JPS5951437B2 - Decorative board manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a decorative board, and more specifically, a decorative board having an uneven pattern that matches the pattern and having surface physical properties such as wear resistance and solvent resistance.

The present invention relates to an improved method for manufacturing decorative laminates. Conventionally, there are roughly two methods for imparting unevenness that matches the pattern on the surface of a thermosetting resin decorative board.

The first method is a physical method called the direct embossing method, in which an embossing plate that matches the design is used and a flat plate press is used to directly create unevenness on the decorative board. It is typified by the method of creating irregularities on the surface of a decorative board.

However, with this method, it is expensive to manufacture the embossing plate and embossing roll, and it is difficult to register the design of the decorative board with the uneven pattern of the embossing plate and embossing roll, which takes time and costs. There was a problem.
The second method is generally called the chemical embossing method, in which a pattern is formed on the base paper for resin impregnation using ink containing a resin polymerization inhibitor, and this creates a difference in the curing speed of the impregnated resin on the surface of the decorative board. A method of forming an embossed pattern on the surface by using the difference between the two layers, or a method of forming a pattern on the base paper for resin impregnation with an ink containing a substance that has a repellent effect on resin, and then forming a pattern on the base paper for resin impregnation, and making use of the difference in the ink area during application or impregnation. There is a method of repelling the resin on top to form an embossed pattern.

These chemical methods are extremely advantageous in terms of matching the design and the embossed pattern, but in the case of the former,
Since it takes time for the resin to harden and only the volumetric contraction of the resin is utilized, the width of the depressed recess is naturally limited, making it impossible to form a deep recess with an arbitrary width. Thermosetting resins molded under heat and pressure, such as urea resin, melamine resin, and tap resin, are not very effective.

On the other hand, various experiments were conducted on the latter, but the repelling effect alone was not sufficient.
There was a problem that a sufficient embossing effect could not be obtained with heat and pressure molding type resins. It is an object of the present invention to eliminate the above-mentioned drawbacks and to produce, by a relatively simple method, an embossed decorative board that can be applied to heat-press molding type thermosetting resin.

That is, the present invention provides designs on decorative paper using an ink containing a vehicle resin that has releasability to the condensed thermosetting resin to be impregnated, and a substance that reduces the cohesive force of the condensed thermosetting resin to be impregnated. After the above-mentioned vehicle resin is solidified, the entire surface of the decorative paper including the pattern is impregnated with a condensation type thermosetting resin and dried to create an impregnated paper, and then the impregnated paper is layered on the base material. Then, after placing a molded plate or film thereon, heating and pressurizing the thermosetting resin in the non-patterned areas is cured. The gist of the present invention is a method for manufacturing a decorative board, which is characterized in that a thermosetting resin having a low cohesive force is attached to a molded plate or film, and a concave portion is formed by peeling off the molded plate or film.

Hereinafter, the present invention will be explained in more detail with reference to the drawings.

First, the principle of the present invention will be explained using FIGS. 1 to 5.

As shown in FIG. 1, a cloth grain pattern, a wood grain pattern, etc. are printed on decorative paper 1 as a base pattern (not shown) using an ordinary ink or paint composition, or after a base pattern is applied. Coagulation of the vehicle resin and the impregnated thermosetting resin, which has a peeling property for the condensation type thermosetting resin impregnated, is applied only to areas where the painted surface is desired to be indented, such as wood grain patterns and abstract patterns, on the decorative paper. Pattern 2 made with ink containing a substance that reduces force.
After applying, the vehicle resin is solidified.

Next, as shown in the second figure, the printed paper is impregnated with a thermosetting resin 3 by coating or dipping, and after drying, an impregnated decorative paper is obtained.

In the impregnated decorative paper, not only is the thermosetting resin impregnated into the decorative paper 1, but also a thermosetting resin film 3 is formed on the pattern 2 and the back surface of the decorative paper. Next, as shown in Figure 3, impregnated paper is layered on top of the base material 4 with the pattern 2 on the surface, and a molded plate or film 5 such as a metal plate, plastic film, or release paper is placed on top of the impregnated paper. Heat and pressurize by means. Through this heating and pressure forming, the fourth
As shown in the figure, the thermosetting resin in the area other than the pattern 2 is cured, and the cohesive force of the thermosetting resin in the area of the pattern 2 is low, resulting in a hardened area 6 and a area 3' with low cohesive force. .

