JP3060435B2 - Copper-based metal corrosion inhibitor and rust-proof paper for copper-based metal using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel copper and copper alloy (hereinafter, referred to as "copper-based metal") corrosion inhibitor and a method for producing the same, and a rust-proof paper using the corrosion inhibitor.

[0002]

2. Description of the Related Art Conventionally, as a substance for preventing corrosion of a metal product made of a copper-based metal, "a mechanism for inhibiting the corrosion of benzotriazole-based inhibitors and its application"
As disclosed in Taketo Notoya, Japan Rust Prevention Technology Association, pages 1 to 4, benzotriazole having the following structural formula:

[0003]

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Alternatively, tolyltriazole having the following structural formula:

[0005]

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Is known. These substances are applied or impregnated to a base paper to form a rust-proof paper, which is used for anticorrosion packaging of copper-based metal products.

Japanese Patent Publication No. 3-71515 discloses a rust inhibitor composition for copper comprising benzotriazole, a benzotriazole derivative, an alcohol-based solvent, and a phthalic acid-based plasticizer. Benzotriazole monoethanolamine salt, benzotriazole diethylamine salt and the like are mentioned.

In Japanese Patent Publication No. 58-513, benzotriazoles and amines are mixed with a water-insoluble organic solvent to form benzotriazoles into an aqueous solution. Is disclosed.

[0009]

However, the above-mentioned benzotriazole and tolyltriazole have a relatively low vapor pressure at normal temperature (for example, benzotriazole has a low vapor pressure of 0.1%).
004mmHg / 20, 0.003mmHg / 50 for tolyltriazole), so even if copper-based metal is wrapped in a vaporizable rust-proof paper coated or impregnated with these substances on a base paper, the vaporization effect is not sufficient. Therefore, although the effect of suppressing corrosion and discoloration in the contact portion between the rust-proof paper and the copper-based metal is recognized, the contact portion between the same type of copper-based metal or between the copper-based metal and the copper-based dissimilar metal or the overlapped portion. The effect of suppressing corrosion and discoloration generated in the gaps between the portions was insufficient.

[0010] The benzotriazole derivative is
Compared to benzotriazole and tolyltriazole, the vapor pressure is slightly higher, and although the vaporization effect is improved,
Corrosion and discoloration are suppressed at the contact part between rust-proof paper and copper-based metal, and corrosion that occurs between the same type of copper-based metal, or the contact part between copper-based metal and copper-based dissimilar metal or at the gap between overlapping parts And the effect of suppressing discoloration was not sufficient.

In view of the above situation, the present invention relates to a novel copper-based metal corrosion inhibitor which has good vaporization properties and associated permeability, and also has a very high effect of preventing corrosion and discoloration of copper-based metals. The purpose is to provide.

Another object of the present invention is to provide a novel method for producing a copper-based metal corrosion inhibitor which has a good vaporization property and an extremely high effect of preventing corrosion and discoloration of the copper-based metal. And

Further, the present invention provides an excellent rust-preventing effect on a copper-based metal product using the above-mentioned copper-based metal corrosion inhibitor, and suppresses corrosion and discoloration at the contact portion between the rust-proof paper and the copper-based metal. In particular, the present invention provides rust-prevention paper having an extremely high effect of suppressing corrosion and discoloration occurring in a contact portion between copper-based metals of the same type or between a copper-based metal and a copper-based dissimilar metal or in a gap between overlapping portions. The purpose is to do.

[0014]

Means for Solving the Problems The present inventors, as a result of intensive studies in order to achieve the aim and objects of the prior art described above, the following compositions are excellent vaporization properties, moreover copper metal It has been found that the present invention has been found to have a corrosion inhibiting effect on the steel, particularly a remarkable effect on crevice corrosion. That is, the present invention relates to (1) N, N-dimethylethanolamine and benzotriazole in a molar ratio of 0.5: 1.0 to 1.2:
N, N-dimethyl obtained by blending to be 1.0
Ethanolamine Benzotriazole salt copper metal corrosion inhibitor comprising, (2) N, N- dimethylethanolamine and tolyltriazole and a molar ratio of 0.5: 1.0 to 1.2:
N, N-dimethyl obtained by blending to be 1.0
Ethanolamine-tolyltriazole salt copper metal corrosion inhibitor comprising, (3) N, N- diethylethanolamine at a molar ratio of benzotriazole is 0.5: 1.0 to 1.2:
N, N-diethylene obtained by mixing to be 1.0
Ethanolamine Benzotriazole salt copper metal corrosion inhibitor and (4) a N, N-diethylethanolamine and tolyltriazole and a molar ratio of 0.5: 1.0 to 1.2:
N, N-diethylene obtained by mixing to be 1.0
It is a copper-based metal corrosion inhibitor containing ruethanolamine and tolyltriazole salts .

