TWI742275B - Water-based metal surface treatment agent, metal material with substrate treatment layer and manufacturing method thereof - Google Patents

Abstract

The subject of the present invention is to provide a water-based metal surface treatment agent, etc., wherein the water-based metal surface treatment agent system has a surface treatment film that can be formed between a metal material and a coating film, and when the coating film is formed, For metal materials, it provides excellent processing adhesion, chemical resistance and corrosion resistance.

The aforementioned problem is solved by the water-based metal surface treatment agent of the present invention. The aforementioned metal surface treatment agent is characterized by comprising: a specific urethane resin (A) exceeding 10 g/L; a fluorine-containing compound (B), which is also selected from the group consisting of boron, silicon, titanium and zirconium At least one element in the group.

Description

Water-based metal surface treatment agent, metal material with substrate treatment layer and the same Production method

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

Conventionally, metal surface treatment agents capable of forming a film have been developed, and the aforementioned film system can impart various properties to metal materials. For example, Patent Document 1 discloses a technique relating to a water-based coating composition for surface treatment of a metal material containing a specific cationic water-based urethane resin.

[Prior Technical Literature]

[Patent Literature]

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

[Summary of the invention]

However, even after the coating film is formed on the surface of the metal material by the above-mentioned technique, although the coating film formed on the coating film has excellent chemical resistance and corrosion resistance, it is not sufficient in terms of processing adhesion.

Therefore, the present invention aims to provide a water-based metal surface treatment agent, a metal material having the surface treatment film (hereinafter referred to as "substrate treatment layer"), and a method for producing the same. The water-based metal surface treatment agent system has a surface treatment film The surface treatment film can be formed between the metal material and the coating film, and can impart excellent processing adhesion, chemical resistance, and corrosion resistance to the metal material when the coating film is formed.

After conducting in-depth studies, the inventors found that the above-mentioned problems can be solved by using a surface treatment agent containing a specific urethane resin and a specific fluorine-containing compound, and the present invention was completed. The present invention is as follows.

[1] A water-based metal surface treatment agent, characterized by comprising: more than 10g/L of urethane resin (A); fluorine-containing compound (B), which system further contains selected from boron, silicon, titanium and zirconium At least one element in the group consisting of; wherein, the aforementioned urethane resin (A) includes: a structural unit derived from a polyisocyanate having a cyclohexane ring structure represented by the following formula (1); from the following formula (2) The structural unit of the polyol represented by the following formula (3); the structural unit derived from the diol with a weight average molecular weight greater than 600 represented by the following formula (3); A structural unit of a glycol; a structural unit derived from a tertiary amine compound and/or its salt represented by the following formula (5); and, the formula (1): O=C=NR ¹ -N=C=O

(且R⁵、R⁶及R⁷係各自獨立為氫原子或烷基。) ^{(Among them, R 1} in the formula (1) is represented by -R ² -R ³ -R ⁴ -, R ² is a single bond or an alkylene group, and R ³ is [化1]

(And R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group.)

(且其左側的鍵結位置與R³鍵結。)) R ⁴ is [化2] single bond; alkylene;

(And the bonding position on the left is bonded to R ^3. ))

、

(其中，n為整數。) Formula (2): [化3] HO-R ⁸ -OH,

,

(Among them, n is an integer.)

(其右側的鍵結位置與R¹⁰鍵結。)；-R¹³-CO-(其右 側的鍵結位置與R¹⁰鍵結。) ^{(R 8} in formula (2) is represented by -R ⁹ -R ¹⁰ -R ¹¹ -, R ⁹ is a single bond;

(The bonding position on the right side is bonded to R ^10. ); -R ¹³ -CO- (The bonding position on the right side is bonded to R ^10. )

(此等化合 物右側的鍵結位置與CO鍵結。)；又，R¹⁸係直鏈或是支鏈的亞烷基，x係1~5的整數，l為2~4的整數。) (R ¹² is a linear or branched alkylene group; R ¹³ is -R ¹⁸ -O- or

(The bonding position on the right side of these compounds is bonded to CO.); In addition, R ¹⁸ is a linear or branched alkylene group, x is an integer from 1 to 5, and l is an integer from 2 to 4. )

R ¹⁰ series [化5]

、

、

、-CO-R¹³-(除了單鍵以外的上述化合物，左側的 鍵結位置皆與R¹⁰鍵結。) R ¹¹ series [化6] single bond,

,

,

, -CO-R ^13- (Except for the single bond, the bonding positions on the left are all bonded to R ¹⁰ .)

(且 此等化合物右側的鍵結位置與CO鍵結。)；又，R¹⁵及R¹⁶係各自獨立為氫原子、烷基、鹵化烷基或苯基，R¹⁷係氫原子、烷基或苯基，R¹⁸係直鏈或支鏈的亞烷基，x為1~5的整數，l為2~4的整數 (Among them, R ¹² is a linear or branched alkylene group; R ¹³ is -R ¹⁸ -O- or

(And the bonding position on the right side of these compounds is bonded to CO.); In addition, R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group, a halogenated alkyl group or a phenyl group, and R ¹⁷ is a hydrogen atom, an alkyl group or Phenyl, R ¹⁸ is a linear or branched alkylene group, x is an integer from 1 to 5, and l is an integer from 2 to 4

、

(其 中，R¹⁸係直鏈或支鏈的亞烷基，l為2~4的整數。)) R ¹⁴ series [化7] hydrogen atom, alkyl group, phenyl group,

,

(Among them, R ¹⁸ is a linear or branched alkylene group, and l is an integer of 2 to 4.))

Formula (3): HO-R ¹⁹ -H (3)

(且此等化 合物左側的鍵結位置與OH鍵結。) (In formula (3), R ¹⁹ series [化 8]

(The bonding position on the left side of these compounds is bonded to OH.)

或金剛烷環，且 R²¹係亞烷基，m為2~4的整數，n為整數。)) (Wherein R ²⁰ is independently an alkylene group,

Or an adamantane ring, and R ²¹ is an alkylene group, m is an integer of 2 to 4, and n is an integer. ))

Formula (4): HO-R ²² -OH

、金剛烷環、

、

(其中，y係2或3，z 係1~6的整數。)) (In formula (4), R ²² is a [化9] alkylene group,

, Adamantane ring,

,

(Among them, y is 2 or 3, and z is an integer from 1 to 6.)

(式中，R²³係烷基、氨烷基、羥烷基、

、

，R²⁴為羥烷基、 氨烷基或N-烷氨基烷基。)。 Formula (5): [化 10]

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

,

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

[2] The water-based metal surface treatment agent described in [1], wherein the fluorine-containing compound (B) further contains selected from the group consisting of tetrafluoroboric acid, hexafluorotitanic acid, hexafluorozirconic acid, hexafluorosilicic acid and At least one of these metal acid salts or inorganic acid salts.

[3] The water-based metal surface treatment agent as described in [1] or [2], further comprising: a silicon compound (C) selected from the group consisting of water-dispersible silica and silane coupling agent At least one of them.

[4] The water-based metal surface treatment agent described in any one of [1] to [3] above, further comprising: a metal compound (D) selected from the group consisting of Ni, Mn, Co, Mo, V, W, At least one of the group consisting of Ce, Mg, Al, Zn, Fe, Bi, Nb, Sn, and Cr.

[5] The water-based metal surface treatment agent described in any one of [1] to [4], further comprising: a water-soluble or water-dispersible resin (E) selected from the aforementioned urethane resins At least one of the group consisting of urethane resin, phenol resin, silicone resin, epoxy resin, polyester resin, acrylic resin, polyolefin resin and polyamide resin.

[6] The water-based metal surface treatment agent described in any one of [1] to [5], further comprising: a crosslinking agent (F) selected from the group consisting of oxazoline resins and blocked isocyanate resins , At least one of the group consisting of carbodiimide resin, aziridine resin and epoxy resin.

[7] A method of manufacturing a metal material, which is a method of manufacturing a metal material with a substrate treatment layer, comprising: a substrate treatment step of making the water-based metal described in any one of [1] to [6] The surface treatment agent contacts the surface of the metal material to form a base treatment layer.

[8] The method for manufacturing a metal material as described in [7], further comprising: a coating step of coating the metal material after the aforementioned substrate treatment step with paint.

[9] A metal material characterized by comprising: a base treatment layer; a coating film formed on the base treatment layer; wherein the base treatment layer is formed by any one of the aforementioned [1] to [6] The layer formed by the water-based metal surface treatment agent.

According to the present invention, there is provided a water-based metal surface treatment agent, a metal material having the surface treatment film (hereinafter referred to as "substrate treatment layer"), and a method for producing the same. The water-based metal surface treatment agent system has a surface treatment film, and the surface treatment The film system can be formed between the metal material and the coating film, and can impart excellent processing adhesion, chemical resistance, and corrosion resistance to the metal material when the coating film is formed.

Hereinafter, specific embodiments are shown to explain the present invention in detail.

One aspect of the present invention is a water-based metal surface treatment agent. The water-based metal surface treatment agent includes: the urethane resin (A) above 10g/L; and the fluorine-containing compound (B), which also contains the group selected from the group consisting of boron, silicon, titanium and zirconium At least one element in. After forming a base treatment layer on the surface of a metal material by using this water-based metal surface treatment agent, by forming a coating film on the base treatment layer, excellent processing adhesion, chemical resistance, and corrosion resistance can be exhibited.

By reacting a urethane prepolymer with water, the above-mentioned urethane resin (A) can be typically obtained. At this time, in order to promote the reaction, it can also contain A polyamine compound containing a tertiary amine compound. Specifically, the isocyanate group contained in the urethane prepolymer reacts with the amine generated by water or the polyamine compound added as necessary, and after the above reaction, the urea bond is formed , And become a urethane resin.

The urethane prepolymer is a component used to manufacture the urethane resin (A), which is obtained by reacting at least the following compounds: a polyisocyanate with a cyclohexane ring structure; it does not contain nitrogen atoms but contains benzene Ring polyols; diols with a weight average molecular weight greater than 600 without benzene ring and nitrogen atoms (hereinafter, also referred to as high molecular weight diols); without benzene rings and nitrogen atoms with a weight average molecular weight below 500 Glycol (hereinafter, also referred to as low-molecular-weight diol); a tertiary amine compound containing two or more active hydrogens and/or a salt thereof.

