JPH10204661A - Rust/corrosion preventing agent, and rust/corrosion preventing paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To exhibit corrosion preventing effect even on the contact part of metals with each other by adding 2-methyl pentylic acid or its alkali neutralized product into a volatile rust preventing agent commonly used for the prevention of corrosion and rust generation at the time of storing steel metal or zinc metal to improve the clearance infiltration effect of the volatile rust preventing agent. SOLUTION: 2-Methyl pentylic acid or its alkali neutralized product is added into the volatile rust preventing agent of a mixture of one or more kinds selected from among dicryclohexyl amine, the nitrite, cyclohexyl amine, the laurate, diisopropyl amine, sodium nitrite + urea, a sodium nitrite + urotropin base and a heterocyclic compound. A rust/corrosion preventing paper obtained by impregnating and coating a base material having absorption property with the volatile rust preventing agent exhibits excellent clearance infiltration action by the vaporization of the rust corrosion preventing agent, with which the base material is impregnated and coated, and prevents the generation of rust even on a metallic article having a complicated shaped surface and on the contact surface of the metals of the metallic article with each other.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a vaporizable rust inhibitor for suppressing rusting when metal articles such as cold-rolled steel sheets, galvanized steel sheets and zinc alloy-plated steel sheets are stored for a long period of time. It relates to a rust-proof and corrosion-proof paper using the same.

[0002]

2. Description of the Related Art As an agent effective in preventing corrosion of metals, "Rust Prevention Technical School, Industrial Packaging Department Textbook" Vaporizable Rust Preventive Agent ""
(Published by Japan Rust Prevention Technology Association), pages 4-5, dicyclohexylamine, nitrite, cyclohexylamine, laurate, diisopropylamine, sodium nitrite + urea, sodium nitrite + urotropin And vaporizable rust inhibitors such as heterocyclic compounds such as benzotriazole and tolyltriazole.

[0003] Conventionally, a vaporizable rust preventive agent obtained by mixing one or more of the above rust preventive agents with the above group is impregnated and applied to an absorbent substrate such as paper or nonwoven fabric. Rust paper was manufactured.

[0004] The vaporizable rust-preventing paper prevents rusting of the metal packaged article by chemical adsorption and passivation of the impregnated and coated rust preventive agent to the metal.

[0005]

However, when metal articles such as steel or zinc are wrapped using the above-mentioned rust-proof paper, the corrosion and corrosion of the rust-proof paper and the metal at the contact portion with the metal are prevented. Although rusting can be prevented, the effect of suppressing rust, which is generated particularly at the contact portion between metal parts, was not sufficient because of the insufficient vaporization and penetration effect of the rustproof paper.

[0006] The contact point between the metals is, for example,
It is a gap between the same type of steel-based metal, between different types of steel-based metal, between a steel-based metal and a zinc-based metal, between the same type of zinc metal, and between different types of zinc metal.

For this reason, for example, in a state where a plurality of metal plates are in contact with each other, corrosion and rust can be prevented by interposing rust-preventive paper also in the overlapping portion (gap) of the metal plates. We are. However, if this is not done, rust may occur at the contact surface between the metals.

In the case where the metal article is a single-shaped metal plate, rusting can be prevented by the above method.
In the case of a metal article having a complicated shape such as a surface having irregular irregularities, it is very difficult to bring the rust-proof paper into contact with the entire surface.

Accordingly, the rust-proof paper having corrosion-preventing and rust-preventing effects is provided not only on the metal surface with which the rust-proof paper can come into contact, but also on the contact points between metals that are difficult to contact with the rust-proof paper. There is a need for a rust inhibitor for impregnating and coating paper.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been developed in view of the fact that the rust-preventive component of the conventional rust-proof paper has a low permeability to the gaps, and the contact portion between the metals is poor. It was made by paying attention to the fact that rust is generated.

According to the present invention, by further promoting the effect of the vaporizable rust preventive agent in the gap penetration, the rust preventive effect can be exerted up to the contact portion between the metals. The outline of the configuration is as follows.

