JPS5850199B2 - Decorative board manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing diallylphthalate resin decorative laminates having improved corrosion resistance, particularly alkali resistance.

Diaryl phthalate resin decorative boards have a beautiful luster and are excellent in water resistance, heat resistance, abrasion resistance, and weather resistance, and are superior to other thermosetting resin decorative boards in terms of ease of manufacture. However, the only drawback is that diallyl phthalate resin is relatively easily hydrolyzed by alkali.
The alkali resistance of the decorative board is not necessarily satisfactory.

To solve this problem, we tried various methods such as adding a highly reactive monomer to the diallyl phthalate resin impregnating solution to increase the crosslinking density, and greatly increasing the resin content of the impregnated paper, but no satisfactory results were obtained. There wasn't.

When using a weakly alkaline inorganic board as a base material, the corrosion resistance of the molded product is usually improved by applying an alkali-resistant sealer to the base material, but using a sealer can cause blistering during molding, which reduces yield. Therefore, it has been desired to solve the above-mentioned defects in the production of diallyl phthalate resin decorative laminates.

The present invention relates to a method for manufacturing diallyl phthalate resin decorative laminates that have excellent physical properties such as alkali resistance, water resistance, and heat resistance.

That is, the present invention provides an impregnated paper for decorative laminates impregnated with or coated with (a) an epoxy acrylate resin and (b) a diallyl phthalate prepolymer resin or a mixture of the prepolymer resin and a bisphenol unsaturated polyester. A method for producing a decorative laminate using cloth, wherein the ratio of the bath components (a) and (b) is as follows (1) or (
2).

(1) When impregnating or applying components (a) and (b) to paper cloth at the same time, when component (a) is liquid at room temperature, (a) component 5-30% by weight, (b) component 95-95% 70 weight φ, or when component (a) is solid at room temperature, component (a) is 5 to 50 weight φ, and component (b) is 95 to 50 weight φ.

(2) When impregnating or applying component (a) to paper cloth, and then impregnating or applying component (b) to paper cloth, (a)
Component 5 to 50 weight rice cake, component (b) 95 to 50 weight φ.

The present invention makes it possible to obtain a decorative board with excellent performance without using a sealer even when using an alkaline base material such as a pulp cement board. This can be done without changing the molding conditions.

The epoxy acrylate resin used in the present invention refers to an acrylic resin having unsaturated double bonds at both ends obtained by addition-reacting epoxide at both ends of an epoxy resin with acrylic acid, methacrylic acid, or the like.

Various types of epoxy resins can be used, such as bisphenol A type, alicyclic type, and novolak type, but bisphenol A type is preferred in terms of performance.

Epoxy acrylate resins used in the present invention are those that are liquid or solid at room temperature and have a molecular weight of 500 to 3,000.

Epoxy acrylate resins have extremely excellent adhesive properties and chemical resistance, and are particularly excellent in alkali resistance.

The diallyl phthalate prepolymer resin (hereinafter referred to as DAPP resin) in the present invention refers to the following composition.

Diallyl phthalate prepolymer Wharf 0-100% by weight polyunsaturated polyester 0-30% by weight Diallyl phthalate prepolymer is a pre-polymer of diallyl phthalate, usually obtained by polymerization of ortho, iso, and tele monomers. Number average molecular weight 2000~
20,000 refers to a soluble polymer with unreacted allyl groups.

Unsaturated polyester refers to ordinary polyesters consisting of maleic acid, fumaric acid, phthalic acid, etc., ethylene glycol, propylene glycol, etc.

(Excluding terephthalic acid-based unsaturated polyester and bisphenol-based unsaturated polyester resin described below).

These are known in DAPP resin compositions,
It is commonly used.

The blending amount of unsaturated polyester may be 30 weight φ or less,
Addition of more than this is not preferable since it may deteriorate the performance of the decorative board.

Further, a polymerizable hexamer can also be added to the DAPP resin.

