TW201900790A - Water-based metal surface treatment agent and metal material having film and method for producing same - Google Patents

Abstract

A subject of the present invention is to provide a water-based metal surface treatment agent which can form a skin film with excellent corrosion resistance, chemical resistance, coating film adhesion and abrasion resistance on a metal material. A solution of the present invention is to form the above-mentioned skin film on the metal material by using a water-based metal surface treatment agent containing a carbamate resin (A) and a silane compound (B), the aforementioned carbamate resin (A) includes a structural unit derived from a specific polyisocyanate having a cyclohexane ring structure, a structural unit derived from a specific polyol, a structural unit derived from a specific diol having a weight average molecular weight of more than 600, a structural unit derived from a specific diol having a weight average molecular weight of 500 or less, and a structural unit derived from a specific tertiary amine compound and/or a salt thereof.

Description

Water-based metal surface treatment agent, metal material with coating film and manufacturing method thereof

The present invention relates to a water-based metal surface treatment agent, a method for producing a metal material having a film using the same, and a metal material having a film obtained by the production method.

Metal surface treatment agents have been developed which can form films that impart various properties to metal materials. For example, Patent Document 1 discloses a technology for a water-based coating composition for surface treatment of a metal material containing a specific cationic water-based urethane resin.

In addition, Patent Document 2 discloses a metal surface treatment of an aqueous dispersion containing a specific urethane urea resin, a specific hardener, silica particles, and at least one metal compound selected from Ti, Zr, and V. Agent technology.

[Prior Art Document] [Patent Document] [Patent Document 1] International Publication No. 2005/092998 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-231353

[Problems to be Solved by the Invention] However, the above-mentioned technique cannot form a film having excellent corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance on a metal material. Therefore, an object of the present invention is to provide a water-based metal surface treatment agent capable of forming a film having excellent corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance on a metal material, and a metal material having the film and Its manufacturing method.

As a result of repeated in-depth reviews, the inventors of the present invention found that the use of a surface treating agent containing a specific urethane resin and a silane compound can solve the above-mentioned problems and complete the present invention. The present invention includes the following.

[1] A water-based metal surface treatment agent comprising a urethane resin (A) and a silane compound (B), wherein the urethane resin (A) is derived from the following formula (1) A structural unit of a polyisocyanate having a cyclohexane ring structure, a structural unit derived from a polyol represented by the following formula (2), and a diamine derived from a weight average molecular weight of greater than 600 represented by the following formula (3) A structural unit of an alcohol, a structural unit derived from a diol having a weight average molecular weight of 500 or less represented by the following formula (4), and a tertiary amine compound and / or its salt derived from the following formula (5) Structural unit; Formula (1): O = C = NR ¹ -N = C = O (R ¹ in Formula (1) is represented by -R ² -R ³ -R ^4- , and R ² is a single bond or elongation. Alkyl group, R ³ is represented by the following formula (However, R ⁵ , R ⁶ and R ^{7 are each} independently a hydrogen atom or an alkyl group.) R ⁴ is a single bond, an alkylene group, or (The bond on the left and R ³ bond)) Formula (2): [化 3] (In formula (2), R ⁸ is represented by -R ⁹ -R ¹⁰ -R ^11- , and R ⁹ is a [Chemical Formula 4] single bond, (Right bond and R ¹⁰ bond), or -R ¹³ -CO- (Right bond and R ¹⁰ bond) (However, R ¹² is a straight or branched alkylene group, and R ¹³ is- R ¹⁸ -O- (the bond on the right and the bond on CO), or (The right side is branched with CO); R ¹⁸ is a straight or branched alkylene; x is an integer of 1-5; l is an integer of 2-4) R ¹⁰ is [Chemical 5] , R ¹¹ is a [chemical 6] single bond, , , Or -CO-R ^13- (except for single bond, the left branch is bonded to R ¹⁰ ) (however, R ¹² is a straight or branched alkylene group, and R ¹³ is -R ¹⁸ -O- (right (The branches are bonded to CO), or (The right side is branched with CO); R ¹⁵ and R ^{16 are} independently a hydrogen atom, an alkyl group, a halogenated alkyl group, or a phenyl group; R ¹⁷ is hydrogen, an alkyl group, or a phenyl group; R ¹⁸ is a straight chain Or branched chain alkyl; x is an integer of 1-5; l is an integer of 2-4) R ¹⁴ is a hydrogen atom, an alkyl group, a phenyl group, ,or (However, R ¹⁸ is a linear or branched alkylene; l is an integer of 2-4)); Formula (3): HO-R ¹⁹ -H (3) (R ^{19 in} formula (3) is [化 8] , ,or (The bond branch on the left side is bonded to OH) (However, R ^{20 is} independently an alkylene group, , Or adamantane ring, R ²¹ is alkylene, m is an integer of 2-4, n-represents an integer)); the formula ^{(4): HO-R 22} -OH ( Formula (4) R ²² is [of 9 ] Alkyl, , Adamantane ring, ,or (However, y is 2 or 3; z is an integer of 1-6)) Formula (5): [化 10] (Wherein R ²³ is an alkyl group, an amino alkyl group, a hydroxyalkyl group, , ,or R ²⁴ is hydroxyalkyl, aminoalkyl, or N-alkylaminoalkyl). [2] The water-based metal surface treating agent according to the above [1], further comprising a compound (C) containing a compound selected from the group consisting of boron, magnesium, aluminum, titanium, vanadium, manganese, iron, cobalt, nickel, An element of at least one of zinc, molybdenum, tungsten, cerium, niobium, tin, bismuth and zirconium. [3] The water-based metal surface treating agent according to the above [1] or [2], wherein the silane compound (B) contains an amine group. [4] The water-based metal surface treatment agent according to any one of the above [1] to [3], further comprising a member selected from the group consisting of phenol resin, epoxy resin, and polyester resin. ), Water-soluble or water-dispersible resin (D) of at least one of acrylic resin, polyolefin resin, and polyamide resin. [5] The water-based metal surface treating agent according to any one of the above [1] to [4], further comprising a member selected from the group consisting of an oxazoline resin, a blocked isocyanate resin, and carbon dicarbonate. Crosslinking agent (E) of at least one of carbodiimide-based resin, aziridine-based resin and epoxy-based resin. [6] The water-based metal surface treatment agent according to any one of the above [1] to [5], further comprising a lubricant. [7] A method for producing a metal material having a film, comprising a contact step of bringing the water-based metal surface treatment agent according to any one of the above [1] to [6] into contact with the surface of the metal material, and going through the foregoing The heating step of heating and drying the metal material in the contacting step at a temperature of 50 ° C or higher and 250 ° C or lower. [8] A metal material having a film obtained by the method for producing a metal material having a film according to the above [7].

[Effects of the Invention] According to the present invention, it is possible to provide an aqueous metal surface treatment agent capable of forming a coating film having excellent corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance on a metal material, and a coating film having the coating film. Metal material and its manufacturing method.

[Mode for Carrying Out the Invention] Hereinafter, specific embodiments will be described and the present invention will be described in detail. <Aqueous metal surface treatment agent> One aspect of the present invention is an aqueous metal surface treatment agent. The water-based metal surface treatment agent contains a urethane resin (A) and a silane compound (B) described later. By using this water-based metal surface treatment agent to form a film on the surface of a metal material, it is possible to impart excellent corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance to the metal material.

Hereinafter, the components contained in the water-based metal surface treatment agent of this embodiment and the components which can be contained are demonstrated.

<<< urethane resin (A) >> Generally, a urethane resin (A) is obtained by making a urethane prepolymer react with water. In this case, in order to promote the reaction, if necessary, a polyamine compound containing no tertiary amine compound may be contained. Specifically, the isocyanate group contained in the urethane prepolymer reacts with an amine generated by water or a polyamine compound contained as necessary to form a urea bond and becomes a urethane resin.

<Urethane prepolymer> The urethane prepolymer is a component used in the production of a urethane resin, and at least a polyisocyanate having a cyclohexane ring structure, which does not contain a nitrogen atom, and Polyols containing benzene rings, diols without a benzene ring and nitrogen atoms having a weight average molecular weight of more than 600 (hereinafter, also referred to as high molecular weight diols), and those without a benzene ring and nitrogen atoms having a weight average molecular weight of 500 or less A diol (hereinafter, also referred to as a low-molecular-weight diol), which is obtained by reacting with a tertiary amine compound having two or more active hydrogens and / or a salt thereof. From another viewpoint, the urethane prepolymer includes a structural unit derived from a polyisocyanate having a cyclohexane ring structure represented by the following formula (1), and is derived from the following formula (2) The structural unit of the represented polyol, a structural unit derived from a diol having a weight average molecular weight of more than 600 represented by the following formula (3), and a structural unit derived from a weight average molecular weight of 500 or less represented by the following formula (4) A structural unit of a diol and a structural unit derived from a tertiary amine compound and / or a salt thereof represented by the following formula (5).

Specifically, the polyol contained in the formula (2), the high-molecular-weight diol represented by the formula (3), and the hydroxyl group contained in the low-molecular-weight diol represented by the formula (4) are the same as those represented by the formula (1). The isocyanate group contained in the represented polyisocyanate reacts to form a urethane bond. The isocyanate group contained in the polyisocyanate reacts with a hydrogen atom (active hydrogen) contained in the tertiary amine compound represented by Formula (5) and / or a salt thereof to form a urethane bond, Urea bond and so on. The urethane prepolymer used in this embodiment is a polymer derived from a cyclohexane ring structure by reacting with a polyamine compound that does not contain a tertiary amine compound as described above. Isocyanate group.

