JPH0155991B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to decorative paper used in the production of decorative paper, which has excellent physical properties such as surface hardness, solvent resistance, and heat resistance, and is suitable for repainting on its surface. To provide a decorative paper having printability, a simple manufacturing process for the decorative board using this decorative paper, and the decorative paper itself being manufactured at low cost.

Decorative papers used in the production of decorative boards are used to obtain decorative boards with excellent physical properties such as surface hardness, solvent resistance, and heat resistance, such as melamine decorative boards, diallyl phthalate decorative boards, and polyester decorative boards. When manufacturing decorative paper and decorative boards, there are vinyl chloride decorative papers that only require the process of pasting the decorative paper to the substrate with adhesive, but the former decorative paper has a surface with excellent physical properties. On the other hand, in the manufacturing process of decorative paper, a step of drying the paper impregnated with a synthetic resin solution is necessary, and in the process of manufacturing a decorative board using the obtained decorative paper, for example, in the case of melamine decorative board, , it is necessary to laminate the decorative paper with separate core paper, overlay paper, etc. and heat press them, which has the disadvantage of consuming a large amount of thermal energy in each process. Although the manufacturing process for decorative laminates using vinyl chloride decorative paper is simple, the surface properties of the resulting decorative laminate, such as hardness, solvent resistance, and heat resistance, cannot be obtained by using the former decorative paper. It has the disadvantage that it is significantly inferior to decorative laminates.

In order to improve the above-mentioned drawbacks of conventional decorative paper, paper with good permeability that has a pattern printed on one side is impregnated with a synthetic resin solution containing a catalyst. Decorative paper that has been heated and cured, decorative paper that has been impregnated with an electron beam curable substance and has been cured by irradiating it with electron beams, and the like have been developed or studied. When manufacturing a decorative board using this type of decorative paper, it can be manufactured by simply bonding the decorative paper and the substrate together with an adhesive, and it also has good hardness, solvent resistance, heat resistance, etc. Although it is possible to obtain a decorative laminate with excellent surface properties, there is a need for repainting to correct scratches made on the surface of the decorative laminate during the manufacturing process of the decorative laminate or during the process of processing the manufactured decorative laminate. , and its surface is not suitable for printing marks, letters, etc., and the former type of decorative paper requires a heat curing process during its manufacturing process, so it still consumes a large amount of thermal energy during manufacturing. have.

In contrast, the present invention provides an electron beam curable material 95 containing a compound having an ethylenic double bond in the molecule.
Decorative paper obtained by using an impregnating agent consisting of a mixed composition of ~40% by weight and 5-60% by weight of a solvent-soluble resin, that is, a decorative paper with a pattern printed on one side. A paper having a basis weight of 300 g/m ² or less and having good permeability is impregnated substantially uniformly with the impregnating agent, and the electron beam curable substance in the impregnating agent is hardened by electron beam irradiation. It is made of decorative paper with excellent surface properties such as surface hardness, solvent resistance, and heat resistance.The surface is suitable for repainting and printing, and requires a large amount of thermal energy during production. It can be manufactured at a low cost because it does not consume any paper, and it has many special features such as the ability to manufacture decorative boards by simply laminating and laminating conventional paper and woodworking adhesives on a separate substrate. The present invention provides a decorative paper having the following properties.

The structure of the decorative paper of the present invention will be explained below based on illustrated embodiments.

In the figure, the decorative paper indicated by code 1 has a pattern M printed on one side and has a basis weight of 300 g/m ²
The following paper 2 with good permeability has a mixed composition consisting of 95 to 40% by weight of an electron beam curable substance containing a compound having an ethylenic double bond in the molecule and 5 to 60% by weight of a solvent-soluble resin. The object is substantially uniformly impregnated with an impregnating agent as a main component, and the electron beam curable substance in the impregnating agent is cured by electron beam irradiation to form a cured resin 3.

