JP5314547B2 - Surface treatment agent for metal material, surface treatment method, and surface treatment metal material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treatment agent for metal materials used for obtaining surface treated metal steel plate exhibiting excellent characteristics in various performance. <P>SOLUTION: The surface treatment agent for metal materials includes: an organopolysiloxane compound, a metal compound (B) including at least one or more metal elements selected from the group consisting of Zr, Ti and V, a compound (C) having -Si(OH)<SB>3</SB>, and water. The organopolysiloxane compound is composed of any unit selected from the group consisting of a unit M, a unit D, a unit T and a unit Q and has a three-dimensional network-like structure having at least the unit T and/or the unit Q in the molecule. The organopolysiloxane compound has a unit including a group having a functional group (a1) selected from an epoxy group and an amino group as R, and a unit including an alkyl group as R. The ratio of the molar quantity (&beta;) of the total constituent units in one molecule to the total molar quantity (&alpha;) of the unit M, the unit D and the unit T including the functional group (a1) in one molecule, &beta;/&alpha;, is 1.5 or more, and a molecular weight of the organopolysiloxane compound is 200-20,000. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a surface treatment agent for a metal material, a surface treatment method using the surface treatment agent for a metal material, and a surface treatment metal material.

  While metal materials typified by galvanized steel sheets are used in various fields such as automobiles, home appliances, and building materials, they have the problem of corrosion resistance that corrodes in the atmosphere and forms a corrosion product called white rust. Have.

  Therefore, conventionally, a chromate treatment in which a coating layer containing hexavalent chromium and trivalent chromium is formed on the surface of a metal material using a treatment solution containing a chromic acid aqueous solution for the purpose of improving corrosion resistance is generally used. It was given.

  However, compounds harmful to the human body, such as hexavalent chromium, need to be subjected to a special treatment prescribed in the Water Pollution Control Law during wastewater treatment. For this reason, with the recent increase in awareness of global environmental conservation, there is a strong movement to refrain from using it as much as possible.

  Many surface improvement studies are underway for surface treatment that does not use hexavalent chromium. For example, Patent Documents 1 to 6 disclose techniques for directly coating a metal material surface with a chromium-free organic film (resin film).

  Specifically, Patent Document 1 discloses zinc-based coated steel obtained by applying and drying a composition containing an aqueous resin, water, and sulfide ions. Patent Document 2 discloses a zinc-based plated steel sheet coated with a water-dispersed metal surface treatment composition containing a compound having a specific bond, silica, and a resin emulsion. Patent Document 3 discloses a surface-treated metal material in which a film is formed using a water-based treatment agent containing a specific aqueous dispersion resin, silica particles, and an organic inhibitor. Patent Document 4 discloses a surface-treated metal plate obtained by treating a metal material with a surface treatment composition containing a nonionic aqueous resin dispersion, hydrolyzable titanium, an organic phosphate compound, and a vanadium compound. Patent Document 5 discloses a water-dispersed rust preventive coating composition containing an ionomer resin and a water-soluble zirconium and / or water-soluble titanium compound that reacts with a carboxyl group. Patent Document 6 discloses a surface-treated metal plate obtained by treating a metal material with a metal surface treatment composition containing hydrolyzable titanium, an organic phosphate compound, a nonionic aqueous resin dispersion, a vanadium compound, and a zirconium compound. Is disclosed.

Patent Documents 7 to 10 describe a technique for coating a metal material with a chromium-free film mainly composed of an inorganic component.
Specifically, Patent Document 7 discloses a metal plate having a film containing titanium and / or zirconium, a phosphate compound, and a guanidine compound. Patent Document 8 discloses a galvanized steel sheet surface-treated with a treatment agent containing a water-soluble phosphate compound, a chelating agent, and a corrosion inhibitor. Patent Document 9 discloses a surface-treated metal material having a film formed by a surface treatment agent for a metal material containing a vanadium compound and a metal compound such as zirconium. Patent Document 10 proposes a steel sheet having a coating composed of tetravalent vanadium, Si, and a phosphoric acid compound. About these techniques, it is reported that corrosion resistance improves more by using aqueous resin together.

Further, Patent Documents 11 to 13 also propose a technique for coating a steel sheet with a chromium-free film mainly composed of inorganic components.
Specifically, Patent Document 11 discloses a steel sheet having a film obtained using a composition containing phosphoric acid, titanium composed of 4 or more fluorine atoms, zirconium, a silane coupling agent, and the like. . Patent Document 12 discloses a steel sheet having a film obtained by using a silane coupling agent having an amino group, a silane coupling agent having a glycidyl group, a treatment agent containing titanium hydrofluoric acid, and the like. Patent Document 13 proposes a steel sheet having a coating made of a silica sol binder, phosphate ions, fluoride ions, and the like.

JP-A-8-67834 JP-A-9-221595 Japanese Patent Laid-Open No. 2002-241956 JP 2004-238638 A JP 2005-15514 A JP 2006-009121 A JP 2004-2950 A JP 2002-155375 A JP 2002-30460 A JP 2005-48199 A JP 2006-213958 A JP 2007-51365 A JP 2007-177314 A

  The surface of metallic materials such as galvanized steel sheet is required not only to have corrosion resistance, but also to have various performances such as corrosion resistance after alkaline degreasing, earth resistance, heat resistance, paintability (coating adhesion), and fingerprint resistance. Is done.

When the above-described conventional resin film is formed on the surface of the metal material, in order to obtain predetermined corrosion resistance, a film amount of the resin film of 1 g / m ² or more is often required. Moreover, in order to obtain predetermined fingerprint resistance, it is necessary to increase the amount of the resin film. However, when the amount of the coating is increased in this way, the coating becomes insulative, and there is a problem that the grounding property cannot be obtained. That is, in many cases, the corrosion resistance and fingerprint resistance and the grounding property have a trade-off relationship.
Furthermore, since the resin film is decomposed in a high-temperature environment, it is not always satisfactory in terms of heat resistance, and further improvement is desired.

On the other hand, when forming a chromium-free film mainly composed of inorganic components on a steel sheet, for example, a steel sheet having a film described in Patent Documents 11 to 13 exhibits good corrosion resistance and heat resistance. However, since many acid components are present in the obtained film, there are problems in grounding properties and paintability (coating film adhesion).
Moreover, when the steel plate which has a film | membrane is used without coating, there also exists a problem that a fingerprint adheres to the steel plate surface and an external appearance is impaired.

  As described above, surface treatment agents for metal materials that comprehensively satisfy various performances such as corrosion resistance of coatings, corrosion resistance after alkaline degreasing, grounding properties, heat resistance, paintability (coating adhesion), and fingerprint resistance. Has not been obtained and has not yet been replaced by chromate treatment. In particular, the development of a surface treatment agent capable of producing a surface-treated metal material having excellent corrosion resistance, corrosion resistance after alkaline degreasing, grounding properties, and fingerprint resistance is strongly desired.

  Accordingly, the present invention provides a surface-treated metal steel sheet having excellent properties such as corrosion resistance, corrosion resistance after alkaline degreasing, grounding properties, heat resistance, paintability (coating adhesion), and fingerprint resistance. It is an object to provide a surface treatment agent for a metal material, a surface treatment method using the same, and a surface-treated metal material.

As a result of intensive studies to solve the above problems, the present inventors have obtained a predetermined organopolysiloxane compound, a metal compound containing a predetermined metal element, and a compound having a predetermined number of -Si (OH) ₃ groups. The present invention was completed by finding that the above-mentioned problems can be solved by using together.

