JPH02232237A - Surface treatment of polyether sulfone resin molding - Google Patents

Abstract

PURPOSE:To form a film of excellent adhesion by subjecting a polyether sulfone resin molding to a specified pretreatment, sensitization, activation and electroless plating. CONSTITUTION:A degreased and water-washed polyether sulfone resin molding is immersed in a pre-etching solution comprising 100-20wt.% organic solvent- based swelling agent (e.g. N,N-dimethylformamide) for said resin and 0-80wt.% water, treated therewith at 20-60 deg.C for 1-20min, and dried at 50-80 deg.C for 5-20min with hot air after water washing. This molding is immersed in a chromic acid etching solution comprising 2-30g/l of CrO3, 1-30g/l of Cr<3+>, 400-700mol/g of 98% sulfuric acid, 60-200mg/l of 89% phosphoric acid and water, etched at 20-80 deg.C for 5-30min, and neutralized with an aqueous solution containing a base (e.g. NaOH) or an ammonium salt (e.g. ammonia). This molding is subjected to sensitization, activation and electroless plating.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for surface treatment of polyether sulfone (hereinafter referred to as PES) resin molded articles.

[Conventional technology]

PES resin is typically an aromatic polyether-based non-crystalline resin having a repeating unit represented by the formula (JP-A-54-123199, JP-A-54-144456, etc.), Although it is used for various purposes, surface treatments such as plating are difficult, and good plated products have not been obtained. Currently known resins that can be plated include ABS resin, polypropylene, polyphenylene acid, polyamide, and polycarbonate. When plating these resins, steps such as surface roughening (etching), sensitization treatment, and activation treatment are required before imparting conductivity to the resin surface by electroless plating. For example, the surface treatment method for ABS resin is degreasing → etching → sensitization/activation treatment → electroless plating. Dilute hydrochloric acid solution of tin) - activator (dilute hydrochloric acid solution of palladium chloride) method, catalyst (colloidal solution of stannous chloride and palladium chloride) → accelerator (dilute acid such as hydrochloric acid, sulfuric acid, or sodium hydroxide) IJium, etc. The latter method is currently widely used, especially in the case of ABS resin.As the electroless plating solution, an electroless copper plating solution or an alkaline electroless nickel plating solution is used. The acidic electroless nickel plating solution is usually 80%
It is not used because the ABS+M resin molded product may be deformed or the adhesion between the plating film and the resin may be reduced because it is used at temperatures above .degree. When PES II resin is treated with the conventional 8BS resin surface treatment method, the resin surface does not have enough irregularities to provide adhesion between the plating film and the resin, and even if it is plated, it will only have poor adhesion. However, there are disadvantages in that the electroless plating cannot be obtained or electroless plating cannot be formed.

In addition, PES resin is filled with inorganic filler or glass wA fibers, etc., and during etching, the inorganic filler is dissolved or the resin around the glass fibers is eluted, forming unevenness on the resin surface and improving the plating film. There are ways to strengthen adhesion. However, in order to obtain good adhesion, it is necessary to disperse the inorganic filler and glass fibers extremely uniformly during molding, which makes molding very difficult. Furthermore, since it is filled with inorganic fillers and glass fibers, it has a poor appearance and cannot be used for plated products that require a glossy or smooth surface after plating.

[Problem to be solved by the invention]

Therefore, the object of the present invention is to use unfilled (natural grade) PES resins, as well as inorganic fillers and
It is an object of the present invention to provide a method for surface treatment of PES resin molded articles, which can form a plating film with good adhesion even on PES resin filled with glass fibers or the like.

[Means to solve the problem]

The above-mentioned object of the present invention is to provide a PES resin molded product (a) to a PES resin molded product containing an organic solvent as a main component; After treatment with a pre-etching solution containing a T-fat swelling agent, 7+) etching with a chromic acid-based etching solution, 7+) then treatment with a solution containing at least one of an ammonium salt and a base, 2) subsequently This is achieved by a method for surface treatment of PES resin molded articles, which is characterized by applying phantom electroless plating after sensitization and activation treatment.

The present invention will be explained in more detail below. (a) Pre-etching treatment According to the present invention, a PES resin molded article is first cleaned with an acidic, neutral or alkaline degreasing agent, if necessary.

