JPH05239658A - Method for applying plating on polyester resin - Google Patents

Abstract

PURPOSE:To provide an etching liquid which can form a plating film having good adhesion on a polyester resin contg. inorg. fillers, such as glass fibers. CONSTITUTION:This method for applying plating on the polyester resin consists of a pretreating stage for immersing the surface to be plated of the polyester resin contg. the glass fibers and wollastonite into the etching liquid and subjecting the surface to an etching treatment and a plating stage for forming the plating film on the polyester resin subjected to the etching treatment. The above-mentioned polyester resin contains the glass fibers and the wollastonite and the above-mentioned etching liquid is a soln. of phosphoric acid, acidic ammonium fluoride or acid mixture composed thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a printed circuit, EMI
The present invention relates to a method for forming a plating film on the surface of a polyester resin containing an inorganic filler that can be used for shields, ornaments and the like.

[0002]

2. Description of the Related Art Conventionally, a method of plating a resin surface is generally a method of dispersing a rubber component in a resin, dissolving the rubber component with a strong acid such as sulfuric acid (referred to as etching), and then performing electroless plating. Known to. Electroless plating is a surface adjustment etching process for removing dirt on the surface of the material, degreasing for enhancing adhesion, applying catalyst easily, and enhancing adhesion, Pd, Ag, Au,
It comprises a step of activating the surface by applying a noble metal catalyst such as Pt, and a plating step of immersing the activated material substrate in an electroless plating solution to form an electroless plating film. Then, after forming an electroplating film on the electroless plating film, a heat treatment step is performed to enhance the adhesion between the plating film and the resin surface.

This conventional method is applied to ABS resin and polyacetal resin. In the case of ABS resin or polyacetal resin, recesses are formed on the surface by an etching solution composed of a mixed solution of sulfuric acid and chromic acid. Therefore, in the electroless plating step, the recess can be filled in like an anchor to form a plating film, and the adhesion between the resin surface and the plating film is high. However, in the case of a resin in which an effective recess is not formed on the surface by an etching solution, it is difficult to form a plating film having good adhesion because the plating film is not anchored.

Japanese Patent Laid-Open No. 63-83279 discloses an electroless plating method for a non-metal member (for example, a ceramic member) which is difficult to be subjected to a usual etching treatment. A method of forming is disclosed. However, the irradiation process of the laser beam has to add a new process in addition to the conventional process, and its application to the resin plating process is not always effective.

[0005]

The present invention has been made in view of the above circumstances, and by examining the composition of the etching solution, good adhesion can be obtained on a polyester resin containing an inorganic filler such as glass fiber. The purpose is to form a plating film.

[0006]

In the method of plating on a polyester resin of the present invention, the surface to be plated of the polyester resin containing glass fibers and wollastonite is immersed in an etching solution to carry out an etching treatment. In a method of plating on a polyester resin comprising a pretreatment step and a plating step of forming a plating film on the etched polyester resin, the polyester resin contains glass fibers and wollastonite, and is etched. The liquid is characterized by being phosphoric acid, ammonium acid fluoride, or a mixed acid solution thereof.

As the polyester resin to which the plating method of the present invention is applied, aromatic polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, and the like, in which glass fiber and wollastonite are blended, and a mixture thereof. Applicable to resin. As the glass fiber blended with this resin, any glass fiber blended with an ordinary resin can be used. The wollastonite is preferably a granular material having an aspect ratio of 1 to 20, and a surface-treated material may be used to enhance compatibility with the resin.

The glass fiber and wollastonite are preferably mixed in an amount of 10% by weight or more. Further, as the upper limit of the blending amount of the glass fiber and wollastonite, it is preferable that the sum of the blending amounts of both of them is about 50% by weight or less within the range of the blending amount of a usual inorganic filler. Aromatic polyester resin containing this glass fiber and wollastonite, when subjected to degreasing, pretreatment and then phosphoric acid of etching solution, ammonium acid fluoride solution and its mixed acid solution, the surface to be plated is moderately The adhesion with the electroless plating film which is applied after being subjected to roughening and cleaning, and then subjected to activation treatment such as catalyzing and accelerator is improved. The reason for this is not clear due to the presence of wollastonite in addition to glass fiber in the resin, but the adhesion of the electroless plating film is improved. That is, a comparative example (No. 1) in which the same amount of alumina powder was blended instead of wollastonite.
As in the case of 1), the adhesion of the plating film is not improved. Further, even if other sulfuric acid or oxalic acid is used as an etching solution, the adhesion of the plating film does not increase.

This is because the presence of both glass fibers and wollastonite makes it possible to enhance the adhesion, which is similar to the anchoring effect, especially at the interface between the resin layer and the glass fibers of the inorganic filler and wollastonite. It is estimated that the surface is likely to be formed. As the etching solution, a phosphoric acid aqueous solution or an ammonium acid fluoride aqueous solution is used alone or as a mixed acid aqueous solution in which both are mixed. Usual etching conditions can be applied to this etching solution.

