JP2010144205A - Rust-preventive agent and surface-treated metal material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rust-preventive agent which makes it possible to visually determine whether the agent has been surely applied over the metal surface or not, while having a superior rust-preventing effect. <P>SOLUTION: The rust-preventive agent includes a compound which has a hydrophobic group and a chelate group in its molecular structure, and a coloring matter that is compatible with the hydrophobic group of the compound. It is preferable that the coloring matter to be blended is a dye, an organic pigment having the maximal absorption wavelength (λmax) of a visible region in 500-700 nm, or a carbon black of which the surface has been treated so as to acquire hydrophobicity. It is also preferable that the content of the coloring matter is in a range of 0.0001-10 mass%. It is preferable that the hydrophobic group of the compound is a long-chain alkyl group, a cyclic alkyl group or the like. The chelate group of the compound preferably represents polyphosphate, an aminocarboxylic acid, 1,3-diketone, acetoacetic acid (ester), a hydroxy carboxylic acid or the like. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a rust preventive agent and a surface-treated metal material, and more specifically, a rust preventive agent suitable for application to the metal surface of various metal materials in order to prevent the occurrence of rust, and a surface treatment using the same. It relates to metal materials.

  Conventionally, metal materials have been used in various fields, and metal materials play an important role in industry. However, the metal material has a property of being easily rusted, and it is necessary to perform a rust prevention treatment in order to stably fulfill its role over a long period of time. Therefore, conventionally, various rust prevention methods corresponding to the metal species have been proposed for various metal materials.

  As a rust prevention method for a metal material, for example, a method for plating a metal surface, a method for coating a metal surface, and the like are well known. In these methods, a film is formed on the metal surface and the metal surface is physically covered to prevent the entry of factors causing rust such as water and oxygen, thereby exhibiting a rust prevention effect. However, plating and painting tend to be large scale methods.

  On the other hand, as a relatively simple rust prevention method, a method of applying a rust inhibitor to a metal surface is known. For example, a method of applying various types of petroleum jelly, grease, or the like to a metal surface is known. Patent Document 1 discloses a method of applying a rust-preventing agent to the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet, and a film made of a polymer chelating agent having a specific polyamino compound as an organic polymer resin matrix. A method for forming a metal surface on a metal is disclosed.

JP-A-11-166151

  However, since any rust preventive agent is a colorless material, there has been a problem that it cannot be visually determined whether it has been reliably applied to a metal surface. Even if the rust preventive agent is colored so that it can be visually judged, the compatibility between the rust preventive agent and the coloring component becomes a new problem. When these compatibility is bad, there exists a problem that disorder | damage | failure will arise on a coating surface and the fall of a rust prevention effect will be caused.

  The problem to be solved by the present invention is to provide a rust preventive agent that is excellent in the rust preventive effect and can be visually judged as to whether it has been reliably applied to a metal surface, and a surface-treated metal material using the same. .

  In order to solve the above problems, the rust preventive agent according to the present invention includes a compound having a hydrophobic group and a chelate group in a molecular structure and a dye compatible with the hydrophobic group of the compound. Is.

  In this case, the dye is preferably a dye or an organic pigment having a maximum absorption wavelength (λmax) in the range of 500 to 700 nm in the visible light region, or carbon black whose surface has been treated to be hydrophobic. The dye is preferably a nonionic dye.

  The pigment content is preferably in the range of 0.0001 to 10% by mass.

  In this case, as the hydrophobic group, one or more groups selected from a long-chain alkyl group and a cyclic alkyl group can be suitably shown.

  Examples of the chelate group include polyphosphate, aminocarboxylic acid, 1,3-diketone, acetoacetic acid (ester), hydroxycarboxylic acid, polyamine, amino alcohol, aromatic heterocyclic base, phenols, and oximes. Preferably derived from one, two or more chelating ligands selected from Schiff bases, tetrapyrroles, sulfur compounds, synthetic macrocycles, phosphonic acids, and hydroxyethylidenephosphonic acids it can.

  At this time, the hydrophobic group and the chelate group are preferably bonded via one or more bonds selected from an ester bond, an ether bond, a thioester bond, a thioether bond, and an amide bond.

  And the said rust preventive agent is suitable for the rust preventive agent for metal surface application | coating.

  On the other hand, the gist of the surface-treated metal material according to the present invention is that the rust preventive agent is applied to the surface of the metal material.

