JPH0598474A - Surface treatment of metal - Google Patents

Abstract

PURPOSE:To prevent the rust of the copper (alloy) circuit part of a printed circuit board and to improve the solderability by carrying out surface treatment with a preflux soln. contg. a salt of a compd. or a deriv. thereof represented by a prescribed chemical formula. CONSTITUTION:A preflux soln. contg. a salt of a compd. or a deriv. thereof represented by the chemical formula [where R is 0-6C alkyl, (m) is 2-7, (n) is 0-3.0, (o) is 0-4 and (p) is 0-4] is prepd. The surface of a metal or the surface of a printed circuit board is coated with the preflux soln. or this surface-treated board is further subjected to complex forming treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment of metal, and is particularly suitable as a heat-resistant preflux for preventing the circuit portion of a printed wiring board made of copper or copper alloy from rusting and improving solderability. Is.

[0002]

2. Description of the Related Art Pre-flux, which has been conventionally used for the purpose of preventing corrosion of a circuit portion made of copper or a copper alloy of a printed wiring board and maintaining solderability, is roughly classified into rosins for coating the entire printed wiring board. System preflux,
There are two types of alkylimidazole-based preflux that selectively chemically react with copper or copper alloys. For the former, apply natural rosin, rosin ester, rosin-modified maleic acid resin, etc. dissolved in an organic solvent with a roll coater, or spray or dip it on the entire printed wiring board and dry to form a film. Used in the method. Therefore, there is a drawback that the working environment and safety are significantly impaired by the volatilization of the organic solvent. The rosin-based preflux also has a drawback that it involves a risk of ignition during work because it uses a volatile solvent. On the other hand, the alkylimidazole-based preflux is water-soluble and is excellent in terms of working environment and safety, but when the chemically reacted alkylimidazole copper complex is exposed to high temperatures, it is a catalyst for oxygen and copper in the air. It deteriorates by the action and inhibits the action of postflux,
It has the drawback of deteriorating the solderability.

[0003]

In recent years, a surface mounting method has been widely adopted as a method for soldering an electronic component to a printed wiring board. The surface mounting method, the reflow of solder paste solder for electronic components, the printed wiring board is often exposed to high temperatures, and the heat resistance of the pre-flux used to maintain the solderability of the printed wiring board, That is, the pre-flux performance is required to have excellent solderability after the printed wiring board is exposed to high temperature. Further, it is desired to develop a preflux which does not use a volatile solvent having a problem in air pollution and has excellent solderability even after being exposed to a high temperature.

[0004]

In view of such circumstances, the inventors of the present invention have made extensive studies on a preflux which does not use a volatile solvent and has good solderability even after being exposed to a high temperature. As a result, acetic acid, capric acid, glycolic acid,
Paranitrobenzoic acid, paratoluenesulfonic acid, picric acid, oxalic acid, formic acid, succinic acid, phosphorous acid, maleic acid,
Acrylic acid, fumaric acid, tartaric acid, adipic acid, lactic acid,
Organic acids such as oleic acid, hydrochloric acid, sulfuric acid, phosphoric acid, or zinc acetate, lead acetate, zinc hydroxide, lead hydroxide, zinc sulfide, zinc phosphate, zinc oxide, zinc chloride, ferrous chloride, ferric chloride ,
Ferrous oxide, ferric oxide, cuprous chloride, cupric chloride, cuprous oxide, cupric oxide, copper hydroxide, copper phosphate, copper carbonate,
At least one liquid selected from the group consisting of an aqueous solution containing a metal compound such as copper acetate and copper sulfate, or a water-soluble solvent such as methanol, ethanol, isopropyl alcohol, butanol, and acetone, and 1)
When a solution prepared by mixing one kind or two or more kinds of the compounds represented by the above is used as a metal surface treatment agent, it was found that the above-mentioned conventional problems can be solved and the intended purpose can be achieved, and the present invention has been completed. It has come to do. (Chemical formula 1)
The above-mentioned organic acids used for solubilizing or emulsifying the compound represented by are organic acids, salts of organic acids,
Alternatively, water-soluble solvents such as alcohols can be used alone, respectively, or can be mixed and used at an arbitrary ratio. For example, the above water-soluble solvent may be used alone or in combination with other organic acids. In particular, when the organic acid or the like alone makes it difficult to dissolve the compound represented by (Chemical Formula 1) or its derivative, It is preferable to contain a water-soluble solvent, and in this case, it is often appropriate that the content is 0.01 to 60%. The solution obtained by dissolving with each of the above-mentioned solvents contains 0.01 to 20% of the above-mentioned active ingredient,
Preferably a solubilization solution containing 0.5-5%, or
The method of dipping in an emulsified solution is generally used, and dipping is 0
In the temperature range of 100 ° C to 100 ° C, the dipping time is preferably in the range of several seconds to several tens of minutes. Also, after forming the chemical conversion film, oxidize infrared rays / near infrared rays / far infrared rays / ultraviolet rays to 0-300
A treatment range of several seconds to several tens of minutes is suitable in the temperature range of ° C. An exposure treatment range of a few seconds to a few tens of minutes is suitable for ozone O ₃ . The range of treatment with a chemical solution such as immersion and spraying for several seconds to several tens of minutes in a concentration of hydrogen peroxide water of 1 to 20% is appropriate.
By performing the treatments 1 to 3, a chemical conversion coating having excellent heat resistance can be obtained. As the active ingredient of the metal surface treating agent of the present invention, (Chemical Formula 1) is exemplified as a preferable example. To apply the surface treatment agent of the present invention to a metal surface or the surface of a printed wiring board, a method of dipping or spraying is used.

