JPS5845357B2 - Transfer sheet for engraving and engraving method using the transfer sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transfer sheet for engraving and engraving that can perform etching and transfer decoration at the same time, and an engraving method using the transfer sheet.

Conventionally, engraving a concave pattern on the surface of a workpiece and coloring the concave pattern has been carried out by etching the workpiece using photo-etching or chemical milling, and then manually coloring the formed concave part. Ta.

First, let's talk about the etching process. In the case of the photoetching method, it involves (1) creation of an original drawing, (2) creation of an original plate using photolithography, and (3) pretreatment of the surface of the workpiece (degreasing, polishing, pickling, etc.). Washing and drying) (4) Applying photosensitive liquid (5) Exposure (6) Development (→Dyeing→Burning) (7) Applying anti-corrosion varnish to the back side of the workpiece (8) Corrosion (9) Washing with water (10)
Resist and anti-corrosion varnish removal Ol) Water washing, drying 02)
Tile product 1 with a large number of processes, including 12 finishing and inspection processes
Since each product requires a large number of materials such as a photosensitive solution, developer, anticorrosion varnish, stripping solution, and corrosive solution, it has the disadvantage that the production time and manufacturing time per product are high.

In addition, in the case of chemical milling method, (1) Creation of a mask (2) Pretreatment of the surface of the workpiece (3) Masking (
4) Corrosion (5) Washing with water (6) Removal of resist (7) Washing with water, drying (8) Finishing and inspection It consists of 8 steps, and although the number of steps is fewer than the photo-etching method, it is less accurate than the photo-etching method. There are drawbacks.

In addition, when corroding the workpiece, the simple immersion method can cause the etching I.
This process is time consuming, requires large side etch, and tends to cause uneven corrosion, so corrosion must generally be carried out by splashing or spraying a corrosive liquid onto the surface of the workpiece, which has the drawback of high equipment costs. .

Furthermore, the lifespan of the corrosive liquid is not very long, and therefore not only does the material cost of the corrosive liquid itself increase, but the quality also tends to vary and the yield decreases, which has the drawback of greatly affecting quality control and work efficiency.

In general, corrosive fluids become damaged after being used several times, so they have the disadvantage of having to be replenished with new fluid or completely discarding the corrosive fluid and replacing it with new fluid.

Furthermore, the used corrosive liquid and cleaning waste liquid cannot be directly disposed of as waste water, and the waste water must be physically and chemically treated to remove harmful components, which has the disadvantage of requiring expensive waste water treatment equipment. .

In the engraving process, not only are there various problems as mentioned above, but it also requires skill to manually apply coloring to match the concave pattern, and it is almost impossible to paint complex patterns. It was close to.

The present invention was completed as a result of research into an engraving and painting method that eliminates the above-mentioned drawbacks.

That is, the first invention is a thermopressure transferable printing ink for etching coloring, which includes an etching liquid and a heat transferable dye, and at least the etching liquid is embedded and microencapsulated in a capsule wall film that can be destroyed by heat and/or pressure. This is a transfer sheet for engraving, which is formed by printing a mirror image of a pattern to be etched on a support using a substrate, and the second invention is a transfer sheet for engraving a pattern by applying the transfer sheet to a material to be processed, heating and pressurizing it, and forming the capsule wall. The film is destroyed, the corrosive liquid flows out from inside the capsule, the workpiece is etched by the corrosive liquid, and the dye on the transfer sheet is transferred onto the workpiece to color the etched recesses. This is an etching method using a transfer sheet for etching decoration, which is characterized by the following.

The present invention will be described in detail below with reference to the drawings.

FIG. 1 shows a transfer sheet 1 for engraving decoration according to the present invention.

The support 2 is coated with a mixture of microcapsules containing an erosive liquid that can be destroyed by heat and/or pressure, a dye having heat transferability, and a vehicle as a main ingredient, and various auxiliary agents such as a drying suitability regulator as needed. A mirror image 6 of a pattern to be etched is printed by a printing method such as gravure printing, offset printing, silk screen printing, or flexo printing using the ink composition 3 to which the ink composition 3 is added.

In the figure, reference numeral 4 indicates a microcapsule of an erosive solution, and 5 indicates a mixed portion of the dye, vehicle, and various auxiliaries.

In the above, the corrosive liquid microcapsule 4 is, as shown in the second diagram, in which a corrosive liquid 41 as a core material is enveloped by a wall film 42 that can be broken by heat and/or pressure.

