JP5673642B2 - Metal surface treatment agent, surface treated steel material and surface treatment method thereof, and coated steel material and method for producing the same - Google Patents

Description

  The present invention includes cold rolled steel, hot rolled steel, stainless steel, electrogalvanized steel, hot dip galvanized steel, zinc-aluminum alloy plated steel, zinc-iron alloy plated steel, zinc-magnesium alloy plated steel, For coated steel materials such as zinc-aluminum-magnesium alloy plated steel, aluminum-based plated steel, aluminum-silicon alloy-plated steel, tin-based plated steel, lead-tin alloy-plated steel, chromium-based plated steel, nickel-based plated steel In particular, the present invention relates to a metal surface treatment agent suitable as a surface treatment material, a surface-treated steel material surface-treated with the treatment agent and a surface treatment method thereof, a coated steel material having an upper layer coating thereon, and a method for producing the same.

  Conventionally, chromium-based surface treatment agents such as chromate and phosphate chromate have been used as metal surface treatment agents, and are still widely used today. However, according to recent trends in environmental regulations, the use of chromium may be limited in the future due to the toxicity of chromium, particularly carcinogenicity. Therefore, it has been desired to develop a metal surface treatment agent that does not contain chromium and has the same adhesion and corrosion resistance as the chromate treatment agent.

  Japanese Patent Application Laid-Open No. 11-29724 (Patent Document 1) proposes a non-chromium antirust treatment agent containing a thiocarbonyl group-containing compound and a phosphate ion, and further water-dispersible silica in an aqueous resin. However, although this system is excellent in corrosion resistance, workability and adhesion to the substrate are not sufficient. Japanese Patent Application Laid-Open No. 8-73775 (Patent Document 2) discloses an acidic surface treatment agent containing two types of silane coupling agents. This system has high corrosion resistance and workability after treating a metal surface. Corrosion resistance is insufficient when required.

  In relation to these, JP 2001-316845 A (Patent Document 3) discloses a non-chromate metal surface treatment agent containing a silane coupling agent, water-dispersible silica, zirconium or titanium ion as an essential component. Although the corrosion resistance and workability are improved, the coating property to the base material and the adhesion strength with the upper layer film are insufficient.

  Japanese Patent Application Laid-Open No. 10-60315 (Patent Document 4) discloses a surface treating agent for steel structures containing a silane coupling agent having a specific functional group that reacts with an aqueous emulsion. The corrosion resistance is only for a relatively mild test such as a wet test, and the corrosion resistance is insufficient as compared to a metal surface treatment agent that can withstand a severe corrosion resistance test such as the present invention.

  Japanese Patent Application Laid-Open No. 2000-297093 (Patent Document 5) describes that an imidazole group-containing organosilicon compound is used for a surface treatment agent such as a metal, but it is not satisfactory in terms of corrosion resistance and deep drawability. There wasn't.

  In Japanese Patent Application Laid-Open No. 2007-297648 (Patent Document 6), a surface for rust prevention containing an aqueous emulsion, a compound in which two molecules of β-diketone and two molecules of water are coordinated to a trivalent transition metal ion, and a silane coupling agent. Although the treatment agent is disclosed and the trivalent transition metal complex becomes a hardly soluble compound by drying, it is characteristic in that it exhibits rust prevention ability and coating film adhesion ability. It was not intended to withstand the harsh environment as in the invention, and there was enough room for improvement.

  In view of the above, it has been desired to develop a metal surface treatment agent that can exhibit various properties such as corrosion resistance, work adhesion, coating property, and adhesive strength in a thin film.

JP-A-11-29724 JP-A-8-73775 JP 2001-316845 A Japanese Patent Laid-Open No. 10-60315 JP 2000-297093 A JP 2007-297648 A

  The present invention has been made in view of the above circumstances, and is most suitable for metals, particularly metal-coated steel materials, does not contain chromium, and provides excellent workability, adhesion, and corrosion resistance as a pretreatment for coatings such as paints. An object of the present invention is to provide a non-chromate metal surface treatment agent that can be treated, a surface-treated steel material surface-treated with the treatment agent, a surface treatment method thereof, a coated steel material having an upper film thereon, and a method for producing the same. .

  As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that an organic silicon having a coordinating functional group effective for the development of corrosion resistance and a reactive silyl group capable of binding to the surface of a metal to be coated by a siloxane bond. By making the compound an essential component of the rust preventive agent, it has been found that a metal surface treatment agent that is chromium-free and excellent in corrosion resistance, work adhesion, coating property, and adhesive strength can be obtained, leading to the present invention. It was.

（式中、Ｒは加水分解性基であり、Ｒ’は炭素数１〜４のアルキル基であり、Ａは直鎖状又は分岐鎖状の炭素数１〜６のアルキレン基であり、Ｘは酸素原子又は硫黄原子であり、Ｚは−ＮＨ−、酸素原子又は硫黄原子であり、Ｍは−ＮＨ−、酸素原子又は硫黄原子であり、Ｒ⁴〜Ｒ⁷はそれぞれ独立に水素原子、炭素数１〜６のアルキル基、アルコキシ基もしくはフルオロアルキル基、又はアミノ基であり、この場合Ｒ⁵とＲ⁶が直接結合して該置換基が結合する炭素間で二重結合を形成してもよく、さらにＲ⁴とＲ⁷でこれらが結合する炭素原子と共に脂肪族又は芳香族環骨格を形成してもよい。ｍは１〜３の整数であり、ｎは０〜３の整数である。）
で示される有機ケイ素化合物を必須成分とし、これを水、有機溶媒、又は水と有機溶媒の混合溶媒に溶解してなると共に、水溶性もしくは水分散性樹脂を含むことを特徴とする金属表面処理剤。
［請求項２］
更に、下記一般式（１４）
Ｒ²⁰ _xＳｉ（ＯＲ²¹）_4-x （１４）
（式中、Ｒ²⁰は炭素数１〜２０の非置換又は置換の一価炭化水素基、Ｒ²¹は炭素数１〜８の非置換又は置換一価炭化水素基を示し、ｘは０〜３の整数である。）
で示されるアルコキシシラン又はその部分加水分解縮合物を含むことを特徴とする請求項１記載の金属表面処理剤。
［請求項３］
更に、有機チタン酸エステル類を含むことを特徴とする請求項１又は２記載の金属表面処理剤。
［請求項４］
更に、水分散性シリカ又は有機溶媒分散性シリカを含むことを特徴とする請求項１〜３のいずれか１項記載の金属表面処理剤。
［請求項５］
更に、Ｆｅ，Ｚｒ，Ｔｉ，Ｖ，Ｗ，Ｍｏ，Ａｌ，Ｓｎ，Ｎｂ，Ｈｆ，Ｙ，Ｈｏ，Ｂｉ，Ｌａ，Ｃｅ及びＺｎから選択されるいずれか１種以上の金属の化合物を含むことを特徴とする請求項１〜４のいずれか１項記載の金属表面処理剤。
［請求項６］
更に、チオカルボニル基含有化合物を含むことを特徴とする請求項１〜５のいずれか１項記載の金属表面処理剤。
［請求項７］
更に、リン酸イオンを含むことを特徴とする請求項１〜６のいずれか１項記載の金属表面処理剤。
［請求項８］
鋼材の表面を請求項１〜７のいずれか１項記載の金属表面処理剤で表面処理することを特徴とする鋼材の表面処理方法。
［請求項９］
鋼材が金属被覆鋼材である請求項８記載の表面処理方法。
［請求項１０］
請求項８又は９記載の方法で得られる表面処理鋼材。
［請求項１１］
請求項１〜７のいずれか１項記載の金属表面処理剤で鋼材を処理した後、更に上層被膜層を設けることを特徴とする塗装鋼材の製造方法。
［請求項１２］
請求項１１記載の方法で得られる塗装鋼材。
［請求項１３］
下記一般式（２）