In the present invention, as the paper 2 with good permeability, in addition to sizeless paper usually called titanium paper, linter paper, kraft paper, high-quality paper, etc. can be used, but the decorative paper 1 of the present invention can be obtained. In this case, the electron beam curable substance in the impregnating agent, which is impregnated substantially uniformly into the paper 2 having good permeability, is completely cured by one electron beam irradiation by a self-shielding electron beam accelerator. In order to be treated as cured resin 3, the basis weight must be
It is necessary to use paper with a weight of less than 300 g/m ² .
In addition, 95 to 40% by weight of an electron beam curable material containing a compound having an ethylenic double bond in the molecule and 5 to 60% by weight of a solvent-soluble resin are added to the paper 2 having good permeability.
When applying the impregnating agent to the paper ² as a means of substantially uniformly impregnating the impregnating agent mainly composed of a mixed composition consisting of Since this makes it difficult to uniformly impregnate the paper with the impregnating agent, it is preferable to use paper with a basis weight of 20 g/m ² or more and good permeability.

Note that the picture pattern M provided on the paper 2 with good permeability is similar to the picture pattern on conventional decorative paper. It is provided by forming with printing ink and printing means.

The impregnating agent that is impregnated almost uniformly into the paper 2 with good permeability and which has a pattern printed on one side is an electron beam curable substance containing a compound having an ethylenic double bond in the molecule. The main component is a mixed composition consisting of 5% to 60% by weight of a solvent-soluble resin, and an electron beam curable material containing a compound having an ethylenic double bond in the molecule.
It can be obtained by dissolving the other component, a solvent-soluble resin.

Examples of electron beam curable substances that are components of the impregnating agent include prepolymers or oligomers having ethylenic double bonds in the molecule, such as unsaturated polyesters, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, Various acrylates such as polyol acrylate and melamine acrylate, various methacrylates such as polyester acrylate, epoxy methacrylate, urethane methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate, monomers having ethylenic double bonds, such as styrene, α- Styrenic monomers such as methylstyrene; Acrylic esters such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, ptoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, and phenyl acrylate; Methyl methacrylate , ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate, and other methacrylic acid esters; acrylamide, methacrylamide, and other unsaturated carboxylic acid amides; 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; ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate,
One or a mixture of two or more polyfunctional compounds such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and diethylene glycol dimethacrylate, or a compound having an ethylenic double bond, and two or more thiol groups in the molecule. For example, a mixture of polythiol compounds such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, pentaerythritol tetrathioglycolate, etc. can be used. Examples of solvent-soluble resins include cellulose derivatives such as ethylene cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, and cellulose acetate, styrene resins such as polystyrene and polyα-methylstyrene, styrene copolymer resins, polymethyl methacrylate, (Meth)acrylic resins and (meth)acrylic copolymer resins such as polyethyl methacrylate, polyethyl acrylate, and butyl polyacrylate, maleic acid resins, rosin-modified phenolic resins, rosin ester resins such as polymerized rosin, and polyvinyl acetate. Resins such as coumaron resin, vinyltoluene resin, vinyl chloride resin, polyester resin, polyurethane resin, butyral resin, etc. can be used.

The electron beam curable substance in the mixed composition, which is the main component of the impregnating agent, provides the decorative paper of the present invention with excellent surface hardness, high solvent resistance, heat resistance, etc. The mold resin imparts suitability for repainting and printing on the surface of the decorative paper.
In the mixed composition which is the main component of the impregnating agent, 5% by weight
If the above solvent-soluble resins are not added or mixed, the surface repaintability and printability of the resulting decorative paper will not be sufficiently improved, and more than 40% by weight of electron beam curable substances may be added. If they are not mixed, the surface properties of the resulting decorative paper will not be improved sufficiently, and if the amount of solvent-soluble resin added exceeds 60% by weight, the viscosity of the impregnating agent will become too high.
Another disadvantage is that it becomes difficult to impregnate paper. Therefore, the mixed composition that is the main component of the impregnating agent is
95-40% by weight electron beam curable material and 5-60% by weight
It is necessary that the composition consists of a solvent-soluble resin and a solvent-soluble resin.

