JPH05202492A - Surface treatment of metal - Google Patents

Abstract

PURPOSE:To prevent the rust formation in the metal exposed parts of a printed circuit board and to improve a soldering property by subjecting the printed circuit board to a surface treatment with a preflux soln. contg. a specific benzimidazole deriv. or its salt. CONSTITUTION:The metallic surface of the printed circuit board is treated with the preflux soln. contg. the salt of the compd. expressed by formula I, II (where n=0 to 3) or its deriv. The above-mentioned compd., etc., are incorporated as effective components at about 0.01 to 50% into an aq. soln., solvent, etc., of org. acids, alcohol, etc. The circuit board is immersed into such soln. and is thereby subjected to the surface treatment. The preflux film surface is thereafter subjected to an oxidation treatment to improve the heat resistance. This oxidation treatment is executed by irradiation with IR rays or UV rays, exposing to ozone, immersion into hydrogen peroxide water, etc. As a result, the printed circuit board which has the good spreading property and wettability of cream solder, and soldering rate and wettability after reflow and is excellent in terms of working environment and safety is obtd.

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)
It has been found that, when a solution prepared by mixing one kind or two or more kinds of the compounds represented by (Chemical Formula 11) is used as a metal surface treatment agent, the above-mentioned conventional problems can be solved and the intended purpose can be achieved. The present invention has been completed. As the above-mentioned organic acid or the like used for solubilizing or emulsifying the compounds represented by (Chemical Formula 1) to (Chemical Formula 11), an organic acid, a salt of an organic acid, or a water-soluble solvent such as alcohol is used alone. In addition to the above, it is also possible to mix and use them at an arbitrary ratio. For example, the water-soluble solvent may be used alone or in combination with other organic acids, etc. In particular, the organic acid alone may make it difficult to dissolve the compounds represented by (Chemical Formula 1) to (Chemical Formula 11) or their derivatives. In this case, it is preferable to add a water-soluble solvent, and in this case, it is often appropriate that the content rate is 0.01 to 50%. The solution obtained by dissolving with each of the above-mentioned solvents contains the above-mentioned active ingredient in an amount of 0.01 to 40%, preferably 0.
The method of immersing in a solubilizing solution containing 5 to 5% or an emulsifying solution is generally used. Immersion is suitably performed in a temperature range of 0 to 100 ° C. for an immersion time of several seconds to several tens of minutes. .. Further, after the formation of the chemical conversion film, oxidation treatment of infrared rays / near infrared rays / far infrared rays / ultraviolet rays is carried out at a temperature range of 0 to 300 ° C. for a treatment time of several seconds to several tens of minutes.
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) to (Chemical formula 11) are exemplified as preferable ones. 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- (1-methylpropyl) benzimidazole as an active ingredient was placed in a 5 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 20 cm x 24 cm x
A 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 1% containing 2- (1-methylpropyl) benzimidazole as an active ingredient was prepared. 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. .. Put in hot air dryer 20
It was heated at 0 ° C. for 10 minutes, immersed 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.

[0007]

Example A 1% solution containing 2- (2-methylpropyl) benzimidazole as an active ingredient was placed in a 5 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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- (2-methylpropyl) benzimidazole as an active ingredient is prepared. 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, 200 ℃
Was heated for 10 minutes, immersed 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.

[0008]

EXAMPLE A 1% solution containing 2- (1-methylbutyl) benzimidazole as an active ingredient was placed in a 5 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 prepared into a 1% solution containing 2- (1-methylbutyl) benzimidazole 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, 200 ℃
Was heated for 10 minutes, immersed 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 1.

[0009]

Example A 1% solution containing 2- (1-ethylpropyl) benzimidazole as an active ingredient was placed in a 5 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 the above-mentioned 2- (1-ethylpropyl) benzimidazole 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. .. Put in hot air dryer 200
It was heated at 0 ° 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 1.

[0010]

EXAMPLE A 1% solution containing 2- (2-methylbutyl) benzlumidimidazole as an active ingredient was placed in a 5 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 was prepared into a 1% solution containing 2- (2-methylbutyl) benzimidazole 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, 200 ℃
Was heated for 10 minutes, immersed 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 1.

