JP2014031556A - Metal surface treatment agent, surface-treated steel and method for surface treatment of the same, and painted steel and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-chromate metal surface treatment agent that may provide excellent workability, adhesion and corrosion-resistance as pretreatment of coating a paint and the like.SOLUTION: A metal surface treatment agent represented by the general formula (1) shown below (in the formula (1), R is a hydrolysable group; R' is an alkyl group having 1 to 4 carbons; A is a straight or branched alkylene group having 1 to 8 carbons; X is any one of oxygen atom, sulfur atom and nitrogen atom; Rand Rare independently hydrogen atom, an alkyl group having 1 to 20 carbons, a fluoroalkyl group having 1 to 20 carbons, an aryl group having 6 to 10 carbons, an alkenyl group having 2 to 10 carbons, or a substituent represented by the formula (2) shown below; and m is an integer of 1 to 3)(in the formula (2), R is a hydrolysable group; R' is an alkyl group having 1 to 4 carbons; B is a straight or branched alkylene group having 1 to 8 carbons; and m is an integer of 1 to 3).

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, development of a metal surface treatment agent that does not contain chromium and has the same adhesion and corrosion resistance as the chromate treatment agent is desired.

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 in a water-soluble resin, and further water-dispersible silica. However, this system is mainly intended to improve the bare corrosion resistance (primary rust resistance), the processability of the treated film and the adhesion to the substrate are not sufficient, and the topcoat adhesion of the treated product is good However, the corrosion resistance after painting was not always satisfactory.
Japanese Patent Laid-Open No. 8-073775 (Patent Document 2) discloses an acidic surface treatment agent containing two or more types of silane coupling agents, but this system is expensive after treatment with a metal surface treatment agent. When corrosion resistance and workability are required, corrosion resistance is insufficient.

  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. Corrosion resistance is only for bare corrosion resistance (white rust resistance) against a relatively mild test such as a wet test. Corrosion resistance is higher than that of a metal surface treatment agent that can withstand severe corrosion resistance tests such as the present invention. It is insufficient.

  Japanese Patent Application Laid-Open No. 2000-297093 (Patent Document 5) describes that an imidazole group-containing organosilicon compound is used as a surface treatment agent such as a metal, but a metal material such as an aluminum alloy plate and a resin such as an epoxy resin. It has been proposed to improve the adhesion (adhesive strength) to the coating, and was not sufficiently satisfactory in terms of corrosion resistance and deep drawability as a coated product.

  In Japanese Patent Application Laid-Open No. 2007-297648 (Patent Document 6), an aqueous emulsion, a compound in which trivalent transition metal ions, two β-diketone molecules and two water molecules are coordinated, and a surface treatment for rust prevention containing a silane coupling agent. An agent (chemical conversion treatment liquid) is disclosed, and although it is characteristic in that the trivalent transition metal complex expresses rust prevention ability and coating film adhesion ability by becoming a hardly soluble compound by drying, it is required. The corrosion resistance is not intended to withstand the harsh environment as in the present invention, and there is enough room for improvement.

  In view of the above, it has been desired to develop a metal surface treatment agent that exhibits various properties such as workability, adhesion, and corrosion resistance after coating with a thin film.

JP-A-11-29724 JP-A-8-073775 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 optimal 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. .

（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１〜８のアルキレン基であり、Ｘは酸素原子、硫黄原子、窒素原子のいずれかであり、Ｒ¹、Ｒ²はそれぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のフルオロアルキル基、炭素数６〜１０のアリール基、炭素数２〜１０のアルケニル基、又は下記一般式（２）で示される置換基であり、ｍは１〜３の整数である。）

（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、Ｂは直鎖状又は分岐鎖状の炭素数１〜８のアルキレン基であり、ｍは１〜３の整数である。）
で示される有機ケイ素化合物、
（Ｂ）水及び／又は有機溶剤
を含むことを特徴とする金属表面処理剤。
〔２〕 上記有機ケイ素化合物は、下記一般式（３）

（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１〜８のアルキレン基であり、Ｒ¹〜Ｒ³はそれぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のフルオロアルキル基、炭素数６〜１０のアリール基、炭素数２〜１０のアルケニル基、又は下記一般式（４）で示される置換基であり、ｍは１〜３の整数である。）