That is, this invention is (1)-(8) shown below.
(1) From any unit selected from the group consisting of M unit (R ₃ SiO _1/2 ), D unit (R ₂ SiO), T unit (RSiO _3/2 ), and Q unit (SiO ₂ ) A unit comprising a group having a three-dimensional network structure having at least T units and / or Q units in a molecule, and having a functional group (a1) selected from an epoxy group and an amino group as R in one molecule And the ratio (β / α) of the molar amount (α) of the unit having a unit containing an alkyl group as R and the group having the functional group (a1) and the molar amount (β) of all the structural units Is an organopolysiloxane compound (A) having a weight average molecular weight of 200 to 20000 (wherein R is independently a hydroxy group, an alkyl group, an alkoxy group, or an epoxy group and an amino group) A functional group selected from A group having
A metal compound (B) containing at least one metal element selected from the group consisting of Zr, Ti, and V;
A silane coupling agent having a reactive functional group (c1) and a compound having a functional group (c2) capable of reacting with the reactive functional group (c1) are reacted via the reactive functional group (c1). Compound having two or more functional groups (c) represented by —Si (OH) ₃ in one molecule, and the molecular weight per said functional group (c) (weight average molecular weight / number of functional groups) ) In the range of 100 to 5000,
And a surface treatment agent for a metal material containing water.

(2) The surface treatment agent for a metal material according to (1), wherein either one of the reactive functional group (c1) or the functional group (c2) is an amino group or an epoxy group.
(3) The mass ratio (B / A) between the mass of the organopolysiloxane compound (A) and the mass of the metal element in the compound (B) is 0.020 to 4.597, (1) or ( The surface treatment agent for metal materials as described in 2).
(4) The mass ratio (C / A) between the organopolysiloxane compound (A) and the compound (C) is 0.014 to 1.429, according to any one of (1) to (3). Surface treatment agent for metal materials.
(5) The surface for a metal material according to any one of (1) to (4), further containing at least one compound (D) selected from the group consisting of a water-soluble polymer, an aqueous emulsion resin, and a wax. Processing agent.

(6) The surface treatment agent for a metal material according to any one of (1) to (5), further containing at least one compound (F) selected from the group consisting of silicone oil and modified silicone oil.
(7) The surface treatment agent for a metal material according to any one of (1) to (6) is applied on the surface of the metal material, dried by heating, and a film having a film amount of 25 to 1000 mg / m ² is applied to the metal material. A surface treatment method for a metal material, which is formed on a surface.
(8) A metal material having a film obtained by the surface treatment method for a metal material according to (7).

  According to the present invention, it is possible to obtain a surface-treated metal steel sheet having excellent properties such as corrosion resistance, corrosion resistance after alkaline degreasing, earth resistance, heat resistance, paintability (coating film adhesion), and fingerprint resistance. It is possible to provide a surface treatment agent for a metal material, a surface treatment method using the same, and a surface-treated metal material.

Below, the surface treatment agent for metal materials which concerns on this invention, the surface treatment method using the treatment agent, Furthermore, the metal material which has a film | membrane obtained by the surface treatment method is demonstrated.
First, the surface treatment agent for metal material will be described.

<Surface treatment agent for metal materials>
The surface treatment agent for a metal material according to the present invention contains four components.
Specifically, it includes an organopolysiloxane compound (A) described later, a metal compound (B) containing a predetermined metal element described later, a compound (C) having a —Si (OH) ₃ group, and water. .
Hereinafter, each component contained in the surface treatment agent for a metal material according to the present invention will be described.

<Organopolysiloxane compound (A)>
The organopolysiloxane compound (A) is selected from the group consisting of M units (R ₃ SiO _1/2 ), D units (R ₂ SiO), T units (RSiO _3/2 ), and Q units (SiO ₂ ). A group having a three-dimensional network structure having at least a T unit and / or a Q unit in the molecule, and having a functional group (a1) selected from an epoxy group and an amino group as R. A total molar amount (α) of an M unit, a D unit, and a T unit each having a unit containing, a unit containing an alkyl group as R, and a group having a functional group (a1) as R in one molecule; The ratio (β / α) to the total molar amount (β) of one molecule is 1.5 or more, and the weight average molecular weight is 200 to 20000.

By using the organopolysiloxane compound (A), various properties such as corrosion resistance of the resulting film, corrosion resistance after alkaline degreasing, earth resistance, heat resistance, paintability (coating film adhesion), and fingerprint resistance are improved. be able to.
More specifically, between M unit (R ₃ SiO _1/2 ), D unit (R ₂ SiO), T unit (RSiO _3/2 ), and / or Q unit (SiO ₂ ) in compound (A). A siloxane bond (Si—O bond) is formed, and a hardly soluble film is formed.
In particular, in the organopolysiloxane compound (A), when the structural unit contains a group having a functional group (a1) selected from an epoxy group and an amino group, the adhesion between the compound (A) and the substrate becomes good. Therefore, it is thought that the paintability (coating film adhesion) of the obtained film was improved.
Moreover, it is thought that the structural unit which has an alkyl group takes the structure which turned these groups to the outer side in the film | membrane after drying. Thereby, when the compound (A) has a structural unit having an alkyl group, the barrier property of the resulting film is improved, and as a result, various properties of the film are improved. In particular, the corrosion resistance, the corrosion resistance after alkaline degreasing, and the resistance to resistance are improved. It is thought that the fingerprint property has been improved.
In addition, various performance improves by using together this organopolysiloxane compound (A), the metal compound (B) mentioned later, and the compound (C) mentioned later. For example, even if each single substance or two kinds are used, excellent corrosion resistance or excellent corrosion resistance after alkaline degreasing cannot be obtained. On the other hand, when three are used in combination, excellent corrosion resistance and corrosion resistance after alkaline degreasing can be obtained, which can be said to be a synergistic effect obtained by using three compounds in combination.

  The content of the organopolysiloxane compound (A) in the surface treatment agent for metal materials is not particularly limited, but the corrosion resistance of the resulting film, corrosion resistance after alkaline degreasing, grounding, heat resistance, paintability (coating adhesion) ) Is more preferably 8.3 to 91.1% by mass and more preferably 21.4 to 83.5% by mass with respect to the total solid content in the surface treatment agent for a metal material. The total solid content means a solid component (particularly, the compound (A) and components (B) to (F) described later) constituting a film described later, and does not include a solvent.

The organopolysiloxane compound (A) is selected from the group consisting of M units (R ₃ SiO _1/2 ), D units (R ₂ SiO), T units (RSiO _3/2 ), and Q units (SiO ₂ ). And has a three-dimensional structure (three-dimensional network structure) having at least T units and / or Q units in the molecule. For example, M / D / T system, M / D / T / Q system, M / D / Q system, M / T system, M / T / Q system, M / Q system, D / T system, D / T A combination of / Q system, D / Q system, T system, and T / Q system may be mentioned.

The content (mol%) of each unit in the compound (A) is not particularly limited, but the total mol% of the M unit, D unit, and T unit is preferably 15 mol% or more, and more preferably 20 mol% or more. . The upper limit is not particularly limited, but may be the case where the compound (A) is composed of M units, D units, and T units (total mol%: 100 mol%).
As the measuring method of the mole percent, can be carried out by using such ²⁹ Si-NMR and ¹ H-NMR.

  R in the M unit, the D unit, and the T unit each independently represents a hydroxy group, an alkyl group, an alkoxy group, or a group having a functional group selected from an epoxy group and an amino group.

