JPWO2007037045A1 - Metal rust preventive compound powder and its production method, metal rust preventive composition and metal rust preventive film - Google Patents

Abstract

By making 1 mol of BTA (benzotriazole) or TTA (tolyltriazole) into a 1/2 metal salt bonded with 1/2 mol of an alkali metal or an alkaline earth metal, a novel rust-proofing and high melting point new Providing metal salt compounds and their manufacturing methods, and by kneading them into thermoplastic resins, they are useful for antiseptic and rustproof packaging of products and parts containing metals such as steel, copper, zinc, aluminum and silver and their alloys The right film.

Description

  The present invention is used for packaging metal products and metal parts containing metals such as steel, copper, zinc, aluminum, silver, and alloys thereof, or existing in a space where these metal products and metal parts exist. A novel metal rust preventive compound powder capable of effectively preventing corrosion and discoloration of these metal products and metal parts, a method for producing the same, and a metal rust preventive composition containing the compound powder as an active ingredient, The present invention relates to a metal rust prevention film using the same.

  Conventionally, as a means of rust prevention for metal products, starting with the application of rust-preventive oil, packing with vaporizable rust-proof paper, shielding it from the outside with a sealing film on it, or applying a vaporizable rust-proofing material in the sealing film Methods such as enclosing or spraying have been adopted. Recently, attempts have been made to use a transparent vaporizable rust-proof film from the viewpoint of further labor saving. Under such circumstances, as a method for producing a vaporizable rust-proof film, a chemical having a rust-proofing effect according to the type of metal subject to rust prevention, utilizing the technology of known vaporizable rust-proof materials and vaporizable rust-proof paper A vaporizable rust preventive film has been developed, in which the above is kneaded into a thermoplastic resin, or applied or printed.

  The biggest feature of such a vaporizable rust-proof film is that it is transparent and can be seen through, and can be sealed by heat sealing, but the above-mentioned features are utilized in the method of applying a vaporizable rust-proof material to the film. hard. Therefore, a vaporizable rust preventive film having a rust preventive effect on individual metals has been developed with a transparent kneaded product. On the other hand, most of recent metal products are composites or combinations of various kinds of metals, and there is a need for a rust inhibitor that can exert a rust preventive effect on all these metals.

  Under these circumstances, as a method to prevent corrosion and discoloration of many kinds of metals, hermetically sealed with thick-walled thermoplastic resin film or expensive multilayer film, water vapor, sulfite ion or sulfide ion in the atmosphere There are known methods for preventing such intrusions. However, complete hermetic packaging not only requires a great deal of labor and process control, but also increases the packaging cost and thus the product price.

  On the other hand, many film materials for preventing corrosion, discoloration, oxidative deterioration, etc. of metal products have been proposed. For example, Japanese Patent Application Laid-Open No. 11-071471 discloses a water-soluble glass powder and a vaporizable rust preventive as thermoplastic. A method of kneading into a resin to process it into a film or applying it to a thermoplastic resin film is disclosed. Japanese Patent Application Laid-Open No. 10-158645 discloses a two-component rust preventive agent in which a mixture containing a nitrite in a water-soluble resin and a mixture containing an ammonium compound in a thermoplastic resin coexist. Yes. Furthermore, Japanese Patent Application Laid-Open No. 09-124838 discloses a vaporizable rust preventive obtained by mixing a nitrogen-containing compound such as an amine or an ammonium salt into a thermoplastic resin.

  However, in the method disclosed in Japanese Patent Application Laid-Open No. 11-071471, the rust preventive component volatilizes around 130 ° C., which is the processing temperature of polyethylene, which is a typical thermoplastic resin, and the production environment of the rust preventive film is deteriorated. And may cause a powder blowing phenomenon on the product film. Moreover, it has been pointed out that nitrite used as a rust-preventing component in this method promotes discoloration on the basis of zinc-based metals, and also has a problem of carcinogenicity.

  Further, the two-component rust inhibitor described in JP-A-10-158645 described above is excellent for steel products and the like because vaporizable ammonium nitrite is generated by metathesis reaction after being formed into a rust preventive film. Exhibits rust prevention effect. However, the zinc-based metal causes discoloration as described above.

  Further, p-tertiary butyl benzoic acid alkali metal salt used in the method disclosed in Japanese Patent Application Laid-Open No. 09-124838 shows an excellent rust preventive effect in a state where it is brought into contact with a steel product. The other rust-preventing components that are used are nitrite-based compounds, which adversely affect zinc-based metals. In addition, although tolyltriazole has been exemplified as having a rust-proofing effect on zinc-based metals, since this has a low melting point, for example, if it is kneaded into polyethylene or the like, it is caused by heat during processing into a film or the like. Vaporizes violently and significantly deteriorates the working environment. In addition, molten tolyltriazole adheres to other unmelted materials and agglomerates them, clogging the filter of processing equipment, mixing as foreign matter in the film, and causing the film to break, etc. Adversely affect.

  The present invention has been made paying attention to the circumstances as described above, and its purpose is to produce a metal such as steel, copper, zinc, aluminum, silver, etc. without causing the problems as pointed out in the prior art. Or metal products made of alloys containing these metals, or used in packaging of metal parts, or placed in a space where these metal products or parts exist, corrosion or discoloration of those metal products or parts can be prevented. The present invention provides a novel metal rust preventive compound powder that can be effectively prevented, its useful production method, and further a metal rust preventive composition and a metal rust preventive film using the rust preventive compound powder. Is to provide.

  In particular, even when it is kneaded into a polyolefin resin such as polyethylene and processed into a film shape, it does not cause environmental pollution due to odor and volatilization of carcinogenic components at a high melting point, and with other metal rust preventive components. A new metal rust preventive compound powder that does not cause problems such as agglomeration between them, and further provides a rust preventive composition that exhibits excellent rust preventive ability using the rust preventive compound powder In addition, another object is to provide a metal rust prevention film having excellent film characteristics and rust prevention ability.

  In the metal rust preventive compound powder of the present invention that has solved the above problems, 0.5 mol of an alkali metal or alkaline earth metal compound is bonded to 1 mol of a triazole compound represented by the following formula (1). It is a novel powdery compound having a metal rust prevention property.