（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、Ｂは直鎖状又は分岐鎖状の炭素数１〜８のアルキレン基であり、ｍは１〜３の整数である。）
であることを特徴とする〔１〕記載の金属表面処理剤。
〔３〕 上記有機ケイ素化合物は、下記一般式（５）

（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、Ｒ¹は水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のフルオロアルキル基、炭素数６〜１０のアリール基、炭素数２〜１０のアルケニル基、又は下記一般式（６）で示される置換基であり、ｍは１〜３の整数である。）

（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、ｍは１〜３の整数である。）
であることを特徴とする〔２〕記載の金属表面処理剤。
〔４〕 更に、下記一般式（７）
Ｒ⁴ _xＳｉ（ＯＲ⁵）_4-x （７）
（式中、Ｒ⁴は炭素数１〜２０の非置換又は置換の一価炭化水素基、Ｒ⁵は炭素数１〜８の非置換又は置換の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〔１〕〜〔３〕のいずれかに記載の金属表面処理剤。
〔５〕 更に、有機チタン酸エステルを含むことを特徴とする〔１〕〜〔４〕のいずれかに記載の金属表面処理剤。
〔６〕 更に、水分散性シリカ又は有機溶剤分散性シリカを含むことを特徴とする〔１〕〜〔５〕のいずれかに記載の金属表面処理剤。
〔７〕 更に、Ｆｅ，Ｚｒ，Ｔｉ，Ｖ，Ｗ，Ｍｏ，Ａｌ，Ｓｎ，Ｎｂ，Ｈｆ，Ｙ，Ｈｏ，Ｂｉ，Ｌａ，Ｃｅ及びＺｎの群から選択される１種以上の金属の化合物を含むことを特徴とする〔１〕〜〔６〕のいずれかに記載の金属表面処理剤。
〔８〕 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〔１〕〜〔７〕のいずれかに記載の金属表面処理剤。
〔９〕 更に、水溶性樹脂又は水分散性樹脂を含むことを特徴とする〔１〕〜〔８〕のいずれかに記載の金属表面処理剤。
〔１０〕 更に、リン酸イオンを含むことを特徴とする〔１〕〜〔９〕のいずれかに記載の金属表面処理剤。
〔１１〕 鋼材の表面を〔１〕〜〔１０〕のいずれかに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。
〔１２〕 鋼材が金属被覆鋼材である〔１１〕記載の表面処理方法。
〔１３〕 〔１１〕又は〔１２〕記載の表面処理方法で得られる表面処理鋼材。
〔１４〕 〔１〕〜〔１０〕のいずれかに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。
〔１５〕 〔１４〕記載の塗装鋼材の製造方法で得られる塗装鋼材。 In order to achieve the above object, the present invention provides the following metal surface treatment agent, surface-treated steel material and surface treatment method thereof, and coated steel material and production method thereof.
[1] (A) The following general formula (1)

(In the formula, 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 8 carbon atoms, and X is Any one of an oxygen atom, a sulfur atom and a nitrogen atom, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or 6 to 10 carbon atoms. And an aryl group of 2 to 10 carbon atoms, or a substituent represented by the following general formula (2), m is an integer of 1 to 3.

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, B is a linear or branched alkylene group having 1 to 8 carbon atoms, and m is It is an integer from 1 to 3.)
An organosilicon compound represented by
(B) A metal surface treatment agent comprising water and / or an organic solvent.
[2] The organosilicon compound is represented by the following general formula (3)

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 8 carbon atoms, R ¹ to R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or the following general, (It is a substituent represented by Formula (4), and m is an integer of 1 to 3).

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, B is a linear or branched alkylene group having 1 to 8 carbon atoms, and m is It is an integer from 1 to 3.)
[1] The metal surface treatment agent according to [1].
[3] The organosilicon compound is represented by the following general formula (5)

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl having 1 to 20 carbon atoms. Group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a substituent represented by the following general formula (6), and m is an integer of 1 to 3).