  In this case, as the metal material, a material made of one or two or more metals selected from aluminum, iron, copper, an aluminum alloy, an iron alloy, and a copper alloy can be suitably shown.

  The rust preventive agent according to the present invention contains a compound having a hydrophobic group and a chelate group in the molecular structure and a dye compatible with the hydrophobic group of the compound. Since the chelate group in the compound can bind to the metal surface, the rust inhibitor according to the present invention is excellent in adhesion to the metal surface. And since the hydrophobic group connected with this chelate group faces the outside of the metal surface, water repellency can be imparted to the metal surface. This prevents water from entering. Therefore, the rust preventive agent according to the present invention can exhibit an excellent rust preventive effect over a long period of time.

  Furthermore, since the pigment | dye mix | blended with the said compound is compatible with the hydrophobic group of the said compound, the said compound and pigment | dye can be compatible, without inhibiting the binding function to the metal surface of the chelate group of the said compound. Thereby, the fall of the rust prevention effect by mix | blending a pigment | dye can be suppressed. And by mix | blending such a pigment | dye, it can be judged visually whether the rust preventive agent was reliably apply | coated to the metal surface.

  At this time, if the dye is a dye or an organic pigment having a maximum absorption wavelength (λmax) in the range of 500 to 700 nm in the visible light region, or carbon black whose surface has been treated with hydrophobicity, it is more visible. Since the effect is excellent, color recognition is easy even with a small amount. Thereby, since the compounding quantity of a pigment | dye can be suppressed, not only visual confirmation is easy, but the fall of the rust prevention effect estimated that the compounding quantity of a pigment | dye influences can also be suppressed. Therefore, the visual recognition effect is high and the rust prevention effect is also superior.

  And when the said dye is nonionic dye, it is especially easy to be compatible with the hydrophobic group of the said compound. Moreover, when content of the said pigment exists in the said specific range, while having the more excellent antirust effect, it can judge reliably by visual observation.

  At this time, when the hydrophobic group is composed of the various groups, water repellency can be reliably imparted to the metal surface. Further, when the chelate group is composed of the above various groups, it can be surely bonded to the metal surface. In this case, those in which the hydrophobic group and the chelate group are bonded via the various bonds are easy to synthesize and can be widely used.

  On the other hand, according to the surface-treated metal material according to the present invention, since the rust inhibitor is applied to the surface of the metal material, the rust preventive effect can be exhibited stably over a long period of time.

  Next, an embodiment of the present invention will be described in detail. The rust preventive agent according to the present invention contains a compound having a hydrophobic group and a chelate group in the molecular structure as an effective component for rust prevention, and also contains a dye compatible with the hydrophobic group of this compound. The rust preventive agent according to the present invention can be suitably used, for example, as a material applied to the metal surface of a metal material. As the metal material, for example, electric wires, cables, connectors, bodies, etc. in vehicles such as automobiles, high-voltage power cables, electrical / electronic device parts, and the like can be suitably shown. Moreover, as a metal seed | species, aluminum, iron, copper, an aluminum alloy, an iron alloy, a copper alloy etc. can be illustrated, for example.

  In the present invention, a pigment is a substance that gives color to an object by absorption or emission of visible light, and exhibits coloration such that the eyes can feel the color in a normal state. Therefore, color vision identification can be provided.

  In the rust preventive agent according to the present invention, the dye can be satisfactorily compatible with the hydrophobic group of the compound which is an effective component of rust prevention. Specific examples of the dye include dyes having a maximum absorption wavelength (λmax) in the visible light region, organic pigments having a maximum absorption wavelength (λmax) in the visible light region, and carbon whose surface has been treated to be hydrophobic. Black etc. can be mentioned. These may be used alone or in combination of two or more. When two or more types are combined, two or more types of dyes, two or more types of organic pigments, two or more types of carbon blacks can be combined, dye and organic pigment, dye and carbon black, organic pigment And carbon black, or a combination of a dye, an organic pigment, and carbon black.

  In the visible light region, the low wavelength region side usually refers to 360 to 400 nm, and the high wavelength side often refers to 700 to 830 nm. However, in the present invention, in particular, the maximum absorption wavelength (λmax in the visible light region). ) Is preferably in the range of 500 to 700 nm. Below 500 nm, the color tone becomes yellowish. Moreover, in the range exceeding 700 nm, the color tone of green becomes light. Therefore, it becomes difficult to feel the color with the eyes. That is, when the maximum absorption wavelength (λmax) in the visible light region is within the specific range, the color can be further perceived by the eyes. Thereby, the compounding quantity of a pigment | dye can be decreased. If it does so, the fall of the rust prevention effect estimated to originate in the compounding quantity of a pigment | dye can also be suppressed. Therefore, in this case, not only the visual recognition effect is high, but also the rust prevention effect is more excellent.

