KR810001005B1 - Preparing method of laminated board - Google Patents

Abstract

Decorative boards were made by printing paper with ink containing a silicone resin, a fluororesin, an acrylic-modified varnish, or a melamine resin releasable from poly or a similar thermosetting resin to form patterns, impregnating with the thermosetting resins, overlaying on a substate, covering with a film, hardening the thermosetting resin around the patterns, removing the unhardened thermosetting resin to form hollows and irradiating with UV or electron beam to harden the resin around the hollows.

Description

Manufacturing method of the decorative board

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

6 is a conceptual cross-sectional view for explaining a post-treatment step performed as a preferred embodiment of the present invention.

The present invention relates to a method of manufacturing a decorative plate, and more particularly, to a decorative plate having an uneven shape in synchronism with a picture, and further improving surface properties such as wear resistance and solvent resistance. It relates to a manufacturing method.

2. Description of the Related Art Conventionally, there are two methods, in general, as a method of imparting concavities and convexities on the surface of a thermosetting resin decorative plate.

The first method is a physical method called a direct enbossing method, which uses an enbossed plate in accordance with the design, and gives a concave-convex surface directly to the plate by a flat plate press, or directly by using an enbossed allotment. It is represented by the method of giving an unevenness | corrugation on the surface. However, this method is expensive to produce the enbossed plate and the envelope, and it is difficult to adjust the pattern of the decorative plate and the irregularities of the Evo plate and the enbossed roll, which takes time to manufacture. There was a problem.

The second method is a method generally referred to as a chemical enbossing method. An ink containing a polymerization inhibitor of resin is used to form a pattern on a base paper for resin impregnation, and is different from the curing rate of the impregnated resin on the surface of the decorative plate. (Iii) and use the difference to form an embossed pattern on the surface, or to form a pattern on the base paper for resin impregnation with ink containing a substance having a splashing effect on the resin, and applying or There is a method in which the resin on the ink portion is splashed during impregnation to form an ebose pattern.

These chemical methods are very advantageous in terms of matching the pattern and the enbossed pattern, but in the former case, it takes time to cure the resin, and only the volume shrinkage of the resin is used. It naturally limits the width to form a deep tasteful portion having an arbitrary range, and it is not very effective as a thermosetting resin of heat-pressing molding such as urea resin, melamine resin, and duff resin. On the other hand, although the latter experimented variously, only the frying effect had the problem that sufficient enbossing effect did not appear as resin of a heating and press molding process.

On the other hand, in the above-mentioned chemical method, a plastic film is laminated on a surface on which an ink pattern of impregnated paper is provided, and the resin is cured under heat and pressure, and then the plastic film is removed to attach the resin of the uncured portion to the plastic film. The method of forming a recessed part by removing is also known (Japanese Patent Laid-Open No. 49-121863).

This method is excellent in that the recess is formed corresponding to the design. However, studies by the inventors have found that the following problems still exist in this method.

1) Since the colorant resin of the ink to which the hardening inhibitor is added does not harden or solidify, when the thermosetting resin is impregnated, solvent resistance to the solvent of the impregnation solution is insufficient, and the hardening inhibitor is easy to elute. . Therefore, recesses are less likely to be formed, and even when formed, resin tends to remain in the recesses somewhat, and the sharpness of the recesses is lowered.

2) Since the uncured resin remains somewhat in the main part of the ink drawing, solvent resistance is insufficient. Moreover, when a conventional non-solvent ink is used, not only the uncured resin but also the ink drawing by contact with a solvent It also damages itself.

3) In order to use the difference in the curing rate of the surface resin for forming recesses, the resin around the recess also suffers a decrease in the curing rate and the surface area properties are lowered.

The present invention provides an improvement in the method of forming chemically tuned enbosses including active removal of the above-mentioned uncured resin. That is, according to the researches of the inventors of the present invention, 1) and 2) of the drawbacks of this method include a hardening inhibitor of the impregnating resin in an ankdo, and in order to effectively leach it into the impregnating resin, It is in using good ink. For this reason, although the hardening speed of resin falls effectively, it is thought that the fall of peelability of an ink pattern and an impregnated resin, and the solvent resistance of an ink pattern have arisen at the same time.

On the other hand, the inventors of the present invention use an ink containing a resin having good peelability with an impregnated resin, and further contain a hardening inhibitor of the impregnated resin, print it on a base paper, prepare a picture, and heat it once again. The present invention has been found by hardening or solidifying an ink resin to form a solid drawing surface, and then, by impregnating a surface cosmetic resin, hardening of the impregnated resin can be suppressed. That is, in the present invention, the intention is to form a main part picture having excellent surface characteristics by reinforcing the ink picture and active interface peeling between the picture surface and the uncured impregnated resin. And even if the ink contains a peelable resin with the impregnated resin, when it does not contain a hardening inhibitor of the impregnated resin, or when the ink resin is not solidified before application of the impregnated resin, it is excellent in preferred recesses or surface characteristics. Since the main part cannot be formed, it should be distinguished from such a method. Therefore, in the present invention, the manufacturing method of the decorative plate

1) A process of preparing a picture by using ink containing a colorant resin on a cosmetic paper

2) The process of solidifying the colorant resin in the painting on cosmetic paper

3) Impregnate and dry the thermosetting resin on the whole cosmetic paper including this picture to make impregnated paper.