(Polyisocyanate having a cyclohexane ring structure) A polyisocyanate having a cyclohexane ring structure (hereinafter, also simply referred to as "polyisocyanate") is used in the production of a urethane prepolymer and has the following formula (1). Formula (1): O = C = NR ¹ -N = C = O

In formula (1), R ¹ is represented by -R ² -R ³ -R ^4- , R ² is a single bond or an alkylene group, and R ³ is represented by the following formula [Chem. 11] (However, R ⁵ , R ⁶ and R ^{7 are each} independently a hydrogen atom or an alkyl group), and R ⁴ is a single bond, an alkylene group, or (The bond on the left is bonded to R ³ ).

R ^{1 is} preferably (However, R ⁵ , R ⁶ and R ^{7 are each} independently a hydrogen atom or a methyl group), , ,or . In addition, in the above formula, it is more preferable that all of R ⁵ , R ⁶ and R ⁷ are a hydrogen atom or a methyl group. The cyclohexane ring structure also includes a bicyclic structure having a cyclohexane structure. In addition, the cyclohexane ring structure may contain a plurality of polyisocyanates.

(Injection amount of polyisocyanate) In the production of the urethane prepolymer described later, the injection amount of the polyisocyanate is relative to the polyisocyanate used in the production of the urethane prepolymer, the polyol described later, The total amount of the high-molecular-weight diol described below, the low-molecular-weight diol described below, and the tertiary amine compound and / or its salt is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and 40 to 65% by mass % Is even better, and 50 to 60% by mass is particularly good. That is, in the urethane resin (A) used in the present embodiment, the amount of the structural units derived from the polyisocyanate of formula (1) (mass conversion), and the urethane resin (A) It is preferably 20 to 80%, more preferably 30 to 70%, still more preferably 40 to 65%, and particularly preferably 50 to 60%. In the present embodiment, in the production of the urethane prepolymer, when a "polyol having a benzene ring and a nitrogen atom or higher than the triol is used" described later, a triol containing no benzene ring and a nitrogen atom is used. The injection amount of the above-mentioned polyol is included in the above total.

(Type of polyisocyanate) The polyisocyanate is not particularly limited as long as it is a polyisocyanate represented by formula (1) having one or more cyclohexane rings and two or more isocyanate groups, and examples thereof For example, isophorone diisocyanate, 1,3- or 1,4-bis (isocyanatemethyl) cyclohexane, 1,3- or 1,4-diisocyanate cyclohexane, 3-isocyanate -Methyl-3,5,5-trimethylcyclohexyl isocyanate (3-isocyanate-methyl-3,5,5-trimethylcyclohexyl isocyanate), dicyclohexylmethane 4,4'-diisohexylmethane 4,4 ' -diisocyanate) and so on. As an addition product using a polyisocyanate not contained in formula (1) and having a dimer such as a uretdione structure, a trimer having a isocyanurate structure, or a polyfunctional polyol ( adduct), polyisocyanate and the like having three or more isocyanate groups in one molecule, and can be used in combination with the polyisocyanate represented by formula (1). A polyisocyanate may be used individually by 1 type, and may use 2 or more types together.

Among the above, the polyisocyanate is preferably selected from the group consisting of isophorone diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, and dicyclohexylmethane 4,4 'from the viewpoint of further improving the solvent resistance. -A compound of at least one diisocyanate, more preferably dicyclohexylmethane 4,4'-diisocyanate.

(Polyol containing no nitrogen atom and benzene ring) Polyol containing no nitrogen atom and benzene ring (hereinafter also referred to as "polyol") is used for the production of a urethane prepolymer, and It is represented by the following formula (2). Equation (2): [化 14] In formula (2), R ⁸ is represented by -R ⁹ -R ¹⁰ -R ^11- , and R ⁹ is [Chem. 15] a single bond, (The right branch is bonded to R ¹⁰ ), or -R ¹³ -CO- (the right bond is bonded to R ¹⁰ ) (however, R ¹² is a straight or branched alkylene group, and R ¹³ is- R ¹⁸ -CO- (the branch on the right is bonded to CO), or (The bond on the right is bonded with CO). R ¹⁸ is a linear or branched alkylene, x is an integer of 1-5, and l is an integer of 2-4), and R ¹⁰ is [Chem. 16] , R ¹¹ is [化 17] a single bond, ´, , Or -CO-R ^13- (except for the single bond, the bond on the left side is bonded to R ¹⁰ ) (however, R ¹² is a straight or branched alkylene group, and R ¹³ is -R ¹⁸ -O- (right side Bond with CO bond), or (The bond on the right and the bond on CO). R ¹⁵ and R ^{16 are} independently a hydrogen atom, an alkyl group, a halogenated alkyl group, or a phenyl group; R ¹⁷ is a hydrogen atom, an alkyl group, or a phenyl group; R ¹⁸ is a straight or branched alkylene group; x Is an integer of 1 to 5; l is an integer of 2 to 4); R ¹⁴ is a hydrogen atom, an alkyl group, a phenyl group, ,or (However, R ¹⁸ is a linear or branched alkylene group; l is an integer of 2 to 4).

R ^{8 is} preferably , (The right side of the joint and the OH bond) , ,or R ^{12 is} preferably ethyl or isopropyl. R ^{14 is} preferably a hydrogen atom, a methyl group, an isopropyl group, or a phenyl group. R ^{15 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a phenyl group. R ^{16 is} preferably a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, or a phenyl group. R ^{17 is} preferably a hydrogen atom, a methyl group, an isopropyl group, or a phenyl group.

(Injected Amount of Polyol) In the production of the urethane prepolymer described later, the injected amount of the polyol is relative to the polyisocyanate, polyol, and the later described used in the production of the urethane prepolymer. The total amount of the high-molecular-weight diol, the low-molecular-weight diol described later, and the tertiary amine compound and / or a salt thereof may be generally 1 to 40% by mass, but preferably 1 to 30% by mass, and more preferably It is 3 to 25% by mass, and more preferably 6 to 20% by mass. That is, in the urethane resin (A) used in the present embodiment, the amount of the structural units derived from the polyol of the formula (2) (mass conversion) is the same as that of the urethane resin (A). Medium, usually 1 to 40%, preferably 1 to 30%, more preferably 3 to 25%, even more preferably 6 to 20%. In the present embodiment, in the case of a "polyol having a triol or more containing no benzene ring and nitrogen atom" described later in the production of a urethane prepolymer, a triol containing no benzene ring and nitrogen atom will be used. The injection amount of the above-mentioned polyol is included in the total amount.

(Types of Polyols) The polyhydric alcohol is not particularly limited as long as it has one or more benzene rings, two or more hydroxyl groups, and does not have a nitrogen atom represented by formula (2), and examples thereof include, Resorcinol, 2-methylresorcinol, bisphenol A, bisphenol S, bisphenol F and other aromatic polyols; bisphenol A-ethylene oxide 2 mol adduct, Bisphenol A-ethylene oxide 4 mol adduct, bisphenol A-ethylene oxide 6 mol adduct, bisphenol A-ethylene oxide 10 mol adduct, bisphenol A-ring Oxypropane 2 mole additive, bisphenol A-propylene oxide 4 mole additive, bisphenol A-propylene oxide 6 mole additive, bisphenol A-propylene oxide 10 mole additive Polyether polyols with benzene rings; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, etc., with ethylene glycol, propylene glycol, and diethylene glycol Alcohol, triethylene glycol, tetraethylene glycol, 2-methylpropanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanedioxane Polyesters with benzene rings obtained by polycondensation of polyhydric alcohols such as alcohols and 3-methylpentanediol Alcohols; esters of ethyl extending carbonate (ethylene carbonate) of bisphenol A with a polyhydric alcohol exchange reaction of the obtained polycarbonate polyol having a benzene ring and the like. The polyol may be used singly or in combination of two or more kinds.

(High-molecular-weight diol) A high-molecular-weight diol is used for the production of a urethane prepolymer, is represented by the following formula (3), and does not contain a benzene ring and a nitrogen atom. Formula (3): HO-R ¹⁹ -H (3) In formula (3), R ¹⁹ is [Chem. 20] , ,or (The bond branch on the left side is bonded to OH) (However, R20 is independently an alkylene group, Or an adamantane ring, R21 is an alkylene group, m is an integer of 2-4, and n is an integer)).

(Injection amount of high molecular weight diol) In the production of the urethane prepolymer described later, the injection amount of the high molecular weight diol of formula (3) is used relative to the production of the urethane prepolymer. The total amount of polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol described below, and tertiary amine compound and / or salt thereof is usually 1 to 50% by mass, but is preferably 3 ~ 40 mass%, more preferably 5 to 35 mass%, and still more preferably 10 to 30 mass%. That is, in the urethane resin (A) used in this embodiment, the amount of the structural unit derived from the diol of formula (3) (mass conversion) is the same as that of the urethane resin (A). It is usually 1 to 50%, preferably 3 to 40%, more preferably 5 to 35%, and still more preferably 10 to 30%. In the present embodiment, when a "polyol having a triol or more containing no benzene ring and nitrogen atom" described later is used in the production of the urethane prepolymer, a triol or more having no benzene ring and nitrogen atom is used. The injection amount of the polyol is included in the total amount.

(Weight-average molecular weight of high-molecular-weight diol) The weight-average molecular weight of high-molecular-weight diol is greater than 600, but preferably greater than 600 and less than 10,000, more preferably greater than 600 and less than 5,000, and still more preferably 800-4000. It is preferably 1000 ~ 3000. The weight-average molecular weight of each component in this embodiment is, unless otherwise specified, fluorene in terms of polystyrene measured by GPC (gel permeation chromatography).