[0005]

According to the above-mentioned preflux processing method,
It is possible to manufacture a printed wiring board which has good spreadability and wettability of cream solder, a solder rising rate after reflow, and wettability, and is excellent in terms of working environment and safety.

[0006]

EXAMPLE A 1% solution containing 2-cyclopropylbenzimidazole as an active ingredient was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm × 5 cm × 0.
A 3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a sample piece, and the 2-cyclopropylbenzimidazole was used as an active ingredient. It was immersed in a 1% solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Moisture resistance (90% RH / 4
The test piece after the 0 ° C./96 hr) treatment was dipped in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 1.

[0007]

[Example] A 1% solution containing 2-cyclobutylbenzimidazole as an active ingredient was placed in a 1-liter container and the liquid temperature was adjusted to 4
The temperature was adjusted to 0 ° C. On the other hand, 1 cm x 5 cm x 0.3
mm copper plate and 10 cm x 12 cm x 1.6 mm through-hole substrate are degreased, washed with water, soft etching, washed with water,
The surface of the test piece was prepared by pickling and washing with water, and the test piece was prepared. The test piece was immersed in a 1% solution containing 2-cyclobutylbenzimidazole as an active ingredient for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. ..
It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Moisture resistance (90% RH / 40 ° C / 9
6 hr) The treated test piece was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 1.

[0008]

EXAMPLE A 1% solution containing 2-cyclopentylbenzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm × 5 cm × 0.
A 3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare the test piece,
-Dip for 60 seconds in a 1% solution of cyclopentibenzlumidimidazole as the active ingredient. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40
(° C / 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester.
The test results are shown in Table 1.

[0009]

EXAMPLE A 1% solution containing 2-cyclohexylbenzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm × 5 cm × 0.
A 3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare the test piece,
It was immersed for 60 seconds in a 1% solution containing cyclohexylbenzimidazole as the active ingredient. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40
(° C / 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester.
The test results are shown in Table 1.

[0010]

EXAMPLE A 1% solution containing 2-cycloheptylbenzimidazole as an active ingredient was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm × 5 cm × 0.
A 3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare the test piece,
It was immersed for 60 seconds in a 1% solution containing cycloheptylbenzimidazole as the active ingredient. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40
(° C / 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester.
The test results are shown in Table 1.

[0011]

EXAMPLE A 1% solution containing 2-cyclopentylmethylbenzimidazole as an active ingredient was placed in a 1 liter container,
The liquid temperature was adjusted to 40 ° C. by heating. On the other hand, 1 cm x 5 cm
× 0.3mm copper plate and 10cm × 12cm × 1.6m
Prepare the test piece by degreasing, washing with water, soft etching, washing with water, pickling, washing with water on the through-hole substrate of m.
It was immersed for 60 seconds in a 1% solution containing the above-mentioned 2-cyclopentylmethylbenzimidazole as an active ingredient. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. Put in a hot air dryer at 200 ° C for 1
It was heated for 0 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (9
The test piece after the treatment of 0% RH / 40 ° C./96 hr) was dipped in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 1.

[0012]

Example A 1% solution containing 2- (2-cyclopentylethyl) benzimidazole as an active ingredient was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm
× 5 cm × 0.3 mm copper plate and 10 cm × 12 cm ×
A 1.6 mm through-hole substrate was degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and 1% containing 2- (2-cyclopentylethyl) benzimidazole as an active ingredient It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 2.

