JP6432028B2 - Vaporizable rust preventive - Google Patents

Description

  The present invention particularly oxidizes the surface when storing, transporting, transporting or using machinery and parts made of metals that are susceptible to oxidation, such as galvanized bridge wires, various machine parts and automobile parts. The present invention relates to a vaporizable rust preventive for preventing rusting upon receiving.

  As a method that has been widely used as a rust prevention measure for metal members as described above, a method of galvanizing a sacrificial anode on the surface of a steel material, a method of chromating the surface of a steel material, etc., steel For example, a method of coating the surface of the material. Moreover, the method of interrupting | blocking the oxygen and water | moisture content which become a corrosion factor by apply | coating antirust oil to the surface of steel materials etc. and forming an oil film is mentioned.

  Among these, the chromate treatment is mainly performed by immersing the steel material to be treated in a solution containing hexavalent chromium to form a passive state, but hexavalent chromium has an adverse effect on the environment and the human body. There is a fear. Furthermore, the object of the coating on the steel material or the galvanized surface is limited, and for example, the inner surface coating of a bridge wire (cable) such as a suspension bridge cannot be performed. And also in the method of using antirust oil, removal of the oil film after use is complicated.

  On the other hand, the method of galvanizing the surface of steel materials, etc. is safe for the environment and the human body, and it is plated with a nearly uniform thickness even for complicated machined shapes. In addition, once the galvanizing treatment is performed, there is a feature that no post-treatment is required. However, galvanization is likely to be oxidized and dissolved by natural substances such as wind and rain, temperature differences, or corrosive substances such as salt and moisture, and as a result, the base steel material may be exposed. For this reason, the substrate itself (steel materials, etc.) is corroded, and the strength may be reduced to cause a serious problem.

  To give a concrete example, a bridge wire (cable) such as a suspension bridge is made by galvanizing the surface of the cable strand as a sacrificial anode, bundling it, winding a wrapping wire, drawing resin rubber, and painting However, since metal shrinkage due to wind and rain or temperature difference is inevitable, corrosive substances such as salt and moisture may intrude. For this reason, oxidation / dissolution of the zinc plating on the surface of the cable strand and corrosion of the substrate itself resulting from this may occur, and the strength of the cable itself may be reduced.

  As a rust preventive agent for zinc, Patent Document 1 proposes a rust preventive agent containing a desiccant composition and 1,2,3-benzotriazole.

  Further, as a general metal rust preventive agent, Patent Document 2 discloses organic amine and / or metal nitrite, inorganic acid and / or organic acid ammonium salt, hydrogen carbonate metal salt, water retention or A vaporizable rust inhibitor containing a water sustained release aid has been proposed.

JP-A-11-92975 JP 2001-31966 A

  However, in the rust preventive agent described in Patent Document 1, there is a case where a sufficient rust preventive effect cannot be expected in a space where there is traffic to and from the outside air. The present invention has been made paying attention to such circumstances, and its purpose is to provide excellent rust prevention ability (initial rust prevention ability, long-term rust prevention ability) against zinc plating and zinc even under high temperature and high humidity conditions. Is to provide a vaporizable rust preventive capable of exhibiting

  As a result of intensive research to solve the above problems, the present inventors have found that nitrite, which has been considered to have a small rust-preventing effect on zinc and rather promote corrosion, is converted to ammonium salt, metal hydrogen carbonate. It was added to the azole compound under the condition that it coexists with a salt and a water retention aid. Then, surprisingly, the corrosion action of nitrite on zinc is suppressed, and it is excellent in both initial and long-term rust prevention ability and long-distance rust prevention ability against zinc even under high temperature and high humidity conditions. The present invention was completed by finding that a vaporizable rust preventive capable of exhibiting performance was obtained.

  That is, the vaporizable rust preventive according to the present invention includes an azole compound, an organic amine nitrite and / or a metal nitrite, an inorganic acid ammonium salt and / or an organic acid ammonium salt, and a hydrogen carbonate metal salt. And a water retention aid. Further, the content of the ammonium salt is 1 mol or more and 200 mol or less with respect to 100 mol of the nitrite, and the content of the hydrogen carbonate metal salt is 100 mass parts in total with the ammonium salt and nitrite. 0.1 parts by mass or more and 20 parts by mass or less, and the content of the water retention aid is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass in total of the ammonium salt and nitrite. It is preferable that

  The vaporizable rust preventive agent of the present invention preferably further contains a binder as another component. The content of the binder is preferably 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass in total of the nitrite and the ammonium salt.

