JPS62156282A - Pretreating solution for electroless plating - Google Patents

Abstract

PURPOSE:To carry out both degreasing and conditioning with the resulting titled pretreating soln. and to reduce the number of working stages by adding a silane coupling agent, a nonionic surfactant and EDTA. CONSTITUTION:An aqueous soln. contg. a silane coupling agent such as CH2= CHSi(OC2H5)3, a nonionic surfactant such as polyoxyethylene lauryl ether and EDTA, a salt or deriv. thereof is prepd. as a pretreating soln. This pretreating soln. is especially suitable for use as a pretreating soln. for the electroless copper plating of a printed wiring board.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a pretreatment solution for electroless JIs copper plating of printed wiring boards, and in particular to a pretreatment solution for electroless JIs copper plating of printed wiring boards. be.

(Prior art) Printed wiring boards are produced by drilling holes in copper-clad or copper-free laminates.
Manufactured by electroless plating. Conventionally, pre-treatments for electroless steel plating include an alkaline degreasing process, a conditioning process, a knot etching process for the surface steel foil, a pickling process, a sensitization process (catalyst application), a dense layer promotion process, etc. There are two stages of conditioning.

Degreasing as a pretreatment for electroless plating is to clean dirt such as processing oil, cow oil, and other grown products on the surface of the plated object, and conventionally, it is carried out using an alkaline bath solution. I was worried. The function of conditioning is
The surface of the object to be plated, which is lipophilic, is treated with a surfactant, etc.
The purpose is to make it hydrophilic so that it is easy to wet, and to promote the adsorption effect of the catalyst in the so-called sensitizing process that will be carried out later.

(Problem to be solved by the invention) However, there is no method that performs degreasing and conditioning in two steps.
One deplating stopper requires many steps to create strips, which increases equipment costs.

The present invention consists of two processes: degreasing and conditioning.
It is similar to the pretreatment solution for #1 deplating, which can be performed with PN and one solution.

(Means for Solving the Problems) The present invention is a pretreatment for electroless plating consisting of a silane coupling agent, a nonionic surfactant, and a water-soluble substance such as ethylenediaminetetraacetic acid or its insects or their visiting bodies. It is a teaching.

The silane coupling agent forms a monomolecular film on the glass surface, which is the crystalline phase of the laminate, and its terminal group is aqueous, so it is easy to attach a catalyst (for example, Pd) during the subsequent sensitization process. I thought it would happen.

As a silane coupling agent, general formula Xk-5i ((
CH2)l-Y)m (However, X; 0CnH2
n++.

-0COCH3, -0(CH2)nOcHs, CI,
Br, I.

Y; H, -CH:CH2, -NH2, -NH(CH
*HaNH2.

k=1-5, e=1-7, m=1-5) are preferred, and specifically the following are preferred. CHz=CH3i(OC2Hs)s, Ckh=C
H8i(OCH2CH2OCH2.CHz=CH5
iC6a, NH2(C1(2)3Si(OC2Hsha, NH2(C1hhaNH(Ckh)s S 1(OC
H3) 3゜NH2C0NH(CIh)ss 1(OCH
s)s, NH2(CH2)2NH(CHzJxS t
cHs(OCRs)z.

Examples of nonionic surfactants include H, L, and B.

(Hydrophile Lipophile B
a1ance) Those of Nos. 111 to 16 are good, and their hydrophilicity is considered to be suitable for degreasing, and also to improve the water-wetting property of the plated object. These are -fi formula RO(CHzCH2O)nH (however, R;
-CnH2n+x.

−CnH2n+l〈=Σ) is good,
Specifically, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene nonylphenyl ether are used.
,ru.

Ethylenediaminetetraacetic acid, or its derivative (sodium residue) or its spindle is thought to act on gold 4 when the object to be plated is a metal such as copper, create a complex salt, and remove metal oxides. Specifically, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid tetrasodium salt, human mixyethylethylenediaminetriacetic acid tll15 sodium!:M are used.