That is, the rust and corrosion inhibitor of the present invention is
When storing steel metal and zinc metal, vaporizing rust inhibitors that are usually used to prevent corrosion and rust
The present invention is characterized in that by adding 2-methylpentylic acid or an alkali neutralized product of 2-methylpentylic acid, the effect of the vaporizable rust preventive agent to penetrate the gap is improved.

[0013] The present invention is also a rust-preventive paper characterized in that the above-mentioned rust-preventive and anti-corrosive agent is impregnated and applied to a substrate having absorption properties such as paper, and the above-mentioned anti-corrosive and anti-corrosive agent has an excellent gap penetration It can penetrate to the surface of a metal article having a surface with irregular irregularities due to the property and the contact portion between metal parts of the metal article, and can exhibit an excellent rust prevention effect. .

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in more detail.

The rust / corrosion inhibitor of the present invention is obtained by adding crevice 2-methylpentylic acid to a chemical usually used as a vaporizable rust inhibitor to improve crevice permeability and rust / corrosion / corrosion effect. is there.

Here, the above-mentioned vaporizable rust preventives include known dicyclohexylamine, nitrite, cyclohexylamine, laurate, diisopropylamine, sodium nitrite + urea, sodium nitrite + urotropine, and heterocyclic compounds. One or a mixture of two or more of the group consisting of rust preventives can be mentioned. Since these are vaporizable rust preventives and can be used for rust preventive paper, any of them can be applied to the present invention. In addition, benzotriazole, tolyltriazole and the like are known as the heterocyclic compound.

When 2-methylpentylic acid is added to the above-mentioned volatile rust preventive agent, considering the rust preventive effect and the mixing property between the rust preventive agents, the proportion of 2-methylpentylic acid is rust preventive. It is preferably from 4 to 20% by weight based on the total weight of the corrosion inhibitor.

Further, as a method of mixing 2-methylpentylic acid with the above-mentioned volatile rust preventive agent, stirring is carried out in a reaction vessel so that mixing is performed uniformly and loss of a vaporized component of the rust preventive agent can be prevented. Is preferred. At this time, the temperature condition is preferably set to a temperature range of 40 to 60 ° C. in order to prevent thermal decomposition of the rust preventive.

Further, similarly to the above-mentioned 2-methylpentylic acid, an alkali-neutralized product of 2-methylpentylic acid can be used for obtaining the rust-inhibiting and corrosion-inhibiting agent of the present invention.

Here, the alkaline components include diethanolamine, monoethanolamine, diethanolamine, dimethylethanolamine, dibutylethanolamine, diethylethanolamine, triethanolamine, and other ethanolamines having a rust-preventing effect, and cyclohexylamine, dicyclohexyl. Amine, morpholine, benzylamine, diisopropylamine and the like can be used.

When adding an alkali neutralized product of 2-methylpentylic acid to the above-mentioned volatile rust preventive agent, a synergistic effect with another mixed rust preventive agent is considered in the same manner as in 2-methylpentylic acid. It is preferable that the proportion of 2-methylpentylic acid is 4 to 20% by weight based on the total weight of the rust and corrosion inhibitor.

As a mixing method, it is preferable to stir using a reaction vessel in that the loss of vaporization of the rust inhibitor can be prevented. At this time, the temperature is preferably in the range of 40 to 60 ° C. in consideration of prevention of thermal decomposition of the rust inhibitor.

Further, the rustproof and anticorrosive paper of the present invention using the above rustproof and anticorrosive agent will be described.

The simplest constitution of the rust-proof paper of the present invention is a paper obtained by impregnating and coating a substrate having excellent absorbency with the rust-proof and anticorrosive agent of the present invention.

Here, the substrate is preferably excellent in absorptivity in order to hold it impregnated with a rust and corrosion inhibitor, and it is preferable to use paper or synthetic paper made of synthetic resin.

