JP2010229535A - Rust proofing agent and surface treated metallic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rust-proofing agent hardly causes degradation with time and demonstrating rust proofing effect over a long period of time. <P>SOLUTION: The rust-proofing agent contains a compound having a hydrophobic group and a chelate group in a molecular structure as a first component and a compound having a structure equal or similar to the hydrophobic group of the first component as a second component, and further contains wax or ethylenic copolymer compatible with the hydrophobic group in the first component. The hydrophobic group of the first component is preferably a 8-30C linear or cyclic alkyl group and the second component is preferably the compound having a 8-30C alkyl group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a rust inhibitor and a surface-treated metal material, and more particularly, to a rust inhibitor suitable for application to a metal surface such as a conductor or a terminal in an automobile electric wire, and a surface-treated metal material using the same. Is.

  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, all of the conventional rust preventives applied to the metal surface are used to form a continuous film on the metal surface and physically cover the metal surface, thereby exhibiting a rust preventive effect. there were. Therefore, it was easy to flow out from the metal surface. As a result, corrosion locally occurred from a defective portion on the metal surface, and there was a possibility that rust was generated. Further, in the dissimilar metal contact portion, the dissimilar metal contact corrosion is likely to occur, and rust may be generated.

  Further, in the conventional rust preventive agent applied to the metal surface, there has been no improvement in which the deterioration over time is suppressed and the rust preventive effect is maintained over a long period of time.

  The problem to be solved by the present invention is to provide a rust preventive that can hardly deteriorate with time and can exhibit an excellent rust preventive effect over a long period of time, and a surface-treated metal material using the same.

  In order to solve the above problems, a rust inhibitor according to the present invention comprises a first component comprising a compound having a hydrophobic group and a chelate group in the molecular structure, and a compound having the same or similar structure as the hydrophobic group of the first component. The gist is to contain the second component.

  The hydrophobic group of the first component is preferably an alkyl group having 8 to 30 carbon atoms. The alkyl group of the first component may be linear or cyclic. The second component is preferably composed of a compound having the same or similar alkyl group as that of the first component. The second component preferably has a chain or cyclic alkyl group corresponding to the alkyl group of the first component, and the alkyl group of the second component preferably has 8 to 30 carbon atoms.

  The second component is preferably composed of a carboxylic acid or alcohol having the same or similar structure as the hydrophobic group of the first component.

  The rust inhibitor according to the present invention may further contain a third component made of a wax and / or an ethylene copolymer that is compatible with the hydrophobic group of the first component.

  Chelating groups include polyphosphate, aminocarboxylic acid, 1,3-diketone, acetoacetic acid (ester), hydroxycarboxylic acid, polyamine, amino alcohol, aromatic heterocyclic base, phenol, oxime, Schiff base , Tetrapyrroles, sulfur compounds, synthetic macrocycles, phosphonic acids, and those derived from one or more chelating ligands selected from hydroxyethylidenephosphonic acids can be suitably shown.

  The hydrophobic group and the chelate group may be bonded via one or more bonds selected from an ester bond, an ether bond, a thioester bond, a thioether bond, and an amide bond.

  The first component is preferably a neutral compound.

  The rust inhibitor according to the present invention is suitable for a rust inhibitor for metal surface application.

  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.

  As a metal material, what consists of 1 type, or 2 or more types of metals selected from aluminum, iron, copper, tin, gold | metal | money, nickel, chromium, zinc, an aluminum alloy, an iron alloy, and a copper alloy is shown suitably be able to. The metal material may have a surface plated with one or more metals selected from tin, gold, nickel, chromium, zinc, and copper.

  The rust inhibitor according to the present invention includes a first component comprising a compound having a hydrophobic group and a chelate group in the molecular structure, and a second component comprising a compound having the same or similar structure as the hydrophobic group of the first component. In this case, it is possible to exert an excellent rust prevention effect over a long period of time because it is strongly adhered to the metal surface and hardly flows out, and is less likely to deteriorate with time.

  The deterioration of the rust inhibitor over time can be suppressed by the interaction between the first and second components in the rust preventive agent. This is probably because the rust inhibitor is maintained as a dense film.

  In the rust preventive agent according to the present invention, when the hydrophobic group of the first component is a specific alkyl group, high water repellency can be imparted to the metal surface. Due to this high water repellency, the penetration of water into the metal surface coated with a rust inhibitor is further suppressed. Therefore, in combination with the adhesion to the metal surface by the chelate group, an excellent antirust effect can be exhibited over a long period of time.

