JP6986954B2 - Anionic epoxy resin or a salt thereof, an emulsion, a surface treatment agent, a material having a film, and a method for producing the same. - Google Patents

Description

The present invention relates to an anionic epoxy resin or a salt thereof and an emulsion containing the same, a surface treatment agent containing the resin or a salt thereof or the emulsion, and a material having a film formed by the surface treatment agent and a method for producing the same. ..

Conventionally, a technique of forming a film on the surface of a metal material by using a treatment agent containing an anionic epoxy resin has been proposed. For example, Patent Document 1 discloses a technique relating to a dispersion liquid containing a predetermined anionic epoxy resin used for forming a film.

Japanese Patent Publication No. 2005-537338

In recent years, the film is required to have performance such as insulating property and edge covering property. Therefore, the present invention relates to an anionic epoxy resin or a salt thereof for forming a film having excellent insulating properties and edge covering properties and an emulsion containing the same, a surface treatment agent containing the resin or a salt thereof or the emulsion, and a surface treatment agent thereof. It is an object of the present invention to provide a material having a film formed by a surface treatment agent and a method for producing the same.

［式（１）中、Ｒ１は式（１ａ）：

、式（２ａ）：

又は下式（３ａ）：

で表される構造である。式（１ａ）中、Ｒ２は、単結合、Ｃ（ＣＨ_３）_２、ＣＨ（ＣＨ_３）、ＣＨ_２、Ｓ、Ｏ又はＳＯ_２である。式（２ａ）中、Ｒ３〜Ｒ６は各々独立して、水素原子、メチル基、アルキルカルボニル基、アルコキシ基又はアルコキシカルボニル基を表す。］で表される構造単位と、
式（２）：

［式（２）中、Ｒ７は式（４ａ）：

又は式（５ａ）：

で表される構造である。式（５ａ）中、Ｒ１７は水素原子又はアルキル基である。］
及び式（３）：

［式（３）中、Ｒ８は式（６ａ）：

又は式（７ａ）：

で表される構造である。］で表される構造単位のうち少なくとも一つと、
式（４）：

［式（４）中、Ｒ９は式（８ａ）：

又は式（９ａ）：

で表される構造である。式（８ａ）中、Ｒ１１〜Ｒ１３は各々独立して、水素原子、メチル基又はアルコキシ基を表す。］及び式（５）：

［式（５）中、Ｒ１０は式（１０ａ）：

又は式（１１ａ）：

で表される構造である。式（１０ａ）中、Ｒ１４及びＲ１５は各々独立して、水素原子、メチル基又はアルコキシ基を表す。］で表される構造単位のうち少なくとも一つと、
を含む、アニオン性エポキシ樹脂又はその塩；
［２］式（６）：

［式（６）中、Ｒ１６は炭素数１〜２０のアルキレン基である。前記アルキレン基はアルキル基、アルケニル基、アルカジエニル基又はメチレン基を有していてもよい。前記アルキレン基の炭素数が２〜２０である場合、隣り合う炭素原子を介して環を構成してもよい。前記環はアルキル基及びアルケニル基から選択される１又は２種以上の置換基を１又は２以上有していてもよい。］で表される構造単位を含む、上記［１］に記載のアニオン性エポキシ樹脂又はその塩；
［３］上記［１］又は［２］に記載のアニオン性エポキシ樹脂又はその塩を含む、エマルション；
［４］ブロック化ポリイソシアネート硬化剤を含む、上記［３］に記載のエマルション；
［５］上記［１］若しくは［２］に記載のアニオン性エポキシ樹脂若しくはその塩、又は上記［３］若しくは［４］に記載のエマルションを含む、表面処理剤；
［６］上記［５］に記載の表面処理剤を、表面に金属を有する材料の表面又は表面上に接触させる工程と、接触させた前記表面処理剤を焼き付ける工程とを含む、皮膜を有する材料の製造方法；
［７］表面に金属を有する材料の表面又は表面上に、上記［１］又は［２］に記載のアニオン性エポキシ樹脂又はその塩を含む皮膜を有する材料；
などである。 The present invention that achieves the above object
[1] Equation (1):

[In the formula (1), R1 is the formula (1a):

, Equation (2a):

Or the following formula (3a):

It is a structure represented by. In formula (1a), R2 is a single bond, C (CH ₃ ) ₂ , CH (CH ₃ ), CH ₂ , S, O or SO ₂ . In formula (2a), R3 to R6 each independently represent a hydrogen atom, a methyl group, an alkylcarbonyl group, an alkoxy group or an alkoxycarbonyl group. ], And the structural unit represented by
Equation (2):

[In the formula (2), R7 is the formula (4a):

Or formula (5a):

It is a structure represented by. In formula (5a), R17 is a hydrogen atom or an alkyl group. ]
And equation (3):

[In the formula (3), R8 is the formula (6a):

Or formula (7a):

It is a structure represented by. ] At least one of the structural units represented by
Equation (4):

[In the formula (4), R9 is the formula (8a):

Or formula (9a):

It is a structure represented by. In formula (8a), R11 to R13 each independently represent a hydrogen atom, a methyl group or an alkoxy group. ] And formula (5):

[In the formula (5), R10 is the formula (10a):

Or formula (11a):

It is a structure represented by. In formula (10a), R14 and R15 each independently represent a hydrogen atom, a methyl group or an alkoxy group. ] At least one of the structural units represented by
Anionic epoxy resin or a salt thereof, including;
[2] Equation (6):

[In formula (6), R16 is an alkylene group having 1 to 20 carbon atoms. The alkylene group may have an alkyl group, an alkenyl group, an alkazienyl group or a methylene group. When the alkylene group has 2 to 20 carbon atoms, a ring may be formed via adjacent carbon atoms. The ring may have one or more substituents selected from an alkyl group and an alkenyl group. ], The anionic epoxy resin or salt thereof according to the above [1], which comprises the structural unit represented by.
[3] An emulsion containing the anionic epoxy resin or a salt thereof according to the above [1] or [2];
[4] The emulsion according to the above [3], which contains a blocked polyisocyanate curing agent;
[5] A surface treatment agent containing the anionic epoxy resin or salt thereof according to the above [1] or [2], or the emulsion according to the above [3] or [4];
[6] A material having a film, which comprises a step of bringing the surface treatment agent according to the above [5] into contact with the surface or a surface of a material having a metal on the surface, and a step of baking the contacted surface treatment agent. Manufacturing method;
[7] A material having a film containing the anionic epoxy resin or a salt thereof according to the above [1] or [2] on the surface or surface of a material having a metal on the surface;
And so on.