  Among dyes having a maximum absorption wavelength (λmax) in the visible light region, examples of the dye having a maximum absorption wavelength (λmax) in the visible light region in the range of 500 to 700 nm include, for example, azo dyes and quinone dyes Dyes, diphenylmethane dyes, triphenylmethane dyes, polymethine dyes, spiro compound dyes, fluorene dyes, imidazole dyes, perylene dyes, phenazine dyes, phenothiazine dyes, acridine dyes, acridinone dyes, carbo Examples include styryl dyes, coumarin dyes, diphenylamine dyes, quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperinone dyes, and phthalocyanine dyes. Of these, nonionic (nonionic) dyes are preferred from the standpoint of superior compatibility with a compound that is an effective component of rust prevention.

  As an organic pigment, as long as it has a maximum absorption wavelength (λmax) in the visible light region, the compound itself may be an insoluble insoluble pigment, or a lake pigment in which a dye is insolubilized. . Among these, organic pigments having a maximum absorption wavelength (λmax) in the visible light range of 500 to 700 nm include azo pigments, nitro dyes, indanthrene pigments, thioindigo pigments, perinone pigments, and perylenes. Illustrative examples include pigments, dioxazine pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and quinophthalone pigments.

  The carbon black is surface-treated to be hydrophobic so as to be compatible with the hydrophobic group of the compound that is an effective component of rust prevention. Carbon black is generally classified as an inorganic pigment, but is composed of carbon atoms. Therefore, carbon black alone is considered to have higher compatibility with the hydrophobic group of the compound that is an effective component of rust prevention than other inorganic pigments. And since this is surface-treated to hydrophobicity, it is further excellent in the compatibility with the hydrophobic group of the compound used as an active ingredient of rust prevention. Examples of such a resin include resin dispersion grade carbon black “# 1000” manufactured by Mitsubishi Chemical Corporation.

  The content of the dye is preferably in the range of 0.0001 to 10% by mass, more preferably in the range of 0.001 to 5% by mass. When the pigment content is less than 0.0001% by mass, visual confirmation is difficult. On the other hand, when the pigment content exceeds 5% by mass, the rust-preventing effect tends to decrease, but when the pigment content is 10% by mass or less, the rust-preventing effect is high. Furthermore, when the pigment content is 5% by mass or less, the antirust effect is particularly excellent. The reason why the antirust effect tends to decrease depending on the amount of the pigment is not clarified in detail, but it is not simply because the content of the active component of anticorrosion decreases, but when the amount increases, This is presumably because the dye components tend to aggregate and water easily enters through the aggregation interface.

  In the compound which is an effective component of rust prevention of the rust preventive agent according to the present invention, the chelate group is a site that forms a bond with the metal surface to be rust-proofed. When the chelate group is bonded to the metal surface, the rust preventive agent is not easily volatilized or eluted by heat or a solvent. Thereby, it is possible to exhibit the antirust effect stably over a long period of time. It can be confirmed, for example, by multiple total reflection infrared absorption (ATR-IR), microscopic IR, and the like that the chelate group forms a bond with the metal surface and changes to a chelate bond.

  Moreover, in the compound which becomes an active ingredient of rust prevention, the hydrophobic group is arranged so as to protrude outward from the chelate group bonded to the metal surface. The hydrophobic group is provided with water repellency on the chelate group bonded to the metal surface in order to prevent water from entering the metal surface. That is, the rust preventive effect is exhibited not only by physically covering the metal surface but also by preventing water from entering the metal surface by the water repellent effect of the hydrophobic group.

  The hydrophobic group and the chelate group are preferably bonded via a bond such as an ester bond, an ether bond, a thioester bond, a thioether bond, or an amide bond. A structure in which a hydrophobic group and a chelate group are bonded via these bonds can be easily synthesized by a condensation reaction or the like.

  Examples of the hydrophobic group include a long-chain alkyl group and a cyclic alkyl group. These may be contained alone or in combination of two or more. At this time, if a fluorine atom is introduced into the long-chain alkyl group or cyclic alkyl group, the water-repellent effect is more excellent.