Monomers such as methacrylic ester, acrylic ester, vinyl acetate, styrene, divinylbenzene, diallyl phthalate, and diallyl maleate are used as the polymerizable monomer.

Regarding the amount of addition, 10 weight upwind is not preferable because the resin-impregnated paper cloth remains sticky and the curing time becomes slow.

Bisphenol-based unsaturated polyesters include polybasic unsaturated acids such as maleic anhydride, fumaric acid, and itaconic acid, and bisphenol A propylene glycol ether (
Solution method using polyhydric alcohols such as 2,2-bis(P-2'-hydroxypropyloxyphenyl)propane) and bisphenol A ethylene glycol ether (2,2-bis(P-hydroxyethyloxyphenyl)propane). A solid polyester having an acid value of 30 or less, a bromine value of 40 to 50, and a softening temperature of 100°C or less, which has been subjected to dehydration condensation using a conventional method such as a melting method or a melting method.

Hisphenolic unsaturated polyester is alkali resistant,
I) APP because it has excellent chemical resistance such as acid resistance and solvent resistance, as well as excellent heat resistance and boiling water resistance.
When blended into a system resin, it imparts the excellent physical properties described above.

(a) of the resin composition for impregnation or coating in the present invention
(b) The ratio of the two component resins varies depending on the one-stage impregnation method described below, but is within the range of the blending ratio below.

(a) Epoxy acrylate resin 5-50 weight ratio (
b) Mixture consisting of DAPP resin 50-100% by weight and bisphenol-based vesicular polyester 0-50% by weight 50-95% (a)
If the amount of epoxy acrylate resin is liquid at room temperature, when using the one-step impregnation method described below, if it exceeds 30% by weight, the impregnated paper cloth will remain sticky and the workability will deteriorate. This will adversely affect the surface condition of the decorative board.
In the above blending ratio, (a) component 5 to 30% by weight, (
It is preferable to use component b) in a range of 95 to 70 weight φ.

Furthermore, when component (a) is solid at room temperature or when the two-stage impregnation method described below is employed, the problem of stickiness of the impregnated paper cloth is eliminated, so it is used at the above-mentioned mixing ratio.

Furthermore, if the amount of component (a) is less than 5 weight φ, the alkali resistance effect is small.

Regarding the amount of bisphenol-based unsaturated polyester during mixing in component (b), if it exceeds 50 weight φ, the weather resistance will deteriorate, which is not preferable.

In curing the two-component resin composition (a) and (b) of the present invention, common peroxides can be used as curing agents, such as benzoyl peroxide, di-tert-butyl perbenzoate, lauroyl peroxide, methyl ethyl ketone peroxide. , dicumyl peroxide is selected depending on the molding conditions employed.

The amount of the curing agent is preferably in the range of 1 to 6 parts by weight based on 100 parts by weight of the total resin content of the two components (a) and (b).

In addition to the above composition, other additives such as an internal mold release agent, a polymerization inhibitor, a polymerization accelerator, and a coloring agent may be added as necessary.

The resin composition consisting of two components (a) and (b) of the present invention can be used for printing by dissolving the resin composition in a common organic solvent such as acetone, methyl ethyl ketone, acetic ester, or toluene to form an impregnating liquid. decorative paper, cloth,
There is a method of impregnating or applying an impregnated paper cloth to a non-woven fabric, etc. using a conventional method, or a method of applying an impregnating liquid to a base material such as decorative paper, cloth, non-woven fabric, etc. bonded with an adhesive. (a) and (b) a one-step impregnation method in which two components are mixed and dissolved and impregnated or applied at the same time; and a two-step impregnation method in which (a) component is impregnated or applied, and then (b) ff is impregnated or applied. There is.

The one-step impregnation method involves adding a curing agent and other additives to components (a) and (b) z and dissolving them in a solvent to form an impregnating solution, which is then impregnated or applied onto an impregnated paper fabric to obtain an impregnated paper fabric using a conventional method. It's a method.

