JPS58133366A - Electroless copper plating solution - Google Patents

Abstract

PURPOSE:To obtain the electroless copper plating solution which enables to form a copper-plated layer having high tensile strength, by adding metallic silver or the like and pyrrolidone or the like to an electroless copper plating solution contg. copper salt, a complexing agent, a reducing agent and a pH-adjusting agent. CONSTITUTION:At least one of metallic silver, silver iodide and metallic lead, and at least one of alpha-pyrrolidones, alpha-piperidones and aliphatic amino acid are added to an electroless copper plating solution contg. copper salt, a complexing agent, a reducing agent and a pH-adjusting agent. The amount to be added of metallic silver, silver iodide or metallic lead is at about 1mg/l, and its particle size to be used is at about 0.5-5 . The amount to be added of pyrrolidone, alpha-piperidone or aliphatic amino acid is above 0.02g/l, pref. 0.05-10g/l.

Description

[Detailed Description of the Invention] For more details about the present invention 0 no-melting steel plating solution, click here! Regarding electroless steel plating solution obtained from lj [1% plating copper].

Electroless steel milling! The research on N-blunt rounding to improve the mechanical properties of the r-symbols obtained from the pigeon has been actively carried out in recent times, and there are two reasons why it is so popular even in Japan. One is
This electroless steel plating technology has great effects when applied to the circuit formation of printed wiring boards. Compared to the electroplating method, it is less likely to cause hardness on the Jf facing part and the inner wall surface of the through hole, compared to the electroplating method. 0-order electroless steel plating, electric steel plating 1&t-etching, which is expected to occur with electrolytic steel plating, and removing etching from areas other than circuits, undercuts (in the thickness direction of the steel) are removed by etching. In the first surface part, the dimension is maintained by the etching resist film, but as the etching progresses near the substrate, the circuit Tljr direction becomes an inverted trapezoid as the etching progresses. Difficult to make @
In contrast to CnK, in electroless steel plating, only the circuit parts are plated, so there is no undercut problem and the VjJ path is #I trout KJ advantage. samurai et al.
Generally printed on plated copper II! Birophosphate steel, which is used to form circuits on plates, is inferior to steel obtained from electromechanical steel in terms of tensile strength of 1 m [↓ and bending fatigue strength measured by the 4-beam method]. After installing the parts on the Glint distribution board for my friend, I'm going to open Chunichi! ! With ff1Il, etc., there are disadvantages such as one line being cut off and the middle being empty.

Generally, the tensile strength of the steel obtained from birophosphate copper electrolyte is 50 to 60 kg/m, and the nine-hour reduction is required! III
L is 1,500 to 2,100 times.In contrast, L is obtained from electroless steel plating, which is used at an industrial level.
;b* tensile strength of approximately 50kg/m, t7 bending fatigue resistance! ! It can be completed in 800 to 1100 times for 1 KU. Since high-density wiring or high-density wiring is required, it is necessary to use electroless steel at the same time. It is advantageous for increasing the density of wiring, and at present, t is not commonly used.

Unexploded 1j Qtz This L was not found in the point, and it contained copper salt, complexing agent, electroless plating solution containing reducing agent s1-↓ and PH adjuster, metallic silver, yokuwagyome and metallic lead. and at least -ate of pyrrolidones, a-biperidone and aliphatic a()&tq#.
I'm afraid of metal silver, silver iodine, or metal lead,
When added in combination with pyrrolidones, α-piperidone, or aliphatic amino acids, the effect is much worse than in II, where only pyrrolidones, α-piperidone, or aliphatic amino acids are added. It is possible to improve tensile strength 1K, and at the same time ^
1 mg/J of am violet of metallic silver, silver sulfide, or metallic lead is sufficient to obtain high bending fatigue strength IIL. It becomes stable and does not decompose.This is because the solubility of metal-1, silver oxide, or metal lead is extremely low. Metallic steel in water at 25°C is 2,8 x 10-' g/I
, silver carbonate at 20°C 1 K Z, 5 x 10-'
g/4% metallic lead at 24°C 51xlO-'g/
It is j. *m*, I fell in love with the solubility of silver sulfide or gold Jlll lead mentioned above, and it is small, but me-) 1! This is a sufficient negative degree to improve the tensile strength of copper and to obtain high bending fatigue strength at 1W1.

Metallic silver 1M silver chloride or metallic lead is used in the form of 15 to 5m grains or primary powders.・Pyrrolidones, α-
At least %tilt of piperidone and aliphatic ainoshu
- 1 hour of 7 without addition.