4) The impregnated paper is laminated on the substrate so that the drawing surface becomes the surface, and then the molded plate or film is superimposed thereon to form a weight body.

5) The weight is attached to the heating and pressing to cure the above-mentioned thermosetting resin, not the drawing portion, and leave the thermosetting resin on the figure in an uncured state.

6) Pressure-reducing under heating, peeling off the formed plate or film, attaching and removing the uncured resin in the above-mentioned picture, and forming recesses in the picture. Has a peelability with respect to the above-mentioned thermosetting resin, and the said ink contains the hardening inhibitor of the said thermosetting resin. It is characterized by the above-mentioned. However, the decorative plate obtained in this way still contains the fall of the surface characteristic resulting from the fault of said 3), ie, the hardening imperfection of the thermosetting resin around the recessed part. According to a preferred aspect of the present invention, this drawback is solved by irradiating ultraviolet rays or electron beams as a back treatment of the decorative plate obtained by the above method, or by heating or heating and pressing again, to obtain a decorative plate having further improved surface properties. Lose.

EMBODIMENT OF THE INVENTION Next, this invention is demonstrated in detail based on drawing.

First, the principle of this invention is demonstrated based on FIGS.

As shown in FIG. 1, after printing using a conventional ink or composition with a cloth pattern, a wood grain pattern, etc. as a base pattern (not shown) on the toilet paper 1, or without applying the base pattern, It contains only a hardening inhibitor for a thermosetting resin impregnated with a colorant resin having a peelability to a thermosetting resin to be impregnated only to a portion where the surface of the coating film such as wood grain or abstract pattern is to be recessed. After preparing the picture (2) with ink, the above-mentioned color resin is cured.

Next, as shown in FIG. 2, the printing paper is impregnated with coating or dipping the thermosetting resin 3, and dried to obtain impregnated toilet paper. In the impregnated toilet paper, not only the thermosetting resin is impregnated in the toilet paper 1, but also the film 3 of the thermosetting resin is formed on the drawing (2) and the back of the toilet paper. Subsequently, as shown in FIG. 3, the impregnated paper is laminated on the substrate 4 with the surface of the figure 2 as a surface, and then, the plated film 5 such as a metal plate or a plastic film is placed thereon, and a conventional means is used. Pressurize by heating.

By this heat-press molding, as shown in the fourth illustration, the thermosetting resin in the parts other than the picture (2) is cured, and remains uncured of the thermosetting resin in the picture (2) part, and the hardened part 6 and the uncured part (3). ) Occurs. It is thought that this is because the hardening inhibitor contained in the figure (2) moves to the upper part of the painting layer, so that the impregnated thermosetting resin at the top of the painting layer is left uncured. Subsequently, when the molded plate to film 5 is peeled off as shown in FIG. 5, the resin of the above-mentioned uncured part 3 adheres and peels. Since the uncured part 3 lacks the affinity with the colorant resin in the figure 2, it does not remain at all on the figure 2, and since it is uncured, the uncured part 3 is removed from the molded plate or the film by thermal pressure. It is in the state that it is easy to attach very much.

In this way, the decorative plate A having the concave-convex shape synchronized with the image 2 is obtained. In the decorative plate A, the image 2 is exposed because the recessed portion does not have a cured layer of thermosetting resin. Since the above-mentioned color resin in the figure (2) is solidified, it is extremely rich in solidity.

Next, the material etc. of each part are demonstrated in detail.

In the present invention, the cosmetic paper 1 is a sheet-like article made of aggregates of microfibers such as cloth and woven fabrics, such as cotton cloth and glass cloth, for what is called normal paper such as titanium paper, foil paper, and kraft paper. This is written arbitrarily. The weight is suitably used in the range of 20 to 500 g / m 2.

As described above, the cosmetic paper is impregnated with the thermosetting resin 3 after the base pattern and the ink pattern 2 of the portion to be concaved are applied as necessary. Examples of the thermosetting resin include polyaryl ester resins such as diallyl phthalate, diallyl maleate and triaryl cyanurate, and radical moiety-polymerization of unsaturated polyesters, that is, thermosetting resins of a type obtained by addition polymerization. Or one or two or more of these initial condensations to polymers: or an addition condensation type such as delta resin, urea resin, acetguinamine resin, benzoguanamine resin, etc. A radical portion weighted polymerization type in which the curing reaction adds about 10 to 40 wt% of the thermosetting resin of the type obtained by repetition of addition and condensation in the resin powder can be suitably used.

