JPH01219183A - Corrosion inhibitor composition for copper - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a copper anti-corrosion composition that uses benzotriazole or/and a benzotriazole derivative to prevent discoloration of the copper surface over a long period of time.

[Prior art]

Conventionally, during the storage of copper wires and copper stranded wires, or during the manufacturing process and storage of insulated wires, the surfaces of copper wires and stranded wire conductors may discolor, and various rust preventive compositions have been used to prevent this. is proposed. For example, rust preventives are known in which benzotriazole or/and a benzotriazole derivative is dissolved in a solvent, and a benzotriazole derivative is dissolved in liquid paraffin, polybutene, silicone oil, or the like. However, if benzotriazole dissolved in a volatile solvent such as methyl alcohol is applied to copper wire and left in a hot and humid atmosphere even after anti-corrosion treatment, discoloration may occur in a short period of time, or during the wire manufacturing process. If the surface of the copper wire is damaged by rubbing during the process, there is a problem in that the damaged area becomes defective and discolored. This is a rust preventive agent made by dissolving a benzotriazole derivative in liquid paraffin, polybutene, silicone oil, etc. In order to form a rust preventive film on copper wire, the copper wire must be heated to a high temperature, and rust prevention is not possible when applied at room temperature. There is a problem that a film is difficult to form.

[Problem that the invention seeks to solve]

The present invention provides a coating that forms a strong antirust film on the surface of the copper wire or stranded copper wire by applying a rust preventive composition onto the copper wire or stranded copper wire, and further protects the rust preventive film. The object of the present invention is to provide a copper anti-corrosion agent composition that exhibits excellent corrosion resistance and antirust effect even when exposed to a severe corrosive environment.

[Means for solving problems]

As a result of various studies to solve the above problems, the present inventors completed the present invention by creating a blended composition of benzotriazole or/and a benzotriazole derivative, a solvent, and a phosphoric acid plasticizer. This is what I did.

That is, its composition is characterized by comprising 0.1 to 10% by weight of benzotriazole or/and a benzotriazole derivative, 0.5 to 95% by weight of a phosphoric acid plasticizer, and the remainder being a solvent.

The configuration of the present invention will be further explained below.

The reason why the blending amount of benzotriazole and/or benzotriazole is 0.1 to 10% by weight is that even if it is blended at 10% by weight or more, the rust preventive film will not be formed any more, and the rust preventive effect will reach saturation and fail. This is not preferable because it increases the cost due to necessity.

On the other hand, if the amount is less than 0.1% by weight, a sufficient rust-preventive film will not be formed, and therefore no rust-preventive effect will be obtained. From the viewpoint of rust prevention effect and cost, the preferred amount is in the range of 0.5 to 3%.

The benzotriazole derivatives used in the present invention include benzotriazole monoethanolamine salt, benzotriazole diethylamine salt, benzotriazole cyclohexylamine salt, benzotriazole morpholine salt, benzotriazole diisopropylamine salt, methylbenzotriazole cyclohexylamine salt, etc. Can be mentioned.

Next, the blending amount of the phosphoric acid plasticizer should be 0.5 to 95% by weight, because if it is blended in an amount of 95% or more, stickiness will remain on the copper wire or copper stranded wire after application, and benzotriazole or / and it becomes difficult to sufficiently dissolve the rust preventive component of benzotriazole. On the other hand, if the amount is less than 0.5% by weight, the protective effect against the rust preventive film formed by the rust preventive component of benzotriazole or/and the benzotriazole derivative is lacking, and a sufficient rust preventive effect cannot be obtained. In view of the protective effect on the rust preventive film and the solubility of the rust preventive component, the preferred amount of the phosphoric acid plasticizer is in the range of 3 to 70% by weight.

The phosphoric acid plasticizers used in the present invention include trimethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl.・Phosphate, isodecyl diphenyl phosphate, tricresyl phosphate, tritolyl ・
phosphates, tricylenyl phosphates, alkyl allyl phosphates, etc., and one or more of these groups can be used.

The solvent used in the present invention is used to facilitate the dissolution and mixing of the rust preventive component of benzotriazole or/and benzotriazole derivative and the phosphoric acid plasticizer, and to adjust the stickiness of the phosphoric acid plasticizer. However, such solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, and isopropyl alcohol.

In particular, by blending an alcohol solvent, a two-component solution with a phosphoric acid plasticizer is created, and the volatilization temperature of the mixed alcohol is made higher than the boiling point of the alcohol alone, so that the blended alcohol does not volatilize easily. Then, in the presence of alcohol, the chelate bonding reaction between the surface of the copper wire and the anti-rust component is sustained to form a more reliable anti-rust film on the copper wire. When the alcohol solvent evaporates, the remaining phosphoric acid plasticizer forms a protective film on the rust preventive film, further enhancing the rust preventive effect.

Note that the antirust treatment on copper wire using the anticorrosive composition of the present invention can be carried out by ordinary coating means, ie, dipping,
It is sufficient to select appropriate methods such as flowing down or spraying, and when applying, rust prevention treatment may be carried out in one step, or in multiple steps.
For example, by applying rust prevention treatment to both solid wire and stranded wire, a rust prevention film having excellent corrosion resistance can be formed on the copper wire.