（式中、Ｒは水素またはメチル基を表す）

(Wherein R represents hydrogen or a methyl group)

  Moreover, the manufacturing method of this invention provides the method of manufacturing the said novel metal antirust compound powder, Triazole compound shown by said Formula (1): 1 mol, and an alkali metal or alkaline-earth metal: 0 .4 to 0.7 mol is dissolved and reacted in water at a temperature of 50 ° C. or higher, an aqueous solution having a concentration of 10 to 40% by mass is cooled to 40 ° C. or lower, and the resulting crystals are solid-liquid separated and dried. However, it has the characteristics.

  In another method of the present invention, the triazole compound represented by the above formula (1): 1 mol and an alkali metal hydroxide or alkaline earth metal hydroxide: 1/2 mol were dissolved and reacted in water. After that, it is characterized in that it is obtained in powder form by spray drying or freeze drying.

  And the metal rust preventive composition of the present invention is characterized by containing the metal rust preventive compound powder as an active ingredient, preferably in addition to the metal rust preventive compound powder, orthophosphoric acid, Containing at least one amine salt powder selected from the group consisting of organic phosphonic acids, aromatic carboxylic acids and amine salts of aromatic sulfonic acids, or further containing silicon-containing compounds, phosphoric acid compounds, nitric acid compounds, organic acids 1 selected from the group consisting of a compound, a metal compound, mercaptobenzothiazole, mercaptobenzotriazole, (2-benzothiazolylthio) acetic acid, 3- (2-benzothiazolylthio) propionic acid, salicylamide, and a hydroxy fatty acid metal salt Those containing two or more seeds have a further excellent metal rust prevention ability.

  Preferred organic phosphonic acids used above include 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), 2-phosphonobutane. Examples include -1,2,4-tricarboxylic acid.

Moreover, as aromatic carboxylic acid and aromatic sulfonic acid, the compound shown by following formula (2) and (3) is mentioned. In the following formula (2), X represents a carboxyl group or a sulfonic acid group, A ^{1 to} A ⁵ may be the same or different, and any one of a nitro group, an amino group, a hydroxyl group, hydrogen, and an alkyl group Or, it represents a combination of two or more, and in the following formula (3), either Y or Z is a carboxyl group or sulfonic acid group, and among Y and Z, the carboxyl group or sulfonic acid group is substituted. The substituent that is not present and A ^{6 to} A ¹¹ may be the same or different and each represents one or a combination of two or more of a nitro group, an amino group, a hydroxyl group, hydrogen, and an alkyl group.

  Preferred as the aromatic carboxylic acid are benzoic acid, nitrobenzoic acid, anthranilic acid, salicylic acid, dihydroxybenzoic acid, toluic acid, butylbenzoic acid, hydroxynaphthoic acid and the like, and preferred aromatic sulfonic acid is Examples thereof include sulfanilic acid, toluenesulfonic acid, hydroxymethylbenzenesulfonic acid, naphthionic acid, 7-hydroxynaphthalenesulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, and the like. These may be used alone or in combination of two or more as required.

  Preferred as the amine salt are dicyclohexylamine, cyclohexylamine, morpholine, diisopropylamine, dibutylamine, propylamine, ethylamine, methylamine, ammonia, and the like. These can be used alone, and two kinds can be used as necessary. The above may be used in any combination.

  As other components, silicon-containing compounds, phosphoric acid compounds, nitric acid compounds, organic acid compounds, metal compounds, mercaptobenzothiazole, mercaptobenzotriazole, (2-benzothiazolylthio) acetic acid, 3- (2-benzothiazoli If the compound selected from the group consisting of (ruthio) propionic acid, salicylamide, and a hydroxy fatty acid metal salt is used alone or in combination of two or more as required, the rust prevention effect can be further enhanced. Therefore, it is preferable.

  In addition, the powdery metal rust preventive composition according to the present invention preferably has a pH of 4 to 10 in a state of an aqueous solution having a concentration of 1% by mass, and more preferably has a pH of 6 to 9. The composition for rust prevention according to the present invention having characteristics exhibits excellent rust prevention ability particularly for metals such as steel, copper, zinc, aluminum and silver and alloys containing these metals.

  The metal rust preventive composition can be effectively used as a metal rust preventive film by being mixed into a thermoplastic resin such as polyethylene or polypropylene and processed into a film.

  The greatest feature of the present invention is that it has been confirmed to have a rust-preventing effect on zinc, copper and their alloys, but has a low melting point and poor handleability, especially thermoplastic resins such as polyolefin resins. As a triazole compound that emits an irritating odor at the time of mixing into the product, worsens the working environment, or causes problems such as melting with heat during processing and agglomerating with other component powders, for example, benzotriazole (melting point: 98 ° C., Hereinafter, a metal salt (hereinafter, abbreviated as BTA) or tolyltriazole (melting point: 88 ° C., hereinafter abbreviated as TTA) bound to about 0.5 mol of an alkali metal or an alkaline earth metal. By making this a 1/2 metal salt), there is little irritating odor generated when kneading into a thermoplastic resin and the like, and the melting point is 150 ° C., which is easy to handle. Lies was it possible to obtain in powder form above. The above technique can be similarly applied to 4-methylbenzotriazole or 5-methylbenzotriazole.

  By the way, as a triazole compound, for example, BTA has a rust prevention effect on copper, copper alloy, aluminum, silver, etc., and TTA has a rust prevention effect on copper, copper alloy, aluminum, zinc, silver, steel, etc. It is known to have However, these have a low melting point (both 100 ° C. or lower) and are lower than the processing temperature of the thermoplastic resin, so if used as they are, the odor is emitted and the working environment is deteriorated, or the BTA melted by the heat during processing And TTA significantly reduce the viscosity of the resin and cause molding defects, or adhere to other rust preventive components that are not melted and agglomerate them, causing clogging in the filter part of the processing equipment. In some cases, it becomes a granular foreign substance in the film or on the film surface, and the physical properties and appearance of the film are remarkably deteriorated.

  BTA and TTA show weak acidity, and this forms a salt with an alkali metal or the like because NH of NH in the triazole part in the molecular structure acts as active hydrogen. However, 1/1 equimolar salts such as BTA, TTA and alkali metals are highly deliquescent and difficult to obtain as a powder in a normal temperature and humidity atmosphere, and immediately absorb moisture when kneaded with a thermoplastic resin such as polyolefin. As a result, it becomes liquefied and a uniform blend cannot be obtained.