The alkyl group represented as R is not particularly limited, but an alkyl group having 1 to 4 carbon atoms is preferable. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, and a methyl group and an ethyl group are preferable.
Although the alkoxy group represented as R is not specifically limited, For example, a C1-C4 alkoxy group is mentioned preferably. In addition, when carbon number of an alkyl group or an alkoxy group exceeds 4, the compatibility of the compound (A) in a processing agent may fall.

R represents a group having a functional group (a1) selected from an epoxy group and an amino group (hereinafter, appropriately referred to as a group having a functional group (a1)). Such a group is not particularly limited as long as it has the above-mentioned predetermined functional group (a1), and is, for example, a group in which an epoxy group or an amino group is bonded to an alkyl group or an aryl group. May be. In addition, as an epoxy group, an alicyclic epoxy group is also included.
When these groups are contained in the compound (A), the corrosion resistance and paintability (coating film adhesion) are more excellent.

Preferable embodiments of the group having the functional group (a1) include groups represented by the following formula (A).
* -W- (Z) _n formula (A)
In formula (A), W represents a linking group or a single bond. Z represents an epoxy group or an amino group each independently.
The linking group represented by W, for example, an alkylene group (preferably having 1 to 20 carbon atoms), - O -, - S- , an arylene group, -CO -, - NH -, - SO 2 -, - COO -, -CONH-, or a combination thereof. Of these, an alkylene group is preferable.
n represents an integer of 1 to 4 and, among them, 1 to 3 is preferable in that the corrosion resistance and paintability (coating film adhesion) are more excellent. * Indicates a bonding position with a silicon atom (Si atom).

The organopolysiloxane compound (A) has a unit (M unit, D unit, or T unit) containing a group having a functional group (a1) as R. By including the structural unit, the corrosion resistance and paintability (coating film adhesion) of the resulting film are more excellent.
For example, at least one of three Rs in the M unit may be a group having a functional group (a1), and two or three may be a group having a functional group (a1). Among these, M units in which one of three Rs in the M unit is a group represented by the functional group (a1) and the other two Rs are each independently a hydroxy group or an alkoxy group are preferable.
Moreover, what is necessary is just a group in which at least one of two R in D unit has a functional group (a1). Among these, a D unit in which one R in the D unit is a group represented by the functional group (a1) and the other R is a hydroxy group or an alkoxy group is preferable.
In addition, it is preferable to have M unit and T unit containing the group which has a functional group (a1) as R from the point which corrosion resistance is more excellent.

  The ratio (β) of the total molar amount (α) of M units, D units, and T units containing a group having a functional group (a1) as R in one molecule and the total molar amount of constituent units (β) of one molecule / Α) is 1.5 or more, preferably 2.0 to 40.0, and more preferably 2.0 to 30.0. When the ratio is less than 1.5, the resulting film is inferior in corrosion resistance and fingerprint resistance, which is not preferable. Moreover, when this value exceeds 40.0, the compatibility of the compound (A) in a processing agent may fall.

The organopolysiloxane compound (A) has a unit (M unit, D unit, or T unit) containing an alkyl group as R. By including the structural unit, the corrosion resistance and fingerprint resistance after alkali degreasing of the resulting film are further improved. In addition, in one molecule of the compound (A), the number of alkyl groups is preferably larger than the number of groups having the functional group (a1).
For example, at least one of the three Rs in the M unit may be an alkyl group, and two or three may be an alkyl group. Among these, M units in which one of the three Rs in the M unit is an alkyl group and the other two Rs are each independently a hydroxy group or an alkoxy group are preferable.
Moreover, at least 1 should just be an alkyl group among two R in D unit. Among them, a D unit in which one R in the D unit is an alkyl group and the other R is a hydroxy group or an alkoxy group is preferable.

  The ratio (β / γ) of the total molar amount (γ) of M unit, D unit and T unit containing an alkyl group as R in one molecule to the total structural unit molar amount (β) of one molecule is 1 .40 or more is preferable, and 1.42 to 57.20 is more preferable. When the ratio is less than 1.40, the coatability (coating adhesion) of the film may be inferior. Moreover, when this ratio exceeds 57.20, the corrosion resistance and alkali resistance after alkali degreasing of the film may be deteriorated.

  In addition, in the D unit and the T unit containing a plurality (two or three) of R, both the group having the functional group (a1) and the alkyl group may be contained.

The weight average molecular weight of the organopolysiloxane compound (A) is 200 to 20,000, and preferably 300 to 10,000. When the weight average molecular weight is less than 200, it is difficult to synthesize the compound, and the resulting film has poor corrosion resistance, corrosion resistance after alkaline degreasing, and paintability. On the other hand, when the weight average molecular weight exceeds 20000, the compatibility of the compound (A) in the treatment agent decreases.
The molecular weight can be measured by GPC measurement or NMR measurement.

  Although the manufacturing method of an organopolysiloxane compound (A) is not specifically limited, For example, it is preferable to use the silane coupling agent which has a functional group (a1). More specifically, a method of hydrolytic condensation reaction of a silane coupling agent having a functional group (a1) and another kind of alkoxysilane (trialkoxysilane, tetraalkoxysilane, etc.) can be mentioned.

  The production conditions for the organopolysiloxane compound (A) are appropriately selected depending on the compounds used. In the reaction, a solvent may be used as appropriate. Examples of the solvent include methanol, ethanol, propanol, isopropyl alcohol, acetone, methyl ethyl ketone, diacetyl alcohol, water and the like.

When the organopolysiloxane compound (A) is produced using a silane coupling agent having an alkoxy group and / or an alkoxysilane (for example, a silane coupling agent having an alkyl group), the silane coupling agent and the alkoxysilane before the reaction the intensity ratio of the peak intensity derived from the alkoxy group by the ¹ H-NMR measurement of the nuclear magnetic resonance analysis ⁽¹ H-NMR) and the peak intensity derived from the alkoxy group by the measurement, the product after the reaction compound (a) in (Before reaction / after reaction) is preferably 1.1 to 7.0, and more preferably 1.5 to 6.0. When the strength ratio is less than 1.1, the corrosion resistance after alkali degreasing and the fingerprint resistance of the resulting film may be lowered. When the strength ratio exceeds 7.0, the compatibility of the compound (A) in the treatment agent may be reduced.

<Preferred embodiment of compound (A)>
A preferred embodiment of the organopolysiloxane compound (A) includes a compound having a three-dimensional network structure composed of M units, D units, and T units. Use of the compound is preferable in that the resulting film has better corrosion resistance, corrosion resistance after alkaline degreasing, grounding properties, heat resistance, and paintability (coating adhesion).

The structure of the three-dimensional network compound composed of the M unit, the D unit, and the T unit is not particularly limited, but a silane coupling agent having an alkoxy group and a functional group (a1), and other alkoxysilanes (for example, And a compound obtained by a reaction with an alkyl group-containing silane coupling agent).
Although the reaction form is not particularly limited, the reaction usually proceeds by a hydrolysis / condensation reaction between the silane coupling agent and the alkoxysilane. The reaction conditions are not particularly limited as long as a predetermined organopolysiloxane compound (A) is obtained, and an acid / base may be used as necessary.

  Although it does not specifically limit as a silane coupling agent which has a functional group (a1), For example, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, and 2- (3,4-epoxy) Epoxy silanes such as (cyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (aminoethyl) 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane Aminosilane, and the like.

  Moreover, it does not specifically limit as alkoxysilane used for reaction, Trialkoxysilane etc. are mentioned. More specifically, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane , Pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, vinyltrimethoxysilane, 3,3,3-trifluoropropyl Examples include alkoxysilanes having an alkyl group such as trimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

<Metal compound (B)>
The surface treatment agent for a metal material of the present invention includes a metal compound (B) containing at least one metal element selected from the group consisting of Zr, Ti, and V.
The metal compound (B) is immobilized in the film having the three-dimensional crosslinked structure of the compound (A) described above, and as a result, the corrosion resistance of the film, the corrosion resistance after alkaline degreasing, and the grounding property are estimated to be improved.