As the method for forming the plating film, the method used in ordinary resin plating can be applied and no special step is required. Table 1 shows an example. That is, a degreasing process, a pretreatment process, an etching process, a conditioning process, a catalyzing process, an accelerator process, an electroless plating process, an activation process, an electroplating process, and a heat treatment process are sequentially performed. Rinsing with water is performed between each process. In some cases, the activation process, the electroplating process, and the heat treatment process may not be adopted.

When a polyester resin containing glass fiber and wollastonite is treated with the etching solution of the present invention,
The plating film is not limited to copper, and any plating film applicable to nickel or other resins can be used. Furthermore, the usual plating process can be applied as it is.

[0012]

In the plating method of the present invention, the glass fiber and the polyester resin containing wollastonite are subjected to an etching treatment using an etching solution composed of phosphoric acid, ammonium acid fluoride or a mixed acid solution thereof. By this etching treatment, the electroless plating film is easily adhered to the plated surface of the polyester resin containing glass fiber and wollastonite. This is because the glass fiber and wollastonite are dispersed on the surface of the resin to be plated, so the etching solution roughens and cleans the surface and activates the surface of the glass fiber and wollastonite, adhering to the plating film. It is presumed that a highly adherent plated surface is formed. As a result, a plating film having high adhesiveness is formed by the subsequent ordinary plating method.

[0013]

EXAMPLES The present invention will be specifically described below with reference to examples. Table 1 shows the types of chemicals used in each step of forming a copper plating film and the treatment conditions thereof.

[0014]

[Table 1]

In the first degreasing step, the plating surface of the resin to be plated is 50 g / a of A-screen A-200 (trade name).
After treatment with the solution of 1 for 10 minutes at 55 ° C, it is washed with water. In the second pretreatment step, a solution of 200 g / l of sodium hydroxide is treated at 70 ° C. for 20 minutes and then washed with water. In the third etching step, the etching solution shown in Tables 2 and 3 below was used.
It is treated at 10 ° C. for 10 minutes and then washed with water. In the fourth conditioning step, B-Nutrizer (trade name) 200
It is treated in a solution of ml / l at 25 ° C. for 2 minutes and then washed with water. In the fifth catalyzing step, the mixture is treated with a mixed solution of Catalyst C (trade name) and hydrochloric acid at 25 ° C. for 3 minutes and then washed with water.
In the sixth accelerator step, the substrate is treated with a hydrochloric acid solution at 25 ° C. for 10 minutes and then washed with water. In the seventh chemical plating step, the plating solution is treated at 25 ° C. for 10 minutes and then washed with water. In the eighth activation step, the solution is treated with Topsun (trade name) solution at 25 ° C. for 30 seconds and then washed with water. In the ninth electroplating step, an electroplating film is formed on the electroless plating film by applying a current of 4 A / dm ² at 25 ° C. in the plating solution. After washing with water, a plated product is obtained by treatment at 100 ° C. for 5 hours in the tenth heat treatment step. (Example 1) As shown in Table 2 in the above steps, the composition of the etching bath solution was changed by changing the ratio of the glass fiber of the inorganic filler compounded to the polyethylene terephthalate resin or the polybutylene terephthalate resin and the wollastonite. The polyethylene terephthalate resin was plated with copper after being treated differently.

No. 1 is a polyethylene terephthalate resin containing 10% by weight of glass fiber and 15% by weight of wollastonite, and 100 g of ammonium acid fluoride /
A copper-plated product of polyethylene terephthalate resin was produced through the steps shown in Table 1 using an etching solution composed of an aqueous solution of 1 and 200 ml / l of phosphoric acid. No. In 2,
No. 3 except that a polyethylene terephthalate resin was used in which the inorganic filler was compounded in an amount of 20% by weight of glass fiber and 15% by weight of wollastonite. The same etching solution as in 1 was used.

No. In No. 3, except that a polyethylene terephthalate resin containing 10% by weight of glass fiber and 10% by weight of wollastonite was used as an inorganic filler, No. 3 was used.
The same etching solution as in 1 was used. No. In No. 4, No. 4
Using the polyethylene terephthalate resin used in 1,
No. 3 except that the etching solution had a composition of phosphoric acid 100 ml / l and ammonium acid fluoride 100 g / l. The plating treatment was performed under the same conditions as in 1.

No. In No. 5, No. 5 No. 1 except that the polyethylene terephthalate resin used in 1 was used and the composition of the etching solution was ammonium acid fluoride concentration of 50 g / l and phosphoric acid of 100 ml / l. The plating treatment was performed under the same conditions as in 1. No. In No. 6, No. 6 No. 1 except that the polyethylene terephthalate resin used in 1 was used and the composition of the etching solution was 100 g / l of ammonium acid fluoride. The plating treatment was performed under the same conditions as in 1.