As a method of impregnating and coating the above-mentioned base material with the rust and corrosion inhibitor of the present invention, in consideration of the fact that the liquid has a low viscosity, a usual gravure coating method or kiss coating method may be used. preferable. In addition, the coating amount is 1
It is preferable to apply about 12 to 15 g of a rust and corrosion inhibitor per 1 m ² of the base material in consideration of the rust prevention effect and economical efficiency required for long-term storage of about 2 years.

The anticorrosive and anticorrosive paper of the present invention obtained as described above exhibits excellent gap penetration action by vaporization of the anticorrosive and anticorrosive agent impregnated and coated on the base material. Rust can be prevented from being formed on the product and also on the metal-to-metal contact surface of the metal product.

Further, it is necessary to prevent the rust-proofing and corrosion-proofing agent from evaporating and releasing from an unnecessary portion depending on the intended use of the rust-proofing and corrosion-proof paper. Therefore, as shown in FIG. 1, the water-resistant film layer 1
It is also possible to provide 1.

Here, as the film layer on the upper surface of the base material, a synthetic resin film such as polyethylene and polypropylene having excellent water resistance may be used, and the film can be bonded to the base material with an adhesive or laminated. It is.

The film layer prevents the rust-proof and corrosion-proof paper 10 from releasing the vaporized rust-proof and corrosion-proof agent from the surface not in contact with the metal article.

[0031]

EXPERIMENTAL EXAMPLE 1 Diethanolamine caprylate ("DE-CA")
(Trade name: Ewa Shoko Co., Ltd.), urotropin ("Hexamine" (trade name), manufactured by Mitsubishi Gas Chemical Co., Ltd.), sodium nitrite ("sodium nitrite" (trade name), manufactured by Nissan Chemical Industry Co., Ltd.), Four types of benzotriazoles ("Belson Crystal" (trade name) manufactured by Daiwa Kasei Co., Ltd.) were mixed at the weights shown in Table 1 with the respective weights shown in Table 1, and vaporized for comparative examples (corresponding to conventional examples). A rust inhibitor was obtained.

To this, 2-methylpentylic acid ("2-methylpentanoic acid" (trade name) manufactured by Toyo Gosei Co., Ltd.) was mixed to obtain a rust and corrosion inhibitor for Example 1; A neutralized product of diethanolamine (“DE-2P” (trade name) manufactured by Ewa Shoko Co., Ltd.) was mixed to obtain a rust / corrosion inhibitor for Example 2.

[0033]

[Table 1]

Using the vaporizable corrosion inhibitor for the comparative example, the rust / corrosion inhibitor for Example 1 and the rust / corrosion inhibitor for Example 2, 25 gm of polyethylene resin was added to 75 G / m ^{2 of} kraft paper. Extruded lamination paper (“Polyethylene Laminated Paper” (trade name) manufactured by Ewa Shoko Co., Ltd.) was impregnated and coated at a rate of 12 g / m ² ,
Three types of rust-proof paper (Comparative Example, Example 1 and Example 2)
I got

Using the above rustproof paper and rustproof and corrosionproof paper, 6
Each of the rust-proof papers (Comparative Example, Example 1 and Example 2) was prepared by using two cold-rolled steel sheets each having a size of 0 mm × 80 mm × 1 mm or two sheets each superposed on a hot-dip galvanized steel sheet as test pieces. ). The packaging method is shown in FIG.
As shown in (d), two superposed test pieces 20 are placed on the center of the upper surface of the rust-proof paper (a), and both side edges of the rust-proof paper 10 are folded toward the center (b), and the upper and lower sides are further bent. The end was folded to the center side (c), and finally the margin was adhesively fixed with an adhesive tape 15.

Then, the temperature conditions were changed in four stages as shown in Table 2, and this was defined as one cycle (24 hours).
The cycle (96 hours) was repeated to check the rusting state.

[0037]

[Table 2]

The results are shown in Table 3. In the table, ○ indicates that there was no rust, and X indicates that there was rust. □ indicates a state close to ○, and Δ indicates a state close to ×.