  The long chain alkyl group may be linear or branched. Although carbon number of a long-chain alkyl group is not specifically limited, Preferably, it exists in the range of 5-100, More preferably, it exists in the range of 8-50. The cyclic alkyl group may be formed from a single ring or may be formed from a plurality of rings. Although carbon number of a cyclic alkyl group is not specifically limited, Preferably, it exists in the range of 5-100, More preferably, it exists in the range of 8-50. The long chain alkyl group or cyclic alkyl group may contain a carbon-carbon unsaturated bond, an amide bond, an ether bond, an ester bond, or the like.

  The chelate group can be introduced using various chelate ligands. Examples of such a chelate ligand include polyphosphate, aminocarboxylic acid, 1,3-diketone, acetoacetic acid (ester), hydroxycarboxylic acid, polyamine, amino alcohol, aromatic heterocyclic base, phenol And oximes, Schiff bases, tetrapyrroles, sulfur compounds, synthetic macrocycles, phosphonic acids, hydroxyethylidenephosphonic acids, and the like. These compounds have a plurality of unshared electron pairs capable of coordinating bonds. These may be used alone or in combination of two or more.

  More specifically, examples of the polyphosphate include sodium tripolyphosphate and hexametaphosphoric acid. As aminocarboxylic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, ethylenediaminetetraacetic acid, N-hydroxymethylethylenediaminetriacetic acid, N-hydroxyethylethylenediaminetriacetic acid, diaminocyclohexyltetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediaminediacetic acid, hexamethylenediamine N, N, N, N-tetraacetic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, nitrilotri Examples include propionic acid, triethylenetetramine hexaacetic acid, poly (p-vinylbenzyliminodiacetic acid), and the like.

  Examples of the 1,3-diketone include acetylacetone, trifluoroacetylacetone, and tenoyltrifluoroacetone. Examples of acetoacetic acid (ester) include propyl acetoacetate, tert-butyl acetoacetate, isobutyl acetoacetate, hydroxypropyl acetoacetate and the like. Examples of the hydroxycarboxylic acid include N-dihydroxyethyl glycine, ethylene bis (hydroxyphenyl glycine), diaminopropanol tetraacetic acid, tartaric acid, citric acid, gluconic acid and the like. Examples of the polyamine include ethylenediamine, triethylenetetramine, triaminotriethylamine, and polyethyleneimine. Examples of amino alcohols include triethanolamine, N-hydroxyethylethylenediamine, polymetalloylacetone and the like.

  Examples of the aromatic heterocyclic base include dipyridyl, o-phenanthroline, oxine, 8-hydroxyquinoline and the like. Examples of phenols include 5-sulfosalicylic acid, salicylaldehyde, disulfopyrocatechol, chromotropic acid, oxinesulfonic acid, disalicylic aldehyde and the like. Examples of oximes include dimethylglyoxime and salicyladoxime. Examples of the Schiff base include dimethylglyoxime, salicyladoxime, disalicylic aldehyde, and 1,2-propylene dimine.

  Examples of tetrapyrroles include phthalocyanine and tetraphenylporphyrin. Examples of the sulfur compound include toluene dithiol, dimercaptopropanol, thioglycolic acid, potassium ethylxanthate, sodium diethyldithiocarbamate, dithizone, diethyldithiophosphoric acid, and the like. Examples of synthetic macrocyclic compounds include tetraphenylporphyrin and crown ethers. Examples of the phosphonic acid include ethylenediamine N, N-bismethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrismethylenephosphonic acid, and hydroxyethylidene diphosphonic acid.

  A hydroxyl group or an amino group can be appropriately introduced into the chelate ligand. Some of the chelating ligands can exist as salts. In this case, it may be used in the form of a salt. Moreover, you may use the hydrate and solvate of the said chelate ligand or its salt. Further, the chelate ligand includes an optically active compound, but any stereoisomer, a mixture of stereoisomers, a racemate, and the like may be used.

  The long chain alkyl group can be introduced using a long chain alkyl compound. The long-chain alkyl compound is not particularly limited. For example, a long-chain alkyl carboxylic acid, a long-chain alkyl carboxylic acid derivative such as a long-chain alkyl carboxylic acid ester, a long-chain alkyl carboxylic acid amide, a long-chain alkyl alcohol, a long-chain alkyl Examples include alkyl thiols, long chain alkyl aldehydes, long chain alkyl ethers, long chain alkyl amines, long chain alkyl amine derivatives, and long chain alkyl halogens. Of these, long-chain alkyl carboxylic acids, long-chain alkyl carboxylic acid derivatives, long-chain alkyl alcohols, and long-chain alkyl amines are preferred because they can easily introduce chelate groups.