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); a structural unit derived from a polyol represented by the following formula (2) Structural unit; a structural unit derived from a diol with a weight average molecular weight greater than 600 represented by the following formula (3); a structural unit derived from a diol with a weight average molecular weight of less than 500 represented by the following formula (4); derived from the following The structural unit of the tertiary amine compound represented by formula (5) and/or its salt.

Specifically, the hydroxyl group contained in the polyol represented by formula (2), the high molecular weight diol represented by formula (3), and the low molecular weight diol represented by formula (4), and is The isocyanate group contained in the polyisocyanate represented by formula (1) reacts to form a urethane bond. In addition, the isocyanate group contained in the above-mentioned 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 and Urea bond and so on.

In addition, in order to react with the above-mentioned polyamine compound that does not contain water and a tertiary amine compound, the urethane prepolymer used in this embodiment contains a polyisocyanate derived from a cyclohexane ring structure. Isocyanate group.

The polyisocyanate (hereinafter, simply referred to as "polyisocyanate") having a cyclohexane ring structure can be used for the production of a urethane prepolymer, and can be 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 represented by [化11]

(Wherein, R ⁵ , R ⁶ and R ⁷ in the formula are each independently a hydrogen atom or an alkyl group.)

(左側的鍵結位置係與R³鍵結)來表 示。 R ^{4 is} based on [化12] single bond, alkylene or

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

(其中，式中的R⁵、R⁶及R⁷係各自獨立為氫原子 或甲基)。又，上述式中的R⁵、R⁶及R⁷較佳係全部為氫原子或甲基。 R ^{1 is} better [化13]

(In the formula, R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group). In addition, it is ^{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 cyclohexane. In addition, a plurality of cyclohexane ring structures may be included in the polyisocyanate.

In the production of the urethane prepolymer described later, in contrast to the polyisocyanate used in the production of the urethane prepolymer, the polyol described later, the high molecular weight diol described later, and the low molecular weight The total amount of the diol and the third-level amine compound and/or its salt mentioned later, the amount of polyisocyanate is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, particularly preferably 40 to 65% by mass , The best system is 50-60% by mass. In other words, in the urethane resin (A) used in this embodiment, the amount (in terms of mass) of the structural unit derived from the polyisocyanate of formula (1) is preferably that of the urethane resin (A) 20~80%, better 30~70%, particularly good 40~65%, best 50~60%.

In the urethane prepolymer of this embodiment, in the case of using the "polyol with no benzene ring and nitrogen atom or more" mentioned later, "the ternary alcohol without benzene ring and nitrogen atom" is used. The amount of "polyol above alcohol" is also included in the above total amount.

Regarding the polyisocyanate, it 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, but it may be, for example, isocyanate. Ketone diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl) cyclohexane, 1,3- or 1,4-diisocyanate cyclohexane, 3-isocyanate-methyl-3 ,5,5-Trimethylcyclohexyl isocyanate, dicyclohexylmethane 4,4'-diisocyanate, etc.

The following compounds can also be used in combination with the polyisocyanate represented by the formula (1): as a dimer that is not contained in the formula (1) as a polyisocyanate-like isocyanate dimer (Uretdione) structure, such as isocyanate A trimer like a urate structure, or a polyisocyanate having 3 or more isocyanate groups in one molecule as an adduct using a polyfunctional polyol, etc.

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

A polyol that does not contain a nitrogen atom but contains a benzene ring (hereinafter, also simply referred to as "polyol") can be used for the production of a urethane prepolymer, and can be represented by the following formula (2).

、

Formula (2): [化14] HO-R ⁸ -OH,

,

(n is an integer)

(右側的鍵結位置與R¹⁰鍵結)、或-R¹³-CO-(右側的 鍵結位置與R¹⁰鍵結。)(其中，R¹²係直鏈或支鏈的亞烷基，R¹³係-R¹⁸-O-(右 側的鍵結位置與CO鍵結)、

(右側的鍵結位置與CO鍵結)。 又，R¹⁸係直鏈或支鏈的亞烷基，x為1~5的整數，l(小寫的L)為2~4的整數。)又，R¹⁰係[化16]

，且R¹¹係 [化17] 單鍵、

、

、

或-CO- R¹³-(除單鍵之外，上述化合物之左側的鍵結位置與R¹⁰鍵結。)(其中，R¹²係直鏈或支鏈的亞烷基，R¹³係-R¹⁸-O-(右側的鍵結位置與CO鍵結)、或

(右側的鍵結位置與CO鍵結)。又，R¹⁵及R¹⁶係各自獨立為氫 原子、烷基、鹵化烷基或苯基，R¹⁷係氫原子、烷基或苯基，R¹⁸係直鏈或支鏈的亞烷基，x為1~5的整數，l為2~4的整數。) In formula (2), R ⁸ is represented by -R ⁹ -R ¹⁰ -R ¹¹ -, and R ⁹ is [化15] single bond,

(The bonding position on the right is bonded to R ¹⁰ ), or -R ¹³ -CO- (the bonding position on the right is bonded to R ^10. ) (wherein R ¹² is a linear or branched alkylene group, and R ¹³ series -R ¹⁸ -O- (the bonding position on the right is bonded with CO),

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

, And R ¹¹ is [化17] single bond,

,

,

Or -CO- R ^13- (except for single bonds, the bonding position on the left side of the above compound is bonded to R ^10. ) (wherein R ¹² is a linear or branched alkylene group, and R ¹³ is -R ¹⁸ -O- (the bonding position on the right is bonded with CO), or

(The bonding position on the right is bonded with CO). In addition, R ¹⁵ and R ¹⁶ are each 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, and R ¹⁸ is a linear or branched alkylene group, x It is an integer from 1 to 5, and l is an integer from 2 to 4. )

、

。 (其中，R¹⁸係直鏈或支鏈的亞烷基，l為2~4的整數。) In addition, R ¹⁴ is a hydrogen atom, an alkyl group, a phenyl group,

,

. (Among them, R ¹⁸ is a linear or branched alkylene group, and l is an integer of 2 to 4.)

、

(右側的鍵結位置與OH鍵 結)、

。R¹²較佳係乙烯基或丙烯 基。R¹⁴較佳係氫原子、甲基、異丙基或苯基。R¹⁵較佳係氫原子、甲基、三氟甲基或苯基。R¹⁶較佳係氫原子、甲基、乙基、三氟甲基或苯基。R¹⁷較佳係氫原子、甲基、異丙基或苯基。 R ^{8 is} better [化19]

,

(The bonding position on the right is bonded with OH),

. R ^{12 is} preferably vinyl or propenyl. 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.

In the production of the urethane prepolymer described later, compared to the polyisoinate, polyol, the high molecular weight diol described later, and the low molecular weight diol used in the production of the urethane prepolymer The total amount of the molecular weight diol and the third-level amine compound and/or its salt described later, although the amount of polyol is preferably usually 1-40% by mass, it is preferably 1-30% by mass, more preferably 3-25% by mass, especially good 6-20% by mass. In other words, in the urethane resin (A) used in this embodiment, the amount (in terms of mass) of the structural unit derived from the polyol of formula (2) is usually 1 in the urethane resin (A) ~40%, preferably 1~30%, more preferred 3~25%, especially preferred 6~20%.

In the urethane prepolymer of this embodiment, in the case of using the "polyol with no benzene ring and nitrogen atom or more" mentioned later, "the ternary alcohol without benzene ring and nitrogen atom" is used. The amount of "polyol above alcohol" is also included in the above total amount.

If the polyol has one or more benzene rings and two or more hydroxyl groups, and is a polyol represented by formula (2) that does not have a nitrogen atom, it is not particularly limited. Examples include resorcinol, Aromatic polyols such as 2-methylresorcinol, bisphenol A, bisphenol S, and bisphenol F; bisphenol A-ethylene oxide 2 mol Adduct, bisphenol A-ethylene oxide 4 mol adduct, bisphenol A-ethylene oxide 6 mol adduct, bisphenol A-propylene oxide 10 mol adduct, bisphenol A-propylene oxide 2 mol adduct, bisphenol A-propylene oxide 4 mol adduct, bisphenol A-propylene oxide 6 mol adduct, bisphenol A-propylene oxide 10 mol Adducts and other polyether polyols with benzene ring; composed of phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and other aromatic polycarboxylic acids, and ethylene glycol, propylene glycol, diethylene Alcohol, triethylene glycol, tetraethylene glycol, 2-methylpropanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl Polyester polyol with benzene ring obtained by polycondensation of polyols such as base pentanediol; including polycarbonate polyol with benzene ring obtained from the transesterification reaction of ethylene carbonate and polyols such as bisphenol A Wait.

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

The high-molecular-weight diol system can be used for the production of a urethane prepolymer, can be represented by the following formula (3), and does not contain a benzene ring and a nitrogen atom.

Formula (3): HO-R ¹⁹ -H (3)

(各化合物 左側的鍵結位置與OH鍵結。)(其中，R²⁰係獨立地為亞烷基、

、或金剛烷環，且R²¹係亞烷基，m為2~4的整數，n 為整數。) ^{R 19} series in formula (3) [化20]

(The bonding position on the left side of each compound is bonded to OH.) (wherein, R ²⁰ is independently an alkylene group,

, Or an adamantane ring, and R ²¹ is an alkylene group, m is an integer of 2 to 4, and n is an integer. )

In the production of urethane prepolymers, compared to polyisocyanates, polyols, high-molecular-weight diols, low-molecular-weight diols described later, and those used in the production of urethane prepolymers The total amount of the tertiary amine compound and/or its salt, although the amount of high-molecular-weight diol can usually be preferably 1-50% by mass, preferably 3-40% by mass, more preferably 5~35% by mass %, 10-30% by mass, especially good. In other words, in the urethane resin (A) used in this embodiment, the amount (in terms of mass) of the structural unit derived from the diol of formula (3) is usually the amount in the urethane resin (A) 1~50%, preferably 3~40%, more preferably 5~35%, especially good 10~30%.

In the urethane prepolymer of this embodiment, in the case of using the "polyol with no benzene ring and nitrogen atom or more" mentioned later, "the ternary alcohol without benzene ring and nitrogen atom" is used. The amount of "polyol above alcohol" is also included in the above total amount.