No. In No. 7, No. 7 No. 2 except that the polyethylene terephthalate resin used in 2 was used and the composition of the etching solution was ammonium acid fluoride of 50 g / l. The plating treatment was performed under the same conditions as in 1. No. In No. 8, No. 8 No. 3 except that the polyethylene terephthalate resin used in 3 was used and the composition of the etching solution was phosphoric acid of 200 ml / l.
The plating treatment was performed under the same conditions as in 1.

No. In No. 9, No. 9 Except that the polyethylene terephthalate resin used in 1 was used and the composition of the etching solution was phosphoric acid of 100 ml / l,
No. The plating treatment was performed under the same conditions as in 1. No.
No. 10 is No. Using the polyethylene terephthalate resin used in No. 1, No. After plating under the same conditions as 1
It was not heat treated.

[0021]

[Table 2]

No. No. 11 is No. No. 2 except that a polybutylene terephthalate resin containing the same amount of glass fiber and wollastonite as 2 was used. A plating process was performed using the same etching solution as in 1. Table 3 shows the composition. No. No. 12 is No. No. 7 except that a polybutylene terephthalate resin containing the same amount of glass fiber and wollastonite as in No. 7 was used. A plating process was performed using the same etching solution as in 1.

[0023]

[Table 3]

Example 2 A nickel plating film was formed on a polyester resin by the steps and conditions shown in Table 4 (similar to Example 1).

[0025]

[Table 4]

No. 3 in Table 3 As shown in FIG. A reagent for forming a plating film under substantially the same conditions as the copper plating film except that the polyethylene terephthalate resin containing the same amount of glass fiber and wollastonite as 1 is used and ammonium acid fluoride 100 g / l is used as the etching solution. Was used instead of nickel for plating. (Comparative Example) For comparison, as shown in Table 3, the wollastonite of the inorganic filler was changed to alumina, and the resin of the inorganic filler was used as it was, and the etching bath composition was changed to sulfuric acid and oxalic acid. A plating process was performed.

No. No. 15 is a polyethylene terephthalate resin containing 10% by weight of glass fiber and 15% by weight of alumina powder. Etching treatment and plating treatment were performed under the same conditions as in 1. No. No. 16 was No. 16 except that the composition of the etching solution was changed to 100 ml / l of sulfuric acid.
The resin of No. 1 was used to perform the plating treatment under the same conditions.

No. 17 is oxalic acid 20 as an etching solution
Other than changing to 0 g / l, no. The plating treatment was performed under the same conditions using the polyethylene terephthalate resin of No. 1. No. No. 18 is No. without etching treatment. The plating treatment was performed under the same conditions using the polyethylene terephthalate resin of No. 1. (Evaluation) The adhesion of the plated film of each plated product obtained was
It was measured by a peel test method with a width of 20 mm. The results are shown in Tables 2 and 3. The unit of adhesion in the table is kg / cm.

As shown in Tables 2 and 3, the adhesive strength in Examples 1 and 2 is in the range of 1.4 to 0.9 kg / cm, which is higher than that of Comparative Example, 0.5 to 0.3 kg / cm. It has shown that it is excellent in sex. In addition to the copper plating film, the nickel plating film also has a No. Adhesion is 1.1kg / cm as shown in 13
And is the same as copper.

Therefore, by using a solution of phosphoric acid and ammonium acid fluoride as the etching solution, a plating film having excellent adhesion can be formed on the polyester resin in a usual process.

[0031]

EFFECT OF THE INVENTION According to the plating method of the present invention, by specifying the liquid composition used for etching the polyester resin, a plating film having higher adhesion than the conventional plating film can be obtained even when the conventional plating process is applied. Can be formed. The etching solution used in the present invention, phosphoric acid and ammonium acid fluoride are used, but these are low toxicity, ammonium acid fluoride is particularly used as a component such as disinfectant and insect repellent, It is less toxic and safer than conventional sulfuric acid and chromic acid. Therefore,
The environment of the plating process can be made safer.

Front Page Continuation (72) Inventor Kiyotaka Nakai 2-1, Asahi-cho, Kariya City, Aichi Aisin Seiki Co., Ltd. (72) Inventor Yoshio Okada 2-20-65 Tamade Nishi Nishinari-ku, Osaka Satosen Co., Ltd. (72) Inventor Shingo Nishijo 2-2065 Tamade Nishi, Nishinari-ku, Osaka City Satosen Co., Ltd. (72) Inventor Shunsuke Miyashita 3-4-2 Nakanoshima 3-chome, Kita-ku, Osaka City Kanebuchi Kagaku Kogyo Co., Ltd.

Claims (1)

[Claims] 1. A pretreatment step of immersing a surface of a polyester resin containing glass fibers and wollastonite to be plated in an etching solution to perform an etching treatment, and forming a plating film on the etched polyester resin. In a method of plating on a polyester resin comprising a plating step, the polyester resin contains glass fibers and wollastonite, and the etching solution is phosphoric acid, ammonium acid fluoride or a mixed acid solution thereof. A method of plating on a polyester resin, characterized in that