After degreasing and washing with water, pre-etching is performed.

Organic solvents in the pre-etching solution that can be used include lower alcohols such as methanol, ethanol, and probanol, polyhydric alcohols such as ethylene glycol and glycerin, and acid amides such as N,N-dimethylformamide and dimethylacetamide. , N-methyl-2-pyrrolidone, pyrrolidones such as 1-phenyl-3-pyrrolidone-2-carboxylic acid, ketones such as inbutyl butyl ketone, cyclohexanone, acetone, acetophenone, ethyl acetate, ethyl formate, methyl salicylate, Esters such as ethyl phthalate, organic chlorine solvents such as methylene chloride, trichloroethylene, and trichloroethane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene can be used; A mixture of two or more selected from pyrrolidones, ketone necks, esters, organic chlorine solvents, and aromatic hydrocarbon solvents can also be used.

Further, in order to perform a uniform pre-etching process, it is preferable that the organic solvent or the mixture thereof contains about 0% to 80% by weight of water.

Further, the pH of the pre-etching solution greatly influences the strength of the pre-etching action, and for the same pre-etching composition, the higher the pH, the stronger the pre-etching action. On the other hand, even when pre-etching is performed with the same composition and under the same conditions, the molding conditions (resin temperature,
The strength of the pre-etching action varies depending on the mold temperature, injection speed, injection pressure, etc.), so the pH of the pre-etching solution should be adjusted to be acidic, neutral, or alkaline, taking into consideration the chemical state of the molded product. It is preferable to use them separately.

Acids that can be used as pH adjusters include hydrochloric acid, sulfuric acid,
Examples include mineral acids such as nitric acid or their salts, organic acids such as formic acid, acetic acid, and citric acid or their salts, and mixtures containing two or more of these.

Examples of alkalis include Na. Examples include bases such as OHSKOH and their salts, amines such as triethanolamine and ethylenediamine and their salts, ammonium hydroxide, hydrazines such as foamy hydrazine and their salt necks, and mixtures of two or more of these. It will be done.

Further, in order to maintain the pH of the pre-etching solution within a certain range, it is preferable to include a pH buffer agent in accordance with each pH. Examples of pH buffers include carboxylic acids such as formic acid, acetic acid, oxalic acid, malonic acid, glycolic acid, and citric acid, and their salts; aliphatic amino acids such as glycine and ethylenediaminetetraacetic acid; and their salts. , potassium chloride, boric acid, potassium dihydrogen phosphate, sodium carbonate, and other inorganic salts, and mixtures of two or more thereof.

Specific examples of preferable pre-etching solutions include N, N-
Dimethylformamide 300-800rnl/β, propanol 50-300ml/1, triethanolamine 10-150rnl! /β, 5 to 50 g of sodium citrate/(!, a mixed solution consisting of remaining water.

The pre-etching treatment is suitably carried out at 20-60°C for 1-20 minutes.

Mouth) Etching treatment After pre-etching, wash with water or warm water,
Dry with hot air at ℃ for 5 to 20 minutes. Next, the surface is roughened or etched using a chromic acid solution, a chromium-sulfuric acid mixture, or a chromium-sulfuric acid-phosphoric acid mixture.

A preferred bath composition is CrCh2-30g/1,C
r""'1~30g/j2, 98% sulfuric acid 400~100
rd. /1, 89% phosphoric acid 50-200ml/6
A mixture consisting of the remainder water is raised. Etching treatment 1t
It is preferable to carry out the reaction at 20=80°C for 5 to 30 minutes.

c) Chromic acid removal treatment Chromic acid remains attached to the resin surface of the etched molded product. If chromic acid remains on the resin surface,
In the next step of sensitization and activation treatment, palladium, which serves as a catalyst nucleus for electroless plating, is inactivated and normal plating becomes difficult, so it is necessary to sufficiently remove it in advance. Therefore,
In the present invention, after the etching process is completed, chromic acid adhering to the resin surface is removed by washing with water and treating with a solution containing at least one of an ammonium salt and a base. Furthermore, by containing at least one type of cationic, nonionic, or anionic surfactant in this solution, palladium can be better adsorbed onto the resin surface.

