JP2019116552A - Anionic epoxy resin or its salt, emulsion, surface treatment agent, and material having film and method for producing the same - Google Patents

Abstract

［式中、Ｒ１、Ｒ７、Ｒ８、Ｒ９、Ｒ１０はそれぞれ特定のアニオン性基又は芳香属の環状構造を含む。］
【選択図】なしAn anionic epoxy resin for forming a film having excellent insulating properties and edge covering properties, and an emulsion containing the same.
A structural unit represented by the following formula (1), and at least one of structural units represented by the following formulas (2) and (3), and the following formulas (4) and (5) And at least one of the structural units represented by).

[Wherein, R 1, R 7, R 8, R 9 and R 10 each contain a specific anionic group or aromatic cyclic structure. ]
【Selection chart】 None

Description

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

  Heretofore, there has been proposed a technology for forming a film on the surface of a metal material using a treating agent containing an anionic epoxy resin. For example, Patent Document 1 discloses a technique related to a dispersion containing a predetermined anionic epoxy resin, which is used to form a film.

Japanese Patent Application Publication No. 2005-537338

  In recent years, the film has been required to have performance such as insulation and edge cover. Therefore, the present invention provides an anionic epoxy resin or a salt thereof for forming a film excellent in insulating properties and edge coverage, an emulsion containing the same, the resin or a salt thereof, or a surface treatment agent containing the emulsion, and An object of the present invention is 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 for achieving the above object is
[1] Formula (1):

[In Formula (1), R1 is Formula (1a):

, Equation (2a):

Or the following formula (3a):

Is a structure represented by In formula (1a), R 2 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. A structural unit represented by
Formula (2):

[In Formula (2), R7 is Formula (4a):

Or Formula (5a):

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

[In the formula (3), R 8 represents the formula (6a):

Or Formula (7a):

Is a structure represented by And at least one of the structural units represented by
Formula (4):

[In Formula (4), R9 is Formula (8a):

Or Formula (9a):

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 Formula (5), R10 is Formula (10a):

Or Formula (11a):

Is a structure represented by In formula (10a), R14 and R15 each independently represent a hydrogen atom, a methyl group or an alkoxy group. And at least one of the structural units represented by
An anionic epoxy resin or a salt thereof;
[2] Formula (6):

[In Formula (6), R16 is a C1-C20 alkylene group. The alkylene group may have an alkyl group, an alkenyl group, an alkadienyl group or a methylene group. When carbon number of the said alkylene group is 2-20, you may comprise a ring via an adjacent carbon atom. The ring may have one or more substituents selected from the group consisting of an alkyl group and an alkenyl group. The anionic epoxy resin or the salt thereof according to the above [1], which comprises the structural unit represented by
[3] An emulsion comprising the anionic epoxy resin as described in the above [1] or [2] or a salt thereof;
[4] The emulsion according to the above [3], which comprises a blocked polyisocyanate curing agent;
[5] A surface treatment agent comprising the anionic epoxy resin according to the above [1] or [2] or a salt thereof, or the emulsion according to the above [3] or [4];
[6] A material having a film, which comprises the steps of bringing the surface treatment agent according to the above [5] into contact with the surface of the material having a metal on the surface or the surface, and baking the contacted surface treatment agent. The manufacturing method of;
[7] A material having a film containing the anionic epoxy resin described in the above [1] or [2] or a salt thereof on the surface or surface of a material having a metal on the surface;
Etc.

  According to the present invention, an anionic epoxy resin or a salt thereof for forming a film excellent in insulating properties and edge coverage, an emulsion containing the same, the resin or a salt thereof, or a surface treatment agent containing the emulsion, and A material having a film formed by a surface treatment agent and a method of manufacturing the same can be provided.

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

  As a combination of structural units in the resin, a combination of each structural unit of formulas (1), (2) and (4); a combination of each structural unit of formulas (1), (2) and (5) Combination of each structural unit of Formula (1), Formula (3) and Formula (4); combination of each structural unit of Formula (1), Formula (3) and Formula (5); Formula (1), Formula (5) 2) Combination of each structural unit of Formula (3) and Formula (4); Combination of each structural unit of Formula (1), Formula (2), Formula (3) and Formula (5); Formula (1), (2), (4) and a combination of each structural unit of formula (5); a combination of each structural unit of a formula (1), a formula (3), a formula (4) and a formula (5); Combinations 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 Formula (1), R1 is a structure represented by the following Formula (1a), the following Formula (2a), or the following Formula (3a).

If R1 is a formula (1a), wherein (1a), R2 is a single _{bond, C (CH 3) 2,} CH (CH 3), a _CH 2, S, O or SO _2. When R1 is a 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 the formula (2a). In addition, although 1 structural unit may be contained in resin among these structural units as a structural unit of Formula (1), 2 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 Formula (2), R7 is a structure represented by the following Formula (4a) or the following Formula (5a).

When R7 is Formula (5a), R17 is a hydrogen atom or an alkyl group in Formula (5a). In addition, although 1 structural unit may be contained in resin among these structural units as a structural unit of Formula (2), 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 Formula (3), R8 is a structure represented by the following Formula (6a) or the following Formula (7a).

In addition, although 1 structural unit may be contained in resin among these structural units as a structural unit of Formula (3), 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 Formula (4), R9 is a structure represented by the following Formula (8a) or the following Formula (9a).

When R9 is a formula (8a), R11-R13 respectively independently represents a hydrogen atom, a methyl group, or an alkoxy group in Formula (8a). In addition, although one structural unit may be contained in resin among these structural units as a structural unit of Formula (4), 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 Formula (5), R10 is a structure represented by the following Formula (10a) or the following Formula (11a).

When R10 is a formula (10a), R14 and R15 respectively independently represent a hydrogen atom, a methyl group, or an alkoxy group in Formula (10a). Preferably, R14 and R15 are hydrogen atoms. In addition, although one structural unit may be contained in resin among these structural units as a structural unit of Formula (5), two or more structural units may be contained.

  By using such a resin, it is possible to form a film excellent in insulation and edge coverability. This coating can also be expected to have excellent corrosion resistance.

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

  In Formula (6), R16 is a C1-C20 alkylene group. The alkylene group may have one or more substituents selected from an alkyl group, an alkenyl group, an alkadienyl group and a methylene group, and is selected from an alkyl group, an alkenyl group, an alkadienyl group and a methylene group It may have one or two or more of each of two or more types of substituents. When R 16 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, and preferably has two substituents of an alkyl group and / or an alkenyl group. When the ring carries 2 substituents, the 2 substituents may be identical or different. As the ring, for example, a bicyclo ring in which two carbon-carbon bonds are double bond in a cyclohexane ring, a cyclohexene ring, a benzene ring, and a decalin ring (eg, 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 group having 5 to 9 carbon atoms, or 5 to 9 carbon atoms. Or two or more substituents selected from an alkyl group, an alkenyl group and an alkadienyl group, or an alkylene group has 2 to 18 carbon atoms and is adjacent via an adjacent carbon atom The ring, which constitutes any of the above-mentioned rings, has two substituents each independently having 5 to 9 carbon atoms, which is an alkyl group, an alkenyl group or an alkadienyl group.

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

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

  The alkenyl group may be linear or branched. As an alkenyl group, a C2-C20 alkenyl group can be mentioned, for example, More specifically, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group And alkenyl groups having 2 to 12 carbon atoms such as decenyl group, undecenyl group and dodecenyl group.

  The alkadienyl group may be linear or branched. Examples of the alkadienyl group include, but are not limited to, alkenyl groups having 4 to 10 carbon atoms such as butadienyl group, pentadienyl group, hexadienyl group, heptadienyl group, octadienyl group, nonadienyl group, decadienyl group, etc. is not.

  In addition, although 1 structural unit may be contained in resin among these structural units as a structural unit of Formula (6), 2 or more structural units may be contained.

  The weight average molecular weight of the resin according to this embodiment is usually in the range of 1000 or more and 1000000 or less, and preferably in the range of 20000 or more and 100000 or less. The value of weight average molecular weight in the present specification is a value measured by GPC (gel permeation chromatography) and converted to polystyrene.

  Examples of the salt of the resin according to this 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 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; Be

<Method for producing resin or salt thereof>
The resin according to the present invention or a salt thereof is a compound having a structural unit represented by the formula (1) in an organic solvent (hereinafter referred to as "compound (1)") according to the combination of structural units in the resin or the salt A compound having a structural unit represented by formula (2) (hereinafter referred to as “compound (2)”), a compound having a structural unit represented by formula (3) (hereinafter referred to as “compound (3)”) Compounds having a structural unit represented by the formula (4) (hereinafter referred to as “compound (4)”), compounds having a structural unit represented by the formula (5) (hereinafter referred to as “compound (5) And so forth) as appropriate, and further optionally compounding a compound having a structural unit represented by formula (6) (hereinafter referred to as “compound (6)”), if necessary, at a predetermined temperature It can manufacture by performing a polymerization reaction. If necessary, a reaction catalyst may be further blended to carry out a polymerization reaction. The polymerization reaction temperature is not particularly limited, but is usually in the range of 70 ° C. or more and 200 ° C. or less. The reaction time is not particularly limited, but is usually in the range of 10 minutes to 24 hours.

  As the compound (1), for example, a dihydroxy compound in which a hydrogen atom is bonded to both ends of the structural unit represented by the formula (1); a glycidyl group is bonded to both ends of the structural unit represented by the formula (1) A diglycidyl ether compound; a reaction product obtained by reacting a hydroxy group at one end or both ends of the dihydroxy compound with an epoxy group in a polyglycidyl oxy compound having two or more glycidyl oxy groups; one end of the diglycidyl ether compound Or 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;

  Examples of the diglycidyl ether compound include compounds in which a hydrogen atom of a hydroxy group at both terminals of both ends is substituted with a glycidyl group such as bisphenol A, bisphenol E, bisphenol F, catechol, resorcinol, hydroquinone, 1,6-dihydroxynaphthalene and the like .

  Examples of dihydroxy compounds include bisphenol compounds such as bisphenol A, bisphenol E, bisphenol F, bis (4-hydroxyphenyl) sulfide, 2,2′-dihydroxydiphenyl ether, 4,4′-dihydroxybiphenyl, etc .; Methyl catechol, 4-methyl catechol, 3-methoxy catechol, 3 ', 4'-dihydroxyacetophenone, ethyl 3,4-dihydroxybenzoate, methyl 2,3-dihydroxybenzoate, 3,4-dihydroxy-2-methylbenzoic acid Acid methyl, 2 ', 3'-dihydroxy-4'-methoxyacetophenone, resorcinol, 5-methoxyresorcinol, 2-methylresorcinol, 5-methylresorcinol, 3', 5'-dihydroxyacetophenone, ', 6'-dihydroxyacetophenone, 2', 4'-dihydroxyacetophenone, methyl 3,5-dihydroxybenzoate, methyl 2,6-dihydroxybenzoate, methyl 3,5-dihydroxy-4-methoxybenzoate, 2, Ethyl 4-dihydroxy-6-methoxybenzoate, hydroquinone, methylhydroquinone, methoxyhydroquinone, 2 ', 5'-dihydroxyacetophenone, 2,3-dimethylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, etc. Dihydroxybenzene compounds; 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,8-dihydroxyki Naphthalene, 1,2-dihydroxynaphthalene, dihydroxynaphthalene and 1,4-dihydroxynaphthalene; and the like.

  Examples of polyglycidyl oxy compounds include, in addition to diglycidyl ether compounds, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, 1,3-propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, resorcinol diglycidyl ether, polyalkylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, tri Methylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerol alkylene oxide Triglycidyl ether of Id adducts and the like. In addition, you may use the below-mentioned triglycidyl ether compound, a tetraglycidyl ether compound etc. as a polyglycidyl oxy compound.

  Examples of the polyol compound include, in addition to dihydroxy compounds, ethylene glycol, propylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, cyclohexyldimethanol, 1,3-adamantanediol Etc. In addition, you may use the below-mentioned trihydroxy compound, a tetrahydroxy compound, etc. as a polyol compound.

  As the compound (2), for example, a trihydroxy compound in which a hydrogen atom is bonded to three ends in a structural unit represented by the formula (2); a glycidyl group at three ends in a structural unit represented by the formula (2) A triglycidyl ether compound having a bond; a reaction product of one or more hydroxy groups in the trihydroxy compound and an epoxy group in the polyglycidyl oxy compound; one or more epoxy groups in the triglycidyl ether compound; The reaction product which made it react with the hydroxyl group in a polyol compound, etc. are mentioned.

  Examples of triglycidyl ether compounds include α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,1,1-tris (4-hydroxyphenyl) ethane or tris The compound by which the hydrogen atom of the hydroxy group in three terminals, such as 4-hydroxyphenyl) methane, was substituted by the glycidyl group is mentioned.

  Examples of trihydroxy compounds 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.

  As the compound (3), for example, a tetrahydroxy compound in which a hydrogen atom is bonded to four ends in the structural unit represented by the formula (3); a glycidyl group at four ends in the structural unit represented by the formula (3) A tetraglycidyl ether compound having a bond; a reaction product of one or more hydroxy groups in the tetrahydroxy compound and an epoxy group in the polyglycidyl oxy compound; one or more epoxy groups in the tetraglycidyl ether compound; The reaction product which made it react with the hydroxyl group in a polyol compound, etc. are mentioned.

  As a tetraglycidyl ether compound, for example, hydrogen of hydroxy group at four ends such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane or 1,1′-methylenebis (2,7-naphthalenediol) The compound which the atom substituted by the glycidyl group is mentioned.

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

  As the compound (4), for example, a compound in which a hydroxy group or an amino group is bonded to both ends of the structural unit represented by the formula (4) or a salt thereof; a hydroxy group at one terminal in the structural unit; And the like, or a compound or the like, in which an amino group is bonded to the terminal of More specifically, hydroquinone sulfonic acid, 4,6-dihydroxynaphthalene-2-sulfonic acid, 2,3-dihydroxy naphthalene-6-sulfonic acid, 3-amino-4-hydroxybenzene sulfonic acid, 6-amino-1 -Hydroxy-3-naphthalenesulfonic acid, 6-amino-4-hydroxy-2-naphthalenesulfonic acid, 5-amino-1-hydroxy-3-naphthalenesulfonic acid, 1-amino-2-hydroxy-4-naphthalenesulfonic acid Compounds such as 2, 5-diaminobenzenesulfonic acid, 2,4-diaminobenzenesulfonic acid, 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid, 3,4-diaminonaphthalene-1-sulfonic acid Or salts thereof.

  As a compound (5), the compound or its salt etc. which the hydrogen atom couple | bonded with the both terminal of the structural unit represented by Formula (5) is mentioned, for example. 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-naphthalenesulfonic acid or salts thereof.

  As a salt of compound (4) or a salt of compound (5), for example, alkali metal salts such as sodium salt and potassium salt; ammonium salt; monoethanolamine salt, diethanolamine salt, triethanolamine salt, methylethanolamine salt, Alkanolamine salts such as dimethylethanolamine salt; alkylamine salts such as tetramethylamine salt and tetraethylamine salt; benzylamine salts such as methylbenzylamine salt and dimethylbenzylamine salt; alicyclic amines such as pyrrolidine salt and piperidine salt Salt; and the like.

As a compound (6), the dicarboxylic acid compound which the hydrogen atom couple | bonded with the both terminal of the structural unit represented by Formula (6) is mentioned, for example. More specifically, as a dicarboxylic acid compound, for example, malonic acid, succinic acid, glutaric acid, 2,2-dimethyl glutaric acid, 3,3-dimethyl glutaric acid, adipic acid, 2,2-dimethyl adipic acid, Pimelic acid, suberic acid, azelaic acid, 2-ethyl azelaic acid, sebacic acid, 1,9-nonane dicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,15-pentadecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,17-heptadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid 1,19-nonadecane dicarboxylic acid, 1,20-icosan dicarboxylic acid, itacon , Phthalic acid, dimer acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexene dicarboxylic acid and the like. As the dimer acid, for example, commercially available Halidimer 200, 250 or 270S (each Harima Chemicals Group, Inc.); Tsunodime 205, 216, 228, 395 or 346 (each Chikuno Food Industry Co., Ltd.); Unydyme 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 Chemical Co., Ltd.); Empol 1016, 1003, 1026, 1028, 1061, 1062, 1008 or 1012 (each BASF Corporation); hydrogenated dimer acid (average _Mn- 570; Sigma- Aldrich) and the like.

  The compounding amount of each of the compounds (1) to (6) may be appropriately set according to the ratio of each structural unit in the resin that can be manufactured.

  The organic solvent is not particularly limited as long as it can dissolve the compounds (1) to (6). For example, glycols such as ethylene glycol ethyl ether, ethylene glycol n-butyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether An ether-based organic solvent, a ketone-based organic solvent such as methyl ethyl ketone or methyl isobutyl ketone, or an amide-based organic solvent such as dimethylformamide, dimethylacetamide, or 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; 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.

In the resin produced as described above, whether or not a structural unit represented by Formula (1), Formula (2), Formula (3), Formula (4), Formula (5), Formula (6), etc. is included Such confirmation can be performed by measuring ¹ H NMR and / or ¹³ C NMR using a nuclear magnetic resonance apparatus.

<Emulsion>
The emulsion which concerns on this embodiment contains the said anionic epoxy resin or its salt. An 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 more and 50 ° C. or less.

  The emulsion may further comprise a blocked polyisocyanate curing agent which is a curing agent for epoxy resins. In addition, a curing catalyst may be included together with the block polyisocyanate curing agent. When these are included, an emulsion can be obtained by previously mixing an anionic epoxy resin or a salt thereof, a blocked polyisocyanate curing agent and a curing catalyst, and then dispersing the mixture in water by phase inversion emulsification.

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

  Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polymeric MDI (crude MDI: polymethylene polyphenyl polyisocyanate). And 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 blocking agents include lactam compounds such as ε-caprolactam and γ-butyrolactam, oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime, phenol compounds such as phenol, para-t-butylphenol and cresol, n-butanol, Examples thereof include alcohols such as 2-ethylhexanol, and glycol ether compounds such as ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and diethylene glycol monoethyl ether. One of these blocking agents may be used, or two or more thereof may be used in combination, and an appropriate one may be selected depending on the type of the polyisocyanate compound.

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

<Surface treatment agent>
The surface treatment agent which concerns on this embodiment contains the said anionic epoxy resin or its salt, or the said emulsion. The surface treatment agent may further contain known acids, oxidizing agents, various additives and the like used for the surface treatment agent.

  As the acid and the oxidizing agent, for example, hydrofluoric acid or a salt thereof, fluorosilicon acid or a salt thereof, fluorotitanic acid or a salt thereof, iron (III) nitrate, iron (III) sulfate, iron methanesulfonate ( III) Water-soluble iron compounds such as iron (III) fluoride, iron (III) chloride, iron (III) citrate, acetic acid, phosphoric acid, sulfuric acid, nitric acid, hydrogen peroxide, hydrogen peroxide, perchloric acid, permanganic acid, etc. Peroxide etc. are mentioned. 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 salts; alkanolamine salts such as monoethanolamine salt, diethanolamine salt, triethanolamine salt, methylethanolamine salt and dimethylethanolamine salt; 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; and the like.

  Additives include, for example, pH adjusters, ORP adjusters, chelating agents, weathering agents, antibacterial agents, antifungal agents, pigments, fillers, antirust agents, pigments, dyes, film forming aids, inorganic crosslinking agents, Organic crosslinking agents (eg, carbodiimide crosslinking agents, oxazoline crosslinking agents, melamine crosslinking agents, etc.), silane coupling agents, antiblocking agents, viscosity modifiers, leveling agents, antifoaming agents, dispersion stabilizers, light stabilizers, Antioxidants, UV absorbers, inorganic and organic fillers, plasticizers, lubricants, antistatic agents and the like can be mentioned. One of these additives may be used, or two or more thereof may be used in combination.

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

<Material Having Coating and Method of Manufacturing the Same>
A method of manufacturing a material having a film according to the present embodiment (hereinafter simply referred to as “manufacturing method”) comprises a first step of bringing the surface treatment agent into contact with the surface or surface of a material having a metal on the surface; And b) baking the contacted surface treatment agent (uncured film). In this manufacturing method, a step of washing the uncured film may be carried out 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 more and 50 ° C. or less and in the range of 0.1 seconds or more and 1 hour or less.

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

  In the manufacturing method according to the present embodiment, the surface of the material may be subjected to a degreasing treatment 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 agent include, but are not limited to, known acid degreasing agents, alkaline degreasing agents, solvent degreasing agents, and the like. The degreasing method is not particularly limited, and examples thereof include methods such as scrub washing, spray washing (spray washing), and dip (immersion) washing.

  In the manufacturing method according to the present embodiment, after the degreasing process and before the first process, a water washing process may be performed to wash the surface of the material, but after the water washing process, further on the surface of the material before the first process. And drying may be performed. A known method can be applied as the drying method.

  Moreover, after the degreasing treatment step before the first step, the water washing step, the drying step and the like, and before the first step, a chemical conversion treatment step may be performed to form a chemical conversion treatment film on the metal in the material. The chemical conversion treatment is performed by contacting the material with a known chemical conversion treatment agent. The chemical conversion treatment method is not particularly limited, and known methods can be applied. In addition, after the chemical conversion treatment step, a water washing step may be performed before the first step, and further, after the water washing step, a drying step may be performed before the first step.

  By the above manufacturing method, it is possible to manufacture a material having a film containing an anionic epoxy resin or a salt thereof on the surface or surface of a material having a metal on the surface. The form of the anionic epoxy resin or the salt thereof contained in the film may be in the form as it is or in 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 the salt thereof contained in the film is the anionic epoxy resin or a salt thereof, and the blocked polyisocyanate curing agent In the form of a cross-linked product thereof. The thickness of the film is not particularly limited, but is usually in the range of 0.1 μm to 1000 μm.

<Applications such as resin>
The above-mentioned anionic epoxy resin or its salt, emulsion, surface treatment agent, etc., an adhesive, glasses, an optical material (for example, one represented by an imaging lens), a lining agent, an ink, a resist, a liquid resist, a printing plate, Insulating varnishes, insulating sheets, laminates, printed boards, sealants (for example, for semiconductor devices, LED packages, for liquid crystal injection ports, for organic ELs, for optical elements, for electrical insulation, for electronic parts, for separation films Such as molding materials, putties, glass fiber impregnating agents, fillers, passivation films (for example, for semiconductors, solar cells etc.), interlayer insulating films, protective films, prism lens sheets (for example, liquid crystal displays) Equipment used in back lights), Fresnel lens sheets (eg, used in screens of projection televisions etc.), lenticular lenses Lens portion of a lens sheet such as a sheet, or a backlight using such a sheet, an optical lens (for example, a microlens etc.), an optical element, an optical connector, an optical waveguide, a casting agent for optical shaping, etc. It can be used for However, applications of the above-mentioned anionic epoxy resin or a salt thereof, an emulsion, a surface treatment agent and the like are not limited to the above.

  Examples and Comparative Examples will be described for the anionic epoxy resin, the emulsion and the surface treatment agent of the present invention. 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 are added to 536.0 g of N-methyl-2-pyrrolidone and heated to 120 ° C. with stirring. did. Thereafter, while maintaining the temperature, 0.6 g of dimethylbenzylamine was added and reacted for 1.5 hours. Thereafter, 113.0 g of A2 and 60.5 g of D1 were added and allowed to react for 5 hours. Thereafter, the reaction solution was cooled to obtain an anionic epoxy resin having a solid concentration of 46.4% and a weight average molecular weight of about 50,000.

Examples 2 to 24 and Comparative Examples 1 to 4
The anionic epoxy resins of Examples 2 to 24 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1 using predetermined amounts (amount of preparation: parts by mass) of the components shown in Table 1.

Each symbol in Table 1 shows the following components, respectively.
<Component A>
A1: Diglycidyl ether compound of bisphenol A (jER # 828EL, manufactured by Mitsubishi Chemical Corporation)
A2: Bisphenol A (made by Idemitsu Kosan Co., Ltd.)
A3: Diglycidyl ether compound of 1, 6-dihydroxy naphthalene (EPICLON HP-4032D, manufactured by DIC)
A4: resorcinol (made by Tokyo Chemical Industry Co., Ltd.)
<Component B>
B1: Compound in which hydrogen atoms in three hydroxy groups in α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene are substituted with glycidyl group (TECHMORE VG-3101L, Purinetec Co., Ltd. Made)
Triglycidyl ether compound of B2: 1,1,1-tris (4-hydroxyphenyl) ethane (jER # 1032H60, manufactured by Mitsubishi Chemical Corporation)
B3: Tetraglycidyl ether compound of 1,1′-methylenebis (2,7-naphthalenediol) (EPICLON HP-4710, manufactured by DIC)
B4: Tetraglycidyl ether compound of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (jER # 1031S, manufactured by Mitsubishi Chemical Corporation)
<Component C: all manufactured by Tokyo Chemical Industry>
C1: Hydroquinone potassium 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-Diaminobenzenesulfonic acid C6: 3,4-diaminonaphthalene-1-sulfonic acid C7: 4-aminobenzenesulfonic acid sodium C8: 2-amino-1-naphthalenesulfonic acid sodium C9: 4-hydroxybenzenesulfonic acid sodium C10: sodium isethionate <component D>
D1: Dicarboxylic acid compound (Haridimer 270S, manufactured by Harima Chemicals)
D2: Adipic acid (made by Tokyo Chemical Industry Co., Ltd.)
D3: 1,16-hexadecanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

<< Synthesis of Blocked Polyisocyanate Curing Agent >>
<Production Example 1>
After adding 77.1 g of methyl isobutyl ketone to 452.3 g of polymethylene polyphenyl polyisocyanate (Cosmonate M-200, manufactured by Mitsui Chemicals, Inc.) and heating to 70 ° C., 470.7 g of butyl cellosolve is slowly dropped, and the dropping is completed. Then, it was heated to 90 ° C. Subsequently, the reaction was conducted at 90 ° C. for 12 hours to obtain a blocked polyisocyanate curing agent in which the isocyanate group was completely blocked. In addition, that the isocyanate group was blocked was performed by confirming whether the absorption derived from the unreacted isocyanate group was seen by infrared absorption spectrum measurement.

«Emulsion»
Example 25
To 646.5 g of the anionic epoxy resin of Example 1, 353.5 g of pure water was slowly added, and an emulsion having a solid concentration of 30% was produced by the phase inversion emulsification method.

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

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. Then, 453.5 g of pure water was slowly added, and an emulsion having a solid concentration of 30% was produced by the phase inversion emulsification method.

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

«Surface treatment agent»
Example 73
5.5 g of 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.) are added to 333.0 g of the emulsion of Example 25 to obtain 25% by mass sodium hydroxide The pH was adjusted to 3.5 using an aqueous solution, and then the ORP (redox potential) was adjusted to 380 to 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 material having film >>
<Metal material>
As a metal material, SPC: cold rolled steel plate (SPCC-SD, plate thickness: 0.8 mm) was used.

<Degreasing treatment>
Spray with alkaline degreaser [Degreaser mixed with water so that agents A and B of Fine Cleaner E 2001 (made by Nippon Parkerizing Co., Ltd.) become 13 g / kg and 7 g / kg, respectively] at 45 ° C. for 2 minutes And degreased the surface of the metal material.

<Surface treatment>
After the degreased metal material was immersed in the surface treatment agent of Example 73 at 25 ° C. for 1 minute, 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 (Example 121) having a film with a film thickness of 20 μm on the surface.

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 produced in the same manner as the production method of Example 121. The metal material which it has is obtained.

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

<Edge Coverability Test>
The edge of the metal material having various films is observed with a laser microscope (VK-8710, manufactured by Keyence Corporation), and the ratio of the film thickness of the edge to the film thickness (20 μm) at the center of the film of the metal material is calculated. And the edge coverage was evaluated according to the following evaluation criteria.
(Evaluation criteria)
:: ratio [(film thickness at edge) / (film thickness at center of film)] is 0.50 or more x: ratio is less than 0.50

<Insulation test>
The electrical insulation (withstand voltage) of the film in each of 121 to 168 and Comparative Examples 21 to 28 was measured by using a withstanding voltage tester (TOS 9201, 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 boosting speed of 50 V / second, and a cutoff current of 1.0 mA.
(Evaluation criteria)
◎: The withstand voltage of the film is 2 kV or more. :: The withstand voltage of the film is 1 kV or more and less than 2 kV. X: The withstand voltage of the film is less than 1 kV.

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

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

Claims (7)

A structural unit represented by the following formula (1),
At least one of the structural units represented by the following formula (2) and the following formula (3),
At least one of the structural units represented by the following formula (4) and the following formula (5),
And anionic epoxy resins or salts thereof.

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

[In Formula (1a), R 2 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 the salt thereof according to claim 1, comprising a structural unit represented by the following formula (6).

(In the formula (6), R 16 is an alkylene group having 1 to 20 carbon atoms. The alkylene group may have an alkyl group, an alkenyl group, an alkadienyl group or a methylene group. The carbon number of the alkylene group is When it is 2 to 20, it may constitute a ring via adjacent carbon atoms, and the ring has one or more substituents selected from an alkyl group and an alkenyl group. May)   An emulsion comprising the anionic epoxy resin or the salt thereof according to claim 1 or 2.   An emulsion according to claim 3, comprising a blocked polyisocyanate curing agent.   A surface treatment agent comprising the anionic epoxy resin or the salt thereof according to claim 1 or claim 2, or the emulsion according to claim 3 or claim 4.   A method for producing a material having a film, comprising the steps of contacting the surface treatment agent according to claim 5 on the surface of the material having a metal on the surface or baking the surface treatment agent brought into contact.   A material having a film comprising the anionic epoxy resin or the salt thereof according to claim 1 or 2 on the surface or surface of a material having a metal on the surface.