(Types of high molecular weight diols) The high molecular weight diols are diols containing no benzene ring and nitrogen atom, as long as the weight average molecular weight is greater than 600, which is not particularly limited. For example, polyether diols can be used. , Polyester diol, polycarbonate diol, etc. Examples of the polyether glycol include polyethylene glycol, polypropylene glycol, and polybutylene glycol (polytetramethylene ether glycol). Polyether glycol is produced by, for example, addition polymerization of alkylene oxide such as ethylene oxide and propylene oxide under a basic catalyst. Examples of the polyester diol include unsaturated dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and the like, and unsaturated acids such as sebacic acid. Carboxylic acid, etc., and alcohols such as ethylene glycol, propylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5 -Produced by esterification reaction of pentanediol, cyclohexyldimethanol, 1,3-adamantanediol and the like. Examples of the polycarbonate diol include a cyclic ester such as ε-caprolactone and a diol produced by ring-opening polymerization of the diol. Specific examples include dimethyl carbonate and dicarbonate. Ethyl ester, diphenyl carbonate, and the like are produced by reacting with the types of diols listed for the above-mentioned polyester diols. The high molecular weight diol may be used singly or in combination of two or more kinds.

Among the above, the high-molecular-weight diol system preferably contains a polyether diol. As the polyether glycol, a compound selected from at least one kind of polyethylene glycol, polypropylene glycol, and polybutylene glycol is more preferable. When using a polyether diol, it is preferable to use at least one of the above-mentioned polyester diol and polycarbonate diol together.

(Low-molecular-weight diol) A low-molecular-weight diol is used for the production of a urethane prepolymer, and is represented by the following formula (4), and does not contain a benzene ring and a nitrogen atom. Formula (4): HO-R ²² -OH (In formula (4), R ²² is [Chem. 21] alkylene, , Adamantane ring, ,or (However, y is 2 or 3; z is an integer of 1-6).

(Injection amount of low-molecular-weight diol) In the production of the urethane prepolymer to be described later, the injection amount of the low-molecular-weight diol is relative to the polyisocyanate and multi-component used in the production of the urethane prepolymer. The total amount of alcohol, high-molecular-weight diol, low-molecular-weight diol, and tertiary amine compound and / or salt thereof can be usually set to, for example, 1 to 25% by mass, but preferably 1 to 20% by mass, and more preferably 2 to 15% by mass, and more preferably 3 to 10% by mass. That is, in the urethane resin (A) used in this embodiment, the amount of the structural unit (mass conversion) derived from the low-molecular-weight diol derived from the formula (4) is the same as that of the urethane resin ( In A), it is usually 1 to 25%, preferably 1 to 20%, more preferably 2 to 15%, and still more preferably 3 to 10%. In the present embodiment, in the case of producing a urethane prepolymer using a "polyol having a triol or more containing no benzene ring and a nitrogen atom" described later, a triol or more containing no benzene ring and a nitrogen atom is used. The injection amount of the polyol is included in the above total.

(Weight average molecular weight of low molecular weight diol) The weight average molecular weight of low molecular weight diol is 500 or less, but it is preferably 400 or less, and more preferably 250 or less. The lower limit 値 is preferably 60 or more, and more preferably 100 or more.

(Types of low molecular weight diols) Examples of the low molecular weight diols include ethylene glycol (62.07 g / mol), propylene glycol (76.09 g / mol), and 1,5-pentanediol (104.15 g / mol), 1,6-hexanediol (118.17g / mol), 1,7-heptanediol (132.2g / mol), 1,8-octanediol (146.23g / mol), 1, 9-nonanediol (160.25g / mol), 1,10-decanediol (174.28g / mol), neopentyl glycol (104.15g / mol), 2-methyl-1,3-propanedi Alcohol (90.12 g / mol), 3-methyl-1,5-pentanediol (118.17 g / mol), 1,4-cyclohexyl dimethanol (146.14 g / mol), 1,3-adamantane di Alkyl glycols such as alcohols (168.23g / mol), diethylene glycol (106.12g / mol), triethylene glycol (150.17g / mol), tetraethylene glycol (194.23g / mol), pentaethylene glycol Alcohols (238.28g / mol), hexaethylene glycol (282.33g / mol), heptaethylene glycol (323.28g / mol), dipropylene glycol (134.17g / mol), polyalkylene glycol, dimethylol Propionic acid (134 g / mol) and the like. These may be used alone or in combination of two or more.

(Tertiary amine compound or its salt) A tertiary amine compound and / or its salt is used for manufacture of a urethane prepolymer, and is represented by following formula (5). Equation (5): [化 22] (Wherein R ²³ is an alkyl group, an amino alkyl group, a hydroxyalkyl group, , ,or R ²⁴ is hydroxyalkyl, aminoalkyl, or N-alkylaminoalkyl). The aminoalkyl group in R ²³ is preferably-(CH ₂ ) ₂ -NH ₂ or-(CH ₂ ) ₃ -NH ₂ . The aminoalkyl group in R ²⁴ is preferably-(CH ₂ ) ₂ -NH ₂ . The hydroxyalkyl group in R ²³ and R ²⁴ is preferably-(CH ₂ ) ₂ -OH. The N-alkylaminoalkyl group in R ²⁴ is preferably-(CH ₂ ) ₂ -NH-CH ₃ .

By reacting the active hydrogen of the tertiary amine compound and / or its salt with the polyisocyanate described above, a urethane prepolymer (amino group) having a group derived from the tertiary amine compound and / or its salt is introduced. Formate resin). Further, the tertiary amine compound and / or a salt thereof contains two or more active hydrogens. For example, an amino group, a hydroxyl group, or an N-alkylamino group having two or more active hydrogen substituents is preferable. Moreover, as an N-alkylamino group, 2-methylamino group is preferable.

(Injected amount of tertiary amine compound and / or salt thereof) In the production of the urethane prepolymer described later, the injected amount of tertiary amine compound and / or salt thereof is prepolymerized with respect to the urethane The total amount of the polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, and tertiary amine compound and / or its salt used in the production of substances is usually, for example, 1 to 20% by mass, preferably It is 2 to 15% by mass, more preferably 2 to 13% by mass, and even more preferably 3 to 10% by mass. That is, in the urethane resin (A) used in this embodiment, the amount of the structural unit (mass conversion) derived from the tertiary amine compound and / or its salt derived from the formula (5), In the acid ester resin (A), it is usually 1 to 20%, preferably 2 to 15%, more preferably 2 to 13%, and still more preferably 3 to 10%. In the present embodiment, in the case of producing a urethane prepolymer using a "polyol having a triol or more containing no benzene ring and a nitrogen atom" described later, a triol or more containing no benzene ring and a nitrogen atom is used. The injection amount of the polyol is included in the above total.

(Type of tertiary amine compound) The tertiary amine compound is not particularly limited as long as it has three or more active amines, and examples include N-methyldiethanolamine and N-ethyl N-aminoalkyldialkanolamines such as diethanolamine, N-butyldiethanolamine, N-tertiary butyldiethanolamine, N- (3-aminopropyl) diethanolamine, triethanolamine, N, N , N ', N'-(2-hydroxyethyl) ethylenediamine, bis (2-hydroxyethyl) amino reference (hydroxymethyl) methane, 1-bis (2-hydroxyethyl) amine Trialkanolamines which may have a substituent, such as propyl-2-propanol, 2,2'-diamino-N-methyldiethylamine, N, N ', N' '-trimethyldiethylene Tertiary amine compounds such as ethyltriamine and gins (2-aminoethyl) amine. These tertiary amine compounds can be used as salts with organic acids such as formic acid, acetic acid, etc., inorganic acids such as hydrochloric acid, sulfuric acid, etc., using alkylating agents such as dimethyl sulfate, diethyl sulfate, methyl iodide, etc. Grade salinizer. As the tertiary amine compound, N-aminoalkyldialkanolamine, particularly N-methyldiethanolamine is preferred.

The urethane resin (A) in this embodiment may be one in which part or all of the structural part (tertiary amine) derived from a tertiary amine compound is neutralized with an acid or the like. Examples of the acid used in this case include organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, malic acid, malonic acid, and adipic acid; methanesulfonic acid, and ethane. Organic acids such as organic sulfonic acids such as sulfonic acid and trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, hydrobromic acid, and phosphoric acid. These acids may be used singly or in combination of two or more kinds. Further, the urethane resin (A) may be one in which all or a part of the tertiary amine compound-derived structural part (tertiary amine) is quaternized. Specific examples of the quaternizing agent used in the quaternization include sulfates such as dimethyl sulfate and diethyl sulfate; methyl chloride, benzyl chloride, methyl bromide, methyl bromide, Alkyl halides such as methyl iodide; carbonates such as dimethyl carbonate and diethyl carbonate. These quaternizing agents may be used alone or in combination of two or more. It is also possible to use an acid and a quaternizing agent as a neutralizing agent in combination. In addition, in this specification, these acids and a quaternizing agent may be called an ionizing agent.

