KR102388433B1 - Aqueous metal surface treatment agent, metallic material having film and its manufacturing method - Google Patents

Abstract

(Project) To provide a water-based metal surface treatment agent capable of forming a film excellent in corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance on a metal material, and the like.
(Solution) A urethane resin (A) and a silane compound (B) are contained, and the urethane resin (A) is a structural unit derived from a specific polyisocyanate having a cyclohexane ring structure, a structural unit derived from a specific polyol, weight A water-based metal surface comprising a structural unit derived from a specific diol having an 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 By using a processing agent, the said film can be formed in a metal material.

Description

A metal material having a water-based metal surface treatment agent, a film, and a manufacturing method therefor TECHNICAL FIELD

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

A metal surface treatment agent capable of forming a film imparting various properties to a metal material has been developed. For example, Patent Document 1 discloses a technique related to an aqueous coating composition for metal material surface treatment containing a specific cationic aqueous urethane resin.

Moreover, Patent Document 2 discloses a technique related to a metal surface treatment agent containing at least one metal compound selected from a specific water dispersion of a specific urethane urea resin, a specific curing agent, silica particles, Ti, Zr, and V.

International Publication No. 2005/092998 Japanese Patent Laid-Open No. 2011-231353

However, in the above technique, a coating film excellent in corrosion resistance, chemical resistance, coating film adhesion and abrasion resistance could not be formed on a metallic material.

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

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest examination, these inventors discovered that the said subject was solvable by using the surface treatment agent containing a specific urethane resin and a silane compound, and completed this invention. The present invention includes the following.

[1] containing a urethane resin (A) and a silane compound (B);

The urethane resin (A) is a structural unit derived from a polyisocyanate having a cyclohexane ring structure represented by the following formula (1), a structural unit derived from a polyol represented by the following formula (2), and the following formula (3) A structural unit derived from a diol having a weight average molecular weight of more than 600 represented by, 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 represented by the following formula (5); / Or the structural unit derived from its salt, The aqueous|water-based metal surface treatment agent containing.

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

[Formula 1]

represented as,

R ⁴ is

[Formula 2]

am.)

Formula (2):

[Formula 3]

(in formula (2), R ⁸ is represented by -R ⁹ -R ¹⁰ -R ¹¹ -,

R ⁹ is

[Formula 4]

ego,

R ¹⁰ is

[Formula 5]

ego,

R ¹¹ is,

[Formula 6]

ego,

R ¹⁴ is,

[Formula 7]

am.)

Formula (3): HO-R ¹⁹ -H (3)

(R ¹⁹ in formula (3) is,

[Formula 8]

am.)

Formula (4): HO-R ²² -OH

(R ²² in formula (4) is,

[Formula 9]

am.)

Formula (5):

[Formula 10]

[2] A compound containing at least one element selected from boron, magnesium, aluminum, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, molybdenum, tungsten, cerium, niobium, tin, bismuth and zirconium (C ), the water-based metal surface treatment agent according to the above [1].

[3] The aqueous metal surface treatment agent according to [1] or [2], wherein the silane compound (B) contains an amino group.

[4] The above [1] to [4] further containing at least one water-soluble or water-dispersible resin (D) selected from a phenol resin, an epoxy resin, a polyester resin, an acrylic resin, a polyolefin resin, and a polyamide resin. 3] Aqueous metal surface treatment agent in any one of.

[5] The above [1] to [4] further comprising at least one crosslinking agent (E) selected from an oxazoline-based resin, a blocked isocyanate-based resin, a carbodiimide-based resin, an aziridine-based resin, and an epoxy-based resin ] The water-based metal surface treatment agent in any one of.

[6] The water-based metal surface treatment agent according to any one of [1] to [5], further comprising a lubricant.

[7] A contact step in which the aqueous metal surface treatment agent according to any one of [1] to [6] is brought into contact with the surface of the metal material, and the metal material that has undergone the contact step is heated at 50°C or higher and 250°C or lower A method for producing a metal material having a film, comprising: a heating step of drying.

[8] A metallic material having a film obtained by the method for producing a metallic material having a film as described in [7] above.

ADVANTAGE OF THE INVENTION According to this invention, the water-based metal surface treatment agent which can form the film excellent in corrosion resistance, chemical-resistance, coating-film adhesiveness, and abrasion resistance on a metal material, and the metal material which has the film, and its manufacturing method can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, specific embodiment is shown and this invention is demonstrated in detail.

<Water-Based Metal Surface Treatment Agent>

One embodiment of the present invention is an aqueous metal surface treatment agent. A water-based metal surface treatment agent contains a urethane resin (A) and a silane compound (B) which are mentioned later. By forming a film on the surface of a metal material using this water-based metal surface treatment agent, excellent corrosion resistance, chemical resistance, coating film adhesion, and abrasion resistance can be provided with respect to a metal material.

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

<<Urethane resin (A)>>

A urethane resin (A) is typically obtained by making a urethane prepolymer and water react. At this time, in order to accelerate|stimulate reaction, you may make it contain the polyamine compound which does not contain a tertiary amine compound as needed. Specifically, the isocyanate group contained in the urethane prepolymer reacts with an amine produced by water or a polyamine compound contained as necessary to form a urea bond, thereby forming a urethane resin.

<Urethane prepolymer>

A urethane prepolymer is a component used for the production of a urethane resin, and at least, a polyisocyanate having a cyclohexane ring structure, a polyol containing a benzene ring without containing a nitrogen atom, and a benzene ring and a weight not containing a nitrogen atom A diol having an average molecular weight of more than 600 (hereinafter also referred to as a high molecular weight diol), a diol having a weight average molecular weight of 500 or less that does not contain a benzene ring and a nitrogen atom (hereinafter also referred to as a low molecular weight diol), and active hydrogen It is obtained by making the tertiary amine compound which has two or more and/or its salt react.

From another viewpoint, the urethane prepolymer is a structural unit derived from a polyisocyanate having a cyclohexane ring structure represented by the following formula (1), a structural unit derived from a polyol represented by the following formula (2), and the following formula (3) ), a structural unit derived from a diol having a weight average molecular weight of more than 600, 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 represented by the following formula (5) and/or a structural unit derived from a salt thereof.

Specifically, the hydroxyl group contained in the polyol represented by the formula (2), the high molecular weight diol represented by the formula (3), and the low molecular weight diol represented by the formula (4), and the polyisocyanate represented by the formula (1) The resulting isocyanate groups react to form a urethane bond. Moreover, the isocyanate group contained in the said polyisocyanate, and the hydrogen atom (active hydrogen) contained in the tertiary amine compound and/or its salt represented by Formula (5) react, a urethane bond, a urea bond, etc. are formed.

Moreover, in order to make the urethane prepolymer used in this embodiment react with the polyamine compound which does not contain water or a tertiary amine compound as mentioned above, it has an isocyanate group derived from the polyisocyanate which has a cyclohexane ring structure. .

(Polyisocyanate having a cyclohexane ring structure)

Polyisocyanate (hereinafter also simply referred to as "polyisocyanate") having a cyclohexane ring structure is used for production of a urethane prepolymer, and is represented by 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

[Formula 11]

and R ⁴ is

[Formula 12]

am.

R ¹ is preferably,

[Formula 13]

am. Further, in the above formula, all of R ⁵ , R ⁶ and R ⁷ are more preferably a hydrogen atom or a methyl group.

In addition, the bicyclic structure which has a cyclohexane structure is also contained as a cyclohexane ring structure. Moreover, two or more cyclohexane ring structures may be contained in polyisocyanate.

(Input amount of polyisocyanate)

In the production of the urethane prepolymer to be described later, the amount of polyisocyanate to be added is a polyisocyanate used in the production of the urethane prepolymer, a polyol to be described later, a high molecular weight diol to be described later, a low molecular weight diol to be described later, and a tertiary amine compound and/or It is preferable that it is 20-80 mass % with respect to the total amount of the salt, It is more preferable that it is 30-70 mass %, It is still more preferable that it is 40-65 mass %, It is especially preferable that it is 50-60 mass %. That is, in the urethane resin (A) used by this embodiment, it is preferable that the abundance (mass conversion) of the structural unit derived from the polyisocyanate of Formula (1) is 20 to 80 % in a urethane resin (A). and more preferably 30 to 70%, still more preferably 40 to 65%, particularly preferably 50 to 60%.