Silane coupling jl14!0.1~I G g#I
, the nonionic surfactant is used as an aqueous solution of 0.1 to 50 g #1 of ethylenediaminetetra rnrHm hlα2 to l Og/l.

The substrate is immersed in a plating solution (temperature 40-70℃).
℃, time 1 to 10 minutes) and then washing with water.

(Example) Example 1 (double-sided steel-clad glass epoxy mold) fII temporary was soaked in oil diluted with methyl ethyl ketone for 11 days, dried, and then
, is a dirty substrate. Dirt 71. Ta:! Ni Rebellion 1, A-1
100 (r-aminopropylethoxy7 run.

Nippon Unicar Co., Ltd. IK) 2 g/1. Nonion H8-21
0 (Polyoxyethylene octylphenyl ether, Japan Oil 8fJH)2OI? /1% Krewat) OH#500
(Hydroxyethylene 7 amine triacetate e increase, Teikoku Kagaku Sangyo table) 4g/'l pre-preparation for aqueous solution J! 60℃ for l solution
, treated for 4 minutes (degreasing), washed with water, and then added etching solution (1
50g/#Gaga I#R ammonium) for a certain period of time, add 1 to 1, add 1 to the amount before dissolving the copper, and add 2 to acid →
It was determined that the greater the number of i, the better the degreasing power.

Example 2゜Same stain as Example 1, eyebrow sheet metal, A-11001g/1
%Nonion H5-2101g/l, Flewat 0141
Treated for 4 minutes at 60°C with a pretreatment solution containing 500 2g #l,
The jlpi bath M'Bk was determined in the same manner as in Example 1, and the degreasing power was determined.

Actual Mr. 4 Examples 5 The same contaminated substrate as in Example 1 was used with A-M2O (β-aminoethyl-T-aminopropyltrimethoxysilane, Nippon Unicar a4J) 5 g/L nonionic NS-22O (polyoxyethylene nonylphenyl ether). , manufactured by Nihon Yushi Co., Ltd.) 5 g/e, Flewat OH#500 (Hydroxyethylenediamine triacetate tII salt, manufactured by Teikoku Kagaku Sangyo Co., Ltd.) 5 g
Treated with a pretreatment solution containing ZE at 60°C for 4 minutes.

The copper dissolution-fit was determined in the same manner as in Example 1, and the degreasing power was determined.

Comparison? 01゜The same contaminated substrate as in Example 1 was treated with HCR-2O1 (alkaline degreasing liquid, Hitachi Chemical Co., Ltd.) at 60°C for 4 minutes,
Copper bath screens were obtained in the same manner as in Example 1, and the degreasing power was determined.

Comparison? lJ 2゜Same stain as in Example 1 r1. Board 'kcOND-2O1 (
It was treated with a conditioner (manufactured by Hitachi Chemical Co., Ltd. containing a surfactant) at 60°C for 4 minutes, and the amount of copper dissolved in the bath was determined in the same manner as in Example 1, and the total degreasing power was evaluated.

Example 46 Double-sided copper-clad crow epoxy shield prepared by drilling with a 1.0 mm diameter drill at 60°C with the same pretreatment solution as in Example 1.
The hole was placed in a quiet T/C box, and the time taken for the air to escape from the hole was measured, and it was determined that the shorter the time, the better the water was poured.

Example 5 A hole was drilled in a double-sided steel-clad glass epoxy laminated plate using a drill with a diameter of 1.0 mm, and the same pretreatment liquid as in Example 2 (6
The time for air to escape from the philtrum was measured in the same manner as in Example 4 at 0°C), and was determined to be 7'Lff-.

Example 6 Double-sided steel-clad glass epoxy stacking & was drilled with a drill with diameters of 1° and 4. The same pretreatment solution as in Example 6 (6
At 0°C), the time for air to escape from the large medium was added as in Example 4 and 1, and the water content was determined.

Comparative example & Double-sided steel clad glass epoxy stacking hole drilled with a 1.0mm diameter drill'kHcR-2O1 (60℃)
In the same manner as in Example 4, the time for air to escape from the human body was measured,
I fixed 1J of water.

