JPS5936874B2 - 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, it relates to a decorative board having an uneven pattern that matches the design and which has improved surface properties such as abrasion resistance and solvent resistance. This invention relates to a method for manufacturing a board.

Conventionally, there are roughly two methods for imparting unevenness that matches the pattern on the surface of a thermosetting resin decorative board. 1st
This method is 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 irregularities on the decorative board, and an embossing roll is used to directly create irregularities on the decorative board surface. This is typified by the method of applying

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 an ink containing a resin polymerization inhibitor, which creates a difference in the curing speed of the 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 methods are extremely advantageous in terms of matching the design and the embossed pattern, but in the case of the former, it takes time for the resin to harden and only the volumetric contraction of the resin is used. This naturally limits the width of the depressed recess, making it impossible to form a deep recess with an arbitrary width, and thermosetting resins that are molded under heat and pressure, such as urea resin, melamine resin, and tap resin, are not suitable. has no effect.

On the other hand, various experiments were conducted on the latter, but the splash effect alone was not sufficient.
There was a problem in that a sufficient embossing effect could not be achieved with heat and pressure molding type resins. In order to solve the above-mentioned drawbacks, we aimed to manufacture an embossed decorative board using a relatively simple method, at a low cost, and which can be applied to heat-pressing molded thermosetting resins. After creating a pattern on the decorative paper using an ink containing a resin that has releasability for the thermosetting resin to be impregnated and a curing inhibitor for the thermosetting resin to be impregnated, the releasable resin is cured. Then, the entire surface of the decorative paper including the pattern was impregnated with a thermosetting resin and dried to produce an impregnated paper.The impregnated paper was then placed on a base material, and a molded plate or film was placed on top of it. After that, heat and pressure is applied to harden the thermosetting resin in the non-patterned area, and then the uncured resin on the pattern is adhered onto a molded plate or film, and the molded plate or film is peeled off to form a recess. proposed a method for manufacturing decorative laminates characterized by the formation of
(See No. 0).

In the decorative board obtained by the above method, it cannot be said that the thermosetting resin around the recesses is completely cured compared to other parts.
．． Therefore, it may not be applicable in cases where high surface properties are required. Therefore, the present inventors conducted further research and discovered that the surface properties of the decorative laminate obtained by the above method could be significantly improved by irradiating it with ultraviolet rays or electron beams as a post-treatment. This completes the present invention. That is, in the present invention, after providing a pattern on decorative paper with an ink containing a resin that has releasability to the thermosetting resin to be impregnated and a curing inhibitor to the thermosetting resin to be impregnated, The thermosetting resin is cured, and then the entire surface of the decorative paper including the pattern is impregnated with the thermosetting resin and dried to produce impregnated paper.Then, the impregnated paper is layered on a base material, and a molded plate or film is further placed on top of it. is placed, heat and pressure is applied to cure the thermosetting resin in the non-patterned area, and the uncured resin on the pattern is adhered onto the molded plate or film, and the molded plate or film is peeled off. By manufacturing a decorative board having concave portions, and further irradiating the surface of the decorative board with ultraviolet rays or electron beams, the thermosetting resin around the sweetened concave portions (throughout this specification, the thermosetting resin around the concave portions) is removed. As shown by 7 in FIG. 6, the thermosetting resin includes the thermosetting resin in the contact area of the pattern 2 and the adjacent area, and the thermosetting resin impregnated in the decorative paper 1 below the pattern 2. do.

) is characterized by completely curing a decorative board with improved surface properties. below,
The above-mentioned present invention will be explained in detail.

First, the explanation using a principle diagram is as follows.
As shown in Fig. 1, a cloth grain pattern, a wood grain pattern, etc. are printed on the decorative paper 1 as a base pattern using a normal ink or paint composition, or a wood grain pattern, an abstract pattern, etc. is printed directly on the decorative paper 1. After applying the pattern 2 only on the areas where the coating surface is desired to be depressed using ink containing a resin that has releasability to the thermosetting resin to be impregnated and a curing inhibitor to the thermosetting resin to be impregnated. , the above-mentioned releasable resin is cured.