This is considered to be because a substance that reduces the cohesive force of the thermosetting resin contained in the pattern 2 moves to the upper part of the pattern layer and acts on the thermosetting resin impregnated in the upper part of the pattern layer. Then, as shown in Figure 5, when the molded plate or film 5 is peeled off, the resin in the low cohesive force portion 3' adheres and is peeled off.
The part 3' with low cohesive force has poor affinity with the vehicle resin in the pattern 2, so it peels off without leaving any residue on the pattern 2, and since the cohesive force is in a state of low cohesive force, it is extremely hard to form on the molded plate or film due to heat pressure. It is in a state where it is easy to adhere. In this way, a decorative board having an uneven pattern that matches the pattern 2 can be obtained.

In this decorative board, the pattern 2 is exposed because there is no hardened layer of thermosetting resin in the recessed portion, but since the vehicle resin in the pattern 2 is solidified, it is extremely durable. The materials of each part will be explained in more detail below.

In the present invention, the decorative paper 1 includes ordinary papers such as titanium paper, thin paper, and kraft paper, as well as cotton cloth,
A sheet-like material made of a cloth such as glass cloth or an aggregate of fine fibers such as non-woven cloth can be arbitrarily used. Weight 20-500g
/m· range is preferably used. As described above, after the base pattern and the ink pattern 2 of the portion to be depressed are applied as necessary to this decorative paper, it is impregnated with a condensation type thermosetting resin.

Examples of this thermosetting resin include melamine resin, urea resin,
Condensation-type thermosetting resins such as acetoguanamine resins and benzoguanamine resins, or one or more of these initial condensates, or containing these as the main component, and furthermore polyallyl ester resins, unsaturated polyester resins, etc. 10 to 40 wt of addition polymerization type thermosetting resin or their initial condensate or polymer in the resin content.
It is also possible to use a condensed type mixed with about %. These thermosetting resins are, for example, thermosetting resins 20 to 70%
Wt%, solvent 30 to 70 wt%, curing accelerator added as necessary 1 to 5 wt%, and further optionally a mold release agent such as lauric acid, a coloring agent such as a dye or pigment, and a plasticizer. agent, stabilizer, wax/grease, desiccant/
Decorative paper is impregnated as a solution-type or emulsion-type impregnation liquid containing known additives such as auxiliary desiccants, thickeners, dispersants, and fillers.

By adding powder of an inorganic substance that is insoluble in the resin or solvent as a filler in an amount of 1 to 20 wt% of the total resin liquid, the uncured thermosetting resin can be formed into a molded plate or a molded plate after hot and pressure molding. It has been recognized that it tends to adhere to the film, which is desirable.

This is considered to be because the addition of the inorganic powder further reduces the cohesive force of the uncured thermosetting resin. Furthermore, when the molded plate or film is a metal plate, these inorganic powders have a good affinity for the metal plate and are therefore considered to improve the adhesion of the uncured thermosetting resin to the metal plate. Examples of inorganic powders added for this purpose include silica, alumina, metal oxides such as titanium oxide, metal salts such as calcium carbonate and magnesium carbonate, inorganic powders commonly used as extender pigments, and metal powders such as aluminum powder. Those having an average particle size of 0.1 to 50 μm are preferably used.

In this case, the object of the present invention can be achieved if the amount of resin adhered in the impregnated paper is 30 to 200% in terms of solid content based on the weight of the decorative paper, but preferably the amount of resin adhered is 70 to 160%. Use. As a result, not only the decorative paper is impregnated with the ink, but also a dry film of the thermosetting resin having a thickness of usually about 1 to 500 μm is formed on the ink pattern 2. Methods for applying a base pattern such as a cloth grain pattern or a wood grain pattern to the decorative paper prior to impregnating it with a thermosetting resin, and for applying a pattern on a portion to be recessed corresponding to a wood conduit etc. include, for example, a relief printing method, It can be formed by printing, drawing, or painting using a normal printing method such as an offset printing method, a gravure printing method, or a screen printing method, a hand drawing method, or a normal painting method.

The ink or paint composition for applying the base pattern may be a known one, such as an ink or paint vehicle to which a coloring agent such as a dye or pigment is added, and in addition, for example, a plasticizer, a stabilizer, a wax/grease, a drying agent, etc. agent, auxiliary desiccant,
It is possible to use an ink or coating composition prepared by adding optionally known additives such as a curing agent, thickener, dispersant, filler, etc., and thoroughly kneading the composition with a solvent, diluent, etc.

In the above ink or coating composition, the vehicle may be a known vehicle, such as various oils and fats such as linseed oil, soybean oil, synthetic drying oil, rosin, copal, dammar, hardened rosin, rosin ester, or polymerized rosin. Fire resin and caloe resin, rosin modified phenolic resin, 100%
Synthetic resins such as phenolic resin, maleic acid resin, alkyd resin, petroleum resin, vinyl resin, acrylic resin, polyamide resin, epoxy resin, amino alkyd resin, cellulose derivatives such as nitrocellulose and ethyl cellulose, chlorinated rubber , rubber derivatives of oxidized rubber, glue, casein, dextrin, zein, etc. can be used.