Examples of ammonium salts include inorganic acid salts such as ammonium chloride, organic acid salts such as ammonium citrate, and bases such as
Aqueous ammonia, organic bases such as triethanolamine and ethylenediamine, their inorganic and organic acid salts, NaO
H, KOH, NaHCOz. , K 2 CO s and other alkali metal hydroxides, bicarbonates, carbonates, and other inorganic bases. Examples of cationic surfactants include octadecyltrimethylammonium chloride, tetradecyldimethylbenzylammonium chloride, oxyethylenedodecylamine, and octadecylamine acetate. Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene oleyl ether, and polyoxyethylene monolaurate. Further, examples of the anionic surfactant include ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, and the like.

An example of a preferable treatment liquid composition is NaOH5-100
g/i', ammonium citrate 1-100 g/R, ethyl L/7 diamine 1-100 mf/j! , ammonium chloride 1-1.00 g/A, cationic surfactant 0.
01~20g/I! , nonionic surfactant 0.01~
A solution of 20 g/A is mentioned. 20-7 using this
Preferably, the treatment is carried out at 0°C for 2 to 20 minutes.

2) Sensitization/activation treatment After washing with water, sensitization/activation treatment is performed, but the treatment method may be the sensitizer 11 activator method, catalyst → accelerator method, etc., which are usually used in fat plating. . Alternatively, a palladium solution immersion-reduction treatment method used for plating polyamide resins, through-hole substrates, etc. may be used. For example, when using the catalyst → accelerator method, the catalyst bath composition is PdCC 0. 0 3
g/β or more, SnCj! z 1 g/l or more, 36
% Hydrochloric acid 30ml/r or more, or instead of hydrochloric acid, sodium chloride 30g/l or more or hydrochloric acid 15mf/j! More than +
20-50℃ with a solution containing 15g/l or more of sodium chloride
, process for 1-10 minutes. After washing with water, 36% hydrochloric acid 30-20
0ml/l or 98% sulfuric acid 30-200mg/
! Accelerator treatment is performed with the solution at 20 to 60°C for 1 to 10 minutes.

e) Electroless plating Then, after washing with water, perform electroless plating. Any type of electroless plating that is commonly used may be used, including electroless copper plating solutions, alkaline/acidic/neutral electrolytic nickel plating solutions, and electroless copper-nickel plating solutions. ．． The polyethersulfone resin molded product thus subjected to electroless plating is further subjected to electrolytic plating, if necessary.

The present invention will be explained in more detail with reference to Examples below.

Example I PES resin natural grade (unfilled) disc (diameter 1
30mffl, thickness 3mm) first with an acidic degreaser for 40 minutes.
After degreasing at ℃ for 5 minutes and washing with water, 600 d/i' of N,N-dimethylformamide and 250 yd of propanol! /
l, triethanolamine 45ml/l, water 100ml
#, 85% formic acid 5rd/p, sodium formate 10g
/i! Processing was performed at 40° C. for 5 minutes using a pre-etching solution. After that, wash with warm water at 65℃ for 1 minute, and wash at 65℃ for 1 minute.
Hot air drying was performed for 0 minutes.

Then 5 g of CrOa/II SCr”I
O g/1, 98% sulfuric acid 500d#, 89% phosphoric acid 1
Etching was performed at 70°C for 30 minutes with 50ml/1 etching solution, and after washing with water, NaO810g/1 and ethylenediamine 50rrd! /f! , ammonium chloride 50g/1
2. Immersed in a solution of cationic surfactant (octadecyltrimethylammonium chloride>1 g/l at 40°C for 5 minutes. Then, further washed with water, PdCβ20-3 g/l
, NaCI23g/j'-nonionic surfactant (polyoxyethylene nonylphenyl ether>0.5g/l
, for 5 minutes at 40°C and washed with water. after that,
50% hypophosphorous acid 50mj'/f! at 40℃ with a solution of 5
A partial reduction process was performed. After washing with water, plating was performed at 40° C. for 15 minutes with a caustic alkaline electroless nickel plating solution (pH 9.0), followed by activation with a 5% sulfuric acid solution, and acidic copper sulfate plating was applied to 30 μm.