In this case, the compounding method is as follows. A four-necked flask equipped with a condenser, a stirrer, and a thermometer is charged with ion-exchanged water and each amino alcohol, and 100 to 300 rpm.
It is preferable to add each of the triazoles little by little while stirring at, and after completion of the addition, heat until the liquid temperature reaches 80 ° C., maintain the temperature for 20 to 30 minutes, and then gradually cool to room temperature.

[0016]

In this case, the copper-based metal corrosion inhibitors (1) to (4) are respectively represented by the following reaction formulas 1 to 4.
A salt of an amino alcohol and a triazole having the following structural formula is produced, and a synergistic effect of these salts and the remaining amino alcohol or triazole exhibits extremely high vaporization and a corrosion inhibiting effect on copper-based metals. I think that the.

[0018]

(Equation 1)

[0019]

(Equation 2)

[0020]

(Equation 3)

[0021]

(Equation 4)

N, N-dimethylethanolamine / benzotriazole salt

[0023]

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N, N-diethylethanolamine tolyltriazole salt

[0025]

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N, N-dimethylethanolamine / benzotriazole salt

[0027]

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N, N-diethylethanolamine / tolyltriazole salt

[0029]

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Further, a copper-based metal corrosion inhibitor prepared by mixing two or more types of copper-based metal corrosion inhibitors selected from the group consisting of the copper-based metal corrosion inhibitors (1) to (4) is also used. , And can have extremely high vaporization properties and an effect of inhibiting corrosion of copper-based metals. In this case, the mixing ratio of (1) to (4) is not particularly limited.

Further, in the present invention, such a compound, that is, a copper-based metal corrosion inhibitor is applied or impregnated to a base sheet to constitute a rust-proof paper for copper-based metal.

Specifically, it is preferable to use a base paper as the base sheet. As the base paper, it is preferable to use a polyethylene laminated paper using neutral kraft paper in consideration of a small adverse effect on metal. preferable. In addition, as a coating method, gravure coating is used in consideration of the stability of the coating amount, and an aqueous solution having a solid content of 20 to 50% is used as a coating liquid in consideration of the solubility and workability of the drug. It is preferable to use a dryer or oven drying or far infrared drying.

[0033]

Example 1 A four-necked flask equipped with a condenser, a stirrer, and a thermometer was charged with 700 g of ion-exchanged water and 128 g of N, N-dimethylethanolamine, and stirred while stirring at 100 to 300 rpm. 172 g of triazole were added in small portions. After the addition was completed, the mixture was heated until the liquid temperature reached 80 ° C., maintained at the temperature for 20 to 30 minutes, and then gradually cooled to room temperature.

This solution corresponds to a 30% aqueous solution containing N, N-dimethylethanolamine and benzotriazole in a molar ratio of 1: 1.

Example 2 N, N-dimethylethanolamine was 120 g, and instead of benzotriazole, tolyltriazole (“COBRATEC TT-100”, PMC Specilitie)
s Group Inc.) In the same manner as in Example 1 except that the amount was 180 g,
A 30% aqueous solution was prepared in which N, N-dimethylethanolamine and tolyltriazole were mixed at a molar ratio of 1: 1.

Example 3 149 g of N, N-diethylethanolamine instead of N, N-dimethylethanolamine
In the same manner as in Example 1 except that 151 g of benzotriazole was used, a 30% aqueous solution in which N, N-diethylethanolamine and benzotriazole were mixed at a molar ratio of 1: 1 was prepared.

