Azole compound, method for synthesizing said azole compound, and use thereof

Abstract

The present invention provides a novel azole compound, a method for synthesizing the same, and a coupling agent. The azole compound according to the present invention is represented by chemical formula (I). The A in chemical formula (I) represents a group represented by any of formulas (1) through (3), and the substitution groups in formulas (1) through (3) are as defined in the description.

Description

Azole compounds, methods for synthesizing said azole compounds and uses thereof

[0001] The present invention relates to a novel azole compound, a method for synthesizing the azole compound, and use thereof.

[0002] Coupling agents have traditionally been used to bond materials with different properties, such as organic and inorganic materials, and are used in fields such as electronic materials, paints, primers, adhesives, etc. Therefore, coupling agents are essential agents for the development and production of composite materials.

[0003] For example, coupling agents (silane coupling agents) that use compounds composed of organic substances and silicon are known, and these silane coupling agents function as intermediaries that connect organic and inorganic materials that are normally incompatible.

[0004] Furthermore, azole compounds such as triazole compounds have the function of preventing metals from rusting and the function of curing epoxy resins and urethane resins, and therefore various coupling agents using azole compounds have been proposed.

[0005] As a coupling agent, for example, Patent Document 1 proposes a triazole silane compound in which an alkoxysilyl group is introduced into a specific triazole ring. Also, Patent Document 2 proposes a triazole silane compound having a disulfide bond (-S-S-) with two specific triazole rings, and having -CO-NH-(CH ２ ) m-Si(OR) ３ A triazole silane compound into which the following has been introduced has been proposed.

[0006] International Publication No. 2018 / 186476 International Publication No. 2015 / 002158

[0007] In recent years, in the field of electrical and electronic materials, there has been a demand for improved adhesiveness (adhesion) between materials in response to trends toward miniaturization, thinning, precision, high-speed propagation, etc. Although azole compounds such as those disclosed in Patent Documents 1 and 2 can exhibit excellent adhesiveness, compounds that can exhibit even higher adhesiveness have been desired.

[0008] The present invention has been made in view of the above problems, and an object of the present invention is to provide a novel azole compound, a method for synthesizing the same, and a coupling agent.

[0009] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by an azole compound obtained by reacting a certain type of styryl compound with a certain type of triazole compound or tetrazole compound, and have thus completed the present invention. That is, the first invention is an azole compound represented by chemical formula (I):

[0010]

[0011] (In formula (I), A represents a group represented by formulas (1) to (3).)

[0012]

[0013] (In formula (1), R １ and R ２ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a group represented by formula (11), or a group represented by formula (12). ３ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a group represented by formula (21), or a group represented by formula (31). １ and R ２ are simultaneously hydrogen atoms, R １ and R ２ is simultaneously a group represented by formula (11), R １ and R ２ is simultaneously a group represented by formula (12), R １ and R ２ is a group represented by formula (11) or formula (12).

[0014]

[0015] (In formula (11) and formula (12), R ４ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, or an alkylthio group having 1 to 6 carbon atoms. １１ represents a hydrogen atom or a group represented by formula (4), and Y represents a phenylene group, —NH—, or —(CH ２ ) ｎ -, where n is an integer of 0 to 12.

[0016]

[0017] The second invention is a method for synthesizing the azole compound of the first invention, which comprises reacting a styryl compound represented by chemical formula (II) with a triazole compound represented by chemical formula (III) or a tetrazole compound represented by chemical formula (IV).

[0018]

[0019] (In formula (II), X represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)

[0020]

[0021] (In formula (III), R ２１ and R ２２ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a group represented by formula (13), or a group represented by formula (14). ２３ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a group represented by formula (22), or a group represented by formula (32). ２１ and R ２２are simultaneously hydrogen atoms, R ２１ and R ２２ is simultaneously a group represented by formula (13), R ２１ and R ２２ is simultaneously a group represented by formula (14), R ２１ and R ２２ is a group represented by formula (13) or formula (14).

[0022]

[0023] (R in formula (13) and formula (14) ４ and Y in formulas (13), (14), (22) and (32) are the same as defined above.

[0024] The third invention is a coupling agent containing the azole compound of the first invention. The fourth invention is a surface treatment liquid containing the azole compound of the first invention. The fifth invention is the surface treatment liquid of the fourth invention used to treat at least one surface selected from the group consisting of metals, inorganic materials, and resin materials. The sixth invention is the surface treatment liquid of the fourth invention used to bond two materials selected from the group consisting of metals, inorganic materials, and resin materials. The seventh invention is the surface treatment liquid according to the fifth or sixth invention, in which the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. The eighth invention is a surface treatment method in which the surface treatment liquid according to any one of the fourth to seventh inventions is brought into contact with at least one surface selected from the group consisting of metals, inorganic materials, and resin materials. A ninth invention is the surface treatment method according to the eighth invention, wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. A tenth invention is the surface treatment method according to the eighth or ninth invention, wherein the metal is copper or a copper alloy. An eleventh invention is the surface treatment method according to any one of the eighth to tenth inventions, wherein an aqueous solution containing copper ions is brought into contact with the copper or copper alloy surface before the surface treatment liquid is brought into contact with the copper or copper alloy surface. A twelfth invention is the surface treatment method according to any one of the eighth to eleventh inventions, wherein an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the copper or copper alloy surface after the surface treatment liquid has been brought into contact with the copper or copper alloy surface. A thirteenth invention is a bonding method comprising contacting the surface treatment liquid according to any one of the fourth to seventh inventions with at least one material selected from the group consisting of a metal, an inorganic material, and a resin material to form a chemical conversion coating on at least one of the materials, and bonding the materials together via the chemical conversion coating.The fourteenth invention is a method for bonding metal and resin materials, which comprises contacting at least one of the metal and resin material with the surface treatment liquid according to any one of the fourth to seventh inventions to form a chemical conversion film on at least one of the metal and resin material, and bonding the metal and resin material to each other via the chemical conversion film. The fifteenth invention is a printed wiring board in which two materials selected from the group consisting of metals, inorganic materials, and resin materials are bonded via a chemical conversion film formed using the surface treatment liquid according to any one of the fourth to seventh inventions. The sixteenth invention is a semiconductor wafer in which two materials selected from the group consisting of metals, inorganic materials, and resin materials are bonded via a chemical conversion film formed using the surface treatment liquid according to any one of the fourth to seventh inventions. The seventeenth invention is an insulating composition containing the coupling agent according to the third invention and a resin material or an inorganic material. The eighteenth invention is an insulating material containing the insulating composition according to the seventeenth invention. A nineteenth invention is a printed wiring board having an insulating layer obtained from the insulating composition of the seventeenth invention. A twentieth invention is a semiconductor wafer having an insulating layer obtained from the insulating composition of the seventeenth invention.

[0025] The azole compound of the present invention has a polymerizable group (—C ６ H ４ -CH=CH ２ Since the azole compound of the present invention is a compound having an azole ring (triazole ring or tetrazole ring) together with a polymerizable group (-C), it has both the metal rust prevention function characteristic of azole compounds and the function of curing epoxy resins, urethane resins, etc. Therefore, the azole compound of the present invention is useful as a coupling agent or a component of a surface treatment liquid. In addition, the coupling agent of the present invention has a polymerizable group (-C ６ H ４ -CH=CH ２ The surface treatment solution contains an azole compound having the following structure: a metal and an inorganic material; a metal and a resin material; and an inorganic material and a resin material.

[0026] The present invention will be described in detail below. However, the present invention is not limited to the embodiments described below.

[0027] (Azole Compound) The azole compound of the present invention is represented by the above chemical formula (I) (hereinafter, may be referred to as the azole compound of the present invention). The azole compound represented by chemical formula (I) includes azole compounds represented by chemical formulas (I-1) to (I-3).

[0028]

[0029] (In formula (I-1), R １ and R ２ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a group represented by formula (11), or a group represented by formula (12). ３ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a group represented by formula (21), or a group represented by formula (31). １ and R ２ are simultaneously hydrogen atoms, R １ and R ２ is simultaneously a group represented by formula (11), R １ and R ２ is simultaneously a group represented by formula (12), R １ and R ２ is a group represented by formula (11) or formula (12).

[0030]

[0031] (In formula (11) and formula (12), R ４represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, or an alkylthio group having 1 to 6 carbon atoms. １１ represents a hydrogen atom or a group represented by formula (4), and Y represents a phenylene group, —NH—, or —(CH ２ ) ｎ -, where n is an integer of 0 to 12.

[0032]

[0033] R １ , R ２ and R ３Specific examples of the linear alkyl group having 1 to 12 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. Specific examples of the branched alkyl group having 1 to 12 carbon atoms include an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, an isopentyl group, an s-pentyl group, a t-pentyl group, an isohexyl group, an s-hexyl group, and a t-hexyl group. Specific examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a trimethylphenyl group, a tetramethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group. Specific examples of aralkyl groups include benzyl, phenylethyl, phenylpropyl, and methylbenzyl groups. Specific examples of optionally substituted amino groups include amino, methylamino, ethylamino, propylamino, isopropylamino, phenylamino, acetamide, guanidino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, ethylmethylamino, and diphenylamino groups. Specific examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Specific examples of alkylthio groups having 1 to 6 carbon atoms include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, and hexylthio groups.

[0034] R in the group represented by formula (11) and the group represented by formula (12) ４ Specific examples of the linear alkyl group having 1 to 12 carbon atoms, the branched alkyl group having 1 to 12 carbon atoms, the aryl group, the aralkyl group, the amino group which may be substituted, the halogen atom, and the alkylthio group having 1 to 6 carbon atoms, represented by the following formula (I), are the same as those described above.

[0035] In formula (I-1), R １ and R ２are the same or different and are more preferably an amino group or an alkylthio group having 1 to 6 carbon atoms, and even more preferably a primary amino group or an alkylthio group having 1 to 4 carbon atoms. ３ is more preferably an amino group or an alkylthio group having 1 to 6 carbon atoms, and more preferably a primary amino group or an alkylthio group having 1 to 4 carbon atoms.

[0036] Specific examples of the azole compound represented by chemical formula (I-1) include, for example, 3-methyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-methyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-propyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-propyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-isopropyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-isopropyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-butyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-butyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-hexyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-hexyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-octyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-octyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-decyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-decyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-dodecyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-dodecyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3,5-dimethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3,5-diisopropyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-methyl-5-octyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-methyl-3-octyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-ethyl-5-octyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-ethyl-3-octyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-methyl-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-methyl-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-ethyl-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-ethyl-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3,5-diphenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-propyl-3-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-propyl-5-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-benzyl-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-benzyl-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-5-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-3-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-5-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-3-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3,5-diamino-1-(2-vinylbenzyl)-1H-1,2,4-triazole, 3,5-diamino-1-(3-vinylbenzyl)-1H-1,2,4-triazole, 3,5-diamino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-methylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-methylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-ethylthio-5-isopropyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-ethylthio-3-isopropyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-isopropylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-isopropylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-hexylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-hexylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3,5-bis(methylthio)-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-methylthio-5-hexylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-methylthio-3-hexylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-5-methylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-3-methylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-5-isopropylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-3-isopropylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-5-hexylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-3-hexylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-methylamino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-methylamino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3,5-bis(methylamino)-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-5-methylamino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-3-methylamino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-methylamino-5-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-methylamino-3-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-methylamino-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-methylamino-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-methylamino-5-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-methylamino-3-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-phenylamino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-phenylamino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3,5-bis(phenylamino)-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-5-phenylamino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-3-phenylamino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-phenylamino-5-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-phenylamino-3-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-phenylamino-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-phenylamino-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-phenylamino-5-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-phenylamino-3-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-acetamido-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-acetamido-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3,5-bis(acetamido)-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-5-acetamido-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-3-acetamido-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-acetamido-5-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-acetamido-3-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-acetamido-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-acetamido-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-acetamido-5-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-acetamido-3-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-guanidino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-guanidino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3,5-bis(guanidino)-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-amino-5-guanidino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-amino-3-guanidino-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-guanidino-5-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-guanidino-3-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-guanidino-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-guanidino-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-guanidino-5-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-guanidino-3-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-hydroxy-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-hydroxy-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-hydroxy-5-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-hydroxy-3-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-hydroxy-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-hydroxy-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-hydroxy-5-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-hydroxy-3-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-cyano-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-cyano-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-cyano-5-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-cyano-3-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-cyano-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-cyano-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-cyano-5-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-cyano-3-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-chloro-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-chloro-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-chloro-5-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-chloro-3-ethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-bromo-5-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-bromo-3-phenyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 3-iodo-5-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 5-iodo-3-benzyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole, 1-(4-vinylbenzyl)-3,3'-(1,4-phenylene)bis(1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-(1,2-phenylene)bis(5-methyl-1,2,4-1H-triazole), 1-(4-vinylbenzyl)-3,3'-(1,1-(4-vinylbenzyl)-3,3'-(1,4-phenylene)bis(5-amino-1,2,4-1H-triazole), 1-(4-vinylbenzyl)-3,3'-(1,4-phenylene)bis(5-ethylthio-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-iminobis(5-ethyl-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-iminobis(5-p-tolyl-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-iminobis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-iminobis(5-isopropyl-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-bis(5-methyl-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-bis(5-pentyl-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-bis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-bis(5-phenyl-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-5-amino-5'-methyl-3,3'-bi-1H-1,2,4-triazole, 1-(4-vinylbenzyl)-3,3'-methylenebis(5-isobutyl-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-methylenebis(5-hydroxy-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-methylenebis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-ethylenebis(5-ethyl-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-ethylenebis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-tetramethylenebis(5-benzyl-1,2,4-1H-triazole), 1-(4-vinylbenzyl)-3,3'-tetramethylenebis(5-butylthio-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-tetramethylenebis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-pentamethylenebis(1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-pentamethylenebis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-hexamethylenebis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-octamethylenebis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-nonamethylenebis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-decamethylenebis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-undecamethylenebis(5-amino-1H-1,2,4-triazole), 1-(4-vinylbenzyl)-3,3'-dodecamethylenebis(5-amino-1H-1,2,4-triazole), 3,3'-(1,4-phenylene)bis[1-(4-vinylbenzyl)-1H-1,2,4-triazole], 3,3'-(1,2-phenylene)bis[1-(4-vinylbenzyl)-5-methyl-1H-1,2,4-triazole], 3,3'-(1,3-phenylene)bis{1-(4-vinylbenzyl)-5-butyl-1H-1,2,4-triazole], 3,3'-(1,4-phenylene)bis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-(1,4-phenylene)bis[1-(4-vinylbenzyl)-5-ethylthio-1H-1,2,4-triazole], 3,3'-iminobis[1-(4-vinylbenzyl)-5-ethyl-1H-1,2,4-triazole], 3,3'-iminobis[1-(4-vinylbenzyl)-5-p-tolyl-1H-1,2,4-triazole], 3,3'-iminobis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-iminobis[1-(4-vinylbenzyl)-5-isopropyl-1H-1,2,4-triazole], 3,3'-bis[1-(4-vinylbenzyl)-1H-1,2,4-triazole], 3,3'-bis[1-(4-vinylbenzyl)-5-pentyl-1H-1,2,4-triazole], 3,3'-bis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-bis[1-(4-vinylbenzyl)-5-phenyl-1H-1,2,4-triazole], 1,1'-bis(4-vinylbenzyl)-5-amino-5'-methyl-3,3'-bi-1H-1,2,4-triazole, 3,3'-methylenebis[1-(4-vinylbenzyl)-5-isobutyl-1H-1,2,4-triazole], 3,3'-methylenebis[1-(4-vinylbenzyl)-5-hydroxy-1H-1,2,4-triazole], 3,3'-methylenebis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-ethylenebis[1-(4-vinylbenzyl)-5-ethyl-1H-1,2,4-triazole], 3,3'-ethylenebis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-tetramethylenebis[1-(4-vinylbenzyl)-5-benzyl-1,2,4-1H-triazole], 3,3'-tetramethylenebis[1-(4-vinylbenzyl)-5-butylthio-1H-1,2,4-triazole], 3,3'-tetramethylenebis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-pentamethylenebis[1-(4-vinylbenzyl)-1H-1,2,4-triazole], 3,3'-pentamethylenebis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-hexamethylenebis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-octamethylenebis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-nonamemethylenebis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-decamethylenebis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-undecamethylenebis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], 3,3'-dodecamethylenebis[1-(4-vinylbenzyl)-5-amino-1H-1,2,4-triazole], etc.