After leaving the plated disc indoors for a week, JISH 86
When the adhesion strength was measured by the beering test (adhesion test method) described in No. 30, an adhesion strength of 3.0 kg/cm or more was obtained.

Example 2 PES resin natural grade disc (diameter 1.30mm,
After degreasing the N-
Methyl-2-pyrrolidone 500d/j! , ethanol 1
00d/j! , ammonia water 20 d/f, ammonium citrate 30 g/12, remaining water as total amount lβ,
After pre-etching at 20°C for 5 minutes, the same process as in Example 1 was performed up to the reduction treatment, and plating was carried out at 90°C for 1 hour in an acidic electroless nickel plating solution (pH 5.0>). 20% P (P content 8%) plating film
μm was applied. After leaving the plated disc indoors for a week, 20
When a heat resistance test was conducted at 0° C. for 2 hours, no blisters, deformations, cracks, etc. occurred. Furthermore, when the same plated product was polished using puff polishing, no blistering occurred.

Example 3 After degreasing a PES resin natural grade disc (diameter 130 cm, thickness 3 aun), 250 ml/1 of N,N-dimethylformamide and 250 ml of acetone were used. /j! , methanol 300ml/1, sodium hydroxide 5g/l, sodium carbonate 20g/1, total volume 11 with remaining water, 5
After pre-etching at 0°C for 20 minutes, the same method as in Example 1 was used until the reduction treatment, and an ammonia-alkaline electroless nickel plating solution (pH 9.5 > 35°C, 15
After partial plating and activation with a 5% sulfuric acid solution, copper birophosphate plating was applied to a thickness of 30 μm. After the plated product was left indoors for a week, the adhesion was measured by a peeling test, and it was found to be 2.
．． Adhesion strength of 0 kg/cm or more was obtained.

Example 4 Flat plate containing PES1t fat glass filler (150X150
X3aus) was degreased with an alkaline degreaser at 60°C for 5 minutes, washed with water, and then treated with 600 ml of N,N-dimethylformamide.
#, ethylene glycol 150all! / l, ethyl formate 25rnl! /L9B% sulfuric acid 5 rnl/l, boric acid 5 g/l, and remaining water to make a total volume of 1 liter, pre-etched at 40° C. for 10 minutes, and then washed with hot water and dried with hot air.

Next, etching was performed at 70°C for 20 minutes with an etching solution containing 400 g/l of Cr03 and 200 ml/l of 98% sulfuric acid, and after washing with water, it was immersed in a solution of 36% hydrochloric acid 1001 nIl/l at 30°C for 5 minutes, and then washed with water. After that, NaOH 10
g/I! , ethylenediamine 10mj'#, ammonium chloride lOg/1, ammonium citrate lO
g/L anionic surfactant (Immersed in a solution of ammonium lauryl sulfate > 5 g/l at 30°C for 3 minutes. After washing with water,
Catalyst liquid (PdCfzo o. 2 g/1,
SnCIlz l 5 g/1136% hydrochloric acid 200
ml/1> for 4 minutes at 30°C, and after washing with water, an accelerator treatment was carried out by immersing it in a solution of 98% sulfuric acid 100 l/l at 45°C for 4 minutes. After washing with water, plating with ammonia alkaline electroless nickel plating solution (pH 9.5) at 35℃ for 15 minutes.
After fractional plating and activation with a 5% sulfuric acid solution, acidic copper sulfate plating was applied to 30 μm. After the plated product was left indoors for a week, the adhesion strength was measured using a beer ring test.2.
Adhesion strength of 5 kg/cm or more was obtained.

Example 5 Flat plate containing PES resin glass filler (150X150X
3), after defatting, N-methyl-2-pyrrolidone 300
-/f! , Probanol 500mf/β, Potassium hydroxide 20g/l, Sodium acetate 50g/1, Remaining water total I
As J, pre-etching was carried out at 60° C. for 15 minutes, the process from etching to accelerator was carried out in the same manner as in Example 4, and acidic electroless nickel plating was applied to 20 μm under the same conditions as in Example 2.

After the plated product was left indoors for one week, a heat resistance test was conducted at 200°C for 2 hours, and no blistering, deformation, or cracking occurred.