According to the present invention, an anionic epoxy resin or a salt thereof for forming a film having excellent insulating properties and edge covering properties and an emulsion containing the same, a surface treatment agent containing the resin or a salt thereof or the emulsion, and a surface treatment agent thereof. It is possible to provide a material having a film formed by a surface treatment agent and a method for producing the same.

Hereinafter, the present invention will be described in detail with reference to specific embodiments.
<Anionic epoxy resin or its salt>
The anionic epoxy resin (hereinafter, may be simply referred to as “resin”) according to the present embodiment has a structural unit represented by the following formula (1) and the following formulas (2) and (3). It includes at least one of the structural units represented and at least one of the structural units represented by the following equations (4) and (5).

As a combination of structural units in the resin, a combination of each structural unit of the formula (1), the formula (2) and the formula (4); a combination of the structural units of the formula (1), the formula (2) and the formula (5). ; Combination of each structural unit of equation (1), equation (3) and equation (4); Combination of each structural unit of equation (1), equation (3) and equation (5); equation (1), equation ( 2), combination of each structural unit of equation (3) and equation (4); combination of each structural unit of equation (1), equation (2), equation (3) and equation (5); equation (1), Combination of each structural unit of equation (2), equation (4) and equation (5); combination of each structural unit of equation (1), equation (3), equation (4) and equation (5); equation (1) ), The combination of each structural unit of the formula (2), the formula (3), the formula (4) and the formula (5); and the like.

Ｒ１が式（１ａ）である場合、式（１ａ）中、Ｒ２は、単結合、Ｃ（ＣＨ_３）_２、ＣＨ（ＣＨ_３）、ＣＨ_２、Ｓ、Ｏ又はＳＯ_２である。Ｒ１が式（２ａ）である場合、式（２ａ）中、Ｒ３〜Ｒ６は各々独立して、水素原子、メチル基、アルキルカルボニル基、アルコキシ基又はアルコキシカルボニル基を表す。なお、式（１）の構造単位として、これらの構造単位のうち、１の構造単位が樹脂に含まれていてもよいが、２以上の構造単位が含まれていてもよい。 In the formula (1), R1 has a structure represented by the following formula (1a), the lower formula (2a), or the lower formula (3a).

When R1 is of formula (1a), in formula (1a), R2 is a single bond, C (CH ₃ ) ₂ , CH (CH ₃ ), CH ₂ , S, O or SO ₂ . When R1 is of the formula (2a), in the formula (2a), R3 to R6 independently represent a hydrogen atom, a methyl group, an alkylcarbonyl group, an alkoxy group or an alkoxycarbonyl group. As the structural unit of the formula (1), one of these structural units may be contained in the resin, but two or more structural units may be contained.

Ｒ７が式（５ａ）である場合、式（５ａ）中、Ｒ１７は水素原子又はアルキル基である。なお、式（２）の構造単位として、これらの構造単位のうち、１の構造単位が樹脂に含まれていてもよいが、両方の構造単位が含まれていてもよい。 In the formula (2), R7 has a structure represented by the following formula (4a) or the following formula (5a).

When R7 is of the formula (5a), in the formula (5a), R17 is a hydrogen atom or an alkyl group. As the structural unit of the formula (2), one of these structural units may be contained in the resin, but both structural units may be contained.

なお、式（３）の構造単位として、これらの構造単位のうち、１の構造単位が樹脂に含まれていてもよいが、両方の構造単位が含まれていてもよい。 In the formula (3), R8 has a structure represented by the following formula (6a) or the following formula (7a).

As the structural unit of the formula (3), one of these structural units may be contained in the resin, but both structural units may be contained.

Ｒ９が式（８ａ）である場合、式（８ａ）中、Ｒ１１〜Ｒ１３は各々独立して、水素原子、メチル基又はアルコキシ基を表す。なお、式（４）の構造単位として、これらの構造単位のうち、１の構造単位が樹脂に含まれていてもよいが、２以上の構造単位が含まれていてもよい。 In the formula (4), R9 has a structure represented by the following formula (8a) or the following formula (9a).

When R9 is of the formula (8a), in the formula (8a), R11 to R13 each independently represent a hydrogen atom, a methyl group or an alkoxy group. As the structural unit of the formula (4), one of these structural units may be contained in the resin, but two or more structural units may be contained.

Ｒ１０が式（１０ａ）である場合、式（１０ａ）中、Ｒ１４及びＲ１５は各々独立して、水素原子、メチル基又はアルコキシ基を表す。好ましくは、Ｒ１４及びＲ１５が水素原子である。なお、式（５）の構造単位として、これらの構造単位のうち、１の構造単位が樹脂に含まれていてもよいが、２以上の構造単位が含まれていてもよい。 In the formula (5), R10 has a structure represented by the following formula (10a) or the following formula (11a).

When R10 is of the formula (10a), in the formula (10a), R14 and R15 each independently represent a hydrogen atom, a methyl group or an alkoxy group. Preferably, R14 and R15 are hydrogen atoms. As the structural unit of the formula (5), one of these structural units may be contained in the resin, but two or more structural units may be contained.