Into the impregnating agent, prevent the electron beam curable substance in the impregnating agent from curing before electron beam irradiation,
In order to facilitate the impregnation operation with an impregnating agent, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, etc. can also be added as a stabilizer.

The amount of impregnating agent that can be impregnated into the paper 2 with good permeability varies depending on the type of paper 2 used, but
Usually, it is preferable to impregnate at a rate of about 5 to 150 g/m ² .

In order to impregnate the paper 2 with good permeability with the above-mentioned impregnating agent, the paper 2 with good permeability is immersed in a solution of the impregnating agent, or by using a roll coater, curtain flow coater, Miyabar coater, etc. It can be carried out by applying an impregnating agent to paper with good permeability using existing coating methods such as , gravure roll coater, air knife coater, etc.

After the impregnating agent applied to the paper 2 with good permeability is impregnated almost uniformly into the paper 2, an electron beam curable substance containing a compound having an ethylenic double bond in the impregnating agent is heated with an electron beam. It is subjected to a step of curing by irradiation with radiation. The time between the impregnating process with the impregnating agent and the electron beam irradiation process depends on the thickness of the paper 2 with good permeability used, the degree of permeability of the paper 2 itself, the viscosity of the impregnating agent, etc. It will be adjusted accordingly, but
Normally used in terms of productivity and ease of manufacturing of decorative paper.
It is preferable to control the time between about 0.5 seconds and about 10 minutes.

The electron beam irradiation can be performed using a low-energy electron accelerator, such as an electrocurtain manufactured by Energy Science Inc., under a nitrogen atmosphere.
CB200/50/30 or manufactured by Ottodühl
Using NP-ESH/50 etc., acceleration voltage 100~
300KV, irradiation current 0-100mA, 0.5-
This is carried out by means such as irradiation with an electron beam of about 30 Mrad. Since this electron beam irradiation treatment can be performed continuously, in manufacturing the decorative paper 1 of the present invention, the electron beam curable substance in the impregnating agent is cured by the electron beam irradiation treatment, The above-described electron beam irradiation treatment can be performed while continuously winding up the obtained decorative paper 1. From this point of view, the decorative paper 1 of the present invention also has the characteristic that it does not require complicated operations during its manufacturing process.

The decorative paper of the present invention has the above-mentioned structure, in which the permeable paper 2 is coated with an impregnating agent whose main component is a mixed composition consisting of an electron beam curable substance and a solvent-soluble resin. is impregnated with the electron beam curable material and is cured by electron beam irradiation, so the electron beam curable material in the impregnation agent improves surface hardness, solvent resistance, heat resistance, etc. Introducing extremely excellent properties and using solvent-soluble resin,
The effect of making it a decorative paper with repaintability and printability on its surface;
be effective.

Furthermore, since the outermost surface of the decorative paper of the present invention is composed of a resin layer containing a mixture of resin cured by electron beams and solvent-soluble resin, decorative paper is laminated on a substrate to produce a decorative board. When using decorative paper, use existing paper,
The manufacturing process for manufacturing decorative boards is simple, as all you have to do is attach it to the board using wood glue.
It also has the effect of being inexpensive.

Furthermore, when manufacturing the decorative paper of the present invention, due to its structure, there is no need for a drying process of a solvent or thermal energy for curing the impregnated resin, so the manufacturing of the decorative paper itself is simple and It also has the advantage of being inexpensive.

Hereinafter, the specific structure of the decorative paper of the present invention will be explained based on manufacturing examples.

Example 1 A wood grain pattern was gravure printed using gravure ink on one side of a titanium paper with a basis weight of 55 g/ ^m2 , and an impregnating agent having the following composition was applied to the printed surface of this pattern using a gravure reverse coating method. It was applied at a rate of 40 g/m ² to impregnate the entire titanium paper almost uniformly.

