JPS60159198A - Ornamenting method of metallic product - Google Patents

Abstract

PURPOSE:To provide the ornament having excellent appearance and touch and good durability to a metallic product by removing the desired parts of a non- conductive film layer formed on the surface of the metallic product to expose the surface of a conductive metal then coating the exposed surface with a conductive thermosetting paint by electrodeposition painting and plating further the surface thereof. CONSTITUTION:A non-conductive film layer 2 consisting of a coated film layer of a thermosetting paint is formed on the surface of a metallic product 1 formed of a metallic material consisting of Al (alloy), copper (alloy), iron, etc. The desired parts of the layer 2 are removed according to a pattern, etc. to expose the conductive metallic surface 3. A conductive coated film layer 4 is in succession formed on the surface 3 by electrodeposition painting of a conductive thermosetting paint (e.g.; a mixture composed of a cationic type thermosetting resin and fine metallic powder). A plating metal 5 of gold, silver, copper, etc. is thereafter formed on the surface of the layer 4 by which the intended ornament is provided to the metallic product.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for decorating metal products such as plates, pipes, and 1-v products. In detail, the part ψ of the non-quaternary conductive film layer formed on the surface of a metal product is removed, and the removed part is coated with a conductive thermosetting paint to make it conductive. sex? The present invention relates to a method for decorating metal products, which is characterized by forming 4 film layers and performing plating treatment on the surface of the 119 coated layers.

Conventionally, a desired part of the non-conductive film layer formed on the surface of a single product is removed according to characters, designs, etc. to expose the metal surface, and then the metal surface is plated. The method of decoration is known.

However, in the case of this method, the thickness of the non-conductive film is usually in the range of 10 to 30 pm, so the depth of the four parts where it is removed is about 15 to 35 gm.
On the other hand, it is very difficult to fill these four parts into a part by plating, so the added S part of letters, designs, etc. that has been subjected to plating becomes four parts, which is not desirable in appearance 1.

In addition, since the surface is not smooth, it feels rough to the touch, and fourth, the peripheral edges of the four parts are easy to wear, and the decorative parts have poor abrasion and corrosion resistance. There were 41 drawbacks such as:

Of course, it is also possible to make the plating layer thicker by subjecting it to the plating process for a long time to make the four parts of the character 1 design etc. smooth, but in that case, the plating process would take 15 to 30 minutes. This method is not satisfactory in terms of productivity, processing costs, quality, etc., as it not only takes a long time but also poses a risk of corroding other surfaces due to long immersion in the plating bath. isn't it.

The present invention has been made in view of the following (1) and (2), and its purpose is to decorate metal products with excellent appearance and feel as well as good durability. /
J! , to provide the following.

That is, in the method for decorating metal products of the present invention, after forming a non-conductive film layer on the surface of a metal product, a desired portion of the non-conductive film layer is applied in accordance with arbitrary characters, designs, etc. is removed to expose the conductive metal surface, and then a conductive thermosetting paint is electrodeposited on the metal surface to form a q-heavy coating layer, and the I# film layer is It is characterized by a plating treatment applied to the surface.

In the present invention, metal products include, for example, aluminum
It is a plate, tube, processed product, etc. made of a fully bent material such as aluminum alloy, copper, copper alloy, iron, etc., and its shape is not particularly limited.

As a non-conductive film formed on the surface of metal products,
Thermosetting coating 1-4: This is one of the typical film layers. This coating layer is applied to metal products that have undergone cleaning treatment.
Non-conductive materials made of thermosetting resins such as alkyd resins, acrylic resins, epoxy resins, polyurethane resins, and polyester resins can be coated using conventional painting methods such as spray painting, brush painting, roller painting, electrodeposition painting, and electrostatic painting. It is formed by applying a coat of paint and then subjecting it to heat treatment. Here, the thickness of the coating film is not particularly limited, but is usually 20 to 30 Bm.

In addition, if the material of the metal product is aluminum or aluminum alloy, a non-quaternary conductive film layer can be formed on the surface of the metal product by applying anodizing treatment and sealing treatment using the usual method. It is possible.

That is, the surface of the metal product is degreased and cleaned with a sodium pyrolyl acetate solution, etc., and then heated at a current density of 1.0 to 1.5^/dm' in an anodic oxide film forming bath consisting of an aqueous solution of sulfuric acid, anodic acid, sulfuric acid, etc.
Direct current electrolysis is carried out for 20 to 50 minutes, and then, if necessary, it is immersed in a dye solution for dyeing treatment, and then further subjected to a boiling hole sealing treatment in an aqueous solution of nickel acetate, conoheld acetate, etc., or For example, 20-30 at 7A atmospheric pressure 5kg/cm'
This is accomplished by steam sealing for minutes. The thickness of the anodized pore-sealing layer is not particularly limited, but is usually 10 to 151 mm.