[0013]

[Example] A 1% solution containing 2- (2-cyclohexylethyl) benzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm
× 5 cm × 0.3 mm copper plate and 10 cm × 12 cm ×
A 1.6 mm through-hole substrate was degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and 1% containing 2- (2-cyclohexylethyl) benzimidazole as an active ingredient It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 2.

[0014]

EXAMPLE A 1% solution containing 2- (3-cyclohexylpropyl) benzimidazole as an active ingredient was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1c
m × 5cm × 0.3mm copper plate and 10cm × 12cm
A 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and the above-mentioned 2- (3-cyclohexylpropyl) benzimidazole is used as an active ingredient 1. % Solution for 60 seconds. After that, rinse with water and put in a hot air drier for 120
After heating at ℃ for 5 minutes, put it in a hot air dryer at 200 ℃ for 1
After heating for 0 minutes, a post flux was brush-painted before the measurement to measure the solder rise of the through hole. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 2.

[0015]

Example A 1% solution containing 2- (4-cyclohexylbutyl) benzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm
× 5 cm × 0.3 mm copper plate and 10 cm × 12 cm ×
A 1.6 mm through-hole substrate was degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and 1% containing the above-mentioned 2- (4-cyclohexylbutyl) benzimidazole as an active ingredient It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 2.

[0016]

EXAMPLES 2-Cyclopropylbenzimidazole, 2
-A 1% mixed solution containing cyclopentylbenzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled,
The surface was washed by washing with water to prepare a test piece, and the test piece was immersed in a 1% mixed solution containing 2-cyclopropylbenzimidazole and 2-cyclopentylbenzimidazole as active ingredients for 60 seconds. After that, rinse with water and put in a hot air dryer. 1
After heating at 20 ° C for 5 minutes, put in a hot air dryer to 200 ° C
After heating for 10 minutes, the post flux was brush-painted before the measurement to measure the solder rise of the through hole. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 2.

[0017]

Example A 1% solution containing 2- (1-methylcyclopropyl) benzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm
× 5 cm × 0.3 mm copper plate and 10 cm × 12 cm ×
A 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and the above-mentioned 2- (1-methylcyclopropyl) benzimidazole is used as an active ingredient 1. % Solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 2.

[0018]

Example A 1% solution containing 2- (2-methylcyclopropyl) benzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm
× 5 cm × 0.3 mm copper plate and 10 cm × 12 cm ×
A 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and the 2- (2-methylcyclopropyl) benzimidazole is used as an active ingredient 1. % Solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 3.

[0020]

EXAMPLE A 1% solution containing 2- (2,2,3,3-tetramethylpropyl) benzimidazole as an active ingredient
It was put in a liter container, and the liquid temperature was adjusted to 40 ° C. by heating.
On the other hand, 1 cm x 5 cm x 0.3 mm copper plate and 10 cm
A test piece was prepared by degreasing, washing with water, soft etching, washing with water, pickling, washing with water on a through-hole substrate of × 12 cm × 1.6 mm, and preparing the above-mentioned 2- (2,2,3,3-tetramethylpropyl). ) It was immersed for 60 seconds in a 1% solution containing benzimidazole as an active ingredient. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40
(° C / 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester.
The test results are shown in Table 3.

[0021]

[Example] A 1% solution containing 2- (1-methylcyclohexyl) benzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm
× 5 cm × 0.3 mm copper plate and 10 cm × 12 cm ×
A 1.6 mm through-hole substrate was degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and 1% containing 2- (1-methylcyclohexyl) benzimidazole as an active ingredient It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 3.

[0022]

Example A 1% solution containing 2- (2-methylcyclohexyl) benzimidazole as an active ingredient was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm
× 5 cm × 0.3 mm copper plate and 10 cm × 12 cm ×
A 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and 1% containing 2- (2-methylcyclohexyl) benzimidazole as an active ingredient It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 3.

[0023]

[Example] A 1% solution containing 2- (3-methylcyclohexyl) benzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm
× 5 cm × 0.3 mm copper plate and 10 cm × 12 cm ×
A 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and 1% containing 2- (3-methylcyclohexyl) benzimidazole as an active ingredient It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 3.

[0024]

[Example] A 1% solution containing 2- (4-methylcyclohexyl) benzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm
× 5 cm × 0.3 mm copper plate and 10 cm × 12 cm ×
A 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and 1% containing 2- (4-methylcyclohexyl) benzimidazole as an active ingredient It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 4.