In the case of using the "polyol more than triol not containing a benzene ring and a nitrogen atom" to be described later in the production of the urethane prepolymer in the present embodiment, the input amount of the polyol more than a triol not containing a benzene ring and a nitrogen atom is It counts in the said total amount.

(Type of polyisocyanate)

Although it will not specifically limit if it is polyisocyanate represented by Formula (1) which has one or more cyclohexane rings and two or more isocyanate groups as polyisocyanate, For example, Isophorone diisocyanate, 1,3- or 1 ,4-bis(isocyanatemethyl)cyclohexane, 1,3- or 1,4-diisocyanatecyclohexane, 3-isocyanate-methyl-3,5,5-trimethylcyclohexylisocyanate, dicyclohexylmethane 4,4' - Diisocyanate etc. are mentioned.

A polyisocyanate not included in Formula (1), a dimer such as a uretdione structure, a trimer such as an isocyanurate structure, an adduct body using a polyfunctional polyol, a poly having three or more isocyanate groups in one molecule You may use isocyanate etc. together with the polyisocyanate represented by Formula (1).

Polyisocyanate may be used individually by 1 type, and may be used together 2 or more types.

Among the above, polyisocyanate is at least 1 sort(s) chosen from isophorone diisocyanate, 1, 3-bis (isocyanate methyl) cyclohexane, and dicyclohexyl methane 4,4'- diisocyanate from a viewpoint that solvent resistance improves more. It is preferable that it is a compound of, and it is more preferable that it is dicyclohexylmethane 4,4'- diisocyanate.

(polyol containing a benzene ring without containing a nitrogen atom)

A polyol containing a benzene ring without containing a nitrogen atom (hereinafter, simply referred to as "polyol") is used for production of a urethane prepolymer and is represented by the following formula (2).

Formula (2):

[Formula 14]

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

[Formula 15]

and R ¹⁰ is

[Formula 16]

and R ¹¹ is,

[Formula 17]

and R ¹⁴ is,

[Formula 18]

am.

R ⁸ is preferably

[Formula 19]

am. R ¹² is preferably an ethylene group or an isopropylene group. 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.

(Input amount of polyol)

In the production of the urethane prepolymer to be described later, the amount of the polyol to be added is the total amount of polyisocyanate, polyol, high molecular weight diol described later, low molecular weight diol described later, and tertiary amine compound and/or salt thereof used for production of the urethane prepolymer. With respect to it, although it can be usually 1-40 mass %, for example, it is preferable that it is 1-30 mass %, It is more preferable that it is 3-25 mass %, It is still more preferable that it is 6-20 mass %. . That is, in the urethane resin (A) used in the present embodiment, the amount (in terms of mass) of the structural unit derived from the polyol of the formula (2) is usually 1 to 40% in the urethane resin (A), It is preferable that it is 1 to 30 %, It is more preferable that it is 3 to 25 %, It is more preferable that it is 6 to 20 %.

In the present embodiment, in the case of using the "polyol more than triol not containing a benzene ring and a nitrogen atom", which will be described later in the production of the urethane prepolymer, the input amount of the polyol more than triol not containing a benzene ring and a nitrogen atom is the above counted in the total amount.

(Type of polyol)

The polyol is not particularly limited as long as it is a polyol represented by the formula (2) which has one or more benzene rings, two or more hydroxyl groups, and does not have a nitrogen atom, for example, resorcinol, 2-methylesso Aromatic polyols such as lecinol, bisphenol A, bisphenol S, and bisphenol F; bisphenol A-ethylene oxide 2 mole adduct, bisphenol A-ethylene oxide 4 mole adduct, bisphenol A-ethylene oxide 6 mole adduct, and bisphenol A-ethylene benzene rings such as oxide 10 mole adduct, bisphenol A-propylene oxide 2 mole adduct, bisphenol A-propylene oxide 4 mole adduct, bisphenol A-propylene oxide 6 mole adduct, and bisphenol A-propylene oxide 10 mole adduct polyether polyols having; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and trimellitic acid, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2-methylpropanediol, neopentyl glycol Polyester polyol having a benzene ring obtained by polycondensation with polyols such as , 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methylpentanediol; ethylene carbonate and bisphenol A; Polycarbonate polyol which has a benzene ring obtained from transesterification with polyols, such as; etc. are mentioned.

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

(high molecular weight diol)

A high molecular weight diol is used for manufacture 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,

[Formula 20]

am.

(Input amount of high molecular weight diol)

In the production of the urethane prepolymer to be described later, the input amount of the high molecular weight diol of formula (3) is a polyisocyanate, a polyol, a high molecular weight diol, a low molecular weight diol described later, and a tertiary amine compound used in the production of the urethane prepolymer; / Or with respect to the total amount of the salt, although it can be normally set as 1-50 mass %, for example, It is preferable that it is 3-40 mass %, It is more preferable that it is 5-35 mass %, It is 10-30 mass % It is more preferable that That is, in the urethane resin (A) used in the present embodiment, the amount (in terms of mass) of the structural unit derived from the diol of the formula (3) is usually 1 to 50% in the urethane resin (A), It is preferable that it is 3 to 40 %, It is more preferable that it is 5 to 35 %, It is more preferable that it is 10 to 30 %.

In the present embodiment, in the case of using the "polyol more than triol not containing a benzene ring and a nitrogen atom", which will be described later in the production of the urethane prepolymer, the input amount of the polyol more than triol not containing a benzene ring and a nitrogen atom is the above counted in the total amount.

(weight average molecular weight of high molecular weight diol)

Although the weight average molecular weight of high molecular weight diol is more than 600, it is preferable that it is more than 600 and 10000 or less, It is more preferable that it is more than 600 and 5000 or less, It is still more preferable that it is 800-4000, It is especially preferable that it is 1000-3000.

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

(Type of high molecular weight diol)

The high molecular weight diol is a diol that does not contain a benzene ring and a nitrogen atom, and is not particularly limited as long as the weight average molecular weight exceeds 600. For example, polyether diol, polyester diol, polycarbonate diol, etc. may be used. .

As said polyetherdiol, polyethyleneglycol, polypropylene glycol, polybutylene glycol (polytetramethylene ether glycol) etc. are mentioned, for example. The polyetherdiol is produced, for example, by addition polymerization of an alkylene oxide such as ethylene oxide or propylene oxide under a basic catalyst.

The polyesterdiol is, for example, as an acid species, an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, or unsaturated carboxylic acid such as sebacic acid; As alcohol species, ethylene glycol, propylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1, Esterification reaction of 10-decanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, cyclohexyldimethanol, 1,3-adamantanediol, etc. those manufactured by

Examples of the polycarbonate diol include those prepared by ring-opening polymerization of a cyclic ester such as ε-caprolactone with glycol, and specifically, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, etc.; Those prepared by reacting the alcohol species exemplified in the polyesterdiol above may be mentioned.

High molecular weight diol may be used individually by 1 type, and may use 2 or more types together.

Among the above, it is preferable that high molecular weight diol contains polyether diol.

As polyetherdiol, it is more preferable that it is at least 1 sort(s) of compound chosen from polyethyleneglycol, polypropylene glycol, and polybutylene glycol.

When using polyetherdiol, it is preferable to use together at least one of the polyesterdiol and polycarbonate diol mentioned above.

(low molecular weight diol)

A low molecular weight diol is used for manufacture of a urethane prepolymer, is represented by the following formula (4), and does not contain a benzene ring and a nitrogen atom.

Formula (4): HO-R ²² -OH

(R ²² in formula (4) is,

[Formula 21]

am.)