（式中、Ｒは加水分解性基であり、Ｒ’は炭素数１〜４のアルキル基であり、Ａは直鎖状又は分岐鎖状の炭素数１〜６のアルキレン基であり、Ｘは酸素原子又は硫黄原子であり、Ｚは−ＮＨ−、酸素原子又は硫黄原子であり、Ｍは−ＮＨ−、酸素原子又は硫黄原子であり、Ｒ ⁴ 〜Ｒ ⁷ はそれぞれ独立に水素原子、炭素数１〜６のアルキル基、アルコキシ基もしくはフルオロアルキル基、又はアミノ基であり、この場合Ｒ ⁵ とＲ ⁶ が直接結合して該置換基が結合する炭素間で二重結合を形成してもよく、さらにＲ ⁴ とＲ ⁷ でこれらが結合する炭素原子と共に脂肪族又は芳香族環骨格を形成してもよい。ｍは１〜３の整数であり、ｎは０〜３の整数である。）
で示される有機ケイ素化合物を必須成分とし、これを水、有機溶媒、又は水と有機溶媒の混合溶媒に溶解してなる金属表面処理剤で鋼材を処理した後、更に上層被膜層を設けることを特徴とする塗装鋼材の製造方法。
［請求項１４］
請求項１３記載の方法で得られる塗装鋼材。 Accordingly, the present invention provides a metal surface treatment agent, a surface-treated steel material and a surface treatment method thereof, and a coated steel material and a production method thereof as described below.
[Claim 1]
The following general formula (2)

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, A is a linear or branched alkylene group having 1 to 6 carbon atoms, and X is An oxygen atom or a sulfur atom, Z is —NH—, an oxygen atom or a sulfur atom, M is —NH—, an oxygen atom or a sulfur atom, and R ^{4 to} R ⁷ are each independently a hydrogen atom or a carbon number. 1-6 alkyl groups, alkoxy groups or fluoroalkyl groups, or amino groups, in which case R ⁵ and R ⁶ may be directly bonded to form a double bond between the carbons to which the substituent is bonded. Further, an aliphatic or aromatic ring skeleton may be formed together with the carbon atom to which they are bonded at R ⁴ and R ⁷ , m is an integer of 1 to 3, and n is an integer of 0 to 3.)
A metal surface treatment characterized by comprising an organic silicon compound represented by the formula (I) as an essential component, which is dissolved in water, an organic solvent, or a mixed solvent of water and an organic solvent, and contains a water-soluble or water-dispersible resin. Agent.
[Claim 2]
Furthermore, the following general formula (14)
R ²⁰ _x Si (OR ²¹ ) _4-x (14)
Wherein R ²⁰ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to ²⁰ carbon atoms, R ²¹ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and x represents 0 to 3 Is an integer.)
The metal surface treating agent according to claim 1, comprising an alkoxysilane represented by the formula (1) or a partial hydrolysis condensate thereof.
[Claim 3]
The metal surface treatment agent according to claim 1, further comprising an organic titanate ester.
[Claim 4]
The metal surface treatment agent according to claim 1, further comprising water-dispersible silica or organic solvent-dispersible silica.
[Claim 5]
Furthermore, it contains a compound of at least one metal selected from Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn. The metal surface treating agent according to any one of claims 1 to 4, wherein
[Claim 6]
Furthermore, the metal surface treating agent of any one of Claims 1-5 containing a thiocarbonyl group containing compound.
[Claim 7 ]
Furthermore, phosphate ion is included, The metal surface treating agent of any one of Claims 1-6 characterized by the above-mentioned.
[Claim 8 ]
A surface treatment method for a steel material, wherein the surface of the steel material is surface-treated with the metal surface treatment agent according to any one of claims 1 to 7 .
[Claim 9 ]
The surface treatment method according to claim 8 , wherein the steel material is a metal-coated steel material.
[Claim 10 ]
A surface-treated steel material obtained by the method according to claim 8 or 9 .
[Claim 11 ]
A method for producing a coated steel material, further comprising providing an upper coating layer after treating the steel material with the metal surface treatment agent according to any one of claims 1 to 7 .
[Claim 12 ]
A coated steel material obtained by the method according to claim 11 .
[Claim 13]
The following general formula (2)

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, A is a linear or branched alkylene group having 1 to 6 carbon atoms, and X is An oxygen atom or a sulfur atom, Z is —NH—, an oxygen atom or a sulfur atom, M is —NH—, an oxygen atom or a sulfur atom, and R ^{4 to} R ⁷ are each independently a hydrogen atom or a carbon number. 1-6 alkyl groups, alkoxy groups or fluoroalkyl groups, or amino groups, in which case R ⁵ and R ⁶ may be directly bonded to form a double bond between the carbons to which the substituent is bonded. Further , an aliphatic or aromatic ring skeleton may be formed together with the carbon atom to which they are bonded at R ⁴ and R ⁷ , m is an integer of 1 to 3, and n is an integer of 0 to 3.)
After the steel material is treated with a metal surface treatment agent obtained by dissolving the organic silicon compound represented by the above in water, an organic solvent, or a mixed solvent of water and an organic solvent, an upper coating layer is further provided. A method for producing a painted steel material.
[Claim 14]
A coated steel material obtained by the method according to claim 13.

  The metal surface treatment agent of the present invention comprises a silane coupling agent having a coordination property to a metal (ion) as an essential component, and the metal material to be treated and other metal (ion) component and the silane coupling agent In addition to forming a sparingly soluble complex by coordinating bonds and expressing good anti-corrosive ability, it is processed and adhered to the base material and organic / inorganic resin coating layer provided as an upper layer by hydrolyzable silyl group, if necessary Because of its excellent properties, the adhesive strength is high, and therefore the rust and corrosion resistance of the resulting coated steel material is expressed at a high level.

Hereinafter, the present invention will be specifically described.
The metal surface treatment agent of the present invention comprises an organic silicon compound having a coordinating functional group (silane coupling agent) as an essential component and is dissolved in water, an organic solvent or a mixed solvent of water and an organic solvent. is there.

[Organic silicon compound having a coordination functional group (silane coupling agent)]
The organosilicon compound used in the present invention is represented by the following general formulas (1) to (3), and one kind thereof is used alone or two or more kinds are used in combination.

