JPH06316767A - Formation of metal pattern - Google Patents

Abstract

PURPOSE:To accurately form an arbitrary metal pattern on the surfaces having various forms by forming a highly insulating resin layer ontg. black oil-soluble dyes on a substrate, whose surface is metal, removing the resin layer in an arbitrary form by YAC laser beams and depositing a metal on the removed part. CONSTITUTION:On a substrate (brass, etc.) whose surface, at least consists of a metal (Ni plating, Cr plating, etc.), a highly insulating resin layer (acrylic resin, polyester resin, etc.) at least contg. black oil-soluble dyes (nigrosine, etc.) is formed. After the resin layer is irradiated with YAC laser beams to remove it in an arbitrary form, the surface of the substrate at the remove part is treated by electric plating, etc., to deposit a metal. The residual resin layer is removed by a water solution of acid, alkali, etc. As a result, an arbitrary metal pattern is formed on the surface of the substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an arbitrary metal pattern on the surface of a base material at least having a metal surface, which is suitable for decorating writing instruments, watches, cosmetic containers, etc. It is a thing.

[0002]

2. Description of the Related Art Conventionally, various processing methods have been proposed for forming various metallic patterns on a metal for the purpose of decorative effect, display of products, etc., and used for writing instruments, watches, cosmetic containers, etc. There is. These pattern formation techniques are important techniques for enhancing the sense of value of products and the willingness to purchase.

Conventionally, as a method of forming an arbitrary pattern of metal on a metal, a screen printing method or a photoresist method is used, and a resin layer having a high electric insulation property is used. The metal is deposited on the portion where the resin layer is not formed (the pattern to be formed) by electroplating or electroless plating, and then the resin layer is removed.

It is also possible to form a coating film on a transparent resin molded product with a paint containing carbon black and remove the black coating film using a YAG laser to form a pattern. It is performed (used for knobs such as audio). This YA
The reason why the pattern can be formed by removing the black coating film using a G laser is that carbon black is a YAG laser.
It is considered that this is because the light can be efficiently absorbed.

[0005]

The screen printing method is
If it is a flat surface or a tubular shape such as a writing instrument, it is possible to form a highly electrically insulating resin layer with any pattern, but if you try to form a horizontal fine pattern on the axis of the writing instrument, Problems such as the pattern part being crushed due to ink bleeding and the seams being crushed occur.
Further, in the case of a curved surface, a spherical surface, or a three-dimensionally curved surface such as the surface of a pen tip of a fountain pen, pattern formation was impossible. In the present situation, the photoresist method is limited to flat surfaces and cannot be applied to substrates having various surface shapes.

Further, in the method of forming a pattern by forming a coating layer on a metal with a paint containing carbon black and then removing the coating layer with a YAG laser, the coating layer is removed. A thin transparent resin layer remains on the surface of the pattern part formed by, and even if this pattern part is treated by an electroplating method or an electroless plating method, the metal is not deposited. It turned out to be impossible or incomplete. Therefore, if the laser output is increased and the processing is performed, the resin layer can be removed in a part of the pattern part, but it is incomplete, and the metal surface of the base is melted and the metal surface becomes rough. Furthermore, the accuracy of the pattern is lowered because the resin layer is melted by high heat and peeling occurs, which causes a problem such as deterioration.

[Means for Solving the Problems]

The present invention has been made in consideration of these problems, and it is an object of the present invention to provide a method capable of accurately and easily forming an arbitrary metal pattern on various surface shapes. Basically, a special resin layer having high electric insulation (a resin layer capable of efficiently absorbing the YAG laser light and removing it at a low output) and a YAG laser are used.
At least a surface of the base material made of metal, at least forming a resin layer having a high electrical insulation containing a black oil-soluble dye,
After removing the resin layer into an arbitrary shape by irradiating a YAG laser beam, the substrate surface of the removed portion is treated to deposit a metal,
The gist is a method for forming a metal pattern by removing the remaining resin layer.