The term "unsaturated polyester resin" as used herein means a mixture obtained by dissolving an unsaturated polyester in a reactive monomer having an ethylenically unsaturated bond such as styrene, divinylbenzene, and vinyl acetate. Unsaturated polyesters consist of products obtained by esterifying unsaturated acids such as maleic acid, fumaric acid, itaconic acid, or acid anhydrides thereof with glycols such as ethylene glycol, diethylene glycol, propylene glycol, butanediol .

In addition, the polycondensation type thermosetting resin such as melamine resin, urea resin, acetguanamine resin, veloguanamine resin, or one or two or more kinds of the initial condensate thereof, or the main component thereof, Radical curable thermosetting resins such as aryl ester resins and unsaturated polyester resins, or condensation types obtained by mixing an initial condensate or a polymerized product thereof in a resin content of about 10 to 40 wt% can also be used.

These thermosetting resins are composed of, for example, 20 to 70 wt% of thermosetting resins, and, if necessary, release agents such as lauric acid or colorants such as dyes and pigments, plasticizers, stabilizers, ox, grease, drying agents, It is impregnated into a cosmetic paper as a solution type or emulsion type impregnation liquid which added well-known additives, such as an auxiliary drying agent, a midpoint agent, a dispersing agent, and a filler.

As a filler, by adding 1-6wt% of the above-mentioned non-insoluble inorganic substance powder to the resin or the solvent, the uncured thermosetting resin is easily adhered to the molded plate or the film after the hot press molding. It is recognized and is preferable. This is considered to be because the repulsion force of the uncured thermosetting resin is further lowered by the addition of the inorganic powder. In addition, these inorganic powders are considered to improve the adhesion of the uncured thermosetting resin to the metal plate when the molded plate or the film is a metal plate because of its good affinity.

Inorganic powders added for this purpose include inorganic powders such as metal oxides such as silica, alumina and titanium oxide, metal salts such as calcium carbonate and magnesium carbonate, and metal powders such as aluminum powder and aluminum powder. The thing of -50 micrometers is used suitably.

In this case, as the amount of resin deposited during impregnation, the purpose of the present invention can be obtained if it is 30 to 200% as a solid content with respect to the weight of the cosmetic paper. Preferably, the amount of resin deposited is 70 to 160%. This not only impregnates the cosmetic paper, but also forms a dry film of a thermosetting resin of about 1 to 500 µm on the read picture 2.

Prior to impregnation of the thermosetting resin, as a method of applying a base pattern such as a cloth-patterned wood grain pattern, etc. on the toilet paper, and a pattern of the part to be concave corresponding to the wood conduit, for example, iron plate printing method, opa It can be formed by print drawing or painting by a conventional printing method such as a set printing method, a gravure printing method or a screen printing method, a hand drawing method, or a conventional coating method. have.

As the ink or paint composition for applying the base pattern, a coloring agent such as dye or pigment is added to a known one, for example, an ink or paint colorant, and, for example, a plasticizer, a stabilizer, an ox, a grease, a drying agent, an auxiliary agent. Known additives, such as a desiccant, a hardening | curing agent, a midpoint agent, a dispersing agent, and a filler, can be added arbitrarily, and the ink or coating composition kneaded sufficiently with a solvent, a diluent, etc. can be used.

As the colorant in the ink or paint composition described above, various known fats and oils such as amani oil, soybean oil, synthetic dry oil, natural resins such as rosin copal terminal curing rosin, rosin ester or polymerized rosin, and processed resins , Synthetic resins such as rosin modified phenol resin, 100% phenol resin, maleic acid resin, alkyd resin, petroleum resin, vinyl resin, acrylic resin, polyamide resin, epoxy resin, amino alkyd resin, nitrocellulose, Other argon, casein, dextrin, zein etc. can be used for the rubber induction of fibrin derivatives, such as ethyl cellulose, rubber chloride, and cyclization rubber.

Next, the composition used to prepare the picture (2) formed in the five parts in the above contains 5 to 50 wt% of the colorant resin, 20 to 70 wt% of the solvent, and 3 to 60 wt% of the curing inhibitor of the thermosetting resin. In response, pigments or dyes up to 50wt%, and other additives as described above can be added.

The colorant resin needs to be peelable with respect to the thermosetting resin 3 for impregnation. The term "peelability" here means that the adhesion between the solidified colorant resin and the uncured thermosetting resin is less than the adhesion between the molded plate and the film of the uncured thermosetting resin. do.

Such conditions are, for example, solvent-resistant thermoplastics that do not have solubility in solvents for the impregnated thermosetting resins represented by fluorine resins, such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride, as a colorant resin. It is satisfied with a resin or a thermosetting resin of a different type from the thermosetting resin 3 for impregnation. A suitable example of the latter is a thermosetting resin containing an addition condensation type as a type of condensation of melamine resin, urea resin, silicone resin, waste phenol resin and the like when a radical addition polymerization type is used as the impregnated thermosetting resin.