  In the rust preventive agent according to the present invention, when the second component has a specific alkyl group corresponding to the alkyl group of the first component, the effect of maintaining the rust preventive agent as a dense film on the metal surface is excellent. In addition, when the second component is composed of a carboxylic acid or alcohol having the same or similar structure as the hydrophobic group of the first component, the first component and the second component are particularly likely to interact and prevent rust on the metal surface. The agent is easily maintained as a dense film.

  When the rust preventive agent according to the present invention further contains a third component made of a wax and / or an ethylene copolymer that is compatible with the hydrophobic group of the first component, it is excellent in flexibility. For example, when it is used for a metal part such as a conductor or a terminal of an electric wire mounted on a vehicle, the surface to which the anticorrosive agent is applied is not easily cracked even by vibration or a thermal cycle. Thereby, the long-term excellent rust prevention effect can be maintained in the in-vehicle environment.

  In the rust preventive agent according to the present invention, when the chelate group of the first component is made of a specific chelate group, since the effect of binding to the metal surface is high, the adhesion of the rust preventive agent is excellent. Thereby, the antirust effect excellent in the long term can be maintained. When the hydrophobic group and the chelate group are bonded via a specific bond, there is an advantage that the synthesis is easy and the versatility is excellent.

  In the rust preventive agent according to the present invention, if the first component is a neutral compound, for example, even if the rust preventive agent adheres to a portion other than the target application surface, corrosion or influence on the human body can be suppressed. Excellent safety. In addition, since it is neutral, it is not easily affected by the environment and has excellent storage stability.

  And according to the surface treatment metal material which concerns on this invention, since the said rust preventive agent is apply | coated to the surface of a metal material, it can exhibit a rust prevention effect stably over a long period of time.

  Next, an embodiment of the present invention will be described in detail. The rust inhibitor according to the present invention includes a first component comprising a compound having a hydrophobic group and a chelate group in the molecular structure, and a second component comprising a compound having the same or similar structure as the hydrophobic group of the first component. It contains what contains.

  A 1st component turns into a rust prevention component which exhibits rust prevention ability. In the first component, the chelate group is a site that forms a bond with the metal surface to which the antirust agent is applied. 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.

  In the first component, 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.

  In the first component, examples of the hydrophobic group include an alkyl group. The number of carbon atoms of the alkyl group is preferably 8 or more from the viewpoint of excellent hydrophobicity. Moreover, 30 or less are preferable from viewpoints, such as balance of the affinity with respect to the metal surface which applies a rust preventive agent, and hydrophobicity. More preferably, it is in the range of 12 to 26 from the viewpoint of the balance between the affinity for the metal surface and the hydrophobicity. More preferably, it exists in the range of 16-24.

  In the first component, the alkyl group may be a chain alkyl group or a cyclic alkyl group. The chain alkyl group may be a linear alkyl group or a branched alkyl group. The first component may have either a chain alkyl group or a cyclic alkyl group, or may have both. The alkyl group is more preferably a linear alkyl group from the viewpoint of excellent hydrophobicity. When a fluorine atom is introduced into the alkyl group, the water repellent effect is further improved.

  In the first component, the alkyl group is particularly preferably an octadecyl group or a docosyl group from the viewpoint of the balance between the affinity for the metal surface and the hydrophobicity.

  The alkyl group can be introduced using a chain or cyclic alkyl compound. Examples of the alkyl compound include alkyl carboxylic acids, alkyl carboxylic acid derivatives such as alkyl carboxylic acid esters and alkyl carboxylic acid amides, alkyl alcohols, alkyl thiols, alkyl aldehydes, alkyl ethers, alkyl amines, alkyl amine derivatives, and alkyl halogens. Can be illustrated. Of these, alkyl carboxylic acids, alkyl carboxylic acid derivatives, alkyl alcohols, and alkyl amines are preferred because they can easily introduce chelate groups.

  More specifically, as the 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.

  Examples of the cyclic alkyl compound include a cycloalkyl compound, a compound having a steroid skeleton, a compound having an adamantane skeleton, and the like. At this time, it is preferable that a carboxylic acid group, a hydroxyl group, an acid amide group, an amino group, a thiol group, or the like is introduced into these compounds from the viewpoint that a bond can be formed with a chelate ligand. .

  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.

