JPH0223345B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a decorative board using an electron beam curable resin composition.

Traditionally, decorative boards have been manufactured by laminating decorative paper impregnated with melamine resin, polyester resin, or diallyl phthalate resin onto a base material, then heating and pressurizing it, but the heating process requires a large amount of thermal energy. There was a problem. Therefore, decorative paper is coated with a composition that hardens with ultraviolet rays and electron beams.
Attempts have been made to use decorative paper cured by ultraviolet rays or electron beams and to attach it to a substrate with an inexpensive adhesive. However, this method has the problem that the cured decorative paper becomes rigid and requires special care during transportation and lamination, and if it is bent, it will become a defective product.

In addition, decorative paper is pasted on the surface of the base material, and the surface of the decorative paper is further coated with an electron beam curable resin composition.
A method of curing the composition by electron beam irradiation is also being considered. This method requires only one curing step and does not require a large amount of thermal energy. However, when a peel test is conducted using the obtained decorative board, internal destruction of the decorative paper occurs, and it cannot be said that it necessarily satisfies the practical performance. Furthermore, phenomena such as the decorative paper lifting off from the base material can also be obtained. This is thought to be because the electron beam curable resin composition provided on the surface of the decorative paper is not impregnated into the interior by the printed layer of the decorative paper. When an electron beam curable resin composition is cured, it becomes a strong film and has excellent water resistance, etc., but with the decorative board made by the above method, it is true that a good film can be formed on the surface layer, but It cannot be said that it necessarily has sufficient performance.

The present invention provides a method for manufacturing a decorative board that eliminates the above-mentioned drawbacks. By irradiation with electron beam 2
Not only does it have the operational advantage of being able to simultaneously cure a layer or three or more layers of electron beam curable resin compositions, but it also improves the adhesion between the base material and the decorative paper, and especially improves the breaking strength of the decorative paper itself. , it is possible to obtain a decorative board with a very hard surface layer. Furthermore, this method has the advantage that it is possible to manufacture decorative laminates in an in-line process, that is, in a continuous process.

That is, the present invention applies a decorative paper to a base material and then coats the surface of the decorative paper with an electron beam curable resin composition, or uses a decorative paper coated with an electron beam curable resin composition on the surface as a base material. In the method for manufacturing a decorative board, the back side of the decorative paper is coated with an electron beam-curable resin composition, and at least a part of the coated composition is impregnated into the decorative paper. This is a method for manufacturing a decorative board which is then attached to a base material, and furthermore, an electron beam transparent film having releasability is adhered onto the electron beam curable resin composition provided on the surface of the decorative paper. After that, the film is peeled off by irradiating it with an electron beam, and the surface of the decorative paper is coated with an electron beam-transparent film that has releasability and is coated with an electron beam-curable resin composition. It also provides a method of adhering it in contact with paper.

In the method of the present invention, both sides of the decorative paper are coated with an electron beam curable resin composition, the back side is coated before being attached to the base material, and the back side of the decorative paper is coated with the electron beam curable resin composition before being attached to the base material. coat at some point afterward. Further, the electron beam curable resin composition provided on the surface of the decorative paper may be coated in advance with an electron beam transparent film having peelability, and the film may be bonded to the decorative paper. Furthermore, when attaching the decorative paper to the base material, an electron beam curable resin composition may be used as an adhesive in addition to the one coated on the back side of the decorative paper, if necessary. Note that this adhesive may be a conventionally known adhesive that is not an electron beam curing type.

The decorative paper used in the present invention is a paper with good permeability such that at least the back side is impregnated with an electron beam curable resin composition, and the front side is usually printed. The type of paper is not particularly limited as long as it can be used as decorative paper for decorative boards, but paper with a basis weight of 50 to 500 g/m ² is usually used. For example, titanium paper, linter paper, high-quality paper, etc. are selected. Curable ink is preferred as the printing ink printed on the surface of decorative paper, but
Ordinary gravure ink or the like may be used.

As the electron beam curable resin composition according to the present invention, those used as paints or adhesives can be used, including compounds having ethylenically unsaturated bonds in the molecule, resins, sensitizers, thermal polymerization inhibitors, solvent,
It is a composition containing additives such as pigments as appropriate.

A compound having an ethylenically unsaturated bond in the molecule is a component that is necessarily contained, and an electron beam curable resin composition containing this compound alone may be used. As the compound, a prepolymer and/or a monomer having one or more ethylenically unsaturated bonds can be used. Examples of prepolymers include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, melamine acrylate, polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyether methacrylate, polyol methacrylate, melamine methacrylate, unsaturated polyester resin, etc. It is. Examples of monomers include ethylene glycol diacrylate, propylene glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol acrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, ethylene glycol dimethacrylate, and propylene glycol dimethacrylate. , diethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and the like.