Instead of the above ink composition, an ink composition containing as a main ingredient a mixture of etching liquid microcapsules and heat-containing transferable dye microcapsules or an ink composition containing microcapsules containing an etching liquid heat-transferable dye mixture as a main ingredient may be used. good.

As the corrosive liquid 41 which is the core material of the corrosive liquid microcapsules 4, examples include hydric soda, hydrochloric acid, a mixed solution of ferric chloride and hydrochloric acid, ferric chloride, ammonium persulfate and mercuric chloride. Mixed solution, nitric acid, mixed solution of nitric acid and sulfuric acid, mixed solution of nitric acid and hydrochloric acid, mixed solution of chromic acid and sulfuric acid, mixed solution of ferric chloride and nitric acid, mixed solution of nitric acid and silver nitrate, nitric acid and hydrogen peroxide solution A mixed solution of hydrochloric acid and a hydrogen peroxide solution, a mixed solution of butic acid, a persulfate and a hydrogen peroxide, a mixed solution of powdered zinc and hydrochloric acid, etc. can be used.

In this case, if the mixed liquid itself is reactive, such as a mixed liquid of hydrochloric acid or nitric acid and hydrogen peroxide, each is made into capsules separately, and the two types of capsules are mixed to create ink. do it.

Materials for the wall film 42 include, for example, nylon, tetron, polyurethane, polyurea, polycarbonate, formalin-naphthalene sulfonic acid condensate, amino resin, alkyd resin, silicone resin, and other condensation polymers, maleic anhydride copolymers [ethylene, vinyl methyl ether, etc.], copolymers such as acrylic acid and methacrylic acid copolymers, polyvinyl chloride, saran, polyethylene, polystyrene, polyvinyl acecool, polyacrylamide, polyvinylbenzenesulfonic acid, polyvinyl alcohol, synthetic rubber, etc. Curable polymers such as polymer epoxy resins, nitroparaffins, and nitrated polystyrene; Waxy substances such as wax, paraffin, rosin, shellac, tristearin, monoglyceride, beeswax, wood wax, oils and fats, and hydrogenated oils may not be used. Can be done.

The wall membrane material must be selected in consideration of its relationship with the core material.

In other words, if the core material is a mineral acid other than an oxidizing chemical, use a hydrocarbon compound without unsaturated bonds such as polyethylene or polypropylene, or a polyvinyl chloride plastic, phenolic resin, or acrylic resin. ,
If the core material is an inorganic alkali, a hydrocarbon compound free of unsaturated bonds such as polyethylene or polypropylene, or polyvinyl chloride plastic, urea resin, acrylic resin, or epoxy resin is used.

If the core material is oxidizing nitric acid or concentrated hydrochloric acid, only cultured plastics such as polyvinylidene chloride can be used.

Encapsulation can be carried out by methods such as interfacial polymerization, in 5 in situ polymerization, melt-dispersion cooling, phase separation from an organic solution system, and drying in liquid.

In the above, as the dye having thermal transfer properties, any colorant can be used as long as it has the property of being transferred from the transfer sheet to the surface of the processed material by the action of heat, such as sublimation, melting, or evaporation. I can do it.

For example, colorants conventionally used in sublimation transfer methods such as azo-based or anthraquinone-based disperse dyes, oil-soluble dyes, etc. can be used, and specifically, Kayaset Yellow 186, Kayaset Red 912, Kayaset Blue 906 (manufactured by Nippon Kayaku ■), Miketone Polyester Yellow 3G.

Miketon Polyester Red FN (manufactured by Mitsui Toatsu ■)
, Diamix Red R1 Diapolon Red R8,
Diaresin Blue J, PTR71 (manufactured by Mitsubishi Kasei), Sumiplast Orange R1 Sumiplast Blue OG
, Sumiplast Black G (manufactured by Sumitomo Chemical), etc.
A species or two or more species can be used.

The vehicle should be selected in consideration of the relationship between the capsule wall material and the dye, and the following may be mentioned.