(Input amount of low molecular weight diol)

In the production of the urethane prepolymer to be described later, the amount of the low-molecular-weight diol to be added is based on the total amount of polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, and tertiary amine compound and/or salt thereof used in the production of the urethane prepolymer. , Usually, although it can be set as 1-25 mass %, for example, It is preferable that it is 1-20 mass %, It is more preferable that it is 2-15 mass %, It is still more preferable that it is 3-10 mass %. That is, in the urethane resin (A) used in the present embodiment, the amount (in terms of mass) of the structural unit derived from the low-molecular diol of the formula (4) is usually 1 to 25% in the urethane resin (A), , It is preferable that it is 1 to 20 %, It is more preferable that it is 2 to 15 %, It is more preferable that it is 3 to 10 %.

In the present embodiment, in the case of using the "polyol more than triol not containing a benzene ring and a nitrogen atom", which will be described later in the production of the urethane prepolymer, the input amount of the polyol more than triol not containing a benzene ring and a nitrogen atom is the above counted in the total amount.

(weight average molecular weight of low molecular weight diol)

Although the weight average molecular weight of low molecular weight diol is 500 or less, it is preferable that it is 400 or less, and it is more preferable that it is 250 or less. Moreover, it is preferable that it is 60 or more, and, as for a lower limit, it is more preferable that it is 100 or more.

(Type of low molecular weight diol)

As the low molecular weight diol, for example, ethylene glycol (62.07 g/mol), propylene glycol (76.09 g/mol), 1,5-pentanediol (104.15 g/mol), 1,6-hexanediol (118.17 g) /mol), 1,7-heptanediol (132.2 g/mol), 1,8-octanediol (146.23 g/mol), 1,9-nonanediol (160.25 g/mol), 1,10-decanediol ( 174.28 g/mol), neopentyl glycol (104.15 g/mol), 2-methyl-1,3-propanediol (90.12 g/mol), 3-methyl-1,5-pentanediol (118.17 g/mol), Alkyldiols such as 1,4-cyclohexyldimethanol (146.14 g/mol) and 1,3-adamantanediol (168.23 g/mol), diethylene glycol (106.12 g/mol), triethylene glycol (150.17 g) /mol), tetraethylene glycol (194.23 g/mol), pentaethylene glycol (238.28 g/mol), hexaethylene glycol (282.33 g/mol), heptaethylene glycol (323.28 g/mol), dipropylene glycol (134.17 g) /mol), etc. polyalkylene glycol, dimethylol propionic acid (134 g/mol), etc. are mentioned. These may be used individually by 1 type, and may use 2 or more types together.

(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 the following formula (5).

Formula (5):

[Formula 22]

The aminoalkyl group for R ²³ is preferably -(CH ₂ ) ₂ -NH ₂ or -(CH ₂ ) ₃ -NH ₂ . The aminoalkyl group for R ²⁴ is preferably -(CH ₂ ) ₂ -NH ₂ . The hydroxyalkyl group for R ²³ and R ²⁴ is preferably -(CH ₂ ) ₂ -OH. The N-alkylaminoalkyl group for R ²⁴ is preferably -(CH ₂ ) ₂ -NH-CH ₃ .

When the active hydrogen of a tertiary amine compound and/or its salt reacts with said polyisocyanate, the urethane prepolymer (urethane resin) into which the group derived from a tertiary amine compound and/or its salt was introduce|transduced is obtained.

In addition, tertiary amine compounds and/or salts thereof contain two or more active hydrogens, for example, two or more substituents having active hydrogens such as amino groups, hydroxyl groups, N-alkylamino groups, etc. It is preferable to have Moreover, as an N-alkylamino group, a 2-methylamino group is preferable.

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

In the production of the urethane prepolymer to be described later, the input amount of the tertiary amine compound and/or its salt is a polyisocyanate, a polyol, a high molecular weight diol, a low molecular weight diol, and a tertiary amine compound and/or used in the production of the urethane prepolymer. Or with respect to the total amount of the salt, it can be usually 1-20 mass %, for example, It is preferable that it is 2-15 mass %, It is more preferable that it is 2-13 mass %, It is 3-10 mass % more preferably. That is, in the urethane resin (A) used in this embodiment, the abundance (in terms of mass) of the structural unit derived from the tertiary amine compound of Formula (5) and/or its salt is in the urethane resin (A) , usually 1 to 20%, preferably 2 to 15%, more preferably 2 to 13%, still more preferably 3 to 10%.

In the present embodiment, in the case of using the "polyol more than triol not containing a benzene ring and a nitrogen atom", which will be described later in the production of the urethane prepolymer, the input amount of the polyol more than triol not containing a benzene ring and a nitrogen atom is the above counted in the total amount.

(Types of tertiary amine compounds)

The tertiary amine compound is not particularly limited as long as it is a tertiary amine having two or more active hydrogens, and for example, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-aminoalkyl dialkanolamine, such as N-t-butyldiethanolamine and N-(3-aminopropyl)diethanolamine, triethanolamine, N,N,N',N'-tetrakis(2-hydroxyethyl) Trialkanolamine, which may have a substituent such as ethylenediamine, bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane, 1-bis(2-hydroxyethyl)amino-2-propanol, 2,2 Tertiary amine compounds, such as '- polyamino-N-methyldiethylamine, N,N',N''-trimethyldiethylenetriamine, and tris(2-aminoethyl)amine, are mentioned. These tertiary amine compounds may be used as salts with organic acids such as formic acid and acetic acid, inorganic acids such as hydrochloric acid and sulfuric acid, or quaternary chlorinated with an alkylating agent such as dimethyl sulfate, diethyl sulfate, or methyl iodide. do. As a tertiary amine compound, N-aminoalkyl dialkanolamine, especially N-methyldiethanolamine is preferable.

The urethane resin (A) of this embodiment may neutralize a part or all of the structural part (tertiary amine) derived from a tertiary amine compound with an acid etc. 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, ethanesulfonic acid, trifluoromethane organic acids such as organic sulfonic acids such as sulfonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, hydrobromic acid and phosphoric acid. These acids may be used individually by 1 type, and may use 2 or more types together. Moreover, as for the urethane resin (A), a part or all of the structural part (tertiary amine) derived from a tertiary amine compound may be quaternized. Specific examples of the quaternizing agent used for quaternization include sulfuric acid esters such as dimethyl sulfate and diethyl sulfate, alkyl halides such as methyl chloride, benzyl chloride, methyl bromide, benzyl bromide and methyl iodide, and carbonic acid. and carbonate esters such as dimethyl and diethyl carbonate. These quaternization agents may be used individually by 1 type, and may use 2 or more types together. Moreover, you may use together the acid as a neutralizing agent, and a quaternizing agent.

In addition, in this specification, these acids and a quaternizing agent may be called an ionizing agent.

In the present specification, the "alkyl group" or the "alkyl group" contained in a halogenated alkyl group, aminoalkyl group, hydroxyalkyl group, N-alkylaminoalkyl group, etc. is not particularly limited, but is usually an alkyl group having 20 or less carbon atoms and 12 or less carbon atoms. may be an alkyl group of or may be an alkyl group having 6 or less carbon atoms. Typically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, an isohexyl group, 3-methylpentyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. are mentioned.

Moreover, although the "alkylene group" is not specifically limited, either, Usually, it is a C20 or less alkylene group, A C12 or less alkylene group may be sufficient, and a C6 or less alkylene group may be sufficient. Typically, ethylene group, propylene group, butylene group, isobutylene group, tert-butylene group, sec-butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group, isohexylene group, 3-methyl group Pentylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, etc. are mentioned.

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 ingredients that can be used in the preparation of urethane prepolymers)

You may use other components other than the above for manufacture of the urethane prepolymer of this embodiment. As the other components, for example, polyisocyanates other than the polyisocyanate, the polyol, the high molecular weight diol and the low molecular weight diol other than the benzene ring and the polyol containing no nitrogen atom, the organic solvent, the tertiary amine A polyamine compound other than a compound, an ionizing agent, an acid, an organometallic compound, etc. are mentioned.

