foam printing, chemical embossing, polymerization inhibition or acceleration, and methods utilizing paint repellency.

However, in the conventional manufacturing method described above, the mechanical embossing method requires the production of a new expensive embossing plate for each pattern, and furthermore, it is difficult to accurately match the printed pattern and the embossed pattern. In the foam printing method, the ink containing a foaming agent is printed and then heated and foamed, so the convex pattern layer has the disadvantage that it is weak against pressure due to accumulation, etc., and is easily crushed or resistant to abrasion. It has the disadvantage that the rise of the convex pattern layer is not sharp, and the disadvantage is that the physical and chemical properties of the parts where polymerization is not sufficiently carried out are inferior when polymerization suppression or acceleration methods are used. This method has the disadvantage that a sharp rise cannot be achieved.

There is also a method of creating a convex printed pattern layer by taking advantage of the so-called thick build-up of ink produced by gravure printing and silk screen printing, but these methods require the use of ink with a high solid content. For example, a method using polyvinyl chloride paste resin may be considered, but it is difficult to use such ink with a high solid content using various resins depending on the printing target, and moreover, it is difficult to use ink with a high solid content after printing. It needs to be cured and cannot be said to be suitable for all types of printing materials.

The present invention was created as a result of research in view of the drawbacks of the conventional methods as described above, and includes two types of pattern layers, a pattern layer made of normal ink and a convex pattern layer made of an electron beam curable composition, on a base material. A pattern layer usually made of ink and an electron beam curable composition are formed by sequentially providing a pattern layer and then irradiating the convex pattern with an electron beam to cure the convex pattern, or by a printing method on a substrate. Two types of pattern layers of a convex pattern layer consisting of are sequentially provided, and a transparent resin layer is coated on the two types of pattern layers, and after coating, an electron beam is irradiated through the transparent resin layer. However, by hardening the convex pattern, the above drawbacks were successfully overcome.

The details of the present invention will be explained in more detail below.

The base materials used in the present invention include paper such as tissue paper, titanium paper, and gypsum board paper, nonwoven fabrics made from fibers such as polyester and rayon,
Woven fabrics made from glass fiber, etc., various plastic films such as PVC, polyester, and polypropylene, plywood and wood, particle board, fiberboard, gypsum board, perlite board, silica board, asbestos slate board, GRC board, iron plate, and aluminum. A metal plate such as a plate can be used.

Next, for the ordinary ink constituting the pattern layer made of ordinary ink in the present invention, a coloring agent such as a dye or pigment is added to the ink vehicle as necessary, and further, for example, a plasticizer, a stabilizer, a wax, Using an ink composition that has been sufficiently kneaded with a solvent, diluent, etc., with optional addition of known additives such as grease, desiccant, auxiliary desiccant, curing agent, thickener, dispersant, filler, etc. Ink vehicles include, for example, cellulose derivatives such as ethyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, and cellulose acetate, styrene resins and styrene copolymer resins such as polystyrene, poly-α-methylstyrene, and polymethyl methacrylate. , acrylic or methacrylic resin alone or copolymer resin such as polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, rosin, rosin ester resin such as rosin-modified maleic acid resin, rosin-modified phenolic resin, polymerized rosin, Adhesion to the substrate to be printed from polyvinyl acetate resin, coumaron resin, vinyltoluene resin, vinyl chloride resin, polyester resin, polyurethane resin, butyral resin, or a mixture of several of these resins. The material should be selected and used as appropriate, taking into consideration gender, etc.

The pattern layer made of normal ink as described above may be provided on the base material by a known printing method such as a gravure printing method, an offset gravure printing method, an offset printing method, or a silk screen printing method. They may be appropriately selected and used depending on the material and form of the base material.