[0037] Specific examples of the azole compound represented by chemical formula (I-2) include 1-(4-vinylbenzyl)-1H-tetrazole, 5-methyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-ethyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-propyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-isopropyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-butyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-tert-butyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-pentyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-hexyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-octyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-decyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-dodecyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-phenyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-(p-tolyl)-1-(4-vinylbenzyl)-1H-tetrazole, 5-benzyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-phenethyl-1-(4-vinylbenzyl)-1H-tetrazole, 5-methylthio-1-(4-vinylbenzyl)-1H-tetrazole, 5-ethylthio-1-(4-vinylbenzyl)-1H-tetrazole, 5-propylthio-1-(4-vinylbenzyl)-1H-tetrazole, 5-isopropylthio-1-(4-vinylbenzyl)-1H-tetrazole, 5-butylthio-1-(4-vinylbenzyl)-1H-tetrazole, 5-pentylthio-1-(4-vinylbenzyl)-1H-tetrazole, 5-hexylthio-1-(4-vinylbenzyl)-1H-tetrazole, 5-amino-1-(2-vinylbenzyl)-1H-tetrazole, 5-amino-1-(3-vinylbenzyl)-1H-tetrazole, 5-amino-1-(4-vinylbenzyl)-1H-tetrazole, 5-methylamino-1-(4-vinylbenzyl)-1H-tetrazole, 5-ethylamino-1-(4-vinylbenzyl)-1H-tetrazole, 5-phenylamino-1-(4-vinylbenzyl)-1H-tetrazole,5-acetamido-1-(4-vinylbenzyl)-1H-tetrazole, 5-guanidino-1-(4-vinylbenzyl)-1H-tetrazole, 5-hydroxy-1-(4-vinylbenzyl)-1H-tetrazole, 5-cyano-1-(4-vinylbenzyl)-1H-tetrazole, 5-bromo-1-(4-vinylbenzyl)-1H-tetrazole, 1-(4-vinylbenzyl)-5,5'-(1,4-phenylene)bis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-(1,2-phenylene)bis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-(1,3-phenylene)bis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-iminobis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-bi-1H-tetrazole, 1-(4-vinylbenzyl)-5,5'-methylenebis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-ethylenebis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-tetramethylenebis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-pentamethylenebis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-hexamethylenebis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-octamethylenebis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-nonamethylenebis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-decamethylenebis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-undecamethylenebis(1H-tetrazole), 1-(4-vinylbenzyl)-5,5'-dodecamethylenebis(1H-tetrazole), 5,5'-(1,4-phenylene)bis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-(1,2-phenylene)bis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-(1,3-phenylene)bis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-iminobis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-bis[1-(4-vinylbenzyl)-1H-tetrazole],1-(4-vinylbenzyl)-2'-(4-vinylbenzyl)-bi-1,2,3,4-tetrazole, 5,5'-methylenebis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-ethylenebis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-tetramethylenebis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-pentamethylenebis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-hexamethylenebis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-octamethylenebis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-nonamethylenebis[1-(4-vinylbenzyl)-1H-tetrazole], Examples thereof include 5,5'-decamethylenebis[1-(4-vinylbenzyl)-1H-tetrazole], 5,5'-undecamethylenebis[1-(4-vinylbenzyl)-1H-tetrazole], and 5,5'-dodecamethylenebis[1-(4-vinylbenzyl)-1H-tetrazole].

[0038] Specific examples of the azole compound represented by chemical formula (I-3) include, for example, 2-(4-vinylbenzyl)-2H-tetrazole, 5-methyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-ethyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-propyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-isopropyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-butyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-tert-butyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-pentyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-hexyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-octyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-decyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-dodecyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-phenyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-(p-tolyl)-2-(4-vinylbenzyl)-2H-tetrazole, 5-benzyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-phenethyl-2-(4-vinylbenzyl)-2H-tetrazole, 5-methylthio-2-(4-vinylbenzyl)-2H-tetrazole, 5-ethylthio-2-(4-vinylbenzyl)-2H-tetrazole, 5-propylthio-2-(4-vinylbenzyl)-2H-tetrazole, 5-isopropylthio-2-(4-vinylbenzyl)-2H-tetrazole, 5-butylthio-2-(4-vinylbenzyl)-2H-tetrazole, 5-pentylthio-2-(4-vinylbenzyl)-2H-tetrazole, 5-hexylthio-2-(4-vinylbenzyl)-2H-tetrazole, 5-amino-2-(2-vinylbenzyl)-2H-tetrazole, 5-amino-2-(3-vinylbenzyl)-2H-tetrazole, 5-amino-2-(4-vinylbenzyl)-2H-tetrazole, 5-methylamino-2-(4-vinylbenzyl)-2H-tetrazole, 5-ethylamino-2-(4-vinylbenzyl)-2H-tetrazole, 5-phenylamino-2-(4-vinylbenzyl)-2H-tetrazole,5-acetamido-2-(4-vinylbenzyl)-2H-tetrazole, 5-guanidino-2-(4-vinylbenzyl)-2H-tetrazole, 5-hydroxy-2-(4-vinylbenzyl)-2H-tetrazole, 5-cyano-2-(4-vinylbenzyl)-2H-tetrazole, 5-bromo-2-(4-vinylbenzyl)-2H-tetrazole, 2-(4-vinylbenzyl)-5,5'-(1,4-phenylene)bis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-(1,2-phenylene)bis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-(1,3-phenylene)bis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-iminobis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-bi-2H-tetrazole, 2-(4-vinylbenzyl)-5,5'-methylenebis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-ethylenebis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-tetramethylenebis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-pentamethylenebis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-hexamethylenebis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-octamethylenebis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-nonamethylenebis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-decamethylenebis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-undecamethylenebis(2H-tetrazole), 2-(4-vinylbenzyl)-5,5'-dodecamethylenebis(2H-tetrazole), 5,5'-(1,4-phenylene)bis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-(1,2-phenylene)bis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-(1,3-phenylene)bis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-iminobis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-bis[2-(4-vinylbenzyl)-2H-tetrazole],5,5'-methylenebis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-ethylenebis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-tetramethylenebis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-pentamethylenebis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-hexamethylenebis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-octamethylenebis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-nonamemethylenebis[2-(4-vinylbenzyl)-2H-tetrazole], 5,5'-decamethylenebis[2-(4-vinylbenzyl)-2H-tetrazole], Examples thereof include 5,5'-undecamethylenebis[2-(4-vinylbenzyl)-2H-tetrazole] and 5,5'-dodecamethylenebis[2-(4-vinylbenzyl)-2H-tetrazole].

[0039] The azole compound of the present invention can be obtained by reacting a styryl compound represented by chemical formula (II) with a triazole compound represented by chemical formula (III) or a tetrazole compound represented by chemical formula (IV).

[0040]

[0041] (In formula (II), X represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)

[0042]

[0043] (In formula (III), R ２１ and R ２２ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a group represented by formula (13), or a group represented by formula (14). ２３represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a group represented by formula (22), or a group represented by formula (32). ２１ and R ２２ are simultaneously hydrogen atoms, R ２１ and R ２２ is simultaneously a group represented by formula (13), R ２１ and R ２２ is simultaneously a group represented by formula (14), R ２１ and R ２２ is a group represented by formula (13) or formula (14).

[0044]

[0045] (In formula (13) and formula (14), R ４ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, or an alkylthio group having 1 to 6 carbon atoms; and in formulas (13), (14), (22), and (32), Y represents a phenylene group, —NH—, or —(CH ２ ) ｎ -, where n is an integer of 0 to 12.

[0046] X in formula (II) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and from the viewpoints of reactivity and availability of raw materials, a chlorine atom or a bromine atom is preferred. ２１ , R ２２ and R ２３ Specific examples of the linear alkyl group having 1 to 12 carbon atoms, the branched alkyl group having 1 to 12 carbon atoms, the aryl group, the aralkyl group, the amino group which may be substituted, the halogen atom, and the alkylthio group having 1 to 6 carbon atoms, which are represented by the formula (I), and preferred examples thereof are also the same as those shown in chemical formula (I).

[0047] Examples of the styryl compound represented by chemical formula (II) include 2-vinylbenzyl chloride, 3-vinylbenzyl chloride, 4-vinylbenzyl chloride, 2-vinylbenzyl bromide, 3-vinylbenzyl bromide, 4-vinylbenzyl bromide, 2-vinylbenzyl iodide, 3-vinylbenzyl iodide, and 4-vinylbenzyl iodide.

[0048] These styryl compounds exemplified above can be purchased as commercially available reagents or can be synthesized in accordance with the synthesis method described in WO 1998 / 028264.