〔Example〕

Hereinafter, examples according to the present invention, comparative examples, and conventional examples will be compared and explained.

After concentrically twisting 19 pieces of hard copper strands with an outer diameter of 2.0 mmφ, the outer periphery was coated with a rust-preventing solution of each composition shown in Table 1, and the outer periphery was coated with polyethylene insulation by extrusion. 60mm" outdoor polyethylene insulated wires were manufactured. Each of the obtained insulated wires was subjected to the following corrosion resistance tests (Note 1, Note 2, Note 3). The results were compared to the formulation examples in Table 1 ( The composition is shown in the lower column (% by weight).

(Note 1) Cut a 10 cm long sample from an insulated wire with a hacksaw, remove the insulator, and immerse the conductor wire in a sodium sulfide aqueous solution with a concentration of 1100 pp for 30 seconds at room temperature. The state of discoloration was visually observed to determine whether the corrosion resistance was good or bad.

(Note 2) After cutting a 10 cm long sample from the insulated wire with a hacksaw, peeling off the insulator and taking out the hard copper strands, and washing off the anti-rust solution adhering to the surface of the conductor wire with a solvent, Concentration 1
After being immersed in a 100 pp sodium sulfide aqueous solution at room temperature for 30 seconds, it was taken out, and the discoloration state of the surface of the conductor wire was visually observed to determine whether the corrosion resistance was good or bad.

The evaluation criteria for (Note 1) and (Note 2) were as follows: ○ indicates no discoloration, Δ indicates slight discoloration, and X indicates clear discoloration.

(Note 3) Cut a 30cm long sample from an insulated wire with a hacksaw, and add it to an ammonia aqueous solution with a concentration of 1100pp.
After being immersed in a corrosive environment for 8 weeks, the sample was removed, the insulator was stripped off, and the conductor was removed. The average thickness of the copper oxide formed on the surface was determined, and the corrosion resistance was judged from that value.

The evaluation criteria were as follows: ◯ mark indicates a film thickness of less than 0.2 μm, Δ mark indicates a film thickness in the range of 0.2 to 0.3 μm, and X mark indicates a film thickness exceeding 0.3 μm.

As can be seen from the results, Examples 1 to 7 show good results in all tests, but Comparative Example 1 does not form a sufficient corrosion-resistant film with copper because the amount of hensitriazole is small. Comparative Example 2 contains a large amount of cresyl diphenyl phosphate and a small amount of alcohol, so the corrosion resistance test (Note 2) is not favorable. In Comparative Example 3, since the amount of cresyl diphenyl phosphate blended is small, its role as a protective film on the corrosion-resistant film with copper is insufficient. Comparatively considering Comparative Example 4.5.6.7 and Example 3.4.5, the use of silicone oil, liquid paraffin, polybutene, electrical insulating oil, etc. in the comparative example and the use of phosphoric acid-based plasticizer in the example Corrosion resistance tests (Note 1, Note 2,
Note 3), it can be seen that there is a large difference in the results.

Now, considering the corrosion resistance test (Note 2) of the example, it is found that in the example, a corrosion-resistant film with copper is well formed, so even if it is immersed in a sodium sulfide aqueous solution, the corrosion-resistant film that is formed can be used in the harsh corrosive environment. It is presumed that they are showing a sloppy resistance to the situation. Both Conventional Examples 1 and 2 are unfavorable because these tests lack reliability.

Although the above embodiments were carried out with respect to insulated wires, the present invention can also be applied to raw materials, intermediate products, and finished products made of copper plates, copper alloy plates, etc.

〔Effect of the invention〕

As explained above, by applying the copper anti-corrosion agent composition according to the present invention on copper wire or stranded copper wire, an excellent corrosion-resistant film and protective film are formed on the copper surface. The problem of discoloration of bare copper wires and copper stranded wires during the storage of copper stranded wires, the manufacturing process of insulated T/L wires or power cables, and the storage of wires can be sufficiently prevented, and the hard copper of outdoor insulated wires can be sufficiently prevented. If applied to stranded wires, after the insulated wires are overlaid,
It can prevent stress corrosion cracking of hard copper strands even if corrosive rainwater enters from the ends, and it can also prevent discoloration of materials, intermediate products, and finished products made of copper plates and copper alloy plates. Since it can be applied to many areas, its use effect is great.

Applicant: Tak Electric Wire Co., Ltd. Agent, Patent Attorney: Takashi Mizuguchi - Temotori, Masaru Wan -) (Voluntary) Commissioner of the Patent Office Kunio Ogawa
(1) Indication of 1988 Patent Application No. 45277 2 Name of the invention Rust preventive composition for copper 3 Person making the amendment Relationship with 11 Patent applicant Address Osaka Prefecture East 2-3-1-4 Iwata-cho, Osaka City,
Agent 5, Date of amendment order □□ 6. Number of claims increased by supplement + r - 7, Subject of amendment

Claims (1)

[Claims] Benzotriazole or/and benzotriazole derivative 0.1-10% by weight, phosphoric acid plasticizer 0.5-95%
A rust preventive composition for copper, characterized in that the balance by weight is a solvent.