  However, as will be described in detail later, when about 1/2 mol of alkali metal or alkaline earth metal is used for 1 mol of BTA or TTA and reacted under predetermined conditions, 1 mol of BTA or TTA is alkalinized with 1 mol of BTA or TTA. A half metal salt obtained by reacting about 1/2 mole of a metal or an alkaline earth metal can be obtained almost quantitatively, and this half metal salt has a low solubility in water and is stable with low hygroscopicity. It was confirmed to be obtained as a powder.

  That is, when BTA or TTA is reacted with 40 to 70 mol% of alkali metal or alkaline earth metal in an aqueous solution at a temperature of 50 ° C. or higher, and an aqueous solution having a concentration of 10 to 40 mass% is cooled to 40 ° C. or lower. When a 1/2 metal salt of BTA or TTA is precipitated as a crystal, and this is solid-liquid separated, dried and pulverized, a 1/2 metal salt of BTA or TTA can be easily obtained as a powder. Further, BTA or TTA: 1 mol and alkali metal or alkaline earth metal hydroxide: 0.5 mol are reacted in an aqueous solution, preferably at a temperature of 40 ° C. or higher, and then spray-dried or freeze-dried. Also, a powdery compound comprising a 1/2 metal salt of BTA or TTA can be easily obtained.

  Moreover, these ½ metal salts have a high melting point, and do not melt even in the processing temperature range of thermoplastic resins such as polyolefin resins, and also have the problem of irritating gas and polluting the work environment. It was confirmed that it did not occur. Of the alkali metal salts and alkaline earth metal salts, ½Na salt and ½Ca salt are obtained as the lowest hygroscopic and stable powder, and the melting point of BTA · 1 / 2Na salt is The melting point of 218 ° C. and TTA · 1 / 2Na salt is 158 ° C. Neither BTA · 1 / 2Ca salt nor TTA · 1 / 2Ca salt has a melting point of 300 ° C. or lower.

  For example, the 1 / 2Na salt obtained by this method is also considered as a mixture of free BTA or TTA and the respective Na salt. However, when the dried product obtained by crystallization from the neutralization reaction aqueous solution was confirmed by neutralization titration with hydrochloric acid, the neutralization value of the product obtained from BTA and NaOH was “210” (BTA · 1 / 2Na salt). The theoretical neutralization value of the product obtained from TTA and NaOH is “190” (the theoretical neutralization value of TTA · 1 / 2Na salt is 194), which is almost the same as ½Na salt. Confirmed to do.

  Moreover, according to differential thermal analysis, the endothermic peaks at 98 ° C. for BTA and 88 ° C. for TTA disappeared, and the endothermic peak at 218 ° C. for BTA · 1 / 2Na and 158 ° C. for TTA · 1 / 2Na salt. It was confirmed to appear. Further, it has been confirmed that these 1 / 2Na salts can be effectively used as a rust preventive material that does not melt at 150 ° C. or lower and can be kneaded in a powder state in a thermoplastic resin. It was also confirmed that the pH of a 1 mass% aqueous solution prepared by dissolving these 1 / 2Na salt powders in water was around 8.5.

  In addition, TTA that is commercially available is 5-methylbenzotriazole, which exhibits an excellent rust-preventing effect on copper, zinc, and steel, and an excellent rust-preventing effect on copper, while rust-proofing on zinc and steel. It is a mixture with 4-methylbenzotriazole having a weak effect and strong odor, and the content ratio of the former and the latter is about 6: 4 by mass ratio. However, the powder obtained by crystallizing these as ½Na salts and taking them out has a mass ratio of about 9: 1, and has a more excellent antirust effect on zinc and steel, and has a low odor. It was confirmed that benzotriazole became the main TTA · 1 / 2Na salt. It was also confirmed that when the filtrate after crystallization was acidified, it could be taken out as TTA with an increased 4-methylbenzotriazole content.

  By analogy with crystallization or endothermic peak as a crystal from such a reaction aqueous solution, the BTA.1 / 2 metal salt (or TTA.1 / 2 metal salt) according to the present invention is free BTA (or TTA). And a simple mixture of BTA (or TTA) · 1/1 equimolar metal salt, but they are judged to be a new single compound in which they are complexed together.

  In the above description, the ½Na salt is explained, but the same tendency is confirmed for ½K salt and ½Li salt which are other alkali metals, and Mg, Ba, and Ca are divalent metals. However, it was confirmed that these metal salts have almost the same tendency as the alkali metal salts. However, the most preferable from the viewpoints of crystallization from an aqueous solution and hygroscopicity after drying is Na among alkali metals and Ca among alkaline earth metals.

  The triazole compound / 1/2 metal salt powder of the present invention thus obtained has a high melting point as described above, and has a melting point higher than 100 to 150 ° C., which is a normal processing temperature when kneaded into a thermoplastic resin. Therefore, it hardly vaporizes during processing and there is little risk of contaminating the work environment. In addition, the film in which these powders are kneaded exhibits excellent rust prevention effects by contacting metal products and parts made of steel, aluminum, copper, zinc, silver, etc., and the powder gradually vaporizes. Therefore, an excellent rust prevention effect is exhibited even in a non-contact portion.

  Therefore, the BTA (or TTA) 1/2 metal salt powder can be used as a metal rust preventive as it is or after being mixed with a carrier component if necessary and processed into a granular form. It can also be used as a metal rust preventive film by kneading into a resin or the like.

  However, when put into practical use as a composition for metal rust prevention, together with the BTA (or TTA) · 1/2 metal salt powder, as a second component, orthophosphoric acid, organic phosphonic acid, aromatic carboxylic acid, aromatic An amine salt powder of an acid selected from sulfonic acids may be used in combination.

  Incidentally, it has been known that phosphoric acid compounds such as orthophosphoric acid and organic phosphonic acid, salicylic acid, dihydroxybenzoic acid, hydroxynaphthoic acid, etc. have a strong antirust effect against aluminum. This is because the following effects are exhibited when using.