By using such a resin, it is possible to form a film having excellent insulating properties and edge covering properties. This film can also be expected to have excellent corrosion resistance.

The resin as described above may further contain a structural unit represented by the formula (6). By using a resin containing this structural unit, a flexible film can be formed.

In formula (6), R16 is an alkylene group having 1 to 20 carbon atoms. The alkylene group may have one or two or more substituents selected from an alkyl group, an alkenyl group, an alkazienyl group or a methylene group, and is selected from an alkyl group, an alkenyl group, an alkazienyl group and a methylene group. It may have one or two or more substituents of two or more kinds, respectively. When R16 is an alkylene group having 2 to 20 carbon atoms, a ring may be formed via adjacent carbon atoms in the alkylene group. The ring may have one or more substituents selected from an alkyl group and an alkenyl group, preferably having two substituents, an alkyl group and / or an alkenyl group. If the ring has two substituents, the two substituents may be the same or different. Examples of the ring include a bicyclo ring in which two carbon-carbon bonds are double bonds in a cyclohexane ring, a cyclohexene ring, a benzene ring, and a decalin ring (for example, a bicyclo [4.4.0] decane-1,7-diene). Etc.).

More preferably, the alkylene group has 2 to 18 carbon atoms and one methylene group, one or two alkyl groups having 5 to 9 carbon atoms, or 5 to 9 carbon atoms. Has two substituents of one or two selected from an alkyl group, an alkenyl group and an alkazienyl group; or an alkylene group having 2 to 18 carbon atoms and via adjacent carbon atoms. Each of the rings constitutes any of the above rings, and each ring independently has two substituents having 5 to 9 carbon atoms, which are an alkyl group, an alkenyl group or an alkazienyl group.

The alkylene group may be linear or branched. Examples of the alkylene group include an alkylene group having 1 to 20 carbon atoms, and more specifically, a methylene chain, an ethylene chain, a propylene chain, a butylene chain, a pentylene chain, a hexylene chain, a heptylene chain, and an octylene. Examples thereof include alkylene groups having 1 to 12 carbon atoms such as chains, nonylene chains, decylene chains, undecylene chains, and dodecylene chains.

The alkyl group and the alkyl group in the alkylcarbonyl group, the alkoxy group and the alkoxycarbonyl group may be linear or branched. Examples of these alkyl groups include alkyl groups having 1 to 20 carbon atoms, and more specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group. Examples thereof include alkyl groups having 1 to 12 carbon atoms such as a group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

The alkenyl group may be linear or branched. Examples of the alkenyl group include an alkenyl group having 2 to 20 carbon atoms, and more specifically, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group and a nonenyl group. , A alkenyl group having 2 to 12 carbon atoms such as a decenyl group, an undecenyl group and a dodecenyl group can be mentioned.

The alkadienyl group may be linear or branched. Examples of the alkazienyl group include, but are limited to, alkenyl groups having 4 to 10 carbon atoms such as a butazienyl group, a pentadienyl group, a hexadienyl group, a heptadienyl group, an octadienyl group, a nonazienyl group, and a decadenyl group. is not it.

As the structural unit of the formula (6), one of these structural units may be contained in the resin, but two or more structural units may be contained.

The weight average molecular weight of the resin according to the present embodiment is usually in the range of 1000 or more and 1,000,000 or less, preferably in the range of 20,000 or more and 100,000 or less. The value of the weight average molecular weight in the present specification is a value measured by GPC (gel permeation chromatography) and converted into polystyrene.

Examples of the resin salt according to the present embodiment include alkali metal salts such as sodium salt and potassium salt; ammonium salt; monoethanolamine salt, diethanolamine salt, triethanolamine salt, methylethanolamine salt, dimethylethanolamine salt and the like. Alkanolamine salts; alkylamine salts such as tetramethylamine salts and tetraethylamine salts; benzylamine salts such as methylbenzylamine salts and dimethylbenzylamine salts; alicyclic amine salts such as pyrrolidine salts and piperidine salts; Be done.

<Manufacturing method of resin or its salt>
The resin or a salt thereof according to the present invention is a compound having a structural unit represented by the formula (1) in an organic solvent according to the combination of the structural units in the resin or the salt (hereinafter, referred to as “compound (1)”. ), A compound having a structural unit represented by the formula (2) (hereinafter referred to as "compound (2)"), and a compound having a structural unit represented by the formula (3) (hereinafter, "compound (3)". A compound having a structural unit represented by the formula (4) (hereinafter referred to as “compound (4)”), and a compound having a structural unit represented by the formula (5) (hereinafter referred to as “compound (5)”). ) ”) And the like are appropriately blended, and if necessary, a compound having a structural unit represented by the formula (6) (hereinafter referred to as“ compound (6) ”) is further blended to a predetermined temperature. It can be produced by carrying out a polymerization reaction in. If necessary, a reaction catalyst may be further added to carry out the polymerization reaction. The polymerization reaction temperature is not particularly limited, but is usually in the range of 70 ° C. or higher and 200 ° C. or lower. The reaction time is not particularly limited, but is usually within the range of 10 minutes or more and 24 hours or less.

The compound (1) is, for example, a dihydroxy compound in which hydrogen atoms are bonded to both ends of the structural unit represented by the formula (1); glycidyl groups are bonded to both ends of the structural unit represented by the formula (1). Diglycidyl ether compound; a reaction product obtained by reacting a hydroxy group at one end or both ends of the diglycidyl compound with an epoxy group in a polyglycidyloxy compound having two or more glycidyloxy groups; one end of the diglycidyl ether compound. Alternatively, a reaction product obtained by reacting an epoxy group at both ends with a hydroxy group in a polyol compound having two or more hydroxy groups; and the like can be mentioned.