  In the first component, the chelating group can be introduced using a chelating ligand. Preferred chelate ligands include β-dicarbonyl compounds such as 1,3-diketone (β-diketone) and 3-ketocarboxylic acid ester (acetoacetic acid ester, etc.), polyphosphate, aminocarboxylic acid, hydroxycarboxylic acid, Examples include polyamines, amino alcohols, aromatic heterocyclic bases, phenols, oximes, Schiff bases, tetrapyrroles, sulfur compounds, synthetic macrocycles, phosphonic acids, and hydroxyethylidenephosphonic acids. These may be used alone or in combination of two or more.

  More specifically, examples of the chelate ligand 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 the acetoacetate 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, an amino group, or the like can be appropriately introduced into the chelate ligand. Some 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 a chelate ligand or its salt. Further, the chelate ligand includes those of optically active forms, but any stereoisomer, a mixture of stereoisomers, a racemate and the like may be used.

  As the chelate ligand, more preferably, from the viewpoint of not having an acid structure and a base structure in the molecular structure, being a neutral compound, and having excellent safety and storage stability, 1,3- Β-dicarbonyl compounds such as diketones and 3-ketocarboxylic esters.

  The first component has a chelate group, but may be acidic, alkaline, or neutral. Preferably it is neutral. When the first component is a neutral compound, for example, even if the rust preventive agent adheres to a portion other than the target application surface, corrosion of the attached portion due to the rust preventive agent is unlikely to occur. In addition, even if the rust preventive agent adheres to the human skin or the like, there is little influence on the human body such as rough skin. That is, it is excellent in safety. Furthermore, it is less susceptible to environmental influences than acidic compounds and alkaline compounds. Therefore, it is excellent in storage stability.

  Neutral compounds include compounds that do not have an acid structure or base structure in the molecular structure (in this case, the chelate group does not have an acid structure or base structure), or an acid structure in the molecular structure. And a compound having a basic structure but kept neutral.

  The neutral compound may have a pH in the range of about 6-8. The pH of the compound may be measured using a general pH meter, or may be measured using a pH test paper. The pH measurement conditions can follow normal measurement conditions.

  In the first component, 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.

  The rust preventive agent according to the present invention can be obtained, for example, by bringing a compound having a hydrophobic group into contact with a chelate ligand having a chelate group. 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.

  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 a 1st component, Preferably, it exists in the range of 100-1500, More preferably, it exists in the range of 200-800.

  An example of the first component is represented by the structural formula as follows, for example.

  In the formula (1), R represents the 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 chain alkyl group or the cyclic alkyl group and the chelate group are bonded via an ester bond, an ether bond, a thioester bond, or an amide bond.

  More preferable examples of the first component include, for example, a condensation reaction product of tert-butyl acetoacetate and stearyl alcohol, a condensation reaction product of tert-butyl acetoacetate and docosanol, and tert- Condensation reaction product of butyl acetoacetate and octadecyl alcohol, condensation reaction product of tert-butyl acetoacetate and cholesterol, condensation reaction product of tert-butyl acetoacetate and 1-adamantanol, ethylenediaminetetraacetic acid dianhydride Product of polycondensation with octadecyl alcohol, condensation reaction product of diethylenetriaminepentaacetic dianhydride and docosanol, condensation reaction product of hydroxyethyliminodiacetic acid and stearoyl chloride, N- (2-hydroxyethyl) ethylene Condensation reaction product of diamine triacetic acid and stearoyl chloride, condensation reaction product of diaminopropanol tetraacetic acid and stearoyl chloride, condensation reaction product of 1-hydroxyethane-1,1-bisphosphonic acid and stearoyl chloride, ethylenediamine tetra Examples thereof include a condensation reaction product of acetic dianhydride and cholesterol, a condensation reaction product of diethylenetriaminepentaacetic dianhydride and 1-adamantanol, and the like.

  In the present invention, the second component comprises a compound having the same or similar structure as the hydrophobic group of the first component. When the hydrophobic component of the first component is a chain alkyl group, the second component consists of a compound having a chain alkyl group. When the hydrophobic group of the first component is a cyclic alkyl group, the second component consists of a compound having a cyclic alkyl group. When the hydrophobic component of the first component is a linear alkyl group, the second component is composed of a compound having a linear alkyl group. When the hydrophobic group of the first component is a branched alkyl group, the second component consists of a compound having a branched alkyl group. When the first component hydrophobic group is an alkyl group having 8 to 30 carbon atoms, the second component is made of a compound having an alkyl group having 8 to 30 carbon atoms.