The base material at least the surface of which is made of metal used in the present invention includes aluminum and its alloys, copper and its alloys, iron and its alloys, zinc and its alloys, nickel and its alloys, tin and its alloys, and magnesium. And alloys thereof, stainless steel, and the like. Various metals and alloys may be preliminarily formed on the surfaces of these metals by an electroplating method, an electroless plating method, a sputtering method, an ion plating method, a vacuum deposition method, or the like. Other base materials include glass, alumina, ceramics such as zirconia, ABS, AS, polyethylene, polystyrene, nylon, polypropylene, P
ET, PBT, polycarbonate, polyacetal, modified PPO, polyphenylene ether, polyethersulfone resin, PEI, PEEK, etc. are used, and the surface of these substrates is subjected to electroless plating or no electroless plating. After electrolytic plating, various metals or alloys are formed by metal coating by electroplating, sputtering, ion plating, vacuum deposition or the like.

Next, the resin layer having high electric insulation will be described. The resin layer is formed by painting or a screen printing method, and is a property of a paint or a screen printing ink that is dried or reacted and cured at room temperature, or is cured by heating. Therefore, specifically, a resin containing a highly electrically insulating resin such as an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, an alkyd resin, a vinyl resin, a phenol resin, a silicon resin, or a fluorine resin is used.

The black oil-soluble dye contained in the resin layer is a nigrosine black dye, specifically C.I.
I. Acid Black 2, C.I. I. Solvent
Black5, C.I. I. SolventBlack
7, C.I. I. Solvent Black 3, C.I. I.
Solvent Black 22, C.I. I. Solve
nt Black 23, C.I. I. Acid Black
123 etc., which are commercially available include Oil
Black BY, Oil Black BS, Oi
l Black 803, Oil Black HB
B, Special Black EB, Spirit Bl
ack AB (above, Orient Chemical Industry Co., Ltd.), A
size Splon Black BH, Aizen
SpironBlack GSH special (above, Hodogaya Chemical Co., Ltd.), etc. are mentioned, and its concentration is preferably 5 to 40% by weight based on the solid content of the paint or the screen printing ink resin. If necessary,
A coloring material exhibiting absorption characteristics may be appropriately added in the vicinity of 1060 nm.

After the resin layer is formed on the metal surface, if the YAG laser light is irradiated on the resin layer in an arbitrary pattern, the resin can be easily matched with the pattern to remove the surface of the metal substrate. Since it is exposed, this exposed portion may be processed by a known electroplating method or electroless plating method. The removal of the remaining resin layer may be selected according to the type of coating film,
In the case of thermoplastic, an aqueous solution of acid or alkali, or a solvent such as toluene, xylene, trichloroethylene or methylene chloride is used, and in the case of thermosetting, a film peeling agent,
For example, as a commercial product, San-Akon R- from Taiyo Kako Co.
42S, R4ZK of Great Tor Co., etc. may be used for removal.

[0012]

[Function] A paint or screen containing these black oil-soluble dyes
The resin layer is formed by forming a resin layer on the metal using a printing ink and then treating it with a YAG laser.
Since it is possible to absorb the laser light, an arbitrary pattern can be formed, and the pattern portion can be completely removed by the laser light to expose the underlying metal. By processing by a plating method or an electroless plating method, a metal can be uniformly and easily deposited on the exposed metal surface, and then by removing the film,
Since it is possible to obtain a uniform metal pattern, it is possible to decorate a writing instrument, a cosmetic container, a timepiece, etc., and improve the appearance design.

[0013]

【Example】

Example 1 A brass pipe having an inner diameter of 8 mm, a wall thickness of 0.2 mm and a length of 100 mm was buffed, and then, as a known pretreatment for plating, immersion degreasing and cathodic electrolytic degreasing were performed. After that, bright nickel plating is performed to 10 μm and chromium plating is performed to 0.1 μm.
went. The resin film having an insulating property was formed by the following method. Acrylic thermosetting paint (Kansai Paint Co., Ltd. Magiclon clear) was used as the paint, and Nigrosin EX (manufactured by Orient Chemical Industry Co., Ltd.) was used as the black oil-soluble dye for the coating resin solid content of 15 % By weight, dissolved and dispersed, diluted twice with a dedicated thinner, and coated on a brass pipe plated with a sprayer at 160 ° C.
It was dried for 20 minutes and formed to a thickness of 10 μm. Then YA
The coating film was removed with a width of 0.1 mm by processing with a G laser (LAY-724CB manufactured by Toshiba Corp., LAY-724CB) at an output of 28 A into a grid pattern of 0.1 mm. Next, 35.
A laser-processed brass pipe was immersed in 5% concentrated hydrochloric acid to remove the chromium plating layer on the pattern portion, and then bright nickel plating was formed on the pattern portion to 20 μm, and then gold plating was formed to 1 μm. After that, the coating film was peeled off to obtain a pipe having a gold lattice pattern. Gold pattern is 0.1mm
And there was no pattern collapse.