Examples of the diglycidyl ether compound include compounds in which hydrogen atoms of hydroxy groups at both ends such as bisphenol A, bisphenol E, bisphenol F, catechol, resorcinol, hydroquinone, and 1,6-dihydroxynaphthalene are replaced with glycidyl groups. ..

Examples of the dihydroxy compound include bisphenol compounds such as bisphenol A, bisphenol E, bisphenol F, bis (4-hydroxyphenyl) sulfide, 2,2'-dihydroxydiphenyl ether, and 4,4'-dihydroxybiphenyl; catechol, 3-. Methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3', 4'-dihydroxyacetophenone, ethyl 3,4-dihydroxybenzoate, methyl 2,3-dihydroxybenzoate, 3,4-dihydroxy-2-methylbenzoate Methyl acid, 2', 3'-dihydroxy-4'-methoxyacetophenone, resorcinol, 5-methoxyresorcinol, 2-methylresorcinol, 5-methylresorcinol, 3', 5'-dihydroxyacetophenone, 2', 6'-dihydroxy Acetphenone, 2', 4'-dihydroxyacetophenone, methyl 3,5-dihydroxybenzoate, methyl 2,6-dihydroxybenzoate, methyl 3,5-dihydroxy-4-methoxybenzoate, 2,4-dihydroxy-6- Dihydroxybenzene compounds such as ethyl methoxybenzoate, hydroquinone, methylhydroquinone, methoxyhydroquinone, 2', 5'-dihydroxyacetophenone, 2,3-dimethylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, tetramethylhydroquinone; 2, 3-Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 1,4 -Dihydroxynaphthalene such as dihydroxynaphthalene; and the like.

Examples of the polyglycidyloxy compound include succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, and 1,3-propylene glycol diglycidyl ether, in addition to the diglycidyl ether compound. 1,4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, resorcinol diglycidyl ether, polyalkylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylol ethanetriglycidyl ether, tri Examples thereof include methylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl ether as a glycerol alkylene oxide adduct, and the like. As the polyglycidyloxy compound, a triglycidyl ether compound, a tetraglycidyl ether compound, or the like, which will be described later, may be used.

Examples of the polyol compound include dihydroxy compounds, ethylene glycol, propylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. 1,9-Nonandiol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, cyclohexyldimethanol, 1,3-adamantandiol And so on. As the polyol compound, a trihydroxy compound, a tetrahydroxy compound and the like, which will be described later, may be used.

Examples of the compound (2) include a trihydroxy compound in which a hydrogen atom is bonded to three ends in the structural unit represented by the formula (2); and a glycidyl group at the three ends in the structural unit represented by the formula (2). The triglycidyl ether compound to which the compound is bonded; a reaction product obtained by reacting one or more hydroxy groups in the trihydroxy compound with an epoxy group in the polyglycidyloxy compound; one or more epoxy groups in the triglycidyl ether compound and the above. Reaction products obtained by reacting with a hydroxy group in a polyol compound; and the like.

Examples of the triglycidyl ether compound include α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,1,1-tris (4-hydroxyphenyl) ethane or tris ( 4-Hydroxyphenyl) Examples thereof include compounds in which the hydrogen atom of the hydroxy group at the three ends of methane is replaced with a glycidyl group.

Examples of the trihydroxy compound include α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,1,1-tris (4-hydroxyphenyl) ethane or tris (4). -Hydroxyphenyl) methane and the like.

Examples of the compound (3) include a tetrahydroxy compound in which a hydrogen atom is bonded to four ends in the structural unit represented by the formula (3); and a glycidyl group at the four ends in the structural unit represented by the formula (3). The tetraglycidyl ether compound to which the compound is bonded; a reaction product obtained by reacting one or more hydroxy groups in the tetraglycidyl compound with an epoxy group in the polyglycidyloxy compound; and one or more epoxy groups in the tetraglycidyl ether compound and the above. Reaction products obtained by reacting with a hydroxy group in a polyol compound; and the like.

Examples of the tetraglycidyl ether compound include hydrogens having a hydroxy group at four terminals such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane or 1,1'-methylenebis (2,7-naphthalenediol). Examples thereof include compounds in which an atom is replaced with a glycidyl group.

Examples of the tetrahydroxy compound include 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1'-methylenebis (2,7-naphthalenediol) and the like.

The compound (4) is, for example, a compound having a hydroxy group or an amino group bonded to both ends of the structural unit represented by the formula (4) or a salt thereof; a hydroxy group at one end of the structural unit and the other. Examples thereof include a compound having an amino group bonded to the terminal thereof or a salt thereof; and the like. More specifically, hydroquinone sulfonic acid, 4,6-dihydroxynaphthalene-2-sulfonic acid, 2,3-dihydroxynaphthalene-6-sulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 6-amino-1. -Hydroxy-3-naphthalene sulfonic acid, 6-amino-4-hydroxy-2-naphthalene sulfonic acid, 5-amino-1-hydroxy-3-naphthalene sulfonic acid, 1-amino-2-hydroxy-4-naphthalene sulfonic acid , 2,5-Diaminobenzenesulfonic acid, 2,4-diaminobenzenesulfonic acid, 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid, 3,4-diaminonaphthalene-1-sulfonic acid and the like Or the salt thereof.

Examples of the compound (5) include a compound in which hydrogen atoms are bonded to both ends of the structural unit represented by the formula (5), a salt thereof, and the like. More specifically, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2,4-dimethylaniline-5-sulfonic acid, 2-aminobenzenesulfonic acid, 4-aminotoluene-3-sulfonic acid, 4 -Methoxyaniline-2-sulfonic acid, 2-amino-3,5-dimethylbenzenesulfonic acid, 5-aminotoluene-2-sulfonic acid, 4-amino-3-methylbenzenesulfonic acid, 2-amino-1-naphthalene Examples thereof include compounds such as sulfonic acid and 4-amino-1-naphthalene sulfonic acid, or salts thereof.