In this specification, "alkyl" or "alkyl" contained in a halogenated alkyl group, an aminoalkyl group, a hydroxyalkyl group, an N-alkylaminoalkyl group, or the like is not particularly limited, and is usually 20 or less carbon atoms. The alkyl group may be an alkyl group having a carbon number of 12 or less, or an alkyl group having a carbon number of 6 or less. Typically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, secondary butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl , 3-methylpentyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like. The "alkylene group" is not particularly limited, and is usually an alkylene group having a carbon number of 20 or less, and may be an alkylene group having a carbon number of 12 or less and an alkylene group having a carbon number of 6 or less. Typical examples include ethylene, propyl, butyl, isobutyl, tertiary butyl, tertiary butyl, pentyl, isopentyl, neopentyl, hexyl, Isohexyl, 3-methyl-pentyl, heptyl, octyl, nononyl, decyl, undecyl, and dodecyl. Examples of the halogenated alkyl group include those in which one or more hydrogen atoms in the alkyl group are substituted with a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

(Other components that can be used in the production of the urethane prepolymer) In the production of the urethane prepolymer in this embodiment, other components than those described above can be used. Examples of the other components include polyisocyanates other than the polyisocyanate, polyols, high-molecular-weight diols, and low-molecular-weight diols other than benzene rings and nitrogen atoms, organic solvents, and the like Polyamine compounds other than tertiary amine compounds, ionizing agents, acids, organometallic compounds, etc.

(Polyisocyanate other than polyisocyanate) The polyisocyanate other than the polyisocyanate is not particularly limited, and may be, for example, 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanate), and the like. Acid ester, 1,6-hexamethylene diisocyanate, 1,12-dodecyl methylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, etc. Aliphatic diisocyanate; m- or p-phenylene diisocyanate, tolyl-2,4- or 2,6-diisocyanate (tolylene-2,4- or 2,6-diisocyanate), diphenylmethane -4,4'-diisocyanate, 1,3-bis (2-isocyanate-2-propyl) benzene, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 4,4 '-Diisocyanate-3,3'-dimethyldiphenyl ester, 3-methyl-diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, tetramethyl Aromatic diisocyanates such as tetramethylxylylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 2-isocyanate ethyl (2,6-diisocyanate) hexanoate Aliphatic triisocyanates; triphenylmethane triisocyanates, aromatic triisocyanates such as tris (isocyanatephenyl) thiophosphate, etc. The polyisocyanate other than the polyisocyanate may be a dimer having a uretdione structure or a trimer having a trimeric isocyanate structure. As an addition object using a polyfunctional polyol, there may be three or more in one molecule. Isocyanate-based polyisocyanate. Among these, an aromatic polyisocyanate such as an aromatic diisocyanate, an aromatic triisocyanate, or the like is preferably used, and an aromatic diisocyanate is preferably used. As for the content of other components and the amount of the structure derived from other components in the urethane resin (A), those who have ordinary knowledge in this technical field may, as long as the effect of the present invention is not hindered. Set it appropriately.

(Polyol represented by general formula (2), high-molecular-weight diol, low-molecular-weight diol, and other polyhydric alcohols) Other than polyols, high-molecular-weight diols, and low-molecular-weight diols represented by general formula (2) As the polyhydric alcohol, a trihydric or higher polyhydric alcohol containing no benzene ring and nitrogen atom can be used, and examples thereof include trimethylolpropane and neopentyl tetraol. Among triol or higher polyols that do not contain a benzene ring and a nitrogen atom, trimethylolpropane (TMP) is preferred. When a triol or higher polyol containing no benzene ring and nitrogen atom is used in the production of a urethane prepolymer, the injection amount is relative to the polyisocyanate used in the production of the urethane prepolymer. , Polyhydric alcohols, high molecular weight diols, low molecular weight diols, tertiary amine compounds and / or their salts, and the total amount of polyhydric alcohols above triols that do not contain benzene rings and nitrogen atoms, preferably 0.5 to 18% by mass , More preferably 3 to 10% by mass. That is, in the urethane resin (A) used in this embodiment, the amount of the structural unit (mass conversion) derived from a polyhydric alcohol of triol or higher that does not contain a benzene ring and a nitrogen atom is based on the amino group. The formate resin (A) is usually 0.5 to 18%, preferably 3 to 10%.

The urethane resin in this embodiment is preferably one having a branched structure. As the method for introducing a branched structure, as described above, a polyhydric alcohol having a triol or higher that does not contain a benzene ring and a nitrogen atom can be used, but it is not limited to this method.

An organic solvent can be used for manufacture of a urethane prepolymer and / or manufacture of a urethane resin (A). The organic solvent is used as a solvent for reacting the aforementioned components. The organic solvent is not particularly limited, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; and tetrahydrofuran. Ether solvents such as 1,4-dioxane; nitrile solvents such as acetonitrile and acrylonitrile; acrylate solvents such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate; Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and other fluorene-based solvents; dimethylmethylene fluorene and other fluorene-based solvents. These organic solvents may be removed by a reduced-pressure distillation method if necessary after the production of the urethane prepolymer and the urethane resin (A) from the viewpoint of reducing the load on the environment.

<Production method of urethane prepolymer and urethane resin> The urethane prepolymer of this embodiment is at least a polyisocyanate represented by the general formula (1) and the general formula The polyol represented by (2), the high molecular weight diol represented by the general formula (3), the low molecular weight diol represented by the general formula (4), and the tertiary amine represented by the general formula (5) It is obtained by reacting a compound and / or a salt thereof. The urethane resin of this embodiment is obtained by reacting the urethane prepolymer obtained as described above with water. In this case, an amine compound that is a polychain extender may be added as necessary, and the polyamine compound at this time is not a tertiary amine compound.

An example of a method for producing a urethane prepolymer and a urethane resin according to this embodiment (manufacturing methods 1 to 6) is shown below. (Manufacturing method 1) Polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, tertiary amine compound, and the like are dissolved and reacted in an organic solvent to prepare a urethane prepolymer, and if necessary, A method in which part or all of the tertiary amine in the urethane prepolymer is ionized by an ionizing agent and emulsified by adding water. (Manufacturing method 2) Polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, tertiary amine compound, and the like are dissolved and reacted in an organic solvent to prepare a urethane prepolymer, and if necessary, A method in which one or all of the tertiary amines in the urethane prepolymer is ionized by an ionizing agent, and a chain elongation agent such as a polyamine compound is used to emulsify while adding water while extending the chain.

(Manufacturing method 3) Polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, tertiary amine compound, and the like are prepared by reacting (bulk polymerization method) without using an organic solvent. The urethane prepolymer, if necessary, is a method in which a part or all of the tertiary amine in the urethane prepolymer is quaternized by an ionizing agent and emulsified by adding water ( Production method 4) The tertiary amine compound is ionized with an acid or an alkylating agent, and then polyisocyanate, polyol, high-molecular-weight diol, and low-molecular-weight diol are added to react to prepare a urethane prepolymer. Polymer, if necessary, a method in which a part or all of the tertiary amine in the urethane prepolymer is ionized by an ionizing agent and emulsified by adding water

(Manufacturing method 5) Polyisocyanate, polyol, high-molecular-weight diol, and low-molecular-weight diol are added to an organic solvent and reacted, and then a tertiary amine compound is further added to prepare an amine group having a tertiary amine structure at a terminal portion. Formate prepolymer, if necessary, a method in which a part or all of the tertiary amine in the urethane prepolymer is ionized with an ionizing agent, and water is added to emulsify (manufacturing method 6) Polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, etc. are added to an organic solvent and reacted, and then a tertiary amine compound is further added to prepare a urethane prepolymer having a tertiary amine structure at a terminal portion. If necessary, part or all of the tertiary amine in the urethane prepolymer is ionized by an ionizing agent, and water is added by a chain elongator such as a polyamine compound while the chain is extended. As a method of emulsification, a conventional emulsifier can be used in the above-mentioned production methods 1 to 6.

<Polyamine compound> As the polyamine compound used as the chain elongating agent, for example, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1,3-bisaminomethylcyclohexane, 2-aminoethylaminopropyltrimethoxysilane; N-hydroxymethylaminoethylamine, N -Hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; Diethylene triamine, Diethylene Propyltriamine, triethylenetetramine; hydrazine, 1,6-hexamethylenebishydrazine; succinic dihydrazide, dihydrazine adipate, dihydrazine glutarate, decyl Diacid dihydrazide diisohydrazide, diisohydrazide isophthalate; β-semicarbazide propionic acid hydrazide, 3-semicarbazide propylcarbazinate, hemicarbazide Carazine-3-hemiprazine methyl-3,5,5-trimethylcyclohexane and the like. Among them, hydrazine or ethylenediamine is preferably used.

When a chain elongating agent is used, the injection amount of the polyamine compound is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the urethane prepolymer.

<< silane compound (B)> The water-based metal surface treatment agent of this embodiment contains a silane compound (B) in addition to the specific urethane resin (A). Examples of the silane compound (B) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-propyltrimethoxysilane, N-phenyl-3-propyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) aminopropylmethyl Dimethoxysilane, N- (2-aminoethyl) aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropylmethyldiethoxysilane, N- (2-Aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxy Silane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, N-β- (N-vinylbenzylamino (Ethyl) -3-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropylmethyl Diethoxysilane, N-methylamino Trimethoxysilane, N-butylaminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldisiloxane Methoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxy Silane, dimethyldiethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrisilane Ethoxysilane, γ-chloropropylmethyldiethoxysilane, hexamethyldisilazane, γ-anilinepropyltrimethoxysilane, γ-anilinepropylmethyldimethyl Oxysilane, γ-anilinepropyltriethoxysilane, γ-anilinepropylmethyldiethoxysilane, isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, Propyltriethoxysilane, bis (trimethoxysilyl) amino vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethyl Oxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldimethoxysilyl) propyl] chloride Ammonium chloride, octadecyldimethyl [3- (triethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldiethoxysilyl) propyl] chloride Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, and the like. Only one of these may be used, or a plurality of them may be used in combination. These silane compounds can be used alone or in the form of a hydrolysate or homopolymer. Others can also be used as a mixture of two or more silane compounds, or a hydrolyzate or The use of the same homopolymer mixture or copolymer is not particularly limited.