  The vaporizable rust preventive agent of the present invention is preferably formed into a tablet or granule.

  Since the vaporizable rust preventive agent of the present invention contains an azole compound, nitrite, ammonium salt, hydrogen carbonate metal salt, and water retention aid, galvanization and zinc are also performed under high temperature and high humidity conditions. Can exhibit excellent rust prevention ability (initial rust prevention ability, long-term rust prevention ability).

  The vaporizable rust inhibitor of the present invention comprises (A) an azole compound, (B) an organic amine nitrite and / or a metal nitrite, and (C) an inorganic acid ammonium salt and / or an organic acid ammonium salt. And (D) a hydrogen carbonate metal salt and (E) a water retention aid. In the present invention, the vaporizable rust preventive means that the rust preventive component is vaporized and reacts with the target metal surface or adsorbs on the target metal surface, and can suppress rust and corrosion of the metal.

  Conventionally, although (B) nitrite has a high rust-preventing effect on steel materials, etc., it cannot be expected to have a high rust-preventing action on non-ferrous metals such as zinc, and rather it is thought that corrosion is promoted. It was done. However, the present inventors have changed (B) nitrite to (A) azole compound under the condition of coexisting with (C) ammonium salt, (D) metal hydrogencarbonate, and (E) water retention aid. It has been found that when added, a vaporizable rust inhibitor having excellent rust prevention performance against zinc can be obtained. This is considered to be due to the following mechanism of action. First, (A) the azole compound is complexed with zinc to form a salt on the surface of the zinc / zinc plating, and (A) the salt of the azole compound and zinc not only causes moisture and salt content, but also (B) nitrite. It is thought that it is possible to suppress the corrosion of zinc due to the above. And it is thought that (B) nitrite and (C) ammonium salt are hydrolyzed by the mechanism shown by a following formula with the water | moisture content hold | maintained in (E) water retention aid. As a result, ammonium nitrite having a high vapor pressure at room temperature and excellent antirust effect is produced, and the antirust component derived from ammonium nitrite is further adsorbed on the surface of the azole compound and zinc salt. It is considered that the antirust effect can be exhibited even under high temperature and high humidity.

Q ¹・ HNO ₂ + Q ²・ NH ₄ → Q ¹・ Q ² + NH ₄ NO ₂
In the above formula, Q ¹ represents an organic amine or a metal, and Q ² represents an inorganic acid or a conjugate base of an organic acid.

  And since the vaporizable rust preventive of the present invention contains (D) a hydrogen carbonate metal salt, (C) the ammonium ion produced by the decomposition of the ammonium salt can be stabilized as the ammonium carbonate metal salt. Can be controlled to exhibit long-term rust prevention ability.

  The azole compound (A) used in the vaporizable rust preventive agent of the present invention is preferably an azole compound containing 2 or more heteroatoms, and more preferably an azole compound containing 3 or more heteroatoms. Moreover, in a hetero atom, a nitrogen atom is 1 or more, and it is preferable that it is 2 or more. (A) Specific examples of the azole compound include imidazole, pyrazole, oxazole, isoxazole, thiazole, selenazole, 1,2,3-triazole, 1,2,5-oxadiazole, 1,3,4- Monocyclic azole compounds such as oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, tetrazole, 1,2,3,4-thiatriazole; indazole, A bicyclic azole compound such as benzimidazole, benzotriazole, and benzothiazole; and the like, and a bicyclic azole compound is preferable.

The monocyclic azole compound and the bicyclic azole compound may have a substituent. Examples of the substituent of these azole compounds include C _1-4 alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; a C _1-4 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; group; a dimethylamino group, disubstituted C _1-4 alkylamino group such as a diethylamino group; methylamino group, monosubstituted C _1-4 alkylamino groups such as ethylamino group mercapto group; hydroxy group; a hydroxymethyl group, hydroxyethyl And a hydroxy-substituted C _1-4 alkyl group such as an ethyl group; a carboxy group; and the like. A C _1-4 alkyl group is preferable, and a C _1-2 alkyl group is more preferable.