Next, in the above, the composition used to form the pattern 2 formed in the concave portion is 5 to 50 wt% vehicle resin and 20 wt% solvent.
~70 wt%, 3 to 60 wt% of a substance that reduces the cohesive force of the thermosetting resin, and if necessary, 50 wt%
Up to t% of pigments or dyes and other additives such as those described above for the underlying patterning compositions can be added.

The vehicle resin needs to be releasable to the impregnating thermosetting resin.

Such conditions are suitable for dissolving the above-mentioned thermosetting resins for impregnation, such as vehicle resins such as fluorocarbon resins such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride, in a solvent. Solvent-resistant thermoplastic resins with no properties or thermosetting resins of different types from condensation-type thermosetting resins for impregnation, such as diallyl phthalate, unsaturated polyesters, urethane resins, amine-curing epoxy resins, and ethylenic resins. It is an addition polymerizable thermosetting resin such as an addition polymerizable silicone resin into which an unsaturated group has been introduced.

Along with these resins, these resins modified with cellulose, alcohol, alkyd, etc. may be included in the part, for example, 5 to 30 wt% of the vehicle resin, or thermoplastics such as cellulose, acrylic resin, polyvinyl chloride, etc. By mixing 10 to 60 wt% of the resin, the printability of the ink and the conditions for solidifying the vehicle resin after application of the ink can be relaxed, such as shortening the time and lowering the temperature, without reducing the performance of the ink film.
Effects such as this can be obtained. Since these vehicle resins have robustness after curing, there is no problem in terms of performance even if they are exposed as recesses.

Moreover, these vehicle resins have releasability to the thermosetting resin they impregnate, and although there is no need to use additional additives for this purpose in principle, paraffin is added to further improve releasability. , wax silicone oil, etc. can also be added in an amount of 1 to 20 wt % based on the vehicle resin. As the solvent or dispersion medium in the ink, toluene,
Aromatic hydrocarbons such as xylene; aliphatic alcohols such as isopcapyl alcohol, ethyl alcohol, and methyl alcohol; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethylene glycol monomethyl ether, One or a mixture of two or more of ethers such as dioxane and tetrahydrofuran; lactones such as γ-propiolactone and γ-butyrolactone; and amides such as dimethylformamide and dimethylacetamide are used. Water can also be used as a dispersion medium. Incidentally, these solvents or dispersion media are also used for preparing the above-mentioned impregnating resin liquid. As substances that reduce the cohesive force of the thermosetting resin contained in the ink, curing inhibitors, internal plasticizers, foaming agents, etc. are used. Specifically, as the hardening inhibitor, strong basic substances such as hydroxides and oxides of alkali metals or alkaline earth metals, such as sodium hydroxide, potassium hydroxide, calcium oxide, and calcium hydroxide, may be used. I can do it. In addition, prolactam, P-toluenesulfonamide is used as an internal plasticizer, and sodium hydrogen carbonate, sodium borohydride, azobisisobutyronitrile, benzenesulfonylhydrazide, and P-toluenesulfonylhydrazide are used as blowing agents. be able to. These can be added directly to the ink, or can be microencapsulated and added using a thermoplastic resin that can be softened at a temperature of 100 to 200° C. during heating and pressing.

These additives may be used alone, but the effect can be further enhanced by using them in combination.

Particularly effective is the combination of a curing inhibitor or internal plasticizer and a foaming agent. These additives are contained in the ink composition in an amount of 3 to 60 wt% as described above, and preferably 5 to 60 wt%.
It is used at a content of ~40 wt%.

If it is less than 3 wt%, it is difficult to obtain a state of low cohesive force for the thermosetting resin to be impregnated, and it is difficult to obtain an uneven shape with only the releasability from the ink and the strength of adhesion to the molded plate or film. Moreover, if the amount exceeds 60 wt%, it will affect the curing action of the vehicle resin, weakening the robustness of the ink film and making it difficult to peel off from the thermosetting resin.

Pigments or dyes in the ink composition are conventional ones, such as organic dyes or pigments such as azo-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, aniline black; titanium oxide, cadmium-based iron oxide, chromium oxide, etc. One or more of inorganic pigments, carbon black, aluminum powder, etc. may be used, but they may not be used at all.

After the pattern 2 made of this ink composition is provided on the decorative paper 1 as described above, the vehicle resin is solidified.