Example 4 140 g of N, N-diethylethanolamine in place of N, N-dimethylethanolamine
And instead of benzotriazole, tolyltriazole ("COBRATECTT-100", PMC Specilities Group In
c.) A 30% aqueous solution containing N, N-diethylethanolamine and tolyltriazole in a molar ratio of 1: 1 was prepared in the same manner as in Example 1 except that the amount was 160 g.

(Experimental Example 1) Each of the solutions obtained in Examples 1 to 4 was further diluted to 1/10 to prepare a 3% solution, and 100 × 2
00mm base paper (polyethylene laminate specification, 800
g / m ² neutral kraft paper and 25 micrometer thick
3g / m of solid content coating on polyethylene )
² (100 g / m ^{2 of the} coating liquid) was applied using a brush, and then dried to obtain rust-proofing papers.

On the other hand, as conventional benzotriazole derivatives, monoethanolamine / benzotriazole compound (amine: azole = 102 g: 198 g), diethanolamine / benzotriazole compound (amine: azole = 141 g: 159 g), dibutylethanolamine Benzotriazole blend (amine: azole = 178g: 122g
) And a mixture of dibutylethanolamine and tolyltriazole (amine: azole = 170 g: 130 g), respectively, and rust-proofing papers were prepared in the same manner as above.

As a conventional rust preventive paper, a benzotriazole solution (3% benzotriazole solution (methyl alcohol: water = 1: 1)) is solidified on a 100 × 200 mm base paper (polyethylene laminate specification) similar to the above. Dispensed amount 3g
/ m ² (100 g / m ^{2 of} solution) was applied using a brush and then dried to obtain a conventional rust-proof paper.

Further, for comparison, the same 100 ×
The 200 mm base paper was used as general moisture-proof paper (10).

Each of these rust-proof papers (10) was subjected to a test for confirming its rust-preventive effect by using the following test method 1. However, only the phosphor bronze plate test (3 days) was carried out for the rust-proof papers of the above. The results are shown in Table 1 below.

In the table, the criteria were as follows:…: no discoloration,…: slight discoloration, □: slight discoloration, Δ: noticeable discoloration, ×: discoloration of the entire surface.

As is clear from the results shown in Table 1, in the rust-proof paper using the rust-preventive agent according to the present invention, the rust-preventing effect and the discoloration-suppressing effect of the mating surface of the copper-based metal are the same as those of the conventional benzotriazole derivative. It can be seen that the rust-proofing paper and the conventional rust-proofing paper using benzotriazole and the general moisture-proofing paper (10) are significantly improved.

[0045]

[Table 1]

(Test Method 1) Phosphorus-deoxidized copper plate (60 × 80 × 1.
0mm) and tough pitch steel plate (60 x 80 x 1.0mm)
While passing deionized water through # 400 water-resistant abrasive paper, the surface of the test piece was wet-ground in the longitudinal direction, replaced with acetone, air-dried, and washed with warm acetone (wiped with impregnated gauze). The test pieces A and B were obtained by air drying.

On the other hand, a phosphor bronze plate (60 × 80 × 1.0 mm) and a free-cutting brass (60 × 80 × 1.0 mm) were each dry-polished in the longitudinal direction on both sides of a test piece with an AA-240 polishing cloth. Then, warm acetone washing (wiping with impregnated gauze) was repeated twice, followed by natural drying to obtain test pieces C and D, respectively.

Using these test pieces, as shown in FIG. 1, each test piece was packed as a set with two pieces of rust-proof paper subjected to the test, and after packing was completed, aging was performed before the test. It was kept at room temperature for 2 hours.

Thereafter, (1) temperature: 5 ° C., humidity: OFF, time: 3 hours, (2) temperature: 50 ° C., humidity: 95%, time: 3 hours, (3) temperature: 5 ° C., humidity: OFF, time: 2 hours, (4)
Temperature: 50 ° C., humidity: 95%, time: 16 hours, one cycle, and 7 cycles (7
3) (3 days) for the test piece C.

(Experimental Example 2) In a four-necked flask equipped with a condenser, a stirrer and a thermometer, 700 g of exchanged water and N, N-dimethylethanolamine were added, and benzotriazole was added little by little while stirring at 100 to 300 rpm. Was added. After the addition was completed, the mixture was heated until the liquid temperature reached 80 ° C., maintained at the temperature for 20 to 30 minutes, and then gradually cooled to room temperature to prepare a 30% aqueous solution.