Among them, as the (A) azole compound, a bicyclic azole compound having a substituent is preferable, and a benzotriazole having a substituent (preferably a C _1-4 alkyl group) is more preferable.

  (A) The content of the azole compound is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% in 100% by mass of the vaporizable rust inhibitor. It is at least 35% by mass, most preferably at least 35% by mass. (A) When content of an azole compound exists in this range, while a contact with a water | moisture content, salt content, etc. and zinc and zinc plating can be prevented, corrosion of zinc by (B) nitrite can be suppressed. Further, the content of the (A) azole compound is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, particularly preferably in 100% by mass of the vaporizable rust inhibitor. Is 50% by mass or less, and most preferably 45% by mass or less. When the content of the (A) azole compound is within this range, the rust preventive action by (B) nitrite and (C) ammonium salt is effectively exhibited.

Among the nitrites (salts having nitrite ions (NO ₂ ⁻ )), (B) organic amine nitrites and / or metal nitrites are used for the vaporizable rust preventive of the present invention. (B) If it is a nitrite of an organic amine and / or a nitrite of a metal, the hydrolysis reaction with the (C) ammonium salt proceeds efficiently, and excellent rust prevention performance can be obtained. (B) Organic amine nitrites and / or metal nitrites may be used alone or in combination of two or more.

As the organic amine used in the nitrite of the (B) organic amine, primary to tertiary aromatic amines and primary to tertiary alicyclic amines are preferable. (B) The nitrites of organic amines include nitrites of primary amines such as nitroarylamines; nitrites of secondary amines such as dicycloalkylamines; nitrites of tertiary amines, etc. Secondary organic amine nitrites are preferred, dicycloalkylamine nitrites are more preferred, and dicyclohexylamine nitrites are particularly preferred.
Examples of the metal nitrite (B) include alkali metal nitrites such as lithium, sodium and potassium; alkaline earth metal nitrites such as calcium and magnesium; alkali metal nitrites are preferred. Sodium nitrite is particularly preferred.

  (B) The content of organic amine nitrite and / or metal nitrite is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 100% by mass of the vaporizable rust inhibitor. Is 20% by mass or more. (B) When content of nitrite exists in this range, it will become easy to hydrolyze with (C) ammonium salt, and will contribute to rust prevention performance improvement. The content of (B) organic amine nitrite and / or metal nitrite is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. (B) When content of nitrite exists in this range, rust prevention performance can be improved, without corroding zinc.

  In the vaporizable rust preventive agent of the present invention, by using (C) an inorganic acid ammonium salt and / or an organic acid ammonium salt in combination with (B) an organic amine nitrite and / or a metal nitrite, Since the rust preventive substance (ammonium nitrite) is generated by the hydrolytic decomposition, an excellent rust preventive effect is obtained. (C) Ammonium salts of inorganic acids and / or ammonium salts of organic acids may be used alone or in combination of two or more.

Examples of the inorganic acid include boric acid, phosphoric acid, carbonic acid, sulfuric acid, and hydrochloric acid. In addition, ammonium salts of these inorganic acids include ammonium borate such as ammonium metaborate, ammonium orthoborate, and ammonium tetraborate; monoammonium phosphate, diammonium phosphate, triammonium phosphate, diammonium hydrogen phosphate, etc. Ammonium phosphate; ammonium carbonate such as diammonium carbonate, monoammonium carbonate, ammonium hydrogen carbonate; ammonium sulfate; ammonium chloride;
Of these, ammonium borate such as ammonium tetraborate; ammonium phosphate such as diammonium phosphate, triammonium phosphate, and diammonium hydrogen phosphate; monoammonium carbonate; and the like are preferable.

  The organic acid is preferably a monovalent or divalent or higher carboxylic acid, and more preferably a monovalent or higher and trivalent or lower carboxylic acid. The organic acid ammonium salt is preferably one represented by any of the following formulas (C1) to (C3).