Solidification includes curing in thermosetting resins and baking in solvent-resistant thermoplastic resins, and is distinguished from film formation by penetration and drying in ordinary printing inks. The conditions vary widely depending on the resin; for example, for addition-polymerized thermosetting resins, the temperature is 200°C at room temperature for 5 seconds to 15 minutes; for solvent-resistant thermoplastic resins, the temperature is 150°C to 300°C.
, 30 seconds to 30 minutes. Since the curing or baking conditions for these resins are well known for each resin, there is no need to explain them in detail. In any case, it is important to form a strong solidified film by curing or baking at this stage to improve the peelability of the vehicle resin from the impregnating thermosetting resin and the surface solvent resistance of the final decorative board. This is essential for maintaining good physical properties.
In addition, the ink adhesion amount is 2 to 200μ as the dry thickness.
A range of m is preferred. In this way, the impregnated paper provided with the pattern 2 and impregnated with the thermosetting resin 3 is stacked on the base material 4 as shown in FIG. The entire structure is heated and pressurized to obtain the structure shown in FIG.

The heating and pressurizing conditions vary widely depending on the selected thermosetting resin, but since these are just known conditions for each resin, there is no need to describe them again. Generally speaking, the temperature is 100~200℃, 5~150k
This means a pressure of g/d and a time of 3 to 60 minutes.
As the base material 4, plywood, particle board, flexible board, calcium silicate board, pulp cement, etc. are used, and resin-impregnated laminated core paper is also used.

The molded plate or film 5 may be made of metals such as duralumin, stainless steel, polypropylene, etc. that can withstand the heating and pressurizing conditions required for curing thermosetting resins.
Plastics such as vinylon, release paper coated with a release agent, and plates, sheets, films, etc. made of any other material are used.

The molded plate or film must have a greater adhesion to the uncured thermosetting resin than the vehicle resin of the ink pattern 2, and must also be able to be peeled off from the cured thermosetting resin. The contact surface of the molded plate or film 5 with the thermosetting resin 3 may have a surface pattern as well as a flat plate, but the pattern must be within a range that does not impair this releasability. Next, as shown in FIG. 5, when the molded plate or film 5 is peeled off while being left in the heated state, the uncured portion 3 of the thermosetting resin corresponding to the pattern 2 is
Coupled with the releasability of the pattern 2 from the vehicle resin, it adheres to the molded plate or film, leaving a concave portion that matches the pattern 2.

Alternatively, after heating and pressurizing, the structure shown in FIG. 4 can be temporarily cooled while remaining in the pressurized state.

In this cooled state, the uncured resin part 3 does not have adhesiveness, so even if the molded plate or film is peeled off, it will not stick to it, but it will be heated and pressurized again under the conditions of 100 to 200°C and 5 to 50 kg/cm2. After that, the uncured portion 3 is removed by releasing the pressure while still in the pressurized state and peeling off the molded plate or film.
can be removed by adhering to the molded plate or film to form a recess similar to the one described above. By this method, it is possible to prevent a decrease in the adhesiveness between the base material 4 and the decorative paper 1 due to blistering or warping of the base material, which may occur if the molded plate or film is peeled off immediately after heating and pressurizing. can. As is clear from the above description, according to the method for producing a decorative board of the present invention, the following effects can be obtained, for example, in obtaining a decorative board having a concave pattern that matches the pattern on the decorative paper.

(1) The ink pattern formed in the recesses contains a substance that reduces the cohesive force of the thermosetting resin and a vehicle resin that is releasable to the thermosetting resin. Since the thermosetting resin is impregnated with thermosetting resin, the thermosetting resin on the pattern is difficult to harden and is extremely easy to peel off.

Therefore, sharp recesses are formed in sync with the pattern. (2)
Since the vehicle resin in the pattern is solvent resistant and solidified, the concave portions where the pattern is exposed are as solid as the convex portions.

(3) Even if the resin attached to the molded plate or film is peeled off and the next molding is performed without removing it,
It is integrated with thermosetting resin and has no effect on the finished decorative board.

Therefore, since it is not necessary to remove the resin in each decorative laminate production process, the decorative laminate can be manufactured extremely efficiently.
Therefore, the decorative board obtained by the method of the present invention is suitable for various uses, and can be used, for example, as a building material decorative board for doors, wall materials, furniture, musical instruments, kitchens, etc.

Next, the present invention will be explained in more detail with reference to Examples.

"Parts" and percentages in the following text are based on weight. <Example 1> A wood grain pattern was gravure printed on 80 g/M2 titanium paper using a normal gravure ink, and a conduit portion was printed using an ink having the following composition using a gravure printing machine.