(In the formula, R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3).
[2] The metal surface treating agent according to [2].
[4] Furthermore, the following general formula (7)
R ⁴ _x Si (OR ⁵ ) _4-x (7)
(In the formula, R ⁴ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and x represents 0 to 0. It is an integer of 3.)
The metal surface treating agent according to any one of [1] to [3], comprising an alkoxysilane represented by the formula (1) or a partially hydrolyzed condensate thereof.
[5] The metal surface treatment agent according to any one of [1] to [4], further comprising an organic titanate ester.
[6] The metal surface treatment agent according to any one of [1] to [5], further comprising water-dispersible silica or organic solvent-dispersible silica.
[7] Further, a compound of one or more metals selected from the group consisting of 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 [1] to [6], wherein the metal surface treating agent is contained.
[8] The metal surface treatment agent according to any one of [1] to [7], further comprising a thiocarbonyl group-containing compound.
[9] The metal surface treatment agent according to any one of [1] to [8], further comprising a water-soluble resin or a water-dispersible resin.
[10] The metal surface treatment agent according to any one of [1] to [9], further comprising phosphate ions.
[11] 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 [1] to [10].
[12] The surface treatment method according to [11], wherein the steel material is a metal-coated steel material.
[13] A surface-treated steel material obtained by the surface treatment method according to [11] or [12].
[14] A method for producing a coated steel material, characterized by further providing an upper coating layer after treating the steel material with the metal surface treatment agent according to any one of [1] to [10].
[15] A coated steel material obtained by the method for producing a coated steel material according to [14].

  The metal surface treatment agent of the present invention contains a silane coupling agent having a thioamide group as an essential component, and includes a steel material to be treated and another metal (ion) component, and the thioamide group of the silane coupling agent. Coordinating bond forms a poorly soluble complex, expresses good rust prevention ability, and with hydrolyzable silyl group, processing adhesion with steel and organic / inorganic resin coating layer on upper layer as required As a result, the adhesive strength is increased, and as a result, 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 thioamide 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. .

（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１〜８のアルキレン基であり、Ｘは酸素原子、硫黄原子、窒素原子のいずれかであり、Ｒ¹、Ｒ²はそれぞれ独立に水素原子、炭素数１〜２０、好ましくは１〜８のアルキル基、炭素数１〜２０、好ましくは１〜８のフルオロアルキル基、炭素数６〜１０のアリール基、炭素数２〜１０のアルケニル基、又は下記一般式（２）で示される置換基であり、ｍは１〜３の整数である。）

（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、Ｂは直鎖状又は分岐鎖状の炭素数１〜８のアルキレン基であり、ｍは１〜３の整数である。） [Organic silicon compound]
The organosilicon compound used in the present invention is represented by the following general formula (1).

(In the formula, 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 8 carbon atoms, and X is Any one of an oxygen atom, a sulfur atom, and a nitrogen atom, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and 1 to 20 carbon atoms, preferably 1 -8 fluoroalkyl group, C6-C10 aryl group, C2-C10 alkenyl group, or the substituent shown by following General formula (2), m is an integer of 1-3. )

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, B is a linear or branched alkylene group having 1 to 8 carbon atoms, and m is It is an integer from 1 to 3.)

（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１〜８のアルキレン基であり、Ｒ¹〜Ｒ³はそれぞれ独立に水素原子、炭素数１〜２０、好ましくは１〜８のアルキル基、炭素数１〜２０、好ましくは１〜８のフルオロアルキル基、炭素数６〜１０のアリール基、炭素数２〜１０のアルケニル基、又は下記一般式（４）で示される置換基であり、ｍは１〜３の整数である。）

（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、Ｂは直鎖状又は分岐鎖状の炭素数１〜８のアルキレン基であり、ｍは１〜３の整数である。） More preferably, it is represented by the following general formula (3).

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 8 carbon atoms, R ¹ to R ³ each independently represent a hydrogen atom, C1-20, preferably 1-8 alkyl groups, having 1 to 20 carbon atoms, preferably 1-8 fluoroalkyl group, an aryl group having 6 to 10 carbon atoms, (It is a C2-C10 alkenyl group or a substituent represented by the following general formula (4), and m is an integer of 1 to 3.)

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, B is a linear or branched alkylene group having 1 to 8 carbon atoms, and m is It is an integer from 1 to 3.)

（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、Ｒ¹は水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のフルオロアルキル基、炭素数６〜１０のアリール基、炭素数２〜１０のアルケニル基、又は下記一般式（６）で示される置換基であり、ｍは１〜３の整数である。）

（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、ｍは１〜３の整数である。） More preferably, it is represented by the following general formula (5).

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl having 1 to 20 carbon atoms. Group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a substituent represented by the following general formula (6), and m is an integer of 1 to 3).

(In the formula, R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3).

