TWI740038B - Water-based metal surface treatment agent and metal material with film and manufacturing method thereof - Google Patents

Abstract

The subject of the present invention is to provide a water-based metal surface treatment agent, etc., which can form a film with excellent corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance on metal materials.

The solution of the present invention is to form the above-mentioned film on a metal material by using a water-based metal surface treatment agent, the water-based metal surface treatment agent containing a urethane resin (A), a silane compound (B), and the aforementioned urethane The ester resin (A) contains 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 with a weight average molecular weight greater than 600, and a source From a structural unit of 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 its salt.

Description

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

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

A metal surface treatment agent that can form a film that imparts various properties to metal materials has been developed. For example, Patent Document 1 has disclosed a technique regarding a metal material surface treatment water-based coating composition containing a specific cationic water-based urethane resin (urethane resin).

In addition, Patent Document 2 has disclosed the 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 Technical Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 2005/092998

[Patent Document 2] JP 2011-231353 A

However, the above-mentioned technology cannot form a coating film excellent in corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance on metal materials.

Therefore, the object of the present invention is to provide a water-based metal surface treatment agent capable of forming a coating film excellent in corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance on a metal material, and a metal material having the coating film, and其制造方法。 Its manufacturing method.

The inventors of the present invention have repeatedly conducted in-depth studies and found that by using a surface treatment agent containing a specific urethane resin and a silane compound, the above-mentioned problems can be solved, and the present invention has been completed. The present invention includes the following.

(惟，式中R⁵、R⁶及R⁷獨立為氫原子或烷基) [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) The structural unit of the polyisocyanate having a cyclohexane ring structure, the structural unit derived from the polyol represented by the following formula (2), the structural unit derived from the polyol represented by the following formula (3), the weight average molecular weight is greater than 600 Alcohol structural units, structural units derived from diols with a weight average molecular weight of 500 or less represented by the following formula (4), and tertiary amine compounds and/or their salts derived from the following formula (5) The structural unit of; Formula (1): O=C=NR ¹ -N=C=O (In formula (1), R ¹ is represented by -R ² -R ³ -R ⁴ -, and R ² is a single bond or extension Alkyl group, R ³ is represented by the following formula [化1]

(However, in the formula, R ⁵ , R ⁶ and R ^{7 are} independently a hydrogen atom or an alkyl group)

(左側的鍵結枝與R³鍵結)) R ⁴ is [化2] single bond, alkylene, or

(The bonding branch on the left is bonded with R ³ ))

、或

(n為整數) Formula (2): [化3] HO-R ⁸ -OH,

,or

(n is an integer)

(In formula (2), R ⁸ is represented by -R ⁹ -R ¹⁰ -R ¹¹ -, and R ⁹ is [化4]

(右側之鍵結枝與R¹⁰鍵結)、或-R¹³-CO-(右側之鍵結 枝與R¹⁰鍵結) single bond,

(The bonding branch on the right is bonded with R ¹⁰ ), or -R ¹³ -CO- (the bonding branch on the right is bonded with R ¹⁰ )

(右側之鍵結枝與CO鍵結)；又，R¹⁸為直鏈或分支鏈之伸 烷基；x為1-5之整數；l為2-4之整數) (However, R ¹² is a straight or branched chain alkylene, and R ¹³ is -R ¹⁸ -O- (the right side of the branch is bonded to CO), or

(The bonding branch on the right is bonded with CO); Also, R ¹⁸ is a straight or branched chain alkylene; x is an integer of 1-5; l is an integer of 2-4)

R¹¹為[化6] 單鍵、

、

、

、或-CO-R¹³-(單鍵除外，左側的鍵結枝與R¹⁰ 鍵結)(惟，R¹²為直鏈或分支鏈之伸烷基，R¹³為-R¹⁸-O-(右側的鍵結枝與CO鍵 結)、或

(右側的鍵結枝與CO鍵結)；又，R¹⁵及R¹⁶獨立為氫原子、 烷基、鹵化烷基、或苯基，R¹⁷為氫、烷基或苯基；R¹⁸為直鏈或分支鏈之伸烷基；x為1-5之整數；l為2-4之整數) R ¹⁰ is [化5]

R ¹¹ is [化6] single bond,

,

,

, Or -CO-R ^13- (except for single bonds, the bonding branch on the left is bonded to R ¹⁰ ) (However, R ¹² is a straight or branched chain alkylene, R ¹³ is -R ¹⁸ -O- (right The bonding branch and CO bonding), or

(The bonding branch on the right is bonded to CO); In addition, 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 alkylene; x is an integer of 1-5; l is an integer of 2-4)

、或

R ¹⁴ is [化7] hydrogen atom, alkyl group, 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)

、

、或

(各自左側的鍵結枝與OH鍵結) (In formula (3), R ¹⁹ is [化8]

,

,or

(The bonding branch on the left side of each is bonded with OH)

、或 金剛烷環，R²¹為伸烷基，m為2-4之整數，n為整數))；式(4)：HO-R²²-OH (However, R ^{20 is} independently an alkylene group,

, Or adamantane ring, R ²¹ is an alkylene group, m is an integer of 2-4, n is an integer)); formula (4): HO-R ²² -OH

、金剛烷環、

、或

(In formula (4), R ²² is [化9] alkylene,

, Adamantane ring,

,or

(However, y is 2 or 3; z is an integer of 1-6))

(式中，R²³為烷基、胺基烷基、羥基烷基、

、──C(CH₂OH)₃、或

， R²⁴為羥基烷基、胺基烷基、或N-烷基胺基烷基)。 Formula (5): [化 10]

(In the formula, R ²³ is alkyl, aminoalkyl, hydroxyalkyl,

,──C(CH ₂ OH) ₃ , or

, R ²⁴ is hydroxyalkyl, aminoalkyl, or N-alkylaminoalkyl).

[2] The water-based metal surface treatment agent described in [1] above, which further contains a compound (C), which contains a compound selected from boron, magnesium, aluminum, titanium, vanadium, manganese, iron, cobalt, nickel, At least one element of zinc, molybdenum, tungsten, cerium, niobium, tin, bismuth and zirconium.

[3] The water-based metal surface treatment agent described in [1] or [2] above, wherein the silane compound (B) contains an amine group.

[4] The water-based metal surface treatment agent described in any one of [1] to [3] above, which further contains selected from the group consisting of phenol resin, epoxy resin, and polyester resin ), at least one water-soluble or water-dispersible resin (D) of acrylic resin, polyolefin resin and polyamide resin.

[5] The water-based metal surface treatment agent described in any one of [1] to [4] above, which further contains selected from oxazoline resins, blocked isocyanate resins, and carbon dioxide A crosslinking agent (E) of at least one of carbodiimide resin, aziridine resin, and epoxy resin.

[6] The water-based metal surface treatment agent described in any one of [1] to [5] above, which further contains 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 described in any one of [1] to [6] into contact on the surface of the metal material, and undergoing the aforementioned A heating step in which the metal material in the contact step is heated and dried at 50°C or higher and 250°C or lower.

[8] A metal material having a film obtained by the method of manufacturing a metal material having a film as described in [7] above.

According to the present invention, it is possible to provide a water-based metal surface treatment agent capable of forming a coating film with excellent corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance on a metal material, and a metal material having the coating film and its production method.

[Form to implement invention]

Hereinafter, specific embodiments are presented, and the present invention will be described in detail.

<Water-based metal surface treatment agent>

One aspect of the present invention is a water-based metal surface treatment agent. The water-based metal surface treatment agent contains the urethane resin (A) and the silane compound (B) described later. By using this water-based metal surface treatment agent to form a film on the surface of the metal material, excellent corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance can be imparted to the metal material.

Hereinafter, the components contained in the water-based metal surface treatment agent of this embodiment and the components that can be contained will be described.

<<Urethane resin (A)>>

In general, the urethane resin (A) is obtained by reacting a urethane prepolymer with water. At this time, in order to promote the reaction, a polyamine compound that does not contain a tertiary amine compound may be contained as necessary. Specifically, the isocyanate group contained in the urethane prepolymer reacts with the amine generated by water or the 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 manufacture of urethane resins. At least a polyisocyanate having a cyclohexane ring structure, a polyol that does not contain nitrogen atoms and contains a benzene ring, and does not contain benzene Diols with a weight average molecular weight of rings and nitrogen atoms greater than 600 (hereinafter, also referred to as high molecular weight diols), diols with a weight average molecular weight of 500 or less that do not contain benzene rings and nitrogen atoms (hereinafter, also referred to as low molecular weight Diol), obtained by reacting with a tertiary amine compound having two or more active hydrogens and/or its salt.