  The rust preventive agent according to the present invention contains a first component and a second component. For example, in the case of the rust preventive agent consisting only of the first component, the sustainability of the rust preventive effect may be inferior compared with the rust preventive agent according to the present invention. The reason is guessed as follows.

  That is, in the case of a rust inhibitor composed of only the first component, when applied to a metal surface, after application, crystallization starts gradually with the passage of time and tends to be coarse crystals. If it does so, a clearance gap will arise in the interface of a crystal | crystallization and a pore will generate | occur | produce on the surface of the film | membrane formed with the rust preventive agent. Since these pores can be a moisture intrusion route, when moisture reaches the metal surface through this intrusion route, corrosion occurs. In the case of the rust preventive agent consisting only of the first component, it is presumed that the deterioration of the rust preventive effect is inferior because the deterioration with time occurs in this way.

  On the other hand, the rust inhibitor according to the present invention is less likely to deteriorate with time as compared with the rust inhibitor composed of only the first component. This is because, as a result of the interaction between the first component and the second component in the rust preventive agent, the entire rust preventive agent becomes amorphous or refined, so that the rust preventive agent is dense on the metal surface. This is presumed to be maintained as a film.

  The second component is preferably composed of a carboxylic acid or alcohol having the same or similar structure as the hydrophobic group of the first component. In this case, in particular, the first component and the second component are likely to interact, and the rust inhibitor is easily maintained as a dense film on the metal surface.

  It is preferable that content of a 2nd component exists in the range of 1-20 mass parts with respect to 100 mass parts of 1st components from a viewpoint of being excellent in rust prevention ability. More preferably, content of a 2nd component exists in the range of 3-10 mass parts. If content of a 2nd component is less than 1 mass part, the effect by which a rust preventive agent is maintained as a precise | minute film | membrane on a metal surface will fall easily. When the content of the second component exceeds 20 parts by mass, the content of the first component is relatively reduced, and thus the rust prevention effect tends to be reduced.

  The rust inhibitor according to the present invention may further contain a third component made of a wax or an ethylene copolymer that is compatible with the hydrophobic group of the first component. The third component may be either one of wax or ethylene copolymer or both. In addition to the above-mentioned components, other components can be added as needed as long as they do not impair excellent rust prevention performance and the effect of maintaining rust prevention over a long period of time. Examples of other components include a tackifier, an antioxidant, a conductivity imparting agent, a dye, and a pigment.

  In the rust preventive agent according to the present invention, the third component is a component that imparts flexibility and thickening to the rust preventive agent. Thereby, the outflow by a heat | fever, the vibration, and the crack by a cooling-heat cycle can be prevented. Furthermore, it can also play a role of adjusting properties for facilitating application. In addition, since it is compatible with the hydrophobic group of the first component, the mixing with the first component is good and the interaction with the chelate group of the first component is suppressed, and the function of the chelate group of the first component It is hard to disturb. The third component itself may have rust prevention ability or may not have rust prevention ability.

  Examples of the wax include polyethylene wax, synthetic paraffin, natural paraffin, micro wax, chlorinated hydrocarbon, and the like. Examples of the ethylene copolymer include an ethylene- (meth) acrylic acid copolymer and an ethylene-α olefin copolymer. These can be used alone or in combination of two or more.

  The content of the third component is preferably in the range of 5 to 70% by mass. When the third component contains both a wax and an ethylene-based copolymer, the combined amount is preferably in the range of 5 to 70% by mass. When the content of the third component is less than 5% by mass, the effect of imparting flexibility and thickening to the rust preventive agent tends to decrease. When the content of the third component exceeds 70% by mass, the rust prevention effect tends to be lowered. The content of the third component is more preferably in the range of 10 to 50% by mass.

  The tackifier is a component that imparts tackiness to the rust inhibitor. The tackifier can improve the adhesion with the metal surface to which the rust preventive agent is applied. It also has the effect of increasing the flexibility of the rust inhibitor. Any tackifier may be used as long as it is used as a compounding agent in order to impart tackiness to a polymer such as rubber or plastic. Specific examples include rosin and rosin derivatives, polyterpene resins, terpene phenol resins, petroleum resins, and the like. These can be used alone or in combination of two or more.