Although the weight average molecular weight of the high molecular weight diol is greater than 600, it is preferably greater than 600 and less than 10,000, more preferably greater than 600 and less than 5000, particularly preferably 800-4000, and most preferably 1000-3000.

If the weight average molecular weight of each component in this embodiment is not specifically defined, it is a value measured by GPC (gel permeation chromatography) and converted to polystyrene.

As for the high molecular weight diol, it is not particularly limited as long as it does not contain a benzene ring and a nitrogen atom and has a weight average molecular weight greater than 600. For example, polyether diol, polyester diol, Polycarbonate diol and so on.

Examples of the above-mentioned polyether glycols include polyethylene glycol, polypropylene glycol, polybutylene glycol (polytetramethylene ether glycol) and the like. For example, an alkylene oxide such as ethylene oxide or propylene oxide can be subjected to addition polymerization reaction under an alkaline catalyst to produce polyether glycol.

For example, the above-mentioned polyester diols can be made of aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid, sebacic acid and the like as acid species. Saturated carboxylic acid, etc., and ethylene glycol, propylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octane as alcohol species Glycol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, cyclohexane Diol, 1,3-adamantanediol, etc. are produced by esterification reaction.

The above-mentioned polycarbonate diols include, for example, cyclic esters such as ε-caprolactone and the like obtained by ring-opening polymerization of ethylene glycol. Specifically, it refers to dimethyl carbonate Ester, diethyl carbonate, diphenyl carbonate, etc., react with the alcohols listed in the above-mentioned polyester diols to obtain products.

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

The low-molecular-weight diol system can be used for the production of a urethane prepolymer, can be represented by the following formula (4), and does not contain a benzene ring and a nitrogen atom.

Formula (4): HO-R ²² -OH

、金剛烷環、

、

(其中，y係2或3，z 係1~6的整數。) In formula (4), R ²² is a [化21] alkylene group,

, Adamantane ring,

,

(Among them, y is 2 or 3, and z is an integer from 1 to 6.)

In the production of urethane prepolymers, compared to polyisocyanates, polyols, high molecular weight diols, low molecular weight diols and the polyisocyanates used in the production of urethane prepolymers The total amount of the third-level amine compound and/or its salt described later, although the amount of low-molecular diol can usually be 1-25% by mass, it is preferably 1-20% by mass, more preferably 2-15% by mass %, especially good line 3~10% by mass. In other words, 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 usually the urethane resin (A) 1~25% of the medium, preferably 1~20%, more preferably 2~15%, especially good 3~10%.

In the urethane prepolymer of this embodiment, in the case of using the "polyol with no benzene ring and nitrogen atom or more" mentioned later, "the ternary alcohol without benzene ring and nitrogen atom" is used. The amount of "polyol above alcohol" is also included in the above total amount.

Although the weight average molecular weight of the low molecular weight diol is 500 or less, it 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.

For low molecular weight diols, for example, ethylene glycol (62.07g/mol), propylene glycol (76.09g/mol), 1,5-pentanediol (104.15g/mol), 1,6-hexane Diol (118.17g/mol), 1,7-heptanediol (132.2g/mol), 1,8-octanediol (146.23g/mol), 1,9-nonanediol (160.25g/mol) , 1,10-decanediol (174.28g/mol), neopentyl glycol (104.15g/mol), 2-methyl-1.3-propanediol (90.12g/mol), 3-methyl-1,5- Alkyl glycols such as pentanediol (118.17g/mol), 1,4-cyclohexyldimethanol (146.14g/mol), 1,3-adamantanediol (168.23g/mol), etc.; diethylene glycol (106.12g/mol), triethylene glycol (150.17g/mol), tetraethylene glycol (194.23g/mol), pentaethylene glycol (238.28g/mol), hexaethylene glycol (282.33g/mol) , Heptanediol (323.28g/mol), dipropylene glycol (134.17g/mol) and other polyalkylene glycols; dimethylolpropionic acid (134g/mol) and so on. These low-molecular-weight diols may be used singly, or two or more of them may be used in combination.

The tertiary amine compound (hereinafter, simply referred to as tertiary amine) and/or its salt can be used for the production of the above-mentioned urethane prepolymer, and can be represented by the following formula (5).

Formula (5): [化22]

(Wherein R ^{23 in the} formula is alkyl, aminoalkyl, hydroxyalkyl,

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

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

By reacting the active hydrogen of the tertiary amine compound and/or its salt with the above-mentioned polyisocyanate, it is possible to obtain a urethane prepolymer (amino Formate resin).

In addition, the third-stage amine compound and/or its salt contains two or more active hydrogens, for example, preferably contains two or more substituents having active hydrogen such as amino, hydroxyl, or N-alkylamino. In addition, the N-alkylamino group is preferably 2-methylamino group.

In the production of urethane prepolymers, compared to polyisocyanates, polyols, high molecular weight diols, low molecular weight diols and tertiary amines used in the production of urethane prepolymers The total amount of the compound and/or its salt, although the amount of the tertiary amine compound and/or its salt is usually It can be 1-20% by mass, but is preferably 2-15% by mass, more preferably 2-13% by mass, and particularly preferably 3-10% by mass. In other words, 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 is usually carbamic acid 1-20% in the ester resin (A), preferably 2-15%, more preferably 2-13%, particularly preferably 3-10%.

In the urethane prepolymer of this embodiment, in the case of using the "polyol with no benzene ring and nitrogen atom or more" mentioned later, "the ternary alcohol without benzene ring and nitrogen atom" is used. The amount of "polyol above alcohol" is also included in the above total amount.

Regarding the tertiary amine compound, if it is a tertiary amine having two or more active hydrogens, it is not particularly limited, and examples thereof include N-methyldiethanolamine, N-ethyldiethanolamine, and N-butyl N-aminoalkyl dialkanolamines such as diethanolamine, Nt-butyldiethanolamine, N-(3-aminopropyl)diethanolamine; triethanolamine, N,N,N',N'-tetra(2-hydroxylamine) Ethyl)ethylenediamine, bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane, 1-[bis(2-hydroxyethyl)amino]-2-propanol, etc. may also have substituents Trialkanolamine; 2,2'-diamino-N-methyldiethylamine, N,N',N"-trimethyldiethylenetriamine, tris(2-aminoethyl)amine, etc. 3rd level Amines. These tertiary amines can also be used as salts of organic acids such as formic acid and acetic acid; or as salts of inorganic acids such as hydrochloric acid and sulfuric acid; and can also be used after dimethyl sulfate and diethyl sulfate , Methyl iodide and other alkylating agents. The third-level amine compound includes N-aminoalkyl dialkanolamine, and N-methyl bis Ethanolamine.

The urethane resin (A) of the present embodiment is a product that can neutralize part or all of the structural part (third-stage amine) derived from the third-stage amine with acid or the like. As for the acid used at this time, for example, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, malic acid, malonic acid, adipic acid and other organic carboxylic acids; Alkanesulfonic acid, trifluoromethanesulfonic acid and other organic Organic acids such as sulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, bromic acid, and phosphoric acid. These acids may be used individually by 1 type, and may use 2 or more types together.

In addition, part or all of the structural part (third-stage amine) derived from the third-stage amine compound in the urethane resin (A) can be quaternary. Regarding the quaternization agent used in quaternization, specific examples include sulfuric acid esters such as dimethyl sulfate and diethyl sulfate; methyl chloride, benzyl chloride, methyl bromide, and benzyl chloride. Alkyl halides such as methyl bromide and methyl iodide; carbonates such as dimethyl carbonate and diethyl carbonate. These quaternary agents may be used singly, or two or more of them may be used in combination. In addition, it is also possible to use an acid as a neutralizing agent and a quaternary chemical agent in combination. In addition, in this specification, these acids and quaternary agents may be referred to as ionizing agents.

In this specification, although "alkyl" is not particularly limited, or although "alkyl" contained in halogenated alkyl, aminoalkyl, hydroxyalkyl, N-alkylaminoalkyl, etc. is not particularly limited, However, it generally refers to an alkyl group having 20 or less carbon atoms, preferably an alkyl group having 12 or less carbon atoms, and more preferably an alkyl group having 6 or less carbon atoms. For representative alkyl groups, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl Base, hexyl, isohexyl, 3-methylpentyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.

Also, although the "alkylene group" is not particularly limited, it is usually an alkylene group having 20 or less carbon atoms, preferably an alkylene group having 12 or less carbon atoms, and more preferably an alkylene group having 6 or less carbon atoms的alkylene. Representative alkylene groups include, for example, vinyl, propenyl, butenyl, isobutenyl, tert-butenyl, sec-butenyl, pentenyl, isopentenyl, and neopentenyl. , Xylyl, isoxylyl, 3-methylpentenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, etc.

In addition, the halogenated alkyl group may be, for example, an alkyl group in which one or more hydrogen atoms in the above-mentioned alkyl group are substituted with a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

In the production of the urethane prepolymer of this embodiment, components other than the above-mentioned components may also be used. Other components include, for example, polyisocyanates other than the above-mentioned polyisocyanates; polyols other than the above-mentioned polyols, high-molecular-weight diols, and low-molecular-weight diols that do not contain benzene rings and nitrogen atoms; organic solvents; Polyamine compounds other than tertiary amines; ionizing agents; acids; organometallic compounds, etc.

Regarding polyisocyanates other than the above-mentioned polyisocyanates, although not particularly limited, examples thereof include 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanate) hexanoate, and 1,6 -Aliphatic diisocyanates such as hexamethylene diisocyanate, 1,12-dodecyl diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; m- Or p-phenylene diisocyanate, triene-2,4-diisocyanate or triene-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- Aromatic diisocyanates such as methyl-diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, and tetramethyl diisocyanate; 1,3,6-hexamethylenetri Aliphatic triisocyanates such as isocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 2-isocyanate ethyl (2,6-diisocyanate) caproate, etc.; triphenylmethane triisocyanate, tris( Aromatic triisocyanates such as isocyanate phenyl) thiophosphate and the like. The polyisocyanate system other than the above-mentioned polyisocyanate can be a dimer such as an isocyanate dimer (Uretdione) structure, a trimer such as an isocyanurate structure, or as a Use the polyisocyanate etc. which have 3 or more isocyanate groups in 1 molecule of the adduct of a polyfunctional polyol.