（式中、Ｒは加水分解性基であり、Ｒ’は炭素数１〜４のアルキル基であり、Ａは直鎖状又は分岐鎖状の炭素数１〜６のアルキレン基であり、Ｘは酸素原子又は硫黄原子であり、Ｙは−ＮＨ−又は硫黄原子であり、Ｌ¹、Ｌ²は独立に炭素原子又は窒素原子であり、Ｒ¹〜Ｒ³はそれぞれ独立に水素原子、炭素数１〜６のアルキル基、アルコキシ基もしくはフルオロアルキル基、又はアミノ基であり、Ｒ¹とＲ²又はＲ²とＲ³でこれらが結合している炭素原子及びＬ²と共に環骨格を形成してもよい。ｍは１〜３の整数であり、ｎは０〜３の整数である。）

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, A is a linear or branched alkylene group having 1 to 6 carbon atoms, and X is An oxygen atom or a sulfur atom; Y is —NH— or a sulfur atom; L ¹ and L ² are each independently a carbon atom or a nitrogen atom; and R ^{1 to} R ³ are each independently a hydrogen atom and a carbon number of 1 -6 alkyl group, alkoxy group or fluoroalkyl group, or amino group, R ¹ and R ² or R ² and R ³ may form a ring skeleton together with the carbon atom to which they are bonded and L ² M is an integer of 1 to 3, and n is an integer of 0 to 3)

（式中、Ｒ、Ｒ’、Ａ、Ｘ、ｍ及びｎは上記の通りであり、Ｚは−ＮＨ−、酸素原子又は硫黄原子であり、Ｍは−ＮＨ−、酸素原子又は硫黄原子であり、Ｒ⁴〜Ｒ⁷はそれぞれ独立に水素原子、炭素数１〜６のアルキル基、アルコキシ基もしくはフルオロアルキル基、又はアミノ基であり、この場合Ｒ⁵とＲ⁶が直接結合して該置換基が結合する炭素間で二重結合を形成してもよく、さらにＲ⁴とＲ⁷でこれらが結合する炭素原子と共に脂肪族又は芳香族環骨格を形成してもよい。）

Wherein R, R ′, A, X, m and n are as described above, Z is —NH—, an oxygen atom or a sulfur atom, and M is —NH—, an oxygen atom or a sulfur atom. R ^{4 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group or a fluoroalkyl group, or an amino group. In this case, R ⁵ and R ⁶ are directly bonded to each other to form the substituent. A double bond may be formed between carbons to which R is bonded, and an aliphatic or aromatic ring skeleton may be formed together with the carbon atom to which they are bonded at R ⁴ and R ^7. )

（式中、Ｒ、Ｒ’、Ａ、Ｘ、Ｚ、ｍ及びｎは上記の通りであり、Ｒ⁸〜Ｒ¹¹はそれぞれ独立に水素原子、炭素数１〜６のアルキル基、アルコキシ基もしくはフルオロアルキル基、又はアミノ基であり、またＲ⁹とＲ¹⁰が直接結合して該置換基が結合する炭素間で二重結合を形成してもよく、さらにＲ⁸とＲ¹¹でこれらが結合する炭素原子と共に脂肪族又は芳香族環骨格を形成してもよい。）

Wherein R, R ′, A, X, Z, m and n are as described above, and R ^{8 to} R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group or a fluoro group. It is an alkyl group or an amino group, and R ⁹ and R ¹⁰ may be directly bonded to form a double bond between the carbons to which the substituent is bonded, and further R ⁸ and R ¹¹ are bonded to each other. (An aliphatic or aromatic ring skeleton may be formed with a carbon atom.)

Here, in the above formula, examples of R include halogen atoms such as chlorine and bromine, alkoxy groups such as methoxy group, ethoxy group, propoxy group, and butoxy group, alkoxy groups are preferable, and methoxy group and ethoxy group are particularly preferable. . Examples of R ′ include alkyl groups such as a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable. Examples of A include a methylene group, an ethylene group, a propylene group and the like as a straight chain, and a methallyl group, an isopropylene group, an isobutylene group and the like as a branched chain, and a straight chain having 1 to 3 carbon atoms. A chain alkylene group is preferred, and a propylene group is particularly preferred. R ^{1 to} R ³ include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, and a propyl group, a fluoroalkyl group in which part or all of the hydrogen atoms of these groups are substituted with a fluorine atom, a methoxy group, Examples include an alkoxy group such as ethoxy group and propoxy group, and an amino group, and also forms a ring such as a cyclopentyl group and a cyclohexyl group together with carbon atoms to which R ¹ and R ² or R ² and R ³ are bonded. Good. R ^{4 to} R ⁷ include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, and a propyl group, a fluoroalkyl group in which part or all of the hydrogen atoms of these groups are substituted with a fluorine atom, a methoxy group, and an ethoxy group. , an alkoxy group such as a propoxy group, and an amino group, R ⁵ and R ⁶ are bonded directly may form a double bond between the carbon to which they substituent is attached, further R ⁴ and R ⁷ An aliphatic ring skeleton or an aromatic ring skeleton can be formed together with the carbon atom to which they are bonded. R ^{8 to} R ¹¹ include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, and a propyl group, a fluoroalkyl group in which part or all of the hydrogen atoms of these groups are substituted with a fluorine atom, a methoxy group, and an ethoxy group. , an alkoxy group such as a propoxy group, and an amino group, bonded R ⁹ and R ¹⁰ directly may form a double bond between the carbon to which they substituent is attached, further R ⁸ and R ¹¹ An aliphatic or aromatic ring skeleton such as a cyclopentyl group and a cyclohexyl group can be formed together with the carbon atom to which they are bonded. m is an integer of 1 to 3, preferably 2, 3 and particularly preferably 3. n is an integer of 0 to 3, preferably 0, and particularly preferably 0.

As shown by the above formulas (1) to (3), the organosilicon compound having a coordinating functional group used in the present application has the following structures (i) to (iii).
(I) A heterocyclic ring having at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom.
(Ii) a divalent group comprising at least one bond selected from (thio) urethane bond, (thio) urea bond, (thio) amide bond, (thio) ester bond, amino bond, (thio) ether bond and sulfide bond Organic group.
(Iii) Hydrolyzable silyl group.
The heterocyclic ring having at least one of a nitrogen atom, an oxygen atom and a sulfur atom in the structure (i) may be an aliphatic ring or an aromatic ring, and specific examples thereof include the following. However, it is not limited to those exemplified.

（式中、波線は結合手を示す。）

(In the formula, a wavy line indicates a bond.)

  The hydrolyzable silyl group of structure (iii) is a monovalent hydrolyzable atom directly bonded to a silicon atom (an atom that forms a silanol group by reacting with water) and a monovalent hydrolyzable directly bonded to a silicon atom. It is not particularly limited as long as it is a silyl group having at least one of groups (groups that generate a silanol group by reacting with water). Such a hydrolyzable silyl group is hydrolyzed to form a silanol group, and this silanol group undergoes dehydration condensation with an inorganic material to form a chemical bond of formula: ≡Si-OM (M: inorganic material). Form. The hydrolyzable silyl group may be present alone or in the number of two or more in the organosilicon compound of the present invention, and may be the same or different when there are two or more. .

  Examples of the hydrolyzable silyl group having the structure (iii) include a chlorosilyl group, a bromosilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.

  Specific examples of the silane coupling agent having a coordinating functional group of the present invention are represented by the following structural formulas (4) to (11). In the following examples, Et represents an ethyl group. Moreover, what changed the ethyl group (Et) into the methyl group (Me) in the following example is illustrated.

  The organosilicon compound (silane coupling agent) can form a stable coordinate bond such as the following formula (A) with an active proton such as a hydroxyl group.

（式中、Ｑは窒素原子、硫黄原子、又は酸素原子を表し、Ｍは金属（イオン）を表す。）

(In the formula, Q represents a nitrogen atom, a sulfur atom, or an oxygen atom, and M represents a metal (ion).)

  Examples of the remaining components of the present invention include water, an organic solvent that dissolves the organosilicon compound, or a mixed solvent of water and the organic solvent. Examples of the organic solvent include alcohol solvents such as methanol and ethanol. Amide solvents such as formamide, N, N-dimethylformamide, pyrrolidone, N-methylpyrrolidone, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, saturated hydrocarbon solvents such as pentane, hexane, heptane, benzene, Aromatic hydrocarbon solvents such as toluene and xylene are mentioned, and methanol and ethanol are particularly preferable among them, but are not limited to those listed here.