The amount of resin attached to the impregnated paper cloth is preferably 60 weight leeward of the impregnated paper cloth (hereinafter the same applies to the amount of resin attached).

In the two-stage impregnation method, two types of impregnating liquids are prepared by adding a curing agent and other additives to components (a) and (b), respectively, and first, the impregnating liquid consisting of component (a) is applied to impregnated paper. Impregnated or coated and dried to produce an impregnated paper cloth with a resin adhesion of 5 to 30% by weight, and then impregnated or coated with an impregnating liquid consisting of component (b) and dried. )
This is a method for obtaining impregnated paper cloth with a two-component resin adhesion amount of 60 weight φ or less.

According to the two-stage impregnation method, even if a liquid epoxy acrylate resin is used, the amount of resin attached to the impregnated paper cloth is 5% of the total amount of resin attached.
The tackiness of the impregnated paper fabric is improved by two-stage impregnation.

Although the life of the impregnated paper cloth obtained as described above is slightly shorter than that of ordinary paper cloth impregnated with diallyl phthalate resin, it still has a life of two months in summer.

Base materials used in the present invention include plywood, birdboard,
Wooden boards such as particle board, calcium silicate boards,
Examples include inorganic plates such as asbestos cement plates, pulp cement plates, magnesium carbonate plates, glass-reinforced cement plates, and gypsum boards, and metal plates such as steel plates, stainless steel plates, and aluminum plates.

The hot-press molding conditions for the impregnated paper cloth and the base material may be the same as the molding conditions for normal diallyl phthalate resin decorative laminates by the so-called real-hot method, and usually 120 to 1800012 to 25K.
A range of 2 to 20 minutes in terms of g/cTt is appropriate.

The present invention will be explained below with reference to Examples.

Examples 1 to 12 and Comparative Examples 1 to 5 Pattern paper with a basis weight of 80 g/lri' was impregnated with each of the impregnating solutions shown in Table 1 according to a conventional method, and the resin adhesion amount was 55 to 5.
An impregnated paper of 7 weight rice cakes was prepared.

Using lauan plywood with a thickness of 2.7 mm as a base material, the previously prepared impregnated paper was layered on top of it and heated at 125°C and 10 kv.
A decorative board was obtained by hot-pressing molding with CrIL for 5 minutes.

An alkali resistance test was conducted on each decorative board, and the results are shown in Table 2.

Examples 13 to 18 and Comparative Examples 6 and 7 Liquid epoxy acrylate resin (
100 parts by weight of "Lipoxy VR-80
Three types of resin liquids each consisting of 200 parts by weight of 0.0 and 15 (L) were prepared.

Normal printing paper (basis weight 80 g/m" manufactured by Chiyoda Gravure Printing Co., Ltd.) was used as the impregnated paper and was impregnated with the above three types of impregnating liquids to obtain primary impregnated paper with a resin adhesion amount of 10 and 20.27, each weight φ. Ta.

Next, these resin-impregnated papers were treated with an impregnating liquid (B) having the following composition.
Alternatively, secondary impregnation was performed at (0) to produce impregnated papers shown in Table 3.

Impregnating liquid (B) Diaryl phthalate prepolymer 80 parts by weight ("Daiso Tsubu A" manufactured by Osaka Soda Co., Ltd.) Unsaturated polyester 20 parts by weight ("Arilux DH2000J manufactured by Osaka Soda Co., Ltd.") Benzoyl peroxide 3 parts by weight Internal mold release agent (rDR −z
osJ Osaka Soda Co., Ltd.) 0.4 parts by weight acetone 160 parts by weight impregnated paper (
0 Diaryl phthalate prepolymer 80 parts by weight Bisphenol unsaturated polyester 20 parts by weight (Atrac G6553SJ manufactured by Kao Soap Co., Ltd.) Benzoyl peroxide 3 parts by weight Internal mold release agent
0.4 parts by weight acetone 1
60 parts by weight As a comparative example, primary impregnation (impregnation liquid (A))
Impregnated papers as shown in Table 3 were prepared which were impregnated with only impregnating liquid (B) or (C) without performing any of the following steps.

