JPS6021225B2 - Electroless plating body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electroless plated body in which a semiconductor layer is formed on an insulator such as glass, plastic, ceramic, crystal, etc., and a desired metal is plated thereon.

Conventionally, when performing electroless plating on an insulator, the insulator substrate surface is mechanically polished, chemically polished, or both in order to improve the adhesion of the intended metal plating and to obtain a uniform plating film. was used to roughen the surface.

However, in spite of this, it has been difficult to obtain a uniform plating film with good adhesion. The present invention shows a method for obtaining a uniform plating film with good adhesion by forming a semiconductor layer on an insulating substrate without performing a secondary pre-process.

The outline of the electroless sealing according to the present invention is as follows. A semiconductor layer such as ln203, Sn02, Ti02, etc. is formed on an insulating substrate such as glass, plastic, ceramic, crystal, etc. by CVD (chemical vapor deposition), sputtering, vapor deposition, immersion method, etc. The substrate is subjected to the usual pretreatment process of electroless finishing. That is, degreasing is performed by ultrasonic cleaning in an alkaline solution, acid neutralization, and water washing. Next, stannous chloride (SnC)
Z2) Immerse the substrate in the solution. This is a reducing solution used to uniformly reduce and distribute fine particles of catalytic metal, which serve as precipitation nuclei of the metal to be plated, over various parts of the surface, and the process of immersing this solution is called sensitizing. Next, the surface is activated. This is an operation called activating that is performed to automatically start the reaction and improve the adhesion of the plating film by attaching fine particles that act as growth nuclei of the plated metal and act as a catalyst for the plating reaction to the surface of the plated object. . It is said that due to the difference in the tendency of Ga ionization between Sn in SnC〆2 adhering to the surface of the substrate due to the above-mentioned sensitizing and the metal serving as an active catalyst. As the activation liquid, palladium chloride solution (PdCso2), silver nitrate solution (AgN03),
Gold solution (HA) etc. are used. The semiconductor layer formed on the substrate according to the present invention improves the adhesion of the catalyst metal and the adhesion of the electroless finishing film.

However, if the plating thickness of the electroless plate exceeds 2 Am, the rigidity of the plating layer increases and the adhesion with the substrate becomes extremely poor. Therefore, in the present invention, the plating thickness is set to 2 Am or less. Here, sensitizing and activating may be performed simultaneously using a solution containing both stannous chloride and palladium chloride. The activated substrate obtained in the above manner is coated with the three common electroless nickel baths, electroless steel plates, electroless cobalt baths, and electroless gold plates (not substitution type plating, but self-catalytic plating). etc., depending on the appropriate concentration and temperature conditions. The plated film thus obtained was more uniform and had improved adhesion compared to a plated film on a portion to which no semiconductor layer was attached. This will be explained in detail below using examples.

Example 1 Borosilicate glass (25 skins x 10 mosquitoes) coated with Sn02 on one side by CVD (chemical vapor phase lacquering) was coated with 3% KOH.
After degreasing with a solution and washing with water, stannous chloride solution (SnC〆2
Soak for 5 minutes in 1g/night, HC〆lcc/day).

After that, wash thoroughly with water and add palladium chloride solution (PdC solution 2,2
Soak for 5 minutes in the evening (20cc/so). Thereafter, the glass substrate was thoroughly washed with water, and the glass substrate was immersed for 5 minutes in a non-densified nickel bath (50° C.) in which Schumer S Total 0 (manufactured by Nippon Kanigen ■) was diluted 8 times with pure water, and dried after washing with water and hot water. When the resulting plated surface (plating thickness: 1600A) was rubbed 6 times under a pressure of 20 kg, no change was observed on the nickel surface attached to the two layers of S, but the nickel attached directly to the glass surface showed no change. Traces of nickel peeling were seen on the surface. Example 2 Oxygen glass (25 Yanagi x 10 Hiho) with numbers 1 to 03 attached on one side by vapor deposition was nickel plated (1600A thick) using the same plating process as in Example 1.

