JP3112744B2 - Surface protective agent for printed wiring boards - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface protective agent for a printed wiring board. In particular, the present invention relates to a surface protective agent for a printed wiring board having an excellent effect of preventing oxidation of a metal surface of a printed wiring board at high temperature or generation of rust under high humidity.

[0002]

2. Description of the Related Art Conventionally, a printed circuit board generally uses a metal plate made of copper or a copper alloy on a circuit surface thereof. As a method for protecting the surface of the printed circuit board, a resin coating method, a solder coating method, and a coating with a chemical agent are used. The law is roughly divided. As the above resin coating method, generally, rosins, synthetic resins, and the like are dissolved in an organic solvent, applied to the entire surface of the printed wiring board by means of a roller, brush, dipping, spraying, etc., and then dried to form a coating. Is the way. Further, the solder coating method is a method of protecting a circuit surface of a printed wiring board by coating a thin layer of molten solder with a leveler or the like. In the above resin coating method, since an organic solvent solution of the resin is used,
The vaporization and dissipation of the organic solvent is extremely inconvenient in terms of environmental hygiene such as worker poisoning and work fire. In addition, although the solder coating method has excellent protection characteristics of the printed wiring board under high temperature or high humidity, the thickness of the solder coating by the solder coating is not constant, so it is not suitable for high-density mounting of current parts It is. In addition, the cost for coating the solder is relatively high, which is disadvantageous in industrial mass production.

In order to eliminate the above-mentioned drawbacks of the printed wiring board protection method, a method for protecting a rust-preventive film with a chemical has been developed. A method for preventing rust of copper and copper alloys using an imidazole derivative as a rust preventive agent is disclosed (JP-B-46-17046, JP-B-46-34214). But,
These chemicals have the drawback of deteriorating the solderability under high temperature and high humidity. Accordingly, a benzimidazole derivative has been disclosed as a protective agent which has been attempted to further solve the above-mentioned disadvantages (Japanese Patent Laid-Open No. 3-124395).

[0004]

Even with the prior art protective agent containing a benzimidazole derivative as a main component as described in the preceding paragraph, recent years have seen an urgent need to increase the density and surface mounting of components on printed wiring boards. . In addition, not only at the time of soldering, but also under conditions where the time of exposure of the printed wiring board to a high temperature, such as a curing oven or a reflow oven, is increased.
It was difficult to achieve a sufficient rust prevention effect. An object of the present invention is to provide a novel protective agent which can sufficiently satisfy the above-mentioned severe conditions using a protective agent containing a substituted benzimidazole derivative as a main component in a printed wiring board.

[0005]

The inventor of the present invention has conducted intensive studies on a protective agent having a sufficient effect even under the above-mentioned severe processing conditions for a printed wiring board. The inventors have found that an imidazole derivative and a salt thereof can satisfy the requirement, and have completed the present invention.

The present invention is a surface protective agent for a printed wiring board containing a compound represented by the formula (1) as an active ingredient.

Embedded image (Where X is the same or different and is an alkyl group having 1 to 7 carbon atoms, a halogen atom, an amino group, a di-lower alkylamino group, a hydroxy group, a lower alkoxy group, a cyano group, an acetyl group, a benzoyl group, a carbamoyl group, Formyl group,
A carboxyl group, a lower alkoxycarbonyl group or a nitro group; n and p each represent an integer of 0 to 4;
Indicates an integer)

[0007] The active ingredient of the protective agent of the present invention [Chemical Formula 1]
Examples of the compound represented by are 2- (8-phenyloctyl) benzimidazole, 5,6-dimethyl-2- (2-phenylethyl) benzimidazole, and 4-chloro-2- (3
-Phenylpropyl) benzimidazole, 6-dimethylamino-2- (9-phenylnonyl) benzimidazole, 4,7-dihydroxy-2-benzylbenzimidazole, 4-cyano-2- (6-phenylhexyl) benzimidazole, 5,6-dinitro-2-benzylbenzimidazole, 4,7-diethoxy-2- (2-phenylethyl) benzimidazole, 6-amino-2- (4-phenylbutyl) benzimidazole, 6-acetyl-2- Benzylbenzimidazole, 4-benzoyl-2- (5-phenylpentyl) benzimidazole, 6-carbamoyl-2
-(7-phenylheptyl) benzimidazole, 6-ethoxycarbonyl-2-benzylbenzimidazole,
4,5,6-trimethoxy-2- (2-phenylethyl) benzimidazole, 5,6-dimethyl-7-benzoyl-2
-(3-phenylpropyl) benzimidazole, 4,5
-Dichloro-6-n-butyl-2- (9-phenylnonyl) benzimidazole, 4-fluoro-6-formyl-2-benzylbenzimidazole, 6-carbamoyl-5-ethoxy-2- (10-phenyldecyl) Benzimidazole,
5,6-dimethyl-2-{(4-methoxyphenyl) butyl} benzimidazole, 6-chloro-2-{(2-nitrophenyl) ethyl} benzimidazole, 6-carbethoxy-2- (3-bromobenzyl ) Benzimidazole, 4-hydroxy-2-{(4-cyanophenyl) propyl} benzimidazole, 6-dimethylamino-2-
{(4-formylphenyl) propyl} benzimidazole, 6-benzoyl-2-{(4-tert-butylphenyl) ethyl} benzimidazole, 2-{(2-acetylphenyl) pentyl} benzimidazole, 6-carbamoyl- 2-{(2,4-dihydroxyphenyl) ethyl} benzimidazole and the like.