Among these, aromatic polyisocyanates such as aromatic diisocyanates and aromatic triisocyanates are preferably used, and aromatic diisocyanates are more preferably used. The content of the other components and the amount of the structure derived from the other components in the urethane resin (A) can be appropriately set by those skilled in the art within a range that does not impair the effects of the present invention.

For polyols other than the above-mentioned polyols, high-molecular-weight diols, and low-molecular-weight diols, it is possible to use polyols of more than triols that do not contain a benzene ring and a nitrogen atom, such as trimethylolpropane , Pentaerythritol and so on.

Among the polyols containing no benzene ring and nitrogen atom or more, trimethylolpropane (TMP) is preferred.

In the case of using polyols that do not contain a benzene ring and a nitrogen atom or more in the production of a urethane prepolymer, compared to the polyisocyanate used in the production of the urethane prepolymer, The total amount of 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, and do not contain benzene rings and The amount of the polyol above the triol of the nitrogen atom is preferably 0.5-18% by mass, more preferably 3-10% by mass. In other words, in the urethane resin (A) used in this embodiment, the amount (in terms of mass) of structural units derived from polyols that do not contain a benzene ring and a nitrogen atom is usually carbamic acid. 0.5-18% in the ester resin (A), preferably 3-10%.

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

In the production of the urethane prepolymer and/or the production of the urethane resin (A), an organic solvent may also be used. The organic solvent system can be used as a solvent for reacting the above-mentioned components. Such organic solvents are not particularly limited, but examples include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; tetrahydrofuran, Ether solvents such as 1,4-dioxane; Nitrile solvents such as acetonitrile and acrylonitrile; Acrylic solvents such as methacrylate, ethacrylate, methyl methacrylate, and ethyl methacrylate; 2 Amine-based solvents such as methylformamide, dimethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone; sulfenite-based solvents such as dimethyl sulfide, etc. From the viewpoint of reducing the environmental load, these organic solvents can be removed by vacuum distillation as necessary after the production of the urethane prepolymer and/or the production of the urethane resin (A).

The urethane prepolymer of this embodiment is obtained by at least reacting polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, tertiary amine and/or its salt, etc.

In addition, by reacting the urethane prepolymer obtained as described above with water, the urethane resin of this embodiment can be obtained. At this time, a polyamine compound as a chain extender may be added as necessary, and the polyamine compound in this case is not a tertiary amine.

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

(Manufacturing method 1)

By dissolving and reacting polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, and tertiary amine in an organic solvent, a urethane prepolymer is prepared, and if necessary, by The ionizing agent ionizes part or all of the tertiary amine in the urethane prepolymer, and then adds water for emulsification.

(Manufacturing method 2)

By dissolving and reacting polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, and tertiary amine in an organic solvent, a urethane prepolymer is prepared, and if necessary, by The ionizing agent ionizes part or all of the tertiary amine in the urethane prepolymer, and then emulsifies by adding water while extending the chain with a chain extender such as a polyamine compound.

(Manufacturing method 3)

Without using organic solvents, urethane prepolymers are prepared by reacting polyisocyanates, polyols, high molecular weight diols, low molecular weight diols, and tertiary amines (bulk polymerization method), and If necessary, part or all of the tertiary amine in the urethane prepolymer is quaternized with an ionizing agent, and then emulsified by adding water.

(Manufacturing method 4)

After ionizing the tertiary amine with an acidifying agent or an alkalizing agent, add polyisocyanate, polyol, high molecular weight diol, low molecular weight diol, etc., and react to prepare a urethane prepolymer And if necessary, part or all of the tertiary amine in the urethane prepolymer is ionized by an ionizing agent, and then emulsified by adding water.

(Manufacturing method 5)

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

(Manufacturing method 6)

After adding polyisocyanate, polyol, high-molecular-weight diol, low-molecular-weight diol, etc., to the organic solvent and reacting it, a tertiary amine is added to prepare a urethane preform with tertiary amine structure at the end part. If necessary, part or all of the tertiary amine in the urethane prepolymer is ionized by an ionizing agent, and the chain is extended by a chain extender such as a polyamine compound. Emulsify while adding water.

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

As for the polyamine compound used as a chain extender, for example, ethylene diamine, 1,2-propylene diamine, 1,6-hexamethylene diamine, piperazine, 2,5-dimethyl Piperazine, isophorone diamine, 4,4'-dicyclohexylmethane diamine, 3,3'-dimethyl-4,4'-dicyclohexylmethane diamine, 1,4-cyclohexyl Diamine, 1,3-bisaminomethylcyclohexane, 2-aminoethylaminopropyltrimethoxysilane; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropyl Aminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, 1,6-hexamethylene bishydrazine; succinic acid Dihydrazine, dihydrazine adipate, dihydrazine glutarate, dihydrazine sebacate, dihydrazine isophthalate; β -semicarbamate, 3-semicarbazide, 3-semicarbazide propylcarbamate Acid ester, semicarbazide-3-semicarbazide methyl-3,5,5-trimethylcyclohexane, etc. Among these, hydrazine or ethylenediamine is preferably used.

When a chain extender is used, the 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.

The water-based metal surface treatment agent system of this embodiment contains the urethane resin (A) exceeding 10 g/L. Because the water-based metal surface treatment agent contains a higher concentration of urethane resin (A), it is more suitable for the purpose of forming a base treatment layer. Carbamate in water-based metal surface treatment agent The content of the ester resin (A) is preferably 12 g/L or more. Although the upper limit is not particularly limited, it is usually 120 g/L or less.

In addition to the specific urethane resin (A), the water-based metal surface treatment agent of this embodiment also contains: a fluorine-containing compound (B) (hereinafter also simply referred to as "compound B"), which also contains options At least one element from the group consisting of boron, silicon, titanium and zirconium. In the case of forming a coating film on the base treatment layer formed by the water-based metal surface treatment agent of this embodiment, in addition to providing excellent corrosion resistance to metal materials, it is also possible to provide excellent processing adhesion and alkali resistance. Performance such as chemical resistance, acid resistance, etc.

The compound (B) is not particularly limited as long as it contains at least one element selected from the group consisting of boron, silicon, titanium, and zirconium, and fluorine. Specifically, for example, tetrafluoroboric acid, ammonium tetrafluoroborate, lithium tetrafluoroborate, hexafluorosilicic acid, ammonium hexafluorosilicate, sodium hexafluorosilicate, titanium (III) fluoride, titanium fluoride ( IV), hexafluorotitanic acid (H ₂ TiF ₆ ), ammonium hexafluorotitanate, hexafluorozirconate, ammonium hexafluorozirconate, etc. Only one of these may be used, or plural numbers may be used in combination.

In preferred carbamate-based resin (A) in the solid content mass (A _M) and the mass ratio of the compound (B), (B _M) of _{[(B M) / (A} M)] 1/100 ~ Adjust the blending amount of the compound (B) within the range of 4, preferably within the range of 1/50~2, and optimally within the range of 1/20~1.

The water-based metal surface treatment agent of this embodiment preferably further includes a silicon compound (C), which is at least one selected from the group consisting of water-dispersible silica and silane coupling agents. By including the silicon compound (C) in the water-based metal surface treatment agent, the above-mentioned chemical resistance and other properties can be improved. Water-dispersible silica exists as particles in water, and although its size is not limited, it can be in the range of 1 nm to 1 μm as a primary particle. As far as water-dispersible silica is concerned, although there is no special Not limited, but for example, silica sol, fumed silica dispersed in water, lithium silicate, No. 1 Na silicate, No. 2 Na silicate, No. 3 Na silica, and No. 4 silicon Water glass such as acid Na, silicate K, etc.

Specific examples of silica sol include Snowtex C, Snowtex O, Snowtex N, Snowtex NXS, Snowtex OS, Snowtex OUP, Snowtex OL, Snowtex PS-MO, Snowtex PS-S, Snowtex 20, Snowtex 30. Snowtex 40 (all the above are manufactured by Nissan Chemical Industry Company); Silica doll-20, Silica doll-30, Silica doll-40, Silica doll-30S, Silica doll-20AL, Silica doll-20A, Silica doll-20G, Silica doll-20GA, Silica doll-40G-80, Silica doll-20P, Silica doll-12S-4 (all of the above are manufactured by Nissan Chemical Industry Co.); AT-20, AT-30, AT-40, AT-50, AT-20A, AT-300 (all of the above are manufactured by Adeka), etc.

Specific examples of fumed silica include Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil MOX80, Aerosil MOX170 (all of the above are manufactured by Japan Aerosil Corporation); AERODISP VP W7622, AERODISP W7520N (all of the above are manufactured by degussa company); CAB-O-SPERSE 2017A, CAB-O-SPERSEGP32/12, CAB-O-SIL M5 (manufactured by CABOT CORPRATION), NIPGELAY200, NIPGELAY220, NIPGELAY420, NIPGELAY451, NIPGELAY460, NIPGELAY401, NIPGELAY601, NIPGELAY603, NIPGELAZ200, NIPGELAZ201, NIPGELAZ204, NIPGELAZ260, NIPGELAZ360, NIPGELAZ400, NIPGELAZ410, NIPGELAZ600, NIPGELBY200, NIPGEL BY400 (all of the above are manufactured by Japan Silica Industrial Co., Ltd.). Only one of these water-dispersible silicas may be used, or a plurality of them may be used in combination.

The silane coupling agent is not particularly limited, but preferably has a water-soluble functional group. The water-soluble functional group includes, for example, a first-stage amino group, a second-stage amino group, a third-stage amino group, a fourth-stage ammonium group or a salt thereof, a hydroxyl group, an ether group, an epoxy group, and a mercapto group.