The method for removing the non-Jg conductive (supporting) film layer according to desired characters, patterns, etc. may be a physical abrasion method or a laser beam irradiation method.

In terms of physical cutting methods, Guyamont bite.

Ceramic bits, cemented carbide tungsten bits, etc. are applicable.

Also, the laser beam [! The q-irradiation method is to irradiate with a YAG laser beam, C02 cass laser beam, Luhi laser beam, etc., and locally remove the 119 layers of non-quaternary conductive skin by burning it out or dissolving it and causing non-emission. be. This method has good reproducibility and is suitable for the production of melon as it is highly effective.

That is, a mask made of a material that shields laser beams and has a desired character pattern, etc., is applied, the mask is closely attached to a non-conductive film layer of a metal product, and the surface of the mask is scanned with a laser beam. Only the non-conductive coating layer corresponding to the opened portion is irradiated with the laser beam and removed by burning or melting and vaporizing. The material or mask that shields the laser beam varies depending on the type of laser beam, but is formed of, for example, a metal plate of stainless steel, copper alloy, etc., metal foil, metal-containing paint film, or the like. In addition, the conditions for scanning and irradiating the laser beam vary depending on the type and thickness of the non-conductive film layer, the type of laser beam, etc. Although it is difficult to generalize, for example:
For YAG laser, beam diameter: 50-15
〇-φ, output crab l0-40W, feed speed: 200-4
It is possible to remove the non-conductive film layer under the condition of 00 mm/sec.

Furthermore, by using a well-known device that synchronizes original image scanning to read original images such as letters and designs, and laser beam scanning to reproduce and irradiate an image identical to or similar to the original image on the irradiated surface. , there is no need for the aforementioned laser beam shielding mask, and it is possible to quickly and efficiently reproduce desired characters, designs, etc. on the surface of metal products uniformly in the area where the non-conductive film layer has been removed. I can do it.

In this way, a desired portion of the non-conductive film layer is removed and the exposed metal...1 is then electrodeposited with a conductive thermosetting paint. A thermosetting resin containing a thermosetting resin and a fine metal powder is preferably used.

Examples of cationic thermosetting resins include epoxy resins, urethane resins, acrylic resins, and
A polyamino resin or the like is used, and phosphoric acid, acetic acid, lactic acid, citric acid, etc. are preferably used as the neutralizing agent.

Fine metal powders are fine powders of silver, copper, nickel, etc. with good conductivity resistance, and can be processed by well-known methods such as mechanical pulverization, carbonyl method, evaporation method in scum, electrolytic method, and substitution using ionization tendency. It can be obtained by law etc.

In particular, the particle size of the metal fine powder applied to the present invention is 005~
It is preferably within the range of two houses, and its shape is preferably strip-like.

The flaky metal fine powder is first produced by a liquid phase reaction,
Next, it is obtained by mechanical crushing and further sorting.

For example, to obtain fine silver powder, silver oxide is produced by reacting silver nitrate with a caustic sorter, and then reacting with formaldehyde. In this case, each of these reactants may be used as an aqueous solution with a specific concentration. This usually results in a particle size of 0.
．． A fine powder of 5-5 gm is obtained. Furthermore, this fine powder is ball milled with hydrocarbons such as benzene and n-hexane.
If pulverized with a vibrating mill etc., the desired particle size is 0.2~2ILI
It is possible to efficiently obtain fine silver powder of No. 11.

4. The fine powder obtained by crushing with a vibrating mill becomes flaky, and its shape is as follows: the longest particle size is the shortest.
It is about 5 to 10 times the thickness (thickness), but flaky fine powders, including this one, are generally preferred because they exhibit good performance in the process of plating the surface of the JA electroconductive coating layer, which will be described later. It is.

In addition, especially fine metal powder is an aggregate of ultrafine particles obtained by heating metal in an inert scum, evaporating it, and placing it on a cooling surface. It is excellent in making the surface of the conductive layer smooth and increasing the conductivity of the coating layer, and is suitable for plating treatment described below.
It is intended to improve the process.