From another point of view, the urethane prepolymer contains a structural unit derived from a polyisocyanate having a cyclohexane ring structure represented by the following formula (1), derived from the following formula (2) The structural unit of the polyol represented, the structural unit derived from the diol with a weight average molecular weight greater than 600 represented by the following formula (3), and the structural unit derived from the weight average molecular weight represented by the following formula (4) of 500 or less The structural unit of the diol and the structural unit derived from the tertiary amine compound represented by the following formula (5) and/or its salt.

Specifically, the polyol represented by formula (2), the high-molecular-weight diol represented by formula (3), and the hydroxyl group contained in the low-molecular-weight diol represented by formula (4) are the same as those represented by formula (1). The isocyanate group contained in the shown polyisocyanate reacts to form a urethane bond. In addition, the isocyanate group contained in the polyisocyanate reacts with the hydrogen atom (active hydrogen) contained in the tertiary amine compound represented by formula (5) and/or its salt to form a urethane bond, Urea key and so on.

In addition, the urethane prepolymer used in this embodiment, as described above, has a polyamine compound derived from a cyclohexane ring structure by reacting with water or a polyamine compound that does not contain a tertiary amine compound. The isocyanate group of isocyanate.

(Polyisocyanate with cyclohexane ring structure)

The polyisocyanate having a cyclohexane ring structure (hereinafter also referred to as "polyisocyanate") is used in the production of a urethane prepolymer, and is represented by the following formula (1).

Formula (1): O=C=NR ¹ -N=C=O

In the 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 [化11]

(左側的鍵結枝與R³鍵結)。 (However, in the formula, R ⁵ , R ⁶ and R ^{7 are} independently a hydrogen atom or an alkyl group), R ⁴ is a single bond, an alkylene group, or

(The bonding branch on the left is bonded to R ³ ).

(惟，式中R⁵、R⁶及R⁷獨立為氫原子或甲基)、

、

、或

。又，上述式中R⁵、R⁶及R⁷之全部為氫原子 或甲基者更佳。 R ^{1 is} preferably [化13]

(However, in the formula, R ⁵ , R ⁶ and R ^{7 are} independently a hydrogen atom or a methyl group),

,

,or

. In addition, it is more preferable that all of ^{R 5} , R ⁶ and R ^{7 in the above formula are hydrogen atoms or methyl groups.}

In addition, the cyclohexane ring structure also includes a bicyclic structure having a cyclohexane structure. In addition, a plurality of cyclohexane ring structures may be contained in the polyisocyanate.

(Injection amount of polyisocyanate)

In the production of the urethane prepolymer described below, the amount of polyisocyanate injected is relative to the polyisocyanate used in the production of the urethane prepolymer, the polyol described below, the high molecular weight diol described below, The total amount of the low-molecular-weight diol and tertiary amine compound and/or its salt described later is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and more preferably 40 to 65% by mass, 50 ~60% by mass is particularly good. That is, in the urethane resin (A) used in this embodiment, the amount of the structural unit derived from the polyisocyanate of the formula (1) (in terms of mass), in the urethane resin (A) , Preferably 20 to 80%, more preferably 30 to 70%, further preferably 40 to 65%, particularly preferably 50 to 60%.

In the present embodiment, in the production of urethane prepolymers, in the case of using the "polyols more than triols without benzene ring and nitrogen atoms" described later, the triols without benzene ring and nitrogen atoms are used. The above-mentioned injection amount of polyol is calculated into the above-mentioned total amount.

(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 for example, isophorone Diisocyanate (isophorone diisocyanate), 1,3- or 1,4-bis(isocyanate methyl) 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'-diisocyanate (dicyclohexylmethane4,4'-diisocyanate), etc.

As a polyisocyanate not contained in formula (1), it is a dimer such as a uretdione structure, a trimer such as an isocyanurate structure, and an adduct of a polyfunctional polyol ( Adduct) body, polyisocyanate having three or more isocyanate groups in one molecule, etc., 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 isophorone diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, and dicyclohexylmethane 4,4' from the viewpoint of further improving solvent resistance. -A compound of at least one type of diisocyanate, more preferably dicyclohexylmethane 4,4'-diisocyanate.

(Polyol containing no nitrogen atom and benzene ring)

The polyol containing no nitrogen atom and containing a benzene ring (hereinafter also referred to as "polyol") is used for the production of urethane prepolymer and is represented by the following formula (2).

、或

(n為整數) Formula (2): [化14] HO-R ⁸ -OH,

,or

(n is an integer)

(右側的鍵結枝與R¹⁰鍵結)、或-R¹³-CO-(右側的鍵 結枝與R¹⁰鍵結) In formula (2), R ⁸ is represented by -R ⁹ -R ¹⁰ -R ¹¹ -, R ⁹ is a single bond,

(The bonding branch on the right is bonded to R ¹⁰ ), or -R ¹³ -CO- (The bonding branch on the right is bonded to R ¹⁰ )

(右側的鍵結枝與CO鍵結)。又，R¹⁸為直鏈或分支鏈之伸 烷基，x為1-5之整數，l為2-4之整數)，R¹⁰為[化16]

R¹¹為[化17] 單鍵、

、

、

、或-CO-R¹³-(除去單鍵，左側之鍵結枝與R¹⁰ 鍵結) (However, R ¹² is a straight chain or branched chain alkylene, R ¹³ is -R ¹⁸ -CO- (the bond branch on the right is bonded to CO), or

(The bonding branch on the right is bonded with CO). In addition, R ¹⁸ is a linear or branched alkylene, x is an integer of 1-5, and l is an integer of 2-4), R ¹⁰ is [化16]

R ¹¹ is [化17] single bond,

,

,

, Or -CO-R ^13- (Remove the single bond, the left side of the bond branch is bonded to R ¹⁰ )

(右側之鍵結枝與CO鍵結)。又，R¹⁵及R¹⁶獨立為氫原子、 烷基、鹵化烷基、或苯基，R¹⁷為氫原子、烷基、或苯基；R¹⁸為直鏈或分支鏈之伸烷基；x為1至5之整數；l為2至4之整數)；R¹⁴為[化18] 氫原子、烷基、苯基、

、或

(However, R ¹² is a straight or branched chain alkylene, and R ¹³ is -R ¹⁸ -O- (the right side of the branch is bonded to CO), or

(The bonding branch and CO bonding on the right). In addition, 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 linear or branched alkylene group; x Is an integer from 1 to 5; l is an integer from 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; 1 is an integer from 2 to 4).

、

(右側之鍵結肢與OH鍵結)

、或

R ^{8 is} preferably [化19]

,

(The bonding limb on the right is bonded with OH)

,or

R ^{12 is} preferably ethylidene or isopropylidene. 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.

(Injection amount of polyol)

In the production of the urethane prepolymer described below, the injection amount of the polyol is relative to the polyisocyanate, polyol, high molecular weight diol described below, and the polyisocyanate used in the production of the urethane prepolymer. The total amount of the low molecular weight diol, the tertiary amine compound and/or its salt is usually, for example, 1-40% by mass, but preferably 1-30% by mass, more preferably 3-25% by mass, More preferably, it is 6-20 mass %. That is, in the urethane resin (A) used in this embodiment, the amount of the structural unit derived from the polyol of the formula (2) (in terms of mass) is relative to the urethane resin (A) Among them, it is usually 1-40%, preferably 1-30%, more preferably 3-25%, and still more preferably 6-20%.

In this embodiment, in the case of "polyols above triol and more than benzene ring and nitrogen atom" used in the manufacture of urethane prepolymer, the triol which does not contain benzene ring and nitrogen atom is used. The above-mentioned injection amount of polyol is calculated into the above-mentioned total amount.

(Types of polyols)

The polyol 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 is not particularly limited. For example, resorcinol (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-propylene oxide 2 mol Ear adduct, bisphenol A-propylene oxide 4 mol adduct, bisphenol A-propylene oxide 6 mol adduct, bisphenol A-propylene oxide 10 mol adduct, etc. Cyclic polyether polyols; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, etc., by combining with ethylene glycol, propylene glycol, diethylene glycol, and triethyl Glycol, tetraethylene glycol, 2-methylpropanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3- Polyester polyols with benzene ring obtained by polycondensation of polyols such as methylpentanediol; obtained by transesterification reaction of ethylene carbonate and polyols such as bisphenol A Polycarbonate polyol with benzene ring, etc.

A polyol may be used individually by 1 type, and may use 2 or more types together.

(High molecular weight glycol)

High-molecular-weight diols are used in the production of urethane prepolymers, represented by the following formula (3), and do not contain benzene rings and nitrogen atoms.