  The metal compound (B) is not particularly limited as long as it contains the metal element, and examples thereof include nitrates, sulfates, acetates, phosphates, ammonium salts, and fluorides containing the metal.

  More specifically, examples of the metal compound containing Zr include zirconium carbonate ammonium, zirconium nitrate, zirconium oxynitrate, zirconyl acetate, zircon ammonium fluoride, zirconyl sulfate, zircon hydrofluoric acid, and zirconia sol. Moreover, the zirconic acid and its salt which are produced by ion-exchange and alkali neutralizing the aqueous solution of a water-soluble zirconium salt are also mentioned.

  Examples of the metal compound containing Ti include titanyl sulfate, titanyl nitrate, titanium nitrate, titanyl chloride, titanium chloride, titania sol, titanium oxide, ammonium titanium fluoride, potassium oxalate titanate, titanium lactate, titanium acetylacetonate, and diisopropyl titanium. Examples thereof include bisacetylacetone. Further, metatitanic acid obtained by hydrolyzing an aqueous solution of titanyl sulfate, orthotitanic acid obtained by alkali neutralization, and salts thereof are also included.

  Examples of the metal compound containing V include vanadium pentoxide, ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetylacetonate, vanadium acetylacetonate, 3 Examples include vanadium chloride, phosphovanadomolybthenic acid, and vanadium sulfate.

  The content of the metal element in the metal compound (B) in the surface treatment agent for a metal material is not particularly limited, but from the viewpoint that the corrosion resistance of the obtained film, the corrosion resistance after alkaline degreasing, and the grounding property are more excellent. 1.8-38.0 mass% is preferable with respect to the total solid in the surface treatment agent for coating, and 3.4-32.6 mass% is more preferable.

<Compound (C)>
The compound (C) comprises a reactive functional group (c1), a silane coupling agent having a reactive functional group (c1), and a compound having a functional group (c2) capable of reacting with the reactive functional group (c1). And a functional group (c2), a compound obtained by reacting with a functional group (c) having two or more functional groups (c) represented by -Si (OH) ₃ in one molecule. It is a compound (organosilicon compound) having a molecular weight per unit (weight average molecular weight / functional group number) in the range of 100 to 5000.

The compound (C) has two or more functional groups (c) represented by —Si (OH) ₃ in one molecule. Especially, 2-8 pieces are more preferable. In addition, when only one functional group (c) is contained in one molecule, it is not preferable because adhesion to a metal material surface is lowered.
The compound (C) may have a hydrolyzable group represented by a —Si (OX) ₃ group in addition to —Si (OH) ₃ (wherein X represents an alkyl group). However, C1-C4 is preferable.) From the viewpoint of more excellent properties of the resulting film, it is preferable that the film does not substantially contain —Si (OX) ₃ groups.

The compound (C) preferably has a molecular weight (weight average molecular weight / functional group number) per functional group (c) in the range of 100 to 5000, more preferably in the range of 120 to 4000, and particularly preferably. It is in the range of 150 to 3000. When the molecular weight per functional group (c) is less than 100, the synthesis of the compound is difficult, and the corrosion resistance and adhesion of the resulting film are inferior. On the other hand, when it exceeds 5000, the adhesiveness with respect to the metal material surface which is the characteristic of a functional group (c) falls, and is not preferable.
In addition, as a measuring method of molecular weight, it can measure using gel permeation chromatography (GPC) and NMR.

  The skeleton of the compound (C) is not particularly limited, but preferably has a bond such as an ester bond, an ether bond, an acid amide bond, an amide bond, a urethane bond, a urea bond, or a vinyl bond.

  By using the compound (C), a three-dimensional cross-linked structure is formed in the film. Therefore, it is presumed that the corrosion resistance of the obtained film and the corrosion resistance after alkaline degreasing have been improved. In addition, since the functional group (c) of the compound (C) has good adhesion to metal materials (particularly zinc), the resulting corrosion resistance, corrosion resistance after alkaline degreasing, and paintability (coating film adhesion) are improved. I guess it was. Furthermore, since the molecular weight (weight average molecular weight / functional group number) per functional group (c) is in the range of 100 to 5000, it is presumed that the grounding property of the film has been improved.

  The reactive functional group (c1) is not particularly limited as long as it is a group that reacts with other functional groups to form a bond. For example, an epoxy group, an amino group, a mercapto group, an acryloxy group, a ureido group, an isocyanic group. A functional group selected from the group consisting of a nate group and a vinyl group is preferred. Especially, an epoxy group, an amino group, or a vinyl group is preferable from the point which is excellent in the reactivity with the functional group (c2) mentioned later, and is more excellent in the characteristics of the film obtained.

  One preferred embodiment of the silane coupling agent having a reactive functional group (c1) is a compound represented by the general formula (1).

  In General Formula (1), X represents any functional group selected from the group consisting of an epoxy group, an amino group, a mercapto group, an acryloxy group, a ureido group, an isocyanate group, and a vinyl group. L represents a linking group or a simple bond. Y represents a C1-C4 alkyl group, an alkoxy group, or a hydroxyl group each independently. However, at least one of Y represents an alkoxy group or a hydroxyl group.

  In General Formula (1), X represents any functional group selected from the group consisting of an epoxy group, an amino group, a mercapto group, an acryloxy group, a ureido group, an isocyanate group, and a vinyl group. Of these, an epoxy group, an amino group, and a vinyl group are preferable.

In general formula (1), L represents a linking group or a simple bond. Examples of the linking group represented by L include an alkylene group (preferably having 1 to 20 carbon atoms), —O—, —S—, an arylene group, —CO—, —NH—, —SO ₂ —, —COO. -, -CONH-, or a combination thereof. Of these, an alkylene group is preferable. In the case of a simple bond, it means that X in the general formula (1) is directly connected to Si (silicon atom).

In general formula (1), Y represents a C1-C4 alkyl group, an alkoxy group, or a hydroxyl group each independently. Especially, a C1-C3 alkoxy group and a hydroxyl group are preferable.
However, at least one of Y represents an alkoxy group or a hydroxyl group. Especially, it is preferable that 2-3 of Y is an alkoxy group or a hydroxyl group, and it is more preferable that 3 is this group.

  Examples of the silane coupling agent having a reactive functional group (c1) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Epoxy silanes such as trimethoxysilane, aminosilanes such as N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (aminoethyl) 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane; Mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, isocyanate silanes such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, vinyltriethoxysilane, p-styryltrimethoxy Vinyl group-containing silane, such as orchids and the like.

  The functional group (c2) in the compound having the functional group (c2) is not particularly limited as long as it can react with the reactive functional group (c1), and is an epoxy group, an amino group, a mercapto group, an acryloxy group. Ureido group, isocyanate group, vinyl group, and the like, and an epoxy group or an amino group is preferred from the viewpoint of more excellent properties of the resulting film. Of these, a functional group different from the reactive functional group (c1) is preferably exemplified.

  Examples of the compound having the functional group (c2) include silane coupling agents having the reactive functional group (c1), amine compounds such as ethylenediamine and aminopropanethiol, trimethylolpropane polyglycidyl ether, and pentaerythritol poly. Examples thereof include ether compounds such as glycidyl ether, epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolak type epoxy resin. Especially, the silane coupling agent illustrated with the silane coupling agent which has a reactive functional group (c1) is preferable.