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

Next, as shown in Figure 3, impregnated paper is layered on the base material 4 with the pattern 2 on the surface, and a molded plate or film 5 such as a metal plate or plastic film is further placed on top of the impregnated paper, and then a conventional method is used. Heat and pressurize. By this heating and pressure molding, as shown in the fourth diagram, the thermosetting resin in the area other than the pattern 2 is cured, and the thermosetting resin in the area of the pattern 2 remains uncured, and the cured area 6 and the uncured area are 3 occurs.

Does this mean that the hardening inhibitor contained in pattern 2 moves to the upper part of the pattern layer? This is thought to be because the impregnated thermosetting resin on the upper part of the pattern layer is in an uncured state. Next, as shown in Figure 5, when the molded plate or film 5 is peeled off, the resin in the uncured portion 3 is adhered and peeled off. The uncured portion 3 has poor affinity with the removable resin in the pattern 2, so it peels off without leaving any residue on the pattern 2, and since it is in an uncured state, it is extremely likely to adhere to the molded plate or film due to heat and pressure. It is in.
In this way, the decorative board A having a concavo-convex pattern that matches the pattern 2 is created. In this decorative board A, the pattern 2 is exposed because there is no hardened layer of thermosetting resin in the recessed portion, but since the peelable resin in the pattern 2 is hardened, it is extremely durable. However, pattern 2
If we look at the movement of the curing inhibitor contained therein a little more microscopically, we can see that it is not only diffused in the upper part of the pattern layer, but also equally throughout the thermosetting resin centering on pattern 2, so the thermosetting resin is similar to pattern 2. The curing inhibitor is distributed in a high concentration inside the thermosetting resin, while in the thermosetting resin far from the pattern 2, it is distributed in a low concentration. The resin is in an incompletely cured state compared to other parts, and as mentioned above,
It may be unsuitable for decorative laminates that require advanced physical properties. Therefore, as shown in Figure 6, the surface of the decorative board is irradiated with ultraviolet rays or electron beams 8 to produce a completely cured decorative board B with improved surface properties. The principle that an incompletely cured thermosetting resin can be completely cured by irradiation with ultraviolet rays or electron beams is that the polymer, which is stabilized at a low molecular weight due to the curing inhibitor, is irradiated with ultraviolet rays or electron beams. It is thought that bonds are broken and radicals are generated, resulting in higher molecular weight and complete curing.

Therefore, in the case of ultraviolet irradiation, complete curing can be achieved in a short time by adding a substance that generates radicals when exposed to light, that is, an ultraviolet sensitizer, to the thermosetting resin liquid that is pre-impregnated. Furthermore, although the details of the reaction mechanism are unknown, it is effective to irradiate infrared rays immediately before irradiating ultraviolet rays, and the irradiation time of ultraviolet rays can be shortened.
Furthermore, when irradiating with ultraviolet rays or electron beams,
The irradiation time of ultraviolet rays or electron beams can be shortened by irradiating in an inert gas stream or in close contact with an air-blocking film. This seems to be due to the fact that radicals generated by ultraviolet rays or electron beams are consumed by oxygen in the air. In the present invention, the decorative paper may be paper such as titanium paper, thin paper, or kraft paper, cloth such as cotton cloth or glass cloth, or nonwoven fabric.

Furthermore, as a method for applying base patterns such as cloth grain patterns and wood grain patterns, and patterns for areas to be recessed, to these decorative papers, there are conventional printing methods such as letterpress printing, offset printing, gravure printing, or screen printing. It can be formed by printing, drawing, or painting by a hand-drawing method, a normal painting method, or the like. Next, in the present invention, the ink or coating composition for applying the base pattern is a known one, for example, a coloring agent such as a dye or pigment is added to an ink or coating vehicle, and further, for example, a plasticizer, a stabilizer, etc. agent, wax/grease,
An ink or coating composition prepared by optionally adding known additives such as a desiccant, an auxiliary desiccant, a curing agent, a thickener, a dispersant, a filler, etc., and sufficiently mixed with a solvent, a diluent, etc. can be used.