Formula (3): HO-R ¹⁹ -H (3)

、

、或

(各自左側的鍵結枝與OH鍵結) In formula (3), R ¹⁹ is [化20]

,

,or

(The bonding branch on the left side of each is bonded with OH)

、或 金剛烷環，R21為伸烷基，m為2-4之整數，n為整數))。 (However, R20 is independently an alkylene group,

, Or 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 glycol)

In the production of the urethane prepolymer described later, the injection amount of the high molecular weight diol of formula (3) is relative to the polyisocyanate, polyol, and high molecular weight used in the production of the urethane prepolymer The total amount of the diol, the low-molecular-weight diol described below, and the tertiary amine compound and/or its salt is usually, for example, 1 to 50% by mass, but preferably 3 to 40% by mass, more preferably 5 ~35 mass%, more preferably 10-30 mass%. That is, in the urethane resin (A) used in this embodiment, the amount of the structural unit derived from the diol of the formula (3) (in terms of mass) is relative to the urethane resin (A) Among them, it is usually 1-50%, preferably 3-40%, more preferably 5-35%, and still more preferably 10-30%.

In this embodiment, in the case of using the "polyol with more than triol and more than benzene ring and nitrogen atom" described later in the manufacture of urethane prepolymer, the triol and more than triol without benzene ring and nitrogen atom are used. The injected amount of polyol is included in the above total amount.

(Weight average molecular weight of high molecular weight glycol)

The weight average molecular weight of the high molecular weight diol is greater than 600, but is preferably greater than 600 and 10,000 or less, more preferably greater than 600 and 5,000 or less, further preferably 800 to 4,000, particularly preferably 1,000 to 3,000.

Unless otherwise specified, the weight average molecular weight of each component in this embodiment is a value measured by GPC (gel permeation chromatography) and converted to polystyrene.

(Types of high molecular weight diols)

As for the high molecular weight diol, it is a diol that does not contain a benzene ring and a nitrogen atom, as long as the weight average molecular weight is greater than 600, and is not particularly limited. For example, polyether diol, polyester diol, and polycarbonate can be used. Ester diols and so on.

As for the above-mentioned polyether glycol, for example, polyethylene glycol, polypropylene glycol, polybutylene glycol (polytetramethylene ether glycol) and the like can be cited. Polyether glycol is produced, for example, by addition polymerization of alkylene oxides such as ethylene oxide and propylene oxide in an alkaline catalyst.

The above-mentioned polyester diols can be exemplified by unsaturation of aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid, and sebacic acid as the acid species. Carboxylic acid, etc., and 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, etc.

Examples of the above polycarbonate diols include those manufactured by ring-opening polymerization of cyclic esters such as ε-caprolactone and the like. Specifically, they include dimethyl carbonate, dicarbonate Ethyl ester, diphenyl carbonate, etc. are produced by reacting with the diol types listed in the above-mentioned polyester diol.

The high-molecular-weight diol may be used singly, or two or more of them may be used in combination.

Among the above, the high-molecular-weight diol preferably includes polyether diol.

As for the polyether glycol, at least one compound selected from polyethylene glycol, polypropylene glycol and polybutylene glycol is more preferred.

When a polyether diol is used, it is preferable to use at least one of the above-mentioned polyester diol and polycarbonate diol in combination.

(Low molecular weight glycol)

Low-molecular-weight diols are used in the production of urethane prepolymers, represented by the following formula (4), and do not contain benzene rings and nitrogen atoms.

Formula (4): HO-R ²² -OH

、金剛烷環、

、或

(In formula (4), R ²² is [化21] alkylene,

, Adamantane ring,

,or

(However, y is 2 or 3; z is an integer of 1-6)).

(Injection amount of low molecular weight glycol)

In the production of the urethane prepolymer described later, the injection amount of the low molecular weight diol is relative to the polyisocyanate, polyol, high molecular weight diol, and low molecular weight used in the production of the urethane prepolymer The total amount of the diol and the tertiary amine compound and/or its salt is usually, for example, 1 to 25% by mass, but preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably It is 3-10% by mass. That is, in the urethane resin (A) used in this embodiment, the amount (in terms of mass) of the structural unit derived from the low-molecular-weight diol of formula (4) is greater than that of the urethane resin ( In A), it is usually 1 to 25%, preferably 1 to 20%, more preferably 2 to 15%, and further preferably 3 to 10%.

In this embodiment, when the urethane prepolymer is manufactured using the "polyol with more than triol and more than a benzene ring and nitrogen atom" described later, the polyol with more than triol and more than a triol without a benzene ring and nitrogen atom The amount of polyol injected is calculated into the total amount mentioned above.

(Weight average molecular weight of low molecular weight glycol)

The weight average molecular weight of the low molecular weight diol is 500 or less, but is preferably 400 or less, and more preferably 250 or less. In addition, the lower limit is preferably 60 or more, more preferably 100 or more.

(Types of low molecular weight diols)

For low molecular weight glycols, for example, ethylene glycol (62.07g/mol), propylene glycol (76.09g/mol), 1,5-pentanediol (104.15g/mol), 1,6-hexane Alkanediol (118.17g/mol), 1,7-heptanediol (132.2g/mol), 1,8-octanediol (146.23g/mol), 1,9-nonanediol (160.25 g/mol), 1,10-decanediol (174.28g/mol), neopentyl glycol (104.15g/mol), 2-methyl-1,3-propanediol (90.12g/mol), 3-methyl-1,5-pentanediol (118.17g/mol), 1,4-cyclohexyldimethanol (146.14g/mol), 1,3-adamantanediol (168.23g/mol), etc. The alkyl glycol, diethylene glycol (106.12g/mol), triethylene glycol (150.17g/mol), tetraethylene glycol (194.23g/mol), pentaethylene glycol (238.28g/mol), Polyalkylene glycol such as hexaethylene glycol (282.33g/mol), heptaethylene glycol (323.28g/mol), dipropylene glycol (134.17g/mol), dimethylolpropionic acid (134g/mol) Wait. One of these may be used alone, or two or more of them may be used in combination.

(Tertiary amine compound or its salt)

The tertiary amine compound and/or its salt is used in the production of a urethane prepolymer, and is represented by the following formula (5).

(式中，R²³為烷基、胺基烷基、羥基烷基、

、──C(CH₂OH)₃、或

Formula (5): [化22]

(In the formula, R ²³ is alkyl, aminoalkyl, hydroxyalkyl,

,──C(CH ₂ OH) ₃ , 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 .

The active hydrogen of the tertiary amine compound and/or its salt reacts with the above-mentioned polyisocyanate to obtain a urethane prepolymer (amine group Formate resin).

In addition, the tertiary amine compound and/or its salt contains two or more active hydrogens. For example, it is preferable to contain two or more active hydrogen substituents such as an amino group, a hydroxyl group, and an N-alkylamino group. In addition, the N-alkylamino group is preferably a 2-methylamino group.

(Injection amount of tertiary amine compound and/or its salt)

In the production of the urethane prepolymer described below, the injection amount of the tertiary amine compound and/or its salt is relative to the polyisocyanate, polyol, and high molecular weight used in the production of the urethane prepolymer The total amount of diol, low molecular weight diol, and tertiary amine compound and/or its salt is usually, for example, 1-20% by mass, preferably 2-15% by mass, more preferably 2-13 by mass %, more preferably 3-10 quality quantity%. That is, in the urethane resin (A) used in this embodiment, the amount (in terms of mass) of the structural unit derived from the tertiary amine compound of formula (5) and/or its salt, the urethane In the acid ester resin (A), it is usually 1-20%, preferably 2-15%, more preferably 2-13%, and still more preferably 3-10%.

In this embodiment, when the urethane prepolymer is manufactured using the "polyol with more than triol and more than a benzene ring and nitrogen atom" described later, the polyol with more than triol and more than a triol without a benzene ring and nitrogen atom The amount of polyol injected is calculated into the total amount mentioned above.

(Types of tertiary amine compounds)

The tertiary amine compound is not particularly limited as long as it has a tertiary amine having two or more active hydrogens, and examples thereof include N-methyldiethanolamine, N-ethyldiethanolamine, and N-butyldiethanolamine. Ethanolamine, N-tertiary butyldiethanolamine, N-(3-aminopropyl)diethanolamine, etc. N-aminoalkyl dialkanolamine, triethanolamine, N,N,N',N'-IV (2-hydroxyethyl) ethylene diamine, bis(2-hydroxyethyl)amino (hydroxymethyl)methane, 1-bis(2-hydroxyethyl)amino-2-propanol, etc. Trialkanolamine which may have substituents, 2,2'-diamino-N-methyldiethylamine, N,N',N"-trimethyldiethylenetriamine, Ref. (2- Aminoethyl) amine and other tertiary amine compounds. These tertiary amine compounds can be used as salts with organic acids such as formic acid and acetic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. The alkylating agent such as ethyl ester, methyl iodide, etc. is made into a quaternary salted one. As for the tertiary amine compound, N-aminoalkyl dialkanolamine, especially N-methyldiethanolamine is preferred.