  In addition, the reaction form of the reactive functional group (c1) and the functional group (c2) is not particularly limited, and an addition reaction (for example, reaction of epoxy group or isocyanate group with amine group or mercapto group, between vinyl groups Polyaddition, etc.) and polycondensation reactions.

  As the reaction conditions, optimum conditions are appropriately selected depending on the compounds used. In the reaction, a solvent (for example, methanol, ethanol, propanol, isopropyl alcohol, acetone, methyl ethyl ketone, diacetyl alcohol, water, etc.) may be used.

  The reaction ratio between the silane coupling agent having a reactive functional group (c1) and the compound having a functional group (c2) is not particularly limited, but the silane coupling agent / compound (molar ratio) is 9/1 to 1. / 9 is preferable, and 7/3 to 3/7 is more preferable.

<Preferred embodiment of compound (C)>
As one preferred embodiment of the compound (C), a silane coupling agent having a reactive functional group (c1) and a silane coupling agent having a functional group (c2) capable of reacting with the reactive functional group (c1) And the reaction product.
When the reaction product is used, excellent effects are exhibited in various performances of the film such as corrosion resistance, earth resistance, and fingerprint resistance.

As another preferred embodiment of the compound (C), a compound (reaction product) obtained by reaction (polymerization) of a silane coupling agent having a vinyl group and a copolymerizable vinyl compound can be mentioned.
The silane coupling agent having a vinyl group is not particularly limited as long as it has a vinyl group, and examples thereof include γ-methacryloxypropyltriethoxysilane, vinyltrichlorosilane, and vinyltrimethoxycinlane.
In addition, the copolymerizable vinyl compound is not particularly limited, and examples thereof include acrylic acid, butyl acrylate, methyl acrylate, and 2-hydroxyethyl methacrylate.

  The reaction form using the above-mentioned compound is not particularly limited, and examples thereof include anionic polymerization, cationic polymerization, and radical polymerization. Of these, radical polymerization is preferred. In addition, according to the reaction form selected, you may use a well-known polymerization initiator etc. suitably.

<Water>
The surface treatment agent for a metal material of the present invention contains water as a solvent. The content of water in the surface treatment agent for a metal material is not particularly limited, but is preferably 30 to 99 mass% with respect to the total amount of the treatment agent from the viewpoint of easier handling of the treatment agent, and 40 to 95. The mass% is more preferable.

  The mass ratio (B / A) between the mass of the compound (A) and the mass of the metal element in the metal compound (B) in the surface treatment agent for a metal material is preferably 0.020 to 4.597. 0.041 to 1.522 is more preferable. When the mass ratio is less than 0.020, the corrosion resistance may be inferior, and when the mass ratio exceeds 4.597, the paintability may be inferior.

  The mass ratio (C / A) between the compound (C) and the compound (A) in the surface treatment agent for metal materials is preferably 0.014 to 1.429, more preferably 0.042 to 0. .470. When the mass ratio is less than 0.014, the paintability (coating film adhesion) may be inferior, and when the mass ratio exceeds 1.429, the grounding property may be inferior.

In addition to the compounds described above, the surface treatment agent for a metal material of the present invention may contain at least one compound (D) selected from the group consisting of a water-soluble polymer, an aqueous emulsion resin, and a wax.
Below, each component is demonstrated.

<Water-soluble polymer, water-based emulsion resin and / or wax>
The surface treatment agent for a metal material of the present invention may contain at least one compound (D) selected from the group consisting of a water-soluble polymer, an aqueous emulsion resin, and a wax. By adding these components, various properties of the resulting film are improved, and in particular, corrosion resistance, corrosion resistance after alkaline degreasing, and lubricity are improved.

  The water-soluble polymer, water-based emulsion resin and / or wax are not particularly limited. For example, water-soluble polymers such as polyacrylic acid, polymethacrylic acid, polyacrylamide, and polyvinyl alcohol, and acrylic resin dispersed in water. , Urethane resin, epoxy resin, polyester resin, polyamide resin, polyolefin resin, ethylene-acrylic resin, polybutyral resin, polyacetal resin, fluororesin, polyethylene wax, oxidized polyethylene wax, oxidized polypropylene wax, microcrystalline wax, carnauba wax, Solid lubricants such as paraffin wax, montan wax, and Teflon (registered trademark) may be used, and one or more solid lubricants may be used.

  The total content of the compound (D) in the surface treatment agent for metal materials is not particularly limited, but from the viewpoint of more excellent corrosion resistance of the resulting film and corrosion resistance after alkaline degreasing, the total solid content in the treatment agent 1.1-55.2 mass% is preferable, and 5.3-50.5 mass% is more preferable.

  The mass ratio (D / A) between the compound (A) and the compound (D) in the surface treatment agent for a metal material is preferably 0.015 to 2.488, and is 0.077 to 2.050. More preferably. If it is the said suitable range, the corrosion resistance of a membrane | film | coat, grounding property, heat resistance, fingerprint resistance, etc. will be more excellent. In addition, when it is less than 0.015, it may be inferior to corrosion resistance, and when it exceeds 2.488, it may be inferior to heat resistance.

  In addition to the compounds described above, the surface treatment agent for a metal material of the present invention may contain at least one compound (F) selected from the group consisting of silicone oil and modified silicone oil. Below, each component is demonstrated.

<Silicone oil and modified silicone oil>
The surface treatment agent for a metal material of the present invention may contain at least one compound (F) selected from the group consisting of silicone oil and modified silicone oil. By adding these components, various properties of the resulting film are improved, and in particular, corrosion resistance and fingerprint resistance after alkaline degreasing are improved.
Silicone oil and modified silicone oil are linear siloxane polymers mainly composed of M units (R ₃ SiO _1/2 ) and D units (R ₂ SiO).

  Although it does not specifically limit as silicone oil and modified silicone oil (for example, amine modified silicone oil), for example, methyl hydrogen silicone oil, dimethyl silicone oil, diethyl silicone oil, diisopropyl silicone oil, dibutyl silicone oil, diamyl silicone oil, Dihexyl silicone oil, dilauryl silicone oil, distearyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, ethylphenyl silicone oil, isopropylphenyl silicone oil, butylphenyl silicone oil, amylphenyl silicone oil, hexylphenyl silicone oil, laurylphenyl Silicone oil or stearyl phenyl Corn oil and, or, and these ones were charged and emulsified in water by a surfactant and the like.

The surfactant to be used is not particularly limited, and an anionic surfactant, a nonionic surfactant, and a cationic surfactant can be used. For emulsification and dispersion, an agitation device such as a homomixer or a disper mixer, or an emulsification device such as a high-pressure homogenizer or a colloid mill may be used.
Moreover, as the emulsion obtained by emulsifying and dispersing silicone oil and modified silicone oil with a surfactant, those commercially available as emulsion types can be appropriately selected and used.

  The mass ratio (F / A) between the compound (A) and the compound (F) in the surface treatment agent for metal material is preferably 0.007 to 0.217, and preferably 0.015 to 0.115. More preferably. When the mass ratio is less than 0.007, the corrosion resistance may be inferior, and when the mass ratio exceeds 0.217, the paintability may be inferior.

<PH>
2-11 are preferable and, as for pH of the surface treating agent for metal materials of this invention, 3-10 are more preferable. If it is the said suitable range, the earth property of the membrane | film | coat obtained will improve more. In addition, when pH is less than 2, earth property may fall by a metal material being etched excessively. On the other hand, when the pH exceeds 11, the ammonia odor is remarkably inferior in workability, and the obtained film performance may be inferior. For adjusting the pH, it is preferable to use ammonia, carbonic acid, nitric acid, organic acid or the like.