(i) Maleic acid resin for gravure, rosin modified phenolic resin, cyclized comb, ethyl cellulose, nitrocellulose, Seven Rank, polyamide resin, coumaron indene resin, vinyl resin,
A solid binder such as bunral resin, gum arabic, dextrin, rosin-modified alkyd, etc., alone or in a mixture, is mixed with an aromatic solvent such as doluol, kijirole, ethyl ester aromatic solvent, alcohol, hydrocarbon solvent, MEK, etc.
Vehicle (11) Contains linseed stand oil for offset, drying oil-modified alkyd resin (drying oil-modified fucuric acid alkyd resin, isophthalic acid alkyd resin, etc.), rosin-modified phenol resin dissolved in a ketone solvent such as MIBK, Anone, etc. For resin varnishes, etc.), linseed oil stand oil for silk screen, resin varnish made by dissolving maleic acid resin in linseed oil/dehydrated castor oil, drying oil-modified alkyd resin, etc., use a vehicle with the same amount of white spirit added. Vehicles made by dissolving nitrocellulose, ethylcellulose, ethylhydroxy, ethylcellulose, etc. in a solvent and adding an appropriate plasticizer, vehicles made by dissolving shellac in water using borax, vehicles made by dissolving modified butyral resin in an aromatic solvent, etc. iv) Maleic acid resin for flexo, ethyl cellulose, nitrocellulose, rosin-modified phenolic resin, ketone resin, zein, etc. alone or as a mixture of solid denatured alcohols;
A vehicle in which a solid binder such as polyamide resin, acrylic resin, chlorinated rubber, or cellulose derivative is dissolved in a mixed solvent such as alcohol, ester, ketone, or Natsuta, or a glue or text Rin,
In addition to water-soluble materials such as gum arabic, polyvinyl alcohol, and methyl cellulose, water-insoluble materials such as shellac, maleic acid resin, and cein.

The above-mentioned supports include polyester film, acrylic resin, polyethylene, polypropylene, polycarbonate, polyvinyl alcohol, polyamide, polystyrene, and other plastic films, thin paper, high-quality paper, coated paper, and other types of paper, or composite films of paper and plastic. etc. can be used.

FIG. 3 shows an engraving method using the transfer sheet for engraving.

Applying the engraving transfer sheet 1 to the workpiece 7,
Heat and/or pressure is applied to destroy the corrosive liquid microcapsules 4, the corrosive liquid 41 flows out from inside the capsules, and the fourth
As shown in the figure, the workpiece 7 is etched with the corrosive liquid to form recesses 8, and the ink layer 3 on the transfer sheet 1 is etched.
The dye inside is transferred onto the workpiece to form a colored layer 9 on the recess 8, thereby coloring the recess 8.

According to the present invention, metals such as aluminum, anodized aluminum, chromium, gold, molybdenum, silver, stainless steel, steel, titanium, zinc, etc., or glass, shellac, Nesafilm, silicon, germanium, plastic, etc. are etched. can do.

Next, examples of the etching process according to the present invention will be specifically explained.

Example 1 A 37°Be′ ferric chloride solution was used as a core material, and the core material was wrapped in an ethylene-vinyl acetate copolymer to form a 30 to 50μ
We created ferric chloride microcapsules with a particle size of .

Next, using this Michael capsule, a silk screen printing ink having the following composition was prepared.

[Ink composition]

Microcapsule 80 parts Epoxy-modified butyral resin 20 parts Dye: Sumiplast Pink R, C0I, 30 parts (manufactured by Sumitomo Chemical) Aromatic solvent 20 parts Next, apply the above ink to a 25μ polyester film with 100 mesh floral pattern screen plates. A transfer sheet was created by printing a floral pattern using a silk screen printing method.

Next, this transfer sheet was tightly attached to a copper foil with a thickness of 0.5 mm so that the printed side was in contact with the surface of the copper foil.
Heat treatment was performed at 150°C for 5 minutes under pressure of , and after cooling the polyester film was peeled off.
As a result of washing with water and drying, an etched floral pattern with pink recesses was formed on the surface of the copper foil.

The product thus obtained was a new product in which the colored pattern and the etched pattern were applied with high precision and matching, which could not be obtained by conventional methods.

Example 2 A core material was prepared by blending 80 parts of a 37°Be' ferric chloride solution with 20 parts of a dye: Diaresin Resod C,1 (manufactured by Mitsubishi Kasei), and the core material was ethylene-acetic acid. A ferric chloride-dye mixture microcapsule having a particle size of 30 to 50 μm was prepared by wrapping it in a vinyl copolymer.

Next, using this microcapsule, a silk screen printing ink having the following composition was prepared.

[Ink composition]

Microcapsule 85 parts Epoxy modified butyral resin 20 parts Aromatic solvent
15 copies Next, using this ink, a 12μ polyester film and a 23g/- thin paper were laminated together, and a floral pattern was printed on the polyester side of the support using a silk screen printing method using a 100 mesh checkered screen plate, and a transfer sheet was created. Created.