The urethane resin (A) of the present 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. As for the acid used in this case, for example, organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, malic acid, malonic acid, adipic acid, etc.; methanesulfonic acid, ethane Organic sulfonic acids such as sulfonic acid and trifluoromethanesulfonic acid Organic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, hydrobromic acid, phosphoric acid and other inorganic acids. One kind of these acids may be used alone, or two or more kinds may be used in combination. In addition, the urethane resin (A) may be a part or all of the structural part (tertiary amine) derived from the tertiary amine compound that has been quaternized. As the quaternization agent used in the case of quaternization, specifically, sulfuric acid esters 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 quaternary agents can be used singly, or two or more of them can be used in combination. In addition, an acid and a quaternary agent as a neutralizer can also be used in combination.

In addition, in this specification, such acids and quaternary agents may be referred to as ionizing agents.

In this specification, "alkyl" or "alkyl" contained in halogenated alkyl, aminoalkyl, hydroxyalkyl, N-alkylaminoalkyl, etc. are not particularly limited, and usually has 20 or less carbon atoms. The alkyl group may be an alkyl group with 12 or less carbon atoms, or an alkyl group with 6 or less carbon atoms. Typically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, secondary butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl can be enumerated , 3-methylpentyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.

Moreover, the "alkylene group" is not particularly limited, and it is usually an alkylene group having 20 or less carbon atoms, and may be an alkylene group having 12 or less carbon atoms or an alkylene group having 6 or less carbon atoms. Typically, ethylene, propylene, butylene, isobutylene, tertiary butylene, dibutylene, pentylene, isopentyl, neopentyl, hexylene, Isohexyl, 3-methylpentyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.

In addition, examples of the halogenated alkyl system include those in which one or more hydrogen atoms in the above-mentioned alkyl groups are substituted with fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms.

(Other ingredients that can be used in the manufacture of urethane prepolymer)

In the production of the urethane prepolymer of this embodiment, components other than the above can be used. As for other components, for example, polyisocyanates other than the above-mentioned polyisocyanates, the above-mentioned polyols, the above-mentioned high-molecular-weight diols and the above-mentioned low-molecular-weight diols other than polyols that do not contain a benzene ring and nitrogen atoms, organic solvents, and the above Polyamine compounds, ionizing agents, acids, organometallic compounds, etc. other than tertiary amine compounds.

(Polyisocyanate other than polyisocyanate)

The polyisocyanate other than the above-mentioned polyisocyanate is not particularly limited, and may be, for example, 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanate) hexanoate, and 1,6-hexamethylene diisocyanate. Aliphatic diisocyanates such as methylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; m-or p-phenylene diisocyanate, tolylene-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 '-Dimethyl diphenyl ester, 3-methyl-diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, tetramethylxylylene diisocyanate diisocyanate) and other aromatic diisocyanates; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 2-isocyanate ethyl (2,6-diisocyanate group ) Aliphatic triisocyanates such as caproate; aromatic triisocyanates such as triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, etc.

The polyisocyanate other than the above-mentioned polyisocyanate may be a dimer with a uretdione structure or a trimer with a trimeric isocyanate structure. As an addition object using a polyfunctional polyol, it may have three or more in one molecule. The isocyanate-based polyisocyanate.

Among these, aromatic polyisocyanates such as aromatic diisocyanates and aromatic triisocyanates are preferably used, and aromatic diisocyanates are preferably used. In terms of the content of other components and the amount of the structure derived from the other components in the urethane resin (A), within a range that does not hinder the effects of the present invention, those with ordinary knowledge in this technical field may Set it appropriately.

(Polyol represented by general formula (2), high molecular weight diol, low molecular weight diol, and other polyols)

Regarding the polyols, high-molecular-weight diols, and polyols other than low-molecular-weight diols represented by the above general formula (2), polyols of triol or more that do not contain a benzene ring and a nitrogen atom can be used. For example, Trimethylolpropane, neopentylerythritol, etc.

Among the triol or higher polyols that do not contain a benzene ring and a nitrogen atom, trimethylolpropane (TMP) is preferred.

In the case of using a triol or more polyol that does not contain a benzene ring and nitrogen atoms in the production of urethane prepolymers, the injection amount is relative to the polyisocyanate used in the production of urethane prepolymers The total amount of polyols, polyols, high molecular weight diols, low molecular weight diols, tertiary amine compounds and/or their salts, and triols or more polyols that do not contain benzene rings and nitrogen atoms, preferably 0.5-18% by mass , More preferably 3-10% by mass. That is, in the urethane resin (A) used in this embodiment, the amount (in terms of mass) of structural units derived from a triol or higher polyol that does not contain a benzene ring and a nitrogen atom is determined by the amino group In the formate resin (A), it is usually 0.5 to 18%, preferably 3 to 10%.

The urethane resin of this embodiment preferably has a branched structure. As for the method of introducing a branch structure, as described above, the use of a triol or more polyol that does not contain a benzene ring and a nitrogen atom can be exemplified, but it is not limited to this method.

In the production of urethane prepolymer and/or the production of urethane resin (A), an organic solvent can be used. The organic solvent is used as a solvent for reacting the above-mentioned components. Such organic solvents are not particularly limited, and examples 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; acrylic ester solvents such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; Amide-based solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, etc.; and sulfide-based solvents such as dimethyl sulfide. These organic solvents can be removed by vacuum distillation as necessary from the viewpoint of reducing the burden on the environment after the production of the urethane prepolymer and the urethane resin (A).

<Production method of urethane prepolymer and urethane resin>

The urethane prepolymer of this embodiment is made of at least the polyisocyanate represented by the above general formula (1), the polyol represented by the above general formula (2), and the high molecular weight represented by the above general formula (3) Diol, the low molecular weight diol represented by the said general formula (4), and the tertiary amine compound represented by the said general formula (5), and/or its salt, etc. are obtained by reacting. In addition, 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 as a polychain extender can be added as necessary, and the polyamine compound in this case is not a tertiary amine compound.

Hereinafter, an example of the manufacturing method of the urethane prepolymer and the urethane resin of this embodiment (manufacturing methods 1 to 6) is shown.

(Manufacturing method 1)

By dissolving polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, tertiary amine compound, etc., in an organic solvent and reacting, a urethane prepolymer is prepared, and if necessary, the urethane A method in which part or all of the tertiary amine in the ester prepolymer is ionized by an ionizing agent and emulsified by adding water.

(Manufacturing method 2)

By dissolving polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, tertiary amine compound, etc., in an organic solvent and reacting, a urethane prepolymer is prepared, and if necessary, the urethane A method in which part or all of the tertiary amine in the ester prepolymer is ionized by an ionizing agent, and emulsified by adding water while extending the chain by using a chain extender such as a polyamine compound

(Manufacturing method 3)

Polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, tertiary amine compound, etc., are reacted without using an organic solvent (bulk polymerization method) to prepare urethane Prepolymer, if necessary, part or all of the tertiary amine in the urethane prepolymer is quaternized by an ionizing agent, and emulsified by adding water

(Manufacturing method 4)

After the tertiary amine compound is ionized with an acid or an alkylating agent, it is reacted by adding polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, etc. to prepare a urethane prepolymer. If necessary, 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)

After adding polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, etc. to an organic solvent and reacting, a tertiary amine compound is further added to prepare a urethane prepolymer having a tertiary amine structure at the end portion If necessary, part or all of the tertiary amine in the urethane prepolymer is ionized by an ionizing agent, and water is added to emulsify it.

(Manufacturing method 6)

After adding polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, etc. to an organic solvent and reacting, a tertiary amine compound is further added to prepare a urethane prepolymer having a tertiary amine structure at the end portion If necessary, part or all of the tertiary amine in the urethane prepolymer is ionized by an ionizing agent. A chain extender such as a polyamine compound is used to extend the chain while adding water. Emulsification method

In addition, in the above-mentioned manufacturing methods 1 to 6, conventional emulsifiers can be used.