Here, examples of the hydrolyzable group of R in the above formula include halogen atoms such as chlorine and bromine, alkoxy groups having 1 to 4 carbon atoms such as methoxy group and ethoxy group, with alkoxy groups being preferred and methoxy groups being preferred. Particularly preferred. Examples of R ′ include alkyl groups such as a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable. A includes a methylene group, an ethylene group, a propylene group, etc. as a straight chain, and a methallyl group, an isopropylene group, etc. as a branched chain, a straight chain having 1 to 3 carbon atoms. An alkylene group is preferred, and a propylene group is particularly preferred. B may be a methylene group, an ethylene group, a propylene group or the like as a linear one, and a methallyl group, an isopropylene group or the like as a branched one may be a straight chain having 1 to 3 carbon atoms. An alkylene group is preferred, and a propylene group is particularly preferred. X includes an oxygen atom, a sulfur atom, and a nitrogen atom, and a nitrogen atom is particularly preferable. When X becomes a nitrogen atom, it becomes a thiourea type and the coordination power with a metal increases, and it is thought that corrosion resistance increases. R ¹ , R ² , and R ³ include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group, and a part or all of the hydrogen atoms in these groups are fluorine atoms. And an aryl group such as a phenyl group and a tolyl group, and an alkenyl group such as a vinyl group, a butenyl group and a pentenyl group. m is an integer of 1 to 3, preferably 2 or 3, and particularly preferably 3.

  Specific examples of the structure of the organosilicon compound include the following, but are not limited to those exemplified.

  The organosilicon compound is obtained, for example, by reacting a silane compound having an amino group and a hydrolyzable group with an alkyl isothiocyanate, or under a catalyst to a silane compound having an isothiocyanate group and a hydrolyzable group. It is obtained by reacting ammonia, primary amine, or secondary amine.

（式中、Ｘは酸素原子、硫黄原子、又は窒素原子を表し、Ｍは金属（イオン）を表す。Ｒ¹，Ｒ²は上記の通り。） The organosilicon compound (silane coupling agent) can form a stable coordination bond such as the following formula (15) or (16) with a metal (ion).

(In the formula, X represents an oxygen atom, a sulfur atom, or a nitrogen atom, and M represents a metal (ion). R ¹ and R ² are as described above.)

  Examples of the remaining components of the metal surface treatment agent 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 methanol and ethanol. Alcohol solvents such as formamide, N, N-dimethylformamide, amide solvents such as pyrrolidone and N-methylpyrrolidone, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, saturated hydrocarbons such as pentane, hexane and heptane Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among them, methanol and ethanol are particularly preferable, but not limited to those listed here.

  The organosilicon compounds of the above formulas (1) to (6) 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 (6). 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 (6), but the hydrous compound represented by the following general formula (7). An organosilicon compound having a decomposable silyl group or a partially hydrolyzed condensate thereof is preferable.
R ⁴ _x Si (OR ⁵ ) _4-x (7)
Wherein R ⁴ 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 ⁵ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8, particularly 1 to 6 carbon atoms, preferably a methyl group or an ethyl group, 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-dispersible or organic solvent-dispersible silica. The water-dispersible or organic solvent-dispersed 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, Ltd.) and fumed silica such as “Aerosil” (produced by Nippon Aerosil Co., Ltd.). As the chain silica, silica gel such as “Snowtex PS” (manufactured by Nissan Chemical Industries, Ltd.) or the like, and as silica modified with aluminum, commercially available silica gel such as “Adelite AT-20A” (manufactured by ADEKA Corporation) can be used. Can be used.

  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-dispersible or organic solvent-dispersible silica is blended, it is contained in the metal surface treatment agent in a solid content of 0.05 to 100 g / L, particularly 0.5 to 60 g / L. preferable. 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 any one selected from the group of Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn. It is preferable that the compound of the metal more than a seed | species is included. Specific examples 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 ammonium 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 ), ammonium hexafluoroniobate (NH ₄ ) NbF _{6 and the} like. 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, lanthanum oxide, and the like. 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 the zinc (Zn) compound include zinc oxide, zinc hydroxide, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, sodium zincate and the like. 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 polystyrene-reduced weight average molecular weight by gel permeation chromatography. 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 compounds 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, parts represent parts by mass, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and IR is an abbreviation for infrared spectroscopy.

[Synthesis Example 1: Production Method of Organosilicon Compound (8) (Formula (8) below)]
358.6 g (2 mol) of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903) was placed in a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. 146.2 g (2 mol) of methyl isothiocyanate was added dropwise and stirred at room temperature for 1 hour. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isothiocyanate group of the raw material had completely disappeared, and the reaction was completed. The obtained product was a brown liquid, and the reaction product was a single product by gel permeation chromatography (GPC) analysis.