In order to use the compound represented by the formula (1) as the active ingredient of the present invention as the surface protective agent for a printed wiring board of the present invention, the compound is mixed with water or an aqueous solvent in which water is mixed at an arbitrary ratio. It is convenient for use to be dissolved or emulsified in water. Since the compound represented by the formula (1) is generally insoluble in water, when this compound is formed into a salt with an inorganic acid or an organic acid to form an aqueous solution, it becomes an easily usable protective agent.
In this case, the acid forming a salt includes formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, dibromoacetic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, and oxalic acid. Organic acids such as acid, malonic acid, succinic acid, adipic acid, malic acid, tartaric acid, citric acid, maleic acid, fumaric acid, paratoluenesulfonic acid, methanesulfonic acid, etc.
Inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid and nitric acid are used. Examples of the solvent arbitrarily miscible with water include methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, dimethyl sulfoxide, and dimethylformamide.In the case of the protective agent of the present invention, these solvents are necessary. May be added as appropriate. The content of the active ingredient contained in the present solution or emulsion is 0.05 to 30% (weight),
Desirably, it is 0.1 to 5% (weight). If the content of the active ingredient is less than 0.05% (weight), a sufficient protective effect cannot be obtained even when a printed wiring board is applied using this agent,
If it exceeds 30% (weight), the amount of insoluble matter tends to increase, and it is economically disadvantageous.

In addition to the above-mentioned active ingredients, the protective agent for printed wiring boards of the present invention includes, for example, copper formate, copper chloride, copper oxalate, copper acetate, copper phosphate, sulfuric acid as a complex film forming aid with copper. It is preferable to add heavy metal salts such as copper, copper formate, manganese formate, manganese chloride, manganese oxalate, and manganese sulfate. Other auxiliaries usually added to the protective agent used for the purpose of the present invention may be appropriately added.

In the method of forming a protective film on a printed wiring board with the protective agent of the present invention, the copper circuit surface of the printed wiring board is finished by mechanical or chemical polishing according to a general coating method, and then the protective film of the present invention is protected. Immerse in the agent solution. Immersion can usually be carried out in the range of 0-60 ° C, but 10-50 ° C is preferred. Immersion time is 5 seconds to 1 hour, preferably 10 seconds to 10 hours.
Minutes. It should be noted that other coating methods such as a spraying method, a brush, a roller and the like may be used. The coating film obtained as described above has extremely good solderability even under high temperature and high humidity.

Next, embodiments of the present invention and effects thereof will be described.

[0012]

【Example】

Example 1 0.1 g of copper sulfate and 100 g of a 2% (by weight) aqueous solution of tartaric acid
-(8-phenyloctyl) benzimidazole 1.0 g, 2
0.1 g of 5% aqueous ammonia was sequentially added and mixed to obtain an aqueous solution of 2- (8-phenyloctyl) benzimidazole. A test piece of 30.0 mm x 7.5 mm x 0.3 mm copper plate was polished, degreased, soft-etched and washed with water to clean the surface.
C. for 2 minutes. After this coating, it is washed with water, dried with hot air, and then placed in an air-circulating oven at 200 ° C for 5 minutes.
Min, 15 min, 20 min heat deterioration, apply post flux before measurement and apply solder wetting test method (equilibrium method) to JIS-C-0053
Performed according to. The solder spread rate test is JIS-Z-
Performed according to 3197. The results are shown in Table 1 and 90%
0,100,200,500,100 under the condition of 40 ° C in the humidity of
Table 2 shows the results of the solder wetting test and the solder spread test performed after 0 hour in the same manner as the previous test.

Example 2 0.1 g of copper sulfate was added to 100 g of a 2% (by weight) aqueous solution of tartaric acid.
1.0 g of 5,6-dimethyl-2- (2-phenylethyl) benzimidazole and 0.1 g of 25% aqueous ammonia were sequentially added and mixed, and the mixture was mixed with 5,6-dimethyl-2- (2-phenylethyl) benzimidazole. An aqueous solution was obtained. A test piece similar to that of Example 1 was immersed in this liquid, and a solder wetness test, a solder spread test, a solder wet test under high humidity, and a solder spread test were similarly performed. 2>.