[0025]

EXAMPLE A 1% solution containing 2- (4-pentylcyclohexyl) benzimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1c
m × 5cm × 0.3mm copper plate and 10cm × 12cm
A 1.6 mm through-hole substrate was degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and the above-mentioned 2- (4-pentylcyclohexyl) benzimidazole was used as an active ingredient 1. % Solution for 60 seconds. After that, rinse with water and put in a hot air drier for 120
After heating at ℃ for 5 minutes, put it in a hot air dryer at 200 ℃ for 1
After heating for 0 minutes, a post flux was brush-painted before the measurement to measure the solder rise of the through hole. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 4.

[0026]

[Example] A 1% solution containing 2-cyclopentylsilimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm × 5 cm × 0.
A 3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare the test piece,
It was immersed for 60 seconds in a 1% solution containing cyclopentyl silimidazole as the active ingredient. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40
(° C / 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester.
The test results are shown in Table 4.

[0027]

[Example] A 1% solution containing 2- (2-cyclopentylethyl) tosylimidazole as an active ingredient was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm
× 5 cm × 0.3 mm copper plate and 10 cm × 12 cm ×
A 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and 1% containing 2- (2-cyclopentylethyl) tosylimidazole as an active ingredient It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 4.

[0028]

Example A 1% solution containing 2- (1-methylcyclohexyl) tosilylimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1c
m × 5cm × 0.3mm copper plate and 10cm × 12cm
A 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and the above-mentioned 2- (1-methylcyclohexyl) tosilylimidazole is used as an active ingredient. It was immersed in a 1% solution for 60 seconds. After that, rinse with water and put in a hot air drier for 120
After heating at ℃ for 5 minutes, put it in a hot air dryer at 200 ℃ for 1
After heating for 0 minutes, a post flux was brush-painted before the measurement to measure the solder rise of the through hole. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 4.

[0029]

[Example] A 1% solution containing 2-cyclopentylxylylimidazole as an active ingredient was placed in a 1-liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5 cm x
0.3mm copper plate and 10cm × 12cm × 1.6mm
Degreasing, washing with water, soft etching,
The surface of the test piece was prepared by washing with water, pickling, and washing with water to prepare a test piece, which was then immersed in a 1% solution containing 2-cyclopentylxylylimidazole as an active ingredient for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH /
The test piece after the 40 ° C./96 hr) treatment was dipped in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 4.

[0030]

The pre-flux of the present invention has a coating film formed on the surface of copper or a copper alloy, which has excellent heat resistance, spreads cream solder well even after being exposed to high temperature, has good wettability, and has excellent reflow solderability. This is particularly effective in terms of good solderability and wettability, and in terms of working environment and safety, in surface mounting electronic components on a printed wiring board.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 22, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title of method for surface treatment of metal

[Claims]

[Chemical 1]

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal rust preventive treatment, and is suitable as a heat-resistant preflux for preventing a metal exposed portion of a printed wiring board from rusting and improving solderability. Also, solder, electroless solder, nickel
Rust prevention of gold, silver, zinc, etc., connector pinholes, no
Also suitable as a sealing agent with lubricity for electrolytic solder, etc.
It is something.

[0002]

2. Description of the Related Art Preflux, which has been conventionally used for the purpose of preventing corrosion of a circuit portion made of copper or a copper alloy of a printed wiring board and maintaining solderability, is roughly classified into a rosin that coats the entire printed wiring board. System preflux,
There are two types of alkylimidazole-based preflux that selectively chemically react with copper or a copper alloy. For the former, apply natural rosin, rosin ester, rosin-modified maleic acid resin, etc. dissolved in an organic solvent with a roll coater, or spray or dip it on the entire printed wiring board and dry to form a film. Used in the method. Therefore, there is a drawback that the working environment and safety are significantly impaired by the volatilization of the organic solvent. In addition, since rosin-based preflux uses a volatile solvent, it also has a drawback that there is a danger of ignition during work. On the other hand, the alkyl imidazole pre-flux is water-soluble and is excellent in terms of working environment and safety, but when the chemically reacted alkyl imidazole copper complex is exposed to high temperature, it is a catalyst of oxygen and copper in the air. It deteriorates by the action and inhibits the action of postflux,
It has the drawback of deteriorating the solderability.

[0003]

Recently, a surface mounting method has been widely adopted as a method for soldering an electronic component to a printed wiring board. Due to this surface mounting method, reflow of solder paste solder for electronic parts, and the like, the printed wiring board is more often exposed to high temperatures, and the heat resistance of the pre-flux used to maintain the solderability of the printed wiring board, That is, the pre-flux performance is required to have excellent solderability after the printed wiring board is exposed to high temperature. Further, it is desired to develop a preflux which does not use a volatile solvent having a problem of air pollution and has excellent solderability even after being exposed to a high temperature.