[0049] Examples of the triazole compound represented by chemical formula (III) include 3-methyl-1H-1,2,4-triazole, 3-ethyl-1H-1,2,4-triazole, 3-propyl-1H-1,2,4-triazole, 3-isopropyl-1H-1,2,4-triazole, 3-butyl-1H-1,2,4-triazole, 3-hexyl-1H-1,2,4-triazole, 3-octyl-1H-1,2,4-triazole, 3-decyl-1H-1,2,4-triazole, 3-dodecyl-1H-1,2,4-triazole, 3,5-dimethyl-1H-1,2,4-triazole, 3,5-diisopropyl-1H-1,2,4-triazole, 3-ethyl-5-octyl-1H-1,2,4-triazole, 5-methyl-3-octyl-1H-1,2,4-triazole, 3-phenyl-1H-1,2,4-triazole, 3-methyl-5-phenyl-1H-1,2,4-triazole, 3-ethyl-5-phenyl-1H-1,2,4-triazole, 3,5-diphenyl-1H-1,2,4-triazole, 3-benzyl-1H-1,2,4-triazole, 5-propyl-3-benzyl-1H-1,2,4-triazole, 3-benzyl-5-phenyl-1H-1,2,4-triazole, 3-amino-1H-1,2,4-triazole, 3-amino-5-ethyl-1H-1,2,4-triazole, 3-amino-5-phenyl-1H-1,2,4-triazole, 3-amino-5-benzyl-1H-1,2,4-triazole, 3,5-diamino-1H-1,2,4-triazole, 3-methylthio-1H-1,2,4-triazole, 3-ethylthio-5-isopropyl-1H-1,2,4-triazole, 3-isopropylthio-1H-1,2,4-triazole, 3-hexylthio-1H-1,2,4-triazole, 3,5-bis(methylthio)-1H-1,2,4-triazole, 3-methylthio-5-hexylthio-1H-1,2,4-triazole, 3-amino-5-methylthio-1H-1,2,4-triazole, 3-amino-5-isopropylthio-1H-1,2,4-triazole, 3-amino-5-hexylthio-1H-1,2,4-triazole, 3-methylamino-1H-1,2,4-triazole, 3,5-bis(methylamino)-1H-1,2,4-triazole, 3-amino-5-methylamino-1H-1,2,4-triazole, 3-methylamino-5-ethyl-1H-1,2,4-triazole, 3-methylamino-5-phenyl-1H-1,2,4-triazole, 3-methylamino-5-benzyl-1H-1,2,4-triazole, 3-phenylamino-1H-1,2,4-triazole, 3,5-bis(phenylamino)-1H-1,2,4-triazole, 3-amino-5-phenylamino-1H-1,2,4-triazole, 3-phenylamino-5-ethyl-1H-1,2,4-triazole, 3-phenylamino-5-phenyl-1H-1,2,4-triazole, 3-phenylamino-5-benzyl-1H-1,2,4-triazole, 3-acetamido-1H-1,2,4-triazole, 3,5-bis(acetamido)-1H-1,2,4-triazole, 3-amino-5-acetamido-1H-1,2,4-triazole, 3-acetamido-5-ethyl-1H-1,2,4-triazole, 3-acetamido-5-phenyl-1H-1,2,4-triazole, 3-acetamido-5-benzyl-1H-1,2,4-triazole, 3-guanidino-1H-1,2,4-triazole, 3,5-bis(guanidino)-1H-1,2,4-triazole, 3-amino-5-guanidino-1H-1,2,4-triazole, 3-guanidino-5-ethyl-1H-1,2,4-triazole, 3-guanidino-5-phenyl-1H-1,2,4-triazole, 3-guanidino-5-benzyl-1H-1,2,4-triazole, 3-hydroxy-1H-1,2,4-triazole, 3-hydroxy-5-ethyl-1H-1,2,4-triazole, 3-hydroxy-5-phenyl-1H-1,2,4-triazole, 3-hydroxy-5-benzyl-1H-1,2,4-triazole, 3-cyano-1H-1,2,4-triazole, 3-cyano-5-ethyl-1H-1,2,4-triazole, 3-cyano-5-phenyl-1H-1,2,4-triazole, 3-cyano-5-benzyl-1H-1,2,4-triazole, 3-chloro-1H-1,2,4-triazole, 3-chloro-5-ethyl-1H-1,2,4-triazole, 3-bromo-5-phenyl-1H-1,2,4-triazole, 3-iodo-5-benzyl-1H-1,2,4-triazole, 3,3'-(1,4-phenylene)bis(1H-1,2,4-triazole), 3,3'-(1,4-phenylene)bis(5-methyl-1H-1,2,4-triazole), 3,3'-(1,2-phenylene)bis(5-ethyl-1H-1,2,4-triazole), 3,3'-(1,4-phenylene)bis(5-isopropyl-1H-1,2,4-triazole), 3,3'-(1,3-phenylene)bis(5-butyl-1H-1,2,4-triazole), 3,3'-(1,4-phenylene)bis(5-phenyl-1H-1,2,4-triazole), 3,3'-(1,4-phenylene)bis(5-amino-1H-1,2,4-triazole), 3,3'-(1,4-phenylene)bis(5-hydroxy-1H-1,2,4-triazole), 3,3'-(1,4-phenylene)bis(5-ethylthio-1H-1,2,4-triazole), 5-amino-3,3'-(1,4-phenylene)bis(1H-1,2,4-triazole), 3,3'-iminobis(1H-1,2,4-triazole), 3,3'-iminobis(5-methyl-1H-1,2,4-triazole), 3,3'-iminobis(5-hexyl-1H-1,2,4-triazole), 3,3'-iminobis(5-phenyl-1H-1,2,4-triazole), 3,3'-Iminobis(5-benzyl-1H-1,2,4-triazole), 3,3'-Iminobis(5-amino-1H-1,2,4-triazole), 3,3'-Iminobis(5-hydroxy-1H-1,2,4-triazole), 3,3'-Iminobis(5-methylthio-1H-1,2,4-triazole), 5-amino-3,3'-iminobis(1H-1,2,4-triazole), 3,3'-bi-1H-1,2,4-triazole, 3,3'-bis(5-methyl-1H-1,2,4-triazole), 3,3'-bis(5-ethyl-1H-1,2,4-triazole), 3,3'-bis(5-pentyl-1H-1,2,4-triazole), 3,3'-bis(5-p-tolyl-1H-1,2,4-triazole), 3,3'-bis(5-benzyl-1H-1,2,4-triazole), 3,3'-bis(5-amino-1H-1,2,4-triazole), 3,3'-bis(5-hydroxy-1H-1,2,4-triazole), 3,3'-bis(5-hexylthio-1H-1,2,4-triazole), 5-amino-5'-methyl-3,3'-bi-1H-1,2,4-triazole, 3,3'-methylenebis(1H-1,2,4-triazole), 3,3'-methylenebis(5-methyl-1H-1,2,4-triazole), 3,3'-methylenebis(5-isobutyl-1H-1,2,4-triazole), 3,3'-methylenebis(5-phenyl-1H-1,2,4-triazole), 3,3'-methylenebis(5-phenethyl-1H-1,2,4-triazole), 3,3'-methylenebis(5-amino-1H-1,2,4-triazole), 3,3'-methylenebis(5-hydroxy-1H-1,2,4-triazole), 3,3'-methylenebis(5-methylthio-1H-1,2,4-triazole), 5-amino-5'-ethyl-3,3'-methylenebis(1H-1,2,4-triazole), 3,3'-ethylenebis(1H-1,2,4-triazole), 3,3'-ethylenebis(5-propyl-1H-1,2,4-triazole), 3,3'-ethylenebis(5-hexyl-1H-1,2,4-triazole), 3,3'-ethylenebis(5-m-tolyl-1H-1,2,4-triazole), 3,3'-ethylenebis(5-amino-1H-1,2,4-triazole), 3,3'-ethylenebis(5-hydroxy-1H-1,2,4-triazole), 3,3'-ethylenebis(5-isopropylthio-1H-1,2,4-triazole), 5-amino-3,3'-ethylenebis(1H-1,2,4-triazole), 3,3'-trimethylenebis(1H-1,2,4-triazole), 5-methyl-3,3'-trimethylenebis(1H-1,2,4-triazole), 3,3'-trimethylenebis(5-butyl-1H-1,2,4-triazole), 3,3'-trimethylenebis(5-phenyl-1H-1,2,4-triazole), 3,3'-trimethylenebis(5-amino-1H-1,2,4-triazole), 3,3'-trimethylenebis(5-propylthio-1H-1,2,4-triazole), 5-amino-5'-benzyl-3,3'-trimethylenebis(1H-1,2,4-triazole), 3,3'-tetramethylenebis(1H-1,2,4-triazole), 3,3'-tetramethylenebis(5-ethyl-1H-1,2,4-triazole), 3,3'-tetramethylenebis(5-hexyl-1H-1,2,4-triazole), 3,3'-tetramethylenebis(5-benzyl-1H-1,2,4-triazole), 3,3'-tetramethylenebis(5-amino-1H-1,2,4-triazole), 3,3'-tetramethylenebis(5-hydroxy-1H-1,2,4-triazole), 3,3'-tetramethylenebis(5-butylthio-1H-1,2,4-triazole), 5-amino-3,3'-tetramethylenebis(1H-1,2,4-triazole), 3,3'-pentamethylenebis(1H-1,2,4-triazole), 3,3'-pentamethylenebis(5-propyl-1H-1,2,4-triazole), 3,3'-pentamethylenebis(5-amino-1H-1,2,4-triazole), 3,3'-pentamethylenebis(5-hydroxy-1H-1,2,4-triazole), 3,3'-pentamethylenebis(5-pentylthio-1H-1,2,4-triazole), 5-amino-5'-phenyl-3,3'-pentamethylenebis(1H-1,2,4-triazole), 3,3'-hexamethylenebis(1H-1,2,4-triazole), 3,3'-hexamethylenebis(5-pentyl-1H-1,2,4-triazole), 3,3'-hexamethylenebis(5-amino-1H-1,2,4-triazole), 5-hydroxy-3,3'-hexamethylenebis(1H-1,2,4-triazole), 5-phenyl-3,3'-hexamethylenebis(1H-1,2,4-triazole), 5-amino-5'-methylthio-3,3'-hexamethylenebis(1H-1,2,4-triazole), 3,3'-heptamethylenebis(1H-1,2,4-triazole), 3,3'-heptamethylenebis(5-tert-butyl-1H-1,2,4-triazole), 3,3'-heptamethylenebis(5-phenyl-1H-1,2,4-triazole), 3,3'-heptamethylenebis(5-amino-1H-1,2,4-triazole), 5-amino-5'-hydroxy-3,3'-heptamethylenebis(1H-1,2,4-triazole), 3,3'-octamethylenebis(1H-1,2,4-triazole), 3,3'-octamethylenebis(5-isobutyl-1H-1,2,4-triazole), 3,3'-octamethylenebis(5-amino-1H-1,2,4-triazole), 3,3'-octamethylenebis(5-hydroxy-1H-1,2,4-triazole), 5-propylthio-3,3'-octamethylenebis(1H-1,2,4-triazole), 3,3'-nonameethylenebis(1H-1,2,4-triazole), 3,3'-nonameethylenebis(5-isopentyl-1H-1,2,4-triazole), 5-phenyl-3,3'-nonamemethylenebis(1H-1,2,4-triazole), 3,3'-nonamethylenebis(5-amino-1H-1,2,4-triazole), 3,3'-nonamethylenebis(5-methylthio-1H-1,2,4-triazole), 3,3'-decamethylenebis(1H-1,2,4-triazole), 3,3'-decamethylenebis(5-methyl-1H-1,2,4-triazole), 3,3'-decamethylenebis(5-amino-1H-1,2,4-triazole), 5-ethyl-3,3'-decamethylenebis(1H-1,2,4-triazole), 3,3'-undecamethylenebis(1H-1,2,4-triazole), Examples of the triazole include 3,3'-undecamethylenebis(5-propyl-1H-1,2,4-triazole), 3,3'-undecamethylenebis(5-amino-1H-1,2,4-triazole), 3,3'-undecamethylenebis(5-methylthio-1H-1,2,4-triazole), 3,3'-dodecamethylenebis(1H-1,2,4-triazole), 3,3'-dodecamethylenebis(5-ethyl-1H-1,2,4-triazole), 3,3'-dodecamethylenebis(5-amino-1H-1,2,4-triazole), and 3,3'-undecamethylenebis(5-hydroxy-1H-1,2,4-triazole).

[0050] These exemplified triazole compounds can be purchased as commercially available reagents and used, or can be synthesized in accordance with the synthesis methods described in, for example, J. Org. Chem., Vol. 44, p. 4160 (1979), U.S. Pat. No. 5,098,920, Chem. Eur. J., Vol. 18, p. 16742 (2012), J. Applied. Chem., Vol. 82, p. 276 (2009), and U.S. Pat. No. 2,744,116.

[0051] Examples of the tetrazole compound represented by chemical formula (IV) include 1H-tetrazole, 5-methyl-1H-tetrazole, 5-ethyl-1H-tetrazole, 5-propyl-1H-tetrazole, 5-isopropyl-1H-tetrazole, 5-butyl-1H-tetrazole, 5-tert-butyl-1H-tetrazole, 5-pentyl-1H-tetrazole, 5-hexyl-1H-tetrazole, 5-octyl-1H-tetrazole, 5-decyl-1H-tetrazole, 5-dodecyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-(p-tolyl)-1H-tetrazole, 5-benzyl-1H-tetrazole, 5-phenethyl-1H-tetrazole, 5-methylthio-1H-tetrazole, 5-ethylthio-1H-tetrazole, 5-propylthio-1H-tetrazole, 5-isopropylthio-1H-tetrazole, 5-butylthio-1H-tetrazole, 5-pentylthio-1H-tetrazole, 5-hexylthio-1H-tetrazole, 5-amino-1H-tetrazole, 5-methylamino-1H-tetrazole, 5-ethylamino-1H-tetrazole, 5-phenylamino-1H-tetrazole, 5-acetamido-1H-tetrazole, 5-guanidino-1H-tetrazole, 5-hydroxy-1H-tetrazole, 5-cyano-1H-tetrazole, 5-bromo-1H-tetrazole, 5,5'-(1,4-phenylene)bis(1H-tetrazole), 5,5'-(1,2-phenylene)bis(1H-tetrazole), 5,5'-(1,3-phenylene)bis(1H-tetrazole), 5,5'-iminobis(1H-tetrazole), 5,5'-bi(1H-tetrazole), 5,5'-methylenebis(1H-tetrazole), 5,5'-ethylenebis(1H-tetrazole), 5,5'-trimethylenebis(1H-tetrazole), 5,5'-tetramethylenebis(1H-tetrazole), 5,5'-pentamethylenebis(1H-tetrazole), 5,5'-hexamethylenebis(1H-tetrazole), 5,5'-heptamethylenebis(1H-tetrazole), 5,5'-octamethylenebis(1H-tetrazole), 5,5'-nonamethylenebis(1H-tetrazole), 5,Examples include 5'-decamethylenebis(1H-tetrazole), 5,5'-undecamethylenebis(1H-tetrazole), and 5,5'-dodecamethylenebis(1H-tetrazole).

[0052] These exemplified tetrazole compounds can be purchased as commercially available reagents or can be synthesized in accordance with the synthesis methods described in, for example, Chinese Patent No. 109503505 and WO 2015 / 084830.

[0053] The azole compound of the present invention can be synthesized, for example, by reacting a styryl compound represented by chemical formula (II) with a triazole compound represented by chemical formula (III) or a tetrazole compound represented by chemical formula (IV) in the presence of a dehydrohalogenating agent in an appropriate amount of reaction solvent at an appropriate reaction temperature and reaction time. The following reaction scheme (A) shows a reaction scheme for obtaining an azole compound (I-1) in which A is a group represented by formula (1).

[0054]

[0055] (R in formula (I-1) １ and R ２ , X in formula (II) and R in formula (III) ２１ and R ２２ is the same as above.)

[0056] The reaction solvent is not particularly limited as long as it is a solvent inert to the styryl compound represented by chemical formula (II) and the triazole compound represented by chemical formula (III) or the tetrazole compound represented by chemical formula (IV), and examples thereof include hydrocarbon solvents such as hexane, toluene, xylene, etc.; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, cyclopentyl methyl ether, etc.; ester solvents such as ethyl acetate, butyl acetate, etc.; alcohol solvents such as methanol, ethanol, etc.; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; acetonitrile, dimethyl sulfoxide, hexamethylphosphoramide, etc.