Content of Silane Compound (B) it is not particularly limited, preferred to adjust the mass urethane resin (A) of the mass of the solid content of (A _M) of Silane Compound (B) of (B _M) ratio [(B _M) / (A _M )] is in the range of 1/100 or more and 4.0 or less. It is more preferably within a range of 1/10 to 3.5. It is more preferably within a range of 1/5 to 3.

The silane compound (B) is particularly preferably an amine group-containing silane compound. Examples of the amine-containing silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-3-propyltrimethoxysilane , N-phenyl-3-propyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) aminopropylmethyl Dimethoxysilane, N- (2-aminoethyl) aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropylmethyldiethoxysilane, N -(2-aminoethyl) aminopropylmethyldimethoxysilane, γ-anilinepropyltrimethoxysilane, γ-anilinepropylmethyldimethoxysilane, γ-aniline Propyltriethoxysilane, γ-anilinepropylmethyldiethoxysilane octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (triethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldiethoxysilyl) propyl] ammonium chloride and the like. Only one of these may be used, or a plurality of them may be used in combination. These silane compounds can be used alone or in the form of a hydrolysate or a homopolymer. Others can be combined with a mixture of two or more silane compounds, or their hydrolysates, and their equivalents. The mixture of metapolymers or use as a copolymer is not particularly limited.

<<< Compound (C) >> The water-based metal surface treating agent of this embodiment may contain a compound (C) containing a compound selected from the group consisting of boron, magnesium, aluminum, titanium, vanadium, manganese, iron, cobalt, nickel, An element of at least one of zinc, molybdenum, tungsten, cerium, niobium, tin, bismuth and zirconium. Examples of the compound (C) include carbonates, oxides, hydroxides, nitrates, sulfates, phosphates, halides, sulfides, fluoride compounds, organic acid salts, and organic compounds of the aforementioned metals. . Among these, one component may be used, or a plurality of components may be used in combination.

Specific examples of the compound (C) include nickel oxide, nickel hydroxide, nickel carbonate, nickel nitrate, nickel sulfate, nickel phosphate, nickel chloride, and nckel acetylacetonate. Potassium manganate, sodium permanganate, manganese dihydrogen phosphate, manganese nitrate, manganese (II), (III) or (IV), manganese (II) or (III) fluoride, manganese carbonate, manganese (II) acetate Or (III), ammonium manganese sulfate, manganese acetylacetonate, manganese iodide, manganese oxide, manganese hydroxide; cobalt chloride, chloropentaamminecobalt chloride, trichloride Hexaamminecobalt chloride, cobalt sulfate, ammonium cobalt sulfate, cobalt nitrate, cobalt oxide 2 aluminum, cobalt hydroxide, cobalt phosphate; phosphovanadomolybdic acid, molybdenum oxide, molybdic acid, ammonium molybdate, Ammonium paramolybdate, sodium molybdate, molybdophosphoric acid compound (for example, ammonium molybdenum phosphate, sodium molybdenum phosphate, etc.); metatungstic acid, ammonium metatungstate, metatungstate Sodium, paratungstic acid, ammonium paratungstate, sodium paratungstate; cerium oxide , Cerium acetate, cerium (III) or (IV) nitrate, cerium ammonium nitrate, cerium sulfate, cerium chloride; magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium hydroxide, magnesium fluoride, magnesium ammonium phosphate, magnesium hydrogen phosphate, Magnesium oxide; aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, aluminum sulfate, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum iodide; zinc sulfate, zinc carbonate, zinc chloride, iodide Zinc, zinc acetylacetonate, zinc oxide, zinc iodide, zinc dihydrogen phosphate, zinc acetylacetonate, zinc dihydrogen phosphate; iron (II) hydroxide, iron (III) hydroxide , Iron (II) nitrate, iron (III) nitrate, iron (III) acetone, iron (II) chloride, iron (III) chloride, iron (III) citrate, iron (II) oxide, iron oxide (III), iron oxide (II, III), iron hexacyanoferrate (II), iron (III), iron (II) acid, potassium iron (III) cyanate, iron ammonium sulfate ( II), ammonium iron (III) sulfate, iron (II) phosphate; bismuth oxide, bismuth sulfate, bismuth nitrate, bismuth hydroxide, bismuth citrate, bismuth vanadate, vanadium alkoxide, vanadium-containing Chelate Compounds, specifically, vanadium oxide, metavanadate, sodium metavanadate, potassium metavanadate, ammonium metavanadate, diacetylacetonate vanadium, diethylacetonate vanadium, vanadium pentoxide, vanadium trioxide, Vanadium fluoride, vanadium phosphate, vanadium sulfate, vanadium sulfide, vanadium oxalate, vanadium oxytriisopropoxide, vanadium tributoxide, vanadium oxytriethoxide, vanadium triisobutoxide, three Vanadium oxytriethanolaminate, vanadium ammonium citrate, vanadium tributoxy stearate, vanadyl acetylacetonate, tetrapropoxy vanadium, tetrapropoxy vanadium Tetrabutoxy vanadium, etc .; niobium (III) chloride, (IV) or (V), niobium (III) fluoride, (IV) or (V), niobium oxide (II), (IV) or (V); tin (II) or (IV), tin (II) or (IV), tin (II) or (IV), tin (II) or (IV) nitrate, tin hydroxide ( II) or (IV), tin (II) or (IV); zirconium hydrofluoric acid, zirconium fluoride, ammonium fluorozirconate, sodium fluorozirconate, potassium fluorozirconate, zirconium sulfate, nitrate, acetate , Carbonate, chloride salt, etc. Inorganic salts, oxides of zirconium compounds, organic acid salts of zirconium compounds, etc .; titanium hydrofluoric acid, titanium fluoride, ammonium fluorotitanate, sodium fluorotitanate, potassium fluorotitanate, thorium sulfate, nitrate, acetic acid Inorganic salts such as salts, carbonates, and chloride salts, oxides of titanium compounds, organic acid salts of titanium compounds, and the like. One of these ingredients may be used, or a plurality of them may be used in combination.

Since the water-based metal surface treatment agent of this embodiment contains the compound (C), it is preferable that the strength of the film formed by the water-based metal surface treatment agent can be improved. The content of the compound (C) is preferably adjusted by the ratio of the mass (C _M ) of the compound (C) to the solid content mass (A _M ) of the urethane resin (A) [(C _M ) / (A _M )] is in the range of 1/300 or more and 1/2 or less, more preferably in the range of 1/200 or more and 1/3 or less, and more preferably in the range of 1/100 or more and 1/4 or less .

<<< Water-dispersible resin (D) >> In water-based metal surface treatment agents, at least one selected from phenol resin, epoxy resin, polyester resin, acrylic resin, polyolefin resin, and polyamide resin may be further added. Water-soluble or water-dispersible resin (D).

The acrylic resin is obtained by radical polymerization, cationic polymerization, or anionic polymerization of acrylic acid, acrylates, and the like. The monomer used for these polymerization reactions is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, and acrylic acid diacrylate. Butyl acrylate, tertiary butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, 2-hydroxyethyl acrylate, methyl Methyl acrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, secondary butyl methacrylate, trimethacrylate Grade butyl, n-hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methacrylic acid 2 -Hydroxyethyl and the like. A vinyltrimethoxysilane and the like may be further appropriately incorporated to introduce an alkoxysilyl group into the structure. These may be used alone or in combination of two or more.

The epoxy resin is not particularly limited, and for example, phenol, bisphenol A, o-, m-, p-cresol, phthalic acid, isophthalic acid, terephthalic acid, and epichlorine can be used. Glycidyl ethers or esters obtained by the reaction of alcohols (epichlorohydrin), glycidyl groups obtained by the reaction of aromatic compounds with hydroxyl groups such as novolak phenol, poly-p-vinylphenol, and epichlorohydrin Ethers, glycols, polyethylene glycols, propylene glycol, polypropylene glycol, glycerol, sorbitol and other aliphatic polyhydric alcohols and epichlorohydrin obtained by the reaction of glycidyl ethers, etc., and further act with amines Those who introduce water-soluble functional groups. Silanol groups, alkoxysilyl groups, phosphate groups, and phosphate groups can also be introduced into these epoxy resins. Only one of these ingredients may be used, or a plurality of them may be used in combination.

The polyester resin is not particularly limited as long as it is an esterified product of a polybasic acid and a polyhydric alcohol. The polybasic acid is not particularly limited, and examples thereof include phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, and maleic acid. Diprotic acids such as maleic anhydride; trivalent or higher polybasic acids such as trimellitic anhydride and pyromellitic anhydride. The polyol is not particularly limited, and for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 3-methylpentanediol, Neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,4-hexanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol Aliphatic or alicyclic glycols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, neopentyl tetraol, dipentaerythritol Trivalent or higher polyhydric alcohols such as 1,1,2,2- (4-hydroxyphenyl) ethane. Only one of these ingredients may be used, or a plurality of them may be used in combination.

The phenol resin is not particularly limited as long as it is a polymer having a phenol structure, such as a phenol novolac resin, polyvinyl phenol, and polybisphenol A, and can be used for those having no alkoxysilyl group in the structure.

Polyamine resin is not particularly limited as long as it is an esterified product of a polybasic acid and a polyamine. The polybasic acid is not particularly limited, and for example, two protons such as phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, and maleic anhydride can be used. Acids; trivalent or higher polybasic acids such as trimellitic anhydride, pyromellitic anhydride, etc .; as the polyamine, it is not particularly limited, and for example, ethylenediamine, propylenediamine, diethyltriamine , Hexyl diamine, triethylene tetramine, tetra ethylene pentamine, isophorone diamine, piperazine, diphenylmethane diamine, hydrazine, tetramethyl ethylene diamine, etc. Valence amines and so on. Only one of these ingredients may be used, or a plurality of them may be used in combination.