(Polyisocyanates other than polyisocyanates)

Although it does not specifically limit as polyisocyanate other than the said polyisocyanate, For example, 1, 4- tetramethylene diisocyanate, ethyl (2,6- diisocyanate) hexanoate, 1, 6- hexamethylene diisocyanate, aliphatic diisocyanates such as 1,12-dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate;

m- or p-phenylenediisocyanate, 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, 3-methyl-diphenylmethane-4,4 aromatic diisocyanates such as '-diisocyanate, diphenyl ether-4,4'-diisocyanate, and tetramethylxylylene diisocyanate;

aliphatic triisocyanates such as 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, and 2-isocyanate ethyl (2,6-diisocyanate) hexanoate;

Aromatic triisocyanate, such as triphenylmethane triisocyanate and tris (isocyanate phenyl) thiophosphate;

and the like. Polyisocyanate other than the said polyisocyanate may be a dimer like a uretdione structure, a trimer like an isocyanurate structure, It is an adduct body using polyfunctional polyol, The polyisocyanate which has 3 or more isocyanate groups in 1 molecule. may be

Among these, it is preferable to use aromatic polyisocyanate, such as aromatic diisocyanate and aromatic triisocyanate, and it is preferable to use aromatic diisocyanate. A person skilled in the art can set suitably as content of another component and the content of the structure derived from the other component in a urethane resin (A) in the range which does not impair the effect of this invention.

(polyols other than the polyols, high molecular weight diols and low molecular weight diols represented by the general formula (2))

As polyols other than the polyols, high molecular weight diols and low molecular weight diols represented by the general formula (2), a triol or higher polyol containing no benzene ring and nitrogen atom can be used, for example, trimethylolpropane, penta Erythritol etc. are mentioned.

Of the triol or higher polyols not containing a benzene ring and a nitrogen atom, trimethylolpropane (TMP) is preferred.

In the case of using a triol or higher polyol that does not contain a benzene ring and a nitrogen atom for the production of the urethane prepolymer, the input amount is the polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, third It is preferable that it is 0.5-18 mass %, and it is more preferable that it is 3-10 mass % with respect to the total amount of the polyol more than triol which does not contain a primary amine compound and/or its salt, and a benzene ring and a nitrogen atom. That is, in the urethane resin (A) used in this embodiment, the abundance (in terms of mass) of a structural unit derived from a polyol more than triol not containing a benzene ring and a nitrogen atom is, in the urethane resin (A), normal It is 0.5 to 18 %, and it is preferable that it is 3 to 10 %.

It is preferable that the urethane resin of this embodiment has a branched structure. As a method of introducing a branched structure, as described above, a method using a triol or higher polyol containing no benzene ring and nitrogen atom is mentioned, but it is not limited to this method.

Manufacture of a urethane prepolymer and/or manufacture of a urethane resin (A) WHEREIN: You may use the organic solvent. The organic solvent is used as a solvent for making each component mentioned above react. Although it does not specifically limit as such an organic solvent, For example, Ketone solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Ester solvents, such as ethyl acetate and butyl acetate, tetrahydrofuran, 1,4 -ether solvents such as dioxane; nitrile solvents such as acetonitrile and acrylnitrile; acrylate solvents such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate; dimethylformamide, dimethyl acetate Amide solvents, such as amide|amido, N-methylpyrrolidone, and N-ethylpyrrolidone; Sulfoxide-type solvents, such as dimethyl sulfoxide; is mentioned. After manufacture of a urethane prepolymer or a urethane resin (A), you may remove these organic solvents by the vacuum distillation method as needed from a viewpoint of the load reduction with respect to an environment.

<Method for producing urethane prepolymer and urethane resin>

The urethane prepolymer of the present embodiment is a polyisocyanate represented by the general formula (1), a polyol represented by the general formula (2), a high molecular weight diol represented by the general formula (3), and a low molecular weight diol represented by the general formula (4). It is obtained by making a molecular weight diol and the tertiary amine compound and/or its salt etc. represented by the said General formula (5) react at least. Moreover, the urethane resin of this embodiment is obtained by making the urethane prepolymer obtained by the above and water react. At this time, the amine compound which is a poly chain extender may be added as needed, and the polyamine compound at this time is not a tertiary amine compound.

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

(Manufacturing method 1)

Polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, tertiary amine compound, etc. are dissolved in an organic solvent and reacted to prepare a urethane prepolymer, and if necessary, part or all of the tertiary amine in the urethane prepolymer is used as an ionizing agent A method of emulsifying by ionizing and adding water

(Manufacturing method 2)

Polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, tertiary amine compound, etc. are dissolved in an organic solvent and reacted to prepare a urethane prepolymer, and if necessary, part or all of the tertiary amine in the urethane prepolymer is used as an ionizing agent A method of emulsifying by adding water while ionizing with a chain extender such as a polyamine compound and extending the chain with a chain extender such as a polyamine compound

(Manufacturing method 3)

A urethane prepolymer is prepared by reacting polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, tertiary amine compound, etc. without using an organic solvent (bulk polymerization method), and, if necessary, urethane prepolymer A method of emulsifying a part or all of the tertiary amine in the composition by quaternizing it with an ionizing agent and adding water.

(Manufacturing method 4)

After the tertiary amine compound is ionized with an acid or an alkylating agent, polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, etc. are added and reacted to prepare a urethane prepolymer, and, if necessary, a part of the tertiary amine in the urethane prepolymer or a method of ionizing the whole with an ionizing agent and emulsifying by adding water

(Manufacturing method 5)

Polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, etc. are added to an organic solvent and reacted, then a tertiary amine compound is further added to prepare a urethane prepolymer having a tertiary amine structure at the terminal portion, A method of emulsifying by ionizing a part or all of the tertiary amine in the urethane prepolymer with an ionizing agent and adding water as needed

(Manufacturing method 6)

Polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, etc. are added to an organic solvent and reacted, then a tertiary amine compound is further added to prepare a urethane prepolymer having a tertiary amine structure at the terminal portion, A method of emulsifying by adding water while ionizing a part or all of the tertiary amine in the urethane prepolymer as needed with an ionizing agent and extending the chain with a chain extender such as a polyamine compound

Moreover, in the said manufacturing methods 1-6, you may use a well-known emulsifier.

<Polyamine compound>

Examples of the polyamine compound used as the chain extender include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4, 4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1,3-bisaminomethylcyclohexane, 2-aminoethylamino Propyltrimethoxysilane; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetri Amine, dipropylene triamine, triethylenetetramine; hydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide; Isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, 3-semicarbazide propylcarbazine ester, semicarbazide-3-semicarbazide methyl-3,5,5-trimethyl Cyclohexane; etc. can be used. Among these, it is preferable to use hydrazine or ethylenediamine.

When using a chain extender, it is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of urethane prepolymers, and, as for the input amount of a polyamine compound, it is more preferable that it is 0.2-5 mass parts.

<<Silane compound (B)>>

The water-based metal surface treatment agent of this embodiment is added to a specific urethane resin (A), and contains a silane compound (B). As the silane compound (B), for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-propyltrimethoxysilane, N-phenyl-3-propyltriethoxy Silane, N-(2-aminoethyl)aminopropyltrimethoxysilane, N-(2-aminoethyl)aminopropylmethyldimethoxysilane, N-(2-aminoethyl)aminopropyltriethoxysilane, N-( 2-aminoethyl)aminopropylmethyldiethoxysilane, N-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ -Methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, N-β-(N-vinylbenzylaminoethyl)-3-aminopropyltrimethoxysilane, N-β-(N- Vinylbenzylaminoethyl)-3-aminopropylmethyldimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-3-aminopropyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)- 3-Aminopropylmethyldiethoxysilane, N-methylaminopropyltrimethoxysilane, N-butylaminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane , γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrie Toxysilane, γ-mercaptopropylmethyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldiethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldime Toxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldiethoxysilane, isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, ureidepropyltriethoxysilane, bis(trimethoxy Silyl) aminovinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, octade syldimethyl [3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyl dimethyl [3- (triethoxysilyl) propyl] ammonium chloride, octadecyl dimethyl [3- (methyldiethoxysilyl) propyl] ammonium chloride; and γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane. Among these, only 1 type may be used and it may be used in combination of two or more. These silane compounds may be used alone, or may be used in any form of a hydrolyzate or a homopolymer, and in addition, a mixture of two or more silane compounds, or a hydrolyzate thereof, a mixture of homopolymers thereof, or You may use as a copolymer, and it is not specifically limited.