[Synthesis Example 2: Production Method of Organosilicon Compound (9) (Formula (9) below)]
358.6 g (2 mol) of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903) was placed in a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. To the solution, 174.3 g (2 mol) of ethyl isothiocyanate was added dropwise and stirred at room temperature for 1 hour. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isothiocyanate group of the raw material had completely disappeared, and the reaction was completed. The obtained product was a brown liquid, and the reaction product was a single product by gel permeation chromatography (GPC) analysis.

[Synthesis Example 3: Production Method of Organosilicon Compound (10) (Formula (10) below)]
358.6 g (2 mol) of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903) was placed in a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer. To the mixture, 270.4 g (2 mol) of phenyl isothiocyanate was added dropwise and stirred at room temperature for 1 hour. Thereafter, it was confirmed by IR measurement that the absorption peak derived from the isothiocyanate group of the raw material had completely disappeared, and the reaction was completed. The obtained product was a brown liquid, and the reaction product was a single product by gel permeation chromatography (GPC) analysis.

[Synthesis Example 4: Production Method of Organosilicon Compound (13) (Formula (13) below)]
A 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer is charged with 221.4 g (1 mol) of 3-isothiocyanate propyltrimethoxysilane, 500 g of hexane, and 1 g of tin di (2-ethylhexane) ate. And heated to 60 ° C. Ammonia was blown into it, and the blow was stopped when the absorption peak derived from the isothiocyanate group of the raw material disappeared completely by IR measurement. Thereafter, the product obtained by removing the solvent was a yellow liquid, and the reaction product was a single product by gel permeation chromatography (GPC) analysis.

[Example 1]
10 g of the organosilicon compound (8) 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. The obtained metal surface treatment agent was degreased and dried on a commercially available hot-dip galvanized steel sheet (manufactured by Nippon Test Panel Co., Ltd .; 70 × 150 × 0.4 mm). 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. Thereafter, 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 2 to 4]
In Example 1, the metal surface was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 1 was changed to the compounds (9), (10), and (13) obtained in Synthesis Examples 2 to 4. A treating agent was prepared. Using these metal surface treatment agents, test plates were prepared in the same manner as in Example 1 and evaluated. The results obtained are listed in Table 1.

[Examples 5 to 12]
In Example 1, the types and concentrations of silane compounds, organotitanate esters, water-dispersible silica, zirconium ions, thiocarbonyl group-containing compounds, water-soluble resins, and phosphate ion concentrations were formulated as shown in Table 1, respectively. A metal surface treating agent was prepared in the same manner as in Example 1 except that. Using these metal surface treatment agents, test plates were prepared in the same manner as in Example 1 and evaluated. The results obtained are listed in Table 1.

[Comparative Examples 1 and 2]
In Example 1, without using the compound obtained in the synthesis example, the type and concentration of the silane compound, organic titanate, water-dispersible silica, zirconium ion, thiocarbonyl group-containing compound, water-soluble resin, and phosphate ion A metal surface treating agent was prepared in the same manner as in Example 1 except that the concentrations of were mixed as shown in Table 1. Using these metal surface treatment agents, test plates were prepared in the same manner as in Example 1 and evaluated. The results obtained are listed in Table 1.

[Comparative Example 3]
In Example 1, 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 A test plate was prepared and evaluated in the same manner as in Example 1 except that the chromate pigment-containing primer was used, and the results obtained are shown in Table 1.

  In Table 1 below, the following commercially available products are used as 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. It was used.

[Silane compound]
A: KBM-903 (γ-aminopropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.)
B: KBM-403 (γ-glycidoxypropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.)
[Organic titanate]
Titanium tetraisopropoxide [water-dispersible silica]
Methanol silica sol (manufactured by Nissan Chemical Industries, Ltd.)
[Compounds that form zirconium ions]
Zircosol AC-7 (Zirconyl ammonium carbonate; manufactured by Daiichi Rare Element Chemical 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 12 and Comparative Examples 1 to 3 were evaluated based on the following methods and evaluation criteria.

