JPS59158283A - Manufacture of decorated body - Google Patents

Abstract

PURPOSE:To obtain a decorated plate with a deep and beautiful pattern by applying a liquid-like radically hardening type resin on a polymer emulsion in the manufacture of a decorated body, thereby the working efficiency of painting is improved. CONSTITUTION:A polymer emulsion containing an organic peroxide is applied on the surface of a base material to form a film and after a water is scattered from the film, a liquid-like radically hardening type resin containing a promoter is applied thereon. The liquid-like radically hardening type resin is covered with a printing film while remaining unhardened in a liquid or sticky condition and a pattern of the printed film is transferred onto the surface of a hardened resin as the resin is being hardened. Then, a top coat is applied thereon after the removal of the film.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention mainly relates to a base material having hydrophilic or water absorbing properties,
The present invention relates to a method for producing a cosmetic body with a deep and beautiful pattern.

Taking plywood as an example, many attempts have been made to improve the appearance using plywood as a base material, and these can be broadly classified as follows.

(a) A method in which printing paper is adhered to a substrate using an adhesive, and then coated with an unsaturated polyester resin containing a curing catalyst and accelerator. There are flow coater method, film method, etc.

(b) A method of sealing plywood using some method, such as coloring with unsaturated polyester resin, applying an intermediate coating, and finishing with lacquer.

(c) Method of printing directly on plywood.

2) Those that are simply pasted with decorative paper or decorative film on plywood.

(e) Melamine resin decorative board or diallyl phthalate resin decorative board adhered to plywood.

(f) For plywood, the boards are glued together and then painted.

No matter which method is used above, after gluing the board,
Regardless of the method of painting, it is difficult to bring out the flavor of natural wood, and its appearance lacks depth.

If it is a wood grain pattern, it may not require that much depth, but even if it adds even a little depth to the appearance, it will give a significantly more luxurious feel. This is evident from the superior appearance of the products.

Furthermore, in cases where transparency is required, such as marble disease, the method of painting on printed paper-covered plywood, which is the mainstream method for conventional cosmetics, lacks depth and inevitably gives the impression of being cheap.

Furthermore, in all conventional painting methods, the sealing effect is not sufficient, so the unevenness of the base material is directly reflected in the appearance, which is a major problem in that it significantly impairs the aesthetic appearance. For example, most of the plywood used in Japan is made of lauan wood, and as is well known, the surface of this plywood is deeply engraved with unevenness caused by conduits.

For this reason, sealing work is troublesome, and so-called unsaturated polyester decorative plywood, which is made by adhering decorative paper and painting with unsaturated polyester resin, does not eliminate surface irregularities at all and does not have a good appearance.

Sealing when the base is extremely uneven ultimately comes down to how much filler can be mixed with the resin.

In general, unsaturated polyester resins can be made to have a low viscosity of about 1 to 2 voids, but the amount of filler mixed in is based on 100 parts by weight of the resin, and calcium carbonate, which has the least amount of resin absorption, is used. Even so, mixing 150 parts by weight is the limit for painting work.

Furthermore, when using room-temperature curing resins that have a limited pot life, coating methods that are suitable for high-viscosity paints such as roll coating cannot be used, so in the end, manual labor is required.
Alternatively, the method must be paper-covered or hot-pressed, but problems remain in terms of method and efficiency.

Moreover, with this amount of filler mixed in, it is difficult to achieve a satisfactory sealing effect, and even if the resin is coated two or more times, the unevenness of the base cannot be erased due to shrinkage of the resin.

The present inventors have conducted various studies on methods for obtaining a beautiful cosmetic body using inorganic or organic base materials while eliminating the above-mentioned drawbacks, and have discovered that the purpose can be achieved by the following steps, and have developed the present invention. It was completed.

That is, the present invention provides the following methods: (1) coating a polymer emulsion containing an organic peroxide on the surface of a substrate; (2) then containing thereon an accelerator capable of radicalizing the organic peroxide; (3) The liquid radical curing resin is liquid or sticky (4)
The pattern on the printed film surface is transferred to the cured resin surface at the same time as the resin is cured, (5) after the film is removed, (6) a transparent or translucent paint is further applied to the transfer surface. The present invention relates to a method for manufacturing a cosmetic body.

Conventionally, it is well known that a base material is coated using a nitrocellulose lacquer or the like in combination with an organic peroxide, and after the lacquer's solvent has evaporated, an unsaturated polyester resin containing an accelerator is coated on top and cured. be.

However, this method is difficult to use because the curing of the unsaturated polyester resin for the top coat is slow, and when a large amount of filler is mixed in, the volatilization of the solvent is suppressed, resulting in a significant tendency to impair the adhesion of the coating film. - It is not possible to mix fillers with Z-lacquer, so no sealing effect can be expected.In addition to the fact that the lacquer itself contains a large amount of solvent, the viscosity must be controlled by adding solvent, which creates a poor coating environment. This is a decisive difference from the case of using an emulsion.