Although content of a silane compound (B) is not specifically limited, Ratio [(B _{M)/(AM) of solid content mass (AM) of a urethane resin (A), and mass (B M ) of a} silane compound (B) ] is preferably adjusted so as to be in the range of 1/100 or more and 4.0 or less. More preferably, it exists in the range of 1/10 or more and 3.5 or less. More preferably, it exists in the range of 1/5 or more and 3 or less.

As a silane compound (B), it is preferable that it is a silane compound especially containing an amino group. Examples of the amino group-containing silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-propyltrimethoxysilane, N-phenyl-3-propyl Triethoxysilane, N-(2-aminoethyl)aminopropyltrimethoxysilane, N-(2-aminoethyl)aminopropylmethyldimethoxysilane, N-(2-aminoethyl)aminopropyltriethoxysilane, N-(2-aminoethyl)aminopropylmethyldiethoxysilane, N-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldiethoxysilaneoctadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, octadecyldimethyl[3-(methyldimethoxysilyl)propyl] Ammonium chloride, octadecyl dimethyl [3- (triethoxysilyl) propyl] ammonium chloride, octadecyl dimethyl [3- (methyldiethoxy silyl) propyl] ammonium chloride, etc. are mentioned. Among these, only 1 type may be used and it may be used in combination of two or more. These silane compounds may be used alone, or may be used in any form of a hydrolyzate or a homopolymer, and in addition, a mixture of two or more silane compounds, or a hydrolyzate thereof, a mixture of homopolymers thereof, or You may use as a copolymer, and it is not specifically limited.

<<Compound (C)>>

The water-based metal surface treatment agent of the present embodiment is at least one selected from boron, magnesium, aluminum, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, molybdenum, tungsten, cerium, niobium, tin, bismuth, and zirconium. You may contain the compound (C) containing an element. Examples of the compound (C) include carbonates, oxides, hydroxides, nitrates, sulfates, phosphates, halides, sulfides, fluoride complexes, organic acid salts and organic complexes of the above metals. Among these, only one component or a plurality can 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, nickel acetylacetonate;

Permanganic acid, potassium permanganate, 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), ammonium manganese sulfate, manganese acetylacetonate, manganese iodide, manganese oxide, manganese hydroxide;

Cobalt chloride, chloropentaanmine cobalt chloride, hexaanmine cobalt chloride, cobalt sulfate, ammonium cobalt sulfate, cobalt nitrate, cobalt dia aluminum oxide, cobalt hydroxide, cobalt phosphate;

Phosphorous molybdic acid, molybdenum oxide, molybdic acid, ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdophosphoric acid compound (eg, ammonium molybdophosphate, sodium molybdophosphate, etc.);

Metatungstic acid, ammonium metatungstate, sodium metatungstate, 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, sodium aluminum sulfate, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum iodide;

zinc sulfate, zinc carbonate, zinc chloride, zinc iodide, 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) acetylacetonate, iron (II) chloride, iron (III) chloride, iron (III) citrate, iron (II) oxide , iron (III) oxide, iron (II, III) oxide, hexacyanoferrous (II), hexacyanoferric (III), hexacyanoferric (II) acid, hexacyanoferric (III) acid potassium, ammonium sulfate iron (II), iron ammonium sulfate (III), iron phosphate (II);

A chelate complex containing bismuth oxide, bismuth sulfate, bismuth nitrate, bismuth hydroxide, bismuth citrate, bismuth vanadate, vanadium alkoxide, and vanadium, specifically, vanadium oxide, metavanadic acid, sodium metavanadate, meta Potassium vanadate, ammonium metavanadate, vanadium bisacetylacetonato, vanadyl diacetylacetonato, vanadium pentoxide, vanadium trioxide, vanadium fluoride, vanadium phosphate, vanadyl sulfate, vanadium sulfide, vanadyl oxalate, vanadium oxytriiso Propoxide, vanadium oxytributoxide, vanadium oxytriethoxide, vanadium oxytriisobutoxide, vanadium oxytriethanolaminate, vanadium ammonium oxycitrate, vanadium tributoxystearate, vanadylacetylacetonato, tetrapro Poxyvanadium, tetrabutoxyvanadium, etc.;

niobium chloride (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);

Inorganic salts such as zirconium hydrofluoric acid, zirconium fluoride, ammonium fluorozirconate, sodium fluorozirconate, potassium fluorozirconate, zirconium sulfate, nitrate, acetate, carbonate, chloride salt, oxide of zirconium compound, zirconium compound of organic acid salts, etc.;

Inorganic salts, such as hydrotitanium hydrofluoric acid, titanium fluoride, ammonium fluorotitanate, sodium fluorotitanate, potassium fluorotitanate, titanium sulfate, nitrate, acetate, carbonate, chloride salt, oxide of titanium compound, titanium compound of organic acid salts; and the like.

Among these, only one component or a plurality can be used in combination.

By containing the compound (C) in the aqueous metal surface treatment agent of this embodiment, it is preferable at the point which can improve the intensity|strength of the film formed with this aqueous metal surface treatment agent. As for content of compound (C), ratio [( _CM )/( _AM )] of mass ( _CM ) of compound (C) and solid content mass (AM) of urethane resin ( _A ) is 1/300 or more It is preferable to adjust so that it becomes in the range of 1/2 or less, It is more preferable to adjust so that it may become in the range of 1/200 or more and 1/3 or less, It is more preferable to adjust so that it may become in the range of 1/100 or more and 1/4 or less. Do.

<<Water-dispersible resin (D)>>

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

The said acrylic resin is obtained by radical polymerization, cationic polymerization, or anionic polymerization, such as acrylic acid and acrylic acid ester. Although it does not specifically limit as a monomer used for these polymerization reaction, For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, s-butyl acrylate , t-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, 2-hydroxylethyl acrylate, methyl methacrylate , ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclo Hexyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, 2-hydroxyl ethyl methacrylate, etc. are mentioned. It is also possible to introduce an alkoxysilyl group into the structure by appropriately inserting vinyltrimethoxysilane or the like. These may be used independently and may use 2 or more types together.

Although it does not specifically limit as said epoxy resin, For example, glycidyl obtained by reaction of phenol, bisphenol A, o-, m-, p-cresol, phthalic acid, isophthalic acid, terephthalic acid, and epichlorhydrin. Ethers or esters, novolac phenol, glycidyl ethers obtained by reaction of an aromatic compound having a hydroxyl group, such as polyp-vinylphenol, and epichlorohydrin, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene Glycidyl ethers obtained by reaction of epichlorhydrin with aliphatic polyols such as glycol, glycerol, and sorbitol can be used with a water-soluble functional group introduced by reacting with amines. You may introduce|transduce a silanol group, an alkoxysilyl group, a phosphoric acid group, and a phosphoric acid ester group into these epoxy resins. Among these, only one component or a plurality can be used in combination.

The said polyester resin will not be specifically limited if it is an ester product of a polybasic acid and polyhydric alcohol.

Although it does not specifically limit as a polybasic acid, For example, Dibasic acids, such as phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. A polybasic acid having trivalence or higher is used.

Although it does not specifically limit as polyhydric alcohol, For example, ethylene glycol, diethylene glycol, polyethyleneglycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 3-methylpentadiol, neopentylene glycol, Aliphatic or alicyclic dihydric alcohols such as 1,4-butanediol, 1,5-pentanediol, 1,4-hexanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol, glycerin, and trimethylol A polyhydric alcohol of trihydric or higher such as ethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, dipentaerythritol, and 1,1,2,2-tetrakis(4-hydroxylphenyl)ethane may be used. can Among these, only one component or a plurality can be used in combination.