Example 3 To 100 g of a 2% (by weight) aqueous solution of tartaric acid was added 4-chloro-2-
1.0 g of (3-phenylpropyl) benzimidazole was added and mixed to obtain an aqueous solution of 4-chloro-2- (3-phenylpropyl) benzimidazole. A test piece similar to that of Example 1 was immersed in this liquid, and a solder wetness test, a solder spread test, a solder wet test under high humidity, and a solder spread test were similarly performed. 2>.

Example 4 To 75 g of a 3% (by weight) aqueous solution of tartaric acid, 25 g of ethanol and 10 g of 6-dimethylamino-2- (9-phenylnonyl) benzimidazole were added and mixed, followed by mixing with 6-dimethylamino-2.
An aqueous solution of-(9-phenylnonyl) benzimidazole was obtained. A test piece similar to that of Example 1 was immersed in this liquid, and a solder wetness test, a solder spread test, a solder wet test under high humidity, and a solder spread test were similarly performed. 2>.

Example 5 1.0 g of 4,7-dihydroxy-2-benzylbenzimidazole was added to 100 g of a 3% (by weight) aqueous solution of tartaric acid and mixed to obtain an aqueous solution of 4,7-dihydroxy-2-benzylbenzimidazole. A test piece similar to that of Example 1 was immersed in this liquid, and a solder wetness test, a solder spread test, a solder wet test under high humidity, and a solder spread test were similarly performed. 2>.

Example 6 0.1 g of manganese formate was added to 100 g of a 2% (by weight) aqueous solution of tartaric acid.
g, 4-cyano-2- (6-phenylhexyl) benzimidazole (1.0 g) was added and mixed to obtain an aqueous solution of 4-cyano-2- (6-phenylhexyl) benzimidazole. A test piece similar to that of Example 1 was immersed in this liquid, and a solder wetness test, a solder spread rate test, a solder wetness test under high humidity, and a solder spread rate test were similarly performed.
And <Table 2>.

EXAMPLE 7 0.1 g of manganese formate was added to 100 g of a 2% (by weight) aqueous solution of tartaric acid.
g, 5,6-dinitro-2-benzylbenzimidazole
1.0 g was added and mixed to obtain an aqueous solution of 5,6-dinitro-2-benzylbenzimidazole. A test piece similar to that of Example 1 was immersed in this liquid, and a solder wetness test, a solder spread test, a solder wet test under high humidity, and a solder spread test were similarly performed. 2>.

Example 8 4,7-Diethoxy- was added to 100 g of a 2% (by weight) aqueous solution of tartaric acid.
1.0 g of 2- (2-phenylethyl) benzimidazole
Then, the same test piece as in Example 1 was immersed in this liquid, and the solder wetness test, the solder spread rate test, the solder wetness test under high humidity, and the solder spread rate test were performed in the same manner. 1> and <Table 2>.

EXAMPLE 9 0.1 g of copper sulfate was added to 100 g of a 2% (by weight) aqueous solution of tartaric acid.
6-dimethyl-2-{(4-methoxyphenyl) butyl} 1.0 g of benzimidazole and 0.1 g of 25% aqueous ammonia are sequentially added and mixed to give 5,6-dimethyl-2-{(4-methoxyphenyl) butyl}. An aqueous solution of benzimidazole was obtained. A test piece similar to that of Example 1 was immersed in this liquid, and a solder wetness test, a solder spread rate test, a solder wetness test under high humidity, and a solder spread rate test were similarly performed.
And <Table 2>.

Example 10 0.1 g of copper sulfate and 100 g of a 2% (by weight) aqueous solution of tartaric acid
Chloro-2-{(2-nitrophenyl) ethyl} benzimidazole (1.0 g) and 25% aqueous ammonia (0.1 g) were sequentially added and mixed, and 6-chloro-2-{(2-nitrophenyl) ethyl} benzimidazole aqueous solution was added. Obtained. This liquid was tested in the same manner as in Example 1 using the same test piece, and the results are shown in Tables 1 and 2.

EXAMPLE 11 0.1 g of copper sulfate and 100 g of a 2% (by weight) aqueous solution of tartaric acid
1.0 g of carbethoxy-2- (3-bromobenzyl) benzimidazole and 0.1 g of 25% aqueous ammonia were sequentially added and mixed to obtain an aqueous solution of 6-carbethoxy-2- (3-bromobenzyl) benzimidazole. This liquid was tested in the same manner as in Example 1 using the same test piece, and the results are shown in Tables 1 and 2.