Examples of the salt of the compound (4) or the salt of the compound (5) include alkali metal salts such as sodium salt and potassium salt; ammonium salts; monoethanolamine salts, diethanolamine salts, triethanolamine salts, methylethanolamine salts, etc. Alkanolamine salts such as dimethylethanolamine salts; Alkylamine salts such as tetramethylamine and tetraethylamine salts; benzylamine salts such as methylbenzylamine salts and dimethylbenzylamine salts; Salt; etc.

Examples of the compound (6) include a dicarboxylic acid compound in which hydrogen atoms are bonded to both ends of the structural unit represented by the formula (6). More specifically, examples of the dicarboxylic acid compound include malonic acid, succinic acid, glutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, adipic acid, 2,2-dimethyladipic acid, and the like. Pimelliic acid, suberic acid, azelaic acid, 2-ethylazelineic acid, sebacic acid, 1,9-nonandicarboxylic acid, 1,10-decandicarboxylic acid, 1,11-undecandicarboxylic acid, 1,12-dodecandicarboxylic acid, 1,13-Tridecandicarboxylic acid, 1,14-tetradecanediocarboxylic acid, 1,15-pentadecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,17-heptadecanedicarboxylic acid, 1,18-octadecanediocarboxylic acid, Examples thereof include 1,19-nonadecandicarboxylic acid, 1,20-icosandicarboxylic acid, itaconic acid, phthalic acid, dimer acid, 1,2-cyclohexanedicarboxylic acid and 1,2-cyclohexendicarboxylic acid. Examples of the dimer acid include commercially available Hari Dimer 200, 250 or 270S (Harima Kasei Group Co., Ltd.); Tsunodimer 205, 216, 228, 395 or 346 (Tsukuno Food Industry Co., Ltd.); Unidyme 14, 14R. , T-17, 18, T-18, 22, T-22, 27, 35, M-9, M-15, M-35 or 40, or Century D-75, D-77, D-78 or D -1156, or Sylvatal 7001 or 7002 (each Arizona Chemicals); Empol 1016, 1003, 1026, 1028, 1061, 1062, 1008 or 1012 (each BASF); average _Mn ~ 570; Sigma- Aldrich) and the like.

The blending amount of each compound (1) to (6) may be appropriately set according to the ratio of each structural unit in the resin that can be produced.

The organic solvent is not particularly limited as long as it can dissolve the compounds (1) to (6), and for example, glycols such as ethylene glycol ethyl ether, ethylene glycol-n-butyl ether, diethylene glycol ethyl ether, and propylene glycol methyl ether. An ether-based organic solvent, a ketone-based organic solvent such as methyl ethyl ketone and methyl isobutyl ketone, and an amide-based organic solvent such as dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone can be used. These organic solvents may be used alone or in combination of two or more.

The reaction catalyst is not particularly limited as long as it promotes the above-mentioned polymerization reaction, but for example, tertiary amines such as dimethylbenzylamine, triethylamine and tributylamine; and quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide. ; Etc. can be used. These reaction catalysts may be used alone or in combination of two or more.

Whether or not the resin manufactured as described above contains structural units represented by the formula (1), the formula (2), the formula (3), the formula (4), the formula (5), the formula (6) and the like. This can be confirmed by measuring ¹ H NMR and / or ¹³ C NMR using a nuclear magnetic resonance apparatus.

<Emulsion>
The emulsion according to this embodiment contains the above anionic epoxy resin or a salt thereof. The emulsion can be obtained, for example, by dispersing an anionic epoxy resin or a salt thereof in water by a phase inversion emulsification method. The temperature at the time of dispersion is not particularly limited, but is preferably 5 ° C. or higher and 50 ° C. or lower.

The emulsion may further contain a blocked polyisocyanate curing agent, which is a curing agent for the epoxy resin. Further, a curing catalyst may be contained together with the block polyisocyanate curing agent. When these are included, an emulsion can be obtained by premixing an anionic epoxy resin or a salt thereof with a blocked polyisocyanate curing agent and a curing catalyst, and then dispersing the mixture in water by a phase inversion emulsification method.

The blocked polyisocyanate curing agent can be obtained by reacting the isocyanate group of the polyisocyanate compound with the blocking agent to protect the isocyanate group.

Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylenedi isocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, and polypeptide MDI (crude MDI: polymethylene polyphenyl polyisocyanate). ), Bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate and the like. These polyisocyanate compounds may be used alone or in combination of two or more.

Examples of the blocking agent include lactam compounds such as ε-caprolactam and γ-butyrolactam, oxime compounds such as methylethylketooxime and cyclohexanone oxime, phenol compounds such as phenol, para-t-butylphenol and cresol, and n-butanol. Examples thereof include alcohols such as 2-ethylhexanol or glycol ether compounds such as ethylene glycol monobutyl ether, ethylene glycol monohexyl ether and diethylene glycol monoethyl ether. These blocking agents may be used alone or in combination of two or more, and an appropriate one can be selected depending on the type of the polyisocyanate compound.

As the curing catalyst, known catalysts such as tin-based catalysts, bismuth-based catalysts, titanium-based catalysts, zirconium catalysts, amine-based catalysts, carboxylate-based catalysts, and trialkylphosphine-based catalysts can be used. These curing catalysts may be used alone or in combination of two or more.

<Surface treatment agent>
The surface treatment agent according to the present embodiment includes the anionic epoxy resin or a salt thereof, or the emulsion. The surface treatment agent may further contain known acids, oxidizing agents, various additives and the like used in the surface treatment agent.