[0011]

EXAMPLE A 1% solution containing 2- (1-methylpentyl) benzimidazole as an active ingredient was placed in a 5 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 the above 2- (1-methylpentyl) benzimidazole 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. .. Put in hot air dryer 200
It was heated at 0 ° 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 1.

[0012]

Example A 1% solution containing 2- (1-propylbutyl) benzimidazole as an active ingredient was placed in a 5 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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- (1-propylbutyl) benzimidazole as an active ingredient is prepared. 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, 200 ℃
Was heated for 10 minutes, immersed 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-methyl-4,4-dimethylpentyl) benzluimidazole as an active ingredient was placed in a 5 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 20
The test piece is prepared by degreasing, washing with water, soft etching, washing with water, pickling, washing with water the through-hole substrate having a size of cm × 24 cm × 1.6 mm, and preparing the above-mentioned 2- (2-methyl-4
It was immersed for 60 seconds in a 1% solution containing 4-dimethylpentyl) benzimidazole 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% R
The test piece after the H / 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 2.

[0014]

EXAMPLE A 1% solution containing 2- (1-hexylnonyl) benzluimidazole as an active ingredient was placed in a 5 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 the above 2- (1-hexylnonyl) benzimidazole 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. .. Put in hot air dryer 200
It was heated at 0 ° 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- (1-heptyldecyl) benzluimidazole as an active ingredient was placed in a 5 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 prepared into a 1% solution containing the above 2- (1-heptyldecyl) benzimidazole 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 hot air dryer 200
It was heated at 0 ° 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] A 1% mixed solution containing 2- (1-methylethyl) benzimidazole and 2- (1-ethylpropyl) benzimidazole as active ingredients was placed in a 5 liter container and heated to 40 ° C. It was adjusted. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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- (1-methylethyl) benzimidazole, 2- (1-ethylpropyl) was prepared. ) It was immersed for 60 seconds in a 1% mixed 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. .. Put in a hot air dryer, 200 ℃
Was heated for 10 minutes, immersed 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-methylpropyl) tosylimidazole as an active ingredient was placed in a 5 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 then a 1% solution containing 2- (1-methylpropyl) tosylimidazole as an active ingredient was prepared. 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, 200 ℃
Was heated for 10 minutes, immersed 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-methylpropyl) tosylimidazole as an active ingredient was placed in a 5 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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- (2-methylpropyl) tosylimidazole as an active ingredient is prepared. 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, 200 ℃
Was heated for 10 minutes, immersed 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- (1-methylbutyl) tosylimidazole as an active ingredient was placed in a 5 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 20cm × 24cm × 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 in a 1% solution containing 2- (1-methylbutyl) tosylimidazole 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. .. 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 3.

[0021]

Example A 1% solution containing 2- (1-ethylpropyl) tosylimidazole as an active ingredient was placed in a 5 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 6 mm through-hole substrate is degreased, washed with water, soft-etched, washed with water, pickled, and washed with water to prepare a test piece, and a 1% solution containing 2- (1-ethylpropyl) tosylimidazole as an active ingredient is prepared. 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, 200 ℃
Was heated for 10 minutes, immersed 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-methylbutyl) tosylimidazole as an active ingredient was placed in a 5 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 20cm × 24cm × 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 2- (2-methylbutyl) tosylimidazole 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 3.

[0023]

Example A 1% solution containing 2- (1-methylpentyl) tosylimidazole as an active ingredient was placed in a 5 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 prepared into a 1% solution containing 2- (1-methylpentyl) tosylimidazole 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, 200 ℃
Was heated for 10 minutes, immersed 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- (1-propylbutyl) tosylimidazole as an active ingredient was placed in a 5 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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- (1-propylbutyl) tosylimidazole as an active ingredient is prepared. 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, 200 ℃
Was heated for 10 minutes, immersed 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- (2-methyl-4,4-dimethylpentyl) tosylimidazole as an active ingredient was added 5 times.
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 20 cm
The test piece was prepared by degreasing, washing with water, soft etching, washing with water, pickling, washing the surface of a through-hole substrate of × 24 cm × 1.6 mm, and preparing the above-mentioned 2- (2-methyl-4,4-dimethylpentyl). It was immersed for 60 seconds in a 1% solution containing tosylimidazole 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 4.