Comparative Example 4゜Double-sided copper-clad glass epoxy shell/it! If the hole was drilled with a direct 1.0 city drill, it would be C0ND-2O1 (60
℃), the entire time for the air to escape from the large medium was measured in the same manner as in Example 4, and the water level was determined.

Example B: Double-sided copper plated glass epoxy plate with a diameter of 1.0 mm.
The gold sample was prepared using a drill, puff-polished (using Emery Plast), and honed (for Tosa Emery #280).

This sample was treated for 4 minutes at 60°C with a pretreatment solution of 11th generation, and after washing with water, 2O0g/l ammonium persulfate solution (soft etching 1OL), 10% H2S04 (pickling
! i), 270 g/l PD-2O1 (Bridip, Hitachi Chemical Co., Ltd.), H8-2O1B (sensitizer 1 manufactured by Hitachi Chemical Co., Ltd.), ADP-2O1 (adhesion promoter, Hitachi Chemical Co., Ltd.)
Electroless plating pretreatment from (also manufactured by)! All operations, CUST-2O1
(Electroless copper plating solution, manufactured by Hitachi Chemical Co., Ltd.) for 20 minutes, and 5 A/drn for pyrophosphate steel plating.

The test was carried out for 64 minutes, and the presence or absence of through-hole voids was examined.

Example a The same sample as in Example 7 was used, treated with the same pretreatment solution as in Example 2 at 60°C for 4 minutes, washed with water, and then subjected to the same pretreatment as in Example 7: pretreatment for electrolytic plating and electroless copper plating. All pyrophosphate steel plating was performed and the presence or absence of through-hole voids was examined.

Example 9 Using the same sample as in Example 7, treated with the same pretreatment solution as in Example 3 at 60°C for 4 minutes, washed with water, and then subjected to the same electroless plating pretreatment as in Example 7, electroless copper plating, and pyrroline. Acid steel plating was performed to examine the presence or absence of through-hole voids.

The results of Examples 1 to 3 and Comparative Example 1 are shown in Table 1.

Table 1. Degreasing Power As shown in Table 1, the pretreatment liquids of Examples 1 to 3 had good degreasing powers. Since C0ND=2O1 is not a degreasing agent, its degreasing power is low.

Table 2 shows the results of Examples 4 to 6 and Comparative Examples 2 to 6.

Table 2. Miznu 11 items As shown in Table 2, the results for Examples 1 to 5 were also the same.

Compared to HCR-2O1 and C0ND-2O1, the air in the medium escapes quickly and the water resistance is good, but since HCR-2O1 is not a conditioner, its water resistance is low.

Implementation f117-90 items are shown in Table 6.

Table 5: Measuring notes for through holes As shown in Table 3, the ratio of the tusk treatment solution to Example 1 was 30%.

Good plating properties for through holes.

From the results of Examples 1 to 9, HCR-2O1 is free of #L C
It can be seen that 0ND-2O1 only has a conditioning effect, and the uninvented 1st me has both effects.

(Effect of the invention) According to the present invention, no m! 4. Degreasing and conditioning in the 4-milling pre-treatment process can be done in one solution, so there is no reduction in the number of man-hours required for one row.

Claims (1)

[Claims] 1. A pretreatment solution for electroless plating comprising an aqueous solution containing a silane coupling agent, a nonionic surfactant, and ethylenediaminetetraacetic acid or a salt thereof or a derivative thereof. 2. The silane coupling agent has the general formula (Xk・Si((C
H_2)l・Y)m (However, X;-OCnH_2_n_
+_1, -OCOCH_3, -O(CH_2)nOCH
_3, Cl, Br, I, Y; H, -CH=CH_2, -
NH_2, -NH(CH_2)_2NH_2, k: 1~
3, l = 1 to 7, m = 1 to 3), and the nonionic surfactant has the general formula RO(CH_2CH_2O)nH (where R: -CnH_2_n_+_1, CnH_2_n_+
_1■) A pretreatment liquid for electroless plating according to claim 1.