[In Formula (C1), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.
In formula (C2), R ² represents a single bond or a divalent hydrocarbon group which may have a substituent.
In formula (C3), R ³ represents a trivalent hydrocarbon which may have a substituent. ]

Examples of the monovalent hydrocarbon group for R ¹ include alkyl groups such as methyl group, ethyl group, and propyl group; aryl groups such as phenyl group and naphthyl group; Examples of the divalent hydrocarbon group for R ² include alkylene groups such as methylene group, ethylene group, propylene group, and octanediyl; Examples of the trivalent hydrocarbon group for R ³ include alkanetriyl groups such as methanetriyl group, ethanetriyl group, and propanetriyl group; The monovalent R ^1, R ^2, R ^3, 2-valent or, as the trivalent hydrocarbon group substituents which may be possessed by a hydroxy group, or a nitro group is preferred. The monovalent hydrocarbon group having a substituent is preferably a hydroxy-substituted aryl group of a hydroxyphenyl group; a nitro-substituted aryl group such as a nitrophenyl group; and the like. As the divalent hydrocarbon group having a substituent, hydroxy Preferably a hydroxyalkylene group such as an ethylene group or a hydroxypropylene group; the trivalent hydrocarbon group having a substituent includes a hydroxyalkanetriyl group such as a hydroxyethanetriyl group or a hydroxypropanetriyl group; preferable.

Specific examples of the organic acid ammonium salt include monovalent aromatic carboxylic acid ammonium salts such as ammonium benzoate, ammonium salicylate, and ammonium p-nitrobenzoate; monovalent fats such as ammonium formate and ammonium acetate. Carboxylic acid ammonium salt; divalent aliphatic dicarboxylic acid ammonium salt such as ammonium oxalate and diammonium sebacate; divalent hydroxy acid ammonium salt such as malic acid; trivalent hydroxy acid such as ammonium citrate Ammonium salt; and the like.
Among them, ammonium salts of monovalent organic acids and ammonium salts of divalent organic acids are preferable, monovalent aromatic carboxylic acid ammonium salts and divalent aliphatic dicarboxylic acid ammonium salts are more preferable, and benzoic acid. More preferred are ammonium acid and diammonium sebacate.

  (C) As an ammonium salt of an inorganic acid and / or an organic acid, an ammonium salt of an inorganic acid such as ammonium carbonate or diammonium hydrogen phosphate; ammonium benzoate, ammonium salicylate, ammonium p-nitrobenzoate, sebacin Ammonium salts of organic acids such as ammonium acid are preferred, with ammonium benzoate and diammonium hydrogen phosphate being particularly preferred.

  (C) The content of ammonium salt of inorganic acid and / or ammonium salt of organic acid is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 100% by mass of the vaporizable rust inhibitor. Preferably it is 10 mass% or more. When the content of (C) ammonium salt is within this range, it becomes easy to hydrolyze together with (B) nitrite, which contributes to improvement of rust prevention performance. It is preferable that it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less. (C) When content of ammonium salt exists in this range, antirust performance can be improved, without corroding zinc.

  In the vaporizable rust preventive agent of the present invention, the content of (C) ammonium salt is preferably 1 mol or more, more preferably 50 mol or more, further preferably 100 mol of (B) nitrite. It is 80 mol or more, preferably 200 mol or less, more preferably 150 mol or less, and still more preferably 100 mol or less. When the contents of (C) ammonium salt and (B) nitrite are within this range, an excellent rust preventive action can be exhibited over a long period of time.

  Furthermore, in the vaporizable rust inhibitor of the present invention, the total content of (B) nitrite and (C) ammonium salt is preferably 60 parts by mass or more with respect to 100 parts by mass of (A) azole compound. More preferably, it is 70 parts by mass or more, more preferably 80 parts by mass or more, particularly preferably 90 parts by mass or more, preferably 140 parts by mass or less, more preferably 130 parts by mass or less, still more preferably 120 parts by mass. Part or less, particularly preferably 110 parts by weight or less.

  In the vaporizable rust preventive agent of the present invention, (D) by containing a hydrogen carbonate metal salt, (C) ammonium ions produced by decomposition of the ammonium salt can be stabilized as an ammonium carbonate metal salt. ) Controlling the hydrolytic decomposition reaction of nitrite and (C) ammonium salt can exhibit long-term rust prevention ability. In particular, the vaporizable rust preventive agent of the present invention contains (E) a water retention aid, and (D) a metal hydrogen carbonate is used so that even during storage, the (E) water retention aid contains moisture. It is possible to suppress the hydrometathesis reaction due to, and to improve the storage stability of the vaporizable rust inhibitor. Moreover, when shape | molding the vaporizable rust preventive agent of this invention in a tablet form or a granule, since shape retentivity can be improved or collapse can be prevented, it is useful.