[0039]

[Table 3]

As is clear from Table 2, in the comparative example, rust is generated on the joint surface of the steel sheets in both the cold-rolled steel sheet and the hot-dip galvanized steel sheet.

On the other hand, in Examples 1 and 2, rust generation could be prevented not only on the contact surface of the rust-proof and corrosion-proof paper but also on the cold rolled or hot-dip galvanized steel sheet mating surface.

Experimental Example 2 As shown in Table 4 below, the same volatile 2-methylpentylic acid as in Experimental Example 1 ("2-
Methylpentanoic acid ”(trade name, manufactured by Toyo Gosei Kogyo Co., Ltd.) was mixed in seven different addition amounts and ratios, and a rust / corrosion inhibitor for Examples (3, 4, 5, 6) and Comparative Example An anticorrosive for (,,) was obtained.

The proportion of 2-methylpentylic acid added in Example 3 was 4.0 based on the total weight of the mixture.
0% by weight, 7.7% by weight for Example 4, 14.3% by weight for Example 5, and 20.0% by weight for Example 6. 1.6% by weight for the comparative example and 2% for the comparative example.
9.4% by weight and 50.0% by weight for the comparative example.

[0044]

[Table 4]

Examples thus obtained (3 to 6)
Corrosion and corrosion inhibitor for Comparative Example (-) and impregnating agent for Comparative Example (-) were impregnated on polyethylene laminated paper so that the coating amount of the rust and corrosion inhibitor was 12 g / m ² as in Experimental Example 1. 7 types of rust-proof paper (Examples 3 to 6 and Comparative Examples
) Got.

Using the above rust-proof paper, 6
As shown in FIGS. 2A to 2D, two hot-dip galvanized steel sheets each having a size of 0 mm × 80 mm × 1 mm were rust-proofed (Examples 3 to 6 and Comparative Examples).
And stored under the temperature conditions shown in Table 2 in the same manner as in Experimental Example 1 to examine the state of rusting.

The results are shown in Table 5.

[0048]

[Table 5]

As is clear from Table 5, in Examples 3 to 6, the hot-dip galvanized steel sheet did not rust.

On the other hand, in the comparative example, rust was generated on the steel plate mating surface, and in the comparative examples and comparative examples, rust was generated not only on the steel plate mating surface but also on the rust-proof paper contact surface. .

From the above, when 2-methylpentylic acid is mixed into the vaporizable rust preventive, it is preferable to mix it in an amount of about 4 to 20% by weight based on the total weight of the rust preventive and corrosion preventive. Was found to be able to demonstrate.

Experimental Example 3 As shown in Table 6 below, the volatile rust preventive for Comparative Example in Experimental Example 1 was neutralized with 2-methylpentylic acid and diethanolamine as in the case of Example 1. Object ("DE-2
P "(trade name, manufactured by Ewa Shoko Co., Ltd.) was mixed at seven different addition amounts and ratios, and the mixture was mixed with each other to give Examples (Example 7, Example 8, Example 9, Example 10, Example 10). 11,
Example 12) A rust / corrosion inhibitor for Comparative Example and a rust / corrosion inhibitor for Comparative Example were obtained.

The ratio of 2-methylpentylic acid added was 4.0 for Example 7 based on the total weight of the mixture.
%, 7.7% by weight for Example 8 and 1 for Example 9
4.3% by weight, 20.0% by weight for Example 10, 29.4% by weight for Example 11, and 50.0% by weight for Example 12. In the comparative example, the content is 1.6% by weight.

[0054]

[Table 6]

The anticorrosive and anticorrosive agents for Examples 7 to 12 and the anticorrosive agent for Comparative Example thus obtained were applied to polyethylene laminated paper in the same manner as in Experimental Example 1 at a coating amount of 12 g / m 2.
Seven rust paper impregnated coating to be ² (Example 7
To 12, Comparative Example).