Impregnating agent composition (1) Ethyl cellulose N-7 10 parts by weight (2) 1,6-hexanediol diacrylate
90 parts by weight Set the time from the impregnating agent application step to the electron beam irradiation step to be 3 seconds, and apply the impregnating agent applied surface to the titanium paper impregnated with the impregnating agent in a nitrogen atmosphere. The decorative paper of the present invention was obtained by irradiating 5 Mrad with an electron beam accelerated at 175 KV.

The surface of the decorative paper obtained has a hardness higher than the pencil hardness H, and has excellent abrasion resistance, chemical resistance, and solvent resistance. (Lloyd Chemical Co., Ltd.) was suitable for repainting.

In addition, when this decorative paper was laminated to particle board, which is a base material for decorative boards, using a commercially available wood emulsion type adhesive,
A decorative board with high adhesive properties and commercially available was obtained.

Example 2 An impregnating agent having the following composition was applied at a rate of 10 g/m ² by a gravure coating method to the patterned surface of titanium paper having a wood grain pattern in gravure printing similar to that used in Example 1. , the entire titanium paper was impregnated almost uniformly.

The viscosity of the impregnating agent used in the coating process was adjusted to 200 to 300 centipoise by heating.

Impregnating agent composition (1) Polyvinyl acetate 20 parts by weight (2) Trimethylolpropane triacrylate
80 parts by weight (3) Hydroquinone monomethyl ether
0.001 parts by weight Set the time from the impregnating agent application step to the electron beam irradiation step to be 1 second, and apply the impregnating agent applied surface to the titanium paper impregnated with the impregnating agent in a nitrogen atmosphere. The decorative paper of the present invention was obtained by irradiating 3 Mrad with an electron beam accelerated at 175 KV.

The surface of the obtained decorative paper has a hardness higher than the pencil hardness H, and has excellent abrasion resistance, chemical resistance, and solvent resistance. It was suitable for repainting using Fujikura Kasei (manufactured by Fujikura Kasei).

In addition, when this decorative paper was laminated to particle board, which is a base material for decorative boards, using a commercially available wood emulsion type adhesive,
A decorative board with high adhesive properties and commercially available was obtained.

Example 3 In the same manner as in Example 2, impregnating agent (A) and impregnating agent (B) having the following compositions were applied, and the subsequent operations were also the same as in Example 2 to prepare two types of makeup of the present invention. Got paper.

Impregnating agent composition (A) (1) Rosin ester [Marquid No. 33: manufactured by Arakawa Chemical] 30 parts by weight (2) Neopentyl glycol diacrylate
40 parts by weight (3) Trimethylolpropane triacrylate
30 parts by weight Impregnating agent composition (B) (1) Urethane resin [Desmocol 130: manufactured by Sumitomo Bayer Urethane] 30 parts by weight (2) Acrylate oligomer [Aronix
M5700: Toagosei Chemical Co., Ltd.] 50 parts by weight (3) Trimethylolpropane triacrylate
40 parts by weight The surfaces of the two types of decorative paper obtained both have a hardness higher than the pencil hardness H, and have excellent abrasion resistance, chemical resistance, and solvent resistance. It was suitable for repainting with the repair liquid "OX-1108" (manufactured by Fujikura Kasei).

In addition, when these two types of decorative paper were laminated onto particle board, which is a base material for decorative laminates, using a commercially available emulsion type adhesive for woodworking, the adhesive properties were high and it became commercially available. A decorative board was obtained that could be used.

[Brief explanation of drawings]

The figure is an enlarged vertical cross-sectional model diagram showing an example of the decorative paper of the present invention. 1: Decorative paper, 2: Paper with good permeability, M: Pattern, 3: Cured resin.

Claims (1)

[Claims] 1 Basis weight with a pattern printed on one side
Paper with good permeability of 300 g/m2 ^or less contains 95-40% by weight of an electron beam curable material containing a compound having an ethylenic double bond in the molecule and 5-60% by weight of a solvent-soluble resin.
% by weight, and the electron beam curable substance in the impregnating agent is cured by electron beam irradiation. paper.