  It is considered that the weakly acidic compound BTA or TTA and the strong base sodium are inherently weak and coexist with amine salts such as orthophosphoric acid, organic phosphonic acid, aromatic carboxylic acid and aromatic sulfonic acid. Cause a metathesis reaction. And sodium ion etc. which removed from BTA (or TTA) .1 / 2 metal salt reacts with said phosphoric acid, aromatic carboxylic acid, aromatic sulfonic acid, etc., and these phosphoric acids, aromatic carboxylic acid, aromatic The amine that has been removed from the bond with the sulfonic acid is vaporized, and works as an effective vaporizable rust inhibitor for steel and the like. In addition, free BTA and TTA generated by the removal of metal from BTA (or TTA) 1/2 metal salt are vaporized and effective as a vaporizable rust inhibitor for copper, zinc, copper alloy, aluminum, silver, etc. Acts as That is, it is considered that these metathesis reactions exhibit an excellent rust prevention effect for various metals.

  The amine salt of orthophosphoric acid can be crystallized and taken out from an aqueous solution in which an equimolar amount of amine is added to 1 mol of orthophosphoric acid. In the case of organic phosphonic acid, 2 moles of amine is used for 1-hydroxyethylidene-1,1-diphosphonic acid, 3 moles of amine is used for aminotri (methylenephosphonic acid), For ethylenediaminetetra (methylenephosphonic acid), 4 times mole of amine is used, for diethylenetriaminepenta (methylenephosphonic acid), 5 times mole of amine is used, 2-phosphonobutane-1,2,4- For tricarboxylic acid, 2 moles of amine is used, and for aromatic carboxylic acid and aromatic sulfonic acid, equimolar amine is used, and each aqueous solution is crystallized, or the aqueous solution is spray-dried or It can be taken out as a powder by freeze-drying.

  The dry powder obtained from the amine salt of orthophosphoric acid or organic phosphonic acid exhibits a pH of around 4 in the state of a 1% by weight aqueous solution, and the dry powder obtained from the amine salt of aromatic carboxylic acid or aromatic sulfonic acid is 1% by weight. It becomes pH 6 vicinity in the state of aqueous solution. And when these are mixed with the above-mentioned BTA or TTA ½ metal salt powder and adjusted to have a pH of 4 to 10 as a 1% by mass aqueous solution, the rust prevention effect is further improved for various metals. It will have. The more preferable pH of the mixture is 6 to 9. If the pH is too low, the vaporization and rust prevention ability for steel is deteriorated, and if the pH is too high, there is a possibility that the aluminum contacts and deteriorates.

  The blending ratio of the BTA (or TTA) 1/2 metal salt powder and the amine salt powder varies depending on the type of the powder, and thus cannot be determined uniformly. In the range of the former 60 to 10, the latter 40 to 90, more generally in the range of the former 50 to 20 and the latter 50 to 80.

  In the present invention, a third component in addition to the above components includes a silicon-containing compound, a phosphoric acid compound, a nitric acid compound, an organic acid compound, a metal compound, mercaptobenzothiazole, mercaptobenzotriazole, (2-benzothiazolylthio) When at least one powder selected from the group consisting of acetic acid, 3- (2-benzothiazolylthio) propionic acid, salicylamide, and a hydroxy fatty acid metal salt is used in combination, the rust resistance against the metal can be further improved. .

Examples of the silicon-containing compound include silica, siliceous sand, diatomaceous earth, activated clay, aluminum silicate, magnesium silicate, and the like, or kaolin, pearlite, bentonite, and talc, whose main components are silicic acid (SiO ₂ ). When an appropriate amount of these is blended, the rust preventive ability for steel and aluminum is improved.

  Examples of phosphoric acid compounds include calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, apatite, calcium dihydrogen pyrophosphate, calcium pyrophosphate, potassium dihydrogen phosphate, potassium dihydrogen phosphate, and potassium triphosphate. , Potassium pyrophosphate, potassium tripolyphosphate, potassium metaphosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, tetrasodium pyrophosphate, disodium dihydrogen pyrophosphate, sodium tripolyphosphate, tetrapolyphosphoric acid Sodium, sodium pentapolyphosphate, sodium hexametaphosphate, sodium ultrapolyphosphate, sodium acid hexametaphosphate, sodium trimetaphosphate, acid magnesium phosphate, magnesium hydrogen phosphate, normal magnesium phosphate , Magnesium pyrophosphate, primary aluminum phosphate, secondary aluminum phosphate, tertiary aluminum phosphate, sodium hypophosphite, 1 ammonium phosphate, 2 ammonium phosphate, 3 ammonium phosphate, etc. In addition to being able to use each independently, two or more kinds may be added in combination at an arbitrary ratio as required. When an appropriate amount of these is blended, the antirust effect on steel and aluminum is improved.

  Examples of the nitric acid compound include sodium nitrate, potassium nitrate, ammonium nitrate, calcium nitrate, lithium nitrate, and the like, and when an appropriate amount thereof is blended, the rust prevention effect on steel is further improved.

  Examples of the organic acid compound include sodium benzoate, sodium toluate, sodium sebacate, sodium dodecanoate, sodium gluconate, calcium benzoate, magnesium benzoate, calcium gluconate, sodium salicylate, calcium salicylate, and the like. Contributes particularly to the improvement of the rust prevention effect on steel and aluminum.

  Metal compounds include aluminum, barium, calcium, cadmium, cerium, cobalt, copper, iron, gallium, indium, iridium, magnesium, manganese, molybdenum, nickel, lead, palladium, rubidium, scandium, cerium, tin, titanium, vanadium Oxides such as yttrium, zinc and zirconium, inorganic acid salts, organic acid salts, etc., and metal components contained in metal compounds are sulfides that corrode and discolor copper, copper alloys, silver, etc., among metal products. Increases rust prevention by reacting with ions and fixing.

  Further, mercaptobenzothiazole, mercaptobenzotriazole, (2-benzothiazolylthio) acetic acid, 3- (2-benzothiazolylthio) propionic acid, salicylamide, 12-hydroxycalcium stearate, 12-hydroxymagnesium stearate, 12 -Zinc hydroxystearate, aluminum 12-hydroxystearate, etc. improve the rust prevention ability with respect to steel, aluminum, zinc, and copper.