Specific examples of the silane coupling agent include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-propyltrimethoxysilane, N-phenyl-3-propyltriethoxysilane, N-(2-aminoethyl)aminopropyltrimethoxysilane, N-(2-aminoethyl)aminopropylmethyldimethoxy Silane, N-(2-aminoethyl)aminopropyltriethoxysilane, N-(2-aminoethyl)aminopropylmethyl diethoxysilane, N-(2-aminoethyl)amine Propylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane Ethoxysilane, 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 Silane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl methyldimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-epoxy Propoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyl Methyl dimethoxy silane, methyl trimethoxy silane, dimethyl dimethoxy silane, methyl triethoxy silane, dimethyl diethoxy silane, vinyl triethoxy silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldiethoxysilane, hexamethyl Disilazane, γ-aniline propyl trimethoxy silane, γ-aniline propyl methyl dimethoxy silane, γ-aniline propyl triethoxy silane, γ-aniline propyl methyl diethoxy Silane, propyl isocyanate propyl trimethoxy silane, isocyanate propyl triethoxy silane, urea propyl triethoxy silane, bis(trimethoxysilyl) amino vinyl trimethoxy silane, ethylene Methyl dimethoxy silane, vinyl triethoxy silane, vinyl methyl diethoxy silane, octadecyl dimethyl [3-(trimethoxysilyl) propyl] chloride Ammonium, octadecyldimethyl[3-(methyldimethoxysilyl)propyl]ammonium chloride, octadecyldimethyl[3-(triethoxysilyl)propyl Base]ammonium chloride, octadecyldimethyl[3-(methyldiethoxysilyl)propyl]ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercapto Propylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, etc. Only one of these may be used, or plural numbers may be used in combination.

When the above-mentioned water-dispersible silica is used, it can also be used with water-dispersible silica with appropriate acid or basic groups added. As for the acid, for example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrofluoric acid, bromic acid; formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, malic acid, malonic acid, adipic acid , Methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid and other organic acids. The basic group includes, for example, ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, aluminum hydroxide, and the like. Only one of these components may be used, or a plurality of them may be used in combination.

In preferred carbamate-based resin (A) in the solid content mass (A _M) and the mass ratio of silicon compound (C), (C _M) of _{[(C M) / (A} M)] 1/100 Adjust the blending amount of the silicon compound (C) in the range of ~2. It is better to adjust to the range of 3/100 to 1.5, and the best to adjust to the range of 1/10 to 1.

The water-based metal surface treatment agent of this embodiment preferably further includes: a metal compound (D) selected from the group consisting of Ni, Mn, Co, Mo, V, W, Ce, Mg, Al, Zn, Fe, Bi, Nb At least one of the group consisting of Sn, Cr. By blending the metal compound (D) with the water-based metal surface treatment agent, it is possible to improve the above-mentioned chemical resistance and other properties.

The metal compound (D) is not particularly limited as long as it can be selected from the metals exemplified above, and carbonates, oxides, hydroxides, sulfates, nitrates, and phosphates of the above metals can be used. , Halides, hydrofluoric acid (salt), organic acid salts, organic complexes, organic boron compounds, organic titanium compounds, organic zirconium compounds, etc.

Specifically, nickel oxide, nickel hydroxide, nickel carbonate, nickel nitrate, nickel sulfate, nickel phosphate, nickel chloride, nickel acetone; permanganic acid, potassium permanganate, sodium permanganate, manganese dihydrogen phosphate , Manganese nitrate, manganese sulfate (II), manganese sulfate (III) or manganese sulfate (IV), manganese fluoride (II) or manganese fluoride (III), manganese carbonate, manganese acetate (II) or manganese acetate (III) , Ammonium manganese sulfate, manganese acetone acetone, manganese iodide, manganese oxide, manganese hydroxide; cobalt chloride, pentaamine cobalt chloride, hexaamino cobalt chloride, cobalt chromate, cobalt sulfate, cobalt ammonium sulfate, nitric acid Cobalt, cobalt aluminum oxide, cobalt hydroxide, cobalt phosphate; phosphovanadomolybdic acid, molybdenum oxide, molybdic acid, ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdate phosphate compounds (such as ammonium molybdate, sodium molybdate phosphate Etc.); bismuth vanadate, metavanadate, sodium metavanadate, potassium metavanadate, ammonium metavanadate, vanadium diacetone, vanadium diacetone, vanadium pentoxide, vanadium trioxide, vanadium fluoride, Vanadium phosphate, vanadium sulfate, vanadium oxalate, vanadium triisopropyl oxide, vanadium tributoxide, vanadium triethoxide oxide, vanadium triisopropoxide oxide, vanadium triethanolamine oxide, vanadium ammonium citrate oxide, tris Vanadium butoxy mercaptan, vanadium triisopropoxide, vanadium oxide, metavanadic acid, ammonium metavanadate, sodium metavanadate, vanadium trioxide, vanadium fluoride, vanadyl phosphate, vanadyl sulfate, oxalic acid Vanadium, vanadyl acetylacetonate, vanadyl acetylacetonate, vanadium tetrapropoxide, vanadium tetrabutoxide, vanadium tributoxystearate; Metatungstic acid, ammonium metatungstate, sodium metatungstate, p-tungstic acid, ammonium p-tungstate, sodium p-tungstate; cerium oxide, cerium acetate, cerium (III) or cerium nitrate (IV), 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, sulfuric acid Aluminum ammonium, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum iodide; zinc sulfate, zinc carbonate, zinc chloride, zinc iodide, zinc acetone, zinc oxide, zinc iodide, zinc dihydrogen phosphate , Zinc acetone, zinc dihydrogen phosphate; iron (II) or iron hydroxide (III), iron (II) or iron nitrate (III), iron (III) acetone, iron chloride (II) ) Or iron (III) chloride, iron (III) citrate, iron (II) or iron oxide (III), hexacyanoferric (II) or hexacyanoferric (III), hexacyanoferric acid ( II) Potassium hexacyanoferrate (III), ammonium ferric sulfate (II) or ammonium ferric sulfate (III), iron phosphate (II); bismuth oxide, bismuth sulfate, bismuth nitrate, bismuth hydroxide, bismuth citrate; Niobium (III) chloride, niobium chloride (IV) or niobium chloride (V), niobium fluoride (III), niobium fluoride (IV) or niobium fluoride (V), niobium (II), niobium oxide (IV) or niobium oxide (V); tin oxide (II) or tin oxide (IV), tin chloride (II) or tin chloride (IV), tin fluoride (II) or tin fluoride (IV), Tin (II) or tin nitrate (IV), tin hydroxide (II) or tin hydroxide (IV), tin sulfate (II) or tin sulfate (IV); chromium oxide (II), chromium oxide (III), Chromium (IV) oxide or chromium oxide (VI); chromium chloride (II), chromium chloride (III), chromium chloride (IV); chromium fluoride (II), chromium fluoride (III), chromium fluoride (IV), chromium fluoride (V) or chromium fluoride (VI); chromium hydroxide (II) or chromium hydroxide (III); Chromium(III) sulfate; chromium(III) acetate; chromium(III) nitrate; chromium(II) iodide or chromium(III) iodide; chromium(II) bromide or chromium(III) bromide, etc.

These can be anhydrous or hydrates. These compounds may be used alone or in combination of two or more kinds.

Regarding the blending amount of the aforementioned metal compound (D), it is preferable to set the ratio of the mass (A _M ) of the solid content of the urethane resin (A) to the mass (D _M ) of the compound (D) [( D _M )/(A _M )] is adjusted within the range of 1/100~1 to adjust the blending amount of compound (D). It is better to adjust to the range of 1/50~3/4, the best The system is adjusted to the range of 1/25~1/2.

The water-based metal surface treatment agent of this embodiment may further include: water-soluble or water-dispersible resin (E) (hereinafter, also simply referred to as "resin (E)"), which is selected from urethane resins (except The group consisting of phenol resin, silicone resin, epoxy resin, polyester resin, acrylic resin, polyolefin resin, and polyamide resin (other than the urethane resin (A) of this embodiment described above) At least one of them. By blending resin (E), softness or moderate elasticity can be imparted to the formed base treatment layer. As a result, good processing adhesion can be obtained.

The aforementioned acrylic resin can be obtained by radical polymerization, cationic polymerization, or anionic polymerization of acrylic acid, acrylic esters, or the like. The monomers used in these polymerization reactions are not particularly limited, but examples include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, and isobutyl acrylate. , S-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, acrylic acid 2 -Hydroxyethyl ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate Base ester, t-butyl methacrylate, n-hexyl methacrylate, methyl Cyclohexyl acrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, 2-hydroxyethyl methacrylate, etc. Further, an alkoxysilyl group can be introduced into the compound structure by appropriately combining vinyl trimethoxysilane and the like. These systems can be used alone, or two or more of them can be used in combination.

The urethane resin other than the aforementioned urethane resin (A) is not particularly limited as long as it has a cyclohexane ring structure. For example, it can be the following urethane resin: by a conventional method, hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI) ) And other aliphatic, alicyclic or aromatic diisocyanates are polymerized with polyols having amino groups introduced into the chain of polyester polyols, polyether polyols or polycarbonate polyols. Amino polyols, urethane resins obtained by chain extension; and cationic urethanes obtained by quaternizing part or all of the amino groups in the urethane resin using alkyl sulfuric acid, etc. Ester resin. The cationic functional group includes hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a hydroxyalkyl group, etc., as a substituent bonded to nitrogen, but it is not limited thereto. You may use 1 type of urethane resin individually or in combination of 2 or more types.

Although there is no particular limitation on the aforementioned epoxy resin, for example, the following glycidyl ethers or esters, etc., are used to further interact with amines to introduce water-soluble functional groups: Glycidyl ethers obtained by the reaction of phenol, bisphenol A, o-cresol, m-cresol, p-cresol, phthalic acid, isophthalic acid, terephthalic acid and epichlorohydrin Or esters; glycidyl ethers obtained by reacting aromatic compounds with hydroxyl groups such as novolac and polyparavinylphenol with epichlorohydrin; by ethylene glycol, polyethylene glycol, propylene glycol, Polypropylene glycol, glycerin, sorbitol and other aliphatic polyols are reacted with epichlorohydrin to obtain glycerin Oil ethers. Silanol groups, alkoxysilyl groups, phosphoric acid groups, and phosphoric acid ester groups can also be introduced into these epoxy resins. Only one of these components may be used, or plural components may be used in combination.

The aforementioned polyester resin is not particularly limited as long as it is an esterification product of a polybasic acid and a polyhydric alcohol.