Although it will not specifically limit if it is a polymer which has a phenol structure, such as a novolak phenol resin, polyvinyl phenol, and polybisphenol A as a phenol resin, What does not have an alkoxysilyl group in the structure can be used.

The polyamide resin is not particularly limited as long as it is an ester product of a polybasic acid and a polyvalent amine.

Although it does not specifically limit as a polybasic acid, For example, Dibasic acids, such as phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. A polybasic acid having trivalence or higher is used, and the polyhydric alcohol is not particularly limited, but for example, ethylenediamine, propylenediamine, diethyltriamine, hexylenediamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine , divalent amines such as piperazine, diphenylmethanediamine, hydrazine and tetramethylethylenediamine can be used. Among these, only one component or a plurality can be used in combination.

Polyolefin resin will not be specifically limited if it is a polymer of olefins. As the olefins, for example, alkenes such as ethylene, propylene, isoprene and α-butene are used, and those obtained by polymerization reaction such as radical polymerization or cationic polymerization can be used. These polymers may be copolymerized using an acid anhydride or carboxylic acid having a double bond. Among these, only one component or a plurality can be used in combination.

By containing resin (D) in the water-based metal surface treatment agent of this embodiment, it is preferable at the point which can adjust the intensity|strength of the formed film to suitable intensity|strength. As for the content of the resin (D), the ratio [( _DM )/( _AM )] of the solid content mass (DM ) of the resin ( _D ) to the solid content mass (AM ) of the urethane resin ( _A ) is 1/50 It is preferable to adjust so that it becomes in the range of 50/1 or more, it is more preferable to adjust so that it becomes in the range of 1/25 or more and 25/1 or less, It is more preferable to adjust so that it becomes in the range of 1/10 or more and 10/1 or less. desirable.

It is preferable that the said water-soluble or water-dispersible resin (D) is cationic or nonionic, and it is preferable that the existing form in the water is a dissolved state or a dispersed state. In these water-soluble or water-dispersible resins (D), dissolution or dispersion in water may be achieved based on self-solubility or self-dispersibility, and cationic surfactants (eg, tetraalkylammonium etc.) and/or non You may disperse|distribute by presence of an ionic surfactant (for example, alkylphenyl ether etc.).

<<Crosslinking agent (E)>>

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

As these crosslinking agents, a well-known resin can be used, respectively, and crosslinking can be accelerated|stimulated by the functional group contained in resin.

As for the content of the crosslinking agent (E), the ratio [(EM )/( _AM )] of the solid content mass (EM ) of the crosslinking agent (E) to the solid content mass ( _AM ) of the urethane resin ( _A ) is _1/100 It is preferable to adjust so as to be in the range of 5/1 or more, and it is more preferable to adjust so that it is in the range of 1/50 or more and 3/1 or less, and it is further adjusted so that it is in the range of 1/20 or more and 1/1 or less. desirable.

The water-based metal surface treatment agent may further contain a lubricant. Although it does not specifically limit as a lubricant, For example, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, etc. are mentioned. Although content of a lubricant is not specifically limited unless the effect of this invention is impaired, It is 1 mass part or more and 10 mass parts or less normally with respect to 100 mass parts of urethane resins (A).

<<Other components that may be included in the water-based metal surface treatment agent>>

The aqueous metal surface treatment agent of this embodiment may contain components other than the above. As a component other than the above, for example, a film forming aid (organic solvent, etc.) which improves film-forming property and the drying property of a film, surfactant which improves wettability, and an antifoaming agent and leveling agent which suppresses foaming , a conductive material for improving weldability, a colored pigment for improving designability, a rust preventive agent for suppressing the generation of rust, etc. can be blended in a range that does not impair the stability of the water-based metal surface treatment agent or the effect of the present invention.

Although it does not specifically limit as a film-forming auxiliary agent, For example, Alcohols, such as methanol, ethanol, 2-propyl alcohol, t-butyl alcohol; Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monopropyl ether, etc. of glycol alkyl ethers; 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; Aceto Nitrile solvents such as nitrile and acrylnitrile; Acrylate solvents such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N -amide solvents such as ethylpyrrolidone; sulfoxides such as dimethyl sulfoxide; dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, diethyl glutarate, diethyl glutarate Dicarboxylic acid ester solvents, such as ethyl; etc. are mentioned. These film forming auxiliary agents may be used independently and may mix and use 2 or more types.

Examples of the surfactant include nonionic surfactants such as alkylallyl ether, alkyl ether, alkyl ester, and alkylamine, and fatty acid salts, alkyl sulfate ester salts, aliphatic amine sulfates, and dibasic surfactants. Anionic surfactants, such as sulfonate of fatty acid ester, are mentioned. These surfactants may be used independently and may mix and use 2 or more types.

Examples of the conductive material include conductive metal fine powder and carbon fine 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 this embodiment may further contain the well-known various additives used generally as needed. Such additives include, for example, rust preventive pigments, dyes, inorganic crosslinking agents, antiblocking agents, viscosity modifiers, thickeners, dispersion stabilizers, light stabilizers, antioxidants, ultraviolet absorbers, inorganic fillers, organic fillers, plasticizers, lubricants (滑劑) ), an antistatic agent, and the like.

<Method for producing water-based metal surface treatment agent>

The water-based metal surface treatment agent according to the present embodiment is prepared by mixing a urethane resin (A) and a silane compound (B) and, if necessary, components other than the urethane resin (A) and the silane compound (B) in an aqueous solvent. can The aqueous solvent is not particularly limited as long as it contains 50 mass% or more of water based on the mass of all solvents (including the solvent). Examples of solvents other than water contained in the aqueous solvent include alkane-based solvents such as hexane and pentane; aromatic solvents such as benzene and toluene; alcohol-based solvents such as methanol, ethanol, 1-butanol, and ethyl cellosolve Solvent; Ether solvent such as tetrahydrofuran and dioxane; Ester solvent such as ethyl acetate and butoxyethyl acetate; Amide solvent such as dimethylformamide and N-methylpyrrolidone; Sulfoxide such as dimethyl sulfoxide System solvent; Phosphoric acid amide system solvents, such as hexamethyl phosphate triamide; etc. are mentioned. Although these solvents other than water may mix 1 type with water, they may mix with water in combination of 2 or more type. Further, from the viewpoint of the environment and economy, it is preferable to use only water.

<Metal material having a film and manufacturing method therefor>

The method for manufacturing a metallic material having a film according to the present embodiment is a method for manufacturing a metallic material having a metallic material and a film (surface-treated film layer) formed on the surface of the metallic material, the aqueous metal surface of the present embodiment A contacting step (step) of bringing the treating agent into contact with the surface of the metallic material, and a heating step of heating the metallic material to which the water-based metallic surface treating agent is brought into contact within a range of 50° C. or higher and 250° C. or lower to heat and dry the water-based metallic surface treatment agent. (step) has By these two steps, a surface treatment film layer is formed on the metal material surface. In addition, the heating temperature in the said heating process shows the temperature of metal material itself.

<Metal material>

The type of metal material is not particularly limited, and cold rolled steel sheet, hot rolled steel sheet, hot-dip galvanized steel sheet, aluminum-containing galvanized steel sheet, electro galvanized steel sheet, alloyed galvanized steel sheet, zinc nickel plated steel sheet, zinc cobalt coated steel sheet, and vapor deposited zinc Carbon steel plate, alloy steel plate, and plated steel plate, such as plated steel plate, nickel plated steel plate, tin plated steel plate, stainless steel plate, etc.; Generally known materials such as metal plates other than steel plates such as aluminum plate, copper plate, titanium plate, and magnesium plate can be used. there is. A particularly suitable metal material is a galvanized steel sheet such as a hot-dip galvanized steel sheet, an aluminum-containing galvanized steel sheet, an electrogalvanized steel sheet, an alloyed galvanized steel sheet, a zinc nickel plated steel sheet, a zinc cobalt plated steel sheet, and a vapor deposition galvanized steel sheet. Moreover, the shape in particular of a metal material is not restrict|limited, either, A board|plate material may be sufficient, and a molded article may be sufficient.