[0057] Examples of the dehydrohalogenating agent include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, and potassium t-butoxide; alkali carbonates such as sodium carbonate and potassium carbonate; organic bases such as triethylamine and diazabicycloundecene; and sodium hydride.

[0058] In this reaction, the amount (charge amount) of the styryl compound represented by chemical formula (II) used relative to the amount (charge amount) of the triazole compound represented by chemical formula (III) or the tetrazole compound represented by chemical formula (IV) used is preferably 0.8 to 2.4 equivalents, taking into consideration factors such as the reaction temperature and reaction time as well as the types of raw materials and reaction solvent used and the reaction scale. Furthermore, since the dehydrohalogenating agent is used to neutralize the hydrogen halide by-produced in this reaction, its amount (charge amount) may be at least equimolar to the amount of the styryl compound represented by chemical formula (II) used.

[0059] The reaction temperature is not particularly limited as long as it is within a temperature range in which —NH of the azole ring of the triazole compound represented by chemical formula (III) or the tetrazole compound represented by chemical formula (IV) reacts with the styryl compound represented by chemical formula (II). The reaction temperature is preferably in the range of 0 to 150° C., more preferably in the range of 5 to 100° C.

[0060] The reaction time is appropriately determined depending on the reaction temperature, but is preferably in the range of 30 minutes to 48 hours, more preferably in the range of 1 to 24 hours.

[0061] (Coupling Agent) The coupling agent of the present invention contains the azole compound represented by the chemical formula (I) as a component. When using the coupling agent of the present invention, the same surface treatment methods as those used for conventional coupling agents can be employed. Examples of such surface treatment methods include (a) spraying a substrate with a treatment liquid prepared by diluting an appropriate amount of the coupling agent with an organic solvent, (b) spraying a substrate with a treatment liquid prepared by diluting the coupling agent with water and an organic solvent, (c) spraying a substrate with a treatment liquid prepared by diluting the coupling agent with water, (d) immersing a substrate in a treatment liquid prepared by diluting the coupling agent with an organic solvent, (e) immersing a substrate in a treatment liquid prepared by diluting the coupling agent with water and an organic solvent, and (f) immersing a substrate in a treatment liquid prepared by diluting the coupling agent with water.

[0062] Examples of the organic solvent include hydrocarbon solvents such as benzene, toluene, xylene, heptane, hexane, cyclohexane, and n-octane; halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, carbon tetrachloride, chloroform, chlorobenzene, dichlorobenzene, and trichlorobenzene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether, and diethylene glycol monobutyl ether; and alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, 2-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, and propylene glycol.

[0063] Examples of the substrate used in the present invention include granular, needle-like, fibrous, woven, plate-like, foil-like, amorphous, and other substrates formed from metals, inorganic materials, resin materials, and the like.

[0064] Examples of the metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. Plates, foils, and plating films made of these metals can be used as the substrate. Specific examples of the alloy include copper alloys, and are not particularly limited as long as they contain copper. Examples include Cu-Ag, Cu-Te, Cu-Mg, Cu-Sn, Cu-Si, Cu-Mn, Cu-Be-Co, Cu-Ti, Cu-Ni-Si, Cu-Zn-Ni, Cu-Cr, Cu-Zr, Cu-Fe, Cu-Al, Cu-Zn, and Cu-Co alloys. Other alloys include aluminum alloys (Al-Si alloys), nickel alloys (Ni-Cr alloys), and iron alloys (Fe-Ni alloys, stainless steel, and steel). Among these metals, copper and copper alloys are preferred.

[0065] Examples of the inorganic material include silicon, ceramics, inorganic materials used as fillers, and glass. Specific examples include silicon compounds such as silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminosilicates, and mica; oxides such as alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide; hydroxides such as magnesium hydroxide, aluminum hydroxide, and basic magnesium carbonate; carbonates such as calcium carbonate, zinc carbonate, hydrotalcite, and magnesium carbonate; sulfates such as barium sulfate and gypsum; titanates such as barium titanate; nitrides such as aluminum nitride and silicon nitride; and carbon fibers. Among these inorganic materials, silicon, ceramics (alumina, silicon carbide, aluminum nitride, silicon nitride, barium titanate, etc.), and glass are preferred.

[0066] Examples of the resin material include nylon, acrylate resin, epoxy resin, polybenzoxazole resin, silicone resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, polybutadiene resin, olefin resin, fluorine-containing resin, polyetherimide resin, polyether ether ketone resin, liquid crystal resin, etc., and these may be mixed or modified and combined. Among these resin materials, polyphenylene ether resin, polyphenylene oxide resin, liquid crystal resin, acrylate resin, epoxy resin, olefin resin, polybenzoxazole resin, silicone resin, and polyimide resin are preferred.

[0067] By subjecting a substrate to surface treatment with a treatment liquid containing the coupling agent of the present invention, the lipophilicity of the substrate surface is increased, and the affinity (adhesion and adhesion) for resins, etc. may be improved. In order to further enhance the effects of this treatment, the surface-treated substrate may be further subjected to a heat treatment.

[0068] (Insulating composition) The coupling agent of the present invention can be incorporated into a resin material or an inorganic material to form an insulating composition. Alternatively, the insulating composition can be obtained by dissolving the azole compound represented by chemical formula (I) in an organic solvent or the like and mixing the solution with a resin material or an inorganic material.

[0069] The content of the azole compound represented by chemical formula (I) in the insulating composition is preferably 0.001 to 10 wt %, more preferably 0.01 to 5 wt %. When the content of the azole compound represented by chemical formula (I) in the insulating composition is 0.001 wt % or more, the adhesiveness is sufficiently improved. However, when this concentration exceeds 10 wt %, the adhesiveness improvement effect almost reaches a plateau. Therefore, from an economical point of view, the content of the azole compound represented by chemical formula (I) is preferably 10 wt % or less. The insulating composition can be prepared by a known method. For example, the insulating composition can be prepared by dissolving the azole compound represented by chemical formula (I) in an organic solvent and mixing it with a solid or liquid resin material. Alternatively, the insulating composition can be prepared by directly adding and mixing the azole compound represented by chemical formula (I) with a liquid resin material.

[0070] The insulating composition of the present invention provides an insulating material having high adhesive strength, and can therefore be suitably used in various electric and electronic parts and electronic devices such as printed wiring boards.

[0071] Japanese Patent Publication No. 2009-19266 describes a method for forming a silane coupling agent film, which comprises the steps of applying a liquid containing a silane coupling agent to a metal surface, drying the applied metal surface at a temperature of 25 to 150°C for 5 minutes or less, and rinsing the dried metal surface with water. It also states that the metal surface may be pre-treated by forming an adhesive metal layer of tin or the like using an immersion plating solution. The surface treatment solution of the present invention can be used in place of the liquid containing the silane coupling agent. The details of this patent publication are incorporated herein by reference.

[0072] (Surface Treatment Solution) The surface treatment solution of the present invention contains an azole compound represented by the above-mentioned chemical formula (I). The surface treatment solution of the present invention is prepared by mixing the azole compound with water and / or a solubilizing agent. The water used in preparing the surface treatment solution is preferably pure water such as ion-exchanged water or distilled water. Examples of solubilizing agents used in preparing the surface treatment solution include acids, alkalis, and organic solvents. These solubilizing agents may be used alone or in combination of two or more. It is preferable to use a solubilizing agent and water in the surface treatment solution of the present invention in order to promote dissolution (solution) of the azole compound.

[0073] Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, 2-ethylbutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, oleic acid, stearic acid, glycolic acid, lactic acid, gluconic acid, glyceric acid, malonic acid, succinic acid, levulinic acid, benzoic acid, oxalic acid, tartaric acid, malic acid, benzenesulfonic acid, tosylic acid, methanesulfonic acid, 5-sulfosalicylic acid, 4-hydroxybenzenesulfonic acid, 3-methyl-4-hydroxybenzenesulfonic acid, 4-aminobenzenesulfonic acid, camphorsulfonic acid, benzenedisulfonic acid, benzenetrisulfonic acid, sulfamic acid, and amino acids. These acids may be used alone or in combination of two or more.

[0074] Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol, N,N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine, and pyridine. These alkalis may be used alone or in combination of two or more.

[0075] Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, butanol, tert-butyl alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and diethylene glycol monomethyl ether. Examples of the organic solvent include tetrahydrofurfuryl alcohol, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, acetone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, formamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, ethylene carbonate, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, etc. These organic solvents may be used alone or in combination of two or more.

[0076] Regarding the method for preparing the surface treatment liquid when a solubilizing agent and water are used, the azole compound may be mixed with water and then the solubilizing agent may be added, the azole compound may be mixed with a mixed liquid of water and the solubilizing agent, or the azole compound may be mixed with the solubilizing agent and then water may be added.

[0077] The content of the solubilizer in the surface treatment liquid is preferably 0.1 to 99% by weight, more preferably 0.5 to 99% by weight, and even more preferably 1 to 99% by weight.

[0078] The azole compound of the present invention has an azole ring in the molecule, and the azole ring interacts with the surface of the substrate (metal, resin material, inorganic material) to form a chemical bond, thereby improving the adhesion between different materials. For example, in the case of adhesion between copper and a resin material, the azole ring of the azole compound used in the practice of the present invention interacts with the resin and copper to form a chemical bond, and a polymerizable group (-C ６ H ４ -CH=CH ２ ) interacts with the resin to form a chemical bond. Therefore, by bringing copper into contact with the surface treatment solution, a chemical conversion coating derived from the azole compound represented by chemical formula (I) is formed on the surface of the copper through bonding with the azole ring, and when a resin layer made of a resin material is formed on the surface of this chemical conversion coating, the adhesion between the copper and the resin material can be improved compared to when a resin layer is formed directly on the copper surface.

[0079] In carrying out the present invention, the concentration of the azole compound represented by chemical formula (I) in the surface treatment solution is preferably 0.0001 to 1.0000 mol / L, more preferably 0.0010 to 0.5000 mol / L, and even more preferably 0.0100 to 0.1000 mol / L.

[0080] In order to improve the stability of the surface treatment solution and the uniformity of the chemical conversion coating, the surface treatment solution may also contain a substance that generates halide ions such as fluoride ions, chloride ions, bromide ions, and iodide ions, or metal ions such as copper ions, iron ions, and zinc ions.

[0081] Halide ions are effective in forming uniform flat portions of the chemical conversion coating. Examples of substances that generate halide ions include lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, magnesium iodide, calcium iodide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. Halogen compounds may be contained as impurities in other components.

[0082] The content of halide ions in the surface treatment solution is not particularly limited, and is, for example, preferably 0.10 mol / L or less (particularly 0 to 0.10 mol / L), more preferably 0.050 mol / L or less (particularly 0 to 0.050 mol / L), further preferably 0.020 mol / L or less (particularly 0 to 0.020 mol / L), and particularly preferably 0.010 mol / L or less (particularly 0 to 0.010 mol / L).

[0083] Copper ions form complexes with azole compounds, which can increase the strength of chemical conversion coatings and the adhesive strength between metals and resins. The valence of the copper ions may be monovalent or divalent. Examples of substances that generate copper ions include metallic copper, copper sulfate (and its hydrates (particularly the pentahydrate)), copper formate (and its hydrates (particularly the tetrahydrate)), copper nitrate, cuprous chloride, cupric chloride, copper acetate (and its hydrates (particularly the monohydrate)), copper hydroxide, copper oxide, copper sulfide, copper carbonate, cuprous bromide, cupric bromide, copper phosphate, and copper benzoate. Furthermore, the copper ions in the surface treatment solution may include copper ions eluted from metallic copper or copper oxide contained in the copper circuit during treatment of the copper circuit with the surface treatment solution.

[0084] The content of copper ions in the surface treatment solution is not particularly limited, and is, for example, preferably 1.00 mol / L or less (particularly 0 mol / L or more and 1.00 mol / L or less), more preferably 0.50 mol / L or less (particularly 0 mol / L or more and 0.50 mol / L or less), even more preferably 0.10 mol / L or less (particularly 0 mol / L or more and 0.10 mol / L or less), and particularly preferably 0.010 mol / L or less (particularly 0 mol / L or more and 0.010 mol / L or less).

[0085] A known coupling agent may be used in combination as long as it does not impair the effects of the present invention. Examples of known coupling agents include silane coupling agents (silane coupling agents) having a thiol group (mercapto group), a vinyl group, an epoxy group, a (meth)acrylic group, an amino group, a chloropropyl group, or the like.

[0086] Examples of such silane coupling agents include mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, vinylsilane compounds such as vinyltrichlorosilane, vinyltrimethoxysilane and vinyltriethoxysilane, styrylsilane compounds such as p-styryltrimethoxysilane, epoxysilane compounds such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, acryloxysilane compounds such as 3-acryloxypropyltrimethoxysilane, methacryloxysilane compounds such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane, Examples of the silane compound include aminosilane compounds such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; ureidosilane compounds such as 3-ureidopropyltriethoxysilane; chloropropylsilane compounds such as 3-chloropropyltrimethoxysilane; sulfide silane compounds such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanatosilane compounds such as 3-isocyanatopropyltriethoxysilane. Other examples include aluminum-based coupling agents, titanium-based coupling agents, and zirconium-based coupling agents.

[0087] (Treatment Method of the Surface Treatment Solution of the Present Invention) The method for contacting the surface of a substrate with the surface treatment solution of the present invention is not particularly limited, and, as with the coupling agent described above, means such as spraying, immersion, and coating can be used. The time for contacting the surface treatment solution with the substrate (treatment time) is preferably 1 second to 10 minutes, and more preferably 5 seconds to 3 minutes. If the treatment time is less than 1 second, the thickness of the chemical conversion coating formed on the substrate surface will be thin, making it difficult to obtain sufficient adhesion between different materials. On the other hand, even if the treatment time is longer than 10 minutes, there will be no significant difference in the thickness of the chemical conversion coating. Therefore, from the viewpoint of productivity, treatment for 10 minutes or less is preferred. Furthermore, the temperature of the treatment solution when contacting the surface treatment solution with the substrate surface is preferably 5 to 50°C, but may be set appropriately in relation to the treatment time described above.