<Polyamine compound>

With regard to the use of polyamine compounds as chain extenders, for example, ethylene diamine, 1,2-propane diamine, 1,6-hexamethylene diamine, piperazine, 2,5-diamine can be used Methylpiperazine, isophorone diamine, 4,4'-dicyclohexylmethane diamine, 3,3'-dimethyl-4,4'-dicyclohexylmethane diamine, 1,4-ring Hexanediamine, 1,3-bisaminomethylcyclohexane, 2-aminoethylaminopropyl trimethoxysilane; N-hydroxymethylaminoethylamine, N-hydroxyethylamine Ethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, diethylenetriamine, Triethylenetetramine; hydrazine, 1,6-hexamethylene bishydrazine; succinic dihydrazide (succinic dihydrazide), dihydrazide adipic acid, dihydrazine glutarate, dihydrazine sebacate , Dihydrazine isophthalate; β-semicarbazide propionic acid hydrazide (β-semicarbazide propionic acid hydrazide), 3-semicarbazide propionic acid hydrazide (3-semicarbazide) propylcarbazinate), hemicarbazinate-3-semicarbazinate methyl-3,5,5-trimethylcyclohexane, etc. Among them, hydrazine or ethylenediamine is preferably used.

In the case of using a chain extender, the injection amount of the polyamine compound is preferably 0.1-10 parts by mass, more preferably 0.2-5 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). As for the silane compound (B), for example, 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-aminopropyl triethoxysilane, N-β-(N-vinylbenzylaminoethyl)-3-aminopropylmethyl Diethoxysilane, N-methylaminopropyltrimethoxysilane, N-butylaminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-epoxy Propoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyl Trimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methyltrimethoxysilane, two Methyl dimethoxysilane, methyl triethoxy Methyl silane, dimethyl diethoxy silane, vinyl triacetoxy silane, γ-chloropropyl trimethoxy silane, γ-chloropropyl methyl dimethoxy silane, γ-chloropropyl tri Ethoxysilane, γ-chloropropylmethyldiethoxysilane, hexamethyldisilazane (hexamethyldisilazane), γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethyl Oxysilane, γ-anilinopropyl triethoxy silane, γ-anilinopropyl methyl diethoxy silane, isocyanate propyl trimethoxy silane, isocyanate propyl triethoxy silane, ureido propyl Triethoxysilane, bis(trimethoxysilyl)aminovinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxy Silane, octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, octadecyldimethyl[3-(methyldimethoxysilyl)propyl]ammonium chloride , Octadecyldimethyl[3-(triethoxysilyl)propyl]ammonium chloride, octadecyldimethyl[3-(methyldiethoxysilyl)propyl]ammonium chloride , Γ-Chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, etc. Only one kind of these may be used, or plural kinds may be used in combination. These silane compounds can be used alone, or they can also be in the form of a hydrolysate, or a homopolymer. Others can be used as a mixture of two or more silane compounds, or a hydrolysate or other form of the silane compound. The use of mixtures or copolymers of homopolymers and the like 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 within the range of 1/100 to 4.0. More preferably, it is in the range of 1/10 or more and 3.5 or less. More preferably, it is in the range of 1/5 or more and 3 or less.

As for the silane compound (B), particularly an amino group-containing silane compound is preferred. As for the silane compound containing an amino group, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-propyltrimethoxysilane , N-phenyl-3-propyl triethoxy Silane, N-(2-aminoethyl)aminopropyltrimethoxysilane, N-(2-aminoethyl)aminopropylmethyldimethoxysilane, N-(2-aminoethyl) Ethyl)aminopropyl triethoxysilane, N-(2-aminoethyl)aminopropylmethyl diethoxysilane, N-(2-aminoethyl)aminopropylmethyl Dimethoxysilane, γ-anilinopropyl trimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropyl triethoxysilane, γ-anilinopropyl Methyldiethoxysilaneoctadecyldimethyl[3-(trimethoxysilyl)propyl] ammonium chloride, octadecyldimethyl[3-(methyldimethoxysilyl)propyl] Base] ammonium chloride, octadecyl dimethyl [3-(triethoxysilyl) propyl] ammonium chloride, octadecyl dimethyl [3-(methyldiethoxysilyl) propyl Base] ammonium chloride, etc. Only one kind of these may be used, or plural kinds may be used in combination. These silane compounds can be used alone, or can be used in the form of either a hydrolyzate or a homopolymer. In addition, a mixture of two or more silane compounds, or a hydrolysate, or the same can be used in combination. The use of a mixture of meta-polymers or as a copolymer is not particularly limited.

<<Compound (C)>>

The water-based metal surface treatment agent of this embodiment may contain a compound (C) which contains selected from boron, magnesium, aluminum, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, molybdenum, tungsten, cerium, At least one element of niobium, tin, bismuth and zirconium. As for the compound (C), carbonate, oxide, hydroxide, nitrate, sulfate, phosphate, halide, sulfide, aluminum fluoride compound, organic acid salt, organic aluminum compound, etc. of the aforementioned metals are listed . Among these, one kind of component may be used, or a plurality of kinds may be used in combination.

As the compound (C), specifically, nickel oxide, nickel hydroxide, nickel carbonate, nickel nitrate, nickel sulfate, nickel phosphate, nickel chloride, nckel acetylacetonate; Potassium manganate, sodium permanganate, manganese dihydrogen phosphate, manganese nitrate, manganese sulfate (II), (III) or (IV), manganese fluoride (II) or (III), manganese carbonate, manganese acetate (II) or (III), manganese ammonium sulfate, manganese acetylacetonate, manganese iodide, manganese oxide, hydrogen Manganese oxide; cobalt chloride, chloropentaamminecobalt chloride, hexaamminecobalt chloride, cobalt sulfate, cobalt ammonium sulfate, cobalt nitrate, cobalt oxide 2 aluminum, hydroxide Cobalt, cobalt phosphate; phosphovanadomolybdic acid, molybdenum oxide, molybdic acid, ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdophosphoric acid compound (e.g., molybdophosphoric acid compound) , Sodium molybdate phosphate, etc.); metatungstic acid, ammonium metatungstate, sodium metatungstate, paratungstic acid, ammonium paratungstate, sodium paratungstate; cerium oxide, cerium acetate, cerium nitrate (III ) Or (IV), ammonium cerium 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 sodium sulfate, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum iodide; zinc sulfate, zinc carbonate, zinc chloride, zinc iodide, zinc acetone (zinc acetylacetonate), zinc oxide, zinc iodide, zinc dihydrogen phosphate, zinc acetylacetonate, zinc dihydrogen phosphate; iron hydroxide (II), iron hydroxide (III), iron nitrate (II), nitric acid Iron (III), acetone iron (III), iron chloride (II), iron chloride (III), iron citrate (III), iron oxide (II), iron oxide (III), iron oxide (II) , III), iron cyanide (hexacyanoferrate) (II), iron cyanide (III), iron cyanide (II) acid, potassium iron (III) cyanide, iron ammonium sulfate (II), iron ammonium sulfate (III) ), iron phosphate (II); Bismuth oxide, bismuth sulfate, bismuth nitrate, bismuth hydroxide, bismuth citrate, bismuth vanadate, vanadium alkoxide, vanadium-containing chelate complexes, specifically, vanadium oxide, partial Vanadate, sodium metavanadate, potassium metavanadate, ammonium metavanadate, vanadium diacetylacetonate, vanadium diacetylacetone, vanadium pentoxide, vanadium trioxide, vanadium fluoride, vanadium phosphate, vanadium sulfate, vanadium sulfide , Vanadium oxalate, vanadium oxytriisopropoxide, vanadium oxytriisopropoxide, vanadium oxytriethoxide, vanadium oxytriethoxide, vanadium oxytriethanolaminate, vanadium oxytriethanolaminate, ammonium citrate Vanadium, vanadium tributoxy stearate, vanadyl acetylacetonate, tetrapropoxy vanadium, tetrabutoxy vanadium, etc.; chlorinated Niobium (III), (IV) or (V), niobium fluoride (III), (IV) or (V), niobium oxide (II), (IV) or (V); tin oxide (II) or (IV) ), tin chloride (II) or (IV), tin fluoride (II) or (IV), tin nitrate (II) or (IV), tin hydroxide (II) or (IV), tin sulfate (II) Or (IV); zirconium hydrogen fluoride, zirconium fluoride, ammonium fluorozirconate, sodium fluorozirconate, potassium fluorozirconate, zirconium sulfate, nitrate, acetate, carbonate, chloride salt and other inorganic salts, Oxides of zirconium compounds, organic acid salts of zirconium compounds, etc.; titanium hydrofluoric acid, titanium fluoride, ammonium fluorotitanate, sodium fluorotitanate, potassium fluorotitanate, titanium sulfate, nitrate, acetate, carbonate , Inorganic salts such as chloride salts, oxides of titanium compounds, organic acid salts of titanium compounds, etc.

One of these ingredients can be used, or a plurality of them can be used in combination.