[0026]

EXAMPLE A 1% solution containing 2- (1-hexylnonyl) tosylimidazole as an active ingredient was placed in a 5 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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- (1-hexylnonyl) tosylimidazole as an active ingredient is prepared. 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, 200 ℃
Was heated for 10 minutes, immersed 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.

[0027]

[Example] A 1% solution containing 2- (1-heptyldecyl) tosylimidazole as an active ingredient was placed in a 5 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 60% is added to a 1% solution containing 2- (1-heptyldecyl) tosylimidazole as an active ingredient. 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. .. Put in a hot air dryer, 200 ℃
Was heated for 10 minutes, immersed 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-ethylpropyl) xylylimidazole as an active ingredient was placed in a 5 liter container, and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 the above 2- (1-ethylpropyl) xylylimidazole 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. .. Put in hot air dryer 200
It was heated at 0 ° 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- (1-propylbutyl) xylylimidazole as an active ingredient was placed in a 5 liter container and the liquid temperature was adjusted to 40 ° C. On the other hand, 1 cm x 5
cm × 0.3 mm copper plate and 20 cm × 24 cm × 1.
A 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 a 1% solution containing the above 2- (1-propylbutyl) xylylimidazole 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. .. Put in hot air dryer 200
It was heated at 0 ° 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.

[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: Method for surface treatment of metal

[Claims]

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

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. The former is a method in which a natural rosin, a rosin ester, a rosin-modified maleic acid resin, etc. dissolved in an organic solvent is applied by a roll coater, or by spraying or dipping it on the entire printed wiring board and then drying to form a film. Used in. 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. 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, development of 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 has been earnestly desired.

[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, bromacetic 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 (Chemical formula 1) to
When a solution prepared by mixing one kind or two or more kinds of the compounds represented by (Chemical Formula 11) is used as a metal surface treating agent, it was found that the above-mentioned conventional problems can be solved and a desired object can be achieved, The present invention has been completed. As the above-mentioned organic acid or the like used for solubilizing or emulsifying the compounds represented by (Chemical Formula 1) to (Chemical Formula 11), an organic acid, a salt of an organic acid, or a water-soluble solvent such as alcohol is used alone. In addition to the above, it is also possible to mix and use them at an arbitrary ratio. For example, the water-soluble solvent may be used alone or in combination with other organic acids, etc. In particular, the organic acid alone may make it difficult to dissolve the compounds represented by (Chemical Formula 1) to (Chemical Formula 11) or their derivatives. In this case, it is preferable to add a water-soluble solvent, and in this case, it is often appropriate that the content rate is 0.01 to 50%. The solution obtained by dissolving with each of the above-mentioned solvents contains 0.01 to 20%, preferably 0 to 20% of the above-mentioned active ingredient.
A general method is to immerse in a solubilizing solution containing 5 to 5% or an emulsifying solution. Immersion is suitably performed in a temperature range of 0 to 100 ° C. for an immersion time of several seconds to several tens of minutes. Further, after the formation of the chemical conversion film, it is suitable to carry out a complex forming infrared ray / near infrared ray / far infrared ray / ultraviolet ray irradiation treatment in the temperature range of 0 to 300 ° C. for a treatment time of several seconds to several tens of minutes. 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 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) to (Chemical formula 11) are exemplified as preferable ones. 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,
A rust preventive coating with excellent heat resistance can be formed, and the spreadability of cream solder, wettability, and the rate of solder rise after reflow, wettability are good, and the production of printed wiring boards is also excellent in terms of work environment and safety. it can.