[0004]

In view of such circumstances, the present inventors have made earnest studies on a preflux which does not use a volatile solvent and has good solderability even after being exposed to a high temperature. Results acetic acid, iodoacetic acid, bromoacetic acid , paranitrobenzoic acid, paratoluenesulfonic acid, picric acid, oxalic acid, formic acid, succinic acid, phosphorous acid, maleic acid, acrylic acid, fumaric acid, tartaric acid, adipic acid, lactic acid, olein organic acids such as acids, hydrochloric, sulfuric, inorganic acids phosphoric, etc., or zinc acetate, lead acetate, zinc hydroxide, lead hydroxide, bromide, zinc phosphate, zinc oxide, zinc chloride, ferrous chloride, Ferric chloride, cuprous bromide, cupric bromide, cuprous iodide, ants
Copper acid , nickel chloride, cuprous chloride, cupric chloride, cuprous oxide, cupric oxide, copper hydroxide, copper phosphate, copper carbonate, copper acetate, a solution containing a metal compound such as copper sulfate, Or at least one liquid selected from the group consisting of water-soluble solvents such as methanol, ethanol, isopropyl alcohol, butanol, and acetone, and one or more kinds of the compound represented by (Chemical formula 1) as an active ingredient. The present invention has been completed by finding that the above-mentioned conventional problems can be solved and the intended purpose can be achieved when a solution obtained by mixing the above is used as a metal surface treatment agent. As the above-mentioned organic acid or the like used for solubilizing or emulsifying the compound represented by (Chemical Formula 1), an organic acid, a salt of an organic acid, or a water-soluble solvent such as alcohol can be used alone, respectively. It is also possible to mix and use it at an arbitrary ratio. For example, the above water-soluble solvent may be used alone or in combination with other organic acids. In particular, when the organic acid or the like alone makes it difficult to dissolve the compound represented by (Chemical Formula 1) or its derivative, It is preferable to contain a water-soluble solvent, and the content ratio in this case is often appropriate to be 0.01 to 60%. The solution obtained by dissolving each of the above-mentioned solvents contains 0.01 to 20 of the above-mentioned active ingredient.
%, Preferably 0.5 to 5% of a solubilized solution or an emulsified solution is generally used for the immersion treatment. The immersion is performed at a temperature range of 0 to 100 ° C. for an immersion time of several seconds to several tens of minutes. Is appropriate. In addition, after forming the chemical conversion film, complex formation treatment infrared, near infrared, far infrared, and ultraviolet irradiation treatment is performed 0 to 3 times.
A treatment with a treatment time of several seconds to several tens of minutes in the temperature range of 00 ° C. is suitable. Exposure treatment of ozone O ₃ for several seconds to several tens of minutes is appropriate. It is suitable to carry out chemical treatment such as immersion and spraying for several seconds to several tens of minutes in a concentration range of hydrogen peroxide water of 1 to 20%. ~
By carrying out the above treatment, a chemical conversion coating having excellent heat resistance can be formed. As the active ingredient of the metal surface treating agent of the present invention,
(Chemical formula 1) is illustrated as a suitable example. To apply the surface treatment agent of the present invention to a metal surface or the surface of a printed wiring board, a method of dipping or spraying is used.

[0005]

According to the above method of treating preflux,
It is possible to manufacture a printed wiring board which has good spreadability and wettability of cream solder, a solder rising rate after reflow, and wettability, and is excellent in terms of working environment and safety.

[0006]

Examples 2-Cyclopropylbenzimidazole 1
%, Formic acid, ammonia and cupric bromide were placed in a 1 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5 cm x 0.3 mm copper plate and 10 cm x
A 12 cm x 1.6 mm through-hole substrate was degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a sample piece, and prepared into a 1% solution containing 2-cyclopropylbenzimidazole as an active ingredient. It was immersed for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the moisture resistance (90% RH / 40 ° C./96 hr) treatment was dipped in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 1.

[Table 1]

[0007]

Examples 1% of 2-cyclobutylbenzimidazole ,
A solution containing formic acid, ammonia, and cupric chloride was placed in a 1-liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, 1
cm × 5 cm × 0.3 mm copper plate and 10 cm × 12 c
Prepare a test piece by degreasing, washing with water, soft etching, washing with water, pickling, washing the surface of a through-hole substrate of m × 1.6 mm with a 1% solution containing 2-cyclobutylbenzimidazole as an active ingredient. It was immersed for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. Put in a hot air dryer at 200 ° C for 1
It was heated for 0 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Moisture resistance (9
The test piece after 0% RH / 40 ° C./96 hr) treatment was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 2 .