The advantages of the method of the present invention can be summarized as follows.

(a) Since the polymer emulsion can be diluted with water, there is no environmental pollution, unlike conventional methods that use organic solvents.

(b) Since the liquid radical curing resin used for painting contains only an accelerator, there is no limit to the curing time.
Since it is possible to perform coating methods that could not be used with conventionally used resins containing catalysts and accelerators, such as roll coating, it is possible to greatly improve coating efficiency.

(c) The liquid radical-curing resin has a practical topcoat curing speed, and it is easy to transfer a pattern.

2) Polymer emulsions can contain a large amount of filler, so they have a great sealing effect even if the base material is uneven.

(e) Since the polymer in the emulsion is dissolved in the liquid radical-curing resin and cured in the form of a mixture of polymer and resin, a cosmetic body with excellent adhesion between the cured film and the base material can be obtained.

As the base material used in the present invention, both organic and inorganic materials can be used, and the shape thereof is arbitrary. Examples of organic base materials include wood-based materials such as plywood, hardboard, and particle board.
Examples of the inorganic base material include calcium silicate board, slate, wood wool cement board, and gypsum board.

The polymer constituting the polymer emulsion used in the present invention must be of a type that dissolves in components contained in the liquid radical-curing resin to be applied next, such as styrene. Otherwise, the liquid radical curable resin containing the accelerator will not be cured, or even if it is cured, the resulting cured coating will be extremely weak, making it impractical.

Examples of such emulsions include polyvinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, vinyl acetate-acrylic acid ester copolymer emulsion, copolymer emulsion of acrylic acid esters and methacrylic acid esters, and acrylic acid ester. and styrene copolymer emulsions, polyacrylic acid ester emulsions, and types containing small amounts of third and fourth monomer components in the above emulsions.

These polymer emulsions may be used in combination with water-soluble resins commonly found in paints and the like, if necessary. Polymer emulsions are generally produced by emulsion polymerization of monomers, but may also be obtained by post-emulsifying a polymer solution.

The organic peroxide used in combination with the BoIJ-q-emulsion must not destroy the emulsion, but this can be prevented by selecting the composition of the emulsion and appropriately selecting the type of organic peroxide.

To redox polymerize liquid radical curing resin,
Ketone peroxides, hydroperoxides,
is suitable. Typical examples of these include methyl ethyl ketone peroxide and cumene hydroperoxide. The amount of organic peroxide added is 0.1 to 20 parts by weight per 100 parts by weight of the polymer constituting the emulsion.
Parts by weight, more preferably 3 to 10 parts by weight.

The organic peroxide may be stirred and added to the polymer emulsion as it is, or may be dissolved or dispersed in an organic solvent or plasticizer and added as long as it does not destroy the polymer emulsion.

Polymer emulsions contain, for example, calcium carbonate, clay, hydrated alumina,
Fillers such as fine silica powder, talc, etc. may be added. The blending amount of the filler has a significant potency-preventing effect.

Moreover, since water is the dispersed phase of the polymer emulsion, it has good permeability into the interior of wood-based or inorganic base materials, and even when a top coat is applied, air bubbles do not remain and impair commercial value.

The following two types of liquid radical curable resins are used in the present invention.

(1) Unsaturated polyester resin containing α,β-unsaturated polybasic acid as one component, which is obtained by esterifying with polyhydric alcohol with or without any polybasic acid A 100% reactive resin obtained by dissolving alkyd in a copolymerizable monomer.

(2) An oligoacrylate containing one acryloyl group or methacryloyl group in one molecule of unsaturated acrylate resin, and curing is achieved by polymerization of the acrylate group. This unsaturated acrylate resin is divided into the following types.

(a) Epoxy-acrylate (vinyl ester resin) Obtained by the reaction between the epoxy group of an epoxy resin and the carboxyl group of acrylic acid or methacrylic acid. Substantially no epoxy groups remain. It is generally used in the form of a monomer solution.

(b) It is obtained by reacting a urethane-acrylate polyhydroxyl compound or an oligomer (generally a polyol, polyether, or polyester) with a diisocyanate and an unsaturated alcohol containing an acryloyl group or a methacryloyl group.

The unsaturated bonds are bonded to the oligomer via urethane bonds. The simplest form is an unsaturated alcohol reacted with a diisocyanate. The reaction product is
Since it generally has a high viscosity, it is almost always used in combination with a monomer.

(c) Polyester-Acrylate Obtained by directly esterifying acrylic acid or methacrylic acid with a polyhydric alcohol or polybasic acid, and has a crosslinking point at the end of the polyester molecule. Various polyester-acrylates of low to high viscosity are obtained.