In this case, N, N-dimethylethanolamine and benzotriazole were mixed so as to have the mixing molar ratios shown in Table 2 below ().

Each of these solutions was further diluted to 1/10, and applied to a 100 × 200 mm base paper (polyethylene laminate specification, neutral kraft paper 800 g / m ² / polyethylene 25 μm) with a solid content of 3 g / m ² ( The solution was applied with a brush at a coating amount of 100 g / m ² ) and then dried to obtain rust-proof paper.

Similarly, N, N-dimethylethanolamine and tolyltriazole, N, N-diethylethanolamine and benzotriazole, and N, N-diethylethanolamine and tolyltriazole are also shown in Table 2. As shown, anticorrosion paper was prepared by changing the compounding molar ratio.

Each of these rust-proofing papers was subjected to a test for confirming its rust-preventing effect by using the test method 1 described above. The results are shown in Table 3 below.

As is clear from the results shown in Table 3, the best molar ratio of N, N-dimethylethanolamine to benzotriazole is 1: 1 to show the best rust-preventive effect, and the molar ratio of the compound is 0.5 to 0.5. It is understood that the ratio of 1.2: 1.0 is high in the effect of preventing corrosion of copper-based metal.

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

According to the present invention, a novel copper-based metal corrosion inhibitor having a good vaporization property and an extremely high effect of preventing corrosion and discoloration of the copper-based metal in consideration of the present situation. Can be provided.

Further, according to the present invention, there is provided a novel copper-based metal corrosion inhibitor which has a good vaporization property, has a correspondingly improved permeability, and has a very high effect of preventing corrosion and discoloration of the copper-based metal. A manufacturing method can be provided.

Further, according to the present invention, the rust-preventing effect on the copper-based metal product using the above-mentioned copper-based metal corrosion inhibitor is extremely good, and the corrosion or discoloration at the contact portion between the rust-proof paper and the copper-based metal is obtained. And the effect of suppressing corrosion and discoloration occurring in a gap between a contact portion and an overlapping portion between copper-based metals of the same type or between a copper-based metal and a copper-based dissimilar metal is extremely high. Rustproof paper can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating a method for packing a copper-based metal with the rust-proof paper used in Test Method 1.

Continuation of the front page (56) References JP-A-52-155148 (JP, A) JP-B-61-47229 (JP, B2) JP-B-58-36061 (JP, B2) JP-B-53-47775 (JP, A) , B2) JP-B-58-512 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23F 11/00, 11/02, 11/14

Claims (6)

(57) [Claims] 1. The method according to claim 1 , wherein the molar ratio of N, N-dimethylethanolamine and benzotriazole is from 0.5: 1.0.
1.2, 1.0, N, N
-Dimethylethanolamine / benzotriazole salt
Contains copper-based metal corrosion inhibitor. 2. The method according to claim 1 , wherein the molar ratio of N, N-dimethylethanolamine to tolyltriazole is from 0.5: 1.0.
1.2, 1.0, N, N
-Dimethylethanolamine / tolyltriazole salt
Contains copper-based metal corrosion inhibitor. 3. The method according to claim 1 , wherein the molar ratio of N, N-diethylethanolamine and benzotriazole is from 0.5: 1.0.
1.2, 1.0, N, N
-Diethylethanolamine / benzotriazole salt
Contains copper-based metal corrosion inhibitor. 4. The method according to claim 1 , wherein the molar ratio of N, N-diethylethanolamine and tolyltriazole is from 0.5: 1.0.
1.2, 1.0, N, N
-Diethylethanolamine / tolyltriazole salt
Contains copper-based metal corrosion inhibitor. 5. The copper-based metal corrosion inhibitor according to claim 1 ,
The copper-based metal corrosion inhibitor according to claim 2, and the copper-based metal corrosion inhibitor according to claim 3.
A copper-based metal corrosion inhibitor obtained by mixing two or more types of copper-based metal corrosion inhibitors selected from the group consisting of the copper-based metal corrosion inhibitor according to claim 4 and the copper-based metal corrosion inhibitor according to claim 4 . 6. A rust-proof paper for copper-based metal obtained by applying or impregnating a copper-based metal corrosion inhibitor according to any one of claims 1 to 5 to a substrate.