Next, as the electron beam curable composition constituting the convex pattern layer made of the electron beam curable composition in the present invention, a coloring agent such as a dye or pigment is added to the electron beam curable compound as necessary, Furthermore, additives such as fluidity imparting agents, thickeners, dispersants, plasticizers, and solvents can be optionally added and kneaded. Prepolymers or oligomers having unsaturated bonds, such as unsaturated polyesters, polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, various acrylates such as melamine acrylate, polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyether One or more types of methacrylates such as methacrylate, polyol methacrylate, and melamine methacrylate, and monomers having ethylenically unsaturated bonds in the molecule, such as styrene monomers such as styrene and α-methylstyrene; acrylic acid Acrylic acid esters such as methyl, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate Methoxyethyl methacrylate, ethoxytityl methacrylate, phenyl methacrylate, lauryl methacrylate, and other methacrylic acid esters; acrylamide, methacrylamide, and other unsaturated carboxylic acid amides; 2-(N,N-dimethylamino)ethyl acrylate, methacrylic acid 2-(N,N-dimethylamino)ethyl,
2-(N,N-dibenzylamino)ethyl acrylate, methacrylic acid (N,N-dimethylamino)
Substituted amino alcohol esters of unsaturated acids such as methyl and 2-(N,N-diethylamino)propyl acrylate; ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate , polyfunctional compounds such as diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and/or compounds containing two or more thiol groups in the molecule. A mixture of polythiol compounds such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, and pentaerythritol tetrathioglycolate can be used.

As a method for providing a convex pattern layer made of the above-mentioned electron beam curable composition, the method mentioned above as a method for providing a pattern layer made of normal ink can be similarly used, but a convex pattern layer is provided. In this sense, if possible, it is preferable to use a silk screen printing method or, in particular, a gravure printing method using a gravure plate with a large plate depth.

Examples of the transparent resin layer in the present invention include:
Among the electron beam curable compositions constituting the convex pattern layer made of the electron beam curable composition described above, transparent or colored transparent or semitransparent or colored semitransparent ones are used as the base material, the pattern layer, and the convex pattern layer. The transparent resin layer is selected and used as appropriate depending on the material of the pattern layer, the purpose of the decorative material, and the required performance. Depending on the application and required performance of the decorative material, advanced physical and
There are cases where chemical performance is not required, and in such cases, a transparent resin layer made of an electron beam curable composition is not provided, or a transparent resin layer not made of an ordinary electron beam curable composition is provided. It is preferable that
In such a case, apply the above-mentioned ordinary ink without colorants such as dyes or pigments, or apply ink with polyethylene film, polyester film, polyvinyl chloride film, acrylic film, polycarbonate film, polystyrene film, etc. The film or sheet may be laminated by a known lamination method, or by extrusion coating, thermal welding, or other methods.

When a pattern layer made of normal ink is printed on a base material as described above, a convex pattern layer made of an electron beam curable composition is provided on the pattern layer, and then an electron beam is irradiated, or when the base material is irradiated with an electron beam, A pattern layer made of ordinary ink is printed on the material, a convex pattern layer made of an electron beam curable composition is provided on top of the pattern layer, and a transparent resin layer is further covered on top of the pattern layer. The electron beam used when irradiating the electron beam through the layer is accelerated using a low-energy electron beam accelerator, such as Electrocurtain CB200/50/30 manufactured by Energy Science Industry Co., Ltd. or NP-ESH150 manufactured by Otsto Duel. voltage 100
~300kV irradiation current 0~100mA, irradiation dose 0.5~
Preferably, a 30 Mrad electron beam is used.

According to the method for producing a decorative material according to the present invention as described above, it is easy to match the pattern layer made of normal ink and the convex pattern layer in design, and since no heat is required for curing, many base materials can be used. It is effective for application to materials, and high-speed production is possible due to the high energy efficiency of electron beam irradiation, and it has advantages such as being almost completely cured, resistant to pressure from deposition, etc., and resistant to crushing, and excellent abrasion resistance. .

Furthermore, when covering with a transparent resin layer, there are advantages such as significantly improved abrasion resistance, and a decorative material having excellent surface stain resistance and physical and chemical properties.

The present invention will be further specifically explained below using Examples.

Example 1 The following composition was coated on the entire surface of thin paper with a basis weight of 23 g/m ² by a gravure printing method.