Using the above rust-proof paper, 6
Two hot-dip galvanized steel sheets having a size of 0 mm × 80 mm × 1 mm were wrapped in Examples 7 to 12 and Comparative Examples as shown in FIGS. The sample was stored under the same temperature conditions as in Table 1 and shown in Table 2, and the state of rusting was examined.

The results are shown in Table 7.

[0058]

[Table 7]

As is clear from Table 7, Examples 7 to 12
Then, there was no rust on the hot-dip galvanized steel sheet.

On the other hand, in the comparative example, rust was generated on the mating surface of the hot-dip galvanized steel sheet.

From the above, when a neutralized product of 2-methylpentylic acid diethanolamine is mixed into the vaporizable rust preventive, it is preferable that the neutralized product be mixed in an amount of about 4 to 50% by weight based on the total weight of the rust preventive and corrosion preventive. It was found that a great rust prevention effect can be exhibited.

[0062]

The vaporizable rust preventive according to the present invention is a highly volatile rust preventive which has a high gap penetration effect with respect to a commonly used vaporizable rust preventive.
It is a mixture of methylpentylic acid or an alkali neutralized product of 2-methylpentylic acid.

By adding these additives, the inherent penetration effect of the vaporizable rust preventive agent into the crevice is improved, and when metal products such as steel or zinc are wrapped, rust is not generated at the contact points between the metal parts. The suppression effect can be enhanced. In addition, the corrosion between the same type of steel-based metal, between different types of steel-based metal, between steel-based metal and zinc-based metal, between the same type of zinc-based metal, and between the different types of zinc-based metal The suppression effect is improved and improved.

The rust-proofing paper of the present invention is coated with the above-mentioned rust-proofing and corrosion-inhibiting agent by impregnating and coating. In addition, the space wrapped in the rust-preventive paper can be filled with the rust-preventive agent more quickly, and the vaporized rust-preventive agent can reach the gap between the metals to exhibit the rust-preventive effect.

[Brief description of the drawings]

FIG. 1 is a schematic partial sectional view of a rust-proof paper of the present invention.

FIGS. 2A and 2B are top views showing a method for packaging a metal article according to an embodiment of the present invention, wherein FIG. 2A is a top view in which a test piece is placed at the center of the upper surface of rust-proof paper, and FIG. It is a top view in which both ends of the paper were folded to the center side, (c) is a top view in which the upper and lower ends of the anticorrosive paper were folded to the center side, and (d) was adhesively fixed the folding margin with an adhesive tape. It is a top view.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 ... Corrosion-proof corrosion-proof paper 11 ... Coat layer 12 ... Base material 15 ... Adhesive tape 20 ... Test piece

Claims (6)

[Claims] 1. A vaporizable rust preventive used for preventing corrosion and rusting of metal articles, characterized in that 2-methylpentylic acid, which has a strong pore-penetrating effect, is added to the vaporizable rust preventive. Rust and corrosion inhibitor. 2. A vaporizable rust preventive used for preventing corrosion and rusting of a metal article, wherein an alkali neutralized product of 2-methylpentylic acid, which has a strong pore penetration effect, is added to the vaporizable rust preventive. A rust / corrosion inhibitor characterized by being added. 3. The one of the group consisting of dicyclohexylamine, nitrite, cyclohexylamine, laurate, diisopropylamine, sodium nitrite + urea, sodium nitrite + urotropin, and a heterocyclic compound. Or a mixture of two or more kinds of the rust and corrosion inhibitors according to claim 1 or 2. 4. The rust and corrosion inhibitor according to claim 1, wherein the 2-methylpentylic acid accounts for 4 to 20% by weight based on the total weight of the rust and corrosion inhibitor. 5. The alkali-neutralized product of 2-methylpentylic acid is 4 to 80% by weight based on the total weight of the rust and corrosion inhibitor.
The rust / corrosion inhibitor according to claim 2 or 3, wherein 6. A rust-proof and corrosion-proof paper, wherein the vaporizable rust-proofing agent according to any one of claims 1 to 5 is impregnated and applied to a substrate having absorbency.