For the electron beam curable resin composition to be coated on the back side of the decorative paper, in order to improve impregnation into the decorative paper, the monomer content ratio may be increased or a solvent may be used. In addition, when a solvent is used, it is preferable to pre-dry the coating after coating in order to remove the solvent as necessary. Of course, the electron beam curable resin composition provided on the surface or base material of the decorative paper can also have a similar composition.

Furthermore, in the present invention, an electron beam transparent film is laminated onto the electron beam curable resin composition provided on the surface of the decorative paper, or the film is coated with the electron beam curable resin composition in advance, It may be attached to the surface of decorative paper. Note that this step may be performed either before or after pasting the decorative paper on the base material. A film having peelability is used as the film, and the usual method of use is to peel and remove the film after electron beam irradiation. However, in some cases, it is possible to use the decorative board as it is without being peeled off. In this case, the film is preferably a film that has good adhesiveness to the electron beam curable resin composition.

This film is polyester film,
These include various plastic films such as nylon film, cellophane film, polyethylene film, and polypropylene film, paper, polypropylene-impregnated paper, metal foil, or a laminate of two or more of these. Furthermore, the surfaces of the various base sheets described above may be subjected to a treatment such as a peeling treatment.

By irradiating the material with an electron beam while covered with an electron beam transparent film, it is possible to eliminate the problem of suppression of crosslinking reaction due to oxygen in the air and poor curing, thus promoting the crosslinking reaction and accelerating the curing speed. There is also an advantage. The surface of the decorative board obtained using the film is more glossy and has a hard surface. Of course, this film may not be used in the present invention.

Further, the film may be a film with unevenness, and by using a film capable of forming a faded or uneven pattern, a decorative board having other effects can be obtained.

In order to adhere the base material and the decorative paper, an adhesive may not necessarily be required, as the adhesive may be used to bond the base material and the decorative paper using an electron beam curable resin composition coated on the back side of the decorative paper. However, an adhesive such as an electron beam curing type can be used. For example, if a compound having an ethylenically unsaturated bond and an adhesive that swells or dissolves in the presence of water, such as poval or polypropylene oxide, are used, It becomes a tacky adhesive by applying it, and is electron beam curable due to the compound having an ethylenically unsaturated bond.
This is advantageous when laminating decorative paper. However, if the base material is impermeable such as a metal plate, water may cause rust, so in this case it is preferable to apply the method to a permeable base material such as a wooden board or plywood.

As a coating means for electron beam curable resin composition etc., roll coater, curtain flow coater,
A coating machine such as a gravure coater or an air knife coater, a spray method, or a dipping method can be applied.

The solvent may be removed by known methods such as degassing and heating.

In the present invention, the composition provided on the back side of the decorative paper, the composition provided on the surface of the decorative paper, and the adhesive between the base material and the makeup can be made to have good compatibility, and the makeup The paper surface has excellent solvent resistance and hot water resistance, and a decorative board with an extremely hard surface can be obtained. Examples of the base material include various metal plates such as iron plates, stain-free steel plates, zinc plates, copper plates, and aluminum plates, various plastic molded products such as plastic sheets and plastic containers, paper, various types of wood, and plywood.

As the electron beam irradiation device, scan type, curtain type, etc. are known, and a low acceleration voltage type may also be used. The irradiation dose is usually about 0.5 to 20 Mrad, and irradiation can also be performed in a nitrogen gas atmosphere.

The present invention will be explained in detail below using examples. In the examples, "parts" indicate parts by weight.

Example 1 A multicolor wood grain pattern was printed using gravure ink on one side of high-quality paper (basis weight approximately 50 g/m ² ), and 50 g/m of the following electron beam curable resin composition was applied onto the printed surface using a roll coater. m ² (wet) Evenly coated.

{Oligoester acrylate (Aronix M-7100 manufactured by Toagosei Kagaku Co., Ltd.) 60 parts trimethylolpropane triacrylate (NKEster A-TMPT manufactured by Shin Nakamura Chemical Co., Ltd.)
40 parts} Next, the following electron beam curable resin composition was uniformly impregnated from the back side of the decorative paper at a rate of 50 g/m ² .