Nitrocellulose 70 parts by weight Modified alkyd 30 Titanium oxide 100 Iron oxide 10 Cyanine blue 5 Ethyl acetate 80 Toluene 80 Isopropanol 40 N-butyl acetate 10 Furthermore, using the following composition by gravure printing method, cedar Printed wood grain.

Nitrocellulose 70 parts by weight Modified alkyd 30 〃 Polyazo dye Quinacridone Cyanine Blue 5-20 〃 Ethyl acetate 80 〃 Toluene 80 〃 Isopropanol 40 〃 N-butyl acetate 20 〃 Furthermore, apply the following composition over only the winter part of the cedar grain pattern. Electron beam curable composition with 50 lines and plate depth
A convex pattern was printed using a gravure printing method using a 150μ gravure plate.

Epoxy acrylate oligomer (Viscoat #540 manufactured by Osaka Organic Chemical Industry Co., Ltd.) 50 parts by weight 1,6-hexanediol diacrylate monomer 50 parts by weight Then, in-line with printing in a nitrogen stream from the printed pattern side with an acceleration energy of 150 keV , irradiated with an electron beam with an irradiation current of 10 mA and an irradiation dose of 10 Mrad,
The convex pattern was cured to obtain a decorative material.

The decorative material obtained as described above had excellent abrasion resistance, and the convex pattern did not collapse even when it was applied to a board and deposited.

Example 2 An abstract pattern was printed on a 100 μm thick semi-rigid white vinyl chloride sheet by gravure printing using ink having the following composition.

Vinyl chloride resin 80 parts by weight Acrylic resin 20 〃 Plasticizer 20 〃 Methyl ethyl ketone 60 〃 Methyl isobutyl ketone 60 〃 Toluene 40 〃 Polyazo dye quinacridone cyanine blue 5-20 〃 Furthermore, using a gravure plate with 50 lines and a plate depth of 120 μm, A convex pattern was printed by overlaying an electron beam curable composition having the composition shown below on a part of the abstract pattern using a gravure printing method.

Urethane acrylate oligomer (Toagosei Kagaku Kogyo Co., Ltd. TO-381) 50 parts by weight 1,6-hexanediol diacrylate monomer 50 Titanium oxide 20 After that, electron beam irradiation was performed under the same conditions as in Example 1 to form convexities. The decorative material was obtained by curing the pattern. Similar to Example 1, the obtained decorative material had excellent abrasion resistance and was resistant to deposition.

Example 3 After providing cedar wood grain and a convex pattern in the same manner as in Example 1, the following composition was applied over the printed layer to a thickness of 12 μm using a reverse coating method, and inline was applied to the printed layer side. Then, a curtain-shaped electron beam was irradiated with an acceleration energy of 150 keV, an irradiation current of 10 mA, and an irradiation dose of 5 Mrad to harden the convex pattern and obtain a decorative material.

Epoxy acrylate oligomer (Viscoat #540 manufactured by Osaka Organic Chemical Industry Co., Ltd.) 50 parts by weight trimethylolpropane triacrylate
10 〃 1,6-hexanediol diacrylate
40 The obtained decorative material has a convex pattern with excellent abrasion resistance, and even if it is attached to a board and deposited, the convex pattern does not collapse, and since it is coated with a transparent resin layer, the surface It had excellent stain resistance and chemical properties.

Claims (1)

[Claims] 1. Two types of pattern layers, a pattern layer made of normal ink and a convex pattern layer made of an electron beam curable composition, are sequentially provided on a substrate, and then irradiated with an electron beam. . A method for producing a decorative material having a convex pattern, which comprises curing the convex pattern. 2. Two types of pattern layers, a pattern layer made of normal ink and a convex pattern layer made of an electron beam curable composition, are sequentially provided on the base material by a printing method, and the two types of pattern layers described above are further provided. coated with a transparent resin layer,
A method for producing a decorative material having a convex pattern, characterized in that after coating, an electron beam is irradiated through the transparent resin layer to harden the convex pattern.