The electrodeposition coating liquid first contains the cationic thermosetting resin,
If necessary, disperse in purified water with a surfactant to form an emulsion, then neutralize with the neutralizing agent, add the fine metal powder, and stir to incorporate the fine powder into the resin emulsion particles. It can be obtained by adhering it to or around the film, or by dispersing it in purified water, which is a continuous phase. It is also possible to add a thickener such as methylcellulose, polyvinyl alcohol, gelatin, etc. to uniformly disperse the fine metal powder in the coating liquid.

The non-volatile content of 4 electrodeposited M is 10~30'I#,! 6%,
pH is 4-8. The ratio of the metal fine powder to the cationic thermosetting resin may be 2 to 6:28 to 4 by volume, and the ratio by volume may be 7 to 9:3 to 1.

In 1E coating, the metal product is first degreased and cleaned as a pretreatment, and then placed in a bath containing the electrodeposition coating liquid, with the metal product used as a cathode and a stainless steel plate, etc., as an anode, while stirring the electrocoating liquid. , a direct welding current of 50 to 150 V may be applied between the two electrodes by the usual method of applying JII+ current for 1 to 3 minutes, thereby removing the non-conductive film layer and applying conductive heat only to the conductive metal surface. A curable paint is applied.

Next, after washing, wash at a temperature of 120-200°C for 15~
When completely cured by dry heat treatment for 30 minutes, a conductive coating layer with a thickness of 10 to 30 μm is formed. The thickness of this coating layer is determined by taking into consideration the depth of the non-conductive coating layer removed portion (four parts) or the thickness of the plating layer described below, etc., and finally the surface of the plating layer is determined to be the surface of the metal product. 11 (the non-conductive IIφ layer that has not been removed).

Here, when a conductive thermosetting paint containing flaky metal fine powder is used, the corners of the metal fine powder are less likely to protrude on the surface, and a smooth coating layer is formed. This is particularly preferable because a beautiful, smooth, and less uneven plating layer can be obtained in the first plating process, but this effect becomes particularly noticeable when electrodeposition coating is used, and other coating methods, such as e.g. Brush painting, spray painting,
It is difficult to achieve this sufficiently by roller coating or the like.

The surface of the conductive coating layer thus formed is then subjected to plating treatment to form a plating layer of gold, silver, copper, nickel, chromium, cadmium, or the like. The -JJ method can be adjusted as appropriate based on the well-known method of plating a conductive painted surface or resin surface.

The thickness of the gold layer should normally be 3 to 6 gm, and therefore a short plating time of about 3 to 6 minutes is sufficient.

The drawing is a cross-section IA of a mold part showing the method of the present invention in its order. In the drawings, l is a metal product, 2 is a non-conductive film layer formed on the surface of the metal product, and 3 is a conductive metal exposed by removing the non-conductive film layer according to characters, designs, etc. 4 is a conductive coating layer formed by electrodeposition on a metal surface, and 5 is a plating layer formed by plating the surface of the coating layer.・1-Like a lotus, the present invention removes a non-conductive coating layer formed on the surface of a metal product according to characters, designs, etc. and forms a conductive coating layer on the exposed metal surface, Furthermore, the present invention is a decoration method in which the surface of the coating layer is plated, and unlike the conventional decoration method in which the metal surface is directly plated, it has the following advantages.

Iiu, according to the method of the present invention, it is easy to make the part such as the character 5 pattern on which the plating layer is formed on the same surface as the other surface part of the metal product, and the surface of the decorated metal product is Appearance 1- is also preferable because it is smooth as a whole, does not feel rough when touched, and has improved abrasion resistance and corrosion resistance. In addition, since the distance between the surfaces to be plated is shortened, there is no scratching of the surface of the metal product, which occurs when the metal product is immersed in a plating bath for a long time. Furthermore, the compensation process is applied to the surface of the conductive coating layer, which is characters, designs, etc. formed by pre-painting, and even if the characters, designs, etc. are fine or narrow, It is possible to decorate metal products delicately and delicately.Furthermore, especially when the metal fine powder contained in the conductive thermosetting paint has a flaky shape, 1 as sexual desire 11
A smooth, uniform plating layer with less unevenness in thickness can be formed on the surface of the plating layer.

The present invention is applicable to various metal products, but is particularly applicable to metal products used as containers for cosmetics.The present invention is applied to metal products that are used as containers for cosmetics, and is of high quality, extremely beautiful, and durable, with an exterior appearance such as glittering letters and designs. This provides an excellent container.

Next, an example of the present invention and a comparative example will be described.

Note that the present invention is not limited to only what is described in the examples.