[0006]

Example A solution containing 1% of 2- (1-methylpropyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 5 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 20
cm × 24 cm × 1.6 mm through-hole substrate was degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a sample piece, and the above-mentioned 2- (1-methylpropyl) benzimidazole was used as an active ingredient. It was immersed in a 1% solution for 60 seconds. Then, rinse with water, put in a hot air dryer, heat at 120 ° C for 5 minutes, and put in a hot air dryer. 2
It was heated at 00 ° C. for 10 minutes and brushed with post flux 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. Moisture resistance (90% RH / 40 ° C / 96h
r) The treated test piece 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]

Example A solution containing 1% of 2- (2-methylpropyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 5 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 20
cm * 24 cm * 1.6 mm through-hole substrate is degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece and prepare the above-mentioned 2- (2-methylpropyl) benzimidazole as an active ingredient. 6 in 1% solution
It was immersed for 0 seconds. Then, rinse with water, put in a hot air dryer, heat at 120 ° C for 5 minutes, and put in a hot air dryer. 2
It was heated at 00 ° C. for 10 minutes and brushed with post flux 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. Moisture resistance (90% RH / 40 ° C / 96h
r) The treated test piece was dipped 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 A solution containing 1% of 2- (1-methylbutyl) benzimidazole , formic acid, ammonia and cupric chloride was added to 5 parts.
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 20 cm
A test piece is prepared by degreasing, washing with water, soft etching, washing with water, pickling and washing a through hole substrate of × 24 cm × 1.6 mm to prepare a test piece, and the above-mentioned 2- (1-methylbutyl) benzimidazole 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 3 .

[Table 3]

[0009]

EXAMPLE A solution containing 1% of 2- (1-ethylpropyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 5 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 20
cm * 24cm * 1.6mm through-hole substrate is degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece and prepare the above-mentioned 2- (1-ethylpropyl) benzimidazole as an active ingredient. 6 in 1% solution
It was immersed for 0 seconds. Then, rinse with water, put in a hot air dryer, heat at 120 ° C for 5 minutes, and put in a hot air dryer. 2
It was heated at 00 ° C. for 10 minutes and brushed with post flux 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. Against humidity (90% RH / 40 ° C / 96h
r) The treated test piece was dipped 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 A solution containing 1% of 2- (2-methylbutyl) benzimidazole , formic acid, ammonia and cupric chloride was added to 5 parts.
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 20 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 × 24 cm × 1.6 mm, and the above-mentioned 2- (2-methylbutyl) benzimidazole is used as an active ingredient. It was immersed in a 1% solution for 60 seconds. Then rinse with water and put in a hot air dryer to
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 5 .

[Table 5]

[0011]

EXAMPLE A solution containing 1% of 2- (1-methylpentyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 5 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 20
cm * 24 cm * 1.6 mm through-hole substrate is degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, and the 2- (1-methylpentyl) benzimidazole is used as an active ingredient. 6 in 1% solution
It was immersed for 0 seconds. Then, rinse with water, put in a hot air dryer, heat at 120 ° C for 5 minutes, and put in a hot air dryer. 2
It was heated at 00 ° C. for 10 minutes and brushed with post flux 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. Against humidity (90% RH / 40 ° C / 96h
r) The treated test piece was dipped 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- (1-propylbutyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 5 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 20
cm * 24cm * 1.6mm through-hole substrate is degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece and prepare the above-mentioned 2- (1-propylbutyl) benzimidazole as an active ingredient. 6 in 1% solution
It was immersed for 0 seconds. Then, rinse with water, put in a hot air dryer, heat at 120 ° C for 5 minutes, and put in a hot air dryer. 2
It was heated at 00 ° C. for 10 minutes and brushed with post flux 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. Against humidity (90% RH / 40 ° C / 96h
r) The treated test piece was dipped 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]

Examples 1-% 2- (2-methyl-4,4-dimethylpentyl) benzimidazole , formic acid, ammonia, chloride
Put the solution containing cupric acid in a 5 liter container and keep the liquid temperature at 40
The temperature was adjusted to 0 ° C. On the other hand, 1 cm x 5 cm x 0.3 m
The copper plate of m and the through-hole substrate of 20 cm × 24 cm × 1.6 mm are degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare the test piece, and the above-mentioned 2- (2
It was immersed for 60 seconds in a 1% solution containing -methyl-4,4-dimethylpentyl) 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. .. Put in hot air dryer 200
It was heated at 0 ° 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 8 .