) Spiroacetal-acrylate It is a spiroacetal compound that contains a spiroacetal structure in its constituent molecules and behaves just like incyanate of urethane-acrylate. Generally, diarylidene pentaerythritol is used as a linking agent between a hydroxy compound and an unsaturated alcohol. The product has a low viscosity and can be used with or without monomers.

Of course, the above (1) and (2) can be used in any desired mixture. Further, fillers such as those described above may be optionally mixed.

The accelerator that is used in conjunction with liquid radical-curing resin to radicalize the organic peroxide contained in the polymer emulsion through a redox reaction to accelerate the hardening of the resin is the organic peroxide contained in the polymer emulsion. It is preferable to select it appropriately depending on the type.

For example, when the polymer emulsion contains a ketone peroxide, an organic acid salt of cobalt is used as the promoter, and when the polymer emulsion contains a hydroperoxide, a vanadium chelate is used as the promoter.When the polymer emulsion contains an acyl peroxide, the promoter is a vanadium chelate. It is preferable to use an aromatic tertiary amine as a promoter in each case.

The accelerator is added to the liquid radical curable resin, and the amount added is determined in relation to the organic peroxide contained in the polymer emulsion, but generally it is 0.01 parts by weight per 100 parts by weight of the liquid radical curable resin. -10 parts by weight, preferably 01-5 parts by weight.

The liquid radical curable resin containing an accelerator is preferably applied at a stage where a polymer emulsion containing an organic peroxide is applied to a base material to form a coating film, and then water is dispersed from the coating film.

The printing film used in the present invention can be used as long as the ink used has adhesive properties with the resin, has more affinity with the cured resin than the film, and can transfer the pattern from the film surface to the cured resin surface. But that's fine.

The type of vehicle resin constituting the printing ink is not particularly limited, but if a component copolymerizable with the liquid radical curable resin is added, the adhesion between the liquid radical curable resin and the printing ink layer will be significantly improved. This is advantageous because the peeling resistance is further improved.

Any plastic film can be used as the film, preferably polyethylene terephthalate film.

Various conventionally known methods can be used for printing on the film, but in the present invention, it is sufficient to directly print a pattern using gravure printing or offset printing. The printing film is adhered so that the pattern side is in contact with the resin at an uncured stage when the liquid radical curable resin is liquid or sticky, and is peeled off after the resin is cured.

In the present invention, it is necessary to further coat the patterned cured resin surface with a transparent or translucent paint. The paint for this purpose is selected in consideration of the purpose of use, cost, physical properties, etc. Generally unsaturated polyester resins are used, but polyurethane lacquers can also be used. In particular, when hardness is required, a photocurable spiroacetal acrylate resin is used. Furthermore, when high physical properties are not required, acrylic lacquer is used.

When applying a polymer emulsion, liquid radical curing resin, or paint, any part of the resin can be colored as desired.

In order to produce the cosmetic body of the present invention, a polymer emulsion containing an organic peroxide is applied to the surface of a base material to form a coating film, and then an accelerator is applied on top of the coating film after water has dispersed. The liquid radical curing resin containing the liquid radical curing resin is coated, and when the liquid radical curing resin is in a liquid or sticky state, it is covered with a printing film, and at the same time as the resin is cured, the pattern on the printing film is applied to the cured resin surface. The process consists of transferring the film to a film, removing the film, and then applying a top coat.

The method for applying the polymer emulsion containing an organic peroxide, the liquid radical-curing resin containing an accelerator, and the paint may be any conventionally known method and is not particularly limited.

Hereinafter, the present invention will be illustrated in more detail with reference to Examples. In addition, 1 part J and "%" in the examples mean "1 part" and "1 weight %" unless otherwise specified.

Example 1 Lauan plywood cut into 300 x 300 mm, x 4 pieces, acrylic-styrene copolymer emulsion (manufactured by Showa Kobunshi Co., Ltd., Polysol AP-655 modified, solid content 50
%), 300 parts of calcium carbonate, and 5 parts of methyl ethyl ketone peroxide were added and mixed uniformly to obtain a mixed emulsion for a primer, which was then coated with a roll. After about 1 hour, a uniform coating film from which moisture had been removed was obtained, indicating a paintable state. Next, 100 parts of unsaturated polyester resin (Revolac 2250, manufactured by Showa Kobunshi Co., Ltd.) and cobalt naphthenate (6% Co
) 1 part titanium white 5 parts styrene 10 Wait until the degassing is almost complete (it takes about 10 minutes), then add Roman Onix to polyethylene terephthalate while the surface of the resin is sticky and uncured. A transfer film with a gravure-printed pattern was placed so that the pattern was in close contact with the resin, and the film was pressed and left to stand. The resin gelled after about 1 hour.