When the addition condensation type thermosetting resin is used as the impregnating thermosetting resin, addition of thiaryl futarate, unsaturated polyester urethane resin, amine curing epoxy resin, addition polymerization type silicone resin incorporating ethylenically unsaturated group, etc. It is a polymerization thermosetting resin. Together with these resins, those modified with cellulose, alcohol, alkyd and the like are partially contained, for example, 5 to 30 wt% in the colorant resin, or thermoplastic such as cellulose, acrylic resin, polyvinyl chloride, or the like. By mixing 10 to 60 wt% of the resin, it is possible to reduce the printability of the ink and the solidification condition of the colorant resin after the ink is applied, without reducing the performance of the ink coating, for example, to shorten the time and to lower the temperature. Is obtained.

-프로피오락톤,

-브티로락톤 등의 락톤류 : 디메틸아세트 아미드 등의 아미드류 등의 1종 또는 2종 이상의 혼합물이 쓰여진다. 또, 물로 분산매로써 쓰여질 수 있다. 그리고, 이들 용매 내지 분산매는 상기한 함침수지액의 작성에도 쓰여진다.Examples of the solvent or dispersion medium in the ink include aromatic hydrocarbons such as toluene and xylene, aliphatic alcohols such as isopropyl alcohol, ethyl alcohol, and methyl alcohol; esters such as ethyl acetate and butyl acetate: acetone, methyl ethyl ketone, and methyl isofu. Ketones, such as a ryl ketone, are ethers, such as ethylene glycol monomethyl ether, dioxane, tetrahydrofran, etc .:

Propiolactone,

-Lactones, such as butyrolactone: 1 type, or 2 or more types of mixtures, such as amides, such as a dimethylacetamide, are used. It can also be used as a dispersion medium with water. These solvents and dispersion mediums are also used for the preparation of the impregnated resin solution.

As a hardening inhibitor contained in ink, when the thermosetting resin for impregnation of a radical addition polymerization type is used, arbitrary things which suppress radical addition polymerization are used. For example, kinones such as p-benzokinone and naphthinone: hydrokinones such as hydrokinone, metokinone, methylhydrokinone, and pt-butylcatechol: zittaerythybutylparacresol, hydrokinone monomethyl ether, etc. Phenols: Organic and inorganic copper salts, such as copper naphthenic acid: Hydrazine salts, such as phenyl hydrazine hydrochloride: Quaternary ammonium salts, such as a trimethylbenzyl ammonium chloride, etc., These can be used individually or in mixture.

As the hardening inhibitor in the case of using an addition condensation type as a thermosetting resin for impregnation, 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, can be used. These can be added directly to the ink, or microencapsulated by a thermoplastic resin that can be softened to a temperature of 100 to 200 ° C at the time of heating and pressing. Moreover, although the said strong basic substance can also be used independently, by using together the foaming agent foamed at the time of heat pressurization, hardening can be suppressed more effectively. As the blowing agent, one or two or more kinds of sodium hydrogencarbonate, sodium borohydride, azobisisobutyronitrile, benzenesulfonyl hydrazide, and P-toluenesulfonyl hydrazide are 10 to 50 wt% based on the curing inhibitor. I can use it.

These hardening inhibitors are used in an amount of 3 to 60 wt%, particularly preferably 5 to 40 wt%, in the ink composition. If it is less than 3wt%, the effect of hardening inhibition is insufficient for the impregnated thermosetting resin, and thus the cohesive force between the portion affected by the inhibitor between the thermosetting resins and the unaffected portion is large. It is because it is impossible to obtain an uneven shape only by the force attached to the resin. If the amount is more than 60wt%, it affects the hardening action of the color resin, the hardness of the ink coating is weakened, and the peeling with the thermosetting resin deteriorates.

As pigments or dyes in the ink composition, organic dyes or pigments such as conventional ones such as azo, phthalocyanine, kinagridon, anthraquinone, dioxyine, aniline black, etc .: titanium oxide, cadmium iron, Inorganic pigments such as chromium oxide: and one or two or more kinds such as carbon black and aluminum powder are used, but they may not be used at all.

The picture 2 by this ink composition is provided on the cosmetic paper 1 as described above, and the colorant resin is solidified. The solidification includes curing in thermosetting resins and hot pressing of solvent-resistant thermoplastic resins, and is distinguished from film formation due to penetration and drying in ordinary printing inks. The conditions vary greatly depending on the resin. For example, in a condensation type thermosetting resin, 100 to 200 ° C., 10 seconds to 10 minutes: In an addition polymerization type thermosetting resin, room temperature 200 ° C., 5 seconds to 15 minutes. In the forming thermoplastic resin, conditions such as 150 to 300 ° C., 30 seconds ° to 30 minutes ° is foreseen. Since the curing or hot pressing conditions of these resins are well known for the respective resins, they will not need to be described in detail. In any case, at this stage, forming a firm solidified film by curing or hot pressing is a surface property such as peelability with the thermosetting resin for impregnation of the colorant resin and solvent resistance of the final decorative plate. It is necessary to keep it good. The ink deposition amount is preferably in the range of 2 to 200 mu m in thickness at drying.