[0088] After contacting the substrate with the surface treatment solution of the present invention, the substrate may be washed with water and then dried, or may be dried without being washed with water. Drying is preferably carried out at a temperature of room temperature to 150° C. The water used for washing is preferably pure water such as ion-exchanged water or distilled water, but there are no particular restrictions on the method or duration of washing, and it may be washed for an appropriate period of time by means of spraying, immersion, or the like.

[0089] The thickness of the chemical conversion coating is preferably 0.5 to 1,000 nm, more preferably 1 to 200 nm, and even more preferably 1 to 100 nm. A thickness of 0.5 nm or more sufficiently improves the adhesion between the materials, while a thickness of 1,000 nm or less allows the chemical resistance of the chemical conversion coating to be maintained.

[0090] In the present invention, the surface of the dried chemical conversion coating may be modified by treatment with plasma, laser, ion beam, ozone, heating, humidification, etc. Alternatively, the metal surface may be cleaned using mechanical polishing such as plasma, laser, ion beam, or pumice brush, or processing methods such as drilling, in order to remove resin and ion residues from the metal surface.

[0091] When treating the surface of copper or a copper alloy (hereinafter, both may be referred to simply as copper), the copper surface may be subjected to at least one pretreatment selected from pickling treatment, alkali treatment, roughening treatment, heat-resistant treatment, rust-proofing treatment, and chemical conversion treatment before contacting the copper surface with the surface treatment solution of the present invention.

[0092] The pickling treatment is carried out to remove oil and fat components adhering to the copper surface and to remove an oxide film from the copper surface, and can be carried out using solutions such as hydrochloric acid solutions, sulfuric acid solutions, nitric acid solutions, sulfuric acid-hydrogen peroxide solutions, organic acid solutions, inorganic acid-organic solvent solutions, and organic acid-organic solvent solutions.

[0093] The alkali treatment is carried out to remove oil and fat components adhering to the copper surface and to remove residues from previous processes (e.g., dry film resist for forming copper circuits). For this alkali treatment, solutions such as aqueous solutions or organic solvent-based solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amines such as ammonia, ethanolamine, monopropanolamine, and tetramethylammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium acetate, potassium acetate, sodium phosphate, disodium hydrogen phosphate, potassium phosphate, and dipotassium hydrogen phosphate can be used.

[0094] The roughening treatment is carried out to enhance the adhesion between copper and resin through the anchor effect, and imparts an irregular shape to the copper surface, thereby enhancing the adhesion between copper and resin materials. Methods that can be used for this roughening treatment include microetching, electroplating, electroless plating, oxidation (black oxide, brown oxide), oxidation-reduction, brush polishing, and jet scrubbing.

[0095] In the microetching method, for example, etching agents such as organic acid-cupric ion system, sulfuric acid-hydrogen peroxide system, persulfate system, copper chloride system, and iron chloride system can be used. In the electroplating method, minute copper particles are deposited on the copper surface to form irregularities on the copper surface.

[0096] In the heat-resistant treatment, a coating of at least one material selected from nickel, nickel-phosphorus, zinc, zinc-nickel, copper-zinc, copper-nickel, copper-nickel-cobalt, and nickel-cobalt is formed on the surface of the copper. This coating can be formed by a known electroplating method, but is not limited to electroplating, and vapor deposition or other means may also be used.

[0097] The rust prevention treatment is carried out to prevent oxidation corrosion of the copper surface, and can be carried out by forming a zinc or zinc alloy plating film or an electrolytic chromate plating film on the copper surface. Alternatively, a treatment solution containing an organic compound-based rust inhibitor such as a benzotriazole-based rust inhibitor may be brought into contact with the copper surface.

[0098] In the chemical conversion treatment, a method of forming a passivation film of tin or a method of forming a passivation film of copper oxide can be employed.

[0099] Before and / or after contacting the copper surface with the surface treatment solution of the present invention, an aqueous solution containing copper ions may be brought into contact with the copper surface. This aqueous solution containing copper ions has the functions of improving the film-forming properties of the chemical conversion coating formed on the copper surface and uniforming the thickness of the chemical conversion coating formed on the copper surface. The valence of the copper ions is not particularly limited, and they are monovalent or divalent copper ions. The copper ion source for the aqueous solution containing copper ions is not particularly limited as long as it is a copper salt that dissolves in water, and examples of copper salts include copper sulfate, copper nitrate, copper chloride, copper formate, and copper acetate. Ammonia, hydrochloric acid, or the like may be added to solubilize the copper salt in water.

[0100] An acidic or alkaline aqueous solution may be contacted with the copper surface before and / or after contacting the copper surface with the surface treatment solution of the present invention. Like the copper ion-containing aqueous solution, this acidic or alkaline aqueous solution also functions to uniformize the thickness of the chemical conversion coating formed on the copper surface. While the acidic and alkaline aqueous solutions are not particularly limited, examples of the acidic aqueous solution include aqueous solutions containing mineral acids such as sulfuric acid, nitric acid, and hydrochloric acid, and aqueous solutions containing organic acids such as formic acid, acetic acid, lactic acid, glycolic acid, and amino acids. Examples of alkaline aqueous solutions include aqueous solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amines such as ammonia, ethanolamine, monopropanolamine, and tetramethylammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium acetate, potassium acetate, sodium phosphate, disodium hydrogenphosphate, potassium phosphate, and dipotassium hydrogenphosphate.

[0101] Before and / or after contacting the copper surface with the surface treatment liquid of the present invention, an aqueous solution containing a known coupling agent may be brought into contact with the copper surface.

[0102] Before and / or after contacting the copper surface with the surface treatment agent of the present invention, a solution containing an azole compound may be contacted with the copper surface. This solution containing an azole compound has the function of increasing the strength of the chemical conversion coating formed on the copper surface. The azole compound is not particularly limited, and examples thereof include commercially available imidazole compounds, triazole compounds, and tetrazole compounds. Examples of these azole compounds include imidazole, 2-methylimidazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4-triazole, 5-methyltetrazole, 5-aminotetrazole, and 5-phenyltetrazole. The solution containing the azole compound contains water and / or a solubilizing agent in addition to the azole compound. Examples of solubilizing agents include the solubilizing agents described above (acids, alkalis, and organic solvents). The solution containing the azole compound may further contain additives. Examples of additives include copper compounds, halogen compounds, and other additives (for example, ammonium salts such as ammonium sulfate, ammonium formate, ammonium acetate, ammonium chloride, ammonium carbonate, and ammonium nitrate).

[0103] After the surface treatment liquid of the present invention has been brought into contact with the copper surface, the copper surface may be contacted with a treatment liquid containing a known organic compound-based rust inhibitor, such as a benzotriazole-based rust inhibitor.

[0104] The surface treatment liquid of the present invention can be used to treat the surface of at least one substrate selected from the group consisting of metals, inorganic materials, and resin materials. By treating the surface of the substrate with the surface treatment liquid of the present invention, a chemical conversion film can be formed on the surface of the substrate, thereby improving adhesion to other materials.

[0105] In the present invention, two materials selected from the group consisting of metals, inorganic materials, and resin materials can be bonded using the surface treatment liquid of the present invention. By bonding the two materials via a chemical conversion coating layer formed by the surface treatment liquid of the present invention, the affinity between the two materials can be improved, and therefore, even materials of different properties can be bonded more firmly.

[0106] (Bonding Method Using the Surface Treatment Liquid of the Present Invention) Bonding of two materials can be carried out by known methods. Examples include methods in which the surface treatment liquid of the present invention is brought into contact with the surface of a substrate made of a metal, inorganic material, or resin material to form a chemical conversion coating, and then another substrate is applied to part or all of the formed chemical conversion coating by means of coating, pressing, mixing, etc., or by using an adhesive or an adhesive sheet (film), or by combining these methods. Other examples include methods in which the surface treatment liquid of the present invention is brought into contact with the surfaces of two substrates selected from a metal, inorganic material, or resin material to form chemical conversion coatings on the surfaces of the two substrates, and then the two substrates are bonded by means of coating, pressing, mixing, etc., or by using an adhesive or an adhesive sheet (film), or by combining these methods.

[0107] By using the surface treatment liquid of the present invention, two materials, particularly two materials of different properties, can be bonded together as described above, and therefore the surface treatment liquid of the present invention can be suitably used for various electric and electronic components and electronic devices such as semiconductor wafers and printed wiring boards.

[0108] In the present invention, the surface treatment liquid of the present invention can be suitably used for substrates made of metal, particularly copper or copper alloy. For example, it is suitable for surface treatment of copper or copper alloys for the purpose of improving the adhesion (adhesion) between a copper circuit (copper wiring layer) and a semi-cured or cured prepreg or solder resist, or a semi-cured or cured dry film resist (insulating resin layer), and can improve the adhesion between the copper wiring layer and the insulating resin layer in a printed wiring board having an insulating resin layer in contact with the copper wiring layer.

[0109] In an example of use in semiconductor wafers, the present invention is suitable for surface treatment of semiconductor circuits with the aim of increasing the adhesion (tightness) between a semiconductor circuit formed on a semiconductor wafer and a protective film (e.g., an insulating protective film such as a photosensitive positive type, a photosensitive negative type, or a non-photosensitive buffer coat or bump protective film). Furthermore, the present invention is suitable for surface treatment of a copper circuit rewiring layer in a package substrate (WL-CSP, FO-WLP, PLP) or a 2.5-dimensional (2.5D) or three-dimensional (3D) interposer substrate in which a rewiring layer is formed on a semiconductor wafer, with the aim of increasing the adhesion (tightness) between the copper circuit rewiring layer and an insulating material. Examples of the protective film and insulating material include polyimide resin, polybenzoxazole resin, and silicone resin.

[0110] The printed wiring board can be produced by contacting the surface of a copper wiring with the surface treatment solution of the present invention, followed by rinsing and drying, and then forming an insulating resin layer on the copper wiring surface. The contact method is as described above. Immersing the copper wiring in the surface treatment solution or spraying the copper wiring with the treatment solution is simple and reliable, and is preferred. The water-washing method is not particularly limited, but immersing the copper wiring in cleaning water or spraying the copper wiring surface with cleaning water is simple and reliable, and is preferred. The insulating resin layer can be formed by known methods, such as applying a semi-cured resin material or applying a liquid resin material containing a solvent. Next, via holes are formed to connect the upper and lower wirings. Repeating this process can produce a multilayer printed wiring board.

[0111] In the above-mentioned method for forming a circuit on a printed wiring board, an example of a semi-additive process using the surface treatment liquid of the present invention will be described below. (a) preparing an insulating substrate or an insulating substrate having through-holes and via holes, the insulating substrate having a first conductive layer on a first surface and a second surface opposite to the first surface, and on the inner walls of the through-holes and via holes; (b) forming a photocrosslinkable resin layer and a mask layer on the first surface and the second surface, and covering the first conductive layer on the first surface and the second surface and on the inner walls of the through-holes and via holes with the photocrosslinkable resin layer and the mask layer; (c) pattern-exposing the photocrosslinkable resin layer on the first surface and the second surface and around the through-holes and via holes; (d) removing the mask layer on the first surface and the second surface and around the through-holes and via holes; (e) developing and removing the uncured photocrosslinkable resin layer on the first surface and the second surface and around the through-holes and via holes using a photocrosslinkable resin layer removal liquid, thereby exposing the first conductive layer on the first surface, the first conductive layer on the second surface, and the first conductive layer around the through-holes and via holes; (f) forming a second conductive layer by electrolytic plating on the first conductive layer exposed on the first and second surfaces and on the inner walls of the through-holes and via holes; (g) removing the cured photocrosslinkable resin layer on the first and second surfaces and around the through-holes and via holes to expose the first and second conductive layers on the first and second surfaces and on the inner walls of the through-holes and via holes; (h) removing the exposed first conductive layer by flash etching; (i) forming a third conductive layer by electroless plating and electrolytic plating on the first and second conductive layers on the first and second surfaces and on the inner walls of the through-holes and via holes; (j) laminating an insulating resin layer on the first, second, and third conductive layers on the first and second surfaces and on the inner walls of the through-holes and via holes; In the method for manufacturing a circuit board comprising at least one of the above, the surface treatment liquid of the present invention is brought into contact with at least one metal layer or resist layer selected from the first, second, and third conductive layers on the first surface, the second surface, and the inner walls of the through-holes and via holes, the insulating resin substrate, the photo-crosslinkable resin layer used for the etching resist layer or the plating resist layer, and the insulating resin layer, to manufacture a printed wiring board.

[0112] Furthermore, in the above-mentioned method for forming a circuit on a printed wiring board, an example of a subtractive process using the surface treatment liquid of the present invention will be described below. (a) preparing an insulating substrate or an insulating substrate having through-holes and via holes, the insulating substrate having a first conductive layer on a first surface and a second surface opposite to the first surface, and on the inner walls of the through-holes and via holes; (b) forming a photocrosslinkable resin layer and a mask layer on the first surface and the second surface, and covering the first conductive layer on the first surface and the second surface and on the inner walls of the through-holes and via holes with the photocrosslinkable resin layer and the mask layer; (c) pattern-exposing the photocrosslinkable resin layer on the first surface and the second surface and around the through-holes and via holes; (d) removing the mask layer on the first surface and the second surface and around the through-holes and via holes; (e) developing and removing the uncured photocrosslinkable resin layer on the first surface and the second surface and around the through-holes and via holes using a photocrosslinkable resin layer removal liquid, thereby exposing the first conductive layer on the first surface, the first conductive layer on the second surface, and the first conductive layer around the through-holes and via holes; (f) etching and removing the first conductive layer exposed on the first and second surfaces and on the inner walls of the through-holes and via holes; (g) removing the cured photocrosslinkable resin layer on the first and second surfaces and around the through-holes and via holes to expose the first and second conductive layers on the first and second surfaces and on the inner walls of the through-holes and via holes; (h) forming a third conductive layer on the first and second conductive layers on the first and second surfaces and on the inner walls of the through-holes and via holes by electroless plating and electrolytic plating; (i) laminating an insulating resin layer on the first, second, and third conductive layers on the first and second surfaces and on the inner walls of the through-holes and via holes; In the method for manufacturing a circuit board comprising at least one of the above, the surface treatment liquid of the present invention is brought into contact with at least one metal layer or resist layer selected from the first, second, and third conductive layers on the first surface, the second surface, and the inner walls of the through-holes and via holes, the insulating resin substrate, the photo-crosslinkable resin layer used for the etching resist layer or the plating resist layer, and the insulating resin layer, to manufacture a printed wiring board.