Example 12 0.1 g of copper sulfate and 100 g of a 2% (by weight) aqueous solution of tartaric acid
1.0 g of hydroxy-2-{(4-cyanophenyl) propyl} benzimidazole and 0.1 g of 25% aqueous ammonia were sequentially added and mixed, and an aqueous solution of 4-hydroxy-2-{(4-cyanophenyl) propyl} benzimidazole was added. Obtained. This liquid was tested in the same manner as in Example 1 using the same test piece, and the results are shown in Tables 1 and 2.

Example 13 0.1 g of copper sulfate and 100 g of a 2% (by weight) aqueous solution of tartaric acid
1.0 g of dimethylamino-2-{(4-formylphenyl) propyl} benzimidazole, 0.1 g of 25% aqueous ammonia
Were sequentially added and mixed to obtain an aqueous solution of 6-dimethylamino-2-{(4-formylphenyl) propyl} benzimidazole. This liquid was tested in the same manner as in Example 1 using the same test piece, and the results are shown in Tables 1 and 2.

EXAMPLE 14 0.1 g of copper sulfate and 100 g of a 2% (by weight) aqueous solution of tartaric acid
Benzoyl-2-{(4-tert-butylphenyl) ethyl}
1.0 g of benzimidazole and 0.1 g of 25% aqueous ammonia were sequentially added and mixed to obtain an aqueous solution of 6-benzoyl-2-{(4-tert-butylphenyl) ethyl} benzimidazole. This liquid was tested in the same manner as in Example 1 using the same test piece, and the results are shown in Tables 1 and 2.

Example 15 0.1 g of copper sulfate and 100 g of a 2% (by weight) aqueous solution of tartaric acid
1.0 g of {(2-acetylphenyl) pentyl} benzimidazole and 0.1 g of 25% aqueous ammonia were sequentially added and mixed to obtain an aqueous solution of 2-{(2-acetylphenyl) pentyl} benzimidazole. This liquid was tested in the same manner as in Example 1 using the same test piece, and the results are shown in Tables 1 and 2.

Example 16 0.1 g of copper sulfate, 6-
Carbamoyl-2-｛(2,4-dihydroxyphenyl)
1.0 g of ethyl @ benzimidazole, 25% ammonia water
0.1 g is added sequentially and mixed, and 6-carbamoyl-2-
An aqueous solution of {(2,4-dihydroxyphenyl) ethyl} benzimidazole was obtained. This liquid was tested in the same manner as in Example 1 using the same test piece, and the results are shown in Tables 1 and 2.

Comparative Example 1 In place of 2- (8-phenyloctyl) benzimidazole in Example 1, 4-methyl-2-undecylimidazole was added in the same amount to give 4-methyl-2-n-undecylimidazole. Aqueous solution, and the same test piece as in Example 1 was added to this solution at room temperature for 30 minutes.
Dipped for 2 seconds. The test piece thus obtained was subjected to a solder wetting test, a solder spread test, a solder wet test under high humidity and a solder spread test in the same manner as in Example 1, and the results are shown in Tables 1 and 2. Was.

Comparative Example 2 1 g of benzimidazole and 2 g of acetic acid were placed in a 300 ml beaker and stirred until dissolved. Next, 100 g of water was added, 0.05 g of copper chloride and 0.5 g of aqueous ammonia were dissolved, and the liquid temperature was adjusted to 50 ° C. to obtain a 1% (by weight) aqueous solution of benzimidazole.
A test piece similar to that of Example 1 was immersed in this liquid, and a solder wetness test, a solder spread test, a solder wet test under high humidity, and a solder spread test were similarly performed. 2>.

[0030]

[Table 1]

[0031]

[Table 2] As is clear from the above results, the protective agent of the present invention had a shorter solder wetting time, a better rust-preventive effect under high humidity, and a better solder wet time than the protective agent of the comparative example.

[0032]

As described above, the surface protective agent for printed wiring boards of the present invention forms a very good film on the surfaces of copper and alloy on the printed wiring board circuit even after being exposed to heat and high humidity. The present invention is a useful invention which has a very remarkable effect on the protection of the board and the solderability after component mounting.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C23F 11/00 H05K 3/28 C09D 5/08

Claims (2)

(57) [Claims] 1. A surface protective agent for printed wiring boards, comprising a compound represented by the formula (1) as an active ingredient. Embedded image (Where X is the same or different and is an alkyl group having 1 to 7 carbon atoms, a halogen atom, an amino group, a di-lower alkylamino group, a hydroxy group, a lower alkoxy group, a cyano group, an acetyl group, a benzoyl group, a carbamoyl group, Formyl group,
A carboxyl group, a lower alkoxycarbonyl group or a nitro group; n and p each represent an integer of 0 to 4;
Indicates an integer) 2. The protective agent according to claim 1, which comprises an aqueous solution of a salt of the compound represented by the formula (1) as an active ingredient.