As for the polybasic acid, although not particularly limited, for example, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic anhydride, etc. can be used Dibasic acid; Trimellitic anhydride, pyromellitic anhydride and other polybasic acids with more than trivalent.

As for the polyol, although not particularly limited, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 3-methylpentanediol, Aliphatic such as neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,4-hexanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, etc. Or alicyclic divalent alcohol; glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, dipentaerythritol, 1,1,2,2-tetra( 4-hydroxyphenyl) ethane and other trivalent or higher polyvalent alcohols. Only one of these components may be used, or plural components may be used in combination.

The phenol resin is not particularly limited as long as it is a polymer having a phenol structure such as novolak phenol resin, polyvinyl phenol, polybisphenol A, etc., but it can also be used without alkoxysilane in its structure. The base compound.

The aforementioned polyamide resin is not particularly limited as long as it is an esterification product of a polybasic acid and a polyamine.

As far as polybasic acids are concerned, although not particularly limited, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic anhydride, etc. can be used. Polybasic acid; Trimellitic anhydride, pyromellitic anhydride, and other trivalent or higher polybasic acids; as far as polyamines are concerned, although not particularly limited, ethylenediamine, propylenediamine, diethyltriamine, Hexanediamine, triethylenetetramine, tetraethylene Diamines such as pentamine, isophoronediamine, piperazine, diphenylmethanediamine, hydrazine, tetramethylethylenediamine, etc. Only one of these components may be used, or plural components may be used in combination.

The aforementioned silicone resin is not particularly limited as long as it is a dehydrated condensate of silanes. Silanes include, for example, chlorosilanes such as dimethyldichlorosilane, diethyldichlorosilane, and diphenyldichlorosilane; methyltrimethoxysilane, dimethyldiethoxysilane, etc. , N-propyl trimethoxysilane and other alkoxysilanes. Only one of these components may be used, or plural components may be used in combination.

The aforementioned polyolefin resin is not particularly limited as long as it is an olefin-based compound. As for olefins, for example, olefins such as ethylene, propylene, isoprene, and α-butene can be used and obtained by polymerization reactions such as radical polymerization and cationic polymerization. These polymers can also be copolymerized with acid anhydrides or carboxylic acids having double bonds. Only one of these components may be used, or plural components may be used in combination.

The aforementioned resin (E) is preferably cationic or nonionic, and its existing form in water is preferably a dissolved state or a dispersed state. Resin (E) can be dissolved or dispersed in water by self-solubility or self-dispersibility, or by cationic surfactants (such as tetraalkylammonium, etc.) and/or nonionic surfactants ( For example, the presence of alkyl phenyl ether, etc.) is dispersed.

The content of the resin to (E), preferably such that the urethane-based resin (A) in the solid content mass (A _M) and the mass ratio (E _M) resin (E) of [(E _M) /(A _M )] is adjusted within the range of 1/50 or more and 5 or less to adjust the content of resin (E), more preferably adjusted to within the range of 1/25 or more and 3 or less, and optimally adjusted to Within the range of 1/10 or more and 1 or less.

The water-based metal surface treatment agent of this embodiment preferably further includes: a crosslinking agent (F) selected from the group consisting of oxazoline resins, blocked isocyanate resins, carbodiimide resins, and nitrogen At least one of the group consisting of propidium-based resin and epoxy-based resin. By blending it into the base treatment layer that can form the above-mentioned aqueous solution or aqueous emulsion resin, the processing adhesion can be further improved.

Regarding the content of the crosslinking agent (F), it is preferable to set the ratio of the mass (A _M ) of the solid content of the urethane resin (A) to the mass (F _M ) of the crosslinking agent (F) [( F _M )/(A _M )] is adjusted within the range of 1/50 or more and 5 or less to adjust the content of the crosslinking agent (F), and more preferably within the range of 1/25 or more and 3 or less, The best system is adjusted to the range of 1/10 or more and 1 or less.

The water-based metal surface treatment agent of this embodiment can further include: surfactants, tackifiers, defoamers, and additives for Conductive substances to improve solderability, coloring pigments to improve design, extender pigments to adjust the thickness of the coating film.

This embodiment can be manufactured by mixing the urethane resin (A) and the compound (B) in an aqueous solvent, and if necessary, mixing the above-mentioned components other than the urethane resin (A) and the compound (B) A water-based metal surface treatment agent. The aqueous solvent is not particularly limited as long as it contains 90% by mass or more of water based on the mass of the entire solvent. Examples of solvents other than water contained in the aqueous solvent include alcohol solvents such as methanol, ethanol, and butanol; ketones such as acetone; ethylene glycol monoethyl ether; ethylene glycol mono-n-butyl ether Etc glycol monoalkyl ether. Moreover, although these solvents other than water may mix 1 type, you may mix 2 or more types in combination.

The pH value in the water-based metal surface treatment agent of this embodiment is preferably in the range of 2.5 to 12.0, more preferably in the range of 4.0 to 7.0. When pH adjustment is necessary, it can be adjusted by alkaline components such as ammonia, dimethylamine, or triethylamine, or can be adjusted by acidic components such as acetic acid and phosphoric acid.

Regarding the total solid content concentration in the water-based metal surface treatment agent of this embodiment, although it is not particularly limited as long as it can achieve the effect of the invention, it is from the surface of the water-based metal From the viewpoint of the stability of the physical agent, the upper limit thereof is preferably 40% by mass or less. The total solid content concentration is preferably 0.1-40% by mass, more preferably 1-30% by mass, and particularly preferably 5-25% by mass.

Next, the method of forming the base treatment layer and the method of manufacturing the metal material having the base treatment layer of the present embodiment will be described.

The water-based metal surface treatment agent of this embodiment as described above is brought into contact with the surface of the metal material by means of coating or the like to form the base treatment layer of this embodiment. After that, it can be dried without washing with water.

As for the aforementioned metal materials, cold-rolled steel sheets, hot-rolled steel sheets, hot-dip galvanized steel sheets, electro-galvanized steel sheets, melt-alloyed galvanized steel sheets, aluminum-plated steel sheets, aluminum-zinc alloyed steel sheets, and galvanized-aluminum steel sheets can be used. Conventional metal materials such as magnesium alloy steel plate, stainless steel plate, aluminum plate, copper plate, titanium plate, magnesium plate, nickel plated plate, tin plated plate, etc.

The aforementioned metal material is preferably subjected to pretreatment before the substrate treatment by the water-based metal surface treatment agent of this embodiment.

The pre-treatment method includes a degreasing step, a hot water washing step, a solvent washing step, etc., and these steps are used to remove oil and contamination attached to the metal material, using an alkali degreasing agent or an acid degreasing agent Wash. Furthermore, if necessary, after these steps, a surface conditioning step using a conventional surface conditioning agent and/or a chemical conversion treatment step using a conventional chemical conversion treatment agent may be performed. In addition, the degreasing step, the solvent washing step, the surface adjustment step, the chemical conversion treatment step, etc., may be washed with water after the step is completed.

The substrate treatment via the water-based metal surface treatment agent of this embodiment is performed by applying the water-based metal surface treatment agent to contact. After that, it may be dried without washing with water, or it may be dried after washing with water.

The contact method of the water-based metal surface treatment agent of this embodiment is not particularly limited, and examples include roll coating, curtain coating, air spraying, airless spraying, dipping, bar coating, Common methods such as brush coating method. The temperature of the water-based metal surface treatment agent is not particularly limited, but because the solvent of the water-based metal surface treatment agent of this embodiment is mainly water, the temperature of the water-based metal surface treatment agent is preferably 0-60 ℃ Within the range, more preferably within the range of 5-40°C.

When the water-based metal surface treatment agent of the present embodiment is brought into contact and then dried, drying may be performed, for example, by air drying, air blowing, or the like, but heating using a stove or the like may be performed for drying. Regarding the heating and drying temperature, it is preferably in the range of 50 to 250°C, and more preferably in the range of 60 to 220°C. In addition, the temperature of the above-mentioned heating and drying means the temperature of the metal material itself.

In terms of the amount of adhesion that can form the base treatment layer, the mass of elements such as boron, silicon, titanium, and zirconium from the fluorine-containing compound in the dried film is converted into mass (when the dried film contains two or more elements, it is the total amount ), with usually in the range of 0.01 ~ 1g / m ^2, preferably in the range-based 0.02 ~ 0.5g / m ^2, and more preferably in the range-based 0.03 ~ 0.25g / m ² of. By setting the adhesion amount within this range, the above-mentioned corrosion resistance and processing adhesion can be further improved. In addition, the above-mentioned element-converted mass in the film after drying can be obtained by measuring the mass of each element in the film after drying using a fluorescent X-ray analyzer.

In addition, although the base treatment layer formed as described above is usually used as a base treatment layer for a metal material with a coating film, it can also be used as a base for high-functional coating materials because of its excellent adhesion. It is used as the upper layer of the above-mentioned high-functional coating material, and one to three coating layers that can impart fingerprint resistance, lubricity, etc., are used. Moreover, it can also be used as a base for conductive steel sheets or a base for laminated steel sheets.

Next, the manufacturing method of the metal material (hereinafter, also referred to as the pre-coated metal material) having the base treatment layer of the present embodiment will be described.

The manufacturing method of the pre-coated metal material of this embodiment is a manufacturing method of the pre-coated metal material having the following steps: a substrate treatment step, which is to contact the water-based metal surface treatment agent of this embodiment with the surface of the metal material to form a substrate Treatment layer; coating step, which is applied to the aforementioned substrate treatment layer and coating paint.

The base treatment step in the method of manufacturing the precoated metal material of the present embodiment can implement the same steps as in the method of forming the base treatment layer of the present embodiment.

The coating step is as long as the coating film can be formed on the base treatment layer, for example, the following method: after coating a primer on the base treatment layer and drying, then coating the top coat (paint); A coating method that does not use a primer but a topcoat directly; a method of attaching a laminated film, etc. For example, a general coating method can be applied to pre-coated metal materials.