  The organosilicon compounds of the above formulas (1) to (3) are contained in the metal surface treatment agent of the present invention at a concentration of 0.01 to 200 g / L, particularly 0.05 to 100 g / L. However, if the content is too small, the effect of the present invention may be insufficient. If the content is too large, the liquid stability of the paint may be lowered.

The metal surface treatment agent of the present invention preferably further contains an organosilicon compound other than the organosilicon compounds represented by the above formulas (1) to (3). The organosilicon compound is not particularly limited as long as it is a compound having a hydrolyzable silyl group other than the organosilicon compounds represented by the above formulas (1) to (3), but the hydrous compound represented by the following general formula (14). An organosilicon compound having a decomposable silyl group or a partially hydrolyzed condensate thereof is preferable.
R ²⁰ _x Si (OR ²¹ ) _4-x (14)
Wherein R ²⁰ is unsubstituted (preferably methyl, ethyl, propyl, vinyl, phenyl) or substituted (preferably epoxy, (meth) acryloxy) having 1 to ²⁰ carbon atoms, particularly 1 to 15 carbon atoms. Group, mercapto group, amino group, aminoalkylamino group, alkylamino group, isocyanate group, polyether group, halogen-substituted alkyl group, perfluoroalkyl group, perfluoropolyether group) monovalent hydrocarbon group, R ²¹ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms, preferably a methyl group or an ethyl group, and x is an integer of 0 to 3, particularly 0 to 2. Is preferred.)

  Specifically, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane , Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxy Propylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyl Dimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-γ-aminopropylto Methoxysilane, N-aminoethyl-γ-aminopropyltriethoxysilane, N-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-aminoethyl-γ-aminopropylmethyldiethoxysilane, γ-isocyanatopropyltrimethoxy Silane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane 2- (3,4-epoxycyclohexyl) ethyl methyl dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl methyl diethoxy silane, and the like.

  When the organosilicon compound is blended, it is preferably contained in the metal surface treatment agent at a concentration of 0.05 to 100 g / L, particularly 0.5 to 60 g / L. Is preferred. If the content is less than 0.05 g / L, the corrosion resistance may be insufficient, and if it exceeds 100 g / L, the corrosion resistance may be saturated and the productivity may decrease.

  The metal surface treatment agent of the present invention preferably further contains an organic titanate ester. Commercially available organic titanates may be used, and the structure and the like are not particularly limited. Specific examples of organic titanates include tetraethyl titanate, tetraisopropyl titanate, tetranormal butyl titanate, Examples include butyl titanate dimer, tetra (2-ethylhexyl) titanate, and polymers thereof. Titanium acetyl titanate, polytitanium acetylacetonate, titanium octyl glycinate, titanium lactate, titanium lactate ethyl ester, titanium triethanolaminate, etc. These titanium chelate compounds can also be used, and one of these can be used alone or in combination of two or more.

  When blending the above organic titanates, it is preferably contained in the metal surface treatment agent at a concentration of 0.05 to 100 g / L, particularly at a concentration of 0.5 to 60 g / L. Preferably it is. If the content is less than 0.05 g / L, the corrosion resistance may be insufficient, and if it exceeds 100 g / L, the corrosion resistance is saturated, and conversely, the bath stability of the metal surface treatment agent may be reduced.

  The metal surface treatment agent of the present invention preferably further contains water or an organic solvent-dispersible silica. The water or organic solvent-dispersible silica is not particularly limited, but is preferably spherical silica, chain silica, or aluminum modified silica that has few impurities such as sodium and is weakly alkaline. Examples of spherical silica include colloidal silica such as “Snowtex N” and “Snowtex UP” (both manufactured by Nissan Chemical Industries) and fumed silica such as “Aerosil” (manufactured by Nippon Aerosil). In addition, silica gel such as “Snowtex PS” (manufactured by Nissan Chemical Industries) is used as the chain silica, and commercially available silica gel such as “Adelite AT-20A” (manufactured by Asahi Denka Kogyo Co., Ltd.) is used as the aluminum-modified silica. Can do.

  Examples of the organic solvent include alcohols such as methanol, ethanol and isopropanol, and ether compounds such as propylene glycol monomethyl ether and tetrahydrofuran.

  When the water or organic solvent dispersible silica is blended, it is preferably contained in the metal surface treatment agent at a solid content of 0.05 to 100 g / L, particularly 0.5 to 60 g / L. When the content of water or organic solvent-dispersible silica is less than 0.05 g / L, the corrosion resistance may be insufficient, and when it exceeds 100 g / L, the effect of improving corrosion resistance is not seen. May decrease.

The metal surface treatment agent of the present invention is further one or more selected from Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn. It is preferable that the metal compound is included. Specific examples thereof include carbonates, oxides, hydroxides, nitrates, sulfates, phosphates, fluorides, fluoroacids or salts thereof, oxoacid salts, and organic acid salts of the above metals. More specifically, examples of zirconium (Zr) compounds include zirconyl ammonium carbonate, zircon hydrofluoric acid, zircon ammonium fluoride, potassium zircon fluoride, sodium zircon fluoride, zirconium acetylacetonate, zirconium butoxide 1-butanol solution, zirconium n -Propoxide etc. are mentioned. Examples of titanium (Ti) compounds include titanium hydrofluoric acid, ammonium titanium fluoride, titanium potassium oxalate, titanium isopropoxide, isopropyl titanate, titanium ethoxide, titanium-2-ethyl-1-hexanolate, and titanium. Examples include tetraisopropyl acid, tetra-n-butyl titanate, potassium potassium fluoride, and sodium titanium fluoride. Examples of vanadium (V) compounds include vanadium pentoxide (V), vanadium trioxide (III), vanadium dioxide (IV), vanadium hydroxide (II), vanadium hydroxide (III), and vanadium sulfate (II). ), Vanadium sulfate (III), vanadium oxysulfate (IV), vanadium fluoride (III), vanadium fluoride (IV), vanadium fluoride (V), vanadium trichloride VOCl ₃ , vanadium trichloride VCl ₃ , hexa Fluorovanadate (III) or salt thereof (potassium salt, ammonium salt, etc.), metavanadic acid (V) or salt thereof (sodium salt, ammonium salt, etc.), vanadyl acetylacetonate (IV) VO (OC (= CH ₂ ) CH ₂ COCH _{3) 2,} vanadium acetylacetonate (III) _{(OC (= CH 2) CH} 2 COCH 3) 3, phosphovanadomolybdic acid _{H 15-X [PV 12-} X MoO 40] · nH 2O (6 <X <12, n <30) , and the like. Examples of tungsten (W) compounds include tungsten oxide (IV), tungsten oxide (V), tungsten oxide (VI), tungsten fluoride (IV), tungsten fluoride (VI), and tungstic acid (VI) H. ₂ WO ₄ or a salt thereof (ammonium salt, sodium salt, etc.), metatungstic acid (VI) H ₆ [H ₂ W ₁₂ O ₄₀ ] or a salt thereof (ammonium salt, sodium salt, etc.), paratungstic acid (VI) H ₁₀ [H ₁₀ W ₁₂ O ₄₆ ] or a salt thereof (ammonium salt, sodium salt, etc.). Examples of molybdenum (Mo) compounds include phosphovanadomolybdic acid H _15-X [PV _12-X MoO ₄₀ ] .nH _{2 O} (6 <X <12, n <30), molybdenum oxide, molybdic acid H _2. MoO ₄ , ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdophosphoric acid compounds (for example, ammonium molybdate (NH ₄ ) ₃ [PO ₄ Mo ₁₂ O ₃₆ ] · 3H ₂ O, sodium molybdate Na ₃ [PO ₄ Mo ₁₂ O ₃₆ ] .nH ₂ O, etc.). Examples of the aluminum (Al) compound include aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, sodium aluminum sulfate, aluminum aluminum sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, and aluminum hydroxide. Examples of tin (Sn) compounds include tin oxide (IV), sodium stannate Na ₂ SnO ₃ , tin (II) chloride, tin (IV) chloride, tin (II) nitrate, tin (IV) nitrate, Examples include ammonium hexafluorostannate (NH ₄ ) ₂ SnF ₆ . Examples of niobium (Nb) compounds include niobium pentoxide (Nb ₂ O ₅ ), sodium niobate (NaNbO ₃ ), niobium fluoride (NbF ₅ ), and ammonium hexafluoroniobate (NH ₄ ) NbF _6. Is mentioned. Examples of hafnium (Hf) compounds, yttrium (Y) compounds, holmium (Ho) compounds, bismuth (Bi) compounds, and lanthanum (La) compounds include hafnium oxide, hexafluorohafnium hydride, yttrium oxide, yttrium acetyl. Examples include acetonate, holmium oxide, bismuth oxide, and lanthanum oxide. Examples of the cerium (Ce) compound include cerium oxide, cerium acetate Ce (CH ₃ CO ₂ ) ₃ , cerium nitrate (III) or (IV), cerium ammonium nitrate, cerium sulfate, cerium chloride, and the like. Examples of zinc (Zn) compounds include zinc oxide, zinc hydroxide, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, and sodium zincate. The said compound may be used individually by 1 type, and may use 2 or more types together.