  More specifically, as the long-chain alkyl compound, for example, octanoic acid, nonanoic acid, decanoic acid, hexadecanoic acid, octadecanoic acid, icosanoic acid, docosanoic acid, tetradocosanoic acid, hexadocosanoic acid, octadocosanoic acid, octanol, nonanol, decanol , Dodecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetradocosanol, hexadocosanol, octadocosanol, octylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, dodecylcarboxylic acid chloride, hexa Examples thereof include decyl carboxylic acid chloride and octadecyl carboxylic acid chloride. Among these, in terms of easy availability, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, octadecanoic acid, docosanoic acid, octanol, nonanol, decanol, dodecanol, octadecanol, docosanol, octylamine, nonylamine Decylamine, dodecylamine, octadecylamine, dodecylcarboxylic acid chloride, and octadecylcarboxylic acid chloride are preferred.

  The cyclic alkyl group can be introduced using a cyclic alkyl compound. Although it does not specifically limit as a cyclic alkyl compound, For example, the C3-C8 cycloalkyl compound, the compound which has a steroid skeleton, the compound which has an adamantane skeleton etc. can be illustrated. In this case, these various compounds may be introduced with a carboxylic acid group, a hydroxyl group, an acid amide group, an amino group, a thiol group, or the like from the viewpoint that a bond can be formed with the chelate ligand. preferable.

  More specifically, as the cyclic alkyl compound, cholic acid, deoxycholic acid, adamantane carboxylic acid, adamantane acetic acid, cyclohexyl cyclohexanol, cyclopentadecanol, isoborneol, adamantanol, methyl adamantanol, ethyl adamantanol, cholesterol And cholestanol, cyclooctylamine, cyclododecylamine, adamantanemethylamine, adamantaneethylamine and the like. Of these, adamantanol and cholesterol are preferable in terms of easy availability.

  Since the compound which becomes an active ingredient of rust prevention has the hydrophobic group and the chelate group, it can be obtained, for example, by bringing the compound having the hydrophobic group into contact with the chelate ligand having the chelate group. it can. More specifically, it can be obtained by a condensation reaction of a compound having a hydrophobic group and a chelate ligand having a chelate group. At this time, a solvent may be used or stirring may be performed. Further, for the purpose of increasing the reaction rate, heating may be performed or a catalyst may be added. Furthermore, the target product may be obtained in a high yield by removing the by-products and biasing the equilibrium reaction to the production system. Examples of the compound having a hydrophobic group include the long-chain alkyl compounds and cyclic alkyl compounds described above.

  For example, when the compound having the hydrophobic group has a carboxyl group or a hydroxyl group and the chelate ligand has a hydroxyl group or a carboxyl group, the hydrophobic group and the chelate group are bonded via an ester bond. Can be obtained. In addition, for example, when the compound having the hydrophobic group has a carboxyl group or an amino group and the chelate ligand has an amino group or a carboxyl group, the hydrophobic group and the chelate group are bonded with an amide bond. It is possible to obtain what is connected via

  Although it does not specifically limit as molecular weight of the said compound used as the active ingredient of the rust preventive agent which concerns on this invention, Preferably, it exists in the range of 100-1500, More preferably, it exists in the range of 200-800. It is.

  An example of the above compound that is an active ingredient of the rust inhibitor according to the present invention is represented by the following structural formula.

  In the formula (1), R represents the long-chain alkyl group or the cyclic alkyl group, X represents an ester bond site, an ether bond site, a thioester bond site, or an amide bond site, and Y represents The chelate group is shown. That is, the long chain alkyl group or the cyclic alkyl group and the chelate group are bonded through an ester bond, an ether bond, a thioester bond, or an amide bond.

  It is preferable that the compounding quantity of the compound used as an active ingredient of rust prevention is 0.01 mass% or more. More preferably, it exists in the range of 0.05-99.5 mass%. When the blending amount is less than 0.01% by mass, the rust prevention effect tends to be low.