The polyolefin resin is not particularly limited as long as it is an olefin-based polymer. As for the olefins, for example, those obtained by using a polymerization reaction such as radical polymerization, cationic polymerization, and the like using olefins such as ethylene, propylene, isobutylene, and α-butene can be used. These polymers may be copolymerized using an acid anhydride or a carboxylic acid having a double bond. Only one of these ingredients may be used, or a plurality of them may be used in combination.

The water-based metal surface treatment agent of this embodiment is preferably a point at which the resin (D) can be adjusted to a strength suitable for the strength of the film to be formed. The content of the resin (D) is preferably adjusted to the solid content mass (D _M ) of the resin (D) and the solid content mass (A _M ) of the urethane resin (A) [(D _M ) / ( A _M )] is in the range of 1/50 to 50/1, more preferably in the range of 1/25 to 25/1, and more preferably in the range of 1/10 to 10/1 Inside.

The water-soluble or water-dispersible resin (D) is preferably cationic or anionic, and the existing form in the water is preferably a dissolved state or a dispersed state. These water-soluble or water-dispersible resins (D) can be achieved by self-solubility or self-dispersion based on the dissolution or dispersion of water, and can also be achieved by cationic surfactants (such as tetraalkylammonium, etc.) And / or dispersed in the presence of a nonionic surfactant (e.g., alkylphenyl ether, etc.).

<< Crosslinking agent (E) >> The water-based metal surface treatment agent may further contain a member selected from the group consisting of an oxazoline resin, a blocked isocyanate resin, a carbodiimide resin, an aziridine resin, and an epoxy resin At least one crosslinking agent (E) of the resin. These cross-linking agents can use a conventional resin, and promote the cross-linking by the functional group contained in the resin. The content of the crosslinking agent (E) is preferably the solid content mass (E _M ) of the crosslinking agent (E), and the ratio of the solid content mass (A _M ) of the urethane resin (A) [(E _M ) / (A _M )] is adjusted to a range of 1/100 or more and 5/1 or less, more preferably 1/50 or more and 3/1 or less, and even more preferably 1/20 or more 1 Within / 1.

The water-based metal surface treatment agent may further contain a lubricant. The lubricant is not particularly limited, and examples thereof include polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax. The content of the lubricant is not particularly limited as long as the effect of the present invention is not impaired, but it is usually 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the urethane resin (A).

<<< Other components which can be contained in the water-based metal surface treatment agent >> The water-based metal surface treatment agent of this embodiment may contain components other than the above. For components other than the above, for example, a film-forming aid (organic solvent) capable of improving film-forming properties and improving film dryness can be blended within a range that does not impair the stability of the water-based metal surface treatment agent or the effect of the present invention Etc.), surfactants to improve wettability, defoamers or leveling agents to suppress foaming, conductive materials to improve solderability, colored pigments to improve design, and rust prevention to prevent rust Agent.

The film-forming aid is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, 2-propyl alcohol, and tertiary butyl alcohol; ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether Glycol alkyl ethers such as methyl ether, propylene glycol monopropyl ether, etc .; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; etc .; ester solvents such as ethyl acetate, butyl acetate; Ether solvents such as tetrahydrofuran and 1,4-dioxane; nitrile solvents such as acetonitrile, acrylonitrile, and acrylic acid solvents such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate ; Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and other amine solvents; dimethylmethylene and other fluorenes; oxalic acid Methyl ester, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, diethyl glutarate, diethyl adipate, etc. Carboxylate-based solvents. These film-forming aids can be used alone or in combination of two or more.

Examples of the surfactant include nonionic surfactants such as alkylallyl ether-based, alkyl ether-based, alkyl ester-based, and alkylamine-based surfactants, and fatty acid salts and alkyl sulfates. Anionic surfactants such as salts, sulfates of aliphatic amines, and sulfonates of dibasic fatty acid esters. These surfactants can be used alone or in combination of two or more.

Examples of the conductive substance include fine conductive metal powder and fine carbon powder. Examples of the color pigment include inorganic pigments such as carbon black and titanium oxide, and organic pigments such as phthalocyanine.

The water-based metal surface treatment agent of the present embodiment may further contain various known additives which are generally used as necessary. Examples of such additives include antirust pigments, dyes, inorganic crosslinking agents, antiblocking agents, viscosity modifiers, tackifiers, dispersion stabilizers, light stabilizers, antioxidants, and ultraviolet rays. Absorbent, inorganic filler, organic filler, plasticizer, slip agent, antistatic agent, etc.

<Manufacturing method of water-based metal surface treatment agent> The water-based metal surface treatment agent according to the present embodiment may be prepared in an aqueous solvent by using a urethane resin (A) and a silane compound (B) as necessary. It is produced by mixing components other than the urethane resin (A) and the silane compound (B). The aqueous solvent is not particularly limited as long as the mass of the entire solvent (including the solvent) is used as a reference, as long as it contains 50% by mass or more of water. Examples of the solvent other than water contained in the aqueous solvent include paraffin-based solvents such as hexane and pentane; aromatic solvents such as benzene and toluene; methanol, ethanol, 1-butanol, and ethyl Alcohol solvents such as ethyl cellosolve; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as ethyl acetate and butoxyethyl acetate; dimethylformamide, N- Amidamine-based solvents such as methylpyrrolidone, etc .; Amidene-based solvents such as dimethylsulfine, and amidinophosphate-based solvents such as trimethylamine hexamethylphosphate. One of these solvents other than water may be mixed with water, but two or more of them may be combined and mixed with water. From an environmental and economic standpoint, it is preferable to use only water.

<Metal material with film and manufacturing method thereof> A method for manufacturing a metal material with film according to this embodiment is a metal material having a metal material and a film (surface treatment film layer) formed on the surface of the metal material. The manufacturing method includes a contact process (step) for bringing the water-based metal surface treatment agent of this embodiment into contact with the surface of the above-mentioned metal material, and a metal material for bringing the water-based metal surface treatment agent into contact with the temperature range of 50 ° C to 250 ° C. Heating process for heating and drying the aqueous metal surface treatment agent by internal heating (step). Through these two steps, a surface treatment film layer is formed on the surface of the metal material. In addition, the heating temperature in the above-mentioned heating process indicates the temperature of the metal material itself.

<Metal material> The type of metal material is not particularly limited, and cold-rolled steel sheets, hot-rolled steel sheets, hot-dip zinc-coated steel sheets, aluminum-containing galvanized steel sheets, electrical galvanized steel sheets, Carbon steel sheet, alloy steel sheet and plated steel sheet of alloy galvanized steel sheet, galvanized nickel steel sheet, galvanized cobalt steel sheet, vapor-deposited galvanized steel sheet, nickel-plated steel sheet, tin-plated steel sheet, stainless steel sheet, etc. Generally known materials such as metal plates other than steel plates such as magnesium and magnesium plates. Particularly suitable metal materials are galvanized steel sheets such as hot-dip galvanized steel sheets, aluminum-containing galvanized steel sheets, electrical galvanized steel sheets, alloyed galvanized steel sheets, galvanized nickel steel sheets, galvanized cobalt steel sheets, and galvanized steel sheets. . The shape of the metal material is not particularly limited, and may be a plate material or a molded product.

Among them, the metal material may be subjected to a chromate treatment or a phosphate treatment as a surface treatment. In recent years, due to problems of environmental pollution, labor hygiene, safety, etc., the tendency of non-chromization has increased. However, if the surface treatment film layer of the present invention (preferably a film layer not containing chromium and phosphorus) is used, The application of chromate treatment or phosphate treatment can also exhibit sufficient corrosion resistance, chemical resistance, solvent resistance, and paint adhesion.

<Surface treatment film layer> The surface treatment film layer is formed by using the above-mentioned water-based metal surface treatment agent, and the water-based metal surface treatment agent is made by a conventional method (for example, coating method, dipping method, spray method, electrolytic method, etc.). It is formed by contacting the surface of a metal material.

Among them, before the treatment with an aqueous metal surface treatment agent, in order to remove the oil content and dirt attached to the metal material, the degreasing agent (acid-based, alkaline-based) washing, hot water washing, acid washing, solvent washing, etc. are used separately or in combination. . In addition, before treatment with a water-based metal surface treatment agent, the surface may be adjusted for the purpose of further improving the corrosion resistance of the film and further improving the coating adhesion. The method of surface adjustment is not particularly limited, and examples thereof include methods such as chemical conversion coating for attaching metals such as Fe, Co, Ni, Cu, Zn, Mn, Zr, Ti, or V, and phosphoric acid chlorination treatment. . In the case of cleaning the surface of a metal material, from the viewpoint of reducing the amount of detergent remaining on the surface of the metal material, it is preferable to wash it with water after washing.

The temperature of the water-based metal surface treatment agent is not particularly limited, and the solvent-based water of the treatment agent is mainly used. Therefore, the treatment temperature is preferably in the range of 0 to 60 ° C, and more preferably in the range of 5 to 40 ° C.

In this embodiment, the drying temperature after contacting the water-based metal surface treatment agent, that is, the temperature of the above heating process is not particularly limited, but is usually within a range of 50 ° C to 250 ° C, preferably 60 ° C to 220. Within the range below ℃. The drying method is not particularly limited, and a conventional drying method using an oven or the like can be adopted. In addition, in the manufacturing method of this embodiment, after the surface of the metal material is brought into contact with the water-based metal surface treatment agent and before the drying is performed, the surface of the metal material contacted by the water-based metal surface treatment agent may be washed with water. Wash with water.