  The first component (triazole / 1/2 metal salt powder) and the second component (orthophosphoric acid, organic phosphonic acid, aromatic carboxylic acid, and amine salt of aromatic sulfonic acid) and the third component are preferred. The blending ratio varies depending on the type, but the standard is mass ratio (first and second components): third component, 99-30: 1-70, more preferably 95-40: 5. It is in the range of ˜60.

  Each of the above-mentioned rust preventive components is mixed after being pulverized until the average particle size becomes 50 μm or less, or mixed and pulverized to 50 μm or less and then mixed into the thermoplastic resin to form a film. When formed into a film, a film having stable strength and physical properties can be obtained without giving the film a feeling of foreign matter.

  The type of the thermoplastic resin is not particularly limited, and examples thereof include polyolefin resins, polyester resins, polyamide resins, styrene resins, polyvinyl acetate resins, and the most preferable film material is polyethylene, It is a polyolefin resin such as polypropylene, and melt extrusion molding such as an inflation method or a T-die method is suitably used for forming the film.

  Moreover, when manufacturing a masterbatch for rustproof film manufacture, it is good to make content as a rustproofing agent component into the range of 20-50 mass%. By the way, if it is less than 20% by mass, a large amount of masterbatch is required to obtain a rust-proof film having a predetermined rust-preventing ability, and if it has a high concentration exceeding 50% by mass, when preparing a masterbatch, As a result of the occurrence of eye corners, it becomes impossible to produce a continuous masterbatch, and it is necessary to take preventive measures for the eyes.

  When creating a rust preventive film, the rust preventive master batch is preferably 2 to 10% by mass, and the content of the rust preventive component contained in the rust preventive film is in the range of 0.5 to 10% by mass. Is preferred. If the amount is less than 0.5% by mass, the rust-preventing power tends to be insufficient, and if the amount exceeds 10% by mass, the rust-proofing force is saturated and the cost is increased. A more preferable content of the rust preventive component is in the range of 1 to 5% by mass.

  The rust preventive film of the present invention prepared by blending the above metal rust preventive composition is hermetically wrapping metal products and parts that are susceptible to corrosion due to corrosion factors such as moisture, halogen ions, and sulfur-containing gas, The rust preventive component generated by metathesis is vaporized even in the non-contact part as well as the part in contact with the film, and it adheres to the surface of metal products and metal parts to form a rust preventive film, or the corrosion factor in the rust preventive film By blocking or absorbing and fixing, it exhibits excellent rust prevention ability.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following Examples, and may be appropriately changed within a range that can meet the purpose described above and below. It is also possible to carry out by adding these, and they are all included in the technical scope of the present invention. In the following, “parts” and “%” represent “parts by mass” and “mass%” unless otherwise specified.

Example 1
In a 2 L beaker, 266 g (2 mol) of TTA, which is a mixture of 65% of 5-methylbenzotriazole: 35% and 4-methylbenzotriazole: 35%, 48 g (1.2 mol) of sodium hydroxide, deionized Water: 936 g is added, dissolved by heating at 50 ° C., cooled to 25 ° C., and the precipitated crystals are separated into solid and liquid by centrifugation. The solid was dried with hot air at 70 to 80 ° C. or dried under reduced pressure at 40 to 60 ° C. and then pulverized to obtain 105 g of a powdery product.

  The resulting powdery product had a neutralization value of 190 KOH mg / g, which was close to the theoretical neutralization value of TTA · 1 / 2Na, 195 KOH mg / g. Further, the endothermic peak temperature of the melting point by differential thermal analysis of the powder was 158 ° C. The sodium content of the powdery substance by atomic absorption analysis was 7.9%, which was close to 8.0% which is the theoretical concentration of TTA · 1 / 2Na.

  The obtained powdery substance was dissolved in water and then acidified with hydrochloric acid, and then the TTA crystals produced were analyzed by gas chromatography. As a result, 5-methylbenzotriazole: 93.3% and 4-methylbenzotriazole were analyzed. : 6.7% mixture.

Example 2
In a 2 L beaker, BTA: 140 g (1.18 mol), sodium hydroxide: 23.5 g (1.59 mol) and deionized water: 835 g were added and heated at 50 ° C. to completely dissolve. Then, 75 g of a powdery material was obtained by spray drying. The resulting powdery product had a neutralization value of 218 KOH mg / g, which was close to the theoretical neutralization value of BTA · 1 / 2Na of 216 KOH mg / g. The endothermic peak temperature of the powdery product by differential thermal analysis was 218 ° C. The sodium content of the powdery substance by atomic absorption analysis was 8.8%, which was close to the theoretical concentration of BTA · 1 / 2Ca of 8.9%.

Example 3
In a 1 L beaker, 106.4 g (0.8 mol) of TTA, which is a mixture of 65% of 5-methylbenzotriazole: 35% and 4-methylbenzotriazole: 35%, and 29.6 g (0.4 mol) of calcium hydroxide. Mol) and deionized water: 790 g, dissolved by heating at 60 ° C., cooled to 25 ° C., and the precipitated crystals are separated into solid and liquid by centrifugation. The solid was dried with hot air at 70 to 80 ° C. or dried under reduced pressure at 40 to 60 ° C. and then pulverized to obtain 47 g of a powder.

  The obtained powdery product had a neutralization value of 180 KOH mg / g, which was close to the theoretical neutralization value of TTA · 1 / 2Ca of 184 KOH mg / g. Also, an endothermic peak of melting point by differential thermal analysis of the powder was not observed below 300 ° C. The calcium content of the powdery substance by atomic absorption analysis was 13.0%, which was close to 13.1%, which is the theoretical concentration of TTA · 1 / 2Ca.

  The obtained powdery substance was dissolved in water and then acidified with hydrochloric acid, and then the TTA crystals produced were analyzed by gas chromatography. As a result, 5-methylbenzotriazole: 90.1% and 4-methylbenzotriazole were analyzed. : 9.9% mixture.

Example 4
In a 2 L beaker, BTA: 119 g (1.0 mol), calcium hydroxide: 37.1 g (0.5 mol), and deionized water: 700 g are added and heated at 60 ° C. for complete dissolution. After that, 65 g of powder was obtained by spray drying. The obtained powdery product had a neutralization value of 199 KOH mg / g, which was close to the theoretical neutralization value of BTA · 1 / 2Ca, 203 KOH mg / g. According to the differential thermal analysis of the powder, no endothermic peak temperature with a melting point of 300 ° C. or lower was observed. The calcium content of the powdery substance by atomic absorption analysis was 14.1%, which was close to the theoretical concentration of BTA · 1 / 2Ca of 13.9%.