  The rust preventive agent according to the present invention may contain other components in addition to the compound and pigment that are effective components of rust prevention. Examples of other components include organic solvents, waxes, oils, and the like. Other components may have a rust prevention effect on their own, or may not have a rust prevention effect. Other components also have a function as a diluent. That is, the properties of the rust inhibitor to facilitate application, etc., depending on the properties of the above-mentioned compounds and pigments that are active ingredients of the rust inhibitor according to the present invention (liquid, solid, powder, etc.) It also plays the role of coordinating.

  Examples of the organic solvent as another component include alcohols having 1 to 8 carbon atoms, oxygen-containing solvents such as tetrahydrofuran and acetone, alkanes having 6 to 18 carbon atoms, and the like. Examples of the wax include polyethylene wax, synthetic paraffin, natural paraffin, micro wax, and chlorinated hydrocarbon. Examples of the oil include lubricating oil, hydraulic oil, heat transfer oil, and silicone oil.

  When the rust inhibitor according to the present invention is applied to, for example, a metal surface, a mixture of a compound that becomes an active ingredient and a dye, or a mixture of an active ingredient, a dye, and another component is directly used as a metal. Apply to the surface. In this case, as a coating method, any method such as a coating method, a dipping method, or a spray method can be adopted. In addition, after the coating process, dipping process or spraying process using a squeeze coater or the like, the coating amount can be adjusted, the appearance can be made uniform, and the film thickness can be made uniform by an air knife method or a roll drawing method. In the case of application, in order to improve adhesion and corrosion resistance, treatment such as heating or compression can be performed as necessary.

  Next, the surface-treated metal material according to the present invention will be described. The surface-treated metal material according to the present invention is formed by applying the rust preventive according to the present invention to the surface of the metal material. The metal material is preferably made of a metal such as aluminum, iron, copper, an aluminum alloy, an iron alloy, or a copper alloy. At this time, the metal material surface may be plated with a metal such as zinc or aluminum. As a coating method of the rust preventive agent, any coating method described above may be used.

  As the surface-treated metal material according to the present invention, for example, a metal part such as an electric wire, a cable, a connector, or a body in a vehicle such as an automobile, or a metal part such as a high-voltage power cable or an electric / electronic device part is preferably shown. it can.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

(Test material and manufacturer)
The test materials used in the present examples and comparative examples are shown together with the manufacturer, product name, and the like. Some of them were synthesized in the laboratory. For synthetic products, the synthesis method, structural formula, and identification data are shown below. In addition, those without the manufacturer and trade name are those using reagents.

<Synthesis of compounds that are effective rust prevention ingredients>
Synthesis of Compound A (Compound of Formula (2)) 5 g (28.2 mmol) of hydroxyethyliminodiacetic acid was dissolved in 200 mL of DMF, and 9.0 g (28.4 mmol) of nonadecanoic acid chloride was added while cooling and stirring in a water bath. Add little by little. Thereafter, stirring is continued at room temperature for 12 hours. After completion of the reaction, 200 mL of pure water is added little by little while the reaction solution is cooled and stirred in an ice bath. After returning to normal temperature and stirring for 1 hour, the pH is adjusted to 2.0 with a 1N sodium hydroxide solution, and the mixture is concentrated. 200 mL of pure water is added to the obtained brown oil and washed twice by decantation. The washed product is dissolved in hot methanol, cooled, recrystallized, and collected by filtration to obtain a pale yellow powder. The methanol recrystallization was repeated once more to obtain a pale yellow target product (yield 70%). 1H-NMR (DMSO) σ ppm (TMS): 0.86 (t, 3H), 1.25 (m, 40H), 1.58 (t, 2H), 2.34 (t, 2H), 2.44 (T, 2H), 3.48 (m, 6H), 4.03 (t, 2H). IR (cm ⁻¹ ): 2923 (C—H stretch), 1733 (C═O stretch of ester), 1455 (C—O stretch of carboxylic acid), 1220 (C—O stretch of ester), 1056 (C— N expansion and contraction).

但し、Ｒ２はオクタデシル基である。

However, R2 is an octadecyl group.