Example l Yayap made of aluminum [purity sa, s@@% (hereinafter, terminal % is abbreviated as wt%)] was 2wtχ
After degreasing and cleaning with an aqueous sodium hydroxide solution, the film was immersed in an electrolytic bath of 18 wt% sulfuric acid at a temperature of 23°C and directly applied for 30 minutes at a current density of 1.5 A/dm.
Tonoyo 81 oxide film was formed. This was immersed in a deep blue dye solution for 20 minutes, and then immersed in a 5vt% nickel acetate solution at a liquid temperature of 95°C for 20 minutes to seal the holes.

Next, on the top surface of this cap, a mask with the letter A opened in a thin plate made of stainless steel or prepared alloy with a polished surface is placed v=1, and the irradiation surface of this mask (20av+
p'), CO? under the condition of output 36 to 52 J/a/? Irradiate with a gas laser beam (wavelength 10.83-) to
The anodic oxidation sealing layer marked with the letters ``H'' was removed to expose the aluminum metal surface of the conductor H. The roughness of the part from which this anodized one-hole treatment layer was removed was 15.

Next, this cap was placed in an emulsion-type electrodeposition coating bath in which a cationic acrylic coating resin and fine silver powder (particle size: 0.2 to 2.0-) were dispersed in purified water. While stirring the electrodeposition coating solution, place the cap on the cathode.
2 stainless steel plate was used as an anode, and a direct current of 100 V was applied for 1 minute between the two electrodes. The liquid temperature of the electrodeposition coating bath was 23°C, the nonvolatile content was 20wt$, and the pH was 7.0.The weight ratio of the above fine silver powder and electrodeposition coating resin was 9:1, and acetic acid was used as a neutralizing agent. It was used. Next, the temperature of this camp is 150
The electrodeposited coating layer was cured by heating in a heating oven at .degree. C. for 20 minutes, and a conductive @film layer with a thickness of 10 .mu.s was formed on the aluminum metal exposed surface (the part marked with letter A).

Historically, this cap was placed in a silver plating bath with a liquid temperature of 50°C (1 part purified water, cyanide M < + 40g, potassium cyanide: 1803. Potassium Ytiate: 15g)
), and with the cap as the V) - pole and the silver plate as the anode, apply 8 V of direct current between the two poles to 1/2 at a current density of 3 A/d.
A silver plating layer having a thickness of 51 LI11 was formed on the surface of the conductive coating layer.

, A shiny silver A on the amber camp top.
It was possible to decorate characters with high quality compared to high precision.

Note that the plating layer was almost flush with the surface of the cap (the surface of the anodized pore-sealing layer that had not been removed).

Comparative Example l ゛In Example X, the second step of forming a conductive coating layer on the exposed aluminum metal surface was omitted, and the exposed metal surface was subjected to tin substitution treatment in a conventional manner, and then nickel was added. A plating layer having a thickness of 15IiI11 was formed by performing plating and silver plating.

The time required for the plating process was 22 minutes, which was 17 minutes longer than the plating time of 5 minutes in Example 1. Therefore, the top surface of the cap is dyed with i.
The ff color clearly faded, and the thickness of the plating layer also became uneven.

Example 2 In Example 1, the particle size of the fine silver powder dispersed in the weight coating solution was set to 0.05 to 0.5, and the particle size of the fine silver powder and the cationic acrylic electrodeposition coating resin was mixed. The surface of the 6-decorated plating layer, which was subjected to the same treatment as in Example 1 except that the ratio was 7:3, was 1g1 smoother than in Example 1. Further, by making the particle size of the fine silver powder smaller than in Example 1, it was possible to reduce the amount of the fine silver powder added to the electrodeposition coating resin.

Example 3 In Example 1, the shape was flaky and the particle size was 0.2 to
Using two types of silver fine powder, the heavy water ratio of this III fine powder and cation type acrylic resin to coating resin was set to 7.
5: The same treatment as in Example 1 was performed except that the value was set to 2.5.

Even if the amount of silver fine powder added was lower than in Example 1, the surface of the decorated plating layer was smooth and without unevenness.

Example 4 In Example 1, the 002 cass laser beam was irradiated.

Instead of removing the anodized sealing layer of the letter A,
A by physical cutting method using a diamond bit
The same treatment as in Example 1 was performed except that the anodized pore sealing layer with the letters ``'' was removed, and a cap decorated with ``Habo-kai'' was produced.