Example 5
1 part of BTA · 1 / 2Na powder obtained in Example 2 above, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and powder low density polyethylene (trade name “MC manufactured by Tosoh Corporation”) Polymer NM15PW ") 19 parts was uniformly mixed, and an antirust film having a thickness of 100 µm was prepared at a melting temperature of 135 ° C using an inflation apparatus. The pH of the 1% aqueous solution of the used rust preventive powder was 8.6.

Example 6
0.2 part of BTA · 1 / 2Na powder obtained in Example 2 above, 0.8 part of TTA · 1 / 2Na powder obtained in Example 1 above, granular low density polyethylene (trade name “manufactured by Tosoh Corporation” 80 parts of Petrocene 180 ") and 19 parts of powdered low-density polyethylene (trade name" MC Polymer NM15PW "manufactured by Tosoh Corporation) are uniformly mixed, and an antirust film having a melting temperature of 135 ° C and a thickness of 100 µm using an inflation device. It was created. The pH of the 1% aqueous solution of the rust preventive powder used was 8.6.

Example 7
0.1 part of BTA · 1 / 2Na powder obtained in Example 2, 0.5 part of TTA · 1 / 2Na powder obtained in Example 1, 1-hydroxyethylidene-1,1-diphosphonic acid, Reactant powder of 0.9 part of dicyclohexylamine, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and 18 parts of powder low density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) .5 parts were mixed uniformly, and an antirust film having a thickness of 100 μm was prepared at a melting temperature of 135 ° C. using an inflation device. The pH of the 1% aqueous solution of the rust inhibitor powder used was 7.5.

Example 8
0.1 part of BTA · 1 / 2Na powder obtained in Example 2, 0.5 part of TTA · 1 / 2Na powder obtained in Example 1, and reactant powder of paranitrobenzoic acid and dicyclohexylamine 9 parts, 80 parts of granular low-density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and 18.5 parts of powder low-density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) are mixed, and inflation is performed. Using the apparatus, a rust-proof film having a melting temperature of 135 ° C. and a thickness of 100 μm was prepared. The pH of the 1% aqueous solution of the rust preventive powder used was 7.8.

Example 9
0.1 part of BTA · 1 / 2Na powder obtained in Example 2, 0.5 part of TTA · 1 / 2Na powder obtained in Example 1, and reactant powder of β-oxynaphthoic acid and dicyclohexylamine 0.9 parts, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and 18.5 parts of powder low density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) Then, an antirust film having a thickness of 100 μm was prepared at a melting temperature of 135 ° C. using an inflation apparatus. The pH of the 1% aqueous solution of the rust preventive powder used was 7.8.

Example 10
0.1 part of BTA · 1 / 2Na powder obtained in Example 2, 0.2 part of TTA · 1 / 2Na powder obtained in Example 1, 1-hydroxyethylidene-1,1-diphosphonic acid 0.2 parts of reactant powder of dicyclohexylamine, 0.2 parts of reactant powder of orthophosphoric acid and ammonia, 0.2 part of silica powder, 0.2 part of sodium tripolyphosphate powder, granular low density polyethylene ( 80 parts of Tosoh's trade name “Petrocene 180”) and 18.9 parts of low-density polyethylene powder (trade name “MC Polymer NM15PW” made by Tosoh) are mixed and melted at 135 ° C. using an inflation device. A rust-proof film having a thickness of 100 μm was prepared. The pH of the 1% aqueous solution of the rust preventive powder used was 7.9.

Example 11
0.1 part of BTA · 1 / 2Na powder obtained in Example 2, 0.4 part of TTA · 1 / 2Na powder obtained in Example 1, 1-hydroxyethylidene-1,1-diphosphonic acid 0.4 parts of reactant powder of dicyclohexylamine, 0.4 part of reactant powder of orthophosphoric acid and ammonia, 0.5 part of silica powder, 0.2 part of calcium monohydrogen phosphate powder, granular low density 80 parts of polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation) and 18 parts of powder low density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) are mixed and melted at 135 ° C. using an inflation device. A rust-proof film having a thickness of 100 μm was prepared. The pH of the 1% aqueous solution of the rust preventive powder used was 8.0.

Example 12
0.2 part of BTA · 1 / 2Na powder obtained in Example 2, 0.2 part of TTA · 1 / 2Na powder obtained in Example 1, and 2-phosphonobutane-1,2,4-tricarboxylic acid And 0.5 parts of a reaction product powder of morpholine, 0.5 parts of calcium monohydrogen phosphate powder, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and low density polyethylene powder (Tosoh) 18.6 parts of trade name “MC polymer NM15PW” manufactured by the company was mixed, and an antirust film having a thickness of 100 μm was prepared at a melting temperature of 135 ° C. using an inflation device. The pH of the 1% aqueous solution of the rust preventive powder used was 7.7.

Example 13
0.2 part of BTA · 1 / 2Na powder obtained in Example 2, 0.2 part of TTA · 1 / 2Na powder obtained in Example 1, 0.5 part of reactant powder of salicylic acid and dicyclohexylamine 0.5 parts of calcium monohydrogen phosphate powder, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and powder low density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) 18.6 parts were mixed, and a rust-proof film having a thickness of 100 μm was prepared at a melting temperature of 135 ° C. using an inflation apparatus. The pH of the 1% aqueous solution of the rust preventive powder used was 7.8.

Example 14
0.1 part of BTA · 1 / 2Na powder obtained in Example 2, 0.5 part of TTA · 1 / 2Na powder obtained in Example 1, and reactant powder of paranitrobenzoic acid and dicyclohexylamine 6 parts, 0.2 parts of 12-hydroxy magnesium stearate powder, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and powder low density polyethylene (trade name “MC of Tosoh Corporation”) 18.6 parts of polymer NM15PW ") was mixed, and an antirust film having a thickness of 100 µm was prepared at a melting temperature of 135 ° C using an inflation apparatus. The pH of the 1% aqueous solution of the rust preventive powder used was 7.8.