Apply 20kg of pressure to the resulting plated surface with a sander.6
When rubbed several times, no change was observed in the nickel plating on the 103 layer, but traces of nickel peeling were seen on the nickel surface directly attached to the glass surface. Example 3 A PET (polyethylene terephthalate) film with Sn02 attached on only one side by vapor deposition was degreased with 3% KOH and washed with water, and then immersed in a solution diluted with Hitachi Chemical's sensitizer HS-101B by a prescribed method for 3 minutes. After washing with water, the adhesion promoter ADP-201 manufactured by Hitachi Chemical was immersed in a solution diluted 8 times with ion exchange water for 5 minutes, and after washing with water, Schumer S680 manufactured by Nippon Kanigen ■ was diluted 8 times with ion exchange water. Electroless nickel grade (45qo) for 30 minutes (plating grade 1)
It was soaked.

Although nickel was deposited on both sides, the nickel film on the surface on which Sn02 was vapor-deposited was uniform and had a mirror surface.
The surface without 2 was an unevenly plated surface. In order to examine the adhesion of the plating, adhesive tape was applied to both sides and peeled off. The nickel film attached to the surface on which Sn02 was deposited did not peel off, but the nickel film on the surface to which Sn02 was not attached did peel off. Example 4 Glass with Sn02 deposited on only one side by vapor deposition was pretreated in the same process as in Example 3.

The glass substrate activated in this way is treated with cyanide, gold, metal, and potassium mecyanide.
6.5 Tanok potassium hydroxide
11.2 evening/potassium borohydride
It was soaked in a plating grade (7 pi○) of the same composition for 30 minutes, washed with water, and then dried.

A uniform gold plating film was formed on the side where S-2 was attached, but almost no gold plating film was formed on the glass substrate. Example 5 A borosilicate glass coated with SnQ on only one side by vapor deposition was pretreated in the same manner as in Example 3.

As an electroless finishing bath, an activated glass substrate was immersed for 6 minutes in an electroless nickel grade (40°C) prepared by diluting Schumer S680 manufactured by Nippon Kanigen ■ by 8 times with ion-exchanged water, and washed with water. After washing with hot water, it was dried. The nickel plating film (plating thickness 1500A) was uniformly applied to the surface with Sd02, but almost no nickel plating film was applied to the surface without Sd02. In order to check the adhesion, I applied a pressure of 20k9 with a dry cloth and rubbed it 6 times, but no change occurred on the plated surface. As described above, when electroless plating was performed on an insulating substrate using a semiconductor layer as a medium, a plated surface with uniform and strong adhesion was obtained.

An example of application will be explained using figures.

Figure 1 shows the camera's liquid crystal panel for imprinting the date.

1 and 2 are the front and rear substrates of the panel, which are made of glass with a thickness of 0.4 ribs.

3 and 4 are Sn02 transparent electrodes formed by CVD.

5 is a 1200Δ thick nickel plating applied by the means of the present invention.

6 is Gya of 10 Buddhas. This is an epoxy resin sealant containing a sealing agent.

A positive liquid crystal composition 7 having predetermined components is injected into the panel thus constructed. 8 is a polarizing plate.

FIG. 2 is a schematic diagram of the date imprinting mechanism of the camera.
9 is a light source, 10 is the panel shown in FIG. 1 and its support, and 11 is a film.

The panel displays the date and imprints it on the film 11, but if the nickel plating shown in 5 in Figure 1 is not applied, some light will leak through the polarizing plate and the entire outline of the panel will be visible in the photograph. This would be inconvenient as it would appear in the photo. By applying nickel plating, it was possible to prevent light from leaking, and only the date numbers were clearly visible in photographs. Although it is possible to attach other metals to the part 5 in Fig. 1 by means such as vapor deposition or sputtering, from the viewpoint of cost, it is preferable to apply a plastic film to an indium nitrate liquid as an application of the electroless sealing body according to the present invention. and baked at 200°C. This is plated with nickel in the same manner as in Example 2, and etched into a predetermined pattern to form a circuit board. As described above, the present invention can be applied in various ranges.

[Brief explanation of drawings]

FIG. 1 is a main sectional view of the liquid crystal panel. DESCRIPTION OF SYMBOLS 1, 2... Front and back substrates, 3, 4... Transparent electrodes, 5... Nickel plating layer, 6... Sealant, 7... Liquid crystal, 8... Polarizing plate. FIG. 2 is a schematic diagram of the date imprinting mechanism of the camera. 9... Lamp as a light source, 10... Liquid crystal panel and its support, 1 1... Film. Heron' figure hair Z figure

Claims (1)

[Claims] 1. An electroless plated body, characterized in that a target metal is electrolessly plated to a thickness of 2 μm or less on an insulating substrate using a semiconductor layer as a medium.