Ink formulation) Fluorine resin (polyvinylidene fluoride, solid content 50%, manufactured by Kansai Paint Co., Ltd., Futucalon 3000)
15 parts Pigment (carbon black) 20
Part sodium hydroxide 5 parts ethyl acetate 25 parts toluene
20 parts Isopropyl alcohol 15 parts The printing paper was dried at 200° C. for 1 minute to harden the ink in the conduit portion, and impregnated with the following resin mixture at a solid content of 100 g/M 2 .

(Resin combination) Melamine resin (manufactured by Showa Kobunshi Co., Ltd., Polyfix PM-
107) 50 parts water
The impregnated paper impregnated with 20 parts of 30 parts of methanol was dried at 80°C for 10 minutes, and then the impregnated paper was stacked on a 3 m/m thick plywood with the ink side facing up, and a stainless steel plate was placed on top of it. Pressing was carried out at 150°C and 10 kg/Cm2 for 8 minutes.

When the stainless steel plate is released from the mold after pressing, the resin in only the conduit part has poor affinity with the conduit ink, and the resin in this part remains uncured due to the hardening suppressing effect.
Transferred to stainless steel plate, resulting in a sharp and deep matching embossed decorative plate. <Example 2> A wood grain pattern was gravure printed on 80 g/M2 titanium paper using a normal gravure ink, and a conduit portion was printed using an ink having the following composition using a gravure printing machine.

(Ink formulation) Silicone resin (dimethylpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) 15 parts Pigment (ferric oxide) 20 parts ε-caprolactam 7 parts P-toluenesulfonyl hydrazide 3 parts Ethyl acetate
22 parts Toluene 18 parts Isopropyl alcohol 15 parts The printing paper was dried at 150° C. for 1 minute to harden the ink in the conduit portion, and impregnated with the following resin blend at a solid content of 120 g/M 2 .

(Resin formulation) The impregnated paper impregnated with benzoguanamine resin (manufactured by Showa Kobunshi Co., Ltd., Polyfix PG-264) 50 parts water 30 parts methanol 20 parts was dried at 80°C for 10 minutes, and then
The impregnated paper was stacked on a plywood board with a thickness of
kg/An2 for 8 minutes.

When the polyester film is released from the mold after pressing, the resin in the conduit portion has poor affinity with the conduit ink, is internally plasticized, and has the effect of a foaming agent, resulting in extremely low cohesive force. Transferred to polyester film, a sharp and deep matching embossed decorative board was obtained. <Example 3> A wood grain pattern was gravure printed on 80 g/M2 titanium paper using ordinary gravure ink, and a conduit portion was printed using an ink having the following composition using a gravure printing machine.

(Ink formulation) Fluorine resin (same as Example 1) 15 parts Acrylic modified varnish 10 parts Pigment (ferric oxide) 20 parts P-toluenesulfonamide 10 parts Sodium hydrogen carbonate 3 parts Solvent; dimethylacetamide 40 parts Dipenta Erythritol: 0.1 parts Isoboron: 10 parts The printed paper was dried at 200° C. for 1 minute, and further impregnated with the following resin mixture at a solid content of 12 g/m.

(Resin blend) Melamine resin (manufactured by Showa Kobunshi Co., Ltd., Polyfix PG-264) 50 parts.

The impregnated paper impregnated with 20 parts of 30 parts of methanol was dried at 80°C for 10 minutes, and then
The impregnated paper was stacked on a plywood board with a thickness of
It was pressed for 8 minutes at kg/Cm2.

When the polyester film is released from the mold after pressing, the resin in the conduit portion has poor affinity with the conduit ink, is internally plasticized, and has the effect of a foaming agent, resulting in extremely low cohesive force. Transferred to polyester film, a sharp and deep matching embossed decorative board was obtained.

[Brief explanation of the drawing]

FIGS. 1 to 5 are conceptual cross-sectional views for explaining the principle of the method for manufacturing a decorative laminate of the present invention.

Claims (1)

[Claims] 1 After providing a pattern on decorative paper with an ink containing a vehicle resin that has peelability for the condensation type thermosetting resin to be impregnated and a substance that reduces the cohesive force of the condensation type thermosetting resin to be impregnated. , the vehicle resin is solidified, and then the entire decorative paper including the pattern is impregnated with a condensation type thermosetting resin and dried to create an impregnated paper, and then the impregnated paper is laid on a base material, and further on top of it. After placing the molded plate or film, heat and pressurize to harden the thermosetting resin in the non-patterned area, and then attach the thermosetting resin with low cohesive force on the pattern to the molded plate or film. A method for manufacturing a decorative board, which comprises forming recesses by peeling off the molded board or film.