(1) Bending adhesion In a 20 ° C environment, using a conical mandrel testing machine, the test plate is folded 180 ° with a 2 mmφ spacer in between, the folded portion is taped three times, and the degree of peeling is increased 20 times. It observed with the loupe and evaluated by the following reference | standard.
A: No crack B: Crack in front of processed part C: Peeled area is less than 20% of processed part D: Peeled area is not less than 20% to less than 80% of processed part E: Peeled area is not less than 80% of processed part

(2) Deep drawability A test plate with a cross cut in a 20 ° C environment under the conditions of drawing ratio: 2.3, wrinkle suppression pressure: 2 t, punch R: 5 mm, die shoulder R: 5 mm, no oil. A cylindrical squeeze test was conducted. Then, the peeling width | variety of the coating film was measured from the cross cut part of a cylindrical side wall part, and the following reference | standard evaluated.
A: Peel width is less than 1 mm B: Peel width is 1 mm or more and less than 2 mm C: Peel width is 2 mm or more and less than 3 mm D: Peel width is 3 mm or more and less than 5 mm E: Peel width is 5 mm or more

(3) Corrosion resistance (cut part)
A cross cut reaching the galvanized layer was put on the test plate, and after performing a salt spray test based on JIS Z 2371 for 500 hours, the width of blister on one side of the cross cut part (cut part) was measured and evaluated according to the following criteria.
A: The blister width is 0mm
B: The blister width exceeds 0 mm to less than 1 mm C: The blister width is from 1 mm to less than 3 mm D: The blister width is from 3 mm to less than 5 mm E: The blister width is 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.

  Although the present invention has been described with the embodiment, the present invention is not limited to the embodiment shown here, and those skilled in the art will conceive other embodiments, additions, modifications, deletions, and the like. As long as the effects of the present invention are exhibited in any aspect, the present invention is included in the scope of the present invention.

Claims (15)

(A) The following general formula (1)

(In the formula, 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 8 carbon atoms, and X is Any one of an oxygen atom, a sulfur atom and a nitrogen atom, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or 6 to 10 carbon atoms. And an aryl group of 2 to 10 carbon atoms, or a substituent represented by the following general formula (2), m is an integer of 1 to 3.

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, B is a linear or branched alkylene group having 1 to 8 carbon atoms, and m is It is an integer from 1 to 3.)
An organosilicon compound represented by
(B) A metal surface treatment agent comprising water and / or an organic solvent. The organosilicon compound has the following general formula (3)

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 8 carbon atoms, R ¹ to R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or the following general, (It is a substituent represented by Formula (4), and m is an integer of 1 to 3).

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, B is a linear or branched alkylene group having 1 to 8 carbon atoms, and m is It is an integer from 1 to 3.)
The metal surface treatment agent according to claim 1, wherein The organosilicon compound has the following general formula (5)

Wherein R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl having 1 to 20 carbon atoms. Group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a substituent represented by the following general formula (6), and m is an integer of 1 to 3).

(In the formula, R is a hydrolyzable group, R ′ is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3).
The metal surface treating agent according to claim 2, wherein Furthermore, the following general formula (7)
R ⁴ _x Si (OR ⁵ ) _4-x (7)
(In the formula, R ⁴ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and x represents 0 to 0. It is an integer of 3.)
The metal surface treating agent according to any one of claims 1 to 3, comprising an alkoxysilane represented by the formula (1) or a partially hydrolyzed condensate thereof.   Furthermore, organic metal titanate is included, The metal surface treating agent of any one of Claims 1-4 characterized by the above-mentioned.   The metal surface treatment agent according to claim 1, further comprising water-dispersible silica or organic solvent-dispersible silica.   Furthermore, it contains a compound of one or more metals selected from the group of Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn. The metal surface treatment agent according to claim 1, wherein the metal surface treatment agent is a metal surface treatment agent.   The metal surface treatment agent according to claim 1, further comprising a thiocarbonyl group-containing compound.   Furthermore, water-soluble resin or water-dispersible resin is included, The metal surface treating agent of any one of Claims 1-8 characterized by the above-mentioned.   Furthermore, phosphate ion is included, The metal surface treating agent of any one of Claims 1-9 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 10.   The surface treatment method according to claim 11, wherein the steel material is a metal-coated steel material.   A surface-treated steel material obtained by the surface treatment method according to claim 11 or 12.   After processing steel materials with the metal surface treating agent of any one of Claims 1-10, an upper film layer is provided further, The manufacturing method of the coated steel materials characterized by the above-mentioned.   A coated steel material obtained by the method for producing a coated steel material according to claim 14.