  (D) As a hydrogen carbonate metal salt, alkali metal hydrogen carbonate salts, such as potassium hydrogen carbonate and sodium hydrogen carbonate, are preferable. Moreover, (D) metal hydrogencarbonate may be used independently and may use 2 or more types together.

  (D) The content of the hydrogen carbonate metal salt is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% in 100% by mass of the vaporizable rust inhibitor. It is at least mass%. (D) When content of hydrogencarbonate metal salt exists in this range, long-term rust prevention performance will become favorable. Moreover, it is preferable that content of (D) hydrogencarbonate metal salt is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less. When the content of (D) the hydrogen carbonate metal salt is within this range, the rust preventive action due to the hydrolysis reaction of (B) nitrite and (C) ammonium salt is effectively exhibited.

  Further, the content of (D) metal hydrogen carbonate is preferably 0.1 parts by mass or more, more preferably 1 part per 100 parts by mass in total of (B) nitrite and (C) ammonium salt. It is at least part by mass, preferably at most 20 parts by mass, more preferably at most 10 parts by mass.

  In the vaporizable rust preventive agent of the present invention, (E) the water retention aid has a property of retaining or continuously releasing moisture, and is preferably a fibrous material. Thereby, even when it shape | molds in tablet shape or a granular form, the intensity | strength of a tablet or a granular material is ensured by the entanglement of a fiber, and these collapse | crumbles are suppressed. Examples of the fibrous material include animal fibers such as wool; vegetable fibers such as cotton, hemp, and cellulose; regenerated fibers; synthetic fibers such as viscose rayon; activated carbon fibers, and the like. Particularly preferred. In addition, (E) the water retention aid is preferably in the form of a powder from the viewpoint of efficiently retaining and releasing moisture even when it is formed into a tablet or granule.

  (E) The content of the water retention aid is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% in 100% by mass of the vaporizable rust inhibitor. It is preferably at least 5% by mass, more preferably at most 5% by mass, even more preferably at most 3% by mass, even more preferably at most 2% by mass. The content of (E) the water retention aid is preferably 0.001 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass in total of (C) ammonium salt and (B) nitrite. More preferably, they are 0.005 mass part or more and 25 mass parts or less, More preferably, they are 0.01 mass part or more and 20 mass parts or less, Especially preferably, they are 0.02 mass part or more and 15 mass parts or less. (E) When the content of the water retention aid is in this range, the water content in the vaporizable rust preventive agent can be kept moderate, and an excellent rust preventive action can be exhibited over a long period of time.

  The vaporizable rust preventive agent of the present invention may further contain (F) a binder. (F) The binder has a function of interposing between the above components so as not to separate them, and can improve the shape retention of the vaporizable rust inhibitor, Even when molded into a granular form, these collapses can be prevented and long-term rust prevention performance can be ensured. In addition, the binder has the role of preventing moisture from entering the vaporizable rust inhibitor at once and the role of preventing excessive contact between other components, thereby maintaining the long-term rust prevention effect. The function to enhance the effect is demonstrated more effectively. Examples of the binder include solid fats and oils (oils and fats solid at normal temperature (10 to 40 ° C.)), vegetable waxes, animal waxes, and synthetic resins. These may be used alone or in combination of two or more. Among these, solid fats and oils are preferable, and powdered solid fats and oils are more preferable at normal temperature (10 to 40 ° C.).

When (F) the binder is included, the content thereof is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, in 100% by mass of the vaporizable rust inhibitor. It is preferable that it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 12 mass% or less.
The content of the binder (F) is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass with respect to 100 parts by mass of the (A) azole compound. Hereinafter, it is more preferably 10 parts by mass or more and 30 parts by mass or less.
The content of (F) binder is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass with respect to 100 parts by mass in total of (B) nitrite and (C) ammonium salt. Part or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 30 parts by mass or less.

The vaporizable rust preventive agent of the present invention may be in the form of powder, or may be obtained by molding these into tablets or granules. Among these, a tablet shape is preferable. In the present invention, powder means a shape with a maximum diameter of less than 100 μm, granular means a shape with a maximum diameter of 100 μm or more and less than 1 mm, and tablet means a shape with a maximum diameter of 1 mm or more. It shall be. The tablet shape includes pellets, rods, donuts and the like, and the powder includes granules and the like.
Furthermore, when the vaporizable rust preventive agent of the present invention is formed into a tablet or granule, the weight of one unit is preferably 0.1 g or more and 0.5 g or less.