Since the water-based metal surface treatment agent of this embodiment contains the compound (C), it is preferable to increase the strength of the film formed by the water-based metal surface treatment agent. The content of the compound (C) is preferably adjusted to _{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 )] Within the range of 1/300 or more and 1/2 or less, more preferably adjusted to within the range of 1/200 or more and 1/3 or less, and still more preferably adjusted to within the range of 1/100 or more and 1/4 or less .

<<Water-dispersible resin (D)>>

To the water-based metal surface treatment agent, at least one water-soluble or water-dispersible resin (D) selected from phenol resin, epoxy resin, polyester resin, acrylic resin, polyolefin resin, and polyamide resin can be further added.

The aforementioned acrylic resin is obtained by radical polymerization, cationic polymerization or anionic polymerization of acrylic acid, acrylic esters, etc. The monomers used in these polymerization reactions are not particularly limited, and examples include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, and diacrylate. Grade butyl ester, tertiary butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, 2-hydroxyethyl acrylate, methyl acrylate Methyl acrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, secondary butyl methacrylate, three methacrylate Grade butyl ester, n-hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methacrylic acid 2 -Hydroxyethyl and so on. It is also possible to further appropriately incorporate vinyltrimethoxysilane and the like to introduce an alkoxysilyl group into the structure. These can be used alone, or two or more of them can be used in combination.

The aforementioned epoxy resin is not particularly limited. For example, phenol, bisphenol A, o-, m-, p-cresol, phthalic acid, isophthalic acid, terephthalic acid, and epichlorohydrin can be used. Glycidyl ether or ester obtained by the reaction of alcohol (epichlorohydrin), novolak phenol (novolak Glycidyl ethers, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, sorbose obtained by the reaction of aromatic compounds with hydroxyl groups such as polyp-vinylphenol and epichlorohydrin Glycidyl ethers and the like obtained by the reaction of aliphatic polyhydric alcohols such as alcohols and epichlorohydrin further interact with amines to introduce water-soluble functional groups. It is also possible to introduce silanol groups, alkoxysilyl groups, phosphoric acid groups, and phosphoric acid ester groups into these epoxy resins. Only one of these ingredients can be used, or a plurality of them can be used in combination.

The aforementioned polyester resin system 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. For example, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, and maleic acid can be used. Diacid anhydride (maleic anhydride) and other two proton acids; trimellitic anhydride, pyromellitic anhydride (pyromellitic anhydride) and other polybasic acids with more than trivalent.

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 cycloaliphatic diols, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, neopentylerythritol, dineopentaerythritol , 1,1,2,2-4-(4-hydroxyphenyl)ethane and other trivalent or higher polyols. Only one of these ingredients can be used, or a plurality of them can 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 phenol resin, polyvinyl phenol, and polybisphenol A, and it can be used for those having no alkoxysilyl group in the structure.

The polyamide 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. 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. Acid; Trimellitic acid anhydride, pyromellitic acid anhydride, and other trivalent or higher polybasic acids; as the polyamine, it is not particularly limited, and for example, ethylenediamine, propylenediamine, and diethyltriamine can be used , Hexylenediamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, piperazine, diphenylmethanediamine, hydrazine, tetramethylethylenediamine, etc. Valence amines and so on. Only one of these ingredients can be used, or a plurality of them can be used in combination.

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

The water-based metal surface treatment agent of the present embodiment is preferably adjusted to the strength suitable for the strength of the formed film by containing the resin (D). 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 )] Be in the range of 1/50 to 50/1, more preferably to be adjusted to the range of 1/25 to 25/1, and still more preferably to be adjusted to the range of 1/10 to 10/1 Inside.

The aforementioned water-soluble or water-dispersible resin (D) is preferably cationic or anionic, and the state of existence in the water is preferably a dissolved state or a dispersed state. These water-soluble or water-dispersible resins (D) can be achieved based on the self-solubility or self-dispersibility of dissolving or dispersing in water, and can be achieved by cationic surfactants (such as tetraalkylammonium, etc.) And/or the presence of a nonionic surfactant (for example, alkyl phenyl ether, etc.) is dispersed.

<<Crosslinking agent (E)>>

The water-based metal surface treatment agent may further contain at least one crosslinking agent selected from oxazoline resins, blocked isocyanate resins, carbodiimide resins, aziridine resins and epoxy resins ).

These cross-linking agents can use respective conventional resins, and the functional groups contained in the resins promote cross-linking.

Crosslinking agent (E) of the content, preferably the crosslinking agent (E) the mass of the solid content (E _M), and a solid urethane resin (A) of the content mass (A _M) ratio [(E _M )/(A _M )] is adjusted to a range of 1/100 to 5/1, more preferably to a range of 1/50 to 3/1, and still more preferably to a range of 1/20 to 1 Within the range below /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 it does not impair the effect of the present invention, but it is usually 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the urethane resin (A).

<<Other ingredients that can be contained in water-based metal surface treatment agents>>

The water-based metal surface treatment agent of this embodiment may contain components other than the above. As far as the components other than the above are concerned, for example, within the range that does not impair the stability of the water-based metal surface treatment agent or the effects of the present invention, a film-forming auxiliary (organic solvent) that improves the film-forming properties and improves the dryness of the film can be blended. Etc.), surfactants to improve wettability, defoamers or leveling agents to inhibit foaming, conductive substances to improve weldability, coloring pigments to improve design, rust prevention to inhibit rust generation剂 etc.

As for the film forming aids, it is not particularly limited. Examples include alcohols such as methanol, ethanol, 2-propyl alcohol, and tertiary butyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monobutyl, etc. Glycol alkyl ethers such as methyl ether and propylene glycol monopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; Ether solvents such as tetrahydrofuran and 1,4-dioxane; nitrile solvents such as acetonitrile and acrylonitrile; acrylic ester solvents such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, etc. ; Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and other amide-based solvents; dimethyl sulfide and other sub-supples; oxalic acid two Methyl ester, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, diethyl glutarate, diethyl adipate, etc. Carboxylic acid ester-based solvents, etc. These film-forming aids can be used alone, or two or more of them can be mixed for use.

Surfactants include, for example, nonionic surfactants such as alkyl allyl ethers, alkyl ethers, alkyl esters, and alkyl amines, as well as 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 two or more of them can be mixed for use.

Examples of the conductive material include conductive metal fine powder and carbon fine powder.

Examples of coloring pigments include inorganic pigments such as carbon black and titanium oxide, and organic pigments such as phthalocyanine.

The water-based metal surface treatment agent of this embodiment may further contain various well-known additives generally used as necessary. Such additives include, for example, anti-rust pigments, dyes, inorganic crosslinking agents, antiblocking agents, viscosity modifiers, tackifiers, dispersion stabilizers, light stabilizers, antioxidants, and ultraviolet rays. Absorbents, inorganic fillers, organic fillers, plasticizers, slip agents, antistatic agents, etc.

<Manufacturing method of water-based metal surface treatment agent>

In the water-based metal surface treatment agent related to this embodiment, the urethane resin (A) and the silane compound (B) can be mixed with the urethane resin (A) in an aqueous solvent. And components other than the silane compound (B). The aqueous solvent is not particularly limited as long as it contains 50% by mass or more of water when the mass of the entire solvent (including the solvent) is used as a reference. As for the solvents other than water contained in the aqueous solvent, for example, paraffinic solvents such as hexane and pentane; aromatic solvents such as benzene and toluene; methanol, ethanol, 1-butanol, ethyl alcohol, etc. Alcohol solvents such as ethyl cellosolve; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as ethyl acetate and butoxyethyl acetate; dimethylformamide, N- Amide-based solvents such as methylpyrrolidone; sulfenite-based solvents such as dimethyl sulfide; ammonium phosphate-based solvents such as hexamethyltriamide phosphate, etc. One type of solvent other than water may be mixed with water, but two or more types may be combined and mixed with water. In addition, from an environmental and economic point of view, it is preferable to use only water.

<Metal material with coating and its manufacturing method>

The method of manufacturing a metal material with a film related to this embodiment is a method of manufacturing a metal material having a metal material and a film (surface treatment film layer) formed on the surface of the metal material. The contact process (step) in which the metal surface treatment agent contacts the surface of the above-mentioned metal material, and the metal material contacted with the water-based metal surface treatment agent is heated in the range of 50°C to 250°C to heat and dry the water-based metal surface treatment agent Heating engineering (steps). 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 heating process indicates the temperature of the metal material itself.