Synthesis of Compound B (Compound of Formula (3)) 5 g (31.6 mmol) of tert-butyl acetoacetate and 8.5 g (31.4 mmol) of octadecyl alcohol were dissolved in 50 mL of toluene and heated to 110 ° C. with stirring. The reaction is performed for 2 hours while removing the by-product tert-butanol in the Dean-Stark trap. After completion of the reaction, the mixture is concentrated under reduced pressure to obtain a white wax-like composition. Thereto, 20 mL of cold water was added and solidified, and the product was collected by filtration (yield 75%). 1H-NMR (CDCl ₃ ) σ ppm (TMS): 0.89 (t, 3H), 1.26 (m, 30H), 1.64 (m, 2H), 2.27 (s, 3H); 44 (s, 2H), 4.13 (t, 2H). IR (cm ⁻¹ ): 2924 (C—H stretch), 1745, 1720 (β diketone, enol), 1642 (β diketone, enol), 1420 (C—O stretch of carboxylic acid).

但し、Ｒ３はオクタデシル基である。

However, R3 is an octadecyl group.

Synthesis of Compound C (Compound of Formula (4)) In the same manner as Compound B, except that 12.1 g (31.3 mmol) of cholesterol having the structure shown in the following formula (5) was used instead of octadecyl alcohol. Synthesized. (Yield 48%). 1H-NMR (CDCl ₃ ) σ ppm (TMS): 0.5 to 2.0 (m, 41H), 2.28 (m, 2H), 2.26 (s, 3H), 3.41 (s, 2H) ), 3.52 (m, 1H), 5.35 (m, 1H). IR (cm ⁻¹ ): 2925 (C—H stretching), 1745, 1720 (β diketone, enol), 1642 (β diketone, enol), 1440 (C—O stretching of carboxylic acid).

但し、Ｒ４はコレステリル基である。

However, R4 is a cholesteryl group.

<Dye>
・ Sudan Black B (azo dye)
・ Rhodamine 6G (rhodamine dye)
・ Oil violet (azo dye)
・ Basic violet (triphenylmethane dye)
・ Sudan Blue (polymethine dye)
・ Basic blue (phenoxazine dye)
・ Pigment Violet 19 (quinacridone dye)
・ Phthalocyanine blue (phthalocyanine dye)
Carbon black B (resin dispersion grade, surface-treated product) [Mitsubishi Chemical Corporation, trade name “# 1000”]
・ Carbon black A [Mitsubishi Chemical Corporation, trade name "MCF88"]
・ Zinc yellow (inorganic pigment)
・ Titanium white (inorganic pigment)
・ Vat Yellow 4 (quinone dye) [manufactured by Yick-Vic Chemicals & Pharmaceuticals, trade name “DYE-V0806”]
・ Basic orange 14 (acridine dye)

<Other components (additives)>
・ Oil [made by Idemitsu Kosan Co., Ltd., trade name “Daphne Mechanic Oil 10”]

(Preparation of rust inhibitor)
5g of a compound that becomes an active ingredient for rust prevention is heated to 120 ° C in a test tube and melted, and then added components are added, and each component is mixed by stirring for 3 minutes under a 120 ° C heating condition using a stirrer. did. The composition of each example and each comparative example is as shown in Table 1.

(Application method to metal surface)
Each rust preventive agent prepared by the above method is placed on each aluminum plate (10 × 10 × 0.5 mm) that has been washed with ethanol, 1 mg each, heated to 100 ° C. for 5 minutes, melted and fluidized. It was applied uniformly by raising. Thereafter, heating was removed, and each sample piece was naturally cooled to room temperature.

(Visibility evaluation)
About each sample piece, it was investigated whether the application part of a rust inhibitor could be confirmed visually. Those that were easily confirmed by visual observation were marked with “◯”, those that were visually confirmed but not easy were marked with “Δ”, and those that could not be visually confirmed were marked with “X”. The results of the visibility evaluation are as shown in Table 1.

(Rust prevention test method)
10 uL of neutral 5% saline solution was dropped on the surface of each sample piece coated with a rust inhibitor, and 5% salt solution was spotted on the surface and subjected to a high temperature and high humidity test at 80 ° C. and 95% RH for 100 hours. After the test for a certain period of time, the surface was washed with pure water, the surface state of the salt water spot portion of the sample piece was observed, and the presence or absence of white rust was examined. At this time, a photograph of the surface of the part was taken, and the white rust occurrence area ratio with respect to the entire surface coated with the rust inhibitor was determined. As a result, the case where no white rust was generated was indicated as “◎”, and when white rust was generated but the white rust generation area ratio was less than 5%, “○ +”, the white rust generation area ratio was When it is 5% or more and less than 10%, “◯”, when the white rust generation area rate is 10% or more and less than 25%, “○ −”, when the white rust generation area rate is 25% or more and less than 50% Is “Δ”, and the case where the white rust generation area ratio is 50% or more is “×”. The results of the rust prevention test are as shown in Table 1.