Examples of the acid and oxidizing agent include hydrofluoric acid or a salt thereof, silicon fluoride acid or a salt thereof, titanium fluoride acid or a salt thereof, iron nitrate (III), iron sulfate (III), iron methanesulfonate (3). III), water-soluble iron compounds such as iron fluoride (III), iron chloride (III), iron citrate (III), acetic acid, phosphoric acid, sulfuric acid, nitrate, hydrogen peroxide, perchloric acid, permanganic acid, etc. Examples include peroxides. These acids or oxidizing agents can be used alone or in combination of two or more. Examples of the salt include alkali metal salts such as sodium salt and potassium salt; ammonium salt; alkanolamine salt such as monoethanolamine salt, diethanolamine salt, triethanolamine salt, methylethanolamine salt and dimethylethanolamine salt; Alkylamine salts such as tetramethylamine salt and tetraethylamine salt; benzylamine salts such as methylbenzylamine salt and dimethylbenzylamine salt; alicyclic amine salts such as pyrrolidine salt and piperidine salt; and the like can be mentioned.

Additives include, for example, pH adjusters, ORP adjusters, chelating agents, weather resistant agents, antibacterial agents, antifungal agents, pigments, fillers, rust preventives, pigments, dyes, film-forming aids, inorganic cross-linking agents, etc. Organic cross-linking agents (for example, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, melamine-based cross-linking agents, etc.), silane coupling agents, blocking inhibitors, viscosity modifiers, leveling agents, defoaming agents, dispersion stabilizers, light stabilizers, etc. Examples thereof include antioxidants, ultraviolet absorbers, inorganic and organic fillers, plasticizers, lubricants, antioxidants and the like. These additives may be used alone or in combination of two or more.

The surface treatment agent can be produced, for example, by mixing the anionic epoxy resin with an aqueous medium by adding an acid, an oxidizing agent, various additives and the like, if necessary. Further, the above emulsion may be used as a surface treatment agent, or a mixture of the above emulsion with an acid, an oxidizing agent, various additives and the like may be used as a surface treatment agent.

<Material with film and its manufacturing method>
The method for producing a material having a film according to the present embodiment (hereinafter, simply referred to as "manufacturing method") includes a first step of bringing the surface treatment agent into contact with the surface or the surface of the material having a metal on the surface. It includes a second step of baking the contacted surface treatment agent (uncured film). In this manufacturing method, a step of washing the uncured film with water may be performed between the first step and the second step, if necessary.

Examples of the contact method in the first step include, but are not limited to, a dip (immersion) method, a coating method, a spray method, a pouring method, an electrodeposition coating method, and the like. The temperature and time of contact are not particularly limited, but they are usually in the range of 5 ° C. or higher and 50 ° C. or lower, and 0.1 seconds or more and 1 hour or less.

The material having metal on the surface is not particularly limited as long as the surface of all or part of the material contains metal, and the surface of all or part of the material is composed of at least metal. Anything is fine. The metal is not particularly limited, and examples thereof include iron, iron alloys, aluminum, aluminum alloys, copper, and copper alloys.

In the production method according to the present embodiment, a degreasing treatment step may be performed on the surface of the material before the first step. The degreasing treatment can be performed by a known method using a degreasing treatment agent suitable for the material. Examples of the degreasing treatment agent include, but are not limited to, known acidic degreasing agents, alkaline degreasing agents, solvent degreasing agents, and the like. The degreasing treatment method is not particularly limited, and examples thereof include scrub cleaning, spray cleaning (spray cleaning), and dip (immersion) cleaning.

In the production method according to the present embodiment, a water washing step of washing the surface of the material with water after the degreasing treatment step and before the first step may be performed, but after the water washing step and before the first step, the surface of the material is further washed. You may perform a drying step to dry. As a drying method, a known method can be applied.

Further, after the degreasing treatment step, the washing step, the drying step, etc. before the first step, and before the first step, a chemical conversion treatment step of forming a chemical conversion treatment film on the metal in the material may be performed. The chemical conversion treatment is carried out by contacting the material with a known chemical conversion treatment agent. The chemical conversion treatment method is not particularly limited, and a known method can be applied. After the chemical conversion treatment step and before the first step, a water washing step may be performed, and further, after the water washing step and before the first step, a drying step may be performed.

By the above-mentioned production method, a material having a film containing an anionic epoxy resin or a salt thereof on the surface or the surface of the material having a metal on the surface can be produced. The form of the anionic epoxy resin or a salt thereof contained in the film may be the form as it is or the form of a crosslinked product. When the surface treatment agent contains a blocked polyisocyanate curing agent, the form of the anionic epoxy resin or a salt thereof contained in the film is an anionic epoxy resin or a salt thereof and a blocked polyisocyanate curing agent. It may be in the form of a crosslinked product with. The thickness of the film is not particularly limited, but is usually in the range of 0.1 μm or more and 1000 μm or less.

<Use of resin, etc.>
The anionic epoxy resin or its salt, emulsion, surface treatment agent and the like are adhesives, glasses, optical materials (for example, those typified by imaging lenses), lining agents, inks, resists, liquid resists, printing plates, etc. Insulation varnish, insulation sheet, laminated board, printed board, sealant (for example, for semiconductor devices, LED packages, liquid crystal inlets, organic EL, optical elements, electrical insulation, electronic parts, separation membranes) , Etc.), molding material, putty, glass fiber impregnant, sealant, passivation film (for example, for semiconductors / solar cells, etc.), interlayer insulating film, protective film, prism lens sheet (for example, liquid crystal display) (Used for the backlight of the device), Frenel lens sheet (for example, used for the screen of projection TV etc.), the lens part of the lens sheet such as the wrenchular lens sheet, or the backlight using such a sheet. Etc., can be used for applications such as optical lenses (for example, microlenses, etc.), optical elements, optical connectors, optical waveguides, casting agents for optical modeling, and the like. However, the use of the anionic epoxy resin or its salt, emulsion, surface treatment agent and the like is not limited to the above.