<Metal Material>

The types of metal materials are not particularly limited. Cold rolled steel sheets, hot rolled steel sheets, hot-dip zinc-coated steel sheets, aluminum-containing galvanized steel sheets, electrical galvanized steel sheets, and alloyed galvanized steel sheets can be used. Steel plate, galvanized nickel steel plate, galvanized cobalt steel plate, vapor-coated galvanized steel plate, nickel plated steel plate, tin plated steel plate, stainless steel plate, etc. Carbon steel plate, alloy steel plate and plated steel plate; aluminum plate, copper plate, titanium plate, magnesium plate, etc. Commonly known materials such as metal plates other than steel plates. Particularly suitable metal materials are 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, vapor-coated galvanized steel sheets, etc. . In addition, the shape of the metal material is not particularly limited, and it may be a plate material or a molded product.

Among them, the metal material can be subjected to chromate treatment or phosphate treatment as surface treatment.

In addition, in recent years, due to environmental pollution, labor hygiene, safety, etc., the trend toward dechromization has increased. However, if the surface treatment film layer of the present invention (preferably a film layer free of chromium and phosphorus) is present, even if it is not Applying chromate treatment or phosphate treatment can also show sufficient corrosion resistance, chemical resistance, solvent resistance and coating adhesion.

<Surface Treatment Coating 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 applied to the surface of the metal material by a conventional method (for example, coating method, dipping method, spray method, electrolysis method, etc.) Formed by contact.

Among them, before treatment with water-based metal surface treatment agents, in order to remove oil and dirt attached to metal materials, washing with degreasing agents (acid, alkali), hot water washing, pickling, solvent washing, etc., respectively or in combination .

In addition, before the treatment with the water-based metal surface treatment agent, the surface can be adjusted for the purpose of further improving the corrosion resistance of the film and further improving the adhesion of the coating. The method of surface adjustment is not particularly limited. Examples include methods such as chemical conversion coating, phosphoric acid chlorination treatment, etc., to attach metals such as Fe, Co, Ni, Cu, Zn, Mn, Zr, Ti, or V. .

In the case of cleaning the surface of the metal material, from the viewpoint of reducing the amount of detergent remaining on the surface of the metal material, it is better to wash with water after the cleaning.

The temperature of the water-based metal surface treatment agent is not particularly limited. The solvent-based water of this treatment agent is the main body, so the treatment temperature is preferably in the range of 0-60°C, more preferably in the range of 5-40°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 it is usually in the 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 used.

Furthermore, 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, before the drying, the surface of the metal material in contact with 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 mass of the whole film, preferably 30~5,000mg/m ² , more preferably 50~3,000mg/m ² , further preferably 100~2,000mg/m ² . If it is 30 mg/m ² or more, sufficient corrosion resistance and adhesion can be obtained. In addition, if it is 5,000 mg/m ² or less, cracks and the like are less likely to occur in the film, and the adhesiveness of the film itself becomes high.

[Example]

Hereinafter, using examples, the water-based metal surface treatment agent of the present invention will be described in detail. 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, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) ( A3-1 described below) 67g, N-methyldiethanolamine (amino alcohol MDA, manufactured by Nippon Emulsifier Co., Ltd.) (a5-1 described below) 30g, diethylene glycol (diethylene glycol, manufactured by Nippon Shokubai Co., Ltd.) ) (A4-1 described later) 30 g, and 230 g of isophorone diisocyanate (Desmodur I, manufactured by Bayer) (a1-1 described later) were added to 400 g of methyl ethyl ketone to fully dissolve. After reacting this mixed solution at 80°C for about 5 hours, it was confirmed that it contained 3% by mass or less of isocyanate groups, and 25 g of dimethyl sulfate (ionizing agent a7-1 described later) was added. In addition, the isocyanate group content rate is based on JIS K7301: 1995. After dissolving 2 g of the reaction solution in dimethylformamide and adding 10 ml of n-dibutylamine-toluene solution, bromophenol blue is used as The indicator drug is titrated with 0.5mol/L hydrochloric acid solution and can be calculated using the following formula.

(In the formula, A means the volume of hydrochloric acid required for the titration of the amount (mass) of isocyanate used when preparing the specified amount of the reaction solution, and B means the volume of hydrochloric acid required for the titration of the reaction solution The volume, f means "1", N means the molar concentration of the hydrochloric acid standard solution, and S means the mass of the reaction solution).

Next, a urethane emulsion containing 1000 g of deionized water was prepared.

The obtained urethane emulsion was distilled under reduced pressure to remove methyl ethyl ketone to prepare a urethane emulsion having a urethane resin concentration of 25% by mass. Table 1 shows the components used in this synthesis and the injection amount (mass %). In the following, 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 the method described in Synthesis Example 1 with each component and injection amount.

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), the urethane of Synthesis Example 12 was prepared by the same manufacturing method as Synthesis Example 1 Resin.

Except for using 10 g of ionizing agent a7-3 (formic acid) instead of 25 g of ionizing agent a7-1 (dimethyl sulfate), the urethane resin of Synthesis Example 13 was prepared by the same production method as 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), the urethane of Synthesis Example 14 was prepared by the same manufacturing method as Synthesis Example 1 Resin.

The components described in Table 1 are as follows. In addition, the injection amount (mass %) of each component described in Table 1 is calculated based on the total amount of (a1) to (a5) components, and when the (a6) component is used, it is also included in the total amount. In addition, any of the urethane prepolymers obtained according to each synthesis example contains an isocyanate group.

<Polyisocyanate (a1; one of the following parts 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)

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 Co., Ltd.)

a2-2: Aromatic diprotic acid polyester polyol (Tesrack 2508-70, manufactured by Hitachi Chemical Co., Ltd.)

a2-3: Polycarbonate diol (NIPPORAN 981, manufactured by TOSOH)

<Diol (a3; one of the following parts is a diol with a weight average molecular weight greater than 600 that does not contain a benzene ring and a nitrogen atom)>

a3-1: Polyethylene glycol (PEG2000, Mw2000, manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.)

a3-2: Polyester polyol (NIPPORAN 4040, Mw2000, manufactured by TOSOH)

a3-3: Polybutylene glycol (PTMG2000, Mw2000, manufactured by Mitsubishi Chemical Corporation)

a3-4: a3-1+a3-2 (mass ratio 1:1)

a3-5: Polyester diol (K-FLEX XM360, Mw520, manufactured by KING)

<Diol (a4; one of the following parts is a diol with 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 Shokubai Co., Ltd.)

a4-2: 1,5-pentanediol (1,5-pentanediol, Mw104, manufactured by Ube Industries Co., Ltd.)

a4-3: 1,6-hexanediol (1,6-hexanediol, Mw106, manufactured by Ube Industries Co., Ltd.)

a4-4: Polyester polyol (PLACCEL 205, Mw530, manufactured by Daicel Chemical Corporation)

<Tertiary amine compound (a5)>

a5-1: N-methyldiethanolamine (amino alcohol MDA, manufactured by Japan Emulsifier Company)

<Others (polyols above triol without benzene ring and nitrogen atom) (a6)>

a6-1: Trimethylolpropane (TMP, manufactured by Perstorp)

<Ionizing Agent>

Ionizing agent a7-1: Dimethyl sulfate (dimethylsulfuric acid, manufactured by Tsujimoto Chemical Co., Ltd.)

Ionizing agent a7-2: 85% phosphoric acid (manufactured by Nippon Chemical Industry Co., Ltd.)

Ionizing agent a7-3: formic acid (manufactured by Junsei Chemical Co., Ltd.)

Ionizing agent a7-4: Methanesulfonic acid (manufactured by TOSOH)

<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 [compounds (B) to (F)] were mixed in water to prepare Examples 1 to 84 and comparison Examples 1-16 water-based metal surface treatment agents. More specifically, with respect to 100 parts by mass of the urethane resin of the synthesis example and the comparative synthesis example, 125 parts by mass of water and various compounds having a solid content mass ratio as shown in Table 2 were added and mixed thoroughly to prepare Water-based metal surface treatment agents of Examples and Comparative Examples.

The components described in Table 2 are as follows.

(Total test materials)

GI: Hot-dip galvanized steel sheet (plate thickness: 0.8mm)

GL: 55% aluminum galvanized steel sheet (plate thickness: 0.5mm)

Silane compound (B)

B2: γ-aminopropyl triethoxysilane

B3: γ-glycidoxypropyl trimethoxysilane: B2 is a 1:1 mixture

Compound (C)

C1: Zirconium Hydrofluoride Acid

C2: Titanium Hydrofluoride Acid

C3: acetone vanadyl

Water dispersible resin (D)

D1: Acrylic resin

D2: Phenolic 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 alkali degreasing agent [mixing Fine Cleaner E6406 (manufactured by Parkerizing, Japan) and water to a 20 g/L solution], various test materials were degreased by spraying at 60°C for 10 seconds. After that, wash with water by spraying water for 10 seconds.