In this way, the impregnated paper obtained by impregnating the thermosetting resin 3 while providing the drawing (2) is superimposed on the interposition (4) as shown in FIG. ), And it changes drastically in correspondence with the selected thermosetting resin, but since this uses only well-known conditions for each resin, it will not need to be explained newly. Generally speaking, the temperature is 100-200 ° C., the pressure is 5-150 kg / cm 2, and the time is 3-60 minutes.

As the base material 4, plywood, a perforated board, a flexible board, a calcium silicate plate, a pulp secent, and the like are used, and a resin-impregnated laminated core paper may be mentioned.

As the molded plate or the film 5, a plate, sheet, film made of metal such as duralamine, stainless steel, plastic such as polypropylene, vinylon, or any other material that withstands the heating and pressing conditions required for curing the thermosetting resin Etc. are written. The molded plate or the film needs to have a larger adhesion order to the uncured thermosetting resin than the colorant resin of the ink drawing (2), and must be peeled off from the cured thermosetting resin. Although the contact surface with the thermosetting resin 3 of the molded board thru | or film 5 can have not only a flat surface but a surface shape, the shape should be a range which does not impair this peelability.

Subsequently, as shown in FIG. 5, when the pressure is released as a heated human body and the molded plate or the film 5 is peeled off, the uncured portion 3 of the thermosetting resin corresponding to the figure 2 is shown in FIG. The peelability with the colorant resin is also matched with each other, and adhered to the molded plate or the film, leaving the recessed parts synchronized with the picture (2).

Alternatively, after heating and pressing, the structure shown in FIG. 4 may be cooled once after being heated and pressurized. In this cooling state, since the uncured resin portion 3 does not have adhesiveness, the uncured resin portion 3 does not adhere to the molded plate or the film even after peeling, but is heated and pressed again under conditions of 100 to 200 ° and 5 to 50 kg / cm 2. By pressure-release in a pressurized state and peeling a molded plate or a film, the uncured part 3 adheres and removes a molded plate or a film, and can form the recessed part as mentioned above. By this method, it is possible to prevent the adhesion between the substrate 4 and the toilet paper 1 due to swelling and flipping of the substrate, which can occur when the molded plate or film is peeled off immediately after heating and pressing. Can be.

As described above, the decorative plate A of FIG. 5 is exposed as shown in Fig. 2, but since the colorant resin is sufficiently assimilated, it is hard to say as far as the rigidity of this part is concerned.

However, in a more microscopic view, the movement of the hardening inhibitor contained in the picture (2) is not only the top of the picture layer, but also similarly diffuses in the thermosetting resin around the picture (2). In the resin, there is a high concentration of resin, while in the thermosetting resin far from the figure (2), there is a low concentration of hardening inhibitor. After heating and pressure molding, as shown in (7) in Fig. 7, the thermosetting resin around the recess is a different part. Compared to the incomplete curing state, as described above, there is a case where it is unsuitable as a decorative plate which requires high physical properties. For this reason, according to a preferred embodiment of the present invention, in the case of the radical portion weighted polymerization type, the impregnated thermosetting resin ((3) or (7)), as shown in the sixth illustration, the surface of the toilet paper (UV) or electron beam ( 8) and if the impregnated thermosetting resin ((3) or (7)) is a subcondensation type, re-heating or re-heating the decorative plate to produce an improved decorative plate B of completely cured surface properties. will be.

In the case where the impregnated thermosetting resin is a radically weighted polymerization type, the principle of completely curing the thermosetting resin of incomplete curing by irradiating ultraviolet rays or electron beams is a curing inhibitor, so that the polymer stabilized at low molecular weight is stabilized by ultraviolet rays or electron beams. It is thought that the bond is cleaved and radicals are generated so that it is high molecular weight and completely cured. For this reason, in ultraviolet irradiation, it can harden completely in a short time by adding to the substance which radicals generate | occur | produce by light, ie, the thermosetting resin liquid impregnated with an ultraviolet sensitizer in advance.

As the ultraviolet ray, light having a wavelength range of about 200 nm to 500 nm using a low pressure water lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, or the like as a light source is preferable. Moreover, as an electron beam, it is suitable to give the irradiation dose of 0.05-10 Mrad by the acceleration electron beam which has the output of acceleration voltage 300-600kv and about 25-100mA.

Next, as ultraviolet sensitizers added to increase the irradiation efficiency of ultraviolet rays, benzophenone derivatives such as benzophenol, P-chlorobenzophenol and P-benzoyl benzoic acid, benzoin, benzoin methyl ether and benzoin ethyl ether , Benzoin derivatives such as benzoin butyl ether, benzyl and derivatives thereof, and multinucleated kynones such as 1-chloroanthraquinone and 1,4-naphthynone, and the like can be used. It is effective by adding 0.5-10% with respect to.