In the above ink or coating composition, the vehicle may be a known one, such as various oils and fats such as linseed oil, soybean oil, or synthetic drying oil, or natural resins such as rosin, copal dammar, hardened rosin, rosin ester, or polymerized rosin. and synthetic resins such as processed resins, rosin-modified phenolic resins, 100% phenolic resins, maleic acid resins, alkyd resins, petroleum resins, vinyl resins, acrylic resins, polyamide resins, epoxy resins, amino alkyd resins, etc. Around the same time, cellulose derivatives such as nitrocenolose and polytinorecenolose, rubber derivatives such as chlorinated rubber and cyclized rubber,
In addition, glue, casein, dextrin, zein, etc. can be used.

Next, among the constituent components of the ink composition used to form the pattern formed in the recesses in the above, first, as a resin that has releasability to the thermosetting resin to be impregnated, fluorine-based resin etc. Thermoplastic resins or thermosetting resins such as melamine resins, urea resins, silicone resins, etc. are used.

In particular, when using a reactive type resin as the thermosetting resin to be impregnated, it is preferable to use a resin that has a type of releasability different from the curing reaction of the thermosetting resin to be impregnated. For example, condensation type silicone resins or melamine resins are suitable as release resins for diallyl phthalate resins. Further, when the thermosetting resin to be impregnated is a radical polymerization type such as unsaturated polyester jugetsu-ha diallyl phthalate resin, hydroquinone, methoquinone, etc. can be used as a curing inhibitor. When a reactive type resin is used as the resin having peelability at this time, it is necessary to use a condensation type resin. In the above ink composition, the amount of the curing inhibitor used is 3 to 60 wt%, preferably 5 to 40 wt%, based on 100 of the ink composition. If it is less than 3 Wt%, the effect of suppressing curing on the impregnating thermosetting resin is not sufficient, so the cohesive force between the part affected by the suppression sword between the thermosetting resin and the part not affected is large, and the peeling property is reduced. It is impossible to obtain an uneven shape due to insufficient affinity with the resin and the force of adhesion to the molded plate or film, and if the amount exceeds 200 wt%, it will affect the curing effect of the peelable resin and reduce the robustness of the ink film. This is because the properties become weaker and the peeling from the thermosetting resin becomes worse.

The ink compositions shown in ± contain the above-mentioned release resin and curing inhibitor as main components of the vehicle, to which coloring agents such as dyes and pigments are added, and optionally necessary additives are added such as solvents, diluents, etc. It is made by thoroughly kneading it.

Next, in the present invention, the method of impregnating the printing paper with resin includes, for example, immersing the printing paper in a solution type or emulsion type resin liquid and drying it, or Coating or applying the resin liquid as above,
This can be done by a drying method or the like.

As the resin liquid in the above, for example, one or two thermosetting resins such as urea resin, melamine resin, acetoguanamine resin, benzoguanamine resin, unsaturated polyester resin, diallyl phthalate resin, or initial condensates thereof. A resin liquid containing the above as main components can be used.

In this case, the object of the present invention can be achieved if the amount of resin attached to the impregnated paper is 30 to 100% in terms of solid content based on the weight of the impregnated paper, but preferably 40 to 80% of the resin attached. Use quantity.

Further, base materials applicable to the present invention include plywood, particle board, flexible board, calcium silicate board, pulp cement, and resin-impregnated laminated core paper.

In the present invention, during heating and pressure molding, there are metal plates such as duralumin plates and stainless steel plates, polypropylene,
A plastic film such as vinylon can be used as the forming plate or film.

Next, we will explain the ultraviolet rays or electron beams that are irradiated onto the surface of the decorative board after heating and pressure forming. First, ultraviolet rays are light in the wavelength range of about 200 nm to 500 nm, which are sourced from low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, etc. is desirable.