<Fluorine compound>
The surface treatment agent for a metal material of the present invention may contain a fluorine compound as necessary. In particular, in hot-dip galvanized steel sheets with a thick surface oxide film, adding a fluorine compound to improve the etchability of the surface treatment agent for metal materials increases the reaction layer (non-conductive layer) with the material surface. Thus, a further effect of improving corrosion resistance can be expected. However, when a fluorine compound is added to the surface treatment agent for a metal material, since the etching property is increased, the grounding property may be lowered due to dissolution other than the surface oxide film. In addition, the amount of Zn or Fe mixed in the aqueous treatment liquid may increase, which may reduce the stability of the surface treatment agent for metal materials. Since a problem arises, it is preferable to set the range in consideration of these.

  Examples of the fluorine compound include ammonium fluoride, ammonium silicofluoride, ammonium titanium fluoride, and zircon ammonium fluoride.

  Although content of the fluorine compound in the surface treatment agent for metal materials of this invention is not specifically limited, It is preferable to make 50 g an upper limit as a fluorine in 1 kg of processing agents.

<Antifoaming agent>
The surface treatment agent for a metal material of the present invention may contain an antifoaming agent as necessary. The surface treatment agent for metal material containing this antifoaming agent is sprayed or sprayed onto a metal steel plate, the amount of coating is adjusted with a roll or air squeeze, and then dried at a temperature of 50 to 250 ° C. as the maximum plate temperature. It is preferable to form a film on the surface.

  Although it does not specifically limit as an antifoamer, The thing which stably emulsified mineral oil, the fatty acid, silicone, etc., and the thing of a water-soluble activator type can be used. You may use both together.

  The content of the antifoaming agent in the surface treatment agent for a metal material of the present invention is appropriately selected depending on the type used, but is 0.1 to 3.0 g per kg of the treatment liquid. preferable. If the content of the antifoaming agent is too small, the defoaming property cannot be obtained, and if it is too much, the paintability is poor.

  The surface treatment agent for a metal material of the present invention may contain a solvent (for example, alcohol) other than the water as necessary.

  The method for preparing the surface treatment agent for a metal material of the present invention is not particularly limited. For example, it can manufacture by fully mixing a compound (A), a metal compound (B), a compound (C), other additives, and water using a stirrer such as a mixing mixer.

<Surface treatment method>
The surface treatment method using the surface treatment agent for a metal material of the present invention is not particularly limited, but the above-described surface treatment agent for a metal material is applied on the surface of the metal material, dried, and the coating amount is 25 to 1000 mg / m. A surface treatment method in which the film ² is formed on the surface of the metal material is preferable. It is preferably used as a so-called coating type surface treatment agent.
The surface treatment method will be described below.

Prior to application, the metal material may be pretreated for the purpose of removing oil and dirt on the surface of the metal material, if necessary. For example, when a galvanized steel sheet is used as the metal material, rust preventive oil is often applied for the purpose of rust prevention. Moreover, even when not coated with rust preventive oil, there are oil and dirt adhered during the work. By performing the pretreatment, the surface of the galvanized steel sheet is cleaned, and the surface of the galvanized steel sheet is easily wetted by the surface treatment agent for metal material of the present invention.
The pretreatment method is not particularly limited, and examples thereof include hot water washing, solvent washing, and alkaline degreasing washing. In the case where there is no oil or dirt, and the surface of the material is uniformly wetted with the surface treatment agent for a metal material of the present invention, the pretreatment step is not particularly necessary.

Although it does not specifically limit as a metal material used, A zinc containing metal plating steel plate, an aluminum plate, and a stainless steel plate are preferable. Of these, a galvanized steel sheet is preferred. These metal material surfaces may be subjected to pretreatment such as phosphate treatment in advance.
Examples of the galvanized steel sheet include a galvanized steel sheet (GI), an alloyed galvanized steel sheet (GA) alloyed with the galvanized steel sheet, a galvanized Zn-5% Al alloy-plated steel sheet (GF), and a galvanized steel sheet. Examples include 55% aluminum alloy plated steel sheet (GL), electrogalvanized steel sheet (EG), and electrogalvanized-Ni alloy plated steel sheet (Zn-Ni). Moreover, it is applicable also to the iron plate which has not plated.

The method of applying the surface treatment agent for metal material of the present invention to the metal material is not particularly limited as long as the surface treatment agent for metal material can be uniformly applied to the surface of the metal material, and roll coating method, dipping method, spray coating method. Etc.
Further, the treatment (application) temperature and the treatment (application) time are not particularly limited, but in general, the treatment (application) temperature is preferably 10 to 40 ° C., and the treatment (application) time is 0.1 to 10 seconds. Preferably there is.

As heating temperature at the time of drying the coating film formed on the metal material surface, 50-250 degreeC is preferable and 60-180 degreeC is more preferable. If it is the said suitable range, the corrosion resistance of the membrane | film | coat obtained will be more excellent. The heating and drying method is not particularly limited, and the treatment agent may be dried by heating with hot air, an induction heater, infrared rays, near infrared rays, or the like.
The heating time is appropriately selected depending on the type of compound in the surface treatment agent for metal material used. Especially, from points, such as productivity, 0.1-60 seconds are preferable and 1-30 seconds are more preferable.

The amount of coating formed on the metal material surface is preferably ^{25~1000mg / m 2, 100~800mg / m} 2 is more preferable. If it is the said suitable range, the corrosion resistance and heat resistance of the film which are obtained will be more excellent. If it is less than 25 mg / m ² , the surface treatment agent for metal materials cannot be uniformly applied to the surface of the steel sheet, and various desired characteristics such as corrosion resistance and fingerprint resistance of the film cannot be exhibited in a balanced manner. There is a case. If it exceeds 1000 mg / m ² , the grounding property and heat resistance of the film may be lowered. In addition, said film | membrane amount means the film | membrane amount on the single side | surface of a steel plate.

  On the film formed by the above-mentioned surface treatment method, an organic polymer film is formed so that the film thickness after drying becomes 0.1 to 10.0 μm, and further higher corrosion resistance, fingerprint resistance and lubricity Can be granted. As such an organic polymer film, a known resin emulsion such as acrylic, urethane, epoxy, and the like, to which silica, a rust preventive agent, a lubricant, an ultraviolet absorber, a pigment and the like are added can be used.

  The metal material treated by the surface treatment method described above can be applied to various uses. For example, steel sheets for home appliances, steel sheets for building materials, steel sheets for automobiles, and the like can be given.

  As described above, according to the present invention, a surface-treated metal material excellent in various properties such as corrosion resistance, corrosion resistance after alkaline degreasing, earth resistance, heat resistance, paintability (coating film adhesion), and fingerprint resistance is obtained. It is possible to realize a surface treating agent for metal materials that can

  Hereinafter, the working effects of the present invention will be described specifically by way of examples. The following examples do not limit the present invention, and those whose design has been changed in accordance with changes in conditions are included in the technical scope of the present invention.

(1) Test material (material)
The following commercially available materials were used as test materials.
(I) Electrogalvanized steel sheet (EG): thickness 0.8 mm, basis weight = 20/20 (g / m ² )
(Ii) Hot-dip galvanized steel sheet (GI): thickness 0.8 mm, basis weight = 60/60 (g / m ² )
(Iii) Alloyed hot-dip galvanized steel sheet (GA): thickness 0.8 mm, basis weight = 40/40 (g / m ² )
The basis weight indicates the basis weight on the main surface of each steel plate. For example, in the case of an electrogalvanized steel sheet, it is 20/20 (g / m ² ), which means that each side of the steel sheet has a plating of 20 g / m ² .