The vaporizable rust preventive agent of the present invention may be composed of two or more kinds of tablets or granules containing different components. In this case, (A) an azole compound, (E) a water retention aid, optionally (F) a first tablet containing a binder, (B) nitrite, (C) an ammonium salt, ( It is preferable to consist of the 2nd tablet containing D) hydrogencarbonate metal salt, (E) water retention aid, and optionally (F) binder. Thereby, corrosion of zinc and zinc plating by nitrite is further effectively suppressed, and a vaporizable rust inhibitor having excellent rust prevention performance can be obtained.
In this case, in the first tablet, the content of the (A) azole compound is preferably 60% by mass or more and 99% by mass or less, and 70% by mass or more, 98% by mass in 100% by mass of the first tablet. It is more preferable that the amount is not more than mass%. (E) The water retention aid is preferably 1% by mass or more and 40% by mass or less, and preferably 2% by mass or more and 30% by mass or less, in 100% by mass of the first tablet. Furthermore, when (F) the binder is included, the content thereof is preferably 1% by mass or more and 30% by mass or less in 100% by mass of the first tablet, and is preferably 10% by mass or more and 20% by mass or less. It is more preferable that
In the second tablet, the content of (B) nitrite is preferably 20% by mass or more and 70% by mass or less, and more preferably 30% by mass or more, in 100% by mass of the second tablet. 60 mass% or less. Further, the content of (C) ammonium salt is preferably 10% by mass or more and 50% by mass or less, and more preferably 20% by mass or more and 40% by mass or less, in 100% by mass of the second tablet. preferable. (D) Sodium bicarbonate is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 6% by mass or less, in 100% by mass of the second tablet. (E) The water retention aid is preferably 0.1% by mass or more and 5% by mass or less, and 0.5% by mass or more and 3% by mass or less, in 100% by mass of the second tablet. More preferred. Furthermore, when (F) the binder is included, the content thereof is preferably 1% by mass or more and 30% by mass or less in 100% by mass of the second tablet, and is preferably 10% by mass or more and 20% by mass or less. It is more preferable that

  The vaporizable rust preventive of the present invention contains (A) an azole compound, (B) a nitrite, (C) an ammonium salt, (D) a hydrogen carbonate metal salt, and (E) a water retention aid, as necessary. And (F) a binder, and the above ingredients are mixed simultaneously or in any order and mixed uniformly, and this is formed into tablets of any shape, granules, or remains in powder form Use it.

  The vaporizable rust preventive of the present invention contains (A) an azole compound, (B) a nitrite, (C) an ammonium salt, (D) a hydrogen carbonate metal salt, and (E) a water retention aid. By using moisture in the surrounding environment, not only steel, but also copper, zinc, zinc alloys, and galvanization are excellent in high-temperature and high-humidity conditions. Rust ability can be demonstrated.

  The vaporizable rust preventive of the present invention is particularly noticeable in terms of excellent rust preventive performance against zinc and zinc plating (particularly hot dip galvanizing), and is useful as a vaporizable rust preventive for zinc and zinc plating. It is. In addition, for example, in a bridge wire, by introducing the vaporizable rust preventive agent of the present invention into an inspection window or the like of a cable band structure section in which cables are bundled, while suppressing corrosion of zinc by nitrite, (A) azole The compound and the composite rust preventive action by ammonium nitrite by hydrolysis of (B) nitrite and (C) ammonium salt can be exhibited.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
Measurement methods in the examples of the present invention are as follows.