  When the above compound is blended, the metal surface treatment agent is preferably contained at a concentration of 0.01 to 50 g / L, particularly 0.05 to 5 g / L as the amount of metal ions. When the content of each of the above compounds is less than 0.01 g / L, the corrosion resistance may be insufficient. When the content exceeds 50 g / L, the effect of improving the work adhesion performance is not observed, and the bath stability is decreased. There is a case.

  The metal surface treatment agent of the present invention preferably further contains a thiocarbonyl group-containing compound. Examples of the thiocarbonyl group-containing compound include thiourea, dimethylthiourea, 1,3-dimethylthiourea, dipropylthiourea, dibutylthiourea, 1,3-diphenyl-2-thiourea, 2,2-ditolylthiourea, thioacetamide, sodium dimethyl. Dithiocarbamate, tetramethylthiuram monosulfide, tetrabutylthiuram disulfide, zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate, pentamethylenedithiocarbamate piperidine salt, zinc diethyldithiocarbamate, sodium diethyldithiocarbamate, isopropylxanthogenic acid Thiocarbonyl groups such as zinc, ethylenethiourea, dimethylxanthogen sulfide, dithiooxamide, polydithiocarbamic acid or salts thereof Compounds containing one can be exemplified even without. The said compound may be used independently and may use 2 or more types together.

  When the thiocarbonyl group-containing compound is blended, it is preferably contained in the metal surface treating agent of the present invention at a concentration of 0.01 to 100 g / L, particularly 0.1 to 10 g / L. If the content of the above compound is less than 0.01 g / L, the corrosion resistance may be insufficient, and if it exceeds 100 g / L, the corrosion resistance may be saturated, which may be uneconomical.

  The metal surface treatment agent of the present invention preferably further contains a water-soluble or water-dispersible resin. Examples of water-soluble or water-dispersible resins include acrylic resins, epoxy resins, urethane resins, ethylene acrylic copolymers, phenol resins, polyester resins, polyolefin resins, alkyd resins, polycarbonate resins, and the like. These resins may be used alone, in combination of two or more kinds, or further copolymerized and used. Specifically, for example, a water-soluble acrylic resin is a copolymer mainly composed of acrylic acid and / or methacrylic acid, and examples thereof include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Their derivatives and copolymers with other acrylic monomers can also be used. In particular, the acrylic acid and / or methacrylic acid monomer ratio in the copolymer is preferably 70% by mass or more.

  Moreover, when using resin, in order to improve the film forming property and form a more uniform and smooth coating film, an organic solvent may be used. Furthermore, surfactants, leveling agents, wettability improvers, and antifoaming agents may be used.

  The molecular weight of the water-soluble or water-dispersible resin is preferably 10,000 or more in terms of weight average molecular weight. More preferably, it is 300,000 to 2,000,000. If it is less than 10,000, the effect of this invention, especially the deep-drawing property improvement effect of a coating film may not fully be exhibited. Moreover, when it exceeds 2 million, a viscosity will become high and the efficiency of handling work may fall.

  When the water-soluble or water-dispersible resin is blended, it is preferably contained in the metal surface treatment agent at a concentration of 0.1 to 100 g / L, particularly 5 to 80 g / L. If the resin concentration is less than 0.1 g / L, the effect of improving the folding adhesion and deep drawability may be insufficient, and if it exceeds 100 g / L, the effect of improving the bending adhesion and deep drawability is saturated. However, it may be uneconomical.

The metal surface treating agent of the present invention preferably further contains phosphate ions. Corrosion resistance can be further improved by adding phosphate ions. This addition of phosphate ions can be performed by adding a compound capable of forming phosphate ions in water. Examples of such a compound include phosphoric acid, phosphates such as Na ₃ PO ₄ , Na ₂ HPO ₄ , and NaH ₂ PO ₄ , condensed phosphoric acid such as condensed phosphoric acid, polyphosphoric acid, metaphosphoric acid, and diphosphoric acid, or Those salts are mentioned. These may be used alone or in combination of two or more.

  The amount of the phosphate ion added is preferably 0.01 to 100 g / L, more preferably 0.1 to 10 g / L in the metal surface treatment agent. If the amount added is less than 0.01 g / L, the effect of improving the corrosion resistance may be insufficient. If the amount added exceeds 100 g / L, the zinc-plated steel material is excessively etched, resulting in performance degradation or other components. When an aqueous resin is included, gelation may be caused.

  The metal surface treatment agent of the present invention may further contain a known additive as a metal surface treatment agent. Examples thereof include tannic acid or a salt thereof, phytic acid or a salt thereof, and the like.

  The metal surface treatment agent of the present invention includes cold rolled steel, hot rolled steel, stainless steel, electrogalvanized steel, hot dip galvanized steel, zinc-aluminum alloy plated steel, zinc-iron alloy plated steel, zinc-magnesium. Alloy-based plated steel materials, zinc-aluminum-magnesium alloy-based plated steel materials, aluminum-based plated steel materials, aluminum-silicon alloy-based plated steel materials, tin-based plated steel materials, lead-tin alloy-based plated steel materials, chromium-based plated steel materials, nickel-based plated steel materials Although it is used as a surface treatment agent for metal steel materials such as, it is particularly effective for metal coated steel materials (plated steel materials).

  As a method for using this surface treatment agent, that is, as a surface treatment method, the metal surface treatment agent may be applied to an object to be coated, and the object to be coated may be dried after the application. Then, the method of applying the metal surface treatment agent of the present invention and drying using residual heat may be used.

  In any case, the drying conditions may be room temperature to 250 ° C. for 2 seconds to 1 hour, preferably 40 to 180 ° C. for 5 seconds to 20 minutes. If it exceeds 250 ° C., performance deterioration such as adhesion and corrosion resistance may occur.