  It is preferable that content of a tackifier exists in the range of 1-20 mass parts with respect to 100 mass parts of components except a tackifier. More preferably, it exists in the range of 5-15 mass parts with respect to 100 mass parts of components except a tackifier. If content of a tackifier is less than 1 mass part, the effect which improves the adhesiveness with a metal surface and the effect which improves the softness | flexibility of a rust preventive agent will become low easily. On the other hand, when the content of the tackifier exceeds 20 parts by mass, the rust prevention effect tends to be lowered.

  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. In particular, metal materials such as electric wires, cables and connectors for automobiles that are easily exposed to high temperatures and used in an in-vehicle environment in which vibration and a thermal cycle occur can be suitably shown. Examples of the metal species include aluminum, iron, copper, tin, gold, nickel, chromium, zinc, aluminum alloy, iron alloy, and copper alloy. These may be used alone or in combination of two or more. Further, the metal material may have a surface plated with tin, gold, nickel, chromium, zinc, copper or the like.

  When the rust preventive according to the present invention is applied to, for example, a metal surface, the above-described mixture of components is directly applied to the metal 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.

  The rust preventive agent according to the present invention preferably has a predetermined viscosity so as not to easily flow out due to heat or the like. For example, as what is applied to a vehicle-mounted member, the melt viscosity at 80 ° C. is preferably 1000 mPa · s or more. In order for the melt viscosity of the rust inhibitor at 80 ° C. to be 1000 mPa · s or more, the content of the third component is preferably in the range of 5 to 70 mass%. Moreover, it is preferable that content of a tackifier exists in the range of 1-20 mass parts.

  The rust preventive according to the present invention has a thickness that can be easily formed by chemical action of a compound having a hydrophobic group and a chelate group in its molecular structure (adhesion by a chelate group, water repellency by a hydrophobic group, etc.) and coating. Due to the physical action of the film, an excellent rust prevention effect can be obtained even in a complicated structure such as a terminal crimping portion of an automobile electric wire.

  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, tin, nickel, gold, chromium, zinc, an aluminum alloy, an iron alloy, or a copper alloy. The metal material may be made of one of the above metals, or may be made of two or more. In addition, the metal material may be one in which the surface of a base material made of the above metal is plated with a metal such as tin, nickel, gold, chromium, zinc, or copper. The plating material may be one of the above metals or two or more. 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. In the connector, for example, a terminal crimping part or the like can be shown. In the terminal crimping portion, the terminal and the electric wire may be the same type of metal or different types of metals.

  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.

(A) Synthesis of First Component St-AA (Compound of Formula (2)) 5 g (31.6 mmol) of tert-butyl acetoacetate and 8.5 g (31.4 mmol) of stearyl alcohol were dissolved in 50 mL of toluene and stirred. While being heated to 110 ° C., the reaction was carried out for 2 hours while removing the by-product tert-butanol in the Dean-Stark trap. After completion of the reaction, the mixture was 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) σppm} (TMS): 0.89 (t, 3H), 1.26 (m, 32H), 1.64 (m, 2H), 2.27 (s, 3H), 3. 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、Ｒ２はオクタデシル基である。

However, R2 is an octadecyl group.

-Synthesis | combination of DOC-AA (Compound of Formula (3)) It replaced with stearyl alcohol and synthesize | combined like said St-AA except having used docosanol 10.3g (31.5mmol). (Yield 78%). _{1H-NMR (CDCl 3) σppm} (TMS): 0.89 (t, 3H), 1.27 (m, 38H), 1.64 (m, 2H), 2.25 (s, 3H), 3. 44 (s, 2H), 4.10 (t, 2H). IR (cm ⁻¹ ): 2922 (C—H stretch), 1745, 1721 (β diketone, enol), 1650 (β diketone, enol), 1425 (C—O stretch of carboxylic acid).

但し、Ｒ３はドコシル基である。

However, R3 is a docosyl group.

(B) Second component stearic acid (reagent)
・ Stearyl alcohol (reagent)
・ Docosanol (reagent)
・ Docosanoic acid (reagent)

(C) Third component / wax [Mitsui Chemicals, trade name “High Wax 2203A”]
・ Ethylene-acrylic acid copolymer (EAA) [manufactured by Aldrich, reagent]

(Preparation of rust inhibitor)
The first component, the second component added as necessary, and the third component were mixed by stirring for 15 minutes using a stirrer under heating at 120 ° C. so that the composition shown in Table 1 was obtained. . Thereby, a rust preventive was prepared. In Table 1, the second component is shown as a ratio (parts by mass) to 100 parts by mass of the first component. Moreover, in Table 1, the 1st component and the 3rd component are shown by the mass%, and it is 100 mass% combining both.

(Coating method of rust inhibitor)
6 mg of each prepared antirust agent was apply | coated to the terminal crimping | compression-bonding part of the aluminum electric wire (0.75mm < ² >) which crimped | bonded the copper terminal which gave tin plating. A lump of rust preventive agent was placed on a terminal crimping part heated to about 110 ° C., melted and applied. Similarly, a rust inhibitor was also applied on the brass plate (10 mm × 10 mm).

(Rust prevention evaluation)
A salt spray test was performed on the portion where the rust preventive agent was applied to the terminal crimping portion, and rust prevention evaluation was performed by increasing resistance before and after the salt spray test. As salt spray test conditions, a 5% sodium chloride aqueous solution was used, and the mixture was allowed to stand for 96 hours in a 35 ° C. atmosphere.

(Surface observation method)
The surface of the brass plate coated with a rust inhibitor was observed using a laser microscope. The observed distribution density of the pores is in the range of 10 mm × 10 mm. Moreover, the pore depth at this time was measured using the surface shape measurement function of the laser microscope.

  All of the reference examples do not contain the second component. On the other hand, all of the examples include a first component and a second component. From the surface observation results in Table 1, it is confirmed that the examples have a small distribution density of pores and a shallow depth of pores, and the rust inhibitor is maintained as a dense film on the metal surface. did it. On the other hand, in the reference example, the distribution density of the pores is larger than that in the example, and the depth of the pores is deeper.

  Moreover, from the rust prevention evaluation of Table 1, it was confirmed that in the examples, the resistance increase was small, the rust prevention performance was excellent, and the deterioration of the rust prevention performance over time was suppressed. In contrast, the resistance increase in the reference example is larger than that in the example.

  Further, in the examples, the content of the second component in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the first component has a particularly small surface distribution density and a shallow pore depth. In addition, the increase in resistance is particularly small. Therefore, the content of the second component within this range is particularly easy to maintain the rust preventive agent as a dense film on the metal surface, and also has excellent rust prevention performance and rust prevention performance over time. It can be said that the decrease is easily suppressed.

  Furthermore, from Examples 23 to 26, the rust preventive agent according to the present invention is maintained as a dense film on the metal surface even when it contains a flexible component, and is excellent in rust preventive performance. In addition, it was confirmed that the deterioration of the rust prevention performance with time was suppressed. And since it contains a flexible component in this way, it is presumed that cracks are unlikely to occur on the surface of the rust preventive agent even when, for example, vibration or a thermal cycle occurs in an on-vehicle environment.

  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 (13)

A first component comprising a compound having a hydrophobic group and a chelate group in the molecular structure;
A rust preventive agent comprising a second component comprising a compound having the same or similar structure as the hydrophobic group of the first component.   The hydrophobic group of the first component is an alkyl group having 8 to 30 carbon atoms, and the second component is composed of a compound having the same or similar alkyl group as the alkyl group of the first component. The rust preventive agent according to claim 1.   The hydrophobic group of the first component is a chain alkyl group having 8 to 30 carbon atoms, and the second component has a chain alkyl group having a carbon number of 8 to 30. It consists of a compound, The rust preventive agent of Claim 1 or 2 characterized by the above-mentioned.   The hydrophobic group of the first component is a cyclic alkyl group having 8 to 30 carbon atoms, and the second component is a compound having a cyclic alkyl group having 8 to 30 carbon atoms. The rust preventive agent according to claim 1 or 2, wherein   The rust preventive agent according to any one of claims 1 to 4, wherein the second component is composed of a carboxylic acid or an alcohol having the same or similar structure as the hydrophobic group of the first component.   The rust preventive according to any one of claims 1 to 5, further comprising a third component made of a wax and / or an ethylene-based copolymer that is compatible with the hydrophobic group of the first component. Agent.   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 6.   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 8. The rust inhibitor according to any one of Items 1 to 7.   The rust inhibitor according to any one of claims 1 to 8, wherein the first component is a neutral compound.   The rust preventive agent according to any one of claims 1 to 9, 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 10 to a surface of a metal material.   The metal material is made of one or more metals selected from aluminum, iron, copper, tin, nickel, gold, chromium, zinc, an aluminum alloy, an iron alloy, and a copper alloy. The surface-treated metal material according to claim 11.   13. The metal material according to claim 11, wherein the surface is plated with one or more metals selected from tin, nickel, gold, chromium, zinc, and copper. The surface-treated metal material according to 1.