Here, the metal material may be subjected to a chromate treatment or a phosphate treatment as a base treatment.

Moreover, in recent years, although the movement toward non-chromium is increasing due to problems such as environmental pollution, labor hygiene, and safety, if the surface-treated coating layer of the present invention (preferably, a coating layer not containing chromium and phosphorus) is provided, chromate treatment or Even without phosphate treatment, sufficient corrosion resistance, chemical resistance, solvent resistance, and coating adhesion can be expressed.

<Surface treatment film layer>

The surface treatment film layer is formed using the water-based metal surface treatment agent, and a water-based metal surface treatment agent is applied on the surface of the metal material by a known method (eg, coating method, dipping method, spray method, electrolytic method, etc.) formed by contact.

Here, prior to treatment with a water-based metal surface treatment agent, in order to remove oil and dirt adhering to the metal material, washing with a degreasing agent (acid-based, alkali-based), hot water washing, acid washing, solvent washing, etc. You may carry out individually or in combination as appropriate.

Moreover, before performing the process by a water-based metal surface treatment agent, you may surface-condition in order to improve the corrosion resistance of a film more or to improve coating adhesiveness more. Although the method in particular of surface conditioning is not restrict|limited, Methods, such as chemical conversion treatment by which metals, such as Fe, Co, Ni, Cu, Zn, Mn, Zr, Ti, or V, adhere, and a phosphate chemical conversion treatment are mentioned. .

When the surface of a metallic material is wash|cleaned, from a viewpoint of reducing that a detergent remains on the surface of a metallic material, it is preferable to wash with water after washing|cleaning.

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

In the present embodiment, the drying temperature after contacting the water-based metal surface treatment agent, that is, the temperature of the heating step is not particularly limited, but is usually in the range of 50°C or more and 250°C or less, preferably 60°C It is in the range of more than 220 degreeC or less. It does not specifically limit about a drying method, A well-known drying method using oven etc. is employable.

Moreover, in the manufacturing method of this embodiment, after making a water-based metal surface treatment agent contact on the surface of a metal material, before performing the said drying, you may wash with water on the surface of the metal material which made the water-based metal surface treatment agent contact, no need to wash

The amount of coating on the surface of the metallic material is preferably 30 to 5,000 mg/m2, more preferably 50 to 3,000 mg/m2, and still more preferably 100 to 2,000 mg/m2, based on the total film mass. Do. Sufficient corrosion resistance and adhesiveness are obtained as it is 30 mg/m<2> or more. Moreover, when it is 5,000 mg/m<2> or less, a crack etc. are hard to generate|occur|produce in a film, and the adhesiveness 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, this invention is not limited to this.

<Synthesis Example 1>

Bisphenol A-polyoxyethylene 2 mole adduct (Newpole BPE-20T, manufactured by Sanyo Chemical Industries, Ltd.) (a2-1 described later) 63 g, polyethylene glycol (PEG2000, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) (a3-1 described later) 67 g, 30 g of N-methyldiethanolamine (aminoalcohol MDA, manufactured by Nippon Emulsifier Co., Ltd.) (a5-1 to be described later) 30 g, diethylene glycol (diethylene glycol, manufactured by Nippon Catalyst Co., Ltd.) (a4-1 to be described later) 30 g , 230 g of isophorone diisocyanate (Desmodur I, manufactured by Bayer Corporation) (a1-1 to be described later) was added to 400 g of methyl ethyl ketone and sufficiently dissolved. After making this mixed solution react at 80 degreeC for about 5 hours, it confirmed that 3 mass % or less of isocyanate groups were contained, and 25 g of dimethyl sulfate (ionizing agent a7-1 mentioned later) was added. In addition, the content rate of an isocyanate group is based on JISK7301:1995, after dissolving 2 g of reaction solutions in dimethylformamide, adding 10 ml of n-dibutylamine-toluene solutions, bromophenol blue as an indicator It is used and titrated with a 0.5 mol/L hydrochloric acid solution, and can be computed using the following formula|equation.

(wherein A is the volume of hydrochloric acid solution required for titration with respect to the amount (mass) of isocyanate used when preparing a predetermined amount of the reaction solution, B is the volume of hydrochloric acid solution required for titration with respect to the reaction solution, and f is " 1”, N is the molar concentration of the hydrochloric acid standard solution, and S is the mass of the reaction solution.)

Next, 1000 g of deionized water was added to prepare a urethane emulsion.

Methyl ethyl ketone was removed from the obtained urethane emulsion by the vacuum distillation method, and the urethane emulsion whose density|concentration of a urethane resin is 25 mass % was prepared. In Table 1, each component used for this synthesis|combination and input amount (mass %) is shown. Hereinafter, the urethane emulsion obtained in this way is also called 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 in Synthesis Example 1 with each component and input amount.

A urethane resin of 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).

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

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

Each component described in Table 1 is as follows. In addition, the input amount (mass %) of each component described in Table 1 is based on the total amount of (a1)-(a5) components, and when (a6) component was used, this was also included in the total amount and calculated. In addition, all the urethane prepolymers obtained by each synthesis example contained the isocyanate group.

<Polyisocyanate (a1; Some of the following are polyisocyanates having a cyclohexane ring structure)>

a1-1: isophorone diisocyanate (Desmodur I, manufactured by Bayer)

a1-2: Dicyclohexylmethane 4,4'-diisocyanate (Desmodur W, Bayer Co., Ltd.)

a1-3: tolylene diisocyanate (Cosmonate T80, manufactured by Mitsui Chemicals)

a1-4: hexamethylene diisocyanate (50M-HDI, manufactured by Asahi Chemical Co., Ltd.)

<Polyol (a2)>

a2-1: Bisphenol A-polyoxyethylene 2 mol adduct (Newpole BPE20T, manufactured by Sanyo Chemical Industry Co., Ltd.)

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

a2-3: polycarbonate diol (Nipporan 981, manufactured by Tosoh Corporation)

<Diol (a3; some of the following are diols having a weight average molecular weight of more than 600 which do not contain a benzene ring and a nitrogen atom)>

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

a3-2: polyester polyol (Nipporan 4040, Mw2000, manufactured by Tosoh Corporation)

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

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

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

<Diol (a4; some of the following are diols having a weight average molecular weight of 500 or less which do not contain a benzene ring and a nitrogen atom)>

a4-1: diethylene glycol (diethylene glycol, Mw106, manufactured by Nippon Catalyst Co., Ltd.)

a4-2: 1,5-pentanediol (1,5-pentanediol, Mw104, manufactured by Ube Heungsan)

a4-3: 1,6-hexanediol (1,6-hexanediol, Mw106, manufactured by Ube Heungsan)

a4-4: Polyester polyol (Flaxel 205, Mw530, manufactured by Daicel Chemicals)

<tertiary amine compound (a5)>

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

<Others (polyols higher than triols not containing a benzene ring and a nitrogen atom)

(a6)>

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

<Ionizing agent>

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

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

Ionizing agent a7-3: Formic acid (manufactured by Junsei Chemicals)

Ionizing agent a7-4: methanesulfonic acid (manufactured by Tosoh Corporation)

[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)] were mixed in water, and Examples 1 to 84 and Comparative Examples 1 to 16 of water-based metal surface treatment agent was prepared. More specifically, with respect to 100 parts by mass of the urethane resin of the Synthesis Examples and Comparative Synthesis Examples, 125 parts by mass of water and the various compounds are mixed sufficiently so that the solid content mass ratio shown in Table 2 may be added and mixed, and the aqueous metal surface of Examples and Comparative Examples A treatment agent was prepared.

The components described in Table 2 are as follows.