[Table 8]

[0014]

Example A solution containing 1% of 2- (1-hexylnonyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 5 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 20
cm × 24 cm × 1.6 mm through-hole substrate was degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, and the above-mentioned 2- (1-hexylnonyl) benzimidazole was used as an active ingredient. 6 in 1% solution
It was immersed for 0 seconds. Then, rinse with water, put in a hot air dryer, heat at 120 ° C for 5 minutes, and put in a hot air dryer. 2
It was heated at 00 ° C. for 10 minutes and brushed with post flux 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. Against humidity (90% RH / 40 ° C / 96h
r) The treated test piece was dipped 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- (1-heptyldecyl) benzimidazole , formic acid, ammonia and cupric chloride was placed in a 5 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 20
cm * 24cm * 1.6mm through-hole substrate is degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, and the 2- (1-heptyldecyl) benzimidazole is used as an active ingredient. 6 in 1% solution
It was immersed for 0 seconds. Then, rinse with water, put in a hot air dryer, heat at 120 ° C for 5 minutes, and put in a hot air dryer. 2
It was heated at 00 ° C. for 10 minutes and brushed with post flux 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. Against humidity (90% RH / 40 ° C / 96h
r) The treated test piece was dipped 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 Mixed solution containing 0.5% of 2- (1-methylethyl) benzimidazole, 0.5% of 2- (1-ethylpropyl) benzimidazole , formic acid, ammonia and cupric chloride Was placed in a 5 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 20 cm × 24 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece and prepare the above-mentioned 2 It was immersed for 60 seconds in a 1% mixed solution containing-(1-methylethyl) benzimidazole and 2- (1-ethylpropyl) benzimidazole as active ingredients. 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 11 .

[Table 11]

[0017]

EXAMPLES 2- (1-methylpropyl) Mechirubenzu Lee <br/> imidazole 1% formic acid, ammonia, a <br/> solution containing cupric chloride was placed to a 5 liter vessel, a liquid temperature of 40 ° C. It was heated and adjusted. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 20 cm × 24 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece and prepare the above-mentioned 2 1% containing-(1-methylpropyl) methylbenzimidazole 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 12 .

[Table 12]

[0018]

EXAMPLES 2- (2-methylpropyl) Mechirubenzu Lee <br/> imidazole 1% formic acid, ammonia, a <br/> solution containing cupric chloride was placed to a 5 liter vessel, a liquid temperature of 40 ° C. It was heated and adjusted. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 20 cm × 24 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece and prepare the above-mentioned 2 1% containing-(2-methylpropyl) methylbenzimidazole 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 A solution containing 1% 2- (1-methylbutyl) methylbenzimidazole , formic acid, ammonia and cupric chloride was placed in a 5 liter container, and the temperature of the solution was adjusted to 40 ° C. It was heated and adjusted. On the other hand, 1 cm x 5 cm x 0.3 mm copper plate and 2
A 0 cm × 24 cm × 1.6 mm through-hole substrate was degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, and the 2- (1-methylbutyl) methylbenzimidazole 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. 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 14 .

[Table 14]

[0020]

EXAMPLES 2- (1-ethylpropyl) Mechirubenzu Lee <br/> imidazole 1% formic acid, ammonia, a <br/> solution containing cupric chloride was placed to a 5 liter vessel, a liquid temperature of 40 ° C. It was heated and adjusted. On the other hand, 1 cm x 5 cm x 0.3 mm plate and 2
A 0 cm x 24 cm x 1.6 mm through-hole substrate is degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, and the 2- (1-ethylpropyl) methylbenzimidazole 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 15 .

[Table 15]

[0021]

EXAMPLE A solution containing 2- (2-methylbutyl) methylbenzimidazole 1%, formic acid, ammonia and cupric chloride was placed in a 5 liter container, and the solution temperature was adjusted to 40 ° C. It was heated and adjusted. On the other hand, 1 cm x 5 cm x 0.3 mm copper plate and 2
A 0 cm × 24 cm × 1.6 mm through-hole substrate was degreased, washed with water, soft etching, washed with water, pickled, washed with water to prepare a test piece, and the 2- (2-methylbutyl) methylbenzimidazole 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. 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 16 .