Example 15
0.2 part of BTA · 1 / 2Na powder obtained in Example 2, 0.2 part of TTA · 1 / 2Na powder obtained in Example 1, 1 part of sodium sebacate powder, 0. 6 parts, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation) and 18 parts of powder low density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) are mixed, and an inflation device is prepared. An antirust film having a melting temperature of 135 ° C. and a thickness of 100 μm was prepared. The pH of the 1% aqueous solution of the rust preventive powder used was 8.7.

Example 16
0.6 part of TTA · 1 / 2Ca powder obtained in Example 3, 0.3 part of BTA · 1 / 2Ca powder obtained in Example 4, 1-hydroxyethylidene-1,1-diphosphonic acid 0.6 parts of reactant powder of dicyclohexylamine, 0.2 part of sodium salicylate powder, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and powder low density polyethylene (manufactured by Tosoh Corporation) 18.3 parts of a trade name “MC polymer NM15PW”) was mixed, and a rust-proof film having a thickness of 100 μm was prepared at a melting temperature of 135 ° C. using an inflation apparatus. The pH of the 1% aqueous solution of the rust preventive powder used was 8.1.

Comparative Example 1
80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation) and 20 parts of powder low density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) are mixed and melted using an inflation device. A blank film having a thickness of 100 μm was prepared at 135 ° C.

Comparative Example 2
0.2 part of BTA powder used in Example 2, 0.5 part of TTA powder used in Example 1, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and 19.3 parts of powder low-density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) were mixed, and a rust-proof film having a thickness of 100 μm was prepared at a melting temperature of 135 ° C. using an inflation device. The pH of the 1% aqueous solution of the used anticorrosive powder was 5.0.

Comparative Example 3
0.5 parts of BTA powder used in Example 2, 0.5 parts of TTA powder used in Example 1, and reactant powder of 1-hydroxyethylidene-1,1-diphosphonic acid and dicyclohexylamine 5 parts, 0.5 parts of silica powder, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and powder low density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) 18 parts were mixed, and an attempt was made to produce a rust preventive film at a melting temperature of 135 ° C. using an inflation device. However, agglomerates were produced during film production, causing clogging of the internal filter of the inflation device, resulting in breakage of the film and failure to form the film. The pH of the 1% aqueous solution of the used anticorrosive powder was 5.5.

Comparative Example 4
2 parts of dicyclohexylamine benzoate powder, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and 18 parts of powder low density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) And an antirust film having a melting temperature of 135 ° C. and a thickness of 100 μm was prepared using an inflation apparatus. The pH of the 1% aqueous solution of the rust inhibitor powder used was 6.9.

Comparative Example 5
Mix 2 parts of dicyclohexylamine nitrite powder, 80 parts of granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and 18 parts of powder low density polyethylene (trade name “Petrocene NM15PW” manufactured by Tosoh Corporation) Then, an antirust film having a thickness of 100 μm was prepared at a melting temperature of 135 ° C. using an inflation device. The pH of the 1% aqueous solution of the rust preventive powder was 6.8.

Comparative Example 6
Sodium nitrite powder 0.5 part, sodium benzoate powder 1 part, ammonium monohydrogen phosphate powder 0.5 part, granular low density polyethylene (trade name “Petrocene 180” manufactured by Tosoh Corporation), and 18 parts of powder low-density polyethylene (trade name “MC Polymer NM15PW” manufactured by Tosoh Corporation) were mixed, and a rust-proof film having a thickness of 100 μm was prepared at a melting temperature of 135 ° C. using an inflation device. The pH of 1% of the rust preventive powder used was 6.8.

  Table 1 shows the working environment during film production in the above Examples and Comparative Examples and the appearance of the obtained film.

   Moreover, the following rust prevention test was done about each film obtained above, and the result was shown in Table 2.

[Rust prevention test]
Type of test metal plate Steel plate: SPCC-SB (cold rolled steel plate) (60 x 80 x 1.2 mm)
Zinc plate: Old 2 types (60 x 40 x 1.5 mm)
Brass plate: C3713 (free-cutting brass) (60 x 40 x 2 mm)
Copper plate: C1100P (tough pitch copper) (60 x 40 x 1.5 mm)
Aluminum plate: A1050P (60 × 40 × 1.5 mm)
Pretreatment of test metal plate The steel plate was dry-polished with # 240 polishing cloth, degreased with methanol and acetone, washed and dried, and the zinc plate, brass plate, copper plate and aluminum plate were # 320 After polishing in deionized water using water-resistant abrasive paper, degreased with methanol and acetone, washed and dried.

[Rust prevention test method]
Sealing and holding with test film: Bags are made using the anticorrosion films obtained in the above examples and comparative examples. For contact testing, the test metal plate is placed in each bag and the air inside is evacuated. Ventilate and heat-seal and hold the metal specimen in contact with the rust-proof film, and for non-contact testing, insert the test metal plate into the bag made of each rust-proof film. Then, air is blown into the inside and then heat sealed to seal, and the edges other than the edge of the test metal plate are sealed and held in a state where they are not in contact with the rust preventive film.

  Rust prevention test: The above-mentioned hermetically sealed holder is suspended in a moisture tester (49 ± 1 ° C., relative humidity of 95% or more) of “rust prevention oil 5.34 wet test method” specified in JIS K 2246, and each metal Observe the surface condition of the surface of the test plate every day and confirm the number of days until rust and discoloration occur. The test days were censored after 30 days.

  As is clear from Tables 1 and 2, the rust preventive films of Examples 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 cause the problem of environmental pollution at the time of film production. Therefore, a transparent film having no problem in appearance can be produced. The rust preventive film of Example 16 felt a little odor at the time of film preparation as compared with other Examples. This is probably because BTA · 1 / 2Ca and TTA · 1 / 2Ca have weaker bonds than sodium salts, and free BTA and TTA are vaporized at the film formation temperature (135 ° C.). This is consistent with the fact that, in the differential thermal balance measurement of powder, the sodium salt is confirmed to lose weight at 150 ° C. or higher, whereas the calcium salt is confirmed to lose weight at 100 ° C. or higher.