In other words, *X*, the amount of metal lead produced by silver
In order to suppress the decomposition of imeriam, which is easy to cause by adding 7 to 1, pyrrolidone contains polyvinylpyrrolidone, a water bathing polymer, as well as 2-pyrrolidone and 5-pyrrolidone. , N-methyl-2-pyrrolidone,
4-methyl-2-pyrrolidone, 5-methyl-2-py
%N-ethyl-2-pyrrolidone, N-isonorovir-2-pyrrolidone, N-butyl-2-pyrrolidone%N-
Airu 2-pyrrolidone, N-7 cetyl-2-pyrrolidone, 1-7s = 2-pyrrolidone% 4-7s nyl-2-pyrrolidone, 5-phenyl-2-pyrrolidone, N-7 cetyl-4-2 enyl-2- pyrrolidone, 1-
Phenyl-3-pyrrolidone-2-carpone + L1-phenyl-5-pyrrolidone-2-carboxylic acid ether ester @5-7x nyl-5-pyrrolidone-2-carbo; /11
．． 1-7. Nyl-2-pyrrolidone-5-carboxylic acid
1 Phenyl-5-pyrrolidone-3-carboxylic acid, 2-pyrrolidone-5-carboxylic acid, 1-7ono2-
Examples include pyrrolidinone. All pyrrolidones are also effective, but 2-pyrrolidone, methyl-2-pyrrolidone, ethyl-2-pyrrolidone, vinyl-2-pyrrolidone/↓ and phenyl-2-pyrrolidone are particularly good ◎ α-piperidone With a structure similar to 2-pyrrolidone,
While 2-pyrrolidone has a 5-membered ring, α-piperidone has a 6-membered ring.
(CH proverb) Something that is triggered by ncOOH, fi is 1
~5 is a common name, for example, nx2 and β-alanine 11-3 are γ-7 mino #Ae1. m n
=4 is hokipiperidic acid. These bilridones, α-piperidone, and aliphatic amino acids have α02tt/J or more, and are well suited [LO5~10
11/I, maximum 4flL< is 1 to 51/1 ◎ Added amount is less than 102 g/j #h Stability of sweet hameri soup decreases 0 Even if there is a large amount of added weight, there is no adverse effect Generally, #&2Xl exceeding 10 g/4 t is not recommended. The electroless steel plating solution that is the base of the present invention is not particularly suitable. Copper salt.

A common electroless steel plating solution consisting of a complexing agent, a reducing agent and a F4'1wI4 conditioner is used. As a copper salt,
Sulfurized copper, halogenated steel, nitrate steel, acetate steel, etc. are used as complexing agents, such as ethylenediaminetetraacetic acid, a-tsucimel salt, etc.
Formalin, paraformaldehyde, etc. are used as reducing agents, and sodium hydroxide, etc. are used as field conditioners.Q
A typical electroless plating solution is 111 m3 to 20 m3 of sulfur.
g/j s ethylenedi7ine, copper salt wI! Storm 1.2-5 times molar m[il, 37% formalin water #?
%[2~25 mj/Js F'' 11.5~110
Nomo(/J is preferable.) It is best to store the bamboo at a temperature below 90℃.

5 In the electroless @metsukii of the present invention, rJ m polyethylene glycol sPL and its alkyl (preferably u C+
~Cm)
/4 or more, preferably (L05~IQtt/C most preferably 1
In particular, 1 to 5 g/J is planned by C and t Yamararu O.
9 Samurai n Tametsuki steel has mechanical properties same as above, reduced to % @V
The strength obtained from birophosphate electroplating is comparable to that of copper. Ethylenediaminetetravinegar [[LO
5 mol/a, formaldehyde 4103 mol/Jb F
1.812) To the solution, add the rinmat shown in the table below to create an electroless plating solution.

Electroless plating was performed at 70°C by immersing activated round stainless steel 4K on the plating face of cn et al., and plating I film thickness 2.
A 5-55 μm@foil was obtained.

hb-x No. 11 [N is also stable and the tension of the nth sea bream! 1life, the folding resistance strength is given in the table below.

The tensile strength was measured using a test piece of 10 x 70 pieces (using a tensile type universal testing machine made by Toyo Kikunibaji), with a grip interval of 1.
5auoJj 1 turning speed 1 noodle/min.
The test was carried out using a folding fatigue tester conforming to ! For fr9 songs, the percentage of points is #p &21Ia's t is used for 90 this exam-
If ↓n, the bending fatigue resistance is shown by 9 bends and 1 ridge at sample break 1. Rikano Wako J111J [Kakuwa - Shaved, chemical reagent Φ - Procedural amendment (spontaneous) Commissioner of the Japan Patent Office 4 Representative Review of the invention of the specification subject to the 5 amendment IIm's -0

Claims (1)

[Claims] t Electroless end plate rich in salt, -copper chloride, R base agent, ν-Kobita-additives! T solution 4c, metallic silver, Bp silver oxide, at least one stroke of metallic lead, and pyrrolidone-1a-biperidone↓
A small amount of aliphatic amino acid and t-dioxide were added for electroless plating 1. 26 Electroless solution of the first article in which 102 g/j or more of pyrrolidone*, α-piperidone L, and aliphatic anno#t are added.