In addition, although the details of the reactor mechanism are unknown, it is effective to heat the irradiation surface at 50 to 100 ° C. immediately before irradiating ultraviolet rays, and the irradiation time of ultraviolet rays can be shortened. An example of the heating means is irradiation of infrared rays, and surface infrared rays having a wavelength range of about 1 to 25 µm are most preferred.

Furthermore, in the case of irradiating ultraviolet rays or electron beams, the surface of the makeup plate is placed in an inert gas stream atmosphere such as nitrogen or helium, or in transparent or translucent bodies such as polyester films and polyethylene films, or electron beams. Irradiation time of an ultraviolet-ray or an electron beam can be shortened by making an air shielding film, such as an aluminum foil of -100 micrometers, close to a irradiation surface. It is considered that this is a guarantee that radicals generated by ultraviolet rays or electron beams are consumed by oxygen in the air.

When the thermosetting resin to be impregnated is an addition condensation type, the condensation and crosslinking reactions are further advanced by reheating and completely cured. As the reheating means, a conventional hot air heater, a surface infrared ray having a wavelength range of about 1 to 25 μm, and a thermoforming press for molding can be used, and can be completely cured at 130 to 200 ° C. for 5 to 30 minutes. It is more preferable to heat and pressurize again in the shell of 130-200 degreeC, 20 kg / cm <2> -100kg / cm <2>, 3 minutes-20 minutes using the thermoforming press for shaping | molding.

As is clear from the above description, according to the manufacturing method of the decorative plate of the present invention, in order to obtain a decorative plate having a concave-shaped part that is equal to the figure on the toilet paper, the following effects are obtained, for example.

1) The ink drawing formed in the recessed part contains a peelable colorant resin with respect to the hardening inhibitor and the thermosetting resin, and after the solidification, the thermosetting resin shown in the figure is hard to harden and very easily peeled off to impregnate the thermosetting resin. . Thus, a sharp recess is formed in synchronization with the picture.

2) Since the colorant resin in the painting is solvent-resistant and solidifies, the painting is as strong as exposed parts and iron parts.

3) After peeling off the forming plate or film, the resin attached to it is integrated with the thermosetting resin even if the following molding is performed without removing it, and has no effect on the resultant cosmetic plate. Therefore, since it is not necessary to remove a resin in every one manufacturing board manufacturing process, a makeup board can be manufactured very efficiently.

4) In addition, by irradiating ultraviolet or electron beams on the surface of the decorative plate after heating and pressing, or by reheating or reheating, the periphery of the recessed portion can be completely cured. The makeup plate which has can be manufactured.

And the decorative board obtained by the method of this invention is suitable for various uses, For example, it can be used for a door, a wall, a furniture, a musical instrument, a square relationship, etc. as building cosmetic boards.

Next, an Example is given and this invention is demonstrated further more concretely. (Parts) and% in the following sentence are based on weight.

Example 1

Gravure printing was performed on a 80 g / m 2 titanium paper as a conventional gravure ink, and a conduit portion was printed by a gravure printing machine as the ink having the following peelability.

The printing paper was heat-treated at 120 ° C. for 1 minute, and the silicone ink of the conduit portion was cured, and then impregnated with 80 g / m 2 as a solid content in the following resin mixture.

The impregnated impregnation solution is dried at 80 ° C. for 10 minutes, and impregnated paper. Next, this impregnated paper was laminated on the plywood of 3 m / m with the ink surface up, and the mirror surface of the turalamine plate polished thereon was placed so as to have a lower surface and pressed at 140 ° C. and 10 kg / cm 2 for 8 minutes.

After the press type, the duralumin plate is released and the resin of only the conduit is deficient in affinity with the ink layer which formed the conduit portion, and the resin of this part is uncured by the hardening inhibitory effect, so it is transferred to the durumin plate. To obtain a sharp, deep and deep synchronization enbossed cosmetics. The surface of this decorative plate was further irradiated for 20 seconds at an output distance of 10 W with an output 80 W / cm × 75 m high pressure water m silver lamp (manufactured by Nihon Denji Co., Ltd., HI-6A) for 20 seconds to obtain a decorative plate that was not more injured.

Example 2

Gravure printing was performed using a conventional gravure ink on a 80 g / cm 2 titanium paper, and the conduit portion was printed by a gravure printing machine having the following peelability.

The printing paper was heat-treated at 200 ° C. for 1 minute, and the ink in the conduit portion was cured, and 80 g / m 2 was impregnated into the solid content with the following resin mixture.

The impregnated impregnation liquid is dried at 80 ° C. for 10 minutes, and impregnated paper. Next, the impregnated paper was stacked on the 3m / m plywood with the ink surface upward, and the mirror surface of the duralumin plate polished thereon was placed on the lower surface and pressed at 140 ° C. and 10 kg / cm 2 for 8 minutes.