  On the other hand, in Comparative Examples 2, 3, 4 and 5, the odor was generated and the working environment was severely deteriorated, and in Comparative Example 3 in which agglomerates were generated during film production, the film was formed by cutting during inflation molding. could not. In Comparative Examples 2, 4, 5, and 6, bleeding occurred and a transparent film could not be obtained.

  About the rust prevention test result, the rust prevention film of Example 5 has shown the rust prevention ability excellent with respect to all the metal plates compared with the comparative example 1, and the rust prevention film of Example 6 is a comparison. Compared with the rust preventive film of Example 2, the rust preventive effect is clearly superior. Moreover, the improvement of a rust prevention effect is recognized whenever Example 7, 11, 16 and a 2nd, 3rd component are mix | blended.

  In Examples 10, 12, 13, and 15 having a small amount of TTA · 1 / 2Na, the rust prevention effect on the zinc plate is slightly lower than in Examples 6, 7, 8, 9, 11, 14, and 16. In comparison with Comparative Example 4 in which only the organic acid amine salt was blended, an excellent rust prevention effect was obtained. Comparative Examples 5 and 6 using a nitrite-based rust preventive have poor corrosion resistance to zinc plates and brass plates that are zinc alloys and copper plates.

  In the present invention, for example, benzotriazole (melting point: 98 ° C., hereinafter abbreviated as BTA) or tolyltriazole (melting point: 88 ° C., hereinafter abbreviated as TTA), which is a representative example of the triazole compound represented by the formula (1). ) Is obtained as a powdery compound having a metal rust preventive ability with a melting point of 150 ° C. or higher by forming a ½ metal salt in which ½ mol of alkali metal or alkaline earth metal is bonded to 1 mol of By using this as a metal rust preventive component, it can be easily kneaded into a thermoplastic resin such as a polyolefin resin. Moreover, it is possible to easily form a film without deteriorating the working environment due to the release of odor and harmful gas during kneading and without causing aggregation or the like with the amine component. Further, in the film, a metathesis reaction is caused between the amine component and the like, and a further excellent vaporizable rust preventive effect is exhibited. Therefore, by processing this film into a film and sealing metal products and metal parts that are susceptible to corrosion due to corrosion factors such as moisture, halogen ions, and sulfur-containing gases, not only the parts that are in contact with the film but also non-contact Even in this part, the vaporized rust preventive component is adsorbed on the surface of metal products and metal parts to form a rust preventive film, or the rust preventive film blocks corrosion factors and absorbs and immobilizes them. Exhibits rust prevention ability.

Claims (14)

A metal rust preventive compound powder characterized in that 0.5 mol of an alkali metal or alkaline earth metal compound is bonded to 1 mol of a triazole compound represented by the following formula (1).

(Wherein R represents hydrogen or a methyl group)   The triazole compound represented by the formula (1): 1 mol and alkali metal or alkaline earth metal: 0.4 to 0.7 mol are dissolved and reacted in water at a temperature of 50 ° C. or higher, and the concentration is 10 to 40. A method for producing a metal rust preventive compound powder, characterized in that an aqueous solution having a mass% is cooled to 40 ° C. or lower, and the resulting crystals are solid-liquid separated and dried.   The triazole compound represented by the formula (1): 1 mol and alkali metal hydroxide or alkaline earth metal hydroxide: 0.5 mol are dissolved in water, and then spray-dried or freeze-dried. A process for producing a metal rust preventive compound powder characterized by   A metal rust preventive composition comprising the metal rust preventive compound powder according to claim 1.   5. The metal barrier according to claim 4, which contains at least one amine salt powder selected from the group consisting of orthophosphoric acid, organic phosphonic acid, aromatic carboxylic acid and aromatic sulfonic acid amine salt as another component. Rust composition.   The organic phosphonic acid is 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), 2-phosphonobutane-1,2,4. The metal rust preventive composition according to claim 5, which is at least one selected from the group consisting of tricarboxylic acids. The composition for metal rust prevention according to claim 5, wherein the aromatic carboxylic acid and the aromatic sulfonic acid are those represented by the following formulas (2) and / or (3).
In the following formula (2), X represents a carboxyl group or a sulfonic acid group, A ^{1 to} A ⁵ may be the same or different, and any one of a nitro group, an amino group, a hydroxyl group, hydrogen, and an alkyl group Or, it represents a combination of two or more, and in the following formula (3), either Y or Z is a carboxyl group or sulfonic acid group, and among Y and Z, the carboxyl group or sulfonic acid group is substituted. The substituent that is not present and A ^{6 to} A ¹¹ may be the same or different and each represents one or a combination of two or more of a nitro group, an amino group, a hydroxyl group, hydrogen, and an alkyl group.

  The amine salt is at least one selected from the group consisting of dicyclohexylamine, cyclohexylamine, morpholine, diisopropylamine, dibutylamine, propylamine, ethylamine, methylamine, and ammonia. Metal rust preventive composition.   As other components, silicon-containing compounds, phosphoric acid compounds, nitric acid compounds, organic acid compounds, metal compounds, mercaptobenzothiazole, mercaptobenzotriazole, (2-benzothiazolylthio) acetic acid, 3- (2-benzothiazoli The composition for metal rust prevention according to any one of claims 4 to 8, comprising at least one selected from the group consisting of (ruthio) propionic acid, salicylamide, and a hydroxy fatty acid metal salt.   The composition for metal rust prevention according to any one of claims 4 to 9, wherein the pH of the 1 mass% aqueous solution is 4 to 10.   The composition for metal rust prevention according to any one of claims 4 to 10, which is used for rust prevention of a metal material containing steel, copper, zinc, aluminum or silver.   The aromatic carboxylic acid or aromatic sulfonic acid represented by the above formula (2) is at least one selected from the group consisting of benzoic acid, nitrobenzoic acid, aminobenzoic acid, salicylic acid, toluic acid, butylbenzoic acid, and toluenesulfonic acid. It is a seed, The composition for metal rust prevention in any one of Claims 7-11.   The composition for metal rust prevention according to any one of claims 7 to 11, wherein the aromatic carboxylic acid represented by the above formula (3) is at least one selected from the group consisting of hydroxynaphthoic acid.   A film for metal rust prevention, wherein the composition for metal rust prevention according to any one of claims 4 to 13 is mixed with a thermoplastic resin and formed into a film shape.