Next, an accelerated electron beam is suitable as the electron beam. next,
Examples of ultraviolet sensitizers added to increase the efficiency of ultraviolet irradiation include benzophenone, p-chlorobenzophenone,
Benzophenone derivatives such as p-benzoylbenzoic acid, benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzyl and its derivatives, polynuclear quinones such as 1-chloroanthraquinone, 1,4-naphthoquinone, etc. It is effective when added in an amount of 0.5 to 10% to the thermosetting resin liquid to be impregnated.

Further, as the infrared rays to be irradiated immediately before ultraviolet irradiation, far infrared rays in the wavelength range of about 1 μm to 25 μm are most desirable.

Furthermore, when irradiating ultraviolet rays or electron beams, nitrogen, helium, etc. can be used as an inert gas to block oxygen, and as an air blocking film, for ultraviolet rays,
For transparent and semi-transparent materials such as polyester films and polyethylene films, and for electron beams, VC2Oμ to 100μ other than those listed above.
aluminum foil can be used.

As is clear from the above description, in the method of the present invention, since the pattern formed in the recesses contains a releasable resin and a hardening inhibitor, the thermosetting resin is extremely easy to peel off when the recesses are formed. Therefore, the recess is formed sharply.

Further, since the removable resin in the pattern has been cured, the concave portion where the pattern is exposed is as solid as the cured resin in the convex portion. Furthermore, after peeling off the molded plate or film,
If the next molding is performed without removing the resin attached to the plate or film, it will be integrated with the thermosetting resin,
Since it does not have any effect on the finished decorative laminate and does not need to be removed in each decorative laminate manufacturing process, the decorative laminate can be manufactured extremely efficiently. In addition, by irradiating the surface of the decorative board with ultraviolet rays or electron beams after heating and pressure forming, it is possible to completely harden the surrounding areas of the recesses, which are in an incompletely hardened state. We can manufacture decorative boards.

The decorative board obtained by the method of the present invention is suitable for various uses, and can be used, for example, as decorative boards for building materials, such as doors, wall materials, furniture, kitchens, etc.

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

"Parts" in the following text indicate "parts by weight." Example 180
A wood grain pattern was gravure printed on a Y/M2 titanium paper using a normal gravure ink, and a conduit portion was printed using a gravure printing machine using the following releasable ink.

The printing paper was dried at 120°C for 1 minute, the silicone ink on the conduit part was cured, and the solid content was 80°C with the following resin mixture.
7/d impregnation.

The impregnated liquid is dried at 80° C. for 10 minutes to obtain impregnated paper.

Next, place the impregnated paper on a 3% plywood board with the ink side facing up.
A polished duralumin plate was placed thereon with the mirror surface facing downward, and pressed at 140° C. and 10k9/Cd for 8 minutes. After pressing, the duralumin plate was released from the mold and the resin in the conduit part had poor affinity with the ink layer forming the conduit part, and due to the hardening suppressing effect, the resin in this part was uncured and transferred to the duralumin plate. A sharp and deep tonal embossed decorative board was obtained, and the surface of the decorative board was further irradiated with a low-pressure mercury lamp (manufactured by Toshiba, FL4OBL) for 1 hour to obtain a decorative board that was resistant to scratches.

Example 2 Wood grain pattern on 807/wl titanium paper using regular gravure ink? Gravure printing was performed, and the conduit portion was printed using a gravure stamp using ink having the following peeling range.

The printed paper was dried at 200° C. for 1 minute to harden the ink in the conduit portion, and then impregnated with the following resin mixture at a solid content of 80 t/day.

The impregnated liquid was dried at 80° C. for 10 minutes to form t1 impregnated paper.

Next, layer the impregnated paper on the plywood from step 3 with the ink side facing up,
A polished duralumin plate was placed thereon with the mirror surface facing downward and pressed at 140° C. and 101<g/Cd for 8 minutes. After pressing, the duralumin plate was released from the mold, and the resin in only the conduit part had poor affinity with the conduit part, and due to hardening inhibition, the resin in this part was uncured and transferred to the duralumin plate. After obtaining a sharp and deep tone-embossed decorative board, the surface of the decorative board was irradiated with a high-pressure mercury lamp (manufactured by Toshiba, H2OOOL/6) for 50 seconds to obtain a decorative board with excellent physical properties.