Next, a decorative board was produced using lauan plywood and slate board as a base material under the following molding conditions.

(a) Using lauan plywood with a thickness of 2.7 mm, place the previously prepared impregnated paper on the press heating plate at a temperature of 125 °C and a pressure of 10 °C.
Each decorative board was produced by hot-pressing molding at kg/i for 6 minutes.

(b) Using a 3.0 mm thick slate plate (“Asbestos Trax” manufactured by Nippon Asbestos Co., Ltd.), molding conditions 1
It was hot-pressed at 25°C and 20 kg/-.

Performance tests were conducted on each of the decorative boards obtained, and the results are shown in Tables 3 and 46, respectively.

Notes (1) (2) Boilability Test Soak the test piece in boiling water and take it out at specified intervals to observe discoloration, color fading, blistering, etc. on the surface layer.

Tap water immersion test A test piece is immersed in tap water and left at room temperature for a specified period of time, and the surface layer is observed for discoloration, blisters, cracks, etc.

Judgment ○ No change at all △ Slight change × Discoloration, blistering, cracking Example 19 and Comparative Example 8 Using each impregnating solution of Example 7 and Comparative Example 5, the basis weight was 80
g/rn: walnut pattern printing paper was impregnated to produce an impregnated paper with a resin adhesion amount of 55 weight φ.

A 5-inch thick asbestos cement board (R-Asbeston, manufactured by Asahi Asbestos Industries) was layered with the previously prepared impregnated paper as a base material, and then hot-press-formed at 125°C and 10 ky/i for 10 minutes to form a decorative board. I got it.

Table 5 shows the results of the performance tests for each decorative board.

Example 20 and Comparative Example 9 Printing paper (manufactured by Chiyoda Gravure Printing Co., Ltd.) with a basis weight of 80 g/m' was pre-coated with a urea-vinyl acetate adhesive to a thickness of 2.5 mm.
Paper-covered plywood glued to 7mm lauan plywood was prepared.

Next, the impregnating liquid (4) used in Examples 13 to 18, (B)
, Prepare (C), first apply the impregnating liquid (4) on the paper-clad plywood and dry it, so that the resin adhesion amount is 20 ji/m"
paper-covered plywood was obtained.

Next, apply impregnating solution (B) or (C) respectively and dry to obtain a total resin adhesion amount of 749/m' or 71&/
A resin-coated paper-covered plywood of m was obtained.

On the other hand, as a comparative example, the resin adhesion amount after drying when impregnating solution (B) or (0) was applied individually was 77 g/rn:
Or 749/rr? We prepared resin-coated paper-covered plywood.

These resin-coated paper-covered plywood were molded under conditions of 125°C and 10°C.
After hot-pressing for 6 minutes at kg/i, decorative boards with beautiful surfaces were obtained.

When these decorative boards were subjected to an alkali resistance test, those pretreated with the impregnating solution (4) showed significantly better results than those that were not pretreated.

Claims (1)

[Claims] 1. An impregnation for decorative laminates impregnated or coated with (a) an epoxy acrylate resin and (b) a diallyl phthalate prepolymer resin or a mixture of the prepolymer resin and a bisphenol unsaturated polyester. A method for manufacturing a decorative board using paper cloth, comprising the steps (a) and (b) above.
) A method characterized in that the ratio of each component is the following (1) or (2). (1) When impregnating or coating paper cloth with components (a) and (b) at the same time, when component (a) is liquid at room temperature,
(a) component 5-30% by weight, (b) component 95-70% by weight, or when (a) component is solid at room temperature, (a) component 5-50% by weight, (b) component 95-50% by weight φ. (2) When impregnating or applying component (a) to paper cloth, and then impregnating or applying component (b) to paper cloth, (a)
) component 5 to 50 weight φ, component (b) 95 to 50 weight φ.