The adhesion amount of the film on the surface of the metal material is based on the total film mass, preferably 30 to 5,000 mg / m ² , more preferably 50 to 3,000 mg / m ² , and still more preferably 100 to 2,000 mg / m ² . When it is 30 mg / m ² or more, sufficient corrosion resistance and adhesion can be obtained. If it is 5,000 mg / m ² or less, cracks or the like are unlikely to occur in the film, and the adhesion of the film itself becomes high. [Example]

Hereinafter, the water-based metal surface treatment agent of this invention is demonstrated in detail using an Example. However, the present invention is not limited to these examples.

<Synthesis Example 1> 63 g of bisphenol A-polyoxyethylene 2 mol adduct (Newpol BPE-20T, manufactured by Sanyo Chemical Industry Co., Ltd.) (a2-1 described later), polyethylene glycol (PEG2000, Daiichi Industries) (Manufactured by a pharmaceutical company) (a3-1 described later) 67 g, N-methyldiethanolamine (amino alcohol MDA, manufactured by Nippon Emulsifier Co., Ltd.) (a5-1 described later) 30 g, diethylene glycol (diethylene glycol, 30g (made by Japan Catalyst Co., Ltd.) (to be described later a4-1), 230g isophorone diisocyanate (Desmodur I, manufactured by Bayer) (a1-1 to be described later), added to 400g of methyl ethyl ketone, and fully dissolved . After allowing this mixed solution to react at 80 ° C. for about 5 hours, it was confirmed that an isocyanate group containing 3% by mass or less was added, and 25 g of dimethyl sulfate (an ionizing agent a7-1 described later) was added. The content of isocyanate groups was based on JIS K7301: 1995. 2 g of the reaction solution was dissolved in dimethylformamide, 10 ml of an n-dibutylamine-toluene solution was added, and bromophenol blue was used as the content. The indicator is titrated with a 0.5 mol / L hydrochloric acid solution and can be calculated using the following formula. [Number 1] (In the formula, A means the volume of the hydrochloric acid solution required for titration of the amount (mass) of isocyanate used when preparing a predetermined amount of the reaction solution, and B means the hydrochloric acid solution required for the reaction solution. For volume, f means "1", N means the molar concentration of hydrochloric acid standard solution, and S means the mass of the reaction solution).

Next, a urethane emulsion was prepared by adding 1000 g of deionized water. The obtained urethane emulsion was subjected to vacuum distillation to remove methyl ethyl ketone to prepare a urethane emulsion having a urethane resin concentration of 25% by mass. Table 1 shows each component and injection amount (% by mass) used in this synthesis. Hereinafter, the urethane emulsion thus obtained is also referred to as the urethane resin of Synthesis Example 1.

As shown in Table 1, the urethane resins of Synthesis Examples 2 to 11 and Comparative Synthesis Examples 1 to 8 were prepared in the same manner as described in Synthesis Example 1 with each component and the injection amount.

A carbamate in Synthesis Example 12 was prepared in the same manner as in Synthesis Example 1 except that 25 g of ionizing agent a7-2 (85% phosphoric acid) was used instead of 25 g of ionizing agent a7-1 (dimethyl sulfate). Resin.

A urethane resin of Synthesis Example 13 was prepared in the same manner as in Synthesis Example 1 except that 10 g of ionizing agent a7-3 (formic acid) was used instead of 25 g of ionizing agent a7-1 (dimethyl sulfate).

A urethane in Synthesis Example 14 was prepared in the same manner as in Synthesis Example 1 except that 19 g of ionizing agent a7-4 (methanesulfonic acid) was used instead of 25 g of ionizing agent a7-1 (dimethyl sulfate). Resin.

Each component described in Table 1 is as follows. In addition, the injection amount (% by mass) of each component described in Table 1 is calculated based on the total amount of the components (a1) to (a5), and when the component (a6) is used. In addition, any of the urethane prepolymers obtained in each synthesis example contains an isocyanate group. <Polyisocyanate (a1; one of the following is a polyisocyanate having a cyclohexane ring structure)> a1-1: Isophorone diisocyanate (Desmodur I, manufactured by Bayer) a1-2: Dicyclohexylmethane 4,4 '-Diisocyanate (Desmodur W, manufactured by Bayer Corporation) a1-3: Tolyl diisocyanate (COSMONATE T80, manufactured by Mitsui Chemicals) a1-4: hexamethylene diisocyanate (50M-HDI, manufactured by Asahi Kasei Corporation) ＜ Polyol (a2) ＞ a2-1: Bisphenol A-polyoxyethylene 2 mol adduct (Newpol BPE20T, manufactured by Sanyo Chemical Industry Co., Ltd.) a2-2: Aromatic diprotic acid polyester polyol (Tesrack 2508- 70. Hitachi Chemical Co., Ltd.) a2-3: Polycarbonate diol (NIPPORAN 981, TOSOH company)

<Diol (a3; one of the following is a diol having a weight average molecular weight greater than 600 that does not include a benzene ring and a nitrogen atom)> a3-1: Polyethylene glycol (PEG2000, Mw2000, manufactured by Daiichi Pharmaceutical Co., Ltd.) a3- 2: Polyester polyol (NIPPORAN 4040, Mw2000, TOSOH company) a3-3: Polybutanediol (PTMG2000, Mw2000, Mitsubishi Chemical Corporation) a3-4: a3-1 ＋ a3-2 (mass ratio 1: 1) a3-5: Polyester diol (K-FLEX XM360, Mw520, KING company) <diol (a4; the following part is a diol having a weight average molecular weight of 500 or less without benzene ring and nitrogen atom)> a4 -1: Diethylene glycol (diethylene glycol, Mw106, manufactured by Nippon Catalysts) a4-2: 1,5-pentanediol (1,5-pentanediol, Mw104, manufactured by Ube Kosan Co., Ltd.) a4-3: 1,6-hexanediol (1,6-hexanediol, Mw106, manufactured by Ube Kosan Co., Ltd.) a4-4: Polyester polyol (PLACCEL 205, Mw530, Daicel Chemical Co., Ltd.)

<Tertiary amine compound (a5)> a5-1: N-methyldiethanolamine (amino alcohol MDA, manufactured by Japan Emulsifier Co., Ltd.) <Others (polyols of triol or higher containing no benzene ring and nitrogen atom) ( a6) ＞ a6-1: Trimethylolpropane (TMP, manufactured by Perstorp) <Ionizing agent> Ionizing agent a7-1: Dimethyl sulfate (dimethyl sulfate, manufactured by Tsujimoto Chemical Co.) Ionizing agent a7 -2: 85% phosphoric acid (manufactured by Nippon Chemical Industry Co., Ltd.) Ionizing agent a7-3: Formic acid (manufactured by Jungen Chemical Co., Ltd.) Ionizing agent a7-4: methanesulfonic acid (manufactured by TOSOH)

[Table 1]

<Preparation of water-based metal surface treatment agent> As shown in Table 2 (Tables 2-1 to 2-2), various urethane resins and various compounds [compound (B) to compound (F)] are mixed in water In addition, the water-based metal surface treatment agents of Examples 1 to 84 and Comparative Examples 1 to 16 were prepared. More specifically, based on 100 parts by mass of the urethane resin in the Synthesis Examples and Comparative Synthesis Examples, 125 parts by mass of water and various compounds having a solid content mass ratio as shown in Table 2 were added and mixed sufficiently to prepare Water-based metal surface treatment agents in Examples and Comparative Examples.

The components described in Table 2 are as follows. (Common test material) GI: Hot-dip galvanized steel sheet (thickness: 0.8mm) GL: 55% aluminum galvanized steel sheet (thickness: 0.5mm) Silane compound (B) B2: γ-aminopropyltriethoxy Silane B3: γ-glycidoxypropyltrimethoxysilane: B2 is a mixture of 1: 1 Compound (C) C1: Zirconium hydrofluoric acid C2: Titanium hydrofluoric acid C3: Acetylacetone vanadium vanadium Resin (D) D1: acrylic resin D2: phenol resin D3: epoxy resin crosslinking agent (E) E1: blocked isocyanate E2: carbodiimide resin E3: oxazoline resin compound (F) F1: polyethylene wax F2: Paraffin wax

<Surface treatment> Using an alkaline degreasing agent [Fine Cleaner E6406 (made by PARKERIZING, Japan) and water to make a 20 g / L solution], the test materials were degreased by spraying at 60 ° C for 10 seconds. After that, water was sprayed for 10 seconds for washing. After washing with water, the water-based metal surface treatment agent is applied on the surface of various test materials by the bar coat method, and then the temperature is 120 ° C (PMT: maximum plate temperature of the test material when firing). The film was dried to form a film having a film thickness of 1 μm.

<Evaluation test> (Corrosion resistance) As described above, various corrosion resistance tests were performed on various treated boards (No. 1 to 100) subjected to surface treatment. The evaluation methods and evaluation criteria are as follows.