Differences in physical properties were observed before and after UV irradiation as shown in the table below. Example 3 A wood grain pattern was gravure printed on 551/I titanium paper using ordinary gravure ink, and then a conduit portion was printed using a gravure printing machine using the same ink as in Example 1, and then 1
Dry at 20°C for 1 minute to harden the ink on the conduit part, impregnate with the same impregnating resin liquid as in Example 1 at a solid content of 557/I, and dry the impregnated liquid at 80°C for 10 minutes to obtain impregnated paper. And so.

Below, under the same conditions as in Example 1, a vinylon film was used, impregnated paper was placed on a 4% plywood board, heated and pressurized, the vinylon film was released, and the resin on the conduit was transferred to the vinylon film, forming recesses and patterns. After obtaining a completely synchronized Empos decorative board and further irradiating it with far infrared rays (manufactured by Theart, Inc., Infrajet) for 20 seconds, it was continuously exposed to a high-pressure mercury lamp (manufactured by Toshiba, H2OOO).
When L) was irradiated for 30 seconds, a decorative board with very excellent physical properties was obtained.

For comparison, when only a high-pressure mercury lamp was used without irradiating far infrared rays, 60 seconds of irradiation time was required to obtain the same physical properties.

Example 4 A wood grain pattern was gravure printed on 80y/M2 titanium paper using a regular gravure ink, and a conduit portion was printed using a gravure seal with the following ink composition.

(Ink formulation) 15 parts of fluororesin The printing paper was dried at 200°C for 1 minute to cure, impregnated with 967/TI solids with the next resin mixture, and the impregnated liquid was dried at 80°C for 10 minutes. Then, the impregnated paper was stacked on a 3' plywood board with the ink side facing up, and then placed on top of it with the 20% matte side facing down, and heated and pressurized under the same conditions as in Example 1. .

After the pressing was completed, the duralumin board was released from the mold, and a sharp and deep matching embossed decorative board was obtained. Next, an electron beam with an acceleration voltage of 300 was applied in a nitrogen gas stream to a dose of 0.2X.
When irradiated with 106 rad, a decorative board with very excellent physical properties was obtained.

Example 5 A wood grain pattern was gravure printed on 80V/I titanium paper using a regular gravure ink, and a conduit portion was printed using a gravure printing machine using the following releasable ink.

Claims (1)

[Scope of Claims] 1. After providing a pattern on decorative paper with an ink containing a resin that has release properties for the thermosetting resin to be impregnated and a curing inhibitor for the thermosetting resin to be impregnated, The above releasable resin is cured, and then the entire decorative paper including the pattern is impregnated with a thermosetting resin and dried to produce an impregnated paper.Then, the impregnated paper is layered on a base material, and a molded plate is further placed on top of it. After placing the molded plate or film, heat and pressurize to harden the thermosetting resin in the non-picture area, and then adhere the uncured resin on the pattern onto the molded plate or film to form the molded plate or film. A decorative board having recesses is produced by peeling it off, and the surface of the decorative board is further irradiated with ultraviolet rays or electron beams to completely cure the thermosetting resin around the recesses. Improved method for manufacturing decorative laminates. 2. The method for producing a decorative board according to claim 1, wherein ultraviolet rays or electron beams are irradiated in an inert gas stream or with an air-blocking film in close contact with the surface. 3. The method for producing a decorative board according to claim 1 or 2, wherein an ultraviolet sensitizer is added in advance to the thermosetting decorative resin to be impregnated, and ultraviolet rays are used as the irradiation radiation. 4. The decorative board according to claim 1, 2, or 3, further comprising the step of using ultraviolet rays as irradiation radiation, and after peeling off the molded plate or film, irradiating it with infrared rays immediately before irradiation with ultraviolet rays. manufacturing method.