Example 6 A disk containing one PES resin glass filler (diameter 130 fins, thickness 3I!lII1) was pre-etched with xylene at 30°C for 5 minutes, then the etching process was performed in the same manner as in Example 1, and after washing with water, NaOH 10 g/12, ethylenediamine 10 mt'#, ammonium chloride 10 g/1,
Ammonium citrate 1 0g/12, hf one-based surfactant (tetradecyldimethylbenzylammonium chloride>3g/Il, nonionic surfactant (polyoxyethylene nonylphenyl ether>3g/l) at 30℃, After washing with water, catalyst solution (
PdCl2 o. 2 g/! , SnClx 1 5
g/I! , 36% hydrochloric acid 200rnl/f) at 30°C.
, after soaking for 4 minutes and washing with water, perform accelerator treatment with 98% sulfuric acid 100-/ji! The test was carried out by immersing the skin in a solution of 45°C for 4 minutes. After washing with water, plate with ammonia alkaline electroless nickel plating solution (pH 9.5 > 35°C for 15 minutes,
After activation with 5% sulfuric acid solution, acidic copper sulfate plating was performed at 30%
μm was applied. After the plated product was left indoors for one week, the adhesion strength was measured by a beer test, and an adhesion strength of 2.0 kg/cm or more was obtained.

Example 7 A PES resin natural grade disc (diameter: 130, thickness: 311 m) was degreased with an alkaline degreaser at 60°C for 5 minutes, washed with water, and then treated with N,N-dimethylformamide (800 m).
l/i', Probanol 100rd! /j! , 10 ml2/i' of hydrazine hydrate, 10 g/f of glycine, and the remaining water to make a total volume of 1 liter, brieged at 30° C. for 15 minutes, washed with water, and then dried with hot air.

Then, Crys 5 g/I, Cr"I
D g/l, etched with an etching solution of 98% sulfuric acid 500rIIl#, 89% phosphoric acid 150-/β for 30 minutes at 70°C, and after washing with water, CrO* 400 g/j
! , 98% sulfuric acid 200rrd! /1 of. Etched with T-etching solution at 30°C for 10 minutes and then washed with water to give a 36%
After immersing in a solution of 1300 ml/1 hydrochloric acid at 30°C for 5 minutes and washing with water, 10 g/L NaOH x 1 Or ethylenediamine
d! /L ammonium chloride lOg/2, ammonium citrate lOg/1, cationic surfactant (oxyethylene dodecylamine) 0.1g/L nonionic surfactant (polyoxyethylene oleyl ether) I
It was immersed in a solution of g/l at 30°C for 3 minutes.

After washing with water, SnClx 5 g/I! , 36% hydrochloric acid 1
After immersing in a 5-/l Sensitivity solution at 25°C for 3 minutes and washing with water, PdCf20. 1 g/I! , 3 6% hydrochloric acid 1 mj2/jl! activator solution for 3 minutes at 30°C.

After washing with water, plating was performed at 35° C. for 15 minutes with an ammonia alkaline electroless nickel plating solution (pH 9.5), and after activation with a 5% sulfuric acid solution, acidic copper sulfate plating was applied to a thickness of 30 μm. After the plated product was left indoors for one week, the adhesion strength was measured by a beer test, and an adhesion strength of 2.5 kg/c+++ or more was obtained.

Example 8 A PES resin natural grade disk (diameter: 130 mm, thickness: 3 mm) was pre-etched with methylene chloride at 30° C. for 1 minute, and then washed with water, and the etching process was performed in the same manner as in Example 1. After washing with water, 10g of NaOH. /L ethylenediamine 10-/L ammonium chloride 10g/L ammonium citrate 10g/1, cationic surfactant (tetradecyldimethylbenzylammonium chloride) 3g
/l, noni-based surfactant (boroxyethylene nonylphenyl ether) 3g/j! It was immersed in the solution at 30°C for 3 minutes. After washing with water,
/n, Sroc I! ．． 15g/i, 36%
After immersion in 200 dll of hydrochloric acid at 30°C for 4 minutes and washing with water, accelerator treatment was performed by immersing in a solution of 100 rni/l of 98% sulfuric acid at 45°C for 4 minutes. After washing with water, plating was performed at 60° C. for 15 minutes with an electroless copper plating solution, and after activation with a 5% sulfuric acid solution, acidic copper sulfate plating was applied to a thickness of 30 μm. After the plated product was left indoors for one week, the adhesion strength was measured by a beer test, and an adhesion strength of 2.0 kg/cm or more was obtained.