Examples and comparative examples of the anionic epoxy resin, emulsion and surface treatment agent of the present invention will be described. The present invention is not limited to the following examples.

≪Anionic epoxy resin≫
<Example 1>
As shown in Table 1, 235.9 g of A1, 29.8 g of B1 and 24.8 g of C1 were added to 536.0 g of N-methyl-2-pyrrolidone and heated to 120 ° C. with stirring. did. Then, while maintaining the temperature, 0.6 g of dimethylbenzylamine was added and the reaction was carried out for 1.5 hours. Then, 113.0 g of A2 and 60.5 g of D1 were added and reacted for another 5 hours. Then, the reaction solution was cooled to obtain an anionic epoxy resin having a solid content concentration of 46.4% and a weight average molecular weight of about 50,000.

<Examples 2 to 24 and Comparative Examples 1 to 4>
Using a predetermined amount (charged amount: parts by mass) of each component shown in Table 1, anionic epoxy resins of Examples 2 to 24 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1.

Each symbol in Table 1 indicates the following components.
<Ingredient A>
A1: Diglycidyl ether compound of bisphenol A (jER # 828EL, manufactured by Mitsubishi Chemical Corporation)
A2: Bisphenol A (manufactured by Idemitsu Kosan Co., Ltd.)
A3: 1,6-Dihydroxynaphthalene diglycidyl ether compound (EPICLON HP-4032D, manufactured by DIC Corporation)
A4: Resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Ingredient B>
B1: A compound in which the hydrogen atom in the three hydroxy groups of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene is replaced with a glycidyl group (TECHMORE VG-3101L, Printec). Made)
B2: Triglycidyl ether compound of 1,1,1-tris (4-hydroxyphenyl) ethane (jER # 1032H60, manufactured by Mitsubishi Chemical Corporation)
B3: 1,1'-methylenebis (2,7-naphthalenediol) tetraglycidyl ether compound (EPICLON HP-4710, manufactured by DIC Corporation)
B4: 1,1,2,2-Tetrakis (4-hydroxyphenyl) ethane tetraglycidyl ether compound (jER # 1031S, manufactured by Mitsubishi Chemical Corporation)
<Ingredient C: All manufactured by Tokyo Chemical Industry Co., Ltd.>
C1: Potassium hydroquinone sulfonate C2: 2,3-Dihydroxynaphthalene-6-sodium sulfonate C3: 3-amino-4-hydroxybenzene sulfonic acid C4: 6-amino-1-hydroxy-3-naphthalene sulfonic acid C5: 2 , 5-Diaminobenzene Sulfonic Acid C6: 3,4-Diaminonaphthalene-1-sulfonic Acid C7: 4-Aminobenzene Sulfonic Acid Sodium C8: 2-Amino-1-naphthalene Sulfonic Acid Sodium C9: 4-Hydroxybenzene Sulfonic Acid Sodium C10: Sodium Isetionate <Component D>
D1: Dicarboxylic acid compound (Haridimer 270S, manufactured by Harima Chemicals, Inc.)
D2: Adipic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
D3: 1,16-Hexadecanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

≪Synthesis of blocked polyisocyanate curing agent≫
<Manufacturing example 1>
Add 77.1 g of methyl isobutyl ketone to 452.3 g of polymethylene polyphenyl polyisocyanate (Cosmonate M-200, manufactured by Mitsui Chemicals, Inc.), heat to 70 ° C., and then slowly add 470.7 g of butyl cellosolve to complete the dropping. After that, it was heated to 90 ° C. Subsequently, the reaction was carried out under the condition of 90 ° C. for 12 hours to obtain a blocked polyisocyanate curing agent in which the isocyanate group was completely blocked. The fact that the isocyanate group was blocked was performed by confirming whether or not absorption derived from the unreacted isocyanate group was observed by infrared absorption spectrum measurement.

≪Emulsion≫
<Example 25>
353.5 g of pure water was slowly added to 646.5 g of the anionic epoxy resin of Example 1 to prepare an emulsion having a solid content concentration of 30% by a phase inversion emulsification method.

<Examples 26 to 48 and Comparative Examples 5 to 8>
As shown in Table 2, various anionic epoxy resins were used to prepare emulsions of Examples 26 to 48 and Comparative Examples 5 to 8 in the same manner as in Example 25.

<Example 49>
442.1 g of the anionic epoxy resin of Example 1, 97.7 g of the blocked polyisocyanate curing agent synthesized in Production Example 1, and 6.7 g of dioctyl tin (Neostan U-820, manufactured by Nitto Kasei Co., Ltd.) are mixed, and then. , 453.5 g of pure water was slowly added, and an emulsion having a solid content concentration of 30% was produced by a phase inversion emulsification method.

<Examples 50 to 72 and Comparative Examples 9 to 12>
As shown in Table 2, various anionic epoxy resins were used to prepare emulsions of Examples 50 to 72 and Comparative Examples 9 to 12 in the same manner as in Example 49.

≪Surface treatment agent≫
<Example 73>
To 333.0 g of the emulsion of Example 25, 5.5 g of a black pigment (SANDYE DP BLACK CN, manufactured by Sanyo Dye Co., Ltd.) and 53.0 g of NSD-300 (manufactured by Nihon Parkerizing Co., Ltd.) were added, and 25% by mass of sodium hydroxide was added. After adjusting the pH to 3.5 using an aqueous solution, the ORP (oxidation-reduction potential) was adjusted to 380-420 mV using a hydrogen peroxide solution to prepare a surface treatment agent.