Example 2 A 1 mm thick aluminum plate (JIS H1080)
Etching with 0% NaOH aqueous solution, then sulfuric acid 15
%, Temperature 20 ° C., current density 1.5 A / dm ² , anodized for 30 minutes to form alumite. Then, it was dyed with a blue dye and dried. As the paint, a fluorine-based paint (Lumiflon LF200 manufactured by Asahi Glass Co., Ltd.) was used, and the black oil-soluble dye Oil Black was added to the paint resin solids.
20% by weight of BS (manufactured by Orient Chemical Industry Co., Ltd.) was added and dissolved and dispersed. Dilute it twice with a dedicated thinner, add 5% by weight of a dedicated curing agent to the resin solids, and spray.
By coating and drying at 100 ° C for 20 minutes
A resin layer having a thickness of 5 μm was formed. After that, YAG ray
Outputs 30A with The (manufactured by Toshiba Corporation, LAY-724CB)
By forming a random pattern with, the resin layer in the portion subjected to the random pattern processing was completely removed. Next, the aluminum plate on which the random pattern was formed was
It was dipped in aOH to remove the blue-colored alumite layer in the pattern portion. Then, the plate was immersed in a known zincate solution, zinc displacement plating was performed, then electroless nickel plating was performed at 1.0 μm, bright nickel plating was performed at 20 μm, and chromium plating was performed at 0.1 μm. Next, the coating film was removed, treated with ion-exchanged water at 90 ° C. for 20 minutes, the blue-dyed alumite was sealed, and an aluminum plate having a blue-anodized chrome-colored random pattern with metallic luster Got

Example 3 On the aluminum plate used in Example 2, blue dyed alumite was formed under the same conditions as in Example 2. Epoxy type ink (Seiko Advance Co., Ltd. Seiko-1300 medium) is used as the screen printing ink, and black oil soluble dye special Black EB (manufactured by Orient Chemical Industry Co., Ltd.) is used for the ink resin solid content. 30% by weight, and dissolved and dispersed with three rolls. An aluminum plate dyed blue was printed on the entire surface by a screen printing method and dried at 130 ° C. for 30 minutes to form a printed layer of 8 μm. Next, YAG laser (manufactured by Toshiba Corporation, LAY-72)
4CB, output 32A, 0.2m of laren pattern
By forming with a width of m, the resin layer was completely removed from the spiral pattern. Next, in the same manner as in Example 2, zinc substitution plating, electroless nickel plating, and bright nickel plating were performed 1
After forming 0 μm, gold plating was formed to 0.5 μm. Next, the remaining resin layer was peeled off, immersed in ion-exchanged water at 90 ° C. for 20 minutes, sealed, and blue-dyed alumite was used to obtain an aluminum plate having a 0.2 mm golden spiral pattern. It was

Comparative Example 1 The paint used in Example 1 was a black paint in which carbon black was dispersed (acrylic thermosetting paint, Kansai Paint Co., Ltd.).
The same procedure as in Example 1 was carried out except that the bright nickel plating was not deposited on the laser-processed pattern portion.

Comparative Example 2 A black ink in which the screen printing ink used in Example 3 is dispersed in carbon black (Seiko Advance Co., Ltd.).
Seiko-1300) was used and the same as in Example 3 except that zinc displacement plating and electroless nickel plating were not deposited.

Claims (1)

[Claims] 1. A resin layer having a high electrical insulation property containing at least a black oil-soluble dye is formed on a substrate having at least a surface made of metal, and the resin layer is irradiated with YAG laser light to form an arbitrary resin layer. After removing the shape, a metal pattern is formed by treating the surface of the base material of the removed portion to deposit a metal, and then removing the remaining resin layer.
Forming method.