After the end of the press, the duralumin plate is released and the resin of only the conduit portion is deficient in affinity with the conduit portion, and the resin of this portion is uncured by the hardening inhibitory effect, so that it transfers to the duralumin plate and is sharp and deep. I got Dongjo Enbos makeup board. The surface of this decorative plate was further irradiated with 30 w / cm × 700 mm high-pressure mercury lamp (H20000L, manufactured by Toshiba Corporation) at a irradiation distance of 115 cm for 50 seconds to obtain a superior decorative plate. Before and after irradiation with ultraviolet rays, the physical properties showed a difference.

week)

^* 1) A few drops of the solvents described in the above table on the surface of the makeup plate are covered with a small container, and the surface state after the volatilization of the solvent is visually determined for the presence or absence of staining. As a result, all of the ink part was sound, but the periphery of the ink part was in the following state.

○: no stain at all.

(Triangle | delta): A stain may remain slightly.

×: stain remains.

로 구한 마모량. ^* 2) NEMA No. According to LP2-1963, part 6 Hard Bard core Type Decorative Laminates, a test wear ring using a taber abraser was used with CS 17, and the load was 500 g. Wear value represents the number of revolutions (average of three times) when the gram is half disappeared in area, and the Rate of wear per 100 cycles is based on the wear value described above.

The amount of wear found by.

^* 3) The degree of scratches when the surface of the plate is pressed with the fingernails of the hand.

(Circle): It does not hurt at all.

(Triangle | delta): Although a wound was made, it was not easy to see visually.

Example 3

Gravure printing the wood grain pattern with a conventional gravure ink on 55 g / m 2 titanium paper, and then printing the conduit portion by gravure printing using the same ink as in Example 1, and then heat treating at 120 ° C. for 1 minute. The ink was cured, impregnated with 55g / m 2 as a solid content by the same impregnated resin solution as in Example 1, and the impregnated liquid was impregnated by drying at 80 ° C. for 10 minutes.

Hereinafter, the same conditions as in Example 1 were used to place an impregnated paper on a 4 m / m plywood using an ace vinylon film, and to heat and pressurize and release the vinylon film. The resin in the conduit was transferred to the vinylon film, and the yen and the pattern were completely synchronized. Got a Boss Vanity Board. After irradiating 10W / cm of area ultraviolet ray (incorporated by Zaad, Infrajet) for 20 seconds at a irradiation distance of 20 seconds, 30W / cm × 700mm high pressure mercury lamp (H200L, manufactured by Toshiba Corporation) was continuously irradiated for 30 seconds at a irradiation distance of 15cm. As a result, a decorative plate having very excellent physical properties was obtained.

For comparison, irradiated with a high-pressure mercury lamp without irradiating far infrared rays, it required 60 seconds of irradiation period to obtain the same physical properties.

Example 4

Gravure printing was performed on the 80 g / m 2 titanium paper as a conventional gravure ink, and the conduit portion was printed by a gravure printing machine with the following ink formulation.

The printing paper was dried at 200 ° C. for 1 minute to cure, and then impregnated 96 g / m 2 as a solid with the following resin mixture.

The impregnated impregnation liquid was dried at 80 ° C. for 10 minutes, and the impregnated paper was placed on a 3 m / m plywood with the ink side up, and the 20% of the surface was then placed so that the surface of the color was lower than the same as in Example 1 It was heated and pressurized under conditions.

After the end of the press, the duralumin plate was demolished to obtain a sharp and deep tuning enbossed plate.

Subsequently, an irradiation of an electron beam having an acceleration voltage of 300 KV in a nitrogen gas stream of 0.2 x 10 ⁶ rad was irradiated, resulting in a very good decorative plate.

Example 5

The gravure ink was gravure-printed as a typical gravure ink on 80 g / m 2 titanium paper, and the conduit portion was printed by a gravure printing machine with an ink having the following peelability.

The printing paper was dried for 1 minute at 150 ° C., the ink of the conduit portion was cured, and 50 g / m 2 was impregnated into the solid content with the following resin mixture.

The impregnated impregnation liquid is dried at 80 ° C. for 10 minutes, and impregnated paper. Next, this impregnated paper was superimposed on a plywood of 3 m / m, and the polypropylene film was placed thereon and pressed at 140 ° C. and 10 kg / cm 2 for 8 minutes.

When the polypropylene film is released after the press is finished, the resin of the conduit portion lacks affinity with the conduit portion, and the resin of this portion is uncured for the hardening inhibitory effect. A sharp and deep tunable Enbos board was obtained.

Next, the surface of this decorative plate was irradiated with an electron beam having an acceleration voltage of 50 KV at a dose of 1.0 × 10 ⁶ rad. A decorative plate was obtained that passed the test according to LP 2-1961 Part 6, Herd Board core-Type Decoration Laminates.

Example 6

After printing in the same manner as in Example 1, the heat treatment was performed just as well, and the silicone ink of the conduit portion was cured, and 80 g / m 2 was impregnated into solid content with the following resin mixture.