(public goods)

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

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

Silane compound (B)

B2: γ-aminopropyltriethoxysilane

B3 is a mixture of γ-glycidoxypropyltrimethoxysilane: B2 is 1:1

compound (C)

C1: zirconium hydrofluoric acid

C2: Titanium hydrofluoric acid

C3: vanadyl acetylacetonate

Water-dispersible resin (D)

D1: Acrylic resin

D2: Phenolic resin

D3: Epoxy resin

crosslinking agent (E)

E1: Block isocyanate

E2: Carbodiimide resin

E3: Oxazoline resin

compound (F)

F1: Polyethylene Wax

F2: Paraffin wax

<Surface treatment>

Various test materials were degreased by spraying at 60 degreeC for 10 second using the alkali degreasing agent [a solution obtained by mixing Fine Cleaner E6406 (manufactured by Nippon Parker Rising Co., Ltd.) in water to a concentration of 20 g/L]. After that, it was washed with water by spraying water for 10 seconds.

After washing with water, a water-based metal surface treatment agent is applied on the surface of various test materials by a bar coating method, and then dried at 120 ° C (PMT: the highest plate temperature of the test material during baking) to form a film having a thickness of 1 µm did

<Evaluation test>

(corrosion resistance)

Various corrosion-resistance tests were implemented about the various processed boards (No. 1-100) to which the surface treatment was performed as mentioned above. The evaluation method and evaluation criteria are as follows.

(Plane part corrosion resistance test)

Based on the salt spray test method (JIS-Z-2371:2015), after performing neutral salt spray for 240 hours, the area ratio (%) of the white rust which generate|occur|produced was calculated|required, and the following reference|standard evaluated planar part corrosion resistance. In addition, in this evaluation, C or more was made into the 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: 30% or more and less than 40%

D: 40% or more

(Processing part corrosion resistance test)

Two plates of the same type and same thickness as the used test material were stacked and subjected to 180 degree bending so as to be inserted into various treatment plates. Then, after performing neutral salt spray for 72 hours similarly to the flat part corrosion resistance test, the area ratio (%) of the generated white rust was calculated|required, and the following reference|standard evaluated the process part corrosion resistance. In addition, in this evaluation, C or more was made into the 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: 30% or more and less than 40%

D: 40% or more

(Cross cut part corrosion resistance test)

After cross-cutting various treated plates with an NT cutter, as in the flat surface corrosion resistance test, neutral salt spraying was performed for 72 hours, and then the maximum one-sided rust width from the cross (x) cut was obtained, and cross-cut according to the following criteria. The cut part corrosion resistance was evaluated. In this evaluation, C or more was set as the pass.

AAA: less than 2 mm

AA: 2 mm or more and less than 4 mm

A: 4 mm or more and less than 6 mm

B: 6 mm or more and less than 8 mm

C: 8 mm or more and less than 10 mm

D: 10 mm or more

(Alkali resistance test)

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

Thereafter, the color difference (ΔE) before and after the treatment of the aqueous sodium hydroxide solution was determined using a color difference meter (manufactured by Nippon Denshoku Co., Ltd.), and alkali resistance was evaluated based on the following evaluation criteria. In this evaluation, C or more was set as the pass.

AAA: △E is less than 0.5

AA: △E is 0.5 or more but 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 but less than 3

D: △E is 3 or more

(acid resistance test)

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

Thereafter, the color difference (ΔE) before and after the treatment with the aqueous sulfuric acid solution was determined using a color difference meter, and acid resistance was evaluated based on the following evaluation criteria. In this evaluation, C or more was set as the pass.

AAA: △E is less than 0.5

AA: △E is 0.5 or more but 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 but less than 3

D: △E is 3 or more

(Painting primary adhesion test)

Using an amino alkyd-based coating material (Amilac #1000 manufactured by Kansai Paint Co., Ltd.), it was coated on the surfaces of various treatment plates. Coating was performed by the bar coat method, after coating, baking was performed at 130 degreeC (PMT) for 20 minutes, and the coating film with a film thickness of 25 micrometers was formed. After performing extrusion processing of 8 mm with eriksen with respect to the processing plate which has a coating film, the operation (hereinafter referred to as "tape peeling") of sticking and peeling a tape to a processing part was performed, and the coating film was peeled off The ratio (%) of the area was calculated|required, and coating primary adhesiveness was evaluated based on the following evaluation criteria. In this evaluation, C or more was set as the pass.

AAA: peeling area 0% (no peeling)

AA: The peeling area is more 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

(Painting secondary adhesion test)

After immersing the treated plate having the coating film in boiling water for 1 hour, extrusion processing of 8 mm with eriksen was performed, the tape was peeled off the processed portion, and the ratio (%) of the area where the coating film was peeled was the coating Coating secondary adhesiveness was evaluated similarly to the evaluation criteria of a primary adhesive test. In this evaluation, C or more was set as the pass.

(solvent resistance test)

After 10 reciprocating sliding of the gauze impregnated with methyl ethyl ketone (MEK) on various treatment plates under a 1.5 kg load, the color difference (ΔE) before and after sliding was obtained using a colorimeter, and the following evaluation criteria were used. Based on this, solvent resistance was evaluated. In this evaluation, C or more was set as the pass.

AAA: △E is less than 0.5

AA: △E is 0.5 or more but 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 but less than 3

D: △E is 3 or more

(Abrasion resistance test)

After 20 reciprocating motions while pressing a steel ball (SUS304) under a load of 500 g with a Bowden testing machine, the change in the friction coefficient from the start of the test to the end of the test is determined, and the wear resistance is evaluated based on the following evaluation criteria. evaluated. In this evaluation, C or more was set as the pass.

AAA: No change in friction coefficient

AA: Fluctuation of friction coefficient is less than 0.05

A: Fluctuation of friction coefficient is 0.05 or more but less than 0.1

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

C: Fluctuation of friction coefficient is 0.15 or more but less than 0.2

D: Friction coefficient fluctuation is 0.2 or more

<Evaluation result>

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

[Table 2-1]

[Table 2-2]

[Table 3-1]

[Table 3-2]

Claims (8)

It contains a urethane resin (A) and a silane compound (B),
The urethane resin (A) is a structural unit derived from a polyisocyanate having a cyclohexane ring structure represented by the following formula (1), a structural unit derived from a polyol represented by the following formula (2), and the following formula (3) A structural unit derived from a diol having a weight average molecular weight of more than 600 represented by, 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 represented by the following formula (5); / Or the structural unit derived from its salt, The aqueous|water-based metal surface treatment agent containing.
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
[Formula 1]

represented as,
R ⁴ is
[Formula 2]

am.)
Formula (2):
[Formula 3]

(in formula (2), R ⁸ is represented by -R ⁹ -R ¹⁰ -R ¹¹ -,
R ⁹ is
[Formula 4]

ego,
R ¹⁰ is
[Formula 5]

ego,
R ¹¹ is,
[Formula 6]

ego,
R ¹⁴ is,
[Formula 7]

am.)
Formula (3): HO-R ¹⁹ -H (3)
(R ¹⁹ in formula (3) is,
[Formula 8]

am.)
Formula (4): HO-R ²² -OH
(R ²² in formula (4) is,
[Formula 9]

am.)
Formula (5):
[Formula 10]

The method of claim 1,
adding a compound (C) containing at least one element selected from boron, magnesium, aluminum, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, molybdenum, tungsten, cerium, niobium, tin, bismuth and zirconium A water-based metal surface treatment agent comprising: The method of claim 1,
The water-based metal surface treatment agent in which the said silane compound (B) contains an amino group. The method of claim 1,
A water-based metal surface treatment agent further comprising at least one water-soluble or water-dispersible resin (D) selected from a phenol resin, an epoxy resin, a polyester resin, an acrylic resin, a polyolefin resin, and a polyamide resin. The method of claim 1,
A water-based metal surface treatment agent further comprising at least one crosslinking agent (E) selected from an oxazoline-based resin, a blocked isocyanate-based resin, a carbodiimide-based resin, an aziridine-based resin, and an epoxy-based resin. The method of claim 1,
A water-based metal surface treatment agent further comprising a lubricant. A contact step in which the water-based metal surface treatment agent according to any one of claims 1 to 6 is brought into contact with the surface of the metal material, and heating to dry the metal material that has passed through the contact step at 50°C or more and 250°C or less A method for manufacturing a metal material having a film, comprising a step. A metal material having a coating film obtained by the method for producing a metal material having a coating film according to claim 7.