(2) Pretreatment (cleaning)
As a method for preparing the test plate, first, the surface of the test material was treated with Palclean N364S manufactured by Nihon Parkerizing Co. to remove oil and dirt on the surface. Next, after rinsing with tap water and confirming that the surface of the galvanized steel sheet was 100% wet with water, pure water was further poured, and water removed from the oven in a 100 ° C. atmosphere was used as a test plate.

(3) Preparation of surface treatment agent for metal material Each component was mixed in water at the blending amounts shown in Table 1 (No. 1 to No. 3) to obtain a surface treatment agent for metal material (Examples and Comparative Examples). ). The main component other than component (A), component (B), component (C), component (D), and component (F) shown in Table 1 is water.
Moreover, the compounding amount of the component (A), the component (C), the component (D), and the component (F) in Table 1 represents the amount (g) compounded in 1 kg of the metal material surface treatment agent. Moreover, "mass%" of these components represents "mass%" with respect to the total solid content in the surface treating agent for metal materials.
The compounding quantity of the component (B) in Table 1 represents the mass (g) of the metal element in the metal compound (B) compounded in 1 kg of the metal treating agent. Moreover, "mass%" of these components represents mass% of the metal element in a component (B) (metal compound) with respect to the total solid in the surface treating agent for metal materials.
In addition, the calculated solid content in Table 1 represents the total solid content in the surface treatment agent for metal materials. Moreover, ammonia water, nitric acid, etc. were used for pH adjustment.

  The components shown in Table 1 will be described below. In addition, the physical property value (molecular weight, constituent molar amount, etc.) of the compound (A) and the compound (C) described later was obtained by NMR measurement, GPC measurement and the like.

<Compound (A)>
A1: γ-Glycidoxypropyltriethoxysilane (1.0 mol) and methyltriethoxysilane (1.0 mol) were added to deionized water at 50 ° C. to 60 ° C. and stirred for 5 hours. The alkoxy group in the raw material compound changed to a silanol group, and then a condensation reaction between the silanol groups proceeded to obtain Compound A1. ^{When 29} Si-NMR measurement was performed, signals of M units, D units, and T units were detected, but Q units were not detected. ^From the results of ²⁹ Si-NMR measurement and ¹ H-NMR measurement, β / α was about 2.0 and β / γ was about 2.0. When the weight average molecular weight of compound A1 was measured using GPC (polystyrene conversion), it was about 1200.
^{Further, 1 H-NMR (1 H} -NMR: 3.5~3.6ppm vicinity) were measured, and the peak intensity derived from the alkoxy groups derived from the raw material compound before the reaction, the resulting organopolysiloxane compound A1 The peak intensity ratio of the peak intensity derived from the alkoxy group was 3.0, and no peak change of Si—CH ₃ was observed.
Then, it diluted with deionized water so that it might become 5 mass% of solid content concentration.

A2: Compound A2 was obtained by synthesizing by the same method as Compound A1, except that the γ-glycidoxypropyltriethoxysilane of A1 was changed to aminopropyltriethoxysilane (0.5 mol). . ^{When 29} Si-NMR measurement was performed, signals of M units, D units, and T units were detected, but Q units were not detected. ^From the results of ²⁹ Si-NMR measurement and ¹ H-NMR measurement, β / α was about 3.0 and β / γ was about 1.5. It was about 2000 when the weight average molecular weight of compound A2 was measured using GPC (polystyrene conversion).
^{Further, 1 H-NMR (1 H} -NMR: 3.5~3.6ppm vicinity) were measured, and the peak intensity derived from the alkoxy groups derived from the raw material compound before the reaction, the resulting organopolysiloxane compound A2 The peak intensity ratio with the peak intensity derived from the alkoxy group was 2.3, and no peak change of Si—CH ₃ was observed.
Then, it diluted with deionized water so that it might become 5 mass% of solid content concentration.

A3: Compound A1 (0.5 mol) and compound A2 (0.5 mol) were mixed with reference to the measured molecular weight. Thereafter, the reaction solution was stirred at 50 ° C. to 60 ° C. for 5 hours to obtain Compound A3. ^{When 29} Si-NMR measurement was performed, signals of M units, D units, and T units were detected, but Q units were not detected. ^From the results of ²⁹ Si-NMR measurement and ¹ H-NMR measurement, β / α was about 2.3 and β / γ was about 1.7. It was about 1500 when the weight average molecular weight was measured using GPC (polystyrene conversion).
Further, when ¹ H-NMR ( ¹ H-NMR: around 3.5 to 3.6 ppm) was measured, the peak intensity derived from the alkoxy group derived from the raw material compound before the reaction and the obtained organopolysiloxane compound A3 The peak intensity ratio with the peak intensity derived from the alkoxy group was 2.0, and no peak change of Si—CH ₃ was observed.
Then, it diluted with deionized water so that it might become 5 mass% of solid content concentration.

<Metal compound (B)>
B1: ammonium zirconium carbonate (in B1, the content of Zr is 52.8% by mass)
B2: Titanium ammonium fluoride (in Ti, the content of Ti is 20.0% by mass)
B3: ammonium metavanadate (the content of V in B3 is 37.3% by mass)

<Compound (C)>
C1: Hexamethylenediamine (1 mol) and γ-glycidoxypropyltrimethoxysilane (2 mol) were reacted in ethanol to obtain a product. Then, deionized water was added and diluted to a solid content concentration of 5% by mass.
In addition, the number of functional groups (c) in one molecule of the obtained product C1 was 2, and the molecular weight (weight average molecular weight / functional group number) per functional group (c) was about 294. The product C1 substantially did not have a group having an alkoxy group represented by a —Si (OX) ₃ group (X: methyl group).
C2: Aminopropyltriethoxysilane (1 mol) and γ-glycidoxypropyltrimethoxysilane (2 mol) were reacted in ethanol to obtain a product. Then, deionized water was added and diluted with deionized water to a solid content concentration of 5% by mass.
In addition, the number of functional groups (c) in one molecule of the obtained product C2 was 2, and the molecular weight (weight average molecular weight / functional group number) per functional group (c) was about 894. The product C2 substantially did not have a group having an alkoxy group represented by a —Si (OX) ₃ group (X: methyl group).

<Compound (D)>
D1: Acrylic resin (manufactured by Showa Polymer Co., Ltd., Polyzol AM-2386)
D2: Wax (Mitsui Chemicals, Chemipearl W500)

<Compound (F)>
F1: Amine-modified silicone oil (XS65-B8124 manufactured by Momenteive Performance Materials Japan)

(4) Treatment method The above-mentioned surface treatment agent for metal material is coated on each test plate by the bar coat painting method, and then placed in an oven as it is without washing with water at the drying temperature shown in Table 2. The film was dried to form a film having the film amount shown in Table 2. The coating amount refers to the coating amount per one side of the steel plate.
The drying temperature was adjusted by the atmospheric temperature in the oven and the time in the oven. The drying temperature indicates the temperature reached on the test plate surface. The specific method of bar coat painting is as follows.

  Bar coat coating: The treatment agent was dropped onto the test plate and painted with a # 3-5 bar coater. It adjusted so that it might become a predetermined | prescribed film quantity with the count of the bar coater used and the density | concentration of a process liquid.