The impregnated impregnation liquid is dried at 80 ° C. for 10 minutes, and impregnated paper. Next, it shape | molded on the conditions similar to Example 1. After the press was finished, the duralumin plate was released, and thus an uncured duff-based resin on the conduit ink portion adhered to the duralumin plate, and a decorative plate having a very stable and sharp enboss was obtained. Since the fine silica powder was added to the impregnated resin solution, the cohesive force of the uncured duff resin was lowered, and the adhesive force between the fine silica powder and the duralumin plate acted, and the uncured duff resin was considered to adhere to the duralumin plate.

Example 7

After printing and impregnation were carried out just as in Example 1, heating and pressing were carried out again under the same conditions. Thereafter, the press was cooled to room temperature by water cooling without pressure release, and then pressure-reduced, and when the duralumin plate was transferred, the resin did not adhere at all.

The decorative plate was piled up again with the duralumin plate, and pressed at 140 ° C. and 5 kg / cm 2 for 2 minutes, and the resin was attached to the duralumin plate as in Example 1 as it was pressurized under heating.

Comparative Example 1

Gravure printing was performed on the 80 kg / cm 2 titanium paper as a conventional gravure ink, and the conduit portion was printed by a gravure printing machine with ink which removed only hydrokinone from the ink of Example 1.

Using this printing paper, heat treatment impregnation and molding were performed as in Example 1. As a result of releasing the duralumin plate after the end of the press, no resin was adhered to the duralumin plate at all, and only a normal duff cosmetic without enbossing was obtained.

It is considered that this is because only the peelable resin can be expected to reduce the cohesion of the duff resin only by adhering to the duralumin plate.

Comparative Example 2

Gravure printing of wood grains as a typical gravure ink on 80 kg / cm 2 titanium, and printing of the conduit portion by a gravure printing machine with ink obtained by replacing 13 parts of cellulose acetate with silicone resin and naphthenic cobalt in the ink of Example 1 Performed, dried at 80 ° C. for 5 seconds.

This printing paper was impregnated with the same resin solution as in Example 1 under the same conditions, and molded under the same conditions. After the press was finished, the duralumin plate was transferred, and the uncured resin to be removed was not completely peeled off, but only a part of the duralumin plate was attached to the duralumin plate, thereby obtaining an enbossed makeup plate having a recessed portion having a shallow stain.

The following are estimated as this cause.

1. Since the ink was not heat-treated, a film having solvent resistance was not formed and the amount of hydrokinone in the ink was decreased because hydrokinone was eluted in the duff resin liquid during the duff resin impregnation.

2. The cellulose-based resin film has a high adhesive strength with the uncured duff resin because the peelability to the duff resin is reduced. Because of this, it was thought that the uncured duff resin was difficult to attach to the duralumin plate.

In addition, the solvent resistance test was carried out using methyl ethyl ketone as in Example 2 described above. In addition to dissolving the resin in the ink periphery area to form a stain, the ink itself was completely dissolved, and the picture was turned off.

Comparative Example 3

As in Example 1, a titanium paper was printed with the same ink, a toilet paper was prepared, and the same resin was immediately impregnated as in Example 1 without hot treatment, and thermoforming was performed under the same conditions. As a result of releasing the duralumin plate after the end of the press, the adhesion amount of the resin to the duralumin plate was small, and no sharp recesses were obtained.

When methyl ethyl ketone like Example 2 was dripped on the surface of the above-mentioned decorative plate, not only the ink peripheral part but the conduit part ink of the recessed part was melt | dissolved completely, and the picture turned off. There are two reasons why a sharp point was not obtained.

(1) Since the ink was not heat-treated, the hydrokinone dissolved in the solution after the impregnation at the time of resin impregnation, so that the hardening inhibitor dissolved and diffused.

(2) Since the ink was not heat-treated, the peelability of the colorant resin of the ink was deteriorating.

The reason why the solvent resistance was poor was that the ink was not heat-treated, so that the resin was diluted or eluted as a solvent at the time of the next impregnation, and a solidified film having sufficient solvent resistance was not formed even under the subsequent hot press molding conditions. It is thought to be.

Claims (1)

As shown in the drawings and described in the main text, one step of preparing a picture by using ink containing a full color resin on the paper, a second step of solidifying the color resin on the paper, and the entire cosmetic surface including the picture. 3 steps of impregnating and drying the thermosetting resin into the uncured thermosetting resin film to produce the impregnated paper formed on the picture, and impregnating the paper on the drawing surface so that the surface is formed on the substrate. Four steps of forming the weight body by overlapping, attaching the weight body to heating and pressurization, curing the thermosetting resin instead of the part of the picture, leaving five parts of the thermosetting resin in the uncured state, pressure-reducing under pressure and forming Each process includes six steps of removing the plate or film, attaching and removing the uncured resin on the picture, and forming recesses on the picture. The manufacturing method of the makeup plate characterized by having peelability with respect to a thermosetting resin which loses, and an ink containing the hardening inhibitor of a thermosetting resin.

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