[0113] The copper wiring and conductive layer may be produced by any method such as electroless plating, electrolytic plating, vapor deposition, sputtering, or damascene, and may include inner via holes, through holes, connection terminals, etc.

[0114] Furthermore, "copper" in the present invention refers to foils (electrolytic copper foil, rolled copper foil, resin-coated copper foil, carrier-coated copper foil, electroless copper foil, sputtered copper foil, thin copper foil) used in electronic devices such as printed wiring boards and lead frames, decorative items, building materials, etc., plated films (electroless copper plating film, electrolytic copper plating film), thin films formed by vapor deposition, sputtering, damascene method, etc., and particles, needles, fibers, wires, rods, tubes, plates, etc. In the case of copper wiring through which recent high-frequency electrical signals flow, it is preferable that the copper surface be smooth with an average roughness of 0.1 μm or less. The copper surface may be plated with nickel, zinc, chromium, tin, etc. as a pretreatment.

[0115] Furthermore, for example, in the case of use in lead frames during wire bonding mounting, the surface treatment liquid of the present invention is suitable for surface treatment of lead frames aimed at increasing the adhesiveness (adhesion) of the metal surface during the lead frame production process, the metal frame surface after mounting a semiconductor chip (before or after the die bonding and pre-baking processes), the metal frame surface after mounting by wire bonding, and the metal frame surface during processes up to resin sealing (before or after the resin molding and baking processes) with an adhesive when mounting a semiconductor chip.

[0116] Furthermore, for example, in an application example to a lead frame during flip-chip mounting, the surface treatment liquid of the present invention is suitable for surface treatment of the lead frame for the purpose of increasing the adhesiveness (adhesion) with the sealing resin or adhesive used during semiconductor chip mounting on the metal surface during the lead frame production process, the metal surface of the lead frame after a bonding material (solder, Au plating, Sn plating, etc.) has been temporarily placed, the metal surface of the frame after a semiconductor chip has been mounted (before or after alignment, chip mounting, and baking processes), the metal surface of the lead frame after main curing (before or after processes such as reflow heating, thermocompression bonding, ultrasonic waves, and plasma), and the metal surface of the lead frame during processes up to resin sealing.

[0117] Furthermore, for example, in an application example in a fine wiring substrate in which integration technology for closely arranging semiconductor chips has been improved, the surface treatment liquid of the present invention is also suitable for surface treatment of a copper circuit wiring layer for the purpose of increasing the adhesiveness (adhesion) between the copper circuit wiring layer and an insulating material on a 2.5-dimensional (2.5D) organic substrate or glass substrate, a component-embedded substrate (EPS substrate) in which a semiconductor is embedded in the substrate, or a coreless substrate.

[0118] Furthermore, for example, the metal surface treatment liquid of the present invention is suitable for surface treatment of a copper circuit wiring layer intended to enhance the adhesion (adhesion) between the copper circuit wiring layer and an insulating material when pattern wiring is built in and upper and lower layers are subjected to laser via processing and via fill plating, or when a circuit-embedded substrate using MIS (ETS substrate) is used in which copper pillars formed by plating are used for electrical continuity between the upper and lower layers and a molded resin is used for the insulating layer.

[0119] The carrier-attached copper foil to be treated with the surface treatment solution of the present invention is an ultrathin electrolytic copper foil used for printed wiring boards that include a process for forming a circuit by any one of a semi-additive process, a subtractive process, a partly additive process, or a modified semi-additive process, and is provided with a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer. The copper surface may be subjected to at least one pretreatment selected from the group consisting of pickling treatment, roughening treatment, heat-resistant treatment, rust-proofing treatment, and chemical conversion treatment.

[0120] (Resin Composition) The azole compound of the present invention can be used as a raw material for a resin composition. The content of the azole compound of the present invention in this resin composition is preferably 0.001 to 100% by weight.

[0121] A cured product can be obtained by polymerizing the azole compound of the present invention, but by allowing a curable compound other than the azole compound of the present invention to coexist during this polymerization, a cured product can be obtained in which the azole compound of the present invention is copolymerized with the other curable compound. Examples of the other curable compound include an ene compound having a carbon-carbon double bond in the molecule (hereinafter sometimes referred to as a "first curable compound"), and a compound having an epoxy group, an oxetane ring, or a vinyl group in the molecule (hereinafter sometimes referred to as a "second curable compound").

[0122] (First Resin Composition) The first resin composition contains the azole compound of the present invention as an essential component, and optionally contains a first curable compound (an ene compound having a carbon-carbon double bond in the molecule). The first curable compound includes both a polymerizable monomer and a polymerizable oligomer (semi-cured product) having a structure in which the polymerizable monomer is partially polymerized.

[0123] Examples of the polymerizable monomer include (1) (meth)acrylic acid alkyl ester monomers, (2) hydroxyl group-containing monomers, (3) carboxyl group-containing monomers, (4) amino group-containing monomers, (5) acetoacetyl group-containing monomers, (6) isocyanate group-containing monomers, (7) glycidyl group-containing monomers, (8) monomers containing one aromatic ring, (9) monomers containing an alkoxy group and an oxyalkylene group, (10) alkoxyalkyl(meth)acrylamide monomers, (11) (meth)acrylamide monomers, (12) monofunctional unsaturated compounds, and (13) polyfunctional unsaturated compounds.

[0124] (1) Examples of (meth)acrylic acid alkyl ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-propyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and polyisobornyl (meth)acrylate.

[0125] (2) Examples of hydroxyl group-containing monomers include (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth)acrylate; oxyalkylene-modified monomers such as diethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate; and primary hydroxyl group-containing monomers such as 2-acryloyloxyethyl 2-hydroxyethyl phthalate, N-methylol (meth)acrylamide, and hydroxyethyl acrylamide; 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-chloro 2-hydroxypropyl (meth)acrylate, and propylene glycol diglycidyl ether-epoxy di(meth)acrylate. Examples of the monomer include secondary hydroxyl group-containing monomers such as phenol glycidyl ether-epoxy(meth)acrylate and bisphenol A diglycidyl ether-epoxy di(meth)acrylate; and tertiary hydroxyl group-containing monomers such as 2,2-dimethyl 2-hydroxyethyl(meth)acrylate.

[0126] (3) Examples of carboxyl group-containing monomers include (meth)acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamido-N-glycolic acid, and cinnamic acid.

[0127] (4) Examples of amino group-containing monomers include tert-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate.

[0128] (5) Examples of acetoacetyl group-containing monomers include 2-(acetoacetoxy)ethyl (meth)acrylate and allyl acetoacetate.

[0129] (6) Examples of isocyanate group-containing monomers include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.

[0130] (7) Examples of glycidyl group-containing monomers include, in addition to glycidyl (meth)acrylate, epoxy (meth)acrylates which are reaction products of epoxy compounds such as ethylene glycol diglycidyl ether-epoxy (meth)acrylate, resorcinol diglycidyl ether-epoxy (meth)acrylate, bis(4-hydroxyphenyl) sulfide diglycidyl ether-epoxy (meth)acrylate, phenol novolac type epoxy resin-(meth)acrylate, cresol novolac type epoxy resin-(meth)acrylate, bisphenol (e.g., bisphenol A, bisphenol F) type epoxy resin-(meth)acrylate, biphenol (e.g., 3,3',5,5'-tetramethylbiphenol) type epoxy resin-(meth)acrylate, and 1,3,5-tris(2,3-epoxypropyl) isocyanurate-(meth)acrylate with (meth)acrylic acid. Examples include glycidyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate glycidyl ether.

[0131] (8) Examples of monomers containing one aromatic ring include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, styrene, and α-methylstyrene.

[0132] (9) Examples of monomers containing an alkoxy group and an oxyalkylene group include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-butoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, octoxypolyethylene glycol-polypropylene glycol-mono(meth)acrylate, lauroxypolyethylene glycol mono(meth)acrylate, and stearoxypolyethylene glycol mono(meth)acrylate.

[0133] (10) Examples of alkoxyalkyl(meth)acrylamide monomers include methoxymethyl(meth)acrylamide, ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide, isopropoxymethyl(meth)acrylamide, n-butoxymethyl(meth)acrylamide, and isobutoxymethyl(meth)acrylamide.

[0134] (11) Examples of (meth)acrylamide monomers include (meth)acryloylmorpholine, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, and (meth)acrylamide N-methylol(meth)acrylamide.

[0135] (12) Examples of monofunctional unsaturated compounds include biphenyl structure-containing (meth)acrylate compounds, and more specifically, biphenyl(meth)acrylates such as o-biphenyl(meth)acrylate, m-biphenyl(meth)acrylate, and p-biphenyl(meth)acrylate; biphenyloxyalkyl(meth)acrylates such as o-biphenyloxymethyl(meth)acrylate, m-biphenyloxymethyl(meth)acrylate, p-biphenyloxymethyl(meth)acrylate, o-biphenyloxyethyl(meth)acrylate, m-biphenyloxyethyl(meth)acrylate, p-biphenyloxyethyl(meth)acrylate, o-biphenyloxypropyl(meth)acrylate, m-biphenyloxypropyl(meth)acrylate, and p-biphenyloxypropyl(meth)acrylate; (o-biphenyloxy)diethylene glycol(meth)acrylate; Examples of biphenyloxypolyalkylene glycol (meth)acrylates include (m-biphenyloxy)diethylene glycol (meth)acrylate, (p-biphenyloxy)diethylene glycol (meth)acrylate, (o-biphenyloxy)dipropylene glycol (meth)acrylate, (m-biphenyloxy)dipropylene glycol (meth)acrylate, (p-biphenyloxy)dipropylene glycol (meth)acrylate, (o-biphenyloxy)polyethylene glycol (meth)acrylate, (m-biphenyloxy)polyethylene glycol (meth)acrylate, (p-biphenyloxy)polyethylene glycol (meth)acrylate, (o-biphenyloxy)polypropylene glycol (meth)acrylate, (m-biphenyloxy)polypropylene glycol (meth)acrylate, and (p-biphenyloxy)polypropylene glycol (meth)acrylate.

[0136] (13) Examples of polyfunctional unsaturated compounds include bifunctional monomers, trifunctional or higher functional monomers, urethane (meth)acrylates, polyurethane (meth)acrylates, thiourethane (meth)acrylates, polythiourethane (meth)acrylates, the above-mentioned epoxy (meth)acrylates, ester (meth)acrylates, polyester (meth)acrylates, and polyether (meth)acrylates.

[0137] Specific examples of bifunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide-modified di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, Examples of the monomer include ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, isocyanuric acid ethylene oxide-modified diacrylate, and 2-(meth)acryloyloxyethyl acid phosphate diester.

[0138] Specific examples of tri- or higher functional monomers include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene oxide-modified isocyanuric acid tri(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, Examples thereof include ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, and succinic acid-modified pentaerythritol tri(meth)acrylate.

[0139] In addition to the polymerizable monomers mentioned above, divinylbenzene, piperylene, isoprene, pentadiene, vinylcyclohexene, chloroprene, butadiene, methylbutadiene, cyclopentadiene, methylpentadiene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinylpyridine, vinylpyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acryloyl chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, 2-chloroethyl vinyl ether, triallyl isocyanurate, tetraallyl glycoluril, N-vinylpyrrolidone, N-vinylcaprolactam, ethylene glycol diallyl carbonate, trimellitic acid triallyl ester, trifluoroethyl (meth)acrylate, tribromobenzyl (meth)acrylate, Examples thereof include perfluorooctylethyl (meth)acrylate, sulfur-containing (meth)acrylate, sulfur-containing polyfunctional (meth)acrylate, and (meth)acryloyloxypropyltris(methoxy)silane.

[0140] The first resin composition contains the azole compound of the present invention as an essential component, and, if necessary, contains the above-mentioned first curable compound. As this first curable compound, a combination of the above-mentioned polymerizable monomer and polymerizable oligomer may be used. As the polymerizable monomer, a combination of the above-exemplified polymerizable monomers may be used (different types of polymerizable monomers may be used in combination), and as the polymerizable oligomer, a combination of different types of polymerizable oligomers may be used.

[0141] Regarding the content ratio of the azole compound of the present invention and the first curable compound in the first resin composition, the content of the first curable compound is preferably an appropriate ratio in the range of 0 to 1000 times (weight ratio) the content of the azole compound of the present invention, and more preferably an appropriate ratio in the range of 0.01 to 100 times (weight ratio).

[0142] The first resin composition may contain a thiol compound as a curing agent. Examples of the thiol compound include aliphatic thiol compounds such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-2,4-dithiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2-(mercaptomethyl)-2-methyl-1,3-propanedithiol, and 2-ethyl-2-(mercaptomethyl)-1,3-propanedithiol; aromatic thiol compounds such as benzenedithiol, toluenedithiol, and xylenedithiol (p-xylenedithiol); cyclic sulfide compounds such as a 1,4-dithiane ring-containing polythiol compound represented by chemical formula (VI); mercaptoalkyl sulfide compounds such as 3-thiapentane-1,5-dithiol and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol; Mercaptopropionic acid esters such as pentaerythritol tetrakis(3-mercaptopropionate); epoxy resin terminal mercapto compounds; 3,6-dioxa-1,8-octanedithiol, mercaptoalkyl ether disulfide compounds represented by chemical formula (VII), 2,2'-[[2,2-bis[(2-mercaptoethoxy)methyl]-1,3-propanediyl]bis(oxy)]bisethanethiol, 3,3'-[[2,2-bis[(3-mercaptopropoxy)methyl]-1,3-propanediyl]bis(oxy)]bis-1-propanethiol, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, 3-(3-mercaptopropoxy)-2,2-bis[(3-mercaptopropoxy)methyl]-1-propanol, Examples include mercaptoalkyl ether compounds such as 2,2-bis[(3-mercaptopropoxy)methyl]-1-butanol; 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, and 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril, and these may be used in combination.