Example 5 A brass name plate was washed with acid or alkali in the usual manner, and then black epoxy paint was sprayed on the surface of the name plate at an air pressure of 5 kg/a/I.
The four pieces were hardened by heat treatment in a heating furnace at a temperature of 130° C. for 20 minutes. The thickness of the paint film was 30Jin.Next, in order to delete the part that corresponds to the letter 1-B of this name plate, we scanned the original to read the original, and we also created an image that is the same as the original. A YAG laser that synchronizes the laser beam scanning that reproduces and irradiates the irradiated surface.
A beam (wavelength 1.06.) generator was used. This device captures the original image with a TV camera, and turns the image analog data output from the TV camera on and off (ITI).
The laser beam's IQ; In other words, when the vehicle with the letter B is imaged and scanned with a telegraph arm, the image of the letter B is irradiated and scanned with a YAG laser beam to the painting station 19 described in 1ii to remove the paint film. ”, the brass metal surface with the letter B was exposed.The conditions for irradiating the laser beam were: beam diameter: 120 pxnφ, output +12W, Q
Suiwana frequency: 50K)+2, feed speed: 3(
toam/see It happened. Next, this name plate was immersed in an emulsion-type electrodeposition coating bath in which cationic epoxy electrodeposition coating resin and fine nickel powder (particle size: 0.1 to 10 units) were dispersed in purified water. While stirring the electrodeposition coating solution, a 100 V direct current was passed between the two electrodes for 2 minutes using the name plate as the cathode and the stainless steel plate as the anode. The liquid temperature of the electrodeposition coating bath was 28℃, and the nonvolatile content was 25W.
tX, pH huff, 5 te, and tX, pH huff, 5 te. The ratio of Kkel fine powder to resin was 8:1, and phosphoric acid was used as a neutralizing agent. 'Then, heat this name plate to a temperature of 1 μm.
The electrodeposited gossamer film was completely cured by heating in a heating furnace at 60°C for 30 minutes, and a conductive coating film with a thickness of 28P was applied to the exposed brass metal surface (the part marked B). was formed.

Furthermore, this name plate was immersed in a 2:7 Kel key metal bath (1 cup of purified water, 240 g of nickel sulfate, 45 g of dichloride, 45 g of Kel, 30 g of ferrous acid) with a liquid temperature of 50°C.
Use the name plate as the cathode and the nickel plate as the anode.
-5V between l1I8i (7) DC laminate flow tightness 113A/
dIT+'-c energized for 5 minutes, thickness 5. A nickel plating layer was formed on the surface of the conductive coating layer. Next, this name plate was washed with purified water, and immersed in a gold plating bath (purified water, potassium cyanide = 30 g, dibasic potassium phosphate: 30 g) at a liquid temperature of 50°C, and the name plate was used as a cathode. with the anode and 3V 'lI' between the two poles.
J flow was applied to Si for 5 seconds at a flow density of 0.5 A/drn'.

We were able to decorate the black name plate with a high-quality and delicately glittering gold letter B. Note that the plating layer was present on almost the same surface as the surface of the name plate (the surface of the epoxy resin coating film that was not removed).

[Brief explanation of the drawing]

Figures 1, 2 and 3 illustrate the method of the present invention.
FIG. 1 - Metal product, 2 - Non-conductive film layer, 3 - Metal surface (letters, (parts such as A pattern), 4 - 4 electrically conductive film layer,
5 ~ Plating layer

Claims (1)

[Scope of Claims] 1. After forming a non-conductive skin layer on the surface of a LIC product, a desired portion of the non-conductive film layer is removed in accordance with letters, designs, etc. Then remove the conductive metal surface and remove it.
1. Apply a conductive thermosetting paint to the metal surface to form 4 layers of 4'ik property. ,! ; A method for decorating metal products, characterized by subjecting the surface of the paint film layer to a rectification process. 2. A method for decorating a metal product as set forth in claim 1, wherein the entire product is made of aluminum or aluminum alloy, and the product is made of a non-4-electrode coating layer or an R4A polar oxidation sealing film. The decoration power chisel for metal products according to claim 1, wherein the non-tetraelectric coating layer is a non-conductive coating layer. 4. Claims 1 to 3, wherein the method for removing a desired portion of the non-conductive film layer is a physical cutting method.
Decoration of metal products described in any of the paragraphs. 5 Laser beam is the method to remove the desired part of the non-tetraelectric film layer! A method for decorating metal products according to any one of Items 1 to 3 of the Song Dynasty, which is a method of spraying. 6.4 Electrothermosetting paint is cationic thermosetting. 5. A method for decorating a metal product according to any one of claims 1 to 5, which comprises a synthetic resin and gold 14m powder as ingredients.