{1,6-hexanediol diacrylate
50 parts oligoepoxy acrylate (NKEsterA−
9G (manufactured by Shin Nakamura Chemical Co., Ltd.) 50 parts} Apply the following electron beam curable resin composition on particle board to a film thickness of 50 g/m ² (wet) using a roll coder, and then apply the above decorative paper using a rubber roller. It was crimped and irradiated in a nitrogen atmosphere using a curtain beam type electron beam hard irradiation device manufactured by Energy Sciences at a dose of 5 Mrad at 160 KV and 5 mA. Each of the above steps was performed in-line, that is, in a continuous process.

The surface pencil hardness of the obtained decorative board is 4H or higher,
A decorative board with excellent abrasion resistance, adhesiveness, chemical resistance, solvent resistance, and boiling water resistance was obtained. In addition, in the peel test, the decorative paper did not cause interlayer failure.

Adhesive composition {polyethylene glycol (MW, approx. 7500)
10 parts Oligoepoxy acrylate A-14G 70 parts Water 20 parts} Example 2 A solvent-free electron beam curable resin composition consisting of 80 parts of Aronix M-7100 and 20 parts of oligoepoxy acrylate A-14G was rolled onto plywood. The coating was applied to a thickness of 40 μm using a coater, and a decorative paper coated in the same manner as in Example 1 was pressed onto this, and by the same operation as in Example 1, a decorative board with excellent performance was obtained.

Example 3 After adhering the decorative paper to the particle board in the same manner as in Examples 1 and 2, a nylon film (14μ thick) was pressed with a roller, and then Example 1
As a result of electron beam irradiation under the same conditions (but in air), a glossy decorative board with a hard surface hardness of 4H or higher was obtained.

Example 4 The following electron beam curable resin composition was applied to the back side of decorative paper.

{Aronix M-7100 40 parts NKEster A-9G 50 parts A-TMPT 10 parts} On the surface of the decorative paper, apply the following electron beam curable resin composition on the surface of a nylon film (14μ thick) in advance. At the same time, the transfer top layer was dried at 120℃ for 30 seconds and then thermocompressed using a laminator at 100℃.
The same electron beam curable resin composition (adhesive composition) as in Example 1 was applied onto particle board to a thickness of 40 μm, and the adhesive was pressed and irradiated with electron beams. As a result, a decorative board with an excellent decorative board surface was obtained. Obtained.

Example 5 By using an alumite-treated aluminum plate instead of plywood in Example 2, an aluminum decorative plate with good durability was obtained.

Example 6 By using titanium paper (basis weight approximately 80 g/m ² ) in place of the high-quality paper in Example 1, a decorative board having excellent performance as in Example 1 was obtained.

Example 7 After applying the impregnated electron beam curable resin composition from the back side of the decorative paper in the same manner as in Example 1, Aronix M-7100 80 was applied onto the surface of the nylon film.
An electron beam curable resin composition consisting of 20 parts of A-TMPT and 20 parts of A-TMPT was applied, immediately pressed onto a particle board coated with the same adhesive composition as in Example 1 to a thickness of 40μ, and irradiated with an electron beam. As a result, an excellent decorative board was obtained.

Comparative Example 1 A decorative board was produced in the same manner as in Example 1 except that the electron beam curable resin composition applied to the back side of the decorative board in Example 1 was not used. As a result of the peeling test, it was found that the decorative paper was not suitable for practical use because it lifted up due to the influence of the paper.

Claims (1)

[Scope of Claims] 1. After pasting decorative paper to a base material, the surface of the decorative paper is coated with an electron beam curable resin composition, or a decorative paper whose surface is coated with an electron beam curable resin composition is provided. In a method for producing a decorative board in which the decorative paper is adhered to a base material and then irradiated with an electron beam, the back side of the decorative paper is coated with an electron beam curable resin composition, and at least a portion of the coated composition is A method for producing a decorative board, which comprises impregnating decorative paper and then adhering it to a base material. 2. A claim that further includes: an electron beam transparent film having releasability is brought into close contact with the electron beam curable resin composition provided on the surface of the decorative paper, and then the film is peeled off by irradiation with an electron beam. A method for producing a decorative board according to item 1. 3. The method according to claim 1, wherein a releasable electron beam transparent film coated with an electron beam curable resin composition is attached to the surface of the decorative paper so that the coated surface is in contact with the decorative paper. Method of manufacturing decorative board. 4 Claims 1 to 3, in which decorative paper is attached to a base material coated with an electron beam curable resin composition.
A method for producing a decorative laminate according to any one of paragraphs.