Regarding the above-mentioned primer, although there is no particular limitation, it is preferable to use a chromium-free primer. Chromium-free primer refers to the thing that is not blended with chromate-based anti-corrosion pigments. As far as chromium-free primers are concerned, they usually contain resins and necessary coloring pigments or anti-rust pigments. As far as the resin is concerned, it can be in any form such as water-based, solvent-based, and powder-based systems. As far as the type of resin is concerned, although it is not particularly limited as long as it is a conventional resin, it can be used alone, for example, polyacrylic resin, polyolefin resin, polyurethane resin, epoxy resin, and polyester resin. Resins, polybutyraldehyde-based resins, melamine-based resins, fluorine-based resins, and other resins, or a combination of two or more of them can be used.

In addition, a chromium primer blended with a chromium pigment can also be used for the above-mentioned resin. Coloring pigments can also be blended as necessary when using chrome primers.

As for coloring pigments, inorganic pigments such as titanium white, zinc oxide, zirconium oxide, calcium carbonate, barium sulfate, alumina, kaolin, carbon black, iron oxide, etc. can be used; or pigment yellow, pyrazolone orange, azo series Conventional coloring pigments such as organic pigments such as pigments. As far as anti-rust pigments are concerned, conventional ones can be used, for example, phosphoric acid-based anti-rust pigments such as zinc phosphate, iron phosphate, and aluminum phosphate; and molybdic acid-based anti-rust pigments such as calcium molybdate, aluminum molybdate, and barium molybdate. ;Vanadium-based anti-rust pigments such as vanadium oxide; water-dispersible silicon dioxide, fumed silicon dioxide and other particulate silicon dioxide can also be used. In addition, as chromate-based anti-rust pigments, strontium chromate, zinc chromate, calcium chromate, potassium chromate, barium chromate, etc. can also be used. In addition, additives such as defoamers, dispersion aids, and diluents for lowering the viscosity of the paint can also be appropriately blended.

The coating method of the primer is not particularly limited, and a dipping method, spraying method, roll coating method, air spraying method, airless spraying method, etc. can be used. The thickness of the coating film formed by the primer, as a dry film thickness, is preferably in the range of 1 to 30 μm, more preferably in the range of 2 to 20 μm.

The sintering (drying) conditions of the primer are not particularly limited, but the sintering (drying) can be performed at a temperature in the range of 130 to 250°C for 10 seconds to 5 minutes. In addition, after the top coat is applied, a temporary heat drying treatment may be performed.

The topcoat (paint) used in the manufacturing method of the precoated metal material of this embodiment is not particularly limited, and a conventional topcoat for coating can be used. The top coat contains resin, and if necessary, it also contains coloring pigments or anti-rust pigments.

Regarding resins, coloring pigments, anti-corrosion pigments, and other additives, the same ones as those used in the primer can be used.

The coating method or sintering (drying) conditions of the top coat can be the same as the case of the primer. The thickness of the coating film formed by the topcoat, as a dry film thickness, is preferably in the range of 3-50 μm, more preferably in the range of 5-40 μm.

According to the method of manufacturing the precoated metal material of the present embodiment described above, the precoated metal material of the present embodiment obtained is excellent in processing adhesion, chemical resistance, and corrosion resistance.

[Example]

Hereinafter, although examples and comparative examples of the present invention are cited to describe the present invention more specifically, the present invention is not limited to these examples only.

1. Preparation of urethane resin

(Synthesis example 1)

Bisphenol A-polyoxyethylene 2 mol adduct (Newpol BPE-20T, manufactured by Sanyo Kasei Kogyo Co., Ltd.) (b1 described later) 63 g; polyethylene glycol (PEG2000, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) (described later c1) 67g; N-methyldiethanolamine (amino alcohol MDA, manufactured by Nippon Emulsifier Co., Ltd.) (e1 described later) 30 g; Diethylene glycol (diethylene glycol, manufactured by Nippon Shokubai Co., Ltd.) (d1 described later) 30 g; and 230 g of isophorone diisocyanate (Desmodule I, manufactured by Bayer) (a1 described later) was added to 400 g of methyl ethyl ketone and fully dissolved. After reacting this mixed solution at 80°C for about 5 hours, it was confirmed that the isocyanate group was contained at 3% by mass or less, and then 25 g of dimethyl sulfate (ionizing agent g1 described later) was added. In addition, the isocyanate group content rate is based on JIS K7301: 1995. 2 g of the reaction solution is dissolved in dimethylformamide, and 10 ml of n-dibutylamine-toluene solution is added, and bromophenol blue is used as an indicator , Titrate with 0.5mol/L hydrochloric acid solution, and calculate with the following formula.

(In the formula, A represents the volume (mass) of isocyanate used to prepare a specific amount of the reaction solution and the volume of hydrochloric acid required for titration; B represents the volume of hydrochloric acid required for the titration of the reaction solution Volume; f represents "1", N represents the molar concentration of the hydrochloric acid standard solution, and S represents the mass of the reaction solution)

Next, 1000 g of deionized water was added to prepare a polyurethane emulsion (Emulsion). By the vacuum distillation method, methyl ethyl ketone was removed from the obtained polyurethane emulsion, and the urethane resin of Synthesis Example 1 with a urethane resin concentration of 25% by mass was prepared.

As shown in Table 1, the urethane resins of Synthesis Examples 2 to 8 and 12 to 19 were prepared in the same manner as Synthesis Example 1 using various components and amounts (% by mass).

Except that 25 g of ionizing agent g2 (85% phosphoric acid) was used instead of 25 g of ionizing agent g1 (dimethyl sulfate), the urethane resin of Synthesis Example 9 was prepared by the same manufacturing method as Synthesis Example 1.

The urethane resin of Synthesis Example 10 was prepared by the same manufacturing method as Synthesis Example 1 except that 10 g of ionizing agent g3 (formic acid) was used instead of 25 g of ionizing agent g1 (dimethyl sulfate).

Except that 19 g of ionizing agent g4 (methanesulfonic acid) was used instead of 25 g of ionizing agent g1 (dimethyl sulfate), the same production method as in Synthesis Example 1 was used to prepare the urethane resin of Synthesis Example 11.

The components described in Table 1 are as follows. In addition, the amount (% by mass) of each component described in Table 1 is calculated based on the total amount of the components (a) to (e), and when (f) is used, it is also combined into the aforementioned total amount. In addition, all the urethane prepolymers obtained by each synthesis example contained isocyanate groups.

<Polyisocyanate (a; part of the following is a polyisocyanate having a cyclohexane structure)>

a1: Isophorone diisocyanate (Desmodule I, manufactured by Bayer)

a2: Dicyclohexylmethane 4,4'-diisocyanate (DesmoduleW, manufactured by Bayer)

a3: Toluene diisocyanate (Cosmonate T80, manufactured by Mitsui Chemicals Co., Ltd.)

a4: Hexamethylene diisocyanate (50M-HDI, manufactured by Asahi Kasei Corporation)

<Polyol (b)>

b1: Bisphenol A-polyoxyethylene 2 mol adduct (Newpol BPE-20T, manufactured by Sanyo Kasei Kogyo Co., Ltd.)

b2: Aromatic dibasic acid polyester polyol (Teslac 2508-70, manufactured by Hitachi Chemical Co., Ltd.)

b3: Polycarbonate diol (Nipporan 981, manufactured by Tosoh Corporation)

<Diol (c; the following part is a diol with a weight average molecular weight greater than 600 without benzene ring and nitrogen atom)>

c1: Polyethylene glycol (PEG2000, Mw2000, manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.)

c2: Polyester polyol (Nipporan4040, Mw2000, manufactured by Tosoh Corporation)

c3: Polybutylene glycol (PTMG2000, Mw2000, manufactured by Mitsubishi Chemical Corporation)

c4: Polyester glycol (K-FLEX XM360, Mw520, manufactured by KING)

<Diol (d; the following part is a diol with a weight average molecular weight of 500 or less without benzene ring and nitrogen atom)>

d1: Diethylene glycol (Diethylene glycol, Mw106, manufactured by Nippon Shokubai Co., Ltd.)

d2: 1,5-pentanediol (1,5-pentanediol, Mw104, manufactured by Ube Industries Co., Ltd.)

d3: 1,6-hexanediol (1,6-hexanediol, Mw106, manufactured by Ube Kosan Co., Ltd.)

d4: Polyester polyol (Placcel 205, Mw 530, manufactured by Daicel Chemical Co., Ltd.)

<Tier 3 Amine (e)>

e1: N-methyldiethanolamine (amino alcohol MDA, manufactured by Japan Emulsifier Company)

<Others (polyols of more than triols without benzene ring and nitrogen atom) (f)>

f1: Trimethylolpropane (TMP, manufactured by Perstorp)

<Ionizing Agent>

Ionizing agent g1: Dimethyl sulfate (manufactured by Tsujimoto Chemical Co., Ltd.)

Ionizing agent g2: 85% phosphoric acid (manufactured by Nippon Chemical Industry Co., Ltd.)

Ionizing agent g3: formic acid (manufactured by Junsei Chemical Co., Ltd.)

Ionizing agent g4: Methanesulfonic acid (manufactured by Tosoh Corporation)

2. Preparation of water-based metal surface treatment agent

As shown in Table 2, the specific amounts of each component, urethane resin (A), compound (B), silicon compound (C), metal compound (D), resin (E), crosslinking agent (F) The water-based metal surface treatment agents of Examples 1 to 50 and Comparative Examples 1 to 11 were prepared by adding to water in this order. The components described in Table 2 are as follows.

Compound (B)

(B1) Hexafluorotitanic acid (manufactured by Morita Chemical Industry Co., Ltd.)

(B2) Hexafluorosilicic acid (manufactured by Morita Chemical Industry Co., Ltd.)

(B3) Hexafluorozirconic acid (manufactured by Morita Chemical Industry Co., Ltd.)

(B4) Tetrafluoroboric acid (manufactured by Wako Pure Chemical Industries, Ltd.)

Silicon compound (C)

(C1) 3-Aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

(C2) Colloidal silica (manufactured by Nissan Chemical Co.)

Metal compound (D)

(D1) Magnesium oxide (manufactured by Kyowa Chemical Industry Co., Ltd.)

(D2) Manganese acetate (II) tetrahydrate (manufactured by Nacalai Tesque)

(D3) Vanadium acetone (manufactured by Xinxing Chemical Industry Co., Ltd.)

The mass ratio of D1 to D3 used in Example 28 is D1:D3=1:1.