[Table 2]

[0008]

EXAMPLE 2-Cyclobenthylbenzimidazole 1
%, Formic acid, ammonia and cupric chloride were placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5 cm x 0.3 mm copper plate and 10 cm x
A test piece is prepared by degreasing, washing with water, soft etching, washing with water, pickling, washing the surface of a 12 cm × 1.6 mm through-hole substrate, and preparing a test piece, and a 1% solution containing the above-mentioned 2-cyclobenchbenzimidazole as an active ingredient. Was soaked for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 3 .

[Table 3]

[0009]

EXAMPLE 2-Cyclohexylbenzimidazole 1
%, Formic acid, ammonia and cupric chloride were placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. by heating. On the other hand, 1 cm x 5 cm x 0.3 mm copper plate and 10 cm x
A 12 cm × 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and a 1% solution containing 2-cyclohexylbenzimidazole as an active ingredient is added to the 60% solution. Soaked for 2 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 4 .

[Table 4]

[0010]

EXAMPLE 2-Cycloheptylbenzimidazole 1
%, Formic acid, ammonia and cupric chloride were placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5 cm x 0.3 mm copper plate and 10 cm x
Prepare a test piece by degreasing, washing with water, soft etching, washing with water, pickling, washing the surface of a 12 cm × 1.6 mm through-hole substrate, and prepare a 1% solution containing the above 2-cycloheptylbenzimidazole as an active ingredient. It was immersed for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 5 .

[Table 5]

[0011]

Example 1 A solution containing 1% of 2-cyclopentylmethylbenzimidazole , formic acid, ammonia and cupric chloride was used.
In a liter container, the liquid temperature was adjusted to 40 ° C by heating, while the 1 cm x 5 cm x 0.3 mm copper plate and 10 cm x
A 12 cm × 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and then a 1% solution containing 2-cyclopentylmethylbenzimidazole as an active ingredient is prepared. It was immersed for 60 seconds. After that, rinse with water and put in a hot air drier for 120
After heating at ℃ for 5 minutes, put it in a hot air dryer at 200 ℃ for 1
After heating for 0 minutes, a post flux was brush-painted before the measurement to measure the solder rise of the through hole. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 6 .

[Table 6]

[0012]

Example A solution containing 1% of 2- (2-cyclopentylethyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 1 liter container, and the solution temperature was adjusted to 40 ° C. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, 1% containing-(2-cyclopentylethyl) benzimidazole as an active ingredient
It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40 ℃
/ 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 7 .

[Table 7]

[0013]

EXAMPLE A solution containing 1% of 2- (2-cyclohexylethyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 1 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, 1% containing-(2-cyclohexylethyl) benzimidazole as an active ingredient
It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40 ℃
/ 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 8 .

[Table 8]

[0014]

Example: 1% of 2- (3-cyclohexylpropyl) benzimidazole , formic acid, ammonia, cupric chloride
The solution was placed in a 1 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, It was immersed for 60 seconds in a 1% solution containing-(3-cyclohexylpropyl) benzimidazole as an active ingredient. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40
(° C / 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester.
The test results are shown in Table 9 .

[Table 9]

[0015]

Example A solution containing 1% of 2- (4-cyclohexylbutyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, 1% containing-(4-cyclohexylbutyl) benzimidazole as an active ingredient
It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40 ℃
/ 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 10 .

[Table 10]

[0016]

EXAMPLES 2-cyclopropyl benzimidazole 0.
5%, 2-cyclopentylbenzimidazole 0.5%
A solution containing formic acid, ammonia, and cupric chloride was placed in a 1-liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, 1
cm × 5 cm × 0.3 mm copper plate and 10 cm × 12 c
A test piece was prepared by degreasing, washing with water, soft etching, washing with water, pickling, washing with water the through hole substrate of m × 1.6 mm to prepare a test piece, and the above-mentioned 2-cyclopropylbenzimidazole, 2-cyclobenthylbenzimidazole. It was immersed for 60 seconds in a 1% mixed solution containing as an active ingredient. After that, rinse with water, put in a hot air dryer, and heat at 120 ° C for 5 minutes,
It was put in a hot air dryer and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder buildup of the through hole. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90%
The test piece after RH / 40 ° C./96 hr) treatment was dipped in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 11 .