<Examples 74 to 120 and Comparative Examples 13 to 20>
The surface treatment agents of Examples 74 to 120 and Comparative Examples 13 to 20 were prepared in the same manner as in Example 73 except that the emulsion shown in Table 3 was used instead of the emulsion of Example 25.

≪Manufacturing of metal materials with a film≫
<Metallic material>
As a metal material, SPC: cold-rolled steel sheet (SPCC-SD, plate thickness: 0.8 mm) was used.

<Degreasing treatment>
Spray at 45 ° C. for 2 minutes using an alkaline degreasing agent [a degreasing agent mixed with water so that A and B agents of Fine Cleaner E2001 (manufactured by Nihon Parkerizing Co., Ltd.) are 13 g / kg and 7 g / kg, respectively]. This degreased the surface of the metal material.

<Surface treatment>
The degreased metal material was immersed in the surface treatment agent of Example 73 at 25 ° C. for 1 minute, and then the metal material was washed with water. The washed metal material was baked at 180 ° C. (PMT: maximum temperature of the metal material at the time of baking) for 20 minutes to obtain a metal material having a film thickness of 20 μm on the surface (Example 121).

<Examples 122 to 168>
As shown in Table 4, using the surface treatment agents of Examples 74 to 120 and Comparative Examples 13 to 20, the films of Examples 122 to 168 and Comparative Examples 21 to 28 were formed in the same manner as in the production method of Example 121. Obtained a metallic material to have.

<< Evaluation test >>
Various evaluation tests were performed using the metal materials having the coatings of Examples 121 to 168 and Comparative Examples 21 to 28.

<Edge coverage test>
Observe the edge part of the metal material having various films with a laser microscope (VK-8710, manufactured by KEYENCE CORPORATION), and calculate the ratio of the film thickness of the edge part to the film thickness (20 μm) in the center part of the film in the metal material. Then, the edge coverage was evaluated according to the following evaluation criteria.
(Evaluation criteria)
〇: The ratio [(film thickness at the edge portion) / (film thickness at the center portion of the film)] is 0.50 or more. ×: The ratio is less than 0.50.

<Insulation test>
The electrical insulation (withstand voltage) of the coating film in 121-168 and Comparative Examples 21 to 28 was measured with a withstand voltage tester (TOS9201, manufactured by Kikusui Electronics Co., Ltd.), and the insulation was evaluated according to the following evaluation criteria. The measurement conditions were an initial voltage of 50 V, a boost speed of 50 V / sec, and a cutoff current of 1.0 mA.
(Evaluation criteria)
⊚: Withstand voltage of the film is 2 kV or more 〇: Withstand voltage of the film is 1 kV or more and less than 2 kV ×: Withstand voltage of the film is less than 1 kV

<Corrosion resistance test>
The metal material having various films was cut into a cloth (x) shape using a cutter at a depth reaching the metal material, and a 5% sodium chloride aqueous solution (neutral) was sprayed at 35 ° C. for 480 hours. Then, the rust swelling width (maximum swelling width on one side from the cut part) in the cut portion was measured, and the corrosion resistance was evaluated according to the following evaluation criteria.
(Evaluation criteria)
⊚: swelling width is 2.5 mm or less 〇: swelling width is more than 2.5 mm and 3.5 mm or less ×: swelling width is more than 3.5 mm

The results of each evaluation test are shown in Table 4.

Claims (7)

The structural unit represented by the following formula (1) and
At least one of the structural units represented by the following equations (2) and (3), and
At least one of the structural units represented by the following equations (4) and (5), and
Anionic epoxy resin or a salt thereof.

[In the formula (1), R1 has a structure represented by the following formula (1a), the lower formula (2a), or the lower formula (3a). In the formula (2), R7 has a structure represented by the following formula (4a) or the following formula (5a). In the formula (3), R8 has a structure represented by the following formula (6a) or the following formula (7a). In the formula (4), R9 has a structure represented by the following formula (8a) or the following formula (9a). In the formula (5), R10 has a structure represented by the following formula (10a) or the following formula (11a). ]

[In formula (1a), R2 is a single bond, C (CH ₃ ) ₂ , CH (CH ₃ ), CH ₂ , S, O or SO ₂ . In formula (2a), R3 to R6 each independently represent a hydrogen atom, a methyl group, an alkylcarbonyl group, an alkoxy group or an alkoxycarbonyl group. In formula (5a), R17 is a hydrogen atom or an alkyl group. In formula (8a), R11 to R13 each independently represent a hydrogen atom, a methyl group or an alkoxy group. In formula (10a), R14 and R15 each independently represent a hydrogen atom, a methyl group or an alkoxy group. ] The anionic epoxy resin or a salt thereof according to claim 1, which comprises a structural unit represented by the following formula (6).

(In the formula (6), R16 is an alkylene group having 1 to 20 carbon atoms. The alkylene group may have an alkyl group, an alkenyl group, an alkazienyl group or a methylene group. The alkylene group has a carbon number of 1 to 20. When it is 2 to 20, a ring may be formed via adjacent carbon atoms. The ring has one or two or more substituents selected from an alkyl group and an alkenyl group. May be.) An emulsion comprising the anionic epoxy resin according to claim 1 or claim 2 or a salt thereof. The emulsion according to claim 3, which comprises a blocked polyisocyanate curing agent. A surface treatment agent comprising the anionic epoxy resin or salt thereof according to claim 1 or 2, or the emulsion according to claim 3 or 4. A method for producing a material having a film, which comprises a step of bringing the surface treatment agent according to claim 5 into contact with the surface or a surface of a material having a metal on the surface, and a step of baking the contacted surface treatment agent. A material having a film containing the anionic epoxy resin according to claim 1 or claim 2 or a salt thereof on the surface or surface of the material having a metal on the surface.