Comparative Example I A PES resin natural grade circle (diameter: 130 mm, thickness: 3 mm) was plated using the basic process of 8BS17M resin surface treatment. First, degrease with an acidic degreaser at 60°C for 5 minutes, and after washing with water, Crys 380 g/l, 98%
Etching was performed at 70° C. for 10 minutes using an etching solution containing 200 d/1 sulfuric acid. After washing with water, 36% hydrochloric acid 50m//41
! After immersing in a solution of 25°C for 30 seconds and washing with water, the catalyst solution (PdCj!z O.2 g/1, SnCj!,1
It was immersed in 5g/l, 36% hydrochloric acid (200ml/l) at 30°C for 3 minutes and washed with water. After that, accelerator processing is done by 36%
The test was carried out by immersion in a solution of hydrochloric acid foornl/i' at 30°C for 3 minutes. After washing with water, plating was performed at 35° C. for 15 minutes using an ammonia alkaline electroless nickel plating solution (pH 9.5), but the plating did not completely precipitate (skip phenomenon). After that, it was impossible to carry out electroplating.

Comparative Example 2 PES resin natural grade disc (diameter 130IIl
m, thickness 3 mm) was first heated at 60°C with an acidic degreaser.
After degreasing for 5 minutes and washing with water, CrCh 3 80 g/
7 with 200 ml/l of 98% sulfuric acid
Etching was performed at 0° C. for 10 minutes. After washing with water, immerse in a solution of 50 ml/l of 36% hydrochloric acid at 25°C for 30 seconds, and after washing with water,
SnC125 g/1, 36% hydrochloric acid 5 ml/I! After soaking in the sensitizer solution at 25°C for 3 minutes and washing with water, the PdC
i'2 0. 1 g/1, 36% hydrochloric acid 1rrd! /R
It was immersed in the Activate solution at 30°C for 3 minutes. After washing with water, plating was performed at 90° C. using an acidic electroless nickel plating solution (pH 5.0), but blistering occurred within 5 minutes of plating, and thereafter the material and the plating film peeled off.

Comparative Example 3 Grade disk containing PES resin glass filler (diameter 1
30 u, thickness 3n+m) was plated using the basic process of ABS resin surface treatment. First, heat at 60℃ using an acidic degreaser.
After degreasing for 5 minutes and washing with water, CrO = 380g/β, 98%
Etching was performed at 70° C. for 10 minutes using an etching solution containing 200 ml/l of sulfuric acid. After washing with water, 50 d of 36% hydrochloric acid! /1
After immersion in a solution of 25°C for 30 seconds and washing with water, the catalyst solution (Pdl20, 2g/1, SnCl2 15g/L
3 Immerse in 6% salt #200ml/β) at 30℃ for 3 minutes, wash with water, and then perform accelerator treatment with 36% hydrochloric acid 100ml/1
The test was carried out by immersing the sample in a solution at 30°C for 3 minutes. After washing with water, apply an ammonia alkaline electroless nickel plating solution (pH 9.5).
) at 35°C for 15 minutes, but the plating did not completely precipitate (skip phenomenon). After that, it was impossible to carry out electroplating.

Comparative Example 4 Grade disc containing one PES resin glass filler (diameter 13
0mm, thickness 3mm) first at 60℃ with an acidic degreaser.
After degreasing for 5 minutes and washing with water, Cry. 380g/j7,9
8% sulfuric acid 200m! ! /i' J-7 Chinda solution at 70℃
, 10 minutes of etching was performed.