In the surface treatment method, the coating amount of the metal surface treatment agent of the present invention is preferably 0.1 mg / m ² or more after drying. If the coating mass is less than 0.1 mg / m ² , rust prevention may be insufficient. On the other hand, a and the adhesion amount is too much uneconomic as painting pretreatment agent, more preferably from 0.5 to 500 mg / m ^2, more preferably from 1-250 mg / m ^2.

  In the above surface treatment method, the method for applying the metal surface treatment agent is not particularly limited, and it can be applied by commonly used roll coating, shower coating, spraying, dipping, brush coating, or the like. Moreover, the steel material used as the object to be processed is the above-described metal steel material, and is particularly suitable for the treatment of various plated steel materials.

  The method for producing a coated steel material of the present invention is a method in which the metal steel material is surface-treated with the metal surface treatment agent, dried, and then coated with an upper coating layer. Examples of the coating layer include a coating system in which a top coat is further applied after applying and drying a non-chromate primer, if necessary, and a functional coating having functions such as fingerprint resistance and lubricity. The above manufacturing method can be applied not only to pre-coated steel materials but also to post-coated steel materials. In the present invention, the coated steel materials include these. In the present invention, the steel material is a concept including a steel plate.

  As the non-chromate primer that can be used in the present invention, any primer that does not use a chromate rust preventive pigment during blending of the primer can be used. As such a primer, a primer (V / P pigment primer) using a vanadic acid type anticorrosive pigment and a phosphoric acid type anticorrosive pigment or a primer using a calcium silicate type anticorrosive pigment is preferable.

  The applied film thickness of the primer is preferably 1 to 20 μm in terms of dry film thickness. If it is less than 1 μm, the corrosion resistance may be insufficient, and if it exceeds 20 μm, the work adhesion may be lowered.

  The baking and drying conditions for the non-chromate primer can be, for example, a metal surface temperature of 150 to 250 ° C. and a time of 10 seconds to 5 minutes.

  The top coat is not particularly limited, and all usual top coats for painting can be used. Moreover, it does not specifically limit as a functional coating, All the coating etc. which are currently provided on the chromate type pre-treatment film can be used. The method for applying the non-chromate primer, top coat and functional coating is not particularly limited, and generally used roll coat, shower coat, air spray, airless spray, immersion, and the like can be used.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In the following examples, “part” represents “part by mass”, “Et” represents an ethyl group, and “IR” is an abbreviation for “infrared spectroscopy”.

[Synthesis Example 1]
In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 31.4 g (0.33 mol) of 2-aminopyridine was added, 150 g of tetrahydrofuran was added as a solvent, and the mixture was stirred and dissolved. Into this, 82.5 g (0.33 mol) of 3-isocyanatopropyltriethoxysilane was dropped and stirred at 70 ° C. for 4 hours. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared, and instead an absorption peak derived from the urea bond was generated, and the reaction was terminated. Thereafter, the reaction product obtained by distilling off the solvent was a pale yellow liquid, and as a result of measurement with an Ostwald viscometer, the kinematic viscosity was 184 mm ² / s, the specific gravity was 1.094, the refractive index was 1.4975, The reaction product was a single product by gel permeation chromatography (GPC). Moreover, it confirmed that it was a structure shown in following chemical structural formula (4) by NMR spectrum. The NMR spectrum data was as follows.

¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): 0.58 (t, 2H), 1.07 (t, 9H), 1.61 (quint, 2H), 3.28 (t, 2H) ,
3.67 (q, 6H), 6.66 (m, 1H), 6.88 (m, 1H),
7.39 (m, 1H), 7.97 (m, 1H), 9.34 (s, 1H),
10.01 (s, 1H)
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): 7.4, 17.9,
23.2, 42.0, 58.0, 111.9, 116.0, 137.6, 145.4,
153.7, 156.6
²⁹ Si NMR (60 MHz, CDCl ₃ , δ (ppm)): −45.7

[Synthesis Example 2]
In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 31.7 g (0.33 mol) of 2-aminopyrimidine was placed, 150 g of tetrahydrofuran was added as a solvent, and the mixture was stirred and dissolved. Into this, 82.5 g (0.33 mol) of 3-isocyanatopropyltriethoxysilane was dropped and stirred at 70 ° C. for 4 hours. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared, and instead an absorption peak derived from the urea bond was generated, and the reaction was terminated. Thereafter, the reaction product obtained by distilling off the solvent was an orange solid, and the reaction product was a single product by gel permeation chromatography (GPC). From the NMR spectrum, it was confirmed that the reaction product was the following chemical structural formula (5). The NMR spectrum data was as follows.

¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): 0.55 (t, 2H), 1.09 (t, 9H), 1.61 (quint, 2H), 3.31 (t, 2H) ,
3.66 (q, 6H), 6.86 (m, 1H), 7.38 (m, 1H),
7.80 (m, 1H), 9.32 (s, 1H), 10.02 (s, 1H)
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): 7.6, 18.2,
23.2, 42.2, 58.0, 110.8, 113.7, 158.0, 163.2
²⁹ Si NMR (60 MHz, CDCl ₃ , δ (ppm)): −45.7

[Synthesis Example 3]
In a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 89.4 g (0.75 mol) of 2-mercaptothiazoline and 1.3 g of dioctyltin oxide were placed, and 300 g of ethyl acetate was added as a solvent. , Stirred and dissolved. 185.5 g (0.75 mol) of 3-isocyanatopropyltriethoxysilane was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 4 hours. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared, and an absorption peak derived from the thiourethane bond was generated instead, and the reaction was terminated. Thereafter, the reaction product obtained by distilling off the solvent was a pale yellow liquid, and as a result of measurement with an Ostwald viscometer, the kinematic viscosity was 38 mm ² / s, the specific gravity was 1.164, the refractive index was 1.5218, The reaction product was a single product by permeation chromatography (GPC). Further, the reaction product was confirmed to be the following chemical structural formula (6) by NMR spectrum. The NMR spectrum data was as follows.

¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): 0.38 (t, 2H),
0.94 (t, 9H), 1.40 (quint, 2H), 3.02 (m, 2H),
3.04 (t, 2H), 3.54 (q, 6H), 4.42 (m, 2H),
9.52 (m, 1H)
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): 7.2, 17.7,
22.2, 26.6, 42.5, 55.8, 57.8, 151.6, 199.6
²⁹ Si NMR (60 MHz, CDCl ₃ , δ (ppm)): −45.7

[Synthesis Example 4]
In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 33.4 g (0.33 mol) of 2-aminothiazole was placed, 150 g of tetrahydrofuran was added as a solvent, and the mixture was stirred and dissolved. Into this, 82.5 g (0.33 mol) of 3-isocyanatopropyltriethoxysilane was added dropwise and stirred at 80 ° C. for 4 hours. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared, and instead an absorption peak derived from the urea bond was generated, and the reaction was terminated. Thereafter, the reaction product obtained by distilling off the solvent was a brown solid, and the reaction product was a single product by gel permeation chromatography (GPC). The reaction product was confirmed to be the following chemical structural formula (7) by NMR spectrum. The NMR spectrum data was as follows.

¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): 0.65 (t, 2H),
1.19 (t, 9H), 1.68 (quint, 2H), 3.32 (t, 2H),
3.69 (m, 1H), 3.79 (q, 6H), 6.26 (m, 2H),
7.28 (m, 2H)
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): 7.7, 18.2,
23.4, 42.7, 58.3, 111.0, 136.8, 154.8, 162.6
²⁹ Si NMR (60 MHz, CDCl ₃ , δ (ppm)): −45.8

[Synthesis Example 5]
In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 50.1 g (0.33 mol) of 2-aminobenzothiazole was placed, 150 g of tetrahydrofuran was added as a solvent, and the mixture was stirred and dissolved. Into this, 82.5 g (0.33 mol) of 3-isocyanatopropyltriethoxysilane was dropped and stirred at 70 ° C. for 4 hours. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared, and instead an absorption peak derived from the urea bond was generated, and the reaction was terminated. Thereafter, the reaction product obtained by distilling off the solvent was a white solid, and the reaction product was a single product by gel permeation chromatography (GPC). From the NMR spectrum, it was confirmed that the reaction product was the following chemical structural formula (8). The NMR spectrum data was as follows.

¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): 0.68 (t, 2H),
1.20 (t, 9H), 1.71 (quint, 2H), 3.35 (t, 2H),
3.53 (m, 1H), 3.72 (q, 1H), 3.81 (q, 6H),
7.21 (m, 1H), 7.35 (m, 1H), 7.68 (m, 2H)
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): 7.4, 18.2,
23.2, 42.7, 58.4, 119.8, 121.1, 123.3, 126.0,
130.8, 149.0, 154.7, 161.7
²⁹ Si NMR (60 MHz, CDCl ₃ , δ (ppm)): −45.9

[Synthesis Example 6]
In a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 57.5 g (0.5 mol) of N-hydroxysuccinimide and 1.0 g of dioctyltin oxide were placed, and 300 g of tetrahydrofuran as a solvent. In addition, it was stirred and dissolved. Into this, 123.7 g (0.5 mol) of 3-isocyanatopropyltriethoxysilane was added dropwise and stirred at 70 ° C. for 4 hours. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared and an absorption peak derived from the urethane bond was generated instead, and the reaction was terminated. Thereafter, the reaction product obtained by distilling off the solvent was a pale yellow liquid, and as a result of measurement with an Ostwald viscometer, the kinematic viscosity was 38 mm ² / s, the specific gravity was 1.164, the refractive index was 1.5218, The reaction product was a single product by permeation chromatography (GPC). The reaction product was confirmed by NMR spectrum to have the following chemical structural formula (9). The NMR spectrum data was as follows.

¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): 0.35 (t, 2H),
0.94 (t, 9H), 1.38 (quint, 2H), 2.39 (m, 2H),
2.52 (m, 2H), 2.90 (t, 2H), 3.53 (q, 6H),
4.42 (m, 2H), 6.45 (m, 1H)
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): 6.8, 17.6,
22.2, 24.8, 43.7, 57.7, 151.2, 170.2
²⁹ Si NMR (60 MHz, CDCl ₃ , δ (ppm)): −45.4

[Synthesis Example 7]
In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 48.9 g (0.3 mol) of N-hydroxyphthalimide and 1.0 g of dioctyltin oxide were added, and 200 g of ethyl acetate was added as a solvent. , Stirred and dissolved. Into this, 74.2 g (0.3 mol) of 3-isocyanatopropyltriethoxysilane was dropped, and the mixture was heated and stirred at 80 ° C. for 4 hours. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared and an absorption peak derived from the urethane bond was generated instead, and the reaction was terminated. Thereafter, the reaction product obtained by distilling off the solvent was a yellow solid, and the reaction product was a single product by gel permeation chromatography (GPC). The reaction product was confirmed to be the following chemical structural formula (10) by NMR spectrum. The NMR spectrum data was as follows.

¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): 0.60 (t, 2H),
1.14 (t, 9H), 1.65 (quint, 2H), 3.20 (m, 2H),
3.75 (q, 6H), 6.30 (m, 1H), 7.72 (m, 4H)
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): 7.3, 17.9,
22.6, 44.2, 58.3, 123.6, 128.7, 134.5, 152.2,
162.4
²⁹ Si NMR (60 MHz, CDCl ₃ , δ (ppm)): −45.9

[Synthesis Example 8]
In a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 53.2 g (0.3 mol) of N-hydroxymethylphthalimide and 1.0 g of dioctyltin oxide were placed, and 200 g of ethyl acetate as a solvent. In addition, it was stirred and dissolved. Into this, 74.2 g (0.3 mol) of 3-isocyanatopropyltriethoxysilane was dropped, and the mixture was heated and stirred at 80 ° C. for 4 hours. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared and an absorption peak derived from the urethane bond was generated instead, and the reaction was terminated. Thereafter, the reaction product obtained by distilling off the solvent was a white solid, and the reaction product was a single product by gel permeation chromatography (GPC). The reaction product was confirmed by NMR spectrum to have the following chemical structural formula (11). The NMR spectrum data was as follows.

¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): 0.49 (t, 2H),
1.07 (t, 9H), 1.49 (quint, 2H), 3.04 (m, 2H),
3.68 (q, 6H), 5.39 (m, 1H), 5.55 (s, 2H),
7.69 (m, 4H)
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): 7.3, 14.3
17.9, 22.7, 43.1, 57.9, 123.2, 131.4, 134.1
154.5, 166.4
²⁹ Si NMR (60 MHz, CDCl ₃ , δ (ppm)): −45.6

[Reference Example 1]
10 g of the polymer compound obtained in Synthesis Example 1 was added as a nonvolatile component to a mixed solvent of 990 g of methanol and 10 g of water, and the mixture was stirred at room temperature for 5 minutes to obtain a metal surface treating agent. A bar coater no. 20 was applied so that the dry film thickness was 10 μm, and dried at a metal surface temperature of 105 ° C. for 10 minutes. After that, a non-chromate primer containing V / P pigment was added to the bar coater No. 16 was applied so that the dry film thickness was 5 μm, and dried at a metal surface temperature of 215 ° C. for 5 minutes. Furthermore, as a top coat, Flexcoat 1060 (polyester-based top coat; manufactured by Nippon Paint Co., Ltd.) The coating was applied at 36 so that the dry film thickness was 15 μm, and the metal surface temperature was dried at 230 ° C. to obtain a test plate. The obtained test plate was evaluated for bending adhesion, deep drawability, and corrosion resistance according to the following evaluation methods, and the results are shown in Table 1.

[Examples 1 to 3, Reference Examples 2 to 5]
A metal surface treating agent was prepared in the same manner as in Reference Example 1 except that the compound obtained in Synthesis Example 1 was changed to the compound obtained in Synthesis Examples 2-8. Using these metal surface treatment agents, test plates were prepared in the same manner as in Reference Example 1 and evaluated. The results obtained are listed in Table 1.

[Reference Examples 6 to 13]
Table 1 shows the concentrations and concentrations of the compounds obtained in Synthesis Example 1, silane compounds, organic titanates, water-dispersible silica, zirconium ions, thiocarbonyl group-containing compounds, water-soluble resins, and phosphate ions. A metal surface treating agent was prepared in the same manner as in Reference Example 1 except that it was blended as described. Using these metal surface treatment agents, test plates were prepared in the same manner as in Reference Example 1 and evaluated. The results obtained are listed in Table 1.

[Comparative Examples 1-4]
Without using the compounds obtained in the synthesis examples, the types and concentrations of silane compounds, organic titanates, water-dispersible silica, zirconium ions, thiocarbonyl group-containing compounds, water-soluble resins, and phosphate ions A metal surface treating agent was prepared in the same manner as in Reference Example 1 except that the ingredients were blended as described in Table 1. Using these metal surface treatment agents, test plates were prepared in the same manner as in Reference Example 1 and evaluated. The results obtained are listed in Table 1.