Next, this transfer sheet is closely attached to a stainless steel plate with a thickness of 2 mm so that the printed side is in contact with the surface of the stainless steel plate.
Heat treatment was performed at 130° C. for 7 minutes under a pressure of 0 kg/ffl, and the support was peeled off after cooling.
As a result of washing with water and drying, a checkered etched pattern in which the recesses were colored red was formed on the surface of the stainless steel plate.

The product thus obtained was a new product in which the colored pattern and the etched pattern were applied with high precision and matching, which could not be obtained by conventional methods.

Example 3 Ethylene-
Ferric chloride microcapsules having a particle size of 30 to 50 μm were prepared by wrapping them in vinyl acetate copolymer.

Separate dye: Kayaset Blue 906 (manufactured by Nippon Kayaku ■)
was used as a core material, and the core material was wrapped in enalene-vinyl acetate copolymer to prepare dye-containing microcapsules of 30 to 50 μm.

Next, using the above two types of microcapsules, printing ink for silk screen printing having the composition shown in the table below was prepared.

[Creation of ink]

Ferric chloride microcapsules 80 parts Dye-containing microcapsules 30 parts Epoxy-modified butyral resin 30 parts Aromatic solvent
Thirty copies of this ink were then used to print a polka dot pattern on a 25 μm polyester film by silk screen printing using a 100 mesh polka dot screen plate to prepare a transfer sheet.

Next, this transfer sheet was placed in close contact with a 2-inch thick steel plate so that the printed surface was in contact with the surface of the steel plate.
After heat treatment at 130°C for 7 minutes under a pressure of kg/crtt, after cooling, the polyester film was peeled off, washed with water and dried. An engraved pattern was formed on the surface of the steel plate.

The thus obtained product was a new product in which the colored pattern matched the etched pattern with high precision, which could not be obtained by conventional methods.

As detailed above, according to the present invention, since the etching and coloring are simultaneously performed on the same part of the workpiece, the etching and coloring are performed with high precision so that the etching and coloring patterns match. Processed products do not require careful resist pattern creation, corrosion protection process, or coloring process, and can be mass-produced in a short time (and at low cost) with a small number of processes.

Furthermore, since the corrosion rate can be regulated by the microcapsule content, the amount of ink applied, the temperature, etc., the corrosion work can be easily managed and a stable product can be obtained.

In addition, the corrosive liquid used for etching is contained in a small amount of microcapsules, and most of it remains on the pattern-engraved sheet, so only a small amount of corrosive compounds dissolve in the washing water. Therefore, almost no wastewater/treatment equipment is required, and even if necessary, complicated equipment such as a wastewater treatment equipment for corrosive liquid is not required.

[Brief explanation of the drawing]

Fig. 1 is a cross-sectional view of the transfer sheet, Fig. 2 is an enlarged cross-sectional view of the microcapsules containing an etchant, Fig. 3 is a cross-sectional view showing an etching method using the transfer sheet, and Fig. 4 is a cross-sectional view of the etching process using the transfer sheet. FIG. Explanation of the symbols representing the main parts of the figure: 1...Transfer sheet, 2...Support, 3...Printing ink for heat-pressure transferable corrosion coloring, 4. ... Corrosive liquid microcapsule, 41 ... Core material of microcapsule, 42 ... Wall membrane of microcapsule, 5
・・・・・・mixture part of dye, vehicle and various auxiliaries,
6...Mirror image of the pattern to be etched, 7...
...Work material.

Claims (1)

[Claims] 1. A thermopressure transferable etching color printing comprising an etching liquid and a heat transferable dye, at least the etching liquid being incorporated and microencapsulated in a capsule wall membrane that can be destroyed by heat and/or pressure. A transfer sheet for engraving, which is made by printing a mirror image of the pattern to be etched onto a support using ink. 2 Etching using a thermo-pressure transferable etching coloring printing ink containing an etching liquid and a heat-transferable dye, at least the etching liquid being incorporated and microencapsulated in a capsule wall film that can be destroyed by heat and/or pressure. A transfer sheet for engraving, which is made by printing a mirror image of the pattern to be processed on a support, is applied to the material to be processed, heated and pressurized to destroy the capsule wall membrane and cause the corrosive liquid to flow out from inside the capsule. An engraving process using a transfer sheet for etching decoration, characterized in that a workpiece is etched by a transfer sheet, and the dye on the transfer sheet is transferred onto the workpiece to color the etched recesses. Method.