[Table 11]

[0017]

Example: A solution containing 1% of 2- (1-methylcyclopropyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 1 liter container, and the solution temperature was adjusted to 40 ° C. .. On the other hand, a 1 cm × 5 cm × 0.3 mm0 copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and the above-mentioned 2- 1% with (1-methylcyclopropyl) benzimidazole as active ingredient
It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40 ℃
/ 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 12 .

[Table 12]

[0018]

EXAMPLES 2- (2-methylcyclopropyl) benzimidazole 1% formic acid, ammonia, placed in cupric chloride including solution to 1 liter vessel was adjusted by heating at a liquid temperature of 40 ° C.. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, 1% containing-(2-methylcyclopropyl) benzimidazole as an active ingredient
It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40 ℃
/ 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 13 .

[Table 13]

[0019]

Example: 2-Cyclohexylmethylbenzimidazo
1% solution containing formic acid, ammonia and cupric chloride
It was put in a liter container, and the liquid temperature was adjusted to 40 ° C. by heating.
On the other hand, 1 cm x 5 cm x 0.3 mm copper and 10 cm x
Degreasing a 12 cm x 1.6 mm through-hole board with water
Washing, soft etching, washing with water, pickling, washing with water to clean the surface
Then prepare a test piece, and
Soak for 60 seconds in a 1% solution containing zimidazole as the active ingredient.
Pickled After that, wash with water and put in a hot air drier for 120
After heating at ℃ for 5 minutes, put it in a hot air dryer at 200 ℃ for 1
Heat for 0 minutes and brush with post flux before measurement
The solder rise of the through hole was measured. For hot air dryer
Put it in the oven and heat it at 200 ℃ for 10 minutes, and post-
And wetting time is measured using a solder wettability tester
did. After treatment against humidity (90% RH / 40 ° C / 96hr)
Solder wettability test by immersing the test piece of
Wetting time was measured using a vessel. The test results are shown in Table 14.
It was shown to.

[Table 14]

[0020]

Example 1 2- (2,2,3,3-tetramethylpropyl) benzimidazole 1%, formic acid, ammonia, chloride
Put the solution containing cupric acid in a 1 liter container and adjust the temperature to 40
The temperature was adjusted to 0 ° C. On the other hand, 1 cm x 5 cm x 0.3 m
A copper plate of m and a through-hole substrate of 10 cm × 12 cm × 1.6 mm are degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, and the above-mentioned 2-
It was immersed for 60 seconds in a 1% solution containing (2,2,3,3-tetramethylpropyl) benzimidazole as an active ingredient. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 15 .

[Table 15]

[0021]

Example A solution containing 1% of 2- (1-methylcyclohexyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 1 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, 1% containing-(1-methylcyclohexyl) benzimidazole as an active ingredient
It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40 ℃
/ 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 16 .

[Table 16]

[0022]

[Example] A solution containing 1% of 2- (2-methylcyclohexyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C while adjusting the other. 1 cm x 5 cm x 0.3 mm copper plate and 1
A 0 cm x 12 cm x 1.6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, and the 2- (2-methylcyclohexyl) benzimidazole is used as an active ingredient. It was immersed in a 1% solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. ..
It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40 ° C / 9
6 hr) The treated test piece was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 17 .

[Table 17]

[0023]

Example A solution containing 1% of 2- (3-methylcyclohexyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, -(3-Methylcyclohexyl) benzimidazole as an active ingredient 1%
It was immersed in the solution for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40 ℃
/ 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 18 .

[Table 18]

[0024]

EXAMPLE 2- (4-Methylcyclohexyl) benzimidazole 1%, formic acid, ammonia, formic acid, cupric chloride
The solution containing was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. by heating. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, It was immersed for 60 seconds in a 1% solution containing-(4-methylcyclohexyl) benzimidazole as an active ingredient. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 4
The test piece after the 0 ° C./96 hr) treatment was dipped in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 19 .

[Table 19]

[0025]

EXAMPLE 1- (2-Bentylcyclohexyl) benzimidazole 1%, formic acid, ammonia, cupric chloride
The solution was placed in a 1 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, It was immersed for 60 seconds in a 1% solution containing-(4-pentylcyclohexyl) benzimidazole as an active ingredient. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH / 40
(° C / 96 hr) The test piece after the treatment was immersed in post flux and the wetting time was measured using a solder wettability tester.
The test results are shown in Table 20 .