After washing with water, soak in a solution of 50 ml/1 of 36% hydrochloric acid at 25°C for 30 minutes.
After soaking for seconds and washing with water, ethylenediamine 30 mβ/β, ammonium chloride 10 g/l, ammonium citrate 1
Og/j1! , cationic surfactant 1g/! After immersing in a solution of 30° C. for 3 minutes, washing with water and adding Chiyatalist solution (PdCl 2 0.2 g/I!, SnCβ
215g/I! , 36% hydrochloric acid 200mj'/i')
It was immersed at 0°C for 3 minutes and washed with water. After that, accelerator treatment with 36% hydrochloric acid 100mf/j! The test was carried out by immersing the sample in a solution at 30°C for 3 minutes. After washing with water, plating with ammonia alkaline electroless nickel plating solution (pH 9.5) at 35℃ for 15 minutes.
After partial plating and activation with a 5% sulfuric acid solution, acidic sulfuric acid steel plating was applied to 30 μm.

After allowing the plated product to sit indoors for one week, the adhesion strength was measured using a beer test, and the adhesion strength was 1.0 kg/cm or less.

The composition of the plating solution used in each example and comparative example is as follows.

0 Caustic alkaline electroless nickel plating solution (Example 1) - Nickel sulfate 20g/N - Sodium citrate 15g/1 - Sodium hypophosphite 20g/β - Ammonia water
5ml/R・Adjust to 89.0 with caustic soda 0 Ammonia alkaline electroless nickel plating solution (Examples 3, 4, 6, 7, Comparative Examples 1, 3, 4)・Nickel sulfate 20g/1・Citric Ammonium acid 20g/β/sodium hypophosphite
20g/1・adjusted to pH 9.5 with ammonia water 0 acidic electroless nidekel plating solution (Examples 2, 5, comparative example 2)・Nickel sulfate 25g/12・citric acid・soda acetate・sodium hypophosphite・caustic soda I]H5. Electroless copper plating solution adjusted to 0 (Example 8) ・Copper sulfate 15g/f・EDTA
40g/1・rose formaldehyde
8g/1 ・Diviridyl 30■/1 ・Polyethylene glycol Ig/n ・Caustic soda LOg/1 (pH 12
．． 5) 0 acidic copper sulfate electroplating solution (Examples 1, 4, 6,
7, 8, Comparative Example 4) ・Copper sulfate 225g/1・Sulfuric acid
56g/! 1. Brightener (IBAC-
IEP (Ebara Yudyrite @!!) 0 Copper birophosphate electroplating (Example 3) Copper birophosphate
90g/1・Potassium birophosphate 375
g/l ammonia water 3 mf!
/ 1L5g/1 lOg/12 20g/1 ・P ratio 7.5 ・Brightener PyroBly}PY-61 (manufactured by Uemura Kogyo)
[Effects of the Invention] According to the present invention, the polyethersulfone resin molded product has the following properties:
A plating film with good adhesion can be formed without causing blisters, deformations, cracks, etc.

Claims (7)

[Claims] (1) A) After treating the polyethersulfone resin molded product with a pre-etching solution containing a swelling agent for polyethersulfone resin whose main component is an organic solvent, b) Etching with a chromic acid-based etching solution c) then treated with a solution containing at least one of an ammonium salt and a base, d) subsequently subjected to sensitization and activation treatment, and e) subjected to electroless plating. Surface treatment method for resin molded products. (2) The method according to claim (1), wherein the pre-etching solution is a mixture containing one or more selected from the group consisting of water, a pH adjuster, and a pH buffer. (3) The organic solvent contained in the pre-etching solution is a group consisting of alcohols, acid amides, pyrrolidones, ketones, esters, organochlorine solvents, aromatic acid hydrocarbons, and mixtures of two or more of these. Claim (1) selected from
Method described. (4) The pH adjuster contained in the pre-etching solution is
The method according to claim 2, wherein the acid is selected from the group consisting of organic acids, inorganic acids, salts thereof, and mixtures of two or more thereof. (5) The pH adjuster contained in the pre-etching solution is
3. The method according to claim 2, wherein the base is selected from the group consisting of amines, hydrazines, inorganic bases, salts thereof, and mixtures of two or more thereof. (6) The pH buffer contained in the pre-etching solution is
The method according to claim (2), wherein the compound is selected from the group consisting of carboxylic acids and their salts, aliphatic amino acid compounds, inorganic salts, and mixtures of two or more thereof. (7) The method according to claim (1), wherein the treatment liquid used in step (c) contains a surfactant.