After washing with water, apply the water-based metal surface treatment agent to the surface of various test materials by the bar coat method, and then apply the water-based metal surface treatment agent to 120℃ (PMT: the highest plate temperature of the test material during firing) Drying is performed to form a film with a thickness of 1 μm.

<Evaluation Test>

(Corrosion resistance)

As mentioned above, various corrosion resistance tests were performed on various treatment boards (No. 1 to 100) that were subjected to surface treatment. The evaluation method and evaluation criteria are as follows.

(Corrosion resistance test of plane part)

Based on the salt spray test method (JIS-Z-2371: 2015), after 240 hours of neutral salt spray, the area ratio (%) of the generated white rust was obtained, and the corrosion resistance of the flat surface was evaluated based on the following criteria. In addition, in this evaluation, C or higher was regarded as a pass.

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: more than 30% and less than 40%

D: more than 40%

(Corrosion resistance test of processing part)

Overlap two plates of the same type and thickness with the test material used, and bend them at 180 degrees to sandwich them between the various processed plates. Then, after spraying neutral salt water for 72 hours in the same way as the flat surface part corrosion resistance test, the area ratio (%) of the generated white rust was determined, and the corrosion resistance of the processed part was evaluated based on the following criteria. In addition, in this evaluation, C or higher was regarded as a pass.

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: more than 30% and less than 40%

D: more than 40%

(Corrosion resistance test of cross section)

After cross-cutting with NT cutter on various treatment boards, the same as the corrosion resistance test of the flat part, after 72 hours of neutral salt water spray, the single side maximum obtained from the cross (×) cut The rust is wide, and the corrosion resistance of the cross-cut part is evaluated according to the following criteria. In this evaluation, C or higher was regarded as a pass.

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 board was immersed in a 1% sodium hydroxide aqueous solution at room temperature (20°C) for 5 minutes, washed with water, and dried.

After that, a color difference meter (manufactured by Nippon Denshoku Co., Ltd.) was used to determine the color difference (ΔE) before and after the treatment of the sodium hydroxide aqueous solution, and the alkali resistance was evaluated based on the following evaluation criteria. In this evaluation, C or higher was regarded as a pass.

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 board was immersed in a 1% sulfuric acid aqueous solution at room temperature (20°C) for 5 minutes, washed with water, and dried.

After that, 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 regarded as a pass.

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 coating adhesion test)

Amino alkyd paint (Amylac #1000 manufactured by Kansai Paint Co., Ltd.) was used to paint on the surface of various treatment boards. The coating system was performed by a bar coating method, and after coating, firing was performed at 130°C (PMT) for 20 minutes to form a coating film with a film thickness of 25 μm. After extruding the treated board with the coating film to 8 mm with Erichsen, the operation of attaching a tape to the processed part and peeling it off (hereinafter referred to as "tape peeling") was performed to obtain the ratio of the area where the coating film was peeled off ( %), based on the following evaluation criteria, evaluate the first-time adhesion of the coating. In this evaluation, C or higher was regarded as a pass.

AAA: The peeling area is 0% (not peeled)

AA: The peeling area is greater than 0% and less than 5%

A: The peeling area is 5% or more and less than 10%

B: The peeling area is 10% or more and less than 20%

C: The peeling area is 20% or more and less than 30%

D: The peeling area is 30% or more

(Secondary coating adhesion test)

After immersing the treated board with the above-mentioned coating film in boiling water for 1 hour, and extruding 8mm with Erichsen, tape peeling is performed on the processed part, and the ratio (%) of the area where the coating film is peeled off is the same as the one-time denseness of the above-mentioned coating. The evaluation criteria of the adhesion test similarly evaluate the secondary adhesion of the coating. In this evaluation, C or higher was regarded as a pass.

(Solvent resistance test)

The mesh (gauze) impregnated with methyl ethyl ketone (MEK) was slid back and forth 10 times on one side of various treatment plates under a load of 1.5 kg, and then the color difference (ΔE) before and after sliding was obtained using a color difference meter, based on the following evaluation criteria , To evaluate the solvent resistance. In this evaluation, C or higher is regarded as a pass.

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

(Abrasion resistance test)

The steel ball (SUS304) was pressed into the steel ball (SUS304) with a load of 500g with a Bowden testing machine 20 times back and forth, and the friction coefficient change from the start of the test to the end of the test was obtained, and the wear resistance was evaluated based on the following evaluation criteria. In this evaluation, C or higher was regarded as a pass.

AAA: No change in friction coefficient

AA: The variation of friction coefficient is less than 0.05

A: The variation of the friction coefficient is 0.05 or more and less than 0.1

B: The variation of friction coefficient is 0.1 or more and less than 0.15

C: The variation of friction coefficient is 0.15 or more and less than 0.2

D: The variation of friction coefficient is 0.2 or more

<Evaluation Results>

The above evaluation test results are shown in Table 3 (Tables 3-1 to 3-2) below.

[Table 2-2]

Claims (8)

A water-based metal surface treatment agent, which contains a urethane resin (A) and a silane compound (B). The urethane resin (A) is derived from the following formula (1) The structural unit of the polyisocyanate having a cyclohexane ring structure, the structural unit derived from the polyol represented by the following formula (2), and the weight average molecular weight represented by the following formula (3) of 800 to 4000 Structural units of diols, structural units derived from diols having a weight average molecular weight of 500 or less represented by the following formula (4), and tertiary amine compounds derived from the following formula (5) and/or thereof The structural unit of a salt; formula (1): O=C=NR ¹ -N=C=O (in formula (1), R ¹ is represented by -R ² -R ³ -R ⁴ -, and R ² is a single bond or Alkylene, R ³ is represented by the following formula: [化1]

(However, in the formula, R ⁵ , R ⁶ and R ^{7 are} independently a hydrogen atom or an alkyl group) R ⁴ is a single bond, an alkylene group, or

(The bonding branch on the left is bonded to R ³ )) Formula (2): [化3] HO-R ⁸ -OH,

,or

(n is an integer) (In formula (2), R ⁸ is represented by -R ⁹ -R ¹⁰ -R ¹¹ -, R ⁹ is a single bond,

(The bonding branch on the right side is bonded to R ¹⁰ ), or -R ¹³ -CO- (The bonding branch on the right side is bonded to R ¹⁰ ) (However, R ¹² is a straight or branched chain alkylene group, and R ^{13 is-} R ¹⁸ -O- (bonding branch and CO bonding on the right), or

(The bonding branch on the right side is bonded to CO); R ¹⁸ is a straight or branched chain alkylene; x is an integer of 1-5; l is an integer of 2-4) R ¹⁰ is [化5]

R ¹¹ is [化6] single bond,

,

,

, Or -CO-R ^13- (except for single bonds, the bonding branch on the left is bonded to R ¹⁰ ) (However, R ¹² is a straight or branched chain alkylene, R ¹³ is -R ¹⁸ -O- (right The bonding branch and CO bonding), or

(The bonding branch on the right is bonded to CO); In addition, 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 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 bonding branch on the left side of each is bonded to OH) (However, R ^{20 is} independently an alkylene group,

, Or adamantane ring, R ^{2 1} is an alkylene, m is an integer of 2-4, n is an integer)); formula (4): HO-R ²² -OH (in formula (4), R ²² is [化] 9] alkylene,

, Adamantane ring,

,or

(However, y is 2 or 3; z is an integer of 1-6)) Formula (5): [化10]

(In the formula, R ²³ is alkyl, aminoalkyl, hydroxyalkyl,

,──C(CH ₂ OH) ₃ , or

, R ²⁴ is hydroxyalkyl, aminoalkyl, or N-alkylaminoalkyl). The water-based metal surface treatment agent described in claim 1, which further contains a compound (C), which contains a compound selected from boron, magnesium, aluminum, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, molybdenum, At least one element 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 treatment agent described in claim 1, which further contains a resin selected from the group consisting of phenol resin, epoxy resin, polyester resin, acrylic resin, and polyolefin resin A water-soluble or water-dispersible resin (D) of at least one of polyolefin resin and polyamide resin. The water-based metal surface treatment agent according to claim 1, which further contains a resin selected from the group consisting of oxazoline resins, blocked isocyanate resins, carbodiimide resins, and aziridine resins. Crosslinking agent (E) of at least one of resin and epoxy resin. The water-based metal surface treatment agent described in claim 1, which further contains a lubricant. A method for manufacturing a metal material with a film, which comprises a contact step of bringing the water-based metal surface treatment agent described in any one of claims 1 to 6 into contact on the surface of the metal material, and the metal material that has undergone the aforementioned contact step A heating step of heating and drying at a temperature above 50°C and below 250°C. A metal material having a film obtained by the method of manufacturing a metal material of a film as described in claim 7.