[Table 20]

[0026]

EXAMPLES 2 Shikurobenchiru Mechirubenzu imidazole <br/> Le 1% formic acid, ammonia, a solution containing a cupric chloride 1
It was put in a liter container, and the liquid temperature was adjusted to 40 ° C. by heating.
On the other hand, 1 cm x 5 cm x 0.3 mm copper plate and 10 cm
× 12cm × 1.6 mm degreased through hole board, washing with water, soft etching, prepared rinsing, pickling, washed specimens washing surface, the 2-cyclopentyl Mechiruben
It was immersed for 60 seconds in a 1% solution containing zimidazole as an active ingredient. After that, rinse with water and put in a hot air drier for 120
After heating at ℃ for 5 minutes, put it in a hot air dryer at 200 ℃ for 1
After heating for 0 minutes, a post flux was brush-painted before the measurement to measure the solder rise of the through hole. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 21.
It was shown to.

[Table 21]

[0027]

Example 2- (2-cyclopentylethyl) methyl ester
Insimidazole 1%, formic acid, ammonia, cupric chloride
The solution containing is placed in a 1 liter container and the liquid temperature is adjusted to 40 ° C., while the copper plate of 1 cm × 5 cm × 0.3 mm and the through-hole substrate of 10 cm × 12 cm × 1.6 mm are degreased, washed with water, and soft-etched. The test piece was prepared by washing the surface with water, washing with water, washing with water, and immersing it in a 1% solution containing 2- (2-cyclopentylethyl) methylbenzimidazole as an active ingredient for 60 seconds. After that, it was washed with water and then put in a hot air drier and heated at 120 ° C. for 5 minutes, then put in a hot air drier and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder rise of through holes. .. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90% RH
/ 40 ° C./96 hr) The treated test piece was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 22 .

[Table 22]

[0028]

Example 2- (1-methylcyclohexyl) dimethyl
Benz imidazole 1% formic acid, ammonia, cupric chloride
The solution containing was placed in a 1 liter container, and the liquid temperature was adjusted to 40 ° C. by heating. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 10 cm × 12 cm × 1.6 mm through-hole substrate were degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, It was immersed for 60 seconds in a 1% solution containing-(1-methylcyclohexyl) dimethylbenzimidazole as an active ingredient. After that, rinse with water, put in a hot air dryer, and heat at 120 ° C for 5 minutes,
It was put in a hot air dryer and heated at 200 ° C. for 10 minutes, and brushed with post flux before measurement to measure the solder buildup of the through hole. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. Against humidity (90%
The test piece after RH / 40 ° C./96 hr) treatment was dipped in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 23 .

[Table 23]

[0029]

EXAMPLES 2-Cyclopentyl-dimethyl benzimidazole <br/> Lumpur 1% formic acid, ammonia, a solution containing a cupric of 1
It was put in a liter container, and the liquid temperature was adjusted to 40 ° C. by heating.
On the other hand, 1 cm x 5 cm x 0.3 mm 0 copper plate and 10 cm
A test piece is prepared by degreasing, washing with water, soft etching, washing with water, pickling, washing with water on a through-hole substrate of × 12 cm × 1.6 mm to prepare a test piece, and a 1% solution containing the above-mentioned 2-cyclopentyldimethylbenzimidazole as an active ingredient. Was soaked for 60 seconds. After that, rinse with water and put in a hot air dryer,
After heating at 0 ° C. for 5 minutes, it was placed in a hot air drier and heated at 200 ° C. for 10 minutes, and post flux was brush-coated before measurement to measure the solder rise of the through hole. It was placed in a hot air dryer and heated at 200 ° C. for 10 minutes, dipped in post flux before measurement, and the wetting time was measured using a solder wettability tester. The test piece after the treatment against humidity (90% RH / 40 ° C./96 hr) was immersed in post flux and the wetting time was measured using a solder wettability tester. The test results are shown in Table 2.
4 shown in.

[Table 24]

[0030]

The pre-flux of the present invention has a rust preventive coating formed on the surface of a metal , which has excellent heat resistance, spreads cream solder well even after being exposed to high temperatures, has good wettability, and is a solder for reflow solder. It is possible to exert a particularly remarkable effect in surface mounting an electronic component on a printed wiring board from the viewpoints of good rising rate and wettability as well as in terms of working environment and safety.

Claims (2)

[Claims] 1. A method for surface treatment of a metal, which comprises performing surface treatment with a preflux solution containing a salt of the compound represented by (Chemical formula 1) or a derivative thereof. [Chemical 1] 2. A method for treating a metal, which comprises performing a surface treatment with a pre-flux solution containing a salt of a compound represented by (Chemical formula 1) or a derivative thereof, and then performing an oxidation treatment.