[Comparative Example 5]
Instead of the metal surface treatment agent, a commercially available coating type chromate treatment agent (resin-containing type) was applied and dried so that the chromium adhesion amount was 20 mg / m ² , and a chromium-containing primer (strontium chromate pigment-containing primer) A test plate was prepared and evaluated in the same manner as in Reference Example 1 except that was used, and the obtained results are shown in Table 1.

  In Table 1, the following commercially available silane compounds, organic titanates, water-dispersible silica, compounds that form zirconium ions, thiocarbonyl group-containing compounds, water-soluble resins, and compounds that form phosphate ions are listed below. The product was used.

［有機チタン酸エステル］
チタンテトライソプロポキシド
［水分散性シリカ］
メタノールシリカゾル（日産化学工業社製）
［ジルコニウムイオンを形成する化合物］
ジルコノゾールＡＣ−７（炭酸ジルコニルアンモニウム；第一稀元素社製）
［チオカルボニル基含有化合物］
チオ尿素
［水溶性樹脂］
ポリアクリル酸（重量平均分子量１００万）
［リン酸イオンを形成する化合物］
リン酸 [Silane compounds]
A: KBM-903 (aminopropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.)
B: KBM-403 (glycidoxypropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.)
C: Organosilicon compound represented by the following structural formula (12) D: Organosilicon compound represented by the following structural formula (13)

[Organic titanate]
Titanium tetraisopropoxide [water-dispersible silica]
Methanol silica sol (manufactured by Nissan Chemical Industries)
[Compounds that form zirconium ions]
Zirconazole AC-7 (Zirconyl ammonium carbonate; manufactured by Daiichi Rare Element Co., Ltd.)
[Thiocarbonyl group-containing compound]
Thiourea [water-soluble resin]
Polyacrylic acid (weight average molecular weight 1 million)
[Compounds that form phosphate ions]
phosphoric acid

[Evaluation method]
The bending adhesion, deep drawability, and corrosion resistance in Examples 1 to 3, Reference Examples 1 to 13, and Comparative Examples 1 to 5 were evaluated based on the following methods and evaluation criteria.

Bending adhesion:
In an environment of 20 ° C., the test plate was bent 180 ° with a 2 mmφ spacer using a conical mandrel tester, the bent portion was peeled off with tape three times, and the degree of peeling was observed with a magnifier of 20 times. Evaluation based on the criteria.
A: No crack B: Crack on the front of the processed part C: Peeled area is less than 20% of the processed part D: Peeled area is 20% or more to less than 80% of the processed part E: Peeled area is 80% or more of the processed part

Deep drawability:
A cylindrical squeeze test was conducted under the conditions of a squeeze ratio: 2.3, a wrinkle suppression pressure: 2 t, a punch R: 5 mm, a die shoulder R: 5 mm, and no oil coating under an environment of 20 ° C. Then, the peeling width of the coating film was measured from the cross cut part and evaluated according to the following criteria.
A: Blowing width is less than 1 mm B: Blowing width is from 1 mm to less than 2 mm C: Blowing width is from 2 mm to less than 3 mm D: Blowing width is from 3 mm to less than 5 mm E: Blowing width is 5 mm or more

Corrosion resistance:
(Cut part)
A cross-cut was put into the test plate, and a salt spray test based on JIS Z 2371 was conducted for 500 hours, and then the blister width on one side of the cut part was measured and evaluated according to the following criteria.
A: The blister width is 0mm
B: Blowing width exceeds 0 mm to less than 1 mm C: Blowing width of 1 mm or more to less than 3 mm D: Blowing width of 3 mm or more to less than 5 mm E: Blowing width of 5 mm or more (end face)
After a salt spray test based on JIS Z 2371 was performed for 500 hours on the test plate, the blister width from the upper burr end face was evaluated on the same basis as the cut part.

  The results of the above Examples and Comparative Examples demonstrate that the coating formed using the metal surface treatment agent of the present invention gives good rust prevention ability and substrate adhesion.

Claims (14)

The following general formula (2)

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, A is a linear or branched alkylene group having 1 to 6 carbon atoms, and X is An oxygen atom or a sulfur atom, Z is —NH—, an oxygen atom or a sulfur atom, M is —NH—, an oxygen atom or a sulfur atom, and R ^{4 to} R ⁷ are each independently a hydrogen atom or a carbon number. 1-6 alkyl groups, alkoxy groups or fluoroalkyl groups, or amino groups, in which case R ⁵ and R ⁶ may be directly bonded to form a double bond between the carbons to which the substituent is bonded. Further, an aliphatic or aromatic ring skeleton may be formed together with the carbon atom to which they are bonded at R ⁴ and R ⁷ , m is an integer of 1 to 3, and n is an integer of 0 to 3.)
A metal surface treatment characterized by comprising an organic silicon compound represented by the formula (I) as an essential component, which is dissolved in water, an organic solvent, or a mixed solvent of water and an organic solvent, and contains a water-soluble or water-dispersible resin. Agent. Furthermore, the following general formula (14)
R ²⁰ _x Si (OR ²¹ ) _4-x (14)
Wherein R ²⁰ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to ²⁰ carbon atoms, R ²¹ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and x represents 0 to 3 Is an integer.)
The metal surface treating agent according to claim 1, comprising an alkoxysilane represented by the formula (1) or a partial hydrolysis condensate thereof.   The metal surface treatment agent according to claim 1, further comprising an organic titanate ester.   Furthermore, water-dispersible silica or organic-solvent dispersible silica is contained, The metal surface treating agent of any one of Claims 1-3 characterized by the above-mentioned.   Furthermore, it contains a compound of at least one metal selected from Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn. The metal surface treating agent according to any one of claims 1 to 4, wherein   Furthermore, the metal surface treating agent of any one of Claims 1-5 containing a thiocarbonyl group containing compound. Furthermore, phosphate ion is included, The metal surface treating agent of any one of Claims 1-6 characterized by the above-mentioned. A surface treatment method for a steel material, wherein the surface of the steel material is surface-treated with the metal surface treatment agent according to any one of claims 1 to 7 . The surface treatment method according to claim 8 , wherein the steel material is a metal-coated steel material. A surface-treated steel material obtained by the method according to claim 8 or 9 . A method for producing a coated steel material, further comprising providing an upper coating layer after treating the steel material with the metal surface treatment agent according to any one of claims 1 to 7 . A coated steel material obtained by the method according to claim 11 . The following general formula (2)

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, A is a linear or branched alkylene group having 1 to 6 carbon atoms, and X is An oxygen atom or a sulfur atom, Z is —NH—, an oxygen atom or a sulfur atom; M is —NH—, an oxygen atom or a sulfur atom; ^Four ~ R ⁷ Are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group or a fluoroalkyl group, or an amino group. ^Five And R ⁶ May be directly bonded to form a double bond between carbons to which the substituent is bonded, and R ^Four And R ⁷ An aliphatic or aromatic ring skeleton may be formed together with the carbon atom to which they are bonded. m is an integer of 1 to 3, and n is an integer of 0 to 3. )
After the steel material is treated with a metal surface treatment agent obtained by dissolving the organic silicon compound represented by the above in water, an organic solvent, or a mixed solvent of water and an organic solvent, an upper coating layer is further provided. A method for producing a painted steel material. A coated steel material obtained by the method according to claim 13.