(Corrosion resistance test of flat part) Based on the salt water spray test method (JIS-Z-2371: 2015), the area ratio (%) of white iron rust that occurred after 240 hours of neutral salt water spray was determined. The following criteria were used. And evaluate the corrosion resistance of the flat portion. In this evaluation, C or higher was considered acceptable. AAA: less than 5% AA: 5% or more and less than 10% A: 10% or more and less than 20% B: 20% or more and less than 30% C: 30% or more and less than 40% D: 40% or more

(Corrosion resistance test of the processed part) Two sheets of the same type and the same thickness as the test material used were overlapped and subjected to a 180-degree bending process to be sandwiched between various processed sheets. Thereafter, the area ratio (%) of the white iron rust generated was determined after performing a 72-hour neutral saline spray in the same manner as the corrosion resistance test of the flat portion, and the corrosion resistance of the processed portion was evaluated based on the following criteria. In this evaluation, C or higher was considered acceptable. AAA: less than 5% AA: 5% or more and less than 10% A: 10% or more and less than 20% B: 20% or more and less than 30% C: 30% or more and less than 40% D: 40% or more

(Corrosion-resistance test of the cross-section portion) After applying cross-cutting with an NT cutter on various treatment boards, the same as the corrosion-resistance test of the flat portion, a 72-hour neutral saline spray was performed, and the cross-section (cross-section) was determined. (×) cut) The maximum rust width on one side was evaluated for the corrosion resistance of the cross-cut portion according to the following criteria. In this evaluation, C or higher was considered acceptable. AAA: less than 2mm AA: 2mm or more and less than 4mm A: 4mm or more and less than 6mm B: 6mm or more and less than 8mm C: 8mm or more and less than 10mm D: 10mm or more

(Alkali resistance test) The treated plate was immersed in a 1% sodium hydroxide aqueous solution at room temperature (20 ° C) for 5 minutes, washed with water, and dried. Then, the color difference (ΔE) before and after the treatment with the sodium hydroxide aqueous solution was determined using a color difference meter (manufactured by Nippon Denshoku Co., Ltd.), and the alkali resistance was evaluated based on the following evaluation criteria. In this evaluation, C or higher was considered acceptable. AAA: △ E is less than 0.5 AA: △ E is 0.5 or more and less than 1 A: △ E is 1 or more and less than 1.5 B: △ E is 1.5 or more and less than 2 C: △ E is 2 or more and less than 3 D: △ E is 3 or more

(Acid resistance test) The treated plate was immersed in a 1% sulfuric acid aqueous solution at room temperature (20 ° C) for 5 minutes, washed with water, and dried. Then, the color difference (ΔE) before and after the treatment with the sulfuric acid aqueous solution was obtained using a color difference meter, and the acid resistance was evaluated based on the following evaluation criteria. In this evaluation, C or higher was considered acceptable. AAA: △ E is less than 0.5 AA: △ E is 0.5 or more and less than 1 A: △ E is 1 or more and less than 1.5 B: △ E is 1.5 or more and less than 2 C: △ E is 2 or more and less than 3 D: △ E is 3 or more

(One-time coating adhesion test) Using an amino alkyd paint (Amylac # 1000, manufactured by Kansai Paint Co., Ltd.), coating was performed on the surface of various treatment boards. The coating system was performed by a bar coating method. After coating, firing was performed at 130 ° C. (PMT) for 20 minutes to form a coating film having a thickness of 25 μm. After a 8 mm extrusion process was performed on the treated plate having a coating film, Erichsen was extruded, and then an operation was performed in which a tape was attached to the processed portion and peeled (hereinafter, referred to as "tape peeling") to determine the ratio of the area where the coating film was peeled off ( %), Based on the following evaluation criteria, the primary adhesion was evaluated. In this evaluation, C or higher was considered acceptable. AAA: peeled area is 0% (unpeeled) AA: peeled area is more than 0% and less than 5% A: peeled area is 5% or more and less than 10% B: peeled area is 10% or more and less than 20% C: peeled Area is 20% or more and less than 30% D: Peeling area is 30% or more

(Coating secondary adhesion test) After immersing the treated plate having the coating film in boiling water for 1 hour, extruding 8 mm with Erichsen, the tape was peeled off from the processed portion, and the ratio of the area where the coating film was peeled off (%) The secondary adhesion of the paint was evaluated in the same manner as the evaluation criteria for the primary adhesion test of the paint. In this evaluation, C or higher was considered acceptable.

(Solvent resistance test) After a wire mesh (gauze) impregnated with methyl ethyl ketone (MEK) was pressed on various treatment boards with a 1.5 kg load and slid back and forth 10 times, the color difference (ΔE) before and after the slide was determined using a color difference meter. Based on the following evaluation criteria, the solvent resistance was evaluated. In this evaluation, C or higher was considered acceptable. AAA: ΔE is less than 0.5 AA: ΔE is 0.5 or more and less than 1 A: ΔE is 1 or more and less than 1.5 B: △ E is 1.5 or more and less than 2 C: △ E is 2 or more and less than 3 D: △ E is 3 or more

(Abrasion resistance test) The Bowden tester was used to push steel balls (SUS304) under a load of 500 g and 20 times of back-and-forth. The change in friction coefficient from the start of the test to the end of the test was determined based on the following evaluation criteria. , Evaluation of wear resistance. In this evaluation, C or higher was considered acceptable. AAA: No change in friction coefficient AA: Change in friction coefficient is less than 0.05 A: Change in friction coefficient is 0.05 or more and less than 0.1 B: Change in friction coefficient is 0.1 or more and less than 0.15 C: Change in friction coefficient is 0.15 or more and Less than 0.2 D: The change in friction coefficient is 0.2 or more

<Evaluation Results> The results of the above evaluation tests are shown in Table 3 below (Tables 3-1 to 3-2).

[table 2-1]

[Table 2-2]

[Table 3-1]

[Table 3-2]

no

no

Claims (8)

An aqueous metal surface treatment agent comprising a urethane resin (A) and a silane compound (B), and the urethane resin (A) includes a formula derived from the following formula (1) A structural unit of a polyisocyanate having a cyclohexane ring structure, a structural unit derived from a polyol represented by the following formula (2), a structural unit derived from a weight-average molecular weight greater than 600, and a molecular weight derived from the formula (3) A structural unit of an alcohol, a structural unit derived from a diol having a weight average molecular weight of 500 or less represented by the following formula (4), and a tertiary amine compound and / or a salt thereof derived from the following formula (5) Structural unit; Formula (1): O = C = NR ¹ -N = C = O (R ¹ in Formula (1) is represented by -R ² -R ³ -R ^4- , and R ² is a single bond or elongation. Alkyl, R ³ is represented by the formula: [化 1] (However, R ⁵ , R ⁶ and R ^{7 are each} independently a hydrogen atom or an alkyl group.) R ⁴ is a single bond, an alkylene group, or (The bond on the left and R ³ bond)) Formula (2): [化 3] (In formula (2), R ⁸ is represented by -R ⁹ -R ¹⁰ -R ^11- , and R ⁹ is a [Chemical Formula 4] single bond, (Right bond and R ¹⁰ bond), or -R ¹³ -CO- (Right bond and R ¹⁰ bond) (However, R ¹² is a straight or branched alkylene group, and R ¹³ is- R ¹⁸ -O- (the bond on the right and the bond on CO), or (The right side is branched with CO); R ¹⁸ is a straight or branched alkylene; x is an integer of 1-5; l is an integer of 2-4) R ¹⁰ is [Chemical 5] , R ¹¹ is a [chemical 6] single bond, , , Or -CO-R ^13- (except for single bond, the left branch is bonded to R ¹⁰ ) (however, R ¹² is a straight or branched alkylene group, and R ¹³ is -R ¹⁸ -O- (right (The branches are bonded to CO), or (The right side is branched with CO); R ¹⁵ and R ^{16 are} independently a hydrogen atom, an alkyl group, a halogenated alkyl group, or a phenyl group; R ¹⁷ is hydrogen, an alkyl group, or a phenyl group; R ¹⁸ is a straight chain Or branched chain alkylene; x is an integer of 1-5; l is an integer of 2-4), R ¹⁴ is a hydrogen atom, an alkyl group, a phenyl group, ,or (However, R ¹⁸ is a linear or branched alkylene; l is an integer of 2-4)); Formula (3): HO-R ¹⁹ -H (3) (R ^{19 in} formula (3) is [化 8] , ,or (The bond branch on the left side is bonded to OH) (However, R ^{20 is} independently an alkylene group, , Or adamantane ring, R ²¹ is alkylene, m is an integer of 2-4, n-represents an integer)); the formula ^{(4): HO-R 22} -OH ( Formula (4) R ²² is [of 9 ] Alkyl, , Adamantane ring, ,or (However, y is 2 or 3; z is an integer of 1-6)) Formula (5): [化 10] (Wherein R ²³ is an alkyl group, an amino alkyl group, a hydroxyalkyl group, , ,or And R ²⁴ is hydroxyalkyl, aminoalkyl, or N-alkylaminoalkyl). The water-based metal surface treating agent according to claim 1, further comprising a compound (C) containing a compound selected from the group consisting of boron, magnesium, aluminum, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, molybdenum, An element of at least one of tungsten, cerium, niobium, tin, bismuth, and zirconium. The water-based metal surface treatment agent according to claim 1 or 2, wherein the silane compound (B) contains an amine group. The water-based metal surface treating agent according to any one of claims 1 to 3, further comprising a member selected from the group consisting of phenol resin, epoxy resin, polyester resin, and acrylic resin. A water-soluble or water-dispersible resin (D) of at least one of a resin, a polyolefin resin, and a polyamide resin. The water-based metal surface treating agent according to any one of claims 1 to 4, further comprising a member selected from the group consisting of an oxazoline resin, a blocked isocyanate resin, a carbodiimide resin, and nitrogen. Crosslinking agent (E) of at least one of aziridine-based resin and epoxy-based resin. The water-based metal surface treating agent according to any one of claims 1 to 5, further comprising a lubricant. A method for producing a metal material having a coating film, comprising a contact step of bringing the water-based metal surface treatment agent according to any one of claims 1 to 6 onto the surface of the metal material, and a step of contacting the metal material having undergone the contact step with the metal material. A heating step of heating and drying at 50 ° C to 250 ° C. A metal material having a film obtained by the method for producing a metal material for a film according to claim 7.