  From the comparative example 1, when the pigment | dye was not mix | blended, it turned out that the application part of a rust preventive agent cannot be confirmed visually. Also, from Comparative Examples 5 to 6, when a dye having a maximum absorption wavelength in the visible light region of less than 500 nm is blended, if the blending amount is relatively small, the application part of the rust inhibitor cannot be confirmed visually. Or it turned out to be very difficult to confirm. Furthermore, from Comparative Examples 2 to 3, it was found that when the blended dye is composed of an inorganic pigment, the rust prevention property is deteriorated. This is presumably due to the fact that the compounded dye is an inorganic pigment, so that the compatibility with the active ingredient has deteriorated. Moreover, since the compounded pigment | dye is an inorganic pigment, it is guessed that it becomes easy to interact with the chelate group of the compound used as an active ingredient, and inhibits the binding function to the metal surface of a chelate group.

  On the other hand, since the thing of an Example mix | blends the pigment | dye excellent in compatibility with the hydrophobic group of an active ingredient, while being able to fully confirm the application part of a rust preventive agent visually, it continues maintaining a rust prevention effect. I was able to confirm. At this time, as can be seen from Examples 13 and 14, an oil component or the like can also be added, and no effect on the visibility and rust prevention properties of the rust inhibitor was observed. Moreover, although carbon black is used in Example 19, since this is surface-treated so that it can be easily dispersed in the resin, the compatibility with the hydrophobic group of the active ingredient is excellent, resulting in rust prevention. It was confirmed that it was excellent.

  And Example 5, 15-18 has shown the Example which changed content (blending amount) of a pigment | dye. From these, it can be seen that when the content of the pigment exceeds 5% by mass, the rust prevention effect tends to decrease. And while maintaining visibility, it turns out that a rust prevention effect is high when content of a pigment | dye is 10 mass% or less, and it is excellent in a rust prevention effect especially when content of a pigment | dye is 5 mass% or less. .

  This is presumably because the content of the pigment was increased, not simply because the content of the active ingredient was decreased. In fact, Examples 13 and 14, which are systems to which oil is added, are superior to Example 18 in terms of rust prevention, although the content of the active ingredient is smaller. And, this is presumed that the dye component tends to aggregate in the composition as the blending amount increases, and water intrusion easily occurs through the aggregation interface, so that the rust prevention effect tends to decrease. Is done.

  Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

Claims (10)

A compound having a hydrophobic group and a chelate group in the molecular structure;
A rust preventive agent comprising a dye compatible with the hydrophobic group of the compound.   The dye is an organic pigment or a dye or an organic pigment having a maximum absorption wavelength (λmax) in the range of 500 to 700 nm in the visible light region, or carbon black whose surface has been treated to be hydrophobic. 1. A rust preventive according to 1.   The rust preventive agent according to claim 2, wherein the dye is a nonionic dye.   The rust preventive agent according to any one of claims 1 to 3, wherein the content of the pigment is in the range of 0.0001 to 10 mass%.   The rust preventive agent according to any one of claims 1 to 4, wherein the hydrophobic group is one or more groups selected from a long-chain alkyl group and a cyclic alkyl group.   The chelate group includes polyphosphate, aminocarboxylic acid, 1,3-diketone, acetoacetic acid (ester), hydroxycarboxylic acid, polyamine, amino alcohol, aromatic heterocyclic base, phenol, oxime, Schiff base It is derived from one or two or more chelating ligands selected from the group consisting of tetrapyrroles, sulfur compounds, synthetic macrocycles, phosphonic acids, and hydroxyethylidenephosphonic acids. The rust preventive according to any one of 1 to 5.   The hydrophobic group and the chelate group are bonded via one or more bonds selected from an ester bond, an ether bond, a thioester bond, a thioether bond, and an amide bond. Item 7. A rust inhibitor according to any one of Items 1 to 6.   The rust preventive agent according to any one of claims 1 to 7, wherein the rust preventive agent is used for coating a metal surface.   A surface-treated metal material obtained by applying the rust preventive agent according to any one of claims 1 to 8 to a surface of a metal material.   The surface-treated metal material according to claim 9, wherein the metal material is made of one or more metals selected from aluminum, iron, copper, an aluminum alloy, an iron alloy, and a copper alloy. .