[Table 16]

[0022]

EXAMPLES 2- (1-methylpentyl) Mechirubenzu Lee <br/> imidazole 1% formic acid, ammonia, a <br/> solution containing cupric chloride was placed to a 5 liter vessel, a liquid temperature of 40 ° C. It was heated and adjusted. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 20 cm × 24 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece and prepare the above-mentioned 2 1% containing-(1-methylpentyl) methylbenzimidazole 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 17 .

[Table 17]

[0023]

EXAMPLES 2- (1-propyl-butyl) Mechirubenzu Lee <br/> imidazole 1% formic acid, ammonia, a <br/> solution containing cupric chloride was placed to a 5 liter vessel, a liquid temperature of 40 ° C. It was heated and adjusted. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 20 cm × 24 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece and prepare the above-mentioned 2 It was immersed for 60 seconds in a 1% solution containing-(1-propylbutyl) tylbenzimidazole 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 / 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 18 .

[Table 18]

[0024]

Examples 1-% 2- (2-methyl-4,4-dimethylpentyl) methylbenzimidazole , formic acid, ammonium
(A) A solution containing cupric chloride was placed in a 5 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 20 cm x 24 cm x 1.6 mm
Degreasing, washing with water, soft etching,
Wash the surface with water, pickle, and water to prepare a test piece, and prepare the above-mentioned 2- (2-methyl-4,4-dimethylpentyl) methyl.
It was immersed for 60 seconds in a 1% solution containing benzimidazole as an active ingredient. 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. This test result is a table
19 shows.

[Table 19]

[0025]

EXAMPLES 2- (1-hexyl-nonyl) Mechirubenzu Lee <br/> imidazole 1% formic acid, ammonia, a <br/> solution containing cupric chloride was placed to a 5 liter vessel, a liquid temperature of 40 ° C. It was heated and adjusted. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 20 cm × 24 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece and prepare the above-mentioned 2 1% containing-(1-hexylnonyl) methylbenzimidazole 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 20 .

[Table 20]

[0026]

EXAMPLES 2- (1-Hepuchirudeshiru) Mechirubenzu Lee <br/> imidazole 1% formic acid, ammonia, placed <br/> solution containing cupric chloride to a 5 liter vessel, a liquid temperature of 40 ° C. heating I adjusted it. On the other hand, a 1 cm × 5 cm × 0.3 mm copper plate and a 20 cm × 24 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, 1% containing 1- (1-heptyldecyl) methylbenzimidazole 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 21 .

[Table 21]

[0027]

EXAMPLE 2- (1-Ethylpropyl) dimethylbenzimidazole 1%, formic acid, ammonia, cupric chloride
The solution was placed in a 5 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 20 cm × 24 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, It was immersed for 60 seconds in a 1% solution containing-(1-ethylpropyl) dimethylbenzimidazole 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 22 .

[Table 22]

[0028]

EXAMPLE 2- (1-Propylbutyl) dimethylbenzimidazole 1%, formic acid, ammonia, cupric chloride
The solution was placed in a 5 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 20 cm × 24 cm × 1.6 mm through-hole substrate are degreased, washed with water, soft-etched, washed with water, pickled, washed with water to prepare a test piece, It was immersed for 60 seconds in a 1% solution containing-(1-propylbutyl) dimethylbenzimidazole 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 23 .

[Table 23]

[0029]

EFFECTS OF THE INVENTION The coating formed on the surface of a metal with the pre-flux of the present invention is excellent in rust prevention and heat resistance, spreads cream solder even after being exposed to high temperature, has good wettability, and has excellent reflow solderability. With the effect of good solderability and wettability,
In addition, in terms of working environment and safety, it is possible to exert a particularly remarkable effect in surface-mounting electronic components on a printed wiring board.

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 a compound represented by (Chemical formula 1) to (Chemical formula 11) or a derivative thereof. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] [Chemical 10] [Chemical 11] 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) to (Chemical formula 11) or a derivative thereof and then performing an oxidation treatment.