[0143]

[0144] (In formula (VI), p may be the same or different and represents an integer of 1 to 5.)

[0145]

[0146] (In formula (VII), q represents an integer of 1 to 20.)

[0147] In the first resin composition, the content of the thiol compound is preferably 0.1 to 100 parts by weight, and more preferably 0.5 to 20 parts by weight, relative to 100 parts by weight of the curable compound (the total of the azole compound of the present invention and the first curable compound).

[0148] Methods for polymerizing (curing) the first resin composition include photocuring and thermal curing. Photocuring methods include a method of irradiating with active energy rays, preferably a method in which a photopolymerization initiator is used in combination. Examples of active energy rays include light, radiation, electromagnetic waves, and electron beams, with electron beams or light in the ultraviolet to infrared wavelength range being preferred. As the light source, for example, an ultra-high pressure mercury light source or a metal halide light source can be used for ultraviolet irradiation, a metal halide light source or a halogen light source can be used for visible light irradiation, and a halogen light source can be used for infrared irradiation. Furthermore, light sources such as lasers and LEDs that are capable of emitting light of various wavelengths, which have become increasingly popular in recent years, may also be used. The irradiation dose of active energy rays can be appropriately set depending on the type of light source, etc.

[0149] The photopolymerization initiator can be selected from a photoradical polymerization initiator and a photoanionic polymerization initiator, and either of them may be contained in the resin composition. In addition, in order to improve production efficiency and the properties of the cured product, thermal polymerization (thermal curing) may be used in combination with the photocuring.

[0150] As the photoradical polymerization initiator, any photoradical polymerization initiator that is commonly used can be used without any particular limitation. For example, Acetophenones such as acetophenone, diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, acetophenone dimethyl ketal, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. benzoins such as benzophenone, hydroxybenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 4,4'-bis(methylamino)benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethoxy]ethoxy] benzophenones such as (4-benzoylbenzyl)benzenemethanaminium bromide and (4-benzoylbenzyl)trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride;Examples of such compounds include acylphosphonoxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and methylphenyl glyoxylate. These compounds may be used alone or in combination of two or more.

[0151] The photoanionic polymerization initiator may be any commonly used one without any particular limitation, and examples thereof include onium salts, carbamates, etc. Examples of onium salts include 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidium 2-(3-benzoylphenyl)propionate and 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, and examples of carbamates include 2-nitrophenylmethylpiperidine-1-carboxylate, 1-(anthraquinone-2-yl)ethylimidazolecarboxylate, 1-(3-(2-hydroxyphenyl)-2-propenoyl)piperidine, and 9-anthranylmethyldiethylcarbamate.

[0152] In the first resin composition, the content of the photopolymerization initiator is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the curable compound (the total of the azole compound of the present invention and the first curable compound).

[0153] The first resin composition may also contain an auxiliary for the photoradical polymerization initiator, such as triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0154] In addition, the first resin composition may contain a sensitizer to expand the photosensitive wavelength range and increase sensitivity. Examples of sensitizers include benzophenone, p,p'-tetramethyldiaminobenzophenone, p,p'-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, thioxanthone, benzil, acridine orange, benzoflavin, setoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, and benzoquinone. , 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3'-carbonyl-bis(5,7-dimethoxycarbonylcoumarin), coronene, and the like.

[0155] In the first resin composition, the content of the sensitizer is, for example, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the curable compound (the total of the azole compound of the present invention and the first curable compound).

[0156] On the other hand, methods for thermally curing the first resin composition include a method in which a thermal polymerization initiator is used in combination. The thermal polymerization initiator can be selected from a thermal radical polymerization initiator and a thermal anionic polymerization initiator, and both can be contained in the resin composition. The thermal curing conditions, such as heating temperature and heating time, can be set appropriately, but are preferably set in the range of 60 to 130°C / 30 to 240 minutes, and more preferably in the range of 70 to 125°C / 30 to 120 minutes. Examples of heating methods include hot air circulation, infrared heating, and high-frequency heating. Furthermore, a sealed curing oven or a tunnel oven capable of continuous curing can be used as the curing device.

[0157] As the thermal radical polymerization initiator, any commonly used one can be used without any particular limitation, and examples thereof include diisopropyl peroxydicarbonate, benzoyl peroxide, t-butyl peroxyisobutyrate, t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-hexyl peroxypivalate, and t-butyl peroxyneodecanoate. peroxides such as benzoyl peroxide, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1,1-bis(t-hexylperoxy)cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and lauroyl peroxide; and azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and dimethyl 2,2'-azobis(2-methylpropionate), and these may be used in combination.

[0158] The thermal anionic polymerization initiator may be any commonly used one without any particular limitation, and examples thereof include amines, imidazoles, etc., which may be used in combination. Examples of amines include diethylenetriamine, triethylenetetramine, isophoronediamine, xylylenediamine, diaminodiphenylmethane, 1,3,4,6-tetrakis(3-aminopropyl)glycoluril, etc. Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc.

[0159] The content of the thermal polymerization initiator in the first resin composition is preferably 0.001 to 20% by weight, more preferably 0.01 to 10% by weight, based on the entire resin composition (total amount).

[0160] In addition, when the first resin composition contains an epoxy resin (epoxy compound) as an additive (modifier), a photocationic polymerization initiator or a thermal cationic polymerization initiator may be used. Any commonly used photocationic polymerization initiator can be used without particular limitation, and examples thereof include onium salts and organometallic complexes. Examples of onium salts include diazonium salts, sulfonium salts, and iodonium salts. Examples of organometallic complexes include iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Examples of commercially available photocationic polymerization initiators include ADEKA Corporation's "ADEKA Optomer SP-150 (trade name)" and "ADEKA Optomer SP-170 (trade name)," General Electric Company's "UVE-1014 (trade name)," Sartomer Corporation's "CD-1012 (trade name)," and San-Apro Corporation's "CPI-100P (trade name)." The counter anion of the photocationic polymerization initiator is SbF ６ － , AsF ６ － , B(C ６ F ５ ) ４ － , P.F. ６ － etc.

[0161] The thermal cationic polymerization initiator may be any commonly used one without particular limitation. Examples of the thermal cationic polymerization initiator include various onium salts such as quaternary ammonium salts, phosphonium salts, and sulfonium salts, and organometallic complexes, and these may be used in combination. Examples of commercially available onium salts include "ADEKAOPTON CP-66 (trade name)" and "ADEKAOPTON CP-77 (trade name)" manufactured by ADEKA Corporation, "SAN-AID SI-60L (trade name)," "SAN-AID SI-80L (trade name)," and "SAN-AID SI-100L (trade name)" manufactured by Sanshin Chemical Industry Co., Ltd., and "CI Series (trade name)" manufactured by Nippon Soda Co., Ltd., and the like. Examples of organometallic complexes include alkoxysilane-aluminum complexes.

[0162] The first resin composition may further contain, so long as the effects of the present invention are not impaired, pigments (titanium white, cyanine blue, watching red, red iron oxide, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc.), inorganic fillers (calcium carbonate, kaolin, clay, talc, mica, barium sulfate, lithopone, gypsum, zinc stearate, perlite, quartz, quartz glass, silica powders such as fused silica and spherical silica, oxides such as spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, titanium oxide, and zirconium oxide, nitrides such as boron nitride, silicon nitride, and aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, metals and alloys such as copper, silver, iron, aluminum, nickel, and titanium, and carbon-based materials such as diamond and carbon). Thermoplastic resins and thermosetting resins (high-density, medium-density, low-density polyethylene, homopolymers such as polypropylene, polybutene, polypentene, ethylene-propylene copolymers, nylon-6, nylon-6,6 and the like, polyamide resins such as vinyl chloride resins, nitrocellulose resins, vinylidene chloride resins, acrylic resins (including curable compounds other than the above-mentioned polymerizable monomers), acrylamide resins, styrene resins, vinyl ester resins, polyester resins, phenolic resins (phenolic compounds), epoxy resins (epoxy compounds), silicone resins, fluorine-based resins, various elastomer resins such as acrylic rubber and urethane rubber, graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymers and acrylonitrile-butadiene-styrene graft copolymers), reinforcing agents (glass fiber, carbon fiber, etc.), anti-sagging agents (hydrogenated castor oil, fine particle silicic anhydride, etc.), matting agents (fine powder silica, paraffin wax, etc.), abrasives (zinc stearate, etc.), internal mold release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearic acid amide, fatty acid esters, polyolefin wax, paraffin wax, etc.), It may contain additives (modifiers) such as diluents (organic solvents such as n-butyl alcohol, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and toluene, water, and mixtures of organic solvents and water), coupling agents (silane coupling agents such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane), chain transfer agents (thiol compounds such as pentaerythritol tetrakis(3-mercaptopropionate)), surfactants, leveling agents, antifoaming agents, fragrances, flame retardants, and dyes.

[0163] The thermoplastic resins and thermosetting resins mentioned above include resins (compounds) having a cardo structure (a skeletal structure in which four aromatic rings are bonded to a carbon atom), as represented by chemical formula (VIII).

[0164]

[0165] (In formula (VIII), n represents the degree of polymerization.)

[0166] Examples of compounds having a cardo structure include monomers such as 9,9-bis(4-glycidyloxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis(cyanomethyl)fluorene, and 9,9-bis(3-aminopropyl)fluorene.

[0167] The content of the additive (modifier) ​​in the first resin composition may be 0.01 to 50% by weight based on the entire resin composition (total amount).

[0168] The method for preparing the first resin composition is not particularly limited, and the first resin composition can be prepared, for example, by mixing the azole compound of the present invention with the first curable compound, a photopolymerization initiator and / or a thermal polymerization initiator, and an additive (modifier), or by mixing a solution in which the naphthalene compound of the present invention is dissolved or dispersed in a diluent (organic solvent) with the first curable compound, a photopolymerization initiator and / or a thermal polymerization initiator, and an additive (modifier). Known methods can be used as the mixing means.

[0169] (Second Resin Composition) The second resin composition contains the azole compound of the present invention as an essential component, and optionally contains a second curable compound (a compound having an epoxy group, an oxetane ring, or a vinyl group in the molecule). The second curable compound includes both a polymerizable monomer and a polymerizable oligomer (semi-cured product) having a structure in which the polymerizable monomer is partially polymerized.

[0170] Examples of this polymerizable monomer include known epoxy compounds (note: sometimes referred to as epoxy resins), oxetane compounds, epoxy-oxetane compounds (having an oxirane ring and an oxetane ring in the molecule), vinyl-based monomers, etc.

[0171] The epoxy compound can be used without any particular limitation as long as it has an oxirane ring (epoxy group / glycidyl group) in the molecule, and examples thereof include: polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl glycoluril compounds having two or more epoxy groups in the molecule, such as 1,3,4,6-tetraglycidyl glycoluril; alicyclic epoxy compounds such as 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; nitrogen-containing cyclic epoxy compounds such as triglycidyl isocyanurate and hydantoin-type epoxy compounds; Further examples include epoxidized phenol novolac resins, epoxidized cresol novolac resins, epoxidized polyolefins, alicyclic epoxy resins, and urethane-modified epoxy resins, as well as epoxy-modified organopolysiloxane compounds obtained by a hydrosilylation addition reaction between an organic compound having a carbon-carbon double bond and a glycidyl group and a silicon compound having a SiH group (for example, the epoxy-modified organopolysiloxane compounds disclosed in JP-A-2004-99751 and JP-A-2006-282988), and these may be used in combination.

[0172] The oxetane compound can be used without any particular limitation as long as it has an oxetane ring (oxetanyl group / oxetane group) in the molecule, and examples thereof include 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl(3-ethyl-3-oxetanylmethyl)ether, isobornyloxyethyl(3-ethyl-3-oxetanylmethyl)ether, isobornyl(3-ethyl-3-oxetanylmethyl)ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3'-(1,3-(2-methyleneyl)propanediylbis(oxymethylene))bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene(3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, Pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, Examples include PO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, and EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether.

[0173] Any epoxy-oxetane compound can be used without particular limitation as long as it has an oxirane ring (ibid.) and an oxetane ring (ibid.) in the molecule, and examples thereof include those described in U.S. Pat. No. 3,457,193, JP 2005-002191 A, JP 2007-270070 A, JP 2010-111713 A, and JP 2011-208089 A. The epoxy-oxetane compounds described in these documents are incorporated by reference into the disclosure of this specification.

[0174] The vinyl monomer may be any vinyl monomer capable of cationic polymerization, and examples thereof include styrenes, alkenyl ethers, indene, and N-vinylcarbazole. Preferred are styrenes and alkenyl ethers. Examples of styrenes include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chlorostyrene, m-chlorostyrene, and p-chlorostyrene. Examples of alkenyl ethers include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, n-amyl vinyl ether, and isoamyl vinyl ether; fluoroalkyl vinyl ethers such as trifluoromethyl vinyl ether, pentafluoroethyl vinyl ether, and 2,2,2-trifluoroethyl vinyl ether; alkoxyalkyl vinyl ethers such as 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-tetrahydropyranyl vinyl ether, and 2-tetrahydrofuranyl vinyl ether; cyclopentyl vinyl ether, cyclohexyl vinyl ether, cycloheptyl vinyl ether, cyclooctyl vinyl ether, 2-bicyclo[2.2.1]heptyl vinyl ether, 2-bicyclo[2.2.2]octyl vinyl ether, and 8-tricyclo[5.2.1.0]octyl vinyl ether. ２，６cycloalkyl vinyl ethers such as 1-decanyl vinyl ether, 1-adamantyl vinyl ether, and 2-adamantyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether, 4-methylphenyl vinyl ether, 4-trifluoromethylphenyl vinyl ether, and 4-fluorophenyl vinyl ether; and arylalkyl vinyl ethers such as benzyl vinyl ether and 4-fluorobenzyl vinyl ether.