When the film was removed after being left for one night, the Roman onyx pattern on the film was transferred to the surface of the cured unsaturated polyester resin.

Next, as a top coat on the transfer surface, a resin made by mixing 100 parts of the same unsaturated polyester resin as in Section 2, 1 part of cobalt naphthenate (6% CO), and 1 part of methyl ethyl ketone peroxide was applied, and then the surface was coated. It was covered with vinylon film and cured.

When the film was removed after curing, a deep Roman onyx-like decorative board was obtained in which the grain of the plywood was almost completely invisible.

Example 2 Polyvinyl acetate emulsion (manufactured by Showa Kobunshi Co., Ltd., Polysol FS-11 winter use, solid content 45
%) 1. A primer prepared by adding 2 parts of methyl ethyl ketone peroxide, 350 parts of hydrated alumina (Hysilite H-32, manufactured by Showa Denko K.K., Ltd., Hisilite H-32), and 5 parts of methanol to 0 parts of O0 and kneading the mixture uniformly was coated with a roll coater.

After about 3 hours, the coating became polishable, so the entire surface was lightly polished with Na320 abrasive paper.

Next, 100 parts of an unsaturated polyester resin (manufactured by Showa Kobunshi Co., Ltd., Revolac 1.608), 10 parts of styrene, 1 part of cobalt naphthenate, 1 part of dimethyl-aniline, and a black pigment (Revolac 1.608) were applied on the polishing coating. Color RC-
81) A uniformly mixed colored resin of 5 parts was roll coated to a thickness of about 03 to 04 mm.

A stage where the surface of the colored resin becomes sticky and is not yet cured - c The floral pattern of a button is printed on the IJ ethylene terephthalate film using offset printing using gold ink until the pattern adheres to the resin. It was crimped and left overnight.

When the film was removed after confirming that the resin had completely cured, the ``botazo'' floral pattern was completely transferred to the cured resin surface.

As a top coat, 0.2% of a photocurable spiran resin (Spirac U-3155, manufactured by Showa Kobunshi Co., Ltd.) was applied.
It was coated with a flow coater to a thickness of mm.

A polyethylene terephthalate film having a thickness of 150 μm was pressed onto the film, and the film was passed through an ultraviolet irradiation device having an output of 50 parts W at a distance of 20 cm below the lamp at a rate of 3 m/min.

The painted product that came out of the irradiation oven was completely cured and the film could be removed immediately.

The resulting product had an elegant luster and a smooth surface, and the floral pattern of the V button stood out against the black base material with the feel of lacquered maki-e, making it extremely beautiful. .

Example 3 A polyacrylic acid ester emulsion (manufactured by Showa Kobunshi Co., Ltd., Polysol AP-604, solid content 50%) was placed on a 300 mm x 300 m 1 x 4 mm hard slate board.
) and 4 parts of cumene hydroperoxide were roll-coated with a semi-paste-like brimer, and then left overnight.

Then on top of that, epoxy resin 3 with an epoxy equivalent weight of 372
80g and methacrylic acid 172. F and 24 parts of trisdimethylaminophenol (for 1,00 parts of preparation)
Epoxy acrylate 10 obtained by reacting with
A resin prepared by adding 2 parts of a 5% chloroform solution of vanadium acetylacetonate to 100 parts of a vinyl ester resin obtained by adding 40 parts of methyl methacrylate monomer to 0 parts was applied with a brush.

As a transfer film, a walnut pattern was printed on a polyethylene terephthalate film and then printed in brown, and this was pressed so that the pattern adhered to the resin when the surface of the resin had become sticky.

The resin was completely cured by standing overnight, and when the film was peeled off, the walnut pattern was transferred to the cured resin surface.

For the top foot, polyurethane paint (Aclink 2060GL Clear, manufactured by Kansai Paint Co., Ltd.) was repeatedly sprayed three times to a thickness of 70 μm, and then finished by puff polishing.

A beautiful decorative slate with the same grain of walnut was obtained.

Patent applicant: Showa Kobunshi Co., Ltd. Representative Patent Attorney Sei Kikuchi

Claims (1)

[Claims] The surface of the substrate is coated with (1) a polymer emulsion containing an organic peroxide; (2) a promoter capable of radicalizing the organic peroxide is then applied thereon; A liquid radical-curing resin that can dissolve the polymer is applied, and (3) while the liquid radical-curing resin is liquid or sticky and uncured, the printing film is attached so that the pattern side is in contact with the resin. (4) At the same time as the resin is cured, the design on the printed film surface is transferred to the cured resin surface, (5) After the film is removed, (6) Further, a transparent or semi-transparent paint is applied to the transfer surface. A method for manufacturing a cosmetic body, characterized by: