JP2006316342A - Metal member, rustproofing agent, and rustproofing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly corrosion-resistant rustproofing-film-coated metal member containing no environmental load substances in conflict with the Law for Promotion of Chemical Management and to provide a rustproofing agent capable of forming the rustproofing film on a metal surface by a one-step treatment. <P>SOLUTION: The metal member is coated with a rustproofing film consisting mainly of an organic compound [component (X)], which dissolves in water in an amount of 1.0 g or more in 100 g of water at 20°C and has a molecular weight of 400 or lower, a silicon oxide atomic group [component (SiO)], and a zirconyl atomic group [component (ZrO)], wherein the relationship ([CSP]+[NOS]):[SZO] is in a range of 97:3 to 10:90, wherein [CSP] is the total mass of the carbonyl groups, sulfinyl groups, or phosphoryl groups of active-hydrogen-containing groups contained in the component (X), [NOS] is the total mass of the N atoms, O atoms, or S atoms as the central atoms of the amino groups, hydroxyl groups, or mercapto groups contained in the component (X), and [SZO] is the total mass of the silicon oxide atomic groups (≡Si-O- and >Si=O) contained in the component (SiO) and the zirconyl atomic group (>Zr=O, ≡Zr-O-, or ZrO<SP>2+</SP>) contained in the component (ZrO). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a metal member having a rust preventive coating formed on at least a part of its surface, a rust preventive agent for forming a rust preventive coating, and a rust preventive treatment method for forming a rust preventive coating.

  In order to improve the corrosion resistance of various metal materials and the adhesion with the top coat film, various film forming treatments are performed on the metal surface. A typical example of a rust preventive film widely used industrially is a chemical conversion treatment film with chromate or phosphate. Among them, the chromate treatment is a passive film containing hexavalent chromium formed on the surface of a metal material. It is a very effective rust preventive film because it exhibits excellent shielding against corrosion factors and self-healing function against film damage. Furthermore, it also functions as a coating ground treatment with excellent adhesion to the top coat film, and is widely used in the fields of home appliances, building materials, automobile parts and the like. When chromate treatment is performed on a steel plate manufacturer's plating line, the processing time required to obtain a coating amount (film thickness) that exhibits sufficient rust prevention is as short as several seconds to several tens of seconds. The ability to perform time processing is also a great advantage.

  However, against the background of increasing interest in global environmental problems in recent years, there is a need for a rust-proof metal material that does not contain hexavalent and trivalent chromium (especially hexavalent chromium with high environmental impact). Development of anti-corrosion technology for hexavalent and trivalent chromium-free metal products that are not used is underway. Among inorganic compounds that do not contain hexavalent or trivalent chromium, some have already been found to form a coating with a certain degree of corrosion inhibiting function on the surface of metal materials. Similar to acid salts, it has been used for rust prevention treatment of metal materials for a long time.

  For example, in phosphate treatment, which is a typical inorganic coating treatment similar to chromate treatment, a chemical conversion treatment film containing zinc phosphate, manganese phosphate, etc. containing no hexavalent or trivalent chromium as the main component is applied to the metal surface. Form. These are widely used for surface treatment and sliding parts of automobile outer panels, home appliance housings, etc., in order to improve corrosion resistance after top coating of metal materials, adhesion of top coat film, lubricity during processing, etc. . However, chemical conversion coatings such as zinc phosphate are crystalline and porous, and therefore have poor barrier properties against corrosion factors, and the rust-preventing power is not as good as that of chromate treatment. In addition, in order to precipitate phosphate crystals uniformly and quickly on the metal surface, the metal surface is preliminarily adjusted with a crystal nucleating agent (for example, titanium colloid), or the component concentration and temperature of the phosphate treatment solution are adjusted. Compared with the chromate treatment, which must be controlled to the optimum state of crystal precipitation, and an amorphous film can be formed by a one-step treatment, the phosphate chemical conversion treatment basically consists of two processes: metal surface conditioning and phosphate film formation. It has the disadvantages of requiring process processing and complicated operation management. Furthermore, in order to improve the film formability, slidability, water resistance secondary adhesion of the top coat, etc., the phosphate chemical conversion treatment solution contains “ In many cases, it contains a Class I designated chemical substance that is subject to the `` Act on Promotion of Improvement '' (hereinafter referred to as the Chemical Substance Management Promotion Law) (e.g., manganese phosphate as a wear-resistant film-forming agent, film crystals Nickel ions and manganese ions as nucleating agents, hydrofluoric acid as metal surface etching agent, etc.). The Class I Designated Chemical Substances subject to the Chemical Substances Management Promotion Act are handled by reporting the amount released to the environment and issuing a product safety data sheet (hereinafter referred to as MSDS (Material Safety Data Sheet)). As an environmentally hazardous substance, it is obligated not only from the viewpoint of environmental protection but also from industrial production and management. As an example of the movement not to use the designated chemical substance in the Chemical Substance Management Promotion Law, a chemical conversion treatment method using a phosphate treatment liquid not containing nickel ions has been disclosed (for example, see Patent Document 1). The configuration described in Patent Document 1 is a complicated two-step process in which a phosphate chemical conversion process is performed after the metal surface adjustment, as in the conventional technique, and is insufficient as an improved technique.

  As an example of other inorganic treatments, treatment agents based on highly oxidizing permanganate significantly reduce the corrosion of metallic materials, but do not reach chromate in terms of stability and efficacy (e.g. Non-Patent Document 1 and Non-Patent Document 2). In addition, vanadate, molybdate, tungstate, etc. are oxo acid compounds similar to chromate and passivate many metal surfaces. It does not reach force. Many of these metal compounds except tungstate are not as good as hexavalent chromium, but also have problems in terms of environmental impact and safety. For example, vanadate is toxic. Permanganate and molybdate, like hexavalent and trivalent chromium compounds, are classified as Class 1 designated chemical substances subject to the Chemical Substance Management Promotion Act, and are industrially manufactured and managed as environmentally hazardous substances. There are big restrictions from the aspect.

  As another example of the inorganic rust prevention treatment for coating a metal material, hexavalent and trivalent chromium-free rust prevention treatment technology using an aqueous treatment agent mainly composed of silica colloid is disclosed (for example, patent document) 2), in the configuration of Patent Document 2, in order to develop a rust preventive power comparable to the chromate treatment on the formed film, the treatment liquid of the cobalt compound, which is a first-class designated chemical substance of the chemical substance management promotion method, is used. As a treatment agent containing environmentally hazardous substances, it is subject to significant restrictions from the industrial production and management aspects. On the other hand, as an example of an inorganic rust prevention treatment having almost no harmful effect, an inorganic polymer film such as polyphosphate or polysilicate that forms a stable protective film on a metal surface is used (for example, , Non-Patent Document 2 and Non-Patent Document 3), the present situation is that it does not reach the rust prevention ability of the chromate-treated film.

  The characteristics of various inorganic treatment technologies that have been implemented or proposed so far have been described. However, this is an inorganic metal surface treatment technology that does not contain the specified chemical substances in the Chemical Substance Management Promotion Law, and has excellent chromate treatment. There were no rust-proofing power and operability (easiness to form a rust-proof film in one process).

  On the other hand, the development of technology for carrying out hexavalent and trivalent chromium-free rust prevention treatment of metal materials using organic resins is also widely promoted. For example, in addition to a water-dispersible or water-soluble resin, a metal surface treatment agent containing silica particles, phosphonic acid derivatives and the like, a zinc-based plated steel sheet coated with the treatment agent (for example, see Patent Document 3), polyhydroxy ether Water dispersible resin having a segment consisting of a segment and a polymer of an unsaturated monomer mixture, phosphoric acid, a metal surface treatment agent containing a phosphoric acid metal compound, a cold-rolled steel sheet coated with the treatment agent, a plated steel sheet (for example, Patent Document 4), zinc-based plated steel sheet coated with a surface treatment agent containing a water-dispersible or water-soluble resin and a polymer chelating agent, aluminum-based plated steel sheet (see, for example, Patent Document 5), aqueous resin, sulfide Surface treatment agents (for example, see Patent Document 6) of uncoated steel and zinc-based coated steel containing ions, or further sparingly soluble sulfides and phosphate ions, are disclosed. Rust prevention treatment (or rust prevention treatment steel sheet described in Patent Literatures 3 to 6) using the treatment liquids described in Patent Literatures 3 to 6 is excellent in rust prevention (or corrosion resistance), and thus chromate treatment (or (Chromate-treated steel sheet) can be substituted, and the water-based organic resin that is the main component of the treatment agent does not contain the target compound of the chemical substance management promotion method, does not use an organic solvent when applying the treatment liquid, hexavalent And it is useful for environmental conservation because it is trivalent chromium free. However, since aqueous organic resins are time-consuming to synthesize, they are more expensive than many organic and inorganic low-molecular compounds, and a rust-proof film composed mainly of organic resins is sufficient on the metal surface. In order to express the rust prevention property, a film thickness several times to 10 times or more that of an inorganic rust prevention film is generally required, and there is a drawback that the film cost is increased.

Japanese Patent Laid-Open No. 2001-49451 JP 2000-328271 A Japanese Patent Laid-Open No. 11-36079 Japanese Patent Laid-Open No. 11-50010 JP 2000-519 JP-A-8-67834 Maeda Shigeyoshi, Surface, 21, 37 (6), 1999 Corrosion and Corrosion Protection Association, "Metal Corrosion Protection Technology Handbook (4th edition)", p.551, published by Nikkan Kogyo Shimbun, 1977 Corrosion and Corrosion Protection Association, "Corrosion Protection Technology Handbook (First Edition)", p.652, published by Nikkan Kogyo Shimbun, 1986

  As described above, there are problems in the prior art. In other words, the coating treatment technology for inorganic coatings involves complicated coating formation processes, containing chemical substances that violate chemical management promotion methods, lack of rust prevention, etc. In the processing technology, there is a problem that a huge film cost is required. An object of the present invention is to solve the above problems, and a low environmental impact rust preventive film that does not contain a designated chemical substance in the Chemical Substance Management Promotion Law can be easily formed in a single process. Another object is to provide a metal member, a rust preventive agent for forming the rust preventive film, and a rust preventive treatment method for forming the rust preventive film.

  As a result of various studies to solve the above problems, the present inventors have solved all of the above problems by a metal member coated with a specific rust preventive film that does not contain a designated chemical substance in the Chemical Substance Management Promotion Law. It was found that this rust preventive film can be easily formed by one-step treatment and exhibits sufficient corrosion resistance.

  The present invention has been completed based on such knowledge, and the gist thereof is as follows.

(1) A metal member in which at least a part of the surface is coated with a rust preventive film,
The rust-preventing film is composed of any one or more of the following (X) components, any one or more of the (SiO) and (ZrO) components, The total mass [CSP] of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the component (X), and the above (X ) The mass of the nitrogen atom (N), oxygen atom (O) or sulfur atom (S) that is the central atom of the amino group (—NH ₂ ), hydroxyl group (—OH) or mercapto group (—SH) contained in the component [NOS], silicon oxide atomic group (≡Si—O—, any one or two of> Si = O) contained in the (SiO) component, and zirconyl atom contained in the (ZrO) component Dan relationship between the total mass of the (> Zr = O, ≡Zr- O- or zirconyl ions (either one or two or more of ^{ZrO 2+)) [SZO],} ([CSP] + [NOS] ): [SZO] = 97: 3 to 10:90.

Component (X): an organic compound having a molecular weight of 400 or less and dissolved in 100 g of water at 20 ° C., having 2 or more active hydrogen-containing groups in one molecule, and 2 groups of the active hydrogen-containing groups The above is a functional group containing a carbonyl group (> C = O), a functional group containing a sulfinyl group (> S = O), a functional group containing a phosphoryl group (≡P = O), an amino group (-NH ₂ ), An organic compound that is one or more of a hydroxyl group (—OH) or a mercapto group (—SH), or a part or all of the active hydrogen is eliminated from the active hydrogen-containing group of the organic compound One or both of the atomic groups.
(SiO) component: silicon oxide atomic group (≡Si-O-,> Si = O, either one or two).
(ZrO) component: Zirconyl atomic group (> Zr = O, ≡Zr-O- or one or more of zirconyl ions (ZrO ²⁺ )).

(2) The functional group containing the carbonyl group (> C = O) is one or more of a carboxyl group (-COOH), an aldehyde group (-CHO), an amide group (-CONH ₂ ) A metal member according to (1).

(3) The functional group containing the sulfinyl group (> S═O) is one or two of a sulfonic acid group (—SO ₃ H) and a sulfinic acid group (—SO ₂ H) (1) Metal parts.

(4) The functional group containing the phosphoryl group (≡P = O) is a phosphate ester of the structural formula O = POH (OR) ₂ or O = P (OH) ₂ (OR) (R is a hydrocarbon group) The metal member according to (1), which is one or two of the polar atomic groups O = P (OH) <or O = P (OH) ₂ -constituting N.

(5) The metal member according to (1), wherein the component (X) is one or more of the following components (a), (b), and (c).

  Component (a): Aliphatic or aromatic carboxylic acid having a molecular weight of 400 or less and having two or more carboxyl groups (-COOH) in one molecule, dissolved in 100 g of water at 20 ° C. A residue of carboxylic acid from which some or all of hydrogen has been eliminated from the carboxyl group of the acid.

  Component (b): Aliphatic or dissolved in 1.0 g or more in 100 g of water at 20 ° C., having a molecular weight of 400 or less, and the total number of carboxyl groups (—COOH) and hydroxyl groups (—OH) in one molecule is 2 or more An aromatic hydroxy acid, or a hydroxy acid residue in which part or all of hydrogen has been eliminated from the carboxyl group or hydroxyl group of the hydroxy acid.

  Component (c): An aliphatic compound having 1.0 g or more dissolved in 100 g of water at 20 ° C. and having a molecular weight of 400 or less, and the total number of carboxyl groups (—COOH) and aldehyde groups (—CHO) in one molecule is 2 or more Aromatic aldehyde acid, or part or all of hydrogen desorbed from the carboxyl group of the aldehyde acid, or one from the aldehyde group of the aldehyde acid, regardless of the presence or absence of hydrogen desorption from the carboxyl group. Aldehydic acid residue from which part or all of hydrogen or oxygen has been eliminated.

(6) A metal member in which at least a part of the surface is coated with a rust preventive film,
The rust-preventing film is shown in the following, (A) component, (B) component, any one or more of (C) component, any one of (SiO) component and (ZrO) component or 2 or more types as main components, the total (CO) of the mass of the carbonyl atom group (> C = O) contained in the component (A), the component (B), the component (C), and the (SiO) Silicon oxide atomic group (≡Si-O-,> Si = O, one or two) included in the component and zirconyl atomic group (> Zr = O, ≡Zr-O) included in the (ZrO) component -The mass ratio of the mass of any one or more of zirconyl ions (ZrO ²⁺ ) to [SZO] is [CO]: [SZO] = 97: 3 to 10:90 A metal member characterized by.

  Component (A): an aliphatic carboxylic acid having 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH), and 0 to 6 carbon atoms excluding the carboxyl carbon, or the fat A residue of a carboxylic acid from which some or all of the hydrogen has been eliminated from the carboxyl group of the group carboxylic acid.

  Component (B): an aliphatic having 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH) and hydroxyl groups (-OH), and 0 to 6 carbon atoms excluding the carboxyl carbon Hydroxy acid or a residue of hydroxy acid from which part or all of hydrogen has been eliminated from the carboxyl group or hydroxyl group of the hydroxy acid.

Component (C): The total number of carbon atoms is 2 to 10, the total number of carboxyl groups (-COOH) and aldehyde groups (-CHO) is 2 to 8, and the number of carbon atoms excluding carboxyl and aldehyde carbons is 0 to 6. Some aliphatic aldehyde acids, or some or all of hydrogen desorbed from the carboxyl groups of the aldehyde acids, or from the aldehyde groups of the aldehyde acids regardless of the presence or absence of hydrogen desorption from the carboxyl groups Residues of aldehyde acids from which some or all of hydrogen or oxygen has been eliminated.
(SiO) component: silicon oxide atomic group (≡Si-O-,> Si = O, either one or two).
(ZrO) component: Zirconyl atomic group (> Zr = O, ≡Zr-O- or one or more of zirconyl ions (ZrO ²⁺ )).

(7) The aliphatic carboxylic acid is a saturated aliphatic dicarboxylic acid having 0 to 5 carbon atoms excluding the carboxyl carbon (the structural formula is HOOC- (CH ₂ ) _(a1) -COOH. (A1) is an integer of 0 ≦ (a1) ≦ 5 — (CH ₂ ) _{(a1) —The} chain portion may contain an aliphatic group other than the methylene group —CH ₂ — or an aliphatic group substituted with a part of hydrogen of the methylene group. Or an unsaturated aliphatic dicarboxylic acid having 2 to 5 carbon atoms excluding the carboxyl carbon (the structural formula is HOOC- (CH ₂ ) _(b1) -CH = CH- (CH ₂ ) _(b2) - COOH, where (b1) and (b2) are integers greater than or equal to 0, 0 ≤ (b1) + (b2) ≤ 3.-(CH ₂ ) _(b1) -chain,-(CH ₂ ) _(b2) -chain moiety May include an aliphatic group other than the methylene group —CH ₂ — or an aliphatic group substituted with a part of the hydrogen of the methylene group.) (5) Or the metal member as described in (6).

(8) wherein the aliphatic carboxylic acid is oxalic acid (HOOC-COOH), malonic acid (HOOC-CH ₂ -COOH), succinic acid (HOOC- (CH _{2) 2} -COOH), glutaric acid (HOOC- (CH ₂ ) ₃ -COOH), adipic acid (HOOC- (CH ₂ ) ₄ -COOH), α-ketoglutaric acid (HOOC-CH ₂ -CH ₂ CO-COOH), maleic acid (cis-HOOC-CH = CH-COOH) The metal member according to (5), (6), or (7), which is any one kind or two or more kinds.

(9) The aliphatic hydroxy acid is an aliphatic hydroxy acid having 1 to 4 carbon atoms excluding the carboxyl carbon (the structural formula is CH _(c1) (-COOH) _(c2) (-OH) _(c3) -[ CH _(d1) (-COOH) _(d2) (-OH) _(d3) ] _(p1) -[CH _(e1) (-COOH) _(e2) (-OH) _(e3) ] _(p2) -[CH _{( f1)} (-COOH) _(f2) (-OH) _(f3) ] _(p3) (p1), (p2), (p3) is 0 or 1. (c1)-(c3), (d1)-( d3), (e1) to (e3), and (f1) to (f3) are all integers of 0 or more, and (c1) + (c2) + (c3) = 3, (d1) + (d2) + ( d3) = 2, (e1) + (e2) + (e3) = 2, (f1) + (f2) + (f3) = 3 Total number of carboxyl groups in the molecule (c2) + (d2) + (e2 ) + (f2) ≧ 1, the total number of hydroxyl groups in the molecule (c3) + (d3) + (e3) + (f3) ≧ 1) is one or more types (5) or (6 Metal member as described in).

(10) The aliphatic hydroxy acid is glycolic acid (CH ₂ (OH) -COOH), lactic acid (CH ₃ CH (OH) -COOH), glyceric acid (CH ₂ (OH) -CH (OH) -COOH) Citric acid (HOOC-CH ₂ -C (OH) (COOH) -CH ₂ -COOH), tartaric acid (HOOC-CH (OH) -CH (OH) -COOH), or malic acid (HOOC-CH (OH The metal member according to (5), (6) or (9), which is any one or more of () -CH ₂ -COOH).

(11) The aliphatic aldehyde acid is an aliphatic aldehyde acid having a carbon number of 0 to 4 excluding carboxyl carbon and aldehyde carbon (the structural formula is CHO-COOH or CH _(g1) (-COOH) _(g2) (-CHO) _(g3) -[CH _(h1) (-COOH) _(h2) (-CHO) _(h3) ] _(q1) -[CH _(i1) (-COOH) _(i2) (-CHO) _{(i3 )} ] _(q2) -[CH _(j1) (-COOH) _(j2) (-CHO) _(j3) ] _(q3) ((q1), (q2), (q3) is 0 or 1. (g1) to (g3), (h1) to (h3), (i1) to (i3), (j1) to (j3) are all integers of 0 or more, and (g1) + (g2) + (g3) = 3, (h1) + (h2) + (h3) = 2, (i1) + (i2) + (i3) = 2, (j1) + (j2) + (j3) = 3 The total number of carboxyl groups in the molecule ( g2) + (h2) + (i2) + (j2) ≥ 1, the total number of aldehyde groups in the molecule (g3) + (h3) + (i3) + (j3) ≥ 1) The metal member according to (5) or (6) above.

(12) The metal member according to (5), (6) or (11), wherein the aliphatic aldehyde acid is glyoxylic acid (CHO-COOH).

(13) metal member according to any of the attached amount of the rust preventing film is ^{0.02g / m 2 ~5.0g / m 2} (1) ~ (12).

(14) One or more of the following (X ^* ) components, one or more of the (SiO ^* ) and (ZrO ^* ) components, and water as the main constituent The total mass [CSP ^* ] of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the component (X ^* ) A nitrogen atom (N), an oxygen atom (O) or a sulfur atom which is the central atom of the amino group (-NH ₂ ), hydroxyl group (-OH) or mercapto group (-SH) contained in the component (X ^* ) The total mass of (S) [NOS ^* ], the silicon oxide atomic group (≡Si-O-) contained in the (SiO ^* ) component and the zirconyl atomic group (> Zr =) contained in the (ZrO ^* ) component The relationship between the total mass [SZO ^* ] of O, ≡Zr-O- or zirconyl ion (one or more of ZrO2 ⁺ ) ([CSP ^* ] + [NOS ^* ]): [SZO ^* ] = 97: 3 to 10:90 A rust inhibitor.

(X ^* ) component: an organic compound having a molecular weight of 400 or less and dissolved in 100 g of water at 20 ° C. and having 2 or more active hydrogen-containing groups in one molecule, 2 of the active hydrogen-containing groups A functional group containing a carbonyl group (> C = O), a functional group containing a sulfinyl group (> S = O), a functional group containing a phosphoryl group (≡P = O), an amino group (-NH ₂ ) An organic compound that is one or more of hydroxyl group (—OH) or mercapto group (—SH), or a part or all of the active hydrogen-containing groups of the organic compound One or both of the salts substituted with a cation.

(SiO ^* ) component: Reactable with a hydrolyzable alkoxy group (-OR ³ , R ³ is a hydrocarbon group having up to 3 carbon atoms) and an active hydrogen-containing group contained in the (X ^* ) component Silane coupling agent with organic functional group.
(ZrO ^* ) component: Zirconyl ion (ZrO ²⁺ ) and acid group salt.

(15) The rust preventive according to (14), wherein the (X ^* ) component is any one or more of the following components: (a ^* ) component, (b ^* ) component, (c ^* ) component Processing agent.

(a ^* ) component: An aliphatic or aromatic carboxylic acid or a fatty acid dissolved in 100 g of water at 20 ° C. in an amount of 1.0 g or more, having a molecular weight of 400 or less, and having two or more carboxyl groups (—COOH) in one molecule Or aromatic carboxylates.

Component (b ^* ): Aliphatic, dissolved in 100 g of water at 20 ° C, 1.0 g or more, molecular weight 400 or less, and the total number of carboxyl groups (-COOH) and hydroxyl groups (-OH) in one molecule is 2 or more Or an aromatic hydroxy acid or an aliphatic or aromatic hydroxy acid salt.

Component (c ^* ): Aliphatic, dissolved in 100 g of water at 20 ° C. in an amount of 1.0 g or more, having a molecular weight of 400 or less, and the total number of carboxyl groups (—COOH) and aldehyde groups (—CHO) in one molecule is 2 or more Or an aromatic aldehyde acid, or an aliphatic or aromatic aldehyde salt.

(16) One or more of (A ^* ) component, (B ^* ) component, (C ^* ) component, and (SiO ^* ) component and (ZrO ^* ) component shown below The total of the mass of the carbonyl atom group (> C = O) contained in the (A ^* ) component, the (B ^* ) component, and the (C ^* ) component, wherein the main component is water or two or more species ^* ], A silicon oxide atomic group (≡Si-O-) contained in the (SiO ^* ) component and a zirconyl atomic group (> Zr = O, ≡Zr-O-, zirconyl) contained in the (ZrO ^* ) component The mass ratio of the total mass of ions (any one or more of ZrO ²⁺ ) to [SZO ^* ] is [CO ^* ]: [SZO ^* ] = 97: 3 to 10:90 Anti-rust treatment agent characterized by

Component (A ^* ): aliphatic carboxylic acid or aliphatic carboxylic acid having 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH), and 0 to 6 carbon atoms excluding carboxyl carbon Acid salt.

Component (B ^* ): Fat with 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH) and hydroxyl groups (-OH), and 0 to 6 carbon atoms excluding carboxyl carbon Group hydroxy acid or aliphatic hydroxy acid salt.

Component (C ^* ): 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH) and aldehyde groups (-CHO), 0 to 6 carbon atoms excluding carboxyl and aldehyde carbons An aliphatic aldehyde acid or an aliphatic aldehyde salt.

(SiO ^* ) component: a hydrolyzable alkoxy group (-OR ³ , R ³ is a hydrocarbon group having up to 3 carbon atoms) and an organic functional group capable of reacting with a carboxyl group, a hydroxyl group or an aldehyde group Has silane coupling agent.
(ZrO ^* ) component: Zirconyl ion (ZrO ²⁺ ) and acid group salt.

(17) The (SiO ^* ) component contains aminoalkylsilane [NH ₂ -R ^* -Si (-OR ³ ) ₃ ] and epoxyalkylsilane [CH _2- (O) -CH-R ^* -Si (-OR ³ ) ₃ ] (R ^* is an organic group having up to 7 carbon atoms, and R ³ is a hydrocarbon group having up to 3 carbon atoms) (14) or (16) The antirust treatment agent as described in 4.

(18) The (SiO ^* ) component contains γ- (2-aminoethyl) aminopropyltrimethoxysilane [NH ₂ (CH ₂ ) ₂ —NH (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ ] and γ— (14), which is any one or more of glycidoxypropyltrimethoxysilane [CH _2- (O) -CH-CH ₂ O- (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ ] The antirust treatment agent according to 16) or (17).

(19) The (ZrO ^* ) component is zirconyl formate (ZrO (HCOO) ₂ ), zirconyl acetate (ZrO (CH ₃ COO) ₂ ), zirconyl propionate (ZrO (C ₂ H ₅ COO) ₂ ), zirconyl butyrate (ZrO (C ₃ H ₇ COO) ₂ ), salt of oxalic acid (HOOC-COOH) and zirconyl ion, salt of malonic acid (HOOC-CH ₂ -COOH) and zirconyl ion, or succinic acid (HOOC- (CH ₂ The antirust treatment agent according to (14) or (16), which is one or more selected from a salt of ₂ ) -COOH) and a zirconyl ion.

(20) A rust prevention treatment method, wherein the rust prevention treatment agent according to any one of (14) to (19) is applied to at least a part of a metal surface and dried to form a rust prevention film.

  Since the metal member according to the present invention does not contain environmentally hazardous substances such as substances designated by the Chemical Substance Management Promotion Law and has excellent corrosion resistance at the chromate treatment material level, it can be used for home appliances, office automation equipment, architecture, civil engineering, or automobiles. It is suitable as a metal member widely used in the field of vehicles and vehicles. Further, by coating the metal surface with the rust preventive agent according to the present invention, a metal member having excellent corrosion resistance at the chromate treatment material level can be provided at a low rust preventive treatment cost.

  Hereinafter, embodiments of the present invention will be described in detail.

  The metal member of the present invention has a rust preventive film that does not contain an environmental load substance on at least a part of its surface. The point of rust prevention film formation for obtaining a metal member that exhibits sufficient corrosion resistance is that these organic compounds dissolve in water, have a molecular weight of 400 or less, and have two or more specific active hydrogen-containing groups. Crosslinking with a specific silane compound or zirconyl compound that easily reacts with an active hydrogen-containing group. In the metal member of the present invention, a rust preventive film is formed by applying a rust preventive agent to the metal surface and drying by heating. At that time, a dense barrier layer is formed on the metal surface by the reaction between the specific organic compound and the specific silane compound or zirconyl compound, thereby suppressing the entry of the aqueous corrosion factor into the metal surface. In addition, these specific organic compounds, silane compounds, and zirconyl compounds not only become constituent compounds of the rust preventive film, but also react with metal corrosion products covering the metal surface or metal surface, and the rust preventive film. It also has the effect of increasing the adhesion between the metal surface and the metal surface. In addition, when overcoating the anticorrosive film, some of the specific organic compounds, silane compounds, and zirconyl compounds interact with the overcoating film, resulting in chemical bonding, hydrogen bonding, adsorption, etc. to the coating film. Also, it has an effect of enhancing the adhesion between the rust-proof coating and the top coat.

In the present invention, the rust-preventing film is composed mainly of any one or more of the (X) components shown below, any one or more of the (SiO) and (ZrO) components. As a component, the total mass [CSP] of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the component (X) and the (X) amino groups present in component (-NH _2), nitrogen atom is the central atom of a hydroxyl group (-OH) or mercapto group (-SH) (N), oxygen atom (O) or sulfur atom ( The total mass [NOS] of S), the silicon oxide atomic group (≡Si-O-,> Si = O, one or two) contained in the (SiO) component, and the (ZrO) component The relationship with the total mass [SZO] of the zirconyl atomic group (> Zr = O, ≡Zr-O- or any one or more of zirconyl ions (ZrO ²⁺ )) contained in ([CSP] + [NOS]): [SZO] = 97: 3 to 10:90. The atomic group here is in accordance with a general definition and is a group of specific atoms contained in a molecule. For example, the silicon oxide atomic group is an atomic group composed of specific atoms of oxygen and silicon, and the zirconyl atomic group is an atomic group composed of zirconium and oxygen.

Here, the component (X) is an organic compound having a molecular weight of 400 or less and dissolved in 100 g of water at 20 ° C. and having 2 or more active hydrogen-containing groups in one molecule, and the active hydrogen Two or more of the containing groups are a functional group containing a carbonyl group (> C = O), a functional group containing a sulfinyl group (> S = O), a functional group containing a phosphoryl group (≡P = O), an amino group ( -NH ₂ ), a hydroxyl group (-OH), or a mercapto group (-SH), one or more organic compounds, or a part or all of the active hydrogen-containing groups of the organic compounds One or both of the atomic groups from which the active hydrogen has been eliminated. The (SiO) component is a silicon oxide atomic group (≡Si-O-, any one or two of Si = O), and the (ZrO) component is a zirconyl atomic group (> Zr = O, ≡Zr—O— or zirconyl ion (ZrO ²⁺ , one or more).

In addition, the rust preventive agent in the present invention is any one or more of the following (X ^* ) components, and one or more of the (SiO ^* ) and (ZrO ^* ) components. The mass of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the component (X ^* ), with water as the main constituent the sum [CSP ^*] of the (X ^*) amino groups present in component (-NH _2), nitrogen atom is the central atom of a hydroxyl group (-OH) or mercapto group (-SH) (N), oxygen Total [NOS ^* ] of mass of atom (O) or sulfur atom (S), silicon oxide atomic group ≡Si-O- contained in the (SiO ^* ) component, and zirconyl atom contained in the (ZrO ^* ) component The relationship between the total mass [SZO ^* ] of the group (> Zr = O, ≡Zr-O- or zirconyl ion (ZrO ²⁺ )) is ((CSP ^* ) + [ NOS ^* ]): [SZO ^* ] = 97: 3 to 10:90.

Here, the component (X ^* ) is an organic compound having a molecular weight of 400 or less and dissolved in 100 g of water at 20 ° C. and having two or more active hydrogen-containing groups in one molecule, Two or more hydrogen-containing groups are a functional group containing a carbonyl group (> C = O), a functional group containing a sulfinyl group (> S = O), a functional group containing a phosphoryl group (≡P = O), an amino group (—NH ₂ ), hydroxyl group (—OH), or mercapto group (—SH), one or more organic compounds, or part or all of the active hydrogen-containing groups of the organic compounds One or both of the salts in which the active hydrogens are replaced with other cations. The (SiO ^* ) component includes a hydrolyzable alkoxy group (-OR ³ , R ³ is a hydrocarbon group having up to 3 carbon atoms), and an active hydrogen-containing group contained in the (X ^* ) component. It is a silane coupling agent having a reactive organic functional group, and the (ZrO ^* ) component is a salt of zirconyl ion (ZrO ²⁺ ) and an acid group.

In the present invention, the organic compound contained in the (X) component or the (X ^* ) component of the rust preventive agent (hereinafter sometimes referred to as the (X + X ^* ) component) constituting the rust preventive film is 20 ° C. It must dissolve at least 1.0 g in 100 g of water and have a molecular weight of 400 or less. The formation of the rust preventive film of the present invention is performed by applying an aqueous rust preventive agent, in which each component constituting the rust preventive agent is uniformly dissolved or finely dispersed in water, to a metal surface and heating and drying. In the case of a poorly soluble organic compound that dissolves less than 1.0 g in 100 g of water at 20 ° C., it cannot be used as a main component constituting the aqueous treatment agent of the present invention because it cannot be dissolved to create an aqueous rust inhibitor. . In addition, when the molecular weight of the organic compound exceeds 400, since the molecule is bulky and the movement in the aqueous rust preventive agent is slow, the organic compound is applied to the metal surface of the aqueous rust preventive agent and heated and dried. Since the cross-linking reaction between the silane compound and the zirconyl compound is slow and a dense barrier layer is not formed on the metal surface, the penetration of the aqueous corrosion factor into the metal surface cannot be suppressed.

In the present invention, the organic compound contained in the (X + X ^* ) component needs to have two or more active hydrogen-containing groups. When there is no active hydrogen-containing group or only one group, since the number of active reaction sites per molecule of these organic compounds is 1 or less, the reaction with the coexisting silane compound or zirconyl compound increases the molecular weight. A crosslinked body cannot be formed, and a dense barrier layer cannot be formed on the metal surface.

In the present invention, the organic compound having two or more active hydrogen-containing groups contained in the component (X + X ^* ) is a functional group in which two or more of these active hydrogen-containing groups contain a carbonyl group (> C═O). , A functional group containing a sulfinyl group (> S = O), a functional group containing a phosphoryl group (≡P = O), an amino group (-NH ₂ ), a hydroxyl group (-OH), or a mercapto group (-SH) Must be one or more of A hydrogen-containing group other than these is a dense barrier layer on the metal surface because the crosslinking treatment with the silane compound or zirconyl compound is slow or does not react at all in the step of applying the aqueous treatment agent to the metal surface and heating and drying. Can not form.

At least a part of the organic compound is applied to a metal surface of an aqueous treatment agent, and is subjected to a crosslinking reaction with a coexisting silane compound or zirconyl compound in a heat drying process, or metal corrosion covering the metal surface or the metal surface. By reaction with the product, etc., it becomes an atomic group in which some or all of the active hydrogen is eliminated from the active hydrogen-containing group, and becomes a part of a high molecular weight cross-linked complex that forms a dense barrier film on the metal surface. . Accordingly, the component (X), which is one of the constituent components of the rust-preventing film in the present invention, is an atomic group in which a part or all of the active hydrogen is eliminated from the organic compound or the active hydrogen-containing group of the organic compound. , One or both of. Further, in the aqueous treating agent of the present invention, the organic compound is dissolved or dispersed in the treating agent as a salt in which part or all of the active hydrogen-containing groups are substituted with other cations. Therefore, the component (X ^* ), which is one of the components of the rust preventive agent in the present invention, is a part of or all of the active hydrogen-containing groups of the organic compound or the organic compound. One or both of the salts substituted with a cation.

In the present invention, when the organic compound contained in the component (X + X ^* ) has a functional group containing a carbonyl group (> C═O), the functional group is a carboxyl group (—COOH), an aldehyde group (—CHO). And any one or more of amide groups (—CONH ₂ ) are preferable. These functional groups have a relatively fast cross-linking reaction with a silane compound or zirconyl compound in the process of applying an aqueous treatment agent to a metal surface and heat-drying process, and a metal corrosion product covering the metal surface or metal surface. This is to improve the adhesion between the anticorrosive film and the metal surface.

In the present invention, when an organic acid is used as the organic compound of the (X + X ^* ) component, it is preferable to use one having at least one carboxyl group (—COOH) or carboxyl residue (—COO). If there is no carboxyl group (-COOH) or carboxyl residue (-COO) and other acidic functional groups or residues thereof, such organic acids are too acidic and excessively dampen the metal surface. Etching or forming a high molecular weight cross-linked complex with the (SiO ^* ) component or (ZrO ^* ) component, making it impossible to form an effective rust-preventive coating, and the amount used in the industry is very small and expensive. there's a possibility that. Here, the organic acid is a general term for the organic compounds having acidity, and most of them are carboxylic acids.

  In the present invention, when the organic compound contained in the (X) component of the anticorrosive film has a carboxyl group (-COOH), the (X) component is shown below, (a) component, (b) component, It is more preferable that any one or two or more of component (c) is used. This is because these specific carboxyl compounds have a faster cross-linking reaction with a silane compound or a zirconyl compound in the application of the aqueous treatment agent to the metal surface and the heat drying step than other carboxyl compounds.

  Component (a): Aliphatic or aromatic carboxylic acid having a molecular weight of 400 or less and having two or more carboxyl groups (-COOH) in one molecule, dissolved in 100 g of water at 20 ° C. A residue of carboxylic acid from which some or all of hydrogen has been eliminated from the carboxyl group of the acid.

  Component (b): Aliphatic or dissolved in 1.0 g or more in 100 g of water at 20 ° C., having a molecular weight of 400 or less, and the total number of carboxyl groups (—COOH) and hydroxyl groups (—OH) in one molecule is 2 or more An aromatic hydroxy acid, or a hydroxy acid residue in which part or all of hydrogen has been eliminated from the carboxyl group or hydroxyl group of the hydroxy acid.

  Component (c): An aliphatic compound having 1.0 g or more dissolved in 100 g of water at 20 ° C. and having a molecular weight of 400 or less, and the total number of carboxyl groups (—COOH) and aldehyde groups (—CHO) in one molecule is 2 or more Aromatic aldehyde acid, or a part or all of hydrogen desorbed from the carboxyl group of the aldehyde acid, or one from the aldehyde group of the aldehyde acid irrespective of the presence or absence of hydrogen desorption from the carboxyl group. Aldehydic acid residue from which part or all of hydrogen or oxygen has been eliminated.

In the present invention, when the organic compound contained in the (X + X ^* ) component has a functional group containing a sulfinyl group (> S═O), the functional group is a sulfonic acid group (—SO ₃ H), sulfine One or two acid groups (—SO ₂ H) are preferred. When the organic compound contained in the (X + X ^* ) component has a functional group containing a phosphoryl group (≡P = O), the structural formula O = POH (OR) ₂ or O = P (OH) ₂ (OR) The polar atomic group constituting the phosphate ester of (R is a hydrocarbon group) O═P (OH) ═ or O═P (OH) ₂ — is preferably one or two of them. These functional groups have a relatively fast cross-linking reaction with a silane compound or zirconyl compound in the process of applying an aqueous treatment agent to a metal surface and heat-drying process, and a metal corrosion product covering the metal surface or metal surface. This is to improve the adhesion between the anticorrosive film and the metal surface.

Organic compounds having a sulfonic acid group (—SO ₃ H) and usable for the purposes of the present invention include, for example, hydroxylamine-O-sulfonic acid (molecular formula H ₂ NO—SO ₃ H; to 100 g of water at 20 ° C. Solubility of> 1.0 g; molecular weight 113.09), m-aminobenzenesulfonic acid (molecular formula H ₂ NC ₆ H ₄ —SO ₃ H; solubility in 100 g of water at 20 ° C. 1.4 g; molecular weight 173.19), taurine (molecular formula H ₂ N -CH ₂ -CH ₂ -SO ₃ H; Solubility 2.0 g in 100 g of water at 20 ° C; molecular weight 125.15). Examples of a salt of an organic compound having a sulfinic acid group (—SO ₂ H) and usable for the purpose of the present invention include sodium hydroxymethanesulfinate (molecular formula CH ₂ (OH) —SO ₂ Na; water at 20 ° C. Solubility in 100 g 68 g; molecular weight 154.12) and the like. Examples of organic compounds that can be used for the purpose of the present invention with phosphoric esters of the structural formula O = POH (OR) ₂ or O = P (OH) ₂ (OR) (R is a hydrocarbon group) include, for example, adenosine 5'-1 phosphate (phosphate ester of adenosine, simplified structure O = P (OH) _2- (OR ^ade ) R ^ade portion is an adenosine residue, adenosine is a component of ribonucleic acid in vivo and hydroxyl group ( -OH) and an amino group (-NH ₂ ); solubility in 100 g of water at 20 ° C.> 1.0 g; molecular weight 347.22), cytidine 3′-1 phosphate (phosphate ester of cytidine, simplified structural formula O = P The R ^cyt part of (OH) _2- (OR ^cyt ) is a cytidine residue, cytidine is a constituent of biological ribonucleic acid and contains a hydroxyl group (-OH) and an amino group (-NH ₂ ); 100 g of water at 20 ° C Solubility in water (3.0 g; molecular weight 323.2).

In the present invention, when the organic compound contained in the (X ^* ) component of the rust preventive agent has a carboxyl group (-COOH), the (X ^* ) component is shown below, (a ^* ) component, ( More preferably, one or two or more of b ^* ) component and (c ^* ) component are used. This is because these specific carboxyl compounds have a faster cross-linking reaction with a silane compound or a zirconyl compound in the application to the metal surface of the aqueous treatment agent and the heat drying step than other carboxyl compounds.

(a ^* ) component: An aliphatic or aromatic carboxylic acid or a fatty acid dissolved in 100 g of water at 20 ° C. in an amount of 1.0 g or more, having a molecular weight of 400 or less, and having two or more carboxyl groups (—COOH) in one molecule Or aromatic carboxylates.

Component (b ^* ): Aliphatic, dissolved in 100 g of water at 20 ° C, 1.0 g or more, molecular weight 400 or less, and the total number of carboxyl groups (-COOH) and hydroxyl groups (-OH) in one molecule is 2 or more Or an aromatic hydroxy acid or an aliphatic or aromatic hydroxy acid salt.

Component (c ^* ): Aliphatic, dissolved in 100 g of water at 20 ° C. in an amount of 1.0 g or more, having a molecular weight of 400 or less, and the total number of carboxyl groups (—COOH) and aldehyde groups (—CHO) in one molecule is 2 or more Or an aromatic aldehyde acid, or an aliphatic or aromatic aldehyde salt.

Further, the anticorrosive film in the present invention, the following (A) component, (B) component, any one or two or more of (C) component, any of (SiO) component and (ZrO) component One or two or more main components, and the total (CO) of the mass of the carbonyl group (> C = O) contained in the component (A), component (B), component (C), and Silicon oxide atomic group (≡Si-O-,> Si = O, one or two) contained in the (SiO) component and zirconyl atomic group contained in the (ZrO) component (> Zr = O, ≡Zr-O-, any one or more of zirconyl ions (ZrO ²⁺ ), and the mass ratio to the total [SZO] is [CO]: [SZO] = 97: 3-10: 90.

Here, the component (A) is an aliphatic carboxylic acid having 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH), and 0 to 6 carbon atoms excluding the carboxyl carbon. Or a residue of the carboxylic acid from which part or all of hydrogen has been eliminated from the carboxyl group of the aliphatic carboxylic acid. The component (B) has 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH) and hydroxyl groups (-OH), and 0 to 6 carbon atoms excluding the carboxyl carbon. It is an aliphatic hydroxy acid or a residue of the hydroxy acid from which part or all of hydrogen has been eliminated from the carboxyl group or hydroxyl group of the hydroxy acid. The component (C) has a total carbon number of 2 to 10, a total number of carboxyl groups (-COOH) and aldehyde groups (-CHO) of 2 to 8, and a carbon number other than carboxyl carbon and aldehyde carbon of 0 to 6 An aliphatic aldehyde acid, or a part or all of hydrogen desorbed from a carboxyl group of the aliphatic aldehyde acid, or the aldehyde acid regardless of the presence or absence of hydrogen desorption from the carboxyl group This is a residue of aldehyde acid from which a part or all of hydrogen or oxygen is eliminated from the aldehyde group. The (SiO) component is a silicon oxide atomic group (≡Si—O—, any one or two of Si = O), and the (ZrO) component is a zirconyl atomic group (> Zr = O, ≡Zr—O— or zirconyl ion (ZrO ²⁺ , one or more).

  The (A) component, the (B) component, and the (C) component are not limited in water solubility and molecular weight as in the (X) component. That is, the component (A), the component (B), and the component (C) are not limited to 1.0 g or more in 100 g of water at 20 ° C., and are not limited to a molecular weight of 400 or less. Compared to other carboxyl compounds, the specific carboxyl compound (A) component, (B) component, and (C) component are applied to the metal surface of the aqueous treatment agent, and in the heat drying step, with a silane compound or zirconyl compound. The cross-linking reaction proceeds rapidly, and a very dense polymer barrier film is formed by heat drying for a short time.

In addition, the antirust treatment agent in the present invention includes one or more of the following (A ^* ) component, (B ^* ) component, (C ^* ) component, (SiO ^* ) component, and (ZrO ^* ) Any one or more of the components and water as the main component, the carbonyl atom group (> C = O) contained in the components (A ^* ), (B ^* ), and (C ^* ) the total mass of) the [CO ^*], the (SiO ^*) silicon oxide atomic group present in component (≡Si-O-) and the (ZrO ^*) zirconyl atomic group present in component (> Zr = O, ≡Zr-O-, one or more of zirconyl ions (ZrO ²⁺ ), and the mass ratio to the total [SZO ^* ] is [CO ^* ]: [SZO ^* ] = 97: 3 It is ˜10: 90.

Here, the component (A ^* ) is an aliphatic carboxylic acid having 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH), and 0 to 6 carbon atoms excluding the carboxyl carbon. Acid or aliphatic carboxylate. The component (B ^* ) has 2 to 10 carbon atoms in total, 2 to 8 total carboxyl groups (-COOH) and hydroxyl groups (-OH), and 0 to 6 carbon atoms excluding the carboxyl carbon. An aliphatic hydroxy acid or an aliphatic hydroxy acid salt. The component (C ^* ) has a total carbon number of 2 to 10, a total number of carboxyl groups (-COOH) and aldehyde groups (-CHO) of 2 to 8, and a carbon number other than carboxyl carbon and aldehyde carbon of 0 to 0. It is 6 aliphatic aldehyde acids or aliphatic aldehyde salts. The (SiO ^* ) component is an organic functional group capable of reacting with a hydrolyzable alkoxy group (-OR ³ , R ³ is a hydrocarbon group having up to 3 carbon atoms), a carboxyl group, a hydroxyl group, or an aldehyde group. And the (ZrO ^* ) component is a salt of zirconyl ion (ZrO ²⁺ ) and an acid group.

The (A ^* ) component, (B ^* ) component, and (C ^* ) component are not limited in water solubility or molecular weight as in the (X *) component. That is, the (A ^* ) component, the (B ^* ) component, and the (C ^* ) component are not limited to 1.0 g or more in 100 g of water at 20 ° C., and are not limited to a molecular weight of 400 or less. . Compared to other carboxyl compounds, (A ^* ) component, (B ^* ) component, and (C ^* ) component, which are specific carboxyl compounds, can be applied to the metal surface of an aqueous treatment agent and heated and dried. The cross-linking reaction with the zirconyl compound proceeds fairly quickly, and a very dense polymer barrier film is formed by heat drying for a short time.

In the present invention, the (A) component constituting the rust preventive film, and the aliphatic carboxylic acid or residue or salt thereof (hereinafter referred to as carboxylic acid) suitably used as the (A ^* ) component of the rust inhibitor A saturated or unsaturated aliphatic group having 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH), and 0 to 6 carbon atoms excluding the carboxyl carbon. Carboxylic acid or an aliphatic carboxylic acid residue from which some or all of hydrogen has been eliminated from the carboxyl group of this carboxylic acid, or this residue and another electron-withdrawing (positive) atom or atomic group Carboxylate. Examples of such carboxylates include, for example, alkali metal salts such as Na salts and K salts of aliphatic carboxylic acids, alkaline earth metal salts such as Mg salts and Ca salts, and the like. The carboxylic acid or the like binds to other atoms such as metal atoms on the coated metal surface, constituent atoms of the organic functional group of the (SiO) component, or constituent atoms of the (ZrO) component in the antirust coating. Are adsorbed on the metal surface or the like, or are ionized alone. In addition, such a carboxylic acid or the like partially ionizes in water in the rust preventive agent and exists alone or in an associated state. The component (A) may contain not only the aliphatic carboxylic acid residue from which some or all of the hydrogen has been eliminated from the carboxyl group, but also an aliphatic carboxylic acid from which no hydrogen has been eliminated. The component (A ^* ) includes not only the aliphatic carboxylic acid residue but also an aliphatic carboxylic acid that has not been desorbed with hydrogen. Such an aliphatic carboxylic acid has 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (—COOH), and 0 to 6 carbon atoms excluding the carboxyl carbon.

In the present invention, the component (B) constituting the rust preventive film, and the aliphatic hydroxy acid or residue or salt thereof (hereinafter referred to as hydroxy acid or the like) suitably used as the component (B ^* ) of the rust inhibitor The total number of carbon atoms is 2 to 10, the total number of carboxyl groups (-COOH) and hydroxyl groups (-OH) is 2 to 8, and the number of carbon atoms excluding the carboxyl carbon is 0 to 6 Aliphatic hydroxy acid, or an aliphatic hydroxy acid residue from which some or all of hydrogen has been eliminated from the carboxyl group or hydroxyl group of this hydroxy acid, or this residue and other electron-withdrawing (positive) atoms Alternatively, it is a hydroxy acid salt to which atomic groups are bonded. Here, the hydroxy acid is an organic compound having a carboxyl group (—COOH) and an alcoholic hydroxyl group (—OH) in one molecule.

Examples of the hydroxy acid salt that can be used in the present invention include alkali metal salts such as Na salt and K salt of aliphatic hydroxyl acid, alkaline earth metal salts such as Mg salt and Ca salt, and the like. . Hydroxy acids and the like that can be used in the present invention are the metal atoms on the coated metal surface, the constituent atoms of the organic functional group of the (SiO) component, the constituent atoms of the (ZrO) component, etc. Are bonded to other atoms, adsorbed on the metal surface or the like, or ionized alone. Further, in the rust preventive agent, a part of such a hydroxy acid is ionized in water and exists alone or in an associated state. The component (B) may contain not only the aliphatic hydroxy acid residue from which some or all of the hydrogen has been eliminated from the carboxyl group or hydroxyl group, but also an aliphatic hydroxy acid from which no hydrogen has been eliminated. . The component (B ^* ) includes not only the aliphatic hydroxy acid residue but also an aliphatic hydroxy acid that has not been desorbed with hydrogen. Such aliphatic hydroxy acids have 2 to 10 carbon atoms in total, 2 to 8 total carboxyl groups (-COOH) and hydroxyl groups (-OH), and 0 to 6 carbon atoms excluding the carboxyl carbon. It is.

In the present invention, the (C) component constituting the rust preventive film, and the aliphatic aldehyde acid or residue or salt thereof (hereinafter referred to as aldehyde acid etc.) suitably used as the (C ^* ) component of the rust preventive agent The total number of carbon atoms is 2 to 10, the total number of carboxyl groups (-COOH) and aldehyde groups (-CHO) is 2 to 8, and the number of carbon atoms excluding carboxyl carbon and aldehyde carbon is 0 to 6 A part or all of hydrogen is eliminated from the aliphatic aldehyde acid or the carboxyl group of the aldehyde acid, or part or all of hydrogen or oxygen is eliminated from the aldehyde group of the aldehyde acid. It is an aldehyde acid residue, or an aldehyde salt in which this residue is combined with another electron-withdrawing (positive) atom or atomic group. Here, the aldehyde acid is an organic compound having a carboxyl group (—COOH) and an aldehyde group (—CHO) in one molecule.

Examples of aldehyde salts that can be used in the present invention include, for example, alkali metal salts such as Na salts and K salts of aliphatic aldehyde acids, alkaline earth metal salts such as Mg salts and Ca salts, and the like. . Aldehydic acid and the like that can be used in the present invention are metal atoms on the coated metal surface, constituent atoms of the organic functional group of the (SiO) component, constituent atoms of the (ZrO) component, etc. Are bonded to other atoms, adsorbed on the metal surface or the like, or ionized alone. In addition, such aldehyde acids and the like are partly ionized in water and exist alone or in an associated state in the rust preventive agent. The component (C) includes not only the aliphatic aldehyde acid residue from which some or all of hydrogen or oxygen is eliminated from a carboxyl group or aldehyde group, but also an aliphatic aldehyde acid from which no hydrogen or oxygen is eliminated. May be included. The component (C ^* ) includes not only the aliphatic aldehyde acid residue but also an aliphatic aldehyde acid from which no hydrogen or oxygen is eliminated. Such aliphatic aldehyde acids have a total carbon number of 2 to 10, a total number of carboxyl groups (-COOH) and aldehyde groups (-CHO) of 2 to 8, and 0 carbon atoms excluding the carboxyl carbon and aldehyde carbon. ~ 6.

Component (A), (B) component, (C) component suitably used as the main component of the rust preventive film of the present invention, and (A ^* ) preferably used as the main component of the rust preventive agent of the present invention The molecules constituting the component, the (B ^* ) component, and the (C ^* ) component have at least one carboxyl group (—COOH) or carboxyl residue (—COO) in the molecule. Without these at all, the (SiO) component or (ZrO) component, or (SiO *) component or (ZrO *) component, or the interaction such as bonding or adsorption with the metal surface is slightly insufficient, An effective rust preventive film may not be formed.

In the present invention, the molecules constituting the (A) component, (B) component, (C) component, and (A ^* ) component, (B ^* ) component, (C ^* ) component have a total carbon number per molecule. It must be 2 or more, and preferably 10 or less. Since the residue (HCOO) desorbed from a carboxylic acid having 1 carbon atom (i.e., formic acid (HCOOH)) has only one site that can be bound or adsorbed (here, -COO), The (SiO) component or (ZrO) component, or the (SiO *) component or (ZrO *) component and the high molecular weight crosslinked complex cannot be formed, and an effective rust preventive film cannot be formed. Also, there are no hydroxy acids or aldehyde acids with 1 carbon. On the other hand, if the total number of carbon atoms exceeds 10, the molecular weight of the original carboxylic acid, hydroxy acid, and aldehyde acid involved in the film formation reaction on the surface of the metal member becomes excessive, and these are difficult to dissolve in water. Often impossible. In addition, even if the treatment agent can be manufactured, these molecules are large and cannot move quickly in the treatment agent, so the (SiO) component or (ZrO) component, or (SiO ^* ) component or (ZrO ^* ) Cross-linking reaction with components is slow, and film formation is difficult. For the same reason as described above, the molecules constituting the component (A), the component (B), the component (C), and the component (A ^* ), the component (B ^* ), and the component (C ^* ) The number of carbon atoms excluding carboxyl carbon and aldehyde carbon is preferably 0-6.

(A) component, (B) component, (C) component, and (A ^* ) component, (B ^* ) component, (C ^* ) component constituting the carboxyl group, hydroxyl group, aldehyde group and these The total number of residues must be 2 or more per molecule, and preferably 8 or less. When the total number is 1, it is an aliphatic monocarboxylic acid or a residue thereof, as in the case of the formic acid, (SiO) component or (ZrO) component, or (SiO ^* ) component or (ZrO ^* ) A component and a high molecular weight crosslinked complex cannot be formed, and an effective rust preventive film cannot be formed. On the other hand, if it exceeds 8, the number of polar functional groups is too large and the water resistance is lowered, so that an effective rust preventive film may not be formed.

(A) component, (B) component, (C) component essential aliphatic carboxylic acid or residue thereof, aliphatic hydroxy acid or residue thereof, preferably used as a main component of the anticorrosive film, Although it is not easy to comprehensively show an aliphatic aldehyde acid or all of its residues in one chemical structural formula, it can be summarized into several as follows. That is, oxalic acid (HOOC-COOH) or its residue (HOOC-COO, OOC-COO), glyoxylic acid (OHC-COOH) or its residue (OHC-COO, OC-COOH, HC-COOH, OC-COO, HC-COO) and R ⁶ (-COOH) _a (-COO) _b (-OH) _c (-O) _d (-CHO) _e (-CO) _f (- CH) _g (wherein R ⁶ is a hydrocarbon group having 1 to 6 carbon atoms, —COO is a carboxyl residue, —O is a hydroxyl residue, and —CO and —CH are aldehyde residues. A, b, c, d, e, f, g are integers of 0 or more, and the total number of carboxyl group, hydroxyl group, aldehyde group and these residues is 2 ≦ a + b + c + d + e + f + g ≦ 8, the total number of carboxyl groups and carboxyl residues is 1 ≦ a + b ≦ 8, the total number of hydroxyl groups, aldehyde groups and these residues is 0 ≦ c + d + e + f + g ≦ 7 Any one) or two or more. (A ^* ) component, (B ^* ) component, (C ^* ) component which is preferably used as a main component of the antirust treatment agent, an aliphatic carboxylic acid or a residue thereof, an aliphatic hydroxy acid or The chemical structure formula of the residue, aliphatic aldehyde acid or the residue is also the same as the above.

  In the present invention, the (SiO) component and the (ZrO) component constituting the rust preventive film are each a silicon oxide atomic group composed of one silicon atom and one oxygen atom, one zirconium atom and one Is a zirconyl atomic group consisting of oxygen atoms, and in the rust-preventive coating, combined with (X) component having two or more active hydrogen-containing groups, or (A) component, (B) component, (C) component It forms a high molecular weight cross-linked composite and is part of a dense rust-proof coating. Moreover, it couple | bonds with the surface of the metal coat | covered with the rust preventive film of this invention, or its oxide, and has improved the adhesiveness of the said metal, its oxide, and a rust preventive film.

In the present invention, the starting compound (original compound before the reaction) in which a part or all of the reaction becomes the (SiO) component or the (ZrO) component, or the reaction route thereof is not particularly limited. The (SiO ^* ) component and the (ZrO ^* ) component contained in the antirust treatment agent of the invention are preferred. These (SiO ^* ) component and (ZrO ^* ) component are (X ^* ) component or (A ^* ) component contained in the rust preventive agent when applied to the metal surface to be coated and dried. It reacts with the component, the (B ^* ) component, the (C ^* ) component, or the metal surface and becomes a residue containing the (SiO) component and the (ZrO) component, respectively, and becomes a constituent component of the rust preventive film.

Among these, the (SiO ^* ) component is a hydrolyzable Si-OR ³ group (R ³ is a hydrocarbon group having up to 3 carbon atoms), an active hydrogen-containing group of the (X ^* ) component, It is a silane coupling agent having a carboxyl group of the component (A ^* ), a carboxyl group or a hydroxyl group of the component (B ^* ), and an organic functional group capable of reacting with the carboxyl group or aldehyde group of the component (C ^* ). The Si-OR ³ group exists stably at room temperature in the absence of moisture, but in the presence of water (for example, in the rust preventive agent of the present invention), the Si-OR ³ group alkoxy group ( The —OR ³ ) site is hydrolyzed to a silanol group (Si—OH). The silanol group is dehydrated and condensed with the hydroxyl group if a hydroxy acid as a base of the component (X) or the component (B) or a metal surface having a hydroxyl group (-OH) coexists, respectively. A covalent bond of Si-hydroxyl acid residue or a covalent bond of Si-O-metal surface is formed to form a cross-linked complex that becomes a part of the rust preventive film component. To improve the adhesion. Some commercially available silane coupling agents use a halogen atom such as Cl as a hydrolyzable substituent directly bonded to the Si atom. Silane coupling agents with (e.g., Si-Cl) are very hydrolysable, and when mixed with water, a large amount of silanol groups (Si-OH) are formed immediately, and these silanol group-containing molecules quickly To form a large amount of a compound containing an inactive siloxane bond (Si—O—Si) in a short time. Even when an aqueous treatment agent containing such a compound is applied to a metal, the siloxane bonding site of the compound is not limited to the hydroxyl group on the surface of the metal or its oxide, the (X ^* ) component or the (B ^* ) component. Since it does not react with a hydroxyl group or the like, a high-molecular-weight crosslinked complex in close contact with the metal surface cannot be formed, and an effective rust preventive film cannot be formed. On the other hand, in the silane coupling agent having the Si-OR ³ group, the alkoxy group (-OR ³ ) has a relatively mild hydrolyzability, so that when mixed with water, a silanol group (Si-OH) is formed. Generate gradually. When an aqueous treatment agent containing such a compound is applied to a metal, the compound reacts with a hydroxyl group on the surface of the metal or its oxide, a hydroxyl group of the (X ^* ) component or (B ^* ) component, or the like. Therefore, it is possible to form a high molecular weight cross-linked complex in close contact with the metal surface or the oxide surface thereof, and an effective rust preventive film can be formed. Therefore, as the silane coupling agent of the (SiO ^* ) component of the present invention, those in which the substituent directly bonded to the Si atom is the alkoxy group (—OR ³ ) are used. Examples of the organic functional group capable of reacting with the active hydrogen-containing group of the (X ^* ) component at the functional group of the silane coupling agent include, for example, an epoxy group (CH _2- (O) -CH-), amino Group (—NH ₂ ), vinyl group (CH ₂ ═CH—) and the like.

The (ZrO ^* ) component contained in the antirust treatment agent of the present invention is a salt of zirconyl ion (ZrO ²⁺ ) and an acid group. As described above, in the present invention, a starting compound (original compound before the reaction) in which a part or all of it becomes a (ZrO) component in the film by the reaction, or the reaction route thereof is not particularly limited, The (ZrO ^* ) component is preferred. When the antirust treatment agent of the present invention containing the (ZrO ^* ) component is applied to a metal surface and dried, the (X ^* ) component or the (A ^* ) component contained in the antirust treatment agent, (B ^* ) Component, (C ^* ) component, or the surface of the metal surface or its oxide and the (ZrO ^* ) component react with each other to form a zirconyl atomic group (> Zr = O, ≡Zr-O- or zirconyl ion ( ZrO ²⁺ )) is produced. These zirconyl residues are part of a high molecular weight cross-linked complex by covalent bond, coordinate bond or ionic bond with the active hydrogen-containing group of component (X) in the rust preventive film, and Adhesion between the metal or oxide and the anticorrosive film is enhanced by covalent bonding, coordination bonding or ionic bonding with the surface of the metal or oxide thereof coated with the anticorrosive film of the invention.

In the rust preventive film of the present invention, the mass of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the component (X). The total [CSP] and the nitrogen atom (N), oxygen atom (O) which is the central atom of the amino group (—NH ₂ ), hydroxyl group (—OH) or mercapto group (—SH) contained in the component (X) ) Or the sum of the mass of sulfur atoms (S) [NOS], the silicon oxide atomic group (≡Si-O-,> Si = O, either one or two) contained in the (SiO) component and the above (ZrO) The relationship with the total mass [SZO] of the zirconyl atomic group (> Zr = O, ≡Zr-O- or any one or more of zirconyl ions (ZrO ²⁺ )) contained in the component , ([CSP] + [NOS]): [SZO] = 97: 3 to 10:90, preferably ((CSP) + [NOS]): [SZO] = 90: 10 to 30:70 is there.

In the rust preventive agent of the present invention, the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the component (X ^* ). the total mass of) the [CSP ^*], wherein (X ^*) amino groups present in component (-NH _2), nitrogen atom is the central atom of a hydroxyl group (-OH) or mercapto group (-SH) (N ), The total mass of oxygen atoms (O) or sulfur atoms (S) [NOS ^* ], silicon oxide atomic group ≡Si-O- contained in the (SiO ^* ) component, and contained in the (ZrO ^* ) component The relationship with the total mass [SZO ^* ] of the zirconyl atomic group (> Zr = O, ≡Zr-O- or one or more of zirconyl ions (ZrO ²⁺ )) is ((CSP ^* ] + [NOS ^* ]): [SZO ^* ] = 97: 3-10: 90, preferably ((CSP ^* ) + [NOS ^* ]): [SZO ^* ] = 90: 10-30: 70 It is.

In the case of the above rust preventive film or rust preventive agent, if the mass ratio of [SZO] (or the mass ratio of [SZO ^* ]) is less than 3%, the (SiO) component and the (ZrO) component that affect the crosslinking reaction The total of (or the sum of (SiO ^* ) component and (ZrO ^* ) component) is less than the (X) component (or (X ^* ) component), so the (SiO) component and (ZrO) component in the film The number of sites where the component (X) is interposed is reduced, a dense cross-linking network is not formed, and the rust prevention property of the film is insufficient. When the mass ratio of [SZO] (or the mass ratio of [SZO ^* ]) exceeds 90%, the sum of (SiO) component and (ZrO) component (or the sum of (SiO ^* ) component and (ZrO ^* ) component) However, since it is more than the component (X) (or (X ^* ) component), it is not incorporated in the crosslinked polymer with the component (X) in the film and is not bonded to the metal surface coated with the film ( (SiO) component and (ZrO) component increase. Most of the (SiO) component and (ZrO) component in the film are constituent groups of unreacted low molecular weight silicon oxide compounds and low molecular weight zirconyl compounds, and these are the cross-linked polymers of the (X) component. Since the denseness of the network structure to be produced is lowered, the corrosion factor easily penetrates the film, and as a result, the rust prevention property is insufficient.

Further, in the rust preventive coating of the present invention, the total (CO) of the mass of the carbonyl atom group (> C = O) contained in the component (A), the component (B), the component (C), and the (SiO) Silicon oxide atomic group (≡Si-O-,> Si = O, one or two) included in the component and zirconyl atomic group (> Zr = O, ≡Zr-O) included in the (ZrO) component -, The mass ratio with the sum [SZO] of the mass of any one or more of zirconyl ions (ZrO ²⁺ ) is [CO]: [SZO] = 97: 3 to 10:90, Preferably, [CO]: [SZO] = 90: 10 to 30:70.

Further, in the rust preventive agent of the present invention, the total (CO ^* ) of the mass of the carbonyl atom group (> C = O) contained in the (A ^* ) component, (B ^* ) component, and (C ^* ) component Any of atomic groups ≡Si-O- contained in the (SiO ^* ) component and atomic groups (> Zr = O, ≡Zr-O-, zirconyl ion (ZrO ²⁺ ) contained in the (ZrO ^* ) component Or the mass ratio of the mass of [SZO ^* ] is [CO ^* ]: [SZO ^* ] = 97: 3 to 10:90, preferably [CO ^* ]: [SZO ^* ] = 90:10 to 30:70.

In the case of the above rust preventive film or rust preventive agent, if the mass ratio of [SZO] (or the mass ratio of [SZO ^* ]) is less than 3%, the (SiO) component and the (ZrO) component that affect the crosslinking reaction (Or the sum of (SiO ^* ) component and (ZrO ^* ) component) is the sum of (A) component, (B) component and (C) component (or (A ^* ) component and (B ^* ) component) (C ^* ) total component) is less than the total (C) component in the film, the number of (A) component, (B) component, (C) component interlinked sites through the (SiO) component and (ZrO) component are reduced, A dense cross-linking network is formed as in the case where the (SiO) component, (ZrO) component (or (SiO ^* ) component, (ZrO ^* ) component) coexist with the (X) component (or (X ^* ) component). The film is not sufficiently rustproof. When the mass ratio of [SZO] (or the mass ratio of [SZO ^* ]) exceeds 90%, the sum of (SiO) component and (ZrO) component (or the sum of (SiO ^* ) component and (ZrO ^* ) component) Is larger than the total of (A), (B), and (C) components (or the total of (A ^* ), (B ^* ), and (C ^* ) components). The amount of (SiO) component and (ZrO) component that are not incorporated in the crosslinked polymer with component (A), component (B), and component (C), and are not bonded to the metal surface coated with the film increases. Many of such (SiO) component and (ZrO) component in the film are constituent groups of unreacted low molecular weight silicon oxide compound and low molecular weight zirconyl compound, which are (A) component and (B) component. Since the density of the network structure formed by the cross-linked polymer of component (C) is lowered, the corrosion factor is likely to penetrate the film, resulting in insufficient rust prevention.

In the present invention, the adhesion amount of rust preventing film onto the metal surface is preferably 0.02~5.0g / m ^2, particularly preferably 0.1~2.0 g / m ^2. If it is less than 0.02 g / m ² , the permeation inhibiting effect of the corrosion factor is small, and there is a possibility that sufficient rust prevention property may not be obtained.If it exceeds 5.0 g / m ² , the permeation inhibiting effect of the corrosion factor is excellent, It is not practical because the coating cost increases and the conductivity and weldability are poor.

The aliphatic carboxylic acid contained in the component (A) that can be used as a constituent of the rust preventive film of the present invention, and the fat contained in the component (A ^* ) that can be used as a constituent of the rust preventive agent of the present invention The aliphatic carboxylic acid is a saturated aliphatic dicarboxylic acid having 0 to 5 carbon atoms excluding the carboxyl carbon (the structural formula is HOOC- (CH ₂ ) _(a1) -COOH. (A1) is an integer and 0 ≦ (a1) ≦ 5.-(CH ₂ ) _{(a1) -The} chain part may contain an aliphatic group other than methylene group -CH _2- or an aliphatic group substituted with a part of hydrogen of the methylene group), and And an unsaturated aliphatic dicarboxylic acid having 2 to 5 carbon atoms excluding the carboxyl carbon (the structural formula is HOOC- (CH ₂ ) _(b1) -CH = CH- (CH ₂ ) _(b2) -COOH. (B1) And (b2) are integers of 0 or more, and 0 ≦ (b1) + (b2) ≦ 3 .- (CH ₂ ) _(b1) -chain,-(CH ₂ ) _(b2) -Methylene group at the chain site- Any one of the aliphatic groups other than CH ₂ — or an aliphatic group substituted with a part of the hydrogen of the methylene group. It is preferable that it is 1 type or 2 types or more. When such an aliphatic carboxylic acid is used, a good rust preventive film can be obtained in terms of rust prevention and cost. The structural formula of a saturated aliphatic dicarboxylic acid residue occurring saturated aliphatic dicarboxylic acids of the is eliminated _{hydrogen, HOOC- (CH 2) (a2} ) -COO - and _{^{- OOC- (CH 2) (a3}} ) -COO ^- ((a2), (a3) is an integer, 0 ≦ (a2) ≦ 5, 0 ≦ (a3) ≦ 5.-(CH ₂ ) _(a2) -chain,-(CH ₂ ) _{(a3) -chain} The site may include an aliphatic group other than the methylene group —CH ₂ — or an aliphatic group substituted with a part of the hydrogen of the methylene group. Further, the structural formula of the unsaturated aliphatic dicarboxylic acid residue generated by hydrogen elimination of the unsaturated aliphatic dicarboxylic acid is HOOC- (CH ₂ ) _(b3) -CH = CH- (CH ₂ ) _(b4) -COO ^- and _{^{- OOC- (CH 2) (b5}} ) -CH = CH- (CH 2) (b6) -COO - ((b3), (b4), (b5), (b6) is an integer of 0 or more 0 ≦ (b3) + (b4) ≦ 3, 0 ≦ (b5) + (b6) ≦ 3,-(CH ₂ ) _{(b3) -chain} ,-(CH ₂ ) _{(b4) -chain} ,-( CH ₂ ) _{(b5) -chain} ,-(CH ₂ ) _{(b6) -The} chain portion contains an aliphatic group other than the methylene group -CH _2- or an aliphatic group substituted with part of the hydrogen of the methylene group. Or any one or more of them.

Furthermore, in the present invention, the saturated or unsaturated aliphatic carboxylic acid contained in the component (A) that can be used as a component of the rust preventive film of the present invention, and usable as a component of the rust preventive agent of the present invention. The saturated or unsaturated aliphatic carboxylic acid contained in the component (A ^* ) is oxalic acid (HOOC-COOH), malonic acid (HOOC-CH ₂ -COOH), succinic acid (HOOC- (CH ₂ ) ₂ -COOH) , Glutaric acid (HOOC- (CH ₂ ) ₃ -COOH), adipic acid (HOOC- (CH ₂ ) ₄ -COOH), α-ketoglutaric acid (HOOC-CH ₂ -CH ₂ CO-COOH), maleic acid (cis -HOOC-CH = CH-COOH) is more preferably one or more. When such an aliphatic carboxylic acid is used, a better rust preventive film can be obtained in terms of rust prevention and cost.

Further, in the present invention, the aliphatic hydroxy acid contained in the component (B) that can be used as a component of the rust preventive film of the present invention, and a component that can be used as a component of the rust preventive agent of the present invention (B ^* The aliphatic hydroxy acid contained in the component is an aliphatic hydroxy acid having 1 to 4 carbon atoms excluding the carboxyl carbon (the structural formula is CH _(c1) (-COOH) _(c2) (-OH) _(c3) - [CH _(d1) (-COOH) _(d2) (-OH) _(d3) ] _(p1) -[CH _(e1) (-COOH) _(e2) (-OH) _(e3) ] _(p2) -[CH _(f1) (-COOH) _(f2) (-OH) _(f3) ] _(p3) (p1), (p2), (p3) is 0 or 1. (c1)-(c3), (d1)- (d3), (e1) to (e3), (f1) to (f3) are all integers of 0 or more, and (c1) + (c2) + (c3) = 3, (d1) + (d2) + (d3) = 2, (e1) + (e2) + (e3) = 2, (f1) + (f2) + (f3) = 3 Total number of carboxyl groups in the molecule (c2) + (d2) + ( It is preferable that one or more of e2) + (f2) ≧ 1 and the total number of hydroxyl groups in the molecule (c3) + (d3) + (e3) + (f3) ≧ 1). When such an aliphatic hydroxy acid is used, a good rust preventive film can be obtained in terms of rust prevention and cost. The structural formula of the aliphatic hydroxy acid residue generated by hydrogen elimination of the aliphatic hydroxy acid is CH _(c4) (-COOH) _(c5) (-COO) _(c6) (-OH) _(c7) (- O) _(c8) -[CH _(d4) (-COOH) _(d5) (-COO) _(d6) (-OH) _(d7) (-O) _(d8) ] _(p4) -[CH _(e4) ( -COOH) _(e5) (-COO) _(e6) (-OH) _(e7) (-O) _(e8) ] _(p5) -[CH _(f4) (-COOH) _(f5) (-COO) _{(f6 ) (-OH) (f7) (} -O) (f8)] (p6) (-COO carboxyl residues, -O hydroxyl residues. (p4), (p5) , (p6) is 0 or 1. (c4) to (c8), (d4) to (d8), (e4) to (e8), (f4) to (f8) are all integers of 0 or more, and (C4) + (C5) + (C6 ) + (C7) + (C8) = 3, (d4) + (d5) + (d6) + (d7) + (d8) = 2, (e4) + (e5) + (e6) + (e7) + (e8) = 2, (f4) + (f5) + (f6) + (f7) + (f8) = 3 Total number of carboxyl groups and carboxyl residues in the molecule (c5) + (c6) + (d5) + (d6) + (e5) + (e6) + (f5) + (f6) ≧ 1, total number of hydroxyl groups and hydroxyl residues in the molecule (c7) + (c8) + (d7) + (d8) + (e7) + (e8) + (f7) + (f8) ≧ 1)).

Furthermore, in the present invention, the aliphatic hydroxy acid contained in the component (B) that can be used as a component of the rust preventive film of the present invention, and a component that can be used as a component of the rust preventive agent of the present invention (B ^* The aliphatic hydroxy acid contained in the component is glycolic acid (CH ₂ (OH) -COOH), lactic acid (CH ₃ CH (OH) -COOH), glyceric acid (CH ₂ (OH) -CH (OH) -COOH) ), citric acid _{(HOOC-CH 2 -C (OH} ) (COOH) -CH 2 -COOH), tartaric acid (HOOC-CH (OH) -CH (OH) -COOH), or malic acid (HOOC-CH ( More preferably, one or more of (OH) —CH ₂ —COOH). When such an aliphatic hydroxy acid is used, a better rust preventive film can be obtained in terms of rust prevention and cost.

Further, in the present invention, the aliphatic aldehyde acid contained in the component (C) that can be used as a component of the rust preventive film of the present invention, and the component that can be used as a component of the rust preventive agent of the present invention (C ^* The aliphatic aldehyde acid contained in the component is an aliphatic aldehyde acid having 0 to 4 carbon atoms excluding carboxyl carbon and aldehyde carbon (the structural formula is CHO-COOH or CH _(g1) (-COOH) _{(g2 )} (-CHO) _(g3) -[CH _(h1) (-COOH) _(h2) (-CHO) _(h3) ] _(q1) -[CH _(i1) (-COOH) _(i2) (-CHO) _{( i3)} ] _(q2) -[CH _(j1) (-COOH) _(j2) (-CHO) _(j3) ] _(q3) ((q1), (q2), (q3) is 0 or 1. (g1) ~ (G3), (h1) ~ (h3), (i1) ~ (i3), (j1) ~ (j3) are all integers of 0 or more, and (g1) + (g2) + (g3) = 3 , (H1) + (h2) + (h3) = 2, (i1) + (i2) + (i3) = 2, (j1) + (j2) + (j3) = 3 The total number of carboxyl groups in the molecule (g2) + (h2) + (i2) + (j2) ≧ 1, the total number of aldehyde groups in the molecule (g3) + (h3) + (i3) + (j3) ≧ 1) any one or two It is preferable to have more than species. When an aromatic aldehyde acid is used, a good anticorrosive film can be obtained in terms of rust prevention, cost, etc. The structural formula of the aliphatic aldehyde acid residue generated by elimination of hydrogen or oxygen from the aliphatic aldehyde acid is as follows: , Glyoxylic acid residues OHC-COO, OC-COOH, HC-COOH, OC-COO, HC-COO, or CH _(g4) (-COOH) _(g5) (-COO) _(g6) (-CHO) _{( g7)} (-CO) _(g8) (-CH) _(g9) -[CH _(h4) (-COOH) _(h5) (-COO) _(h6) (-CHO) _(h7) (-CO) _(h8) (-CH) _(h9) ] _(q4) -[CH _(i4) (-COOH) _(i5) (-COO) _(i6) (-CHO) _(i7) (-CO) _(i8) (-CH) _{( i9)} ] _(q5) -[CH _(j4) (-COOH) _(j5) (-COO) _(j6) (-CHO) _(j7) (-CO) _(j8) (-CH) _(j9) ] _{(q6 )} (-COO is a carboxyl residue, -CO and -CH are aldehyde residues. (q4), (q5), and (q6) are 0 or 1. (g4) to (g9), (h4) to (h9), (i4) to (i9), (j4) to (j9) are all integers of 0 or more, and (g4) + (g5) + (g6 ) + (g7) + (g8) + (g9) = 3, (h4) + (h5) + (h6) + (h7) + (h8) + (h9) = 2, (i4) + (i5) + (i6) + (i7) + (i8) + (i9) = 2, (j4) + (j5) + (j6) + (j7) + (j8) + (j9) = 3. Total number of carboxyl groups and carboxyl residues in the molecule (g5) + (g6) + (h5) + (h6) + (i5) + (i6) + (j5) + (j6) ≧ 1, aldehyde group in the molecule And the total number of aldehyde residues (g7) + (g8) + (g9) + (h7) + (h8) + (h9) + (i7) + (i8) + (i9) + (j7) + (j8) + (j9) ≧ 1. 1) or two or more thereof.

Furthermore, in the present invention, the aliphatic aldehyde acid contained in the component (C) that can be used as a component of the rust preventive film of the present invention, and the component that can be used as a component of the rust preventive agent of the present invention (C ^* More preferably, the aliphatic aldehyde acid contained in the component) is glyoxylic acid (CHO-COOH). When glyoxylic acid is used as the aliphatic aldehyde acid, a better rust preventive film is obtained in terms of rust prevention.

The (SiO ^* ) component of the present invention is an organic compound capable of reacting with a hydrolyzable alkoxy group (-OR ³ , R ³ is a hydrocarbon group having up to 3 carbon atoms) and a carboxyl group, a hydroxyl group or an aldehyde group. It is a silane coupling agent having a functional group. In the present invention, the (SiO ^* ) component includes aminoalkylsilane [NH ₂ -R ^* -Si (-OR ³ ) ₃ ] and epoxyalkylsilane [CH _2- (O) -CH-R ^* -Si (- OR ³ ) ₃ ] (R ^* is an organic group having up to 7 carbon atoms, and R ³ is a hydrocarbon group having up to 3 carbon atoms) is preferably one or more. These react well with the (X ^* ) component or the (A ^* ) component, the (B ^* ) component, the (C ^* ) component, and the metal surface or its oxide surface during the formation of the anticorrosive film. Since a strong bond with a dense polymer composite or metal surface is formed, a good rust preventive film can be obtained. The (SiO ^* ) component is composed of γ- (2-aminoethyl) aminopropyltrimethoxysilane [NH ₂ (CH ₂ ) ₂ —NH (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ ] and γ-glycol. It is particularly preferred that one or more of the following: Sidoxypropyltrimethoxysilane [CH ₂ — (O) —CH—CH ₂ O— (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ ]. These react quickly with the (X ^* ) component, or the (A ^* ) component, (B ^* ) component, (C ^* ) component, and the metal surface or its oxide surface during the formation of the anticorrosive film. In particular, since it forms a strong bond with a dense polymer composite or a metal surface, an excellent rust preventive film can be obtained.

Included in the rust prevention agent of the present invention (ZrO ^*) is the component zirconyl ions (ZrO ²⁺⁾ and salts of the acid groups is not particularly limited as long as it is aqueous and acidic, for example, zirconyl nitrate (ZrO (NO ₃ ) ₂ ), zirconyl sulfate (ZrOSO ₄ ) and the like, but preferably a water-soluble salt of a lower carboxylic acid and zirconyl (ZrO ²⁺ ), zirconyl formate (ZrO (HCOO) ₂ ), zirconyl acetate ( ZrO (CH ₃ COO) ₂ ), zirconyl propionate (ZrO (C ₂ H ₅ COO) ₂ ), zirconyl butyrate (ZrO (C ₃ H ₇ COO) ₂ ), oxalic acid (HOOC-COOH) and zirconyl (ZrO ²⁺ ) Salt, malonic acid (HOOC-CH ₂ -COOH) and zirconyl salt, or succinic acid (HOOC- (CH ₂ ) ₂ -COOH) and zirconyl salt are preferably one or more . When these acid salts form a rust preventive film on the metal surface, the (X ^* ) component, or the (A ^* ) component, (B ^* ) component, (C ^* ) component, and the metal surface It reacts well with the surface of the oxide and forms a strong bond with the dense polymer composite or the metal surface, so that a good anticorrosive film can be obtained.

The rust preventive film and rust preventive treatment agent of the present invention must not contain chemical substances specified by the Chemical Substance Management Promotion Law. For example, salts of monochloroacetic acid (CH ₂ Cl-COOH) and zirconyl (ZrO ²⁺ ), which are Class I designated chemical substances in the Chemical Substance Management Promotion Law, are excluded from the (ZrO ^* ) component of the rust inhibitor. The

The anticorrosive film of the present invention and the antirust treatment agent include the component (X), the component (A), the component (B), the component (C), the component (SiO), the component (ZrO), and In addition to the (X ^* ) component, the (A ^* ) component, the (B ^* ) component, the (C ^* ) component, the (SiO ^* ) component, and the (ZrO ^* ) component, an aqueous rust preventive additive is further added. It may be included. As such an anti-rust additive, it exhibits a corrosion-inhibiting function in the anti-rust film, and can be dissolved, uniformly dispersed or suspended in the anti-rust treatment agent of the present invention, and designated as a chemical substance management promotion method Any substance other than chemical substances may be used. Examples of such anticorrosive additives include organic or inorganic compounds having various metal-adsorbing functional groups in the molecule, such as various thiols, amines, carboxylates, thiosulfates, tungstic acid. Salts, phosphates, phosphites, hypophosphites, and various crosslinking agents, such as silane coupling agents other than the (SiO ^* ) component, titanium coupling agents, and anticorrosive pigments, etc. Is mentioned. The rust preventive additive may be added directly to the treatment agent of the present invention, or may be added to the treatment agent after dissolving, dispersing or suspending in water in advance. A wetting agent is used to increase the wettability between the rust preventive additive and water, a dispersant (surfactant) is used to increase the dispersibility of the rust preventive additive in the treatment agent, and a wetting agent and a dispersion are used. A thickener may be added in order to use an agent together or to prevent sedimentation of particles.

  The rust preventive film and the rust preventive treatment agent of the present invention may contain various inorganic or organic compounds in addition to the rust preventive additive as long as the purpose is not impaired. . Examples of such additives include inorganic or organic lubricants, inorganic or organic colloidal particles, various inorganic or organic pigments, various aqueous resins, and the like. When adding various inorganic or organic compounds such as these, the rust preventive film of the present invention, and 20% by mass or less of the total mass of the rust preventive film so as not to impair the purpose of the rust preventive agent, And addition of 20 mass% or less is good with respect to the non-volatile matter total mass of a rust preventive agent.

  In the present invention, the metal to be coated with the rust preventive film may be any metal used in each industrial field as a metal member. For example, aluminum, titanium, zinc, copper, nickel, steel, etc. are applicable. . Among these, when steel is used, the components are not particularly limited, and may be ordinary steel or steel containing additive elements such as Cr.

  Further, the surface of the steel may have a coating plating layer, but the type thereof is not particularly limited, and the applicable plating layer is, for example, any one of zinc, aluminum, cobalt, tin, and nickel. Examples thereof include plating and alloy plating containing these metal elements and other metal elements and non-metal elements. The method for forming the plating layer is not particularly limited, and for example, electroplating, electroless plating, hot dipping, vapor phase plating, or the like can be used. The plating method may be either a continuous type or a batch type. For example, in hot dipping, the continuous type is mainly used for thin plate materials and wire materials, and the batch type plating is used for pipes, rolled materials, processed products, By forming into final products such as bolts, nuts, cast forgings, etc. and then immersing them in a hot dipping bath (so-called post-plating).

  In addition, as the treatment after plating on the steel sheet, there may be zero spangle treatment which is uniform appearance after hot dipping, annealing treatment which is a modification treatment of the plating layer, temper rolling for surface condition and material adjustment, etc. However, these are not particularly limited in the present invention, and any of them can be applied.

In this invention, you may provide the base-treatment film | membrane which does not contain the designated chemical substance of the chemical substance management promotion method in the interface of a rust preventive film | membrane and a metal. Although the film composition is not particularly limited, it is preferably formed of a compound having excellent adhesion and corrosion inhibition ability with respect to each of the metal surface and the upper rust preventive film. For example, metal compounds containing one or more of zirconium, tungsten or rare earth elements, phosphates other than the metal compounds, phosphites, hypophosphites, compounds having a siloxane bond, Examples thereof include one or more compounds selected from silane coupling agents, titanium coupling agents and the like other than the SiO ^* component.

In the present invention, as a method of forming a rust preventive film on a metal surface or a base treatment film on the metal surface, a method of applying the rust preventive agent on at least a part of the metal surface and drying is preferable. On the metal surface coated with the antirust treatment agent, the (X ^* ) component, or the (A ^* ) component, (B ^* ) component, (C ^* ) component, (SiO ^* ) component, ( ZrO ^* ) component forms a dense polymer composite or crosslinked polymer, and some of these components may react with the surface of the metal surface or the metal surface to improve the film adhesion. There is no particular limitation as long as it can be performed. As such a method, for example, after metal dip to the rust preventive agent, rust preventive agent roll coat, bar coat, brush coat, spray, etc., it may be heated and dried with hot air etc. Application and film formation may be carried out by the method described above, and the method is not limited to those described here. However, from the viewpoint of stable production, it is more preferable that the metal surface temperature reaches 60 ° C. or higher after coating.

  In this invention, the coating film which does not contain the chemical substance designated by the chemical substance management promotion method may be formed on the rust preventive film. The composition of the coating film is not particularly limited, but it is preferable that the coating film has excellent adhesion to the rust-proof film. For example, various organic resin coatings, inorganic coatings, organic-inorganic mixed coatings, and multilayer coatings obtained by combining these coatings.

(X) component in the rust preventive film, or (A) component, (B) component, (C) component, (SiO) component, (ZrO) component, and ( X ^* ) component, or (A ^* ) component, (B ^* ) component, (C ^* ) component, (SiO ^* ) component, (ZrO ^* ) component existence confirmation (identification) method and quantitative method Any method may be used. In the case of a rust preventive film, in the film, the (X) component that is an organic compound, or the (A) component, the (B) component, the (C) component, and the (SiO) component that is an inorganic atomic group or (ZrO) Components are bonded to each other to form an organic-inorganic polymer composite or organic-inorganic cross-linked polymer, so in the product obtained by heating and thermal decomposition of the film rather than analyzing the film as it is. It is often easier to identify and quantify each component when analyzing the organic components. Therefore, for example, the (X) component that is an organic compound, or the (A) component, the (B) component, and the (C) component are mixed with the pyrolysis GC-MS method (the sample is thermally decomposed and the decomposition product mixed gas). Can be analyzed using a gas chromatograph and a method in which each decomposition product is identified and quantified by mass spectrometry. The analysis by the pyrolysis GC-MS method is, for example, thermally decomposing a film of about several tens mg removed from the surface of a metal member at 500 ° C. for 5 seconds, and from the quantitative analysis result of each decomposition product, the component (X) or , (A) component, (B) component, and (C) component are determined to be present in the film, and if present, the content in the film is calculated. In addition, the (SiO) component or the (ZrO) component, which is an inorganic atomic group having no organic group, can be identified and quantified by the following method, for example. First, a metal member coated with a rust preventive film is immersed in hydrofluoric acid, and the organic-inorganic polymer composite and the organic-inorganic crosslinked polymer in the film are separated from other components. When hydrofluoric acid is used, the metal portion of the metal member (all metals other than platinum and gold) can be dissolved and removed, and SiO ₂ -based inorganic additives such as colloidal silica, ZrO ₂ such as zirconium oxide, etc. Even when inorganic inorganic additives are contained in the film, they can be easily dissolved and removed, and organic-inorganic polymer composites, organic-inorganic crosslinked polymers, organic resins, organic compounds, etc. that are not affected by hydrofluoric acid It remains as a solid. Next, silicon dioxide (SiO ₂ ) obtained by thermally decomposing this residue in air at 500 ° C. for 5 minutes, zirconium oxide (ZrO ₂ ), atomic absorption analysis, analysis using wide-angle X-ray diffraction method, (SiO) component contained in the organic-inorganic polymer composite or organic-inorganic cross-linked polymer by quantifying by any of X-ray fluorescence analysis etc. and removing the mass of one oxygen from their mass And (ZrO) component can be quantified.

Since (X ^* ) component, (A ^* ) component, (B ^* ) component, (C ^* ) component, (SiO ^* ) component, and (ZrO ^* ) component in the anti-rust treatment agent all have organic groups, It can be quantified by using mass spectrometry, infrared spectroscopic analysis and the like of each compound after separation by liquid chromatography.

From the quantitative values of the above components, in the case of a rust prevention film, the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (> C = O) of the active hydrogen-containing group contained in the component (X) ( ≡P = O) total mass [CSP] and nitrogen atom which is the central atom of amino group (—NH ₂ ), hydroxyl group (—OH) or mercapto group (—SH) contained in the component (X) (N), the sum of the masses of oxygen atoms (O) or sulfur atoms (S) [NOS] and the silicon oxide group (≡Si-O-,> Si = O included in the (SiO) component) 1 type or 2 types) and the zirconyl atomic group (> Zr = O, ≡Zr-O- or any one or more of zirconyl ions (ZrO ²⁺ )) contained in the (ZrO) component) Calculate the total [SZO]. In the case of a rust preventive film containing (A) component, (B) component, and (C) component, the carbonyl atom group (> C = O) contained in (A) component, (B) component, (C) component Calculate the total mass [CO].

In the case of a rust inhibitor, the mass of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the component (X ^* ) the sum [CSP ^*] of the (X ^*) amino groups present in component (-NH _2), nitrogen atom is the central atom of a hydroxyl group (-OH) or mercapto group (-SH) (N), oxygen Total [NOS ^* ] of mass of atom (O) or sulfur atom (S), silicon oxide atomic group ≡Si-O- contained in the (SiO ^* ) component, and zirconyl atom contained in the (ZrO ^* ) component The total mass [SZO ^* ] of the group (> Zr = O, ≡Zr-O- or one or more of zirconyl ions (ZrO ²⁺ )) is calculated. (A ^*) component, (B ^*) component, (C ^*) in the case of rust agents containing components, (A ^*) component, (B ^*) component, (C ^*) carbonyl atomic group included in the component The total mass [CO ^* ] of (> C = O) is calculated.

In addition, among the components of the rust preventive film to be investigated, when it is known that the component (X) is limited to a component containing a carbonyl group (> C = O), or a component of the rust preventive film to be investigated Is known to be any of (A) component, (B) component, and (C) component containing a carbonyl group (> C = O), and further, a constituent component of the rust preventive agent to be investigated Among these, when it is known that the component (X ^* ) is limited to a component containing a carbonyl group (> C = O), or the constituent component of the rust inhibitor is carbonyl group (> C = O ) Containing (A ^* ) component, (B ^* ) component, and (C ^* ) component, it is known that [CSP], [CSP ^* ], [CO] or [CO ^* ] Can be quantified comparatively easily by spectroscopic analysis of the rust preventive film or rust preventive agent as it is. For example, quantification by strong infrared characteristic absorption of carbonyl group (absorption spectrum based on CO stretching vibration, appearance wave number is around 1700 cm ^-1 ), and in the case of rust preventive agent, UV absorption spectrum of solution (CO The wavelength spectrum of the absorption spectrum can be determined by 270-300 nm.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples.

[Metal type]
1. EG: Electro-galvanized steel sheet (thickness 0.8mm)
2. GA: Alloyed hot-dip galvanized steel sheet (thickness 0.8mm)

[Formation of rust prevention film]
1. Anticorrosive film of the present invention The (X ^* ) component, the (SiO ^* ) component, and the (ZrO ^* ) component of the present invention were used as constituents of the aqueous rust preventive agent. The chemicals used are shown in Tables 1 and 2. Of the components (X ^* ) used for the formation of the rust-preventive film, those corresponding to any of the (A ^* ) component, (B ^* ) component, (C ^* ) component, (A ^* ) component, The (B ^* ) component and (C ^* ) component are listed separately. The (A ^* ) component, (B ^* ) component, and (C ^* ) component used here are all (X ^* ) components, and any of the (A ^* ) component, (B ^* ) component, and (C ^* ) component Or not (X ^* ) component (for example, (A ^* ) component, (B ^* ) component, (C ^* ) component that dissolves less than 1.0 g in 100 g of water at 20 ° C.), or (A ^* ) component, (B ^* ) component, and (C ^* ) component having a molecular weight exceeding 400) were not used.

Water was added to the (X ^* ) component in Table 1, and the (SiO ^* ) component or (ZrO ^* ) component was further added to prepare the aqueous rust preventive agent of the present invention. The total mass [CSP ^* ] of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the (X ^* ) component, wherein (X ^*) amino groups present in component (-NH _2), nitrogen atom is the central atom of a hydroxyl group (-OH) or mercapto group (-SH) (N), oxygen atom (O) or sulfur atom ( the total mass of S) [NOS ^*] to the combined ^{([CSP *] + [NOS} *]) and, (SiO ^*) silicon oxide atomic group ≡Si-O-and contained in component (ZrO ^*) component The ratio of the zirconyl atomic group (> Zr = O, ≡Zr-O- or any one or more of zirconyl ions (ZrO ²⁺ ) contained in to the total mass [SZO ^* ] ([CSP ^* ]) + [NOS ^* ]): [SZO ^* ] was determined from the amount of the (X ^* ) component, (SiO ^* ) component, and (ZrO ^* ) component added. This rust preventive is applied to the metal surface with a bar coater, left in a hot air oven at 250 ° C. for about 10 seconds so that the metal surface temperature reaches 80 ° C., dried to form a film, and allowed to cool. The test material was used. Here, the total mass of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the component (X) in the film [CSP And a nitrogen atom (N), an oxygen atom (O) or sulfur that is the central atom of the amino group (—NH ₂ ), hydroxyl group (—OH) or mercapto group (—SH) contained in the component (X) The total of the masses of atoms (S) [NOS] ([CSP] + [NOS]) was quantified from the intensity of infrared characteristic absorption of the target functional group. Further, a silicon oxide atomic group (≡Si-O-, any one or two of Si = O) contained in the (SiO) component in the film and a zirconyl atomic group contained in the (ZrO) component (> The total mass [SZO] of Zr = O, ≡Zr-O- or zirconyl ion (ZrO ²⁺ ) is one or two or more) is obtained by thermally decomposing the film in air at 500 ° C for 5 minutes. It calculated from the mass of the obtained silicon dioxide (SiO ₂ ) and zirconium oxide (ZrO ₂ ).

2. Comparative material
(1) (X ^* ) component of the present invention shown in Table 1, organic compounds other than (X ^* ) component, and (SiO ^* ) component of the present invention other than (SiO ^* ) component shown in Table 2 silane compounds, (ZrO ^*) component of the present invention, a zirconyl compound other than (ZrO ^*) component was used. In the same manner as described above, water was added to the (X ^* ) component, and further, a silane compound other than the (SiO ^* ) component or a zirconyl compound other than the (ZrO ^* ) component was added to prepare a treatment agent. It was applied onto a metal surface, dried by heating, and formed into a film. In addition, water was added to an organic compound other than the (X ^* ) component, and further, the (SiO ^* ) component or the (ZrO ^* ) component of the present invention was added to prepare a treatment agent, as described above. It was applied onto a metal surface, dried by heating, and formed into a film.

(2) The total mass of carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in component (X ^* ) [CSP ^* And a nitrogen atom (N), an oxygen atom (O) or a central atom of the amino group (—NH ₂ ), hydroxyl group (—OH) or mercapto group (—SH) contained in the component (X ^* ) The sum of the masses of sulfur atoms (S) [NOS ^* ] ([CSP ^* ] + [NOS ^* ]), the silicon oxide atomic group ≡Si-O- contained in the (SiO ^* ) component, and the above Mass with total mass [SZO ^* ] of zirconyl atomic group (> Zr = O, ≡Zr-O- or one or more of zirconyl ions (ZrO2 ⁺ )) contained in (ZrO ^* ) component A treatment agent having a ratio of ([CSP ^* ] + [NOS ^* ]): [SZO ^* ] = 98: 2 or 5:95 was prepared, applied to a metal surface in the same manner as described above, dried by heating, and formed a film. .

The carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the organic compound in the treating agent (1) or (2) above. total mass and [CSP ^*], an amino group (-NH _2), nitrogen atom is the central atom of a hydroxyl group (-OH) or mercapto group (-SH) (N), oxygen atom (O) or sulfur atom ( the total mass of S) [NOS ^*] to the combined ^{([CSP *] + [NOS} *]) and, (SiO ^*) silicon oxide atomic group ≡Si-O-and contained in component (ZrO ^*) component The ratio ([CSP ^* ]) to the total mass [SZO ^* ] of the zirconyl atomic group (> Zr = O, ≡Zr-O- or any one or more of zirconyl ions (ZrO ²⁺ )) contained in + [NOS ^* ]): [SZO ^* ] was determined from the amount of the organic compound, silane compound, and zirconyl compound used. In addition, with respect to what can be formed on the metal surface, the mass of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the film The total [CSP] and the nitrogen atom (N), oxygen atom (O) which is the central atom of the amino group (—NH ₂ ), hydroxyl group (—OH) or mercapto group (—SH) contained in the component (X) ) Or the sum of the masses of sulfur atoms (S) [NOS] ([CSP] + [NOS]) was quantified from the intensity of infrared characteristic absorption of the target functional group. Silicon oxide group (≡Si-O-,> Si = O, one or two) contained in the (SiO) component contained in the film and zirconyl group (> Zr =) contained in the (ZrO) component The total mass [SZO] of O, ≡Zr-O- or zirconyl ion (ZrO ²⁺ ) is obtained by thermally decomposing the film in air at 500 ° C for 5 minutes. The mass was calculated from the masses of silicon dioxide (SiO ₂ ) and zirconium oxide (ZrO ₂ ).

Tables 3 to 6 show the constituents of each treatment agent and the mass ratio ([CSP ^* ] + [NOS ^* ]): [SZO ^* ]. The mass ratio ([CSP] + [NOS]): [SZO] is shown in Tables 7 to 10.

[Formation of comparative chromate film]
As a comparative material for the above-mentioned treatment film, each metal described above was subjected to a coating chromate treatment with a coating amount of 14 mg / m ² of Cr using a coating chromate treatment agent ZM1300-AN manufactured by Nihon Parkerizing Co., Ltd. The corrosion resistance was relatively compared with the metal on which the rust-proofing film was formed.

[Evaluation of corrosion resistance]
(1) Flat plate corrosion resistance For the above rust-prevented metal materials and comparative chromate materials, a salt spray test in accordance with JIS-Z2371 was performed, and the area where white rust was generated after 48 hours was compared. The pass / fail of the corrosion resistance was judged by comparing the white rust generation area of the chromate material relative to each other. Assuming that the white rust generation area ratio of rust-proof metal and comparative chromate material is X% and Y%, respectively, the judgment criteria are
Score 4 X <Y
3 X ≒ Y
2 Y <X <2Y
1 2Y ≦ X
A score of 3 or higher was accepted.

(2) Corrosion resistance of the processed part The above-mentioned rust-proof metal material and comparative chromate material are subjected to 7 mm Erichsen processing, a salt spray test in accordance with JIS-Z2371 is performed, and the area where white rust occurs in the processed part after 48 hours is measured. And the pass / fail of the process part corrosion resistance was determined by comparing the white rust generation | occurrence | production area of the comparative chromate material corresponding to a rust prevention metal material. The judgment criteria are the same as in the case of the flat plate corrosion resistance,
Score 4 X <Y
3 X ≒ Y
2 Y <X <2Y
1 2Y ≦ X
A score of 3 or higher was accepted.

  The evaluation results of the corrosion resistance are collectively shown in Tables 7 to 10.

  When a rust preventive agent that satisfies the requirements of the present invention is applied to a metal surface and then dried by heating, a metal member coated with a rust preventive film that satisfies the requirements of the present invention is obtained, and its corrosion resistance is comparable to the level of the chromate treatment material. It turns out that it is. These rust preventive agents and the rust preventive coating that coats the surface of the metal member do not contain chemical substances designated by the Chemical Substance Management Promotion Law and have low environmental impact. Moreover, when the rust preventive agent of the present invention is used, a film can be easily formed by a one-step treatment on a metal surface.

On the other hand, when the organic compound component contained in the treatment agent is other than the (X ^* ) component used in the present invention, or when the silane compound contained in the treatment agent is other than the (SiO ^* ) component used in the present invention, the treatment When the compound contained in the agent is a component other than the (ZrO ^* ) component used in the present invention, even if the film cannot be formed on the metal surface or the film can be formed, the corrosion resistance of the site where the film is formed is the level of the chromate treatment material. Less than Further, the organic compound component contained in the treatment agent is the (X ^* ) component used in the present invention, and the silane compound and zirconyl compound contained in the treatment agent are each used in the present invention (SiO ^* ) component, ( ZrO ^* ) component of the active hydrogen-containing group carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) contained in the component (X ^* ). total mass and [CSP ^*], wherein (X ^*) amino groups present in component (-NH _2), nitrogen atom is the central atom of a hydroxyl group (-OH) or mercapto group (-SH) (N), The sum of the masses of oxygen atoms (O) or sulfur atoms (S) [NOS ^* ] ([CSP ^* ] + [NOS ^* ]) and the silicon oxide atomic group ≡Si contained in the (SiO ^* ) component total mass of -O- and (ZrO ^*) zirconyl atomic group present in component (> Zr = O, ≡Zr- O- or zirconyl ions (ZrO ²⁺⁾ any one or two or more) [SZO ^* ] ratio of ^{([CSP *] + [NOS} *]): [SZO *] is allowed in the present invention If you are outside the range that is, it does not extend to the level of chromate treated material corrosion resistance of the portion to form a film.

Claims (20)

A metal member having at least a part of the surface coated with a rust preventive film,
The rust-preventing film is composed of any one or more of the following (X) components, any one or more of the (SiO) and (ZrO) components, The total mass [CSP] of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the component (X), and the above (X ) The mass of the nitrogen atom (N), oxygen atom (O) or sulfur atom (S) that is the central atom of the amino group (—NH ₂ ), hydroxyl group (—OH) or mercapto group (—SH) contained in the component [NOS], silicon oxide atomic group (≡Si—O—, any one or two of> Si = O) contained in the (SiO) component, and zirconyl atom contained in the (ZrO) component Dan relationship between the total mass of the (> Zr = O, ≡Zr- O- or zirconyl ions (either one or two or more of ^{ZrO 2+)) [SZO],} ([CSP] + [NOS] ): [SZO] = 97: 3 to 10:90.
Component (X): an organic compound having a molecular weight of 400 or less and dissolved in 100 g of water at 20 ° C., having 2 or more active hydrogen-containing groups in one molecule, and 2 groups of the active hydrogen-containing groups The above is a functional group containing a carbonyl group (> C = O), a functional group containing a sulfinyl group (> S = O), a functional group containing a phosphoryl group (≡P = O), an amino group (-NH ₂ ), An organic compound that is one or more of a hydroxyl group (—OH) or a mercapto group (—SH), or a part or all of the active hydrogen is eliminated from the active hydrogen-containing group of the organic compound One or both of the atomic groups.
(SiO) component: silicon oxide atomic group (≡Si-O-,> Si = O, either one or two).
(ZrO) component: Zirconyl atomic group (> Zr = O, ≡Zr-O- or one or more of zirconyl ions (ZrO ²⁺ )). The functional group containing the carbonyl group (> C═O) is one or more of a carboxyl group (—COOH), an aldehyde group (—CHO), and an amide group (—CONH ₂ ). The metal member according to 1. 2. The metal member according to claim 1, wherein the functional group containing a sulfinyl group (> S═O) is one or two of a sulfonic acid group (—SO ₃ H) and a sulfinic acid group (—SO ₂ H). . The functional group containing the phosphoryl group (≡P = O) constitutes a phosphate ester of the structural formula O = POH (OR) ₂ or O = P (OH) ₂ (OR) (R is a hydrocarbon group) _2. The metal member according to claim 1, wherein one or two of the polar atomic groups O═P (OH) <or O═P (OH) ₂ — is used. 2. The metal member according to claim 1, wherein the component (X) is one or more of the following components (a), (b), and (c).
Component (a): Aliphatic or aromatic carboxylic acid having a molecular weight of 400 or less and having two or more carboxyl groups (—COOH) in one molecule, dissolved in 100 g of water at 20 ° C. A residue of carboxylic acid from which some or all of hydrogen has been eliminated from the carboxyl group of the acid.
Component (b): Aliphatic which dissolves in 1.0 g or more in 100 g of water at 20 ° C., has a molecular weight of 400 or less, and the total number of carboxyl groups (—COOH) and hydroxyl groups (—OH) in one molecule is 2 or more An aromatic hydroxy acid or a residue of a hydroxy acid from which part or all of hydrogen has been eliminated from the carboxyl group or hydroxyl group of the hydroxy acid.
Component (c): An aliphatic compound having 1.0 g or more dissolved in 100 g of water at 20 ° C. and having a molecular weight of 400 or less, and the total number of carboxyl groups (—COOH) and aldehyde groups (—CHO) in one molecule is 2 or more Aromatic aldehyde acid, or a part or all of hydrogen desorbed from the carboxyl group of the aldehyde acid, or one from the aldehyde group of the aldehyde acid irrespective of the presence or absence of hydrogen desorption from the carboxyl group. Aldehyde acid residue from which part or all of hydrogen or oxygen has been eliminated. A metal member having at least a part of the surface coated with a rust preventive film,
The rust-preventing film is shown in the following, (A) component, (B) component, any one or more of (C) component, any one of (SiO) component and (ZrO) component or 2 or more types as the main constituent, the total (CO) of the mass of the carbonyl atom group (> C = O) contained in the component (A), the component (B), the component (C), and the (SiO) Silicon oxide atomic group (≡Si-O-,> Si = O, one or two) included in the component and zirconyl atomic group (> Zr = O, ≡Zr-O) included in the (ZrO) component -The mass ratio of the mass of any one or more of zirconyl ions (ZrO ²⁺ ) to [SZO] is [CO]: [SZO] = 97: 3 to 10:90 A metal member characterized by.
Component (A): an aliphatic carboxylic acid having 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH), and 0 to 6 carbon atoms excluding the carboxyl carbon, or the fat A residue of a carboxylic acid from which some or all of the hydrogen has been eliminated from the carboxyl group of the group carboxylic acid.
Component (B): an aliphatic having 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH) and hydroxyl groups (-OH), and 0 to 6 carbon atoms excluding the carboxyl carbon Hydroxy acid or a residue of hydroxy acid from which part or all of hydrogen has been eliminated from the carboxyl group or hydroxyl group of the hydroxy acid.
Component (C): The total number of carbon atoms is 2 to 10, the total number of carboxyl groups (-COOH) and aldehyde groups (-CHO) is 2 to 8, and the number of carbon atoms excluding carboxyl and aldehyde carbons is 0 to 6. Some aliphatic aldehyde acids, or some or all of hydrogen desorbed from the carboxyl groups of the aldehyde acids, or from the aldehyde groups of the aldehyde acids regardless of the presence or absence of hydrogen desorption from the carboxyl groups Residues of aldehyde acids from which some or all of hydrogen or oxygen has been eliminated.
(SiO) component: silicon oxide atomic group (≡Si-O-,> Si = O, either one or two).
(ZrO) component: Zirconyl atomic group (> Zr = O, ≡Zr-O- or one or more of zirconyl ions (ZrO ²⁺ )). The aliphatic carboxylic acid is a saturated aliphatic dicarboxylic acid having 0 to 5 carbon atoms excluding the carboxyl carbon (the structural formula is HOOC— (CH ₂ ) _(a1) —COOH. (A1) is an integer and 0 ≦ (a1 ) ≦ 5 — (CH ₂ ) _{(a1) —The} chain portion may contain an aliphatic group other than the methylene group —CH ₂ — or an aliphatic group substituted with a part of hydrogen of the methylene group.) or unsaturated aliphatic dicarboxylic acids (structure of carbon atoms except for the carboxyl carbon _{2-5, HOOC- (CH 2) (b1} ) -CH = CH- (CH 2) (b2) -COOH. ( b1) and (b2) are integers of 0 or more and 0 ≦ (b1) + (b2) ≦ 3 .- (CH ₂ ) _(b1) -chain,-(CH ₂ ) _(b2) - 7. An aliphatic group other than a methylene group —CH ₂ — or an aliphatic group substituted with a part of hydrogen of a methylene group may be included. The metal member as described. Wherein the aliphatic carboxylic acid is oxalic acid (HOOC-COOH), malonic acid (HOOC-CH ₂ -COOH), succinic acid _{(HOOC- (CH 2) 2 -COOH} ), glutaric acid (HOOC- (CH _{2) 3} - COOH), adipic acid (HOOC- (CH ₂ ) ₄ -COOH), α-ketoglutaric acid (HOOC-CH ₂ -CH ₂ CO-COOH), maleic acid (cis-HOOC-CH = CH-COOH) 8. The metal member according to claim 5, 6 or 7, which is one type or two or more types. The aliphatic hydroxy acid is an aliphatic hydroxy acid having 1 to 4 carbon atoms excluding the carboxyl carbon (the structural formula is CH _(c1) (-COOH) _(c2) (-OH) _(c3) -[CH _{(d1 )} (-COOH) _(d2) (-OH) _(d3) ] _(p1) -[CH _(e1) (-COOH) _(e2) (-OH) _(e3) ] _(p2) -[CH _(f1) ( -COOH) _(f2) (-OH) _(f3) ] _(p3) (p1), (p2), (p3) is 0 or 1. (c1) to (c3), (d1) to (d3), (e1)-(e3), (f1)-(f3) are all integers of 0 or more, and (c1) + (c2) + (c3) = 3, (d1) + (d2) + (d3) = 2, (e1) + (e2) + (e3) = 2, (f1) + (f2) + (f3) = 3 Total number of carboxyl groups in the molecule (c2) + (d2) + (e2) + ( The metal according to claim 5 or 6, wherein f2) ≧ 1, the total number of hydroxyl groups in the molecule (c3) + (d3) + (e3) + (f3) ≧ 1), or one or more of them. Element. The aliphatic hydroxy acid is glycolic acid (CH ₂ (OH) -COOH), lactic acid (CH ₃ CH (OH) -COOH), glyceric acid (CH ₂ (OH) -CH (OH) -COOH), citric acid (HOOC-CH ₂ -C (OH) (COOH) -CH ₂ -COOH), tartaric acid (HOOC-CH (OH) -CH (OH) -COOH), or malic acid (HOOC-CH (OH) -CH 10. The metal member according to claim 5, 6 or 9, which is any one or more of ( _2- COOH). The aliphatic aldehyde acid is an aliphatic aldehyde acid having a carbon number of 0 to 4 excluding carboxyl carbon and aldehyde carbon (the structural formula is CHO-COOH or CH _(g1) (-COOH) _(g2) (-CHO ) _(g3) -[CH _(h1) (-COOH) _(h2) (-CHO) _(h3) ] _(q1) -[CH _(i1) (-COOH) _(i2) (-CHO) _(i3) ] _{( q2)} -[CH _(j1) (-COOH) _(j2) (-CHO) _(j3) ] _(q3) ((q1), (q2), (q3) is 0 or 1. (g1) to (g3) , (H1) to (h3), (i1) to (i3), (j1) to (j3) are all integers of 0 or more, (g1) + (g2) + (g3) = 3, (h1) + (h2) + (h3) = 2, (i1) + (i2) + (i3) = 2, (j1) + (j2) + (j3) = 3 Total number of carboxyl groups in the molecule (g2) + (h2) + (i2) + (j2) ≧ 1, the total number of aldehyde groups in the molecule (g3) + (h3) + (i3) + (j3) ≧ 1) Any one or more of them The metal member according to claim 5 or 6.   12. The metal member according to claim 5, 6 or 11, wherein the aliphatic aldehyde acid is glyoxylic acid (CHO-COOH). Metal member according to any one of claims 1 to 12 adhered amount is 0.02g / m ² ~5.0g / m ² of the rust preventing film. As shown below, any one or more of (X ^* ) component, and one or more of (SiO ^* ) component and (ZrO ^* ) component, water as the main constituent, The total mass [CSP ^* ] of the carbonyl group (> C = O), sulfinyl group (> S = O) or phosphoryl group (≡P = O) of the active hydrogen-containing group contained in the component (X ^* ), X ^* ) component nitrogen atom (N), oxygen atom (O) or sulfur atom (S) as the central atom of amino group (-NH ₂ ), hydroxyl group (-OH) or mercapto group (-SH) The total mass of [NOS ^* ], the silicon oxide atomic group (≡Si-O-) contained in the (SiO ^* ) component and the zirconyl atomic group (> Zr = O, ≡) contained in the (ZrO ^* ) component The relationship between the total mass [SZO ^* ] of Zr-O- or zirconyl ion (one or more of ZrO2 ⁺ ) ([CSP ^* ] + [NOS ^* ]): [SZO ^* ] = 97: 3 to 10:90.
(X ^* ) component: an organic compound having a molecular weight of 400 or less and dissolved in 100 g of water at 20 ° C. and having 2 or more active hydrogen-containing groups in one molecule, 2 of the active hydrogen-containing groups A functional group containing a carbonyl group (> C = O), a functional group containing a sulfinyl group (> S = O), a functional group containing a phosphoryl group (≡P = O), an amino group (-NH ₂ ) An organic compound that is one or more of hydroxyl group (—OH) or mercapto group (—SH), or a part or all of the active hydrogen-containing groups of the organic compound One or both of the salts substituted with a cation.
(SiO ^* ) component: Reactable with a hydrolyzable alkoxy group (-OR ³ , R ³ is a hydrocarbon group having up to 3 carbon atoms) and an active hydrogen-containing group contained in the (X ^* ) component Silane coupling agent with organic functional group.
(ZrO ^* ) component: Zirconyl ion (ZrO ²⁺ ) and acid group salt. 15. The antirust treatment agent according to claim 14, wherein the (X ^* ) component is one or more of the following components (a ^* ), (b ^* ), and (c ^* ).
(a ^* ) component: Aliphatic or aromatic carboxylic acid or fatty acid dissolved in 100 g of water at 20 ° C. in an amount of 1.0 g or more, having a molecular weight of 400 or less, and having two or more carboxyl groups (—COOH) in one molecule Or aromatic carboxylates.
Component (b ^* ): Aliphatic, dissolved in 100 g of water at 20 ° C, 1.0 g or more, molecular weight 400 or less, and the total number of carboxyl groups (-COOH) and hydroxyl groups (-OH) in one molecule is 2 or more Or an aromatic hydroxy acid or an aliphatic or aromatic hydroxy acid salt.
Component (c ^* ): Aliphatic, dissolved in 100 g of water at 20 ° C. in an amount of 1.0 g or more, having a molecular weight of 400 or less, and the total number of carboxyl groups (—COOH) and aldehyde groups (—CHO) in one molecule is 2 or more Or an aromatic aldehyde acid, or an aliphatic or aromatic aldehyde salt. Any one or more of (A ^* ) component, (B ^* ) component, (C ^* ) component, and (SiO ^* ) component and (ZrO ^* ) component shown below The total [CO ^* ] of the mass of the carbonyl atom group (> C = O) contained in the (A ^* ) component, the (B ^* ) component, and the (C ^* ) component, with at least the seeds and water as the main constituent component , Silicon oxide atomic group (≡Si-O-) contained in the (SiO ^* ) component and zirconyl atomic group (> Zr = O, ≡Zr-O-, zirconyl ion (ZrO) contained in the (ZrO ^* ) component. ²⁺ )), and the total mass ratio of [SZO ^* ] is [CO ^* ]: [SZO ^* ] = 97: 3 to 10:90, Antirust treatment agent.
Component (A ^* ): aliphatic carboxylic acid or aliphatic carboxylic acid having 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH), and 0 to 6 carbon atoms excluding carboxyl carbon Acid salt.
Component (B ^* ): Fat with 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH) and hydroxyl groups (-OH), and 0 to 6 carbon atoms excluding carboxyl carbon Group hydroxy acid or aliphatic hydroxy acid salt.
Component (C ^* ): 2 to 10 total carbon atoms, 2 to 8 total carboxyl groups (-COOH) and aldehyde groups (-CHO), 0 to 6 carbon atoms excluding carboxyl and aldehyde carbons An aliphatic aldehyde acid or an aliphatic aldehyde salt.
(SiO ^* ) component: a hydrolyzable alkoxy group (-OR ³ , R ³ is a hydrocarbon group having up to 3 carbon atoms) and an organic functional group capable of reacting with a carboxyl group, a hydroxyl group or an aldehyde group Has silane coupling agent.
(ZrO ^* ) component: Zirconyl ion (ZrO ²⁺ ) and acid group salt. The (SiO ^* ) component comprises aminoalkylsilane [NH ₂ -R ^* -Si (-OR ³ ) ₃ ] and epoxyalkylsilane [CH _2- (O) -CH-R ^* -Si (-OR ³ ) ₃ The rust preventive according to claim 14 or 16, wherein R ^* is an organic group having up to 7 carbon atoms, and R ³ is a hydrocarbon group having up to 3 carbon atoms. Processing agent. The (SiO ^* ) component is γ- (2-aminoethyl) aminopropyltrimethoxysilane [NH ₂ (CH ₂ ) ₂ —NH (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ ] and γ-glycidoxy The propyltrimethoxysilane [CH ₂ — (O) —CH—CH ₂ O— (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ ] is one or more of the following: Rust preventive agent as described. The (ZrO ^* ) component is zirconyl formate (ZrO (HCOO) ₂ ), zirconyl acetate (ZrO (CH ₃ COO) ₂ ), zirconyl propionate (ZrO (C ₂ H ₅ COO) ₂ ), zirconyl butyrate (ZrO ( C ₃ H ₇ COO) ₂ ), oxalic acid (HOOC-COOH) and zirconyl ion salt, malonic acid (HOOC-CH ₂ -COOH) and zirconyl ion salt, or succinic acid (HOOC- (CH ₂ ) _2- 17. The antirust treatment agent according to claim 14 or 16, which is one or more selected from salts of (COOH) and zirconyl ions.   20. A rust prevention treatment method comprising applying the rust prevention treatment agent according to any one of claims 14 to 19 to at least a part of a metal surface and drying to form a rust prevention film.