Resin (E)

(E1) Acrylic resin (A-655, manufactured by Kusumoto Chemical Co., Ltd.)

(E2) Urethane resin (Super flex 650, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.)

(E3) Phenol resin (manufactured by IG-1002 DIC)

Crosslinking agent (F)

(F1) Carbodiimide resin (Carbodilite SV-02, manufactured by Nisshinbo Chemical Co., Ltd.)

(F2) Blocked isocyanate resin (TRIXENE AQUA BI 220, manufactured by Baxenden Chemicals Limited)

3. Production of pre-coated steel sheet

3.1 Test materials

(i) Hot-dip galvanized steel sheet (the following symbol: GI) thickness 0.45mm

(ii) 55% aluminum-zinc alloy plated steel sheet (the following symbol: GL) thickness 0.35mm

3.2 Pre-processing

The various test materials were immersed in an alkali degreasing agent (mixing fine detergent E6406 (manufactured by Japan Parker Seiki Co., Ltd.) and water to make the concentration a 20g/L solution) at 60°C for 10 seconds, and Rinse with pure water and dry. For GI materials, after alkali degreasing, they are immersed in a surface conditioner (PL-4015 (manufactured by Japan Parker Seiki Co., Ltd.) and water are mixed, and the concentration becomes a 100g/L solution) at 50°C, and Rinse with pure water and dry. In addition, the immersion time for immersion in the surface conditioner is the time for adjusting the Ni adhesion amount to 5 mg/m ² .

3.3 Substrate treatment

Using a bar coater, the water-based metal surface treatment agents of the various examples or comparative examples were applied to the surface (single side) of the test material after the pretreatment, without washing, and by heating at 80°C (PMT: ^{Drying at the highest temperature of the test material during drying), to form a 100mg/m 2} base treatment layer based on the mass of elements such as boron, silicon, titanium, and zirconium in the dried film.

3.4 Painting

On the film made in 3.3, apply a primer with epoxy resin as the bottom layer, and dry and sinter at 210°C to form a primer layer with a dry film thickness of 5μm.

Then, coat the topcoat paint with polyester resin as the bottom layer on the primer layer, and dry and sinter at 220°C to form a topcoat layer with a dry film thickness of 15μm to obtain various pre-coated steel sheets ( No.1~64).

4. Evaluation test

The following processing adhesion test, corrosion resistance test, and chemical resistance test were performed on the surface of various pre-coated steel sheets with a primer layer, a primer layer, and a topcoat layer.

The results are shown in Table 3.

4.1.1 One-time processing adhesion test

According to the test method of JIS-G3312:2012, various pre-coated steel plates are bent to 180 degrees. After the cellophane tape was attached to the bent portion, the cellophane tape was peeled off, the peeling state of the coating film was observed with the naked eye, and the processing adhesion was evaluated based on the following evaluation criteria. In addition, this test was performed at a room temperature of 20°C. In addition, in this evaluation, B or higher is considered a pass.

<Evaluation criteria>

A: No peeling

B: The peeling area is less than 10%

C: The peeling area is more than 10% and less than 25%

D: The peeling area is more than 25% and less than 50%

E: The peeling area is more than 50%

4.1.2 Adhesion test for secondary processing

After immersing various pre-coated steel sheets in boiling water for 2 hours, they were dried. After drying, it was left for one day, and the various pre-coated steel sheets were bent to 180 degrees in the same way as the first processing adhesion test. After the cellophane tape was applied to the bent portion, the cellophane tape was peeled off, and the processing adhesion was evaluated. In addition, in this evaluation, B or higher is considered a pass.

<Evaluation criteria>

AA: No peeling

A: The peeling area is less than 10%

B: The peeling area is more than 10% and less than 25%

C: The peeling area is more than 25% and less than 50%

D: The peeling area is more than 50%

4.2 Acid resistance test

Various pre-coated steel sheets were immersed in a 5% sulfuric acid aqueous solution and immersed at room temperature for 72 hours, then washed with water, and then dried. After drying, the number and density of blisters were visually confirmed, and after judging according to the judgment criteria specified in ASTM D714-56, the acid resistance was evaluated based on the following evaluation criteria. In addition, in this evaluation, B or higher is considered a pass.

<Evaluation criteria>

A: Its department is 10

B: Its department is 9F

C: Its line is 8F or 9M

D: It is 7F or 8M

E: It is 6F or 7M or 9MD

4.3 Alkali resistance test

Various pre-coated steel sheets were immersed in a 5% sodium hydroxide aqueous solution and immersed at room temperature (20°C) for 72 hours, washed with water, and then dried. After drying, the number and density of blisters were visually confirmed, and after judging based on the same judgment criteria as the acid resistance test, the alkali resistance was evaluated based on the following evaluation criteria. In addition, in this evaluation, B or higher is considered a pass.

4.4 Corrosion resistance test

On the coating surface of various pre-coated steel sheets, use a spatula to cut x-shaped cuts that reach the metal base layer. According to JIS H8502: 1999, spray neutral salt water for 360 hours. After that, the swelling width of the coating film (the maximum swelling width on one side) from the cut of the intersection (x) was measured. In addition, the expansion width (maximum expansion width) of the coating film from the end of the pre-coated steel sheet was also measured. In addition, in this evaluation, B or higher is considered a pass.

<Evaluation Criteria-x Notch>

A: less than 1mm

B: 1mm or more and less than 3mm

C: 3mm or more and less than 5mm

D: 5mm or more and less than 8mm

E: 8mm or more

<Evaluation Criteria-Ends>

A: Less than 2mm

B: 2mm or more and less than 4mm

C: 4mm or more and less than 6mm

D: 6mm or more and less than 8mm

E: 8mm or more

Claims (9)

A water-based metal surface treatment agent, which is characterized by comprising: more than 10g/L of urethane resin (A); fluorine-containing compound (B), which is also selected from the group consisting of boron, silicon, titanium and zirconium At least one element in the group; wherein, the aforementioned urethane resin (A) includes: a structural unit derived from a polyisocyanate having a cyclohexane ring structure represented by the following formula (1); from the following formula (2) The structural unit of the polyol represented by the following formula (3) is derived from the structural unit of a diol with a weight average molecular weight greater than 600; the structural unit derived from the following formula (4) is a diol with a weight average molecular weight of less than 500 The structural unit of; From the structural unit of the tertiary amine compound represented by the following formula (5) and/or its salt; Also, the formula (1): O=C=NR ¹ -N=C=O (wherein, 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 [化1]

(And R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group) R ⁴ is a single bond; an alkylene group;

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

,

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

(The bonding position on the right side is bonded to R ¹⁰ ) -R ¹³ -CO- (the bonding position on the right side is bonded to R ¹⁰ ) (where R ¹² is a linear or branched alkylene group; R ¹³ series -R ¹⁸ -O-or

, And the bonding position on the right side of these compounds is bonded to CO; In addition, R ¹⁸ is a linear or branched alkylene group, x is an integer from 1 to 5, and l is an integer from 2 to 4) R ¹⁰ [化5]

R ¹¹ series [化6] single bond,

,

,

, -CO-R ^13- (and for the above compounds except for single bonds, the bonding position on the left is all bonded to R ¹⁰ ) (where R ¹² is a linear or branched alkylene group; R ¹³ is- R ¹⁸ -O-or

(The bonding position on the right side of these compounds is bonded to CO) In addition, R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group, a halogenated alkyl group or a phenyl group, and 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, and l is an integer from 2 to 4) R ¹⁴ is a hydrogen atom, an alkyl group, a phenyl group,

,

(Wherein R ¹⁸ is a linear or branched alkylene group, and l is an integer from 2 to 4)) Formula (3): HO-R ¹⁹ -H (3) (R ^{19 in} formula (3) is [化] 8]

(The bonding position on the left side of these compounds is bonded to OH) (wherein R ²⁰ is independently an alkylene group,

Or adamantane ring, an alkylene group and R ²¹ system, m is an integer of 2 to 4, n is an integer)) of formula ^{(4): HO-R 22} -OH ( Formula (4) R ²² lines [Formula 9] Alkylene,

, Adamantane ring,

,

(Where y is 2 or 3, and z is an integer from 1 to 6)) Formula (5): [化10]

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

R ²⁴ is hydroxyalkyl, aminoalkyl or N-alkylaminoalkyl). The water-based metal surface treatment agent according to claim 1, wherein the fluorine-containing compound (B) contains a metal acid selected from the group consisting of tetrafluoroboric acid, hexafluorotitanic acid, hexafluorozirconic acid, hexafluorosilicic acid, and the like At least one of the group consisting of salt or inorganic acid salt. The water-based metal surface treatment agent according to claim 1 or 2, further comprising: a silicon compound (C), which is at least one selected from the group consisting of water-dispersible silica and silane coupling agents. The water-based metal surface treatment agent according to claim 1 or 2, further comprising: a metal compound (D) selected from the group consisting of Ni, Mn, Co, Mo, V, W, Ce, Mg, Al, Zn, Fe, At least one of the group consisting of Bi, Nb, Sn, and Cr. The water-based metal surface treatment agent according to claim 1 or 2, further comprising: a water-soluble or water-dispersible resin (E) selected from the group consisting of urethane resins and phenol resins other than the aforementioned urethane resins , At least one of the group consisting of silicone resin, epoxy resin, polyester resin, acrylic resin, polyolefin resin and polyamide resin. The water-based metal surface treatment agent according to claim 1 or 2, further comprising: a crosslinking agent (F) selected from the group consisting of oxazoline resins, blocked isocyanate resins, carbodiimide resins, and aziridine At least one of the group consisting of pyridine resin and epoxy resin. A method for manufacturing a metal material, which is a method for manufacturing a metal material with a substrate treatment layer, comprising: a substrate treatment step, which uses the water-based metal surface treatment agent according to any one of claims 1 to 6 and the metal material The surface contact, and the formation of the substrate treatment layer. The method for manufacturing a metal material according to claim 7, further comprising: a coating step of coating the metal material after the aforementioned substrate treatment step with paint. A metal material, characterized by comprising: a substrate treatment layer; a coating film formed on the substrate treatment layer; wherein the substrate treatment layer is formed by the water-based metal surface according to any one of claims 1 to 6 Treatment agent, the formed layer.