Hot-dip galvanized accelerated comparative rust prevention test (1) As a test container, a 1 L wide-mouth bottle was used and sealed with a silicone tight stopper with a hanging hook. To the bottom, 10 mL of a 10% NaCl aqueous solution was added as humidity control water.
(2) As a test piece, a hot dip galvanized plate (40 × 60 × 2.3 mm with a hanging hole, SS-400 steel plate inside) manufactured by Nippon Test Panel Co., Ltd. was used. The hot-dip galvanized plate was lightly polished with # 240 wet polishing paper to the extent that no base steel plate was produced, and then washed and dried. Two test pieces were prepared and weighed. In addition, sandwiching two other hot-dip galvanized plates for increasing the heat capacity between the two weighed test pieces, a total of four pieces are tightly bound with an octopus thread, and silicon is placed in the middle of the test container. It was hung on the hook of the stopper.
(3) A vaporizable rust preventive agent (or a blank test) shown in Table 1 was put in a polyethylene net, and attached to a silicon plug hook on the top of the test piece.
(4) The above-mentioned capped wide-mouth bottle was placed in an environmental tester under cycle conditions of 5 ° C. × 3.5 hours and 40 ° C. × 2.5 hours.
(5) After 40 cycles (10 days) and 240 cycles (60 days) have been completed, the octopus yarn of the test piece is removed, the appearance is visually observed, the outside two are washed with acetone, dried and weighed. The difference from the weight before the test: W ₁ (mg) was calculated.
(6) The corrosion product on the outer surface, inner surface, and side surface of the test piece was strongly rubbed with a polyurethane foam sponge for household use, washed, dried, weighed, and the difference from the weight before the test: W ₂ (mg) was calculated. .
(7) Each test was performed twice, and the average of the weights of the four test pieces obtained was calculated. A positive value indicates that the weight has increased from before the test, and a negative value indicates that the weight has decreased from before the test.

Production Example 1
(A) An azole compound, (E) a water retention aid, and (F) a binder were blended in the ratios shown in Table 1 below, and tableted in units of 0.25 g to obtain tablet 1.
Production Example 2
Further, (B) nitrite, (C) ammonium salt, (D) metal hydrogen carbonate, (E) water retention aid, and (F) binder are blended in the ratio shown in Table 1 below, and 0 Tableted in units of .25 g to give tablet 2.

Example 1, Comparative Examples 1 and 2
The vaporizable rust preventives of Example 1 and Comparative Examples 1 and 2 were prepared by blending nitrous acid rust preventives and azole rust preventives in the ratios shown in Table 2. In addition, Table 2 shows the results of an accelerated comparative rust prevention test for these vaporizable rust inhibitors.

In Table 2, in Comparative Examples 1 and 2, white rust peculiar to white powdered zinc was generated before washing in both 40 cycles and 240 cycles. On the other hand, in Example 1, the appearance of a hard solid surface of the original thin tan color of zinc plating was exhibited.
The weight difference W ₁ after washing with acetone after 40 cycles was larger in Comparative Examples 1 and 2 than in Example 1. The weight difference W ₂ after abrasive cleaning is reduced in weight than the original specimen becomes Comparative Examples 1 and 2 both negative values, corrosion until the zinc matrix progresses, the abrasive cleaning It was shown that the corroded part which became weak by friction was removed.
Further, as the test time is increased from 40 cycles to 240 cycles, in Comparative Example 1, the weight difference W ₁ after the acetone cleaning is further increased and W ₂ is further decreased. It was shown to be progressing. On the other hand, in Example 1, both the weight difference W ₁ after the acetone cleaning and the weight difference W ₂ after the polishing cleaning were further increased, indicating that the rust preventive component was further adhered.

Claims (5)

An azole compound,
An organic amine nitrite and / or a metal nitrite;
An inorganic acid ammonium salt and / or an organic acid ammonium salt;
Metal bicarbonate,
A vaporizable rust inhibitor for zinc plating and zinc, characterized by containing a water retention aid. The content of the ammonium salt is 1 mol or more and 200 mol or less with respect to 100 mol of the nitrite,
The content of the hydrogen carbonate metal salt is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass in total of the ammonium salt and nitrite.
The content of the water retention aid is 0.01 parts by mass or more and 20 parts by mass or less based on a total of 100 parts by mass of the ammonium salt and nitrite . A vaporizable rust inhibitor. Furthermore, the vaporizable rust preventive agent for zinc plating and zinc of Claim 1 or 2 containing a binder as another component. The content of the binder is, the 1 part by mass or more per 100 parts by weight of the nitrite with an ammonium salt, 100 parts by weight or less volatile proof for galvanized and zinc according to claim 3, Rust agent. The vaporizable rust preventive agent for zinc plating and zinc according to any one of claims 1 to 4, which is formed into a tablet shape or a granular shape.