(5) Evaluation test method (5-1) Corrosion resistance (and corrosion resistance after alkaline degreasing)
The obtained surface-treated zinc-based plated steel sheet was cut into a size of 70 × 150 mm, and a test piece with the back side and end sealed with cellophane tape was subjected to a salt spray test specified in JIS Z2371, and white rust was 5% ( Area ratio) Time until occurrence was evaluated.
Further, the surface-treated zinc-based plated steel sheet washed with 20 g / L of alkaline degreasing agent (Nippon Parkerizing Co., Ltd., Pulclean N364S), sprayed at 60 ° C. for 2 minutes and then washed with water was evaluated in the same manner as corrosion resistance after alkaline degreasing. The evaluation criteria at this time are shown below.
A: 120 hours or more until 5% of white rust occurs: 48 hours or more and less than 120 hours until occurrence of 5% white rust Δ: 24 hours or more and less than 48 hours until 5% of white rust occurs x: 24% until occurrence of 5% white rust Less than time On the other hand, the evaluation criteria regarding GA are shown below.
◎: 48% or more until white rust 5% occurrence ○: 24 hours or more until white rust occurrence 5%, less than 48 hours △: 12% or more until white rust occurrence 5%, less than 24 hours ×: 12% until white rust occurrence 5% Less than an hour

(5-2) Paintability After applying a melamine paint (Amirac # 1000, manufactured by Kansai Paint Co., Ltd.) to a surface-treated zinc-based plated steel sheet, the coating thickness after baking at 160 ° C. was set to 20 μm. . After coating, the film was immersed in boiling water for 1 hour, and then 100 squares of 1 mm square grids were put into the coating film, extruded 5 mm with an Erichsen extruder, and then the tape was peeled off to evaluate the residual rate of mass. The evaluation criteria at this time are shown below.
A: Remaining rate 91-100%
○: Remaining rate 71-90%
Δ: Remaining rate 51-70%
X: Residual rate 0 to 50%

(5-3) Grounding property The interlayer resistance of the obtained surface-treated galvanized steel sheet was measured with an interlayer resistance measuring machine. Evaluation was made according to the following criteria.
◎: Less than 1Ω
○: 1Ω or more, less than 2Ω
Δ: 2Ω or more, less than 3Ω
×: 3Ω or more

(5-4) Heat resistance The obtained surface-treated galvanized steel sheet was cut into a size of 70 × 150 mm, heated in an oven at 200 ° C. for 2 hours, and then allowed to stand at room temperature for 24 hours. Then, the salt spray test prescribed | regulated to JISZ2371 was implemented about the test piece which sealed the back side and the edge part with the cellophane tape, and time until white rust generate | occur | produces 5% (area ratio) was evaluated.
A: 120 hours or more until 5% of white rust occurs: 48 hours or more and less than 120 hours until occurrence of 5% white rust Δ: 24 hours or more and less than 48 hours until 5% of white rust occurs x: 24% until occurrence of 5% white rust Less than time On the other hand, the evaluation criteria regarding GA are shown below.
◎: 48% or more until white rust 5% occurrence ○: 24 hours or more until white rust occurrence 5%, less than 48 hours △: 12% or more until white rust occurrence 5%, less than 24 hours ×: 12% until white rust occurrence 5% Less than an hour

(5-5) Fingerprint resistance Vaseline is applied to the surface-treated zinc-based plated steel sheet, wiped with gauze, and color change before and after application of petrolatum ΔE = {(ΔL) ² + (Δa) ² + (Δb) ² } Rated ^1/2 . (Measuring device: Nippon Denshoku Industries Co., Ltd., color meter ZE2000)
◎: ΔE is less than 2 ○: ΔE is 2 or more and less than 3 Δ: ΔE is 3 or more and less than 4 ×: ΔE is 4 or more

Table 3 shows the results of the above evaluations (5-1) to (5-5) for the surface-treated metal materials obtained using the surface treatment agents for metal materials of Examples and Comparative Examples. .
From a practical viewpoint, the evaluation item is required to be “◯” or “ま た は”.

  As shown in Table 3, the surface-treated galvanized steel sheet treated with a treating agent using various components specified in the present invention at a predetermined ratio is corrosion resistance, corrosion resistance after alkaline degreasing, grounding resistance, heat resistance, It was found that excellent properties were well-balanced in various properties such as paintability (coating film adhesion) and fingerprint resistance.

  Especially, when Example 9,11,12 was compared, when A3 was used as a compound (A), it turned out that the more superior effect (corrosion resistance) is acquired. Moreover, when Example 17 and 19 were compared, when B1 was used as a compound (B), it turned out that the more superior effect (corrosion resistance) is acquired. Furthermore, when Examples 34-38 were compared, it turned out that the more superior effect (earthing property) is acquired in 3-10 as pH of a solution.

On the other hand, about the processing conditions, when Examples 29-33 were compared, when the film amount was 100-800 mg / m < ² >, it turned out that the more superior effect (coexistence of corrosion resistance and heat resistance) is acquired. Moreover, when Examples 39-43 were compared, when the drying temperature was 60-180 degreeC, it turned out that the more superior effect (it has a corrosion resistance, earth property, and coating property is acquired).

  In the comparative example, a surface-treated galvanized steel sheet that comprehensively satisfies various characteristics could not be obtained. For example, in Comparative Examples 54 to 56 in which any one of the compounds (A) to (C) is not included, the corrosion resistance, the corrosion resistance after alkaline degreasing, the paintability, the fingerprint resistance, and the like are particularly poor. It was.

Claims (8)

Composed of any unit selected from the group consisting of M units (R ₃ SiO _1/2 ), D units (R ₂ SiO), T units (RSiO _3/2 ), and Q units (SiO ₂ ); A unit having a three-dimensional network structure having at least T units and / or Q units in the molecule, and a group having a functional group (a1) selected from an epoxy group and an amino group as R in one molecule; The ratio (β / α) of the molar amount (α) of the unit containing a group having an alkyl group and the group having the functional group (a1) to the molar amount (β) of all structural units is 1. Organopolysiloxane compound (A) having a weight average molecular weight of 200 to 20000 (wherein R is independently selected from a hydroxy group, an alkyl group, an alkoxy group, or an epoxy group and an amino group) Has a functional group And the show.)
A metal compound (B) containing at least one metal element selected from the group consisting of Zr, Ti, and V;
A silane coupling agent having a reactive functional group (c1) and a compound having a functional group (c2) capable of reacting with the reactive functional group (c1) are reacted via the reactive functional group (c1). Compound having two or more functional groups (c) represented by —Si (OH) ₃ in one molecule, and the molecular weight per said functional group (c) (weight average molecular weight / number of functional groups) ) In the range of 100 to 5000,
And a surface treatment agent for a metal material containing water.   The surface treatment agent for metal materials according to claim 1, wherein either one of the reactive functional group (c1) or the functional group (c2) is an amino group or an epoxy group.   The mass ratio (B / A) of the mass of the organopolysiloxane compound (A) and the mass of the metal element in the compound (B) is 0.020 to 4.597. Surface treatment agent for metal materials.   The surface treatment for metal materials according to any one of claims 1 to 3, wherein a mass ratio (C / A) between the organopolysiloxane compound (A) and the compound (C) is 0.014 to 1.429. Agent.   The surface treatment agent for metal materials according to any one of claims 1 to 4, further comprising at least one compound (D) selected from the group consisting of a water-soluble polymer, an aqueous emulsion resin, and a wax.   The surface treatment agent for a metal material according to any one of claims 1 to 5, further comprising at least one compound (F) selected from the group consisting of silicone oil and modified silicone oil. The surface treatment agent for a metal material according to any one of claims 1 to 6 is applied on the surface of the metal material and dried by heating to form a film having a film amount of 25 to 1000 mg / m ² on the surface of the metal material. , Surface treatment method of metal material.   A metal material having a film obtained by the surface treatment method for a metal material according to claim 7.