[0175] The second resin composition contains the azole compound of the present invention as an essential component, and optionally contains the second curable compound described above. The second curable compound may be a combination of the polymerizable monomer and polymerizable oligomer described above. The polymerizable monomer may be a combination of the polymerizable monomers exemplified above (different types of polymerizable monomers may be combined), and different types of polymerizable oligomers may also be combined. Regarding the respective content ratios of the azole compound of the present invention and the second curable compound in the second resin composition, the content of the second curable compound is preferably an appropriate ratio in the range of 0 to 1000 times (weight ratio) the content of the azole compound of the present invention, and more preferably an appropriate ratio in the range of 0.01 to 100 times (weight ratio).

[0176] Methods for polymerizing (curing) the second resin composition include photocuring and thermal curing. Photocuring methods include a method of irradiating with active energy rays, preferably a method in which a photopolymerization initiator is used in combination. Examples of active energy rays include light, radiation, electromagnetic waves, and electron beams, with electron beams or light in the ultraviolet to infrared wavelength range being preferred. As the light source, for example, an ultra-high pressure mercury light source or a metal halide light source can be used for ultraviolet irradiation, a metal halide light source or a halogen light source can be used for visible light irradiation, and a halogen light source can be used for infrared irradiation. Furthermore, light sources such as lasers and LEDs that are capable of emitting light of various wavelengths, which have become increasingly popular in recent years, may also be used. The irradiation dose of active energy rays can be appropriately set depending on the type of light source, etc.

[0177] As the photopolymerization initiator, a photocationic polymerization initiator can be used, and if necessary, a photoradical polymerization initiator can be used in combination, and these can be contained in the resin composition. In addition, in photocuring, a thermal curing method can be used in combination in order to improve production efficiency and the properties of the cured product.

[0178] The cationic photopolymerization initiator may be any commonly used one without any particular limitation, and examples thereof include onium salts and organometallic complexes. The cationic photopolymerization initiator may be any of the above-mentioned cationic photopolymerization initiators. The content of the cationic photopolymerization initiator in the second resin composition is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0179] The photoradical polymerization initiator may be any of the above-mentioned photoradical polymerization initiators. The content of the photoradical polymerization initiator in the second resin composition is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0180] When the second resin composition is photocured, the above-mentioned sensitizer can be used.

[0181] On the other hand, when thermally curing the second resin composition, a thermal polymerization initiator can be used. A thermal cationic polymerization initiator can be used as the thermal polymerization initiator, and this can be contained in the resin composition. Examples of heating methods include hot air circulation, infrared heating, and high-frequency heating. Furthermore, a sealed curing oven or a tunnel oven capable of continuous curing can be used as the curing device. The heating (curing) temperature and heating (curing) time can be appropriately set taking into consideration the composition and shape (thickness) of the resin composition to be irradiated.

[0182] The thermal cationic polymerization initiator may be any commonly used one without any particular limitation, and examples thereof include various onium salts such as quaternary ammonium salts, phosphonium salts, and sulfonium salts, as well as organometallic complexes. The thermal cationic polymerization initiator may be any of the above-mentioned thermal cationic polymerization initiators. The content of the thermal cationic polymerization initiator in the second resin composition is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0183] The second resin composition may further contain the above-mentioned additives (modifiers) in an amount of 0.01 to 50% by weight based on the entire second resin composition (total amount), as necessary, as long as the effects of the present invention are not impaired.

[0184] The method for preparing the second resin composition is not particularly limited, and the second resin composition can be prepared by measuring out predetermined amounts of the above-mentioned components and stirring and mixing them. For example, the second resin composition can be prepared by premixing the components and then mixing or melt-kneading them using a roll mixer, kneader, extruder, or the like. If necessary, an organic solvent (a viscosity-adjusting diluent) may be used.

[0185] A resin composition containing the azole compound of the present invention (hereinafter, referred to as a "first resin composition" and a "second resin composition") is expected to give a cured product having low thermal expansion, excellent heat resistance, and excellent mechanical strength. Therefore, the resin composition containing the azole compound of the present invention is suitable as a material used in producing coating materials, inks, adhesives, pressure-sensitive adhesives, gas barrier films, color filters, optical films, optical lenses, touch panels, etc.

[0186] Examples of applications of the coating material include protection (hard coating) of touch panels, plastic containers, plastic sheets, plastic films, film-type liquid crystal elements, polarizing plates used in liquid crystal display devices, optical components, and building interior materials (flooring materials, wall materials, artificial marble, etc.).

[0187] Examples of the ink include color ink, printing ink, UV ink, inkjet ink, etc. These inks are used for offset printing, flexographic printing, gravure printing, screen printing, inkjet printing, etc.

[0188] The adhesives can be used for semiconductors, optics, optical components, optical waveguide coupling, fixing peripheral members of optical waveguides, and bonding CDs / DVDs.

[0189] The adhesives can be used for adhesive tapes, adhesive sheets, adhesive labels, and the like.

[0190] The gas barrier film can be used in electronic paper, flexible displays, organic EL devices, organic solar cells, and the like.

[0191] The applications of the color filters include color liquid crystal displays (color filter on array (COA)), color imaging devices, organic EL displays, and the like.

[0192] Examples of the optical film include protective films for polarizing plates, films for liquid crystal display devices such as support films for prism sheets and light-guiding films, functional films such as hard coat films, decorative films and transparent conductive films, weather-resistant (light-resistant) films for solar cells, films for LED lighting and organic EL lighting, and transparent heat-resistant films for flexible electronics.

[0193] Examples of the optical lens include lenses for microscopes, endoscopes, telescopes, cameras, and glasses, lenses for laser beam printers, lenses for sensors, prism lenses, and pickup lenses for optical disks.

[0194] The touch panel can be used in personal computers, car navigation systems, mobile phones, electronic dictionaries, office automation and factory automation equipment, and the like.

[0195] The resin composition containing the azole compound of the present invention can be further used in a variety of applications, including transparent materials, optical materials, dicing tapes, insulating materials (wire coatings, etc.), solder resist inks, printed wiring boards, copper-clad laminates, resin-coated copper foils, prepregs, high-voltage insulating materials, interlayer insulating materials, passivation films for TFTs, gate insulating films for TFTs, interlayer insulating films for TFTs, transparent planarizing films for TFTs, insulating packings, insulating coating materials, paints, UV powder paints, molding materials (sheets, films, FRP, etc.), sealants, liquid crystal sealants, sealants for display devices, high-heat-resistant sealants, potting materials, encapsulants (semiconductor encapsulants, encapsulants for electrical materials, encapsulants for organic EL and LED elements, encapsulants for various solar cells), resins, and the like. It is expected to be used as a raw material or component for resist materials (liquid resist materials, color resist materials, dry film resist materials, solder resist materials, color filter resist materials), photospacer materials for liquid crystal cells, stereolithography, solar cell materials, fuel cell materials, display materials, recording materials, photosensitive drums for copiers, solid electrolytes for batteries, and other electrical and electronic materials, as well as vibration-proofing materials, waterproofing materials, moisture-proofing materials, heat-shrinkable rubber tubing, O-rings, gas separation membranes, concrete protective materials, linings, soil injection agents, cold and heat storage materials, sealing materials for sterilization treatment equipment, oxygen-permeable membranes, and as an additive (modifier) ​​to be blended with other resins or resin compositions (thermoplastic, thermosetting, photosetting).

[0196] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The main raw materials used in the examples and synthesis examples are as follows.

[0197] [Main raw materials] ・3,5-Diamino-1H-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd. See chemical formula (III-1)) ・3-Amino-5-methylthio-1H-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd. See chemical formula (III-2)) ・3,5-Dimethyl-1H-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd. See chemical formula (III-3)) ・3-Chloro-1H-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd. See chemical formula (III-4)) ・5-Amino-1H-tetrazole (manufactured by Masuda Chemical Industry Co., Ltd. See chemical formula (IV-1)) ・5-Ethylthio-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd. See chemical formula (IV-2)) ・5-Phenyl-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd. See chemical formula (IV-3)) 5-benzyl-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.; see chemical formula (IV-4)). 4-vinylbenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.; purity 95.9%). 1H-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.). 4-ethylbenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0198]

[0199] The azole compounds used in the comparative examples (evaluation tests) are as follows: [Azole Compounds] Azole compound represented by chemical formula (41) (1-(4-vinylbenzyl)-1H-1,2,4-triazole): synthesized by the method of Synthesis Example 1. A mixture of an azole compound represented by chemical formula (42) and an azole compound represented by chemical formula (43) (5-amino-1-(4-ethylbenzyl)-1H-tetrazole and 5-amino-2-(4-ethylbenzyl)-2H-tetrazole): synthesized by the method of Synthesis Example 2.

[0200]

[0201] Synthesis Example 1 Synthesis of 1-(4-vinylbenzyl)-1H-1,2,4-triazole A solution consisting of 10.0 g (145 mmol) of 1H-1,2,4-triazole and 56 mL of N,N-dimethylformamide was heated to 70°C, and 28.7 g (145 mmol) of 28% sodium methoxide methanol solution was added. After stirring for 1 hour, the mixture was cooled to 40°C and the methanol was distilled off under reduced pressure. Next, 23.0 g (145 mmol) of 4-vinylbenzyl chloride was added, and the mixture was stirred at 55°C for 17 hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a brown viscous product. Subsequently, 200 mL of water was added, and the mixture was stirred at room temperature for 1 hour. The solid was collected by filtration, washed with n-hexane, and then dried to obtain 23.5 g (126.7 mmol, 87.5% yield) of a pale yellow solid.

[0202] The resulting pale yellow solid １ The H-NMR spectrum data was as follows: １ H-NMR (DMSO-d ６ ) δ: 5.26 (d, 1H), 5.40 (s, 2H), 5.83 (d, 1H), 6.72 (dd, 1H), 7.25 (d, 2H), 7.46 (d, 2H), 7.98 (s, 1H), 8.66 (s, 1H). １ From the H-NMR spectrum data, the obtained pale yellow solid was identified as the title azole compound represented by chemical formula (41).

[0203] Synthesis Example 2 Synthesis of a mixture of 5-amino-1-(4-ethylbenzyl)-1H-tetrazole and 5-amino-2-(4-ethylbenzyl)-2H-tetrazole A solution consisting of 10.0 g (118 mmol) of 5-amino-1H-tetrazole and 32 mL of N,N-dimethylformamide was heated to 70°C, 40.1 g (118 mol) of a 20% sodium ethoxide ethanol solution was added, and the mixture was stirred for 1 hour, and then cooled to 40°C, and the ethanol was distilled off under reduced pressure. Next, 18.2 g (118 mmol) of 4-ethylbenzyl chloride was added, and the mixture was stirred at 60°C for 16 hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a solid. Subsequently, 250 mL of water was added, and the mixture was stirred at room temperature for 1 hour, and the solid was collected by filtration. Further, 150 mL of n-hexane was added, and the mixture was stirred at room temperature for 1 hour. The solid was then collected by filtration, washed with n-hexane, and dried to obtain 20.7 g (101.8 mmol, yield 86.6%) of a white powder.

[0204] The resulting white powder １ The H-NMR spectrum data was as follows: １ H-NMR (DMSO-d ６ ) δ: 1.16 (m, 3H), 2.57 (m, 2H), 5.32 (s, 1.2H), 5.56 (s, 0.8H), 6.01 (s, 0.8H), 6.82 (s, 1.2H), 7.19 (m, 4H). this １ From the H-NMR spectrum data, the obtained white powder was identified as a mixture of the title azole compounds represented by chemical formula (42) and chemical formula (43).

[0205] <Synthesis of Azole Compound (I)> The azole compounds of Examples 1 to 8 below were synthesized.

[0206] Example 1 Synthesis of 3,5-diamino-1-(4-vinylbenzyl)-1H-1,2,4-triazole A solution consisting of 54.1 g (159 mmol) of a 20% sodium ethoxide ethanol solution and 46 mL of N,N-dimethylacetamide was heated to 45°C, and 15.8 g (159 mmol) of 3,5-diamino-1H-1,2,4-triazole was added. The temperature was raised to 70°C and the mixture was stirred for 1 hour, after which the mixture was cooled to 50°C and the ethanol was distilled off under reduced pressure. Next, 25.1 g (158 mmol) of 4-vinylbenzyl chloride was added and the mixture was stirred at 50°C for 20 hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a brown viscous product. Subsequently, 200 mL of water was added, and the mixture was stirred at room temperature for 1 hour, and the solid was collected by filtration. Further, 100 mL of ethyl acetate was added, and the mixture was stirred at room temperature for 1 hour. The solid was then collected by filtration, washed with ethyl acetate, and dried to obtain 17.8 g (82.7 mmol, yield 52.3%) of a pale yellow powder.

[0207] The obtained pale yellow powder １ The H-NMR spectrum data was as follows: １ H-NMR (DMSO-d ６ ) δ: 4.72 (s, 2H), 4.84 (s, 2H), 5.23 (dd, 1H), 5.80 (dd, 1H), 6.00 (s, 2H), 6.70 (dd, 1H), 7.17 (d, 2H), 7.42 (d, 2H). １ From the H-NMR spectrum data, the obtained pale yellow powder was identified as the title azole compound represented by chemical formula (I-1-1).

[0208]

[0209] Example 2 Synthesis of a Mixture of 3-amino-5-methylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole and 5-amino-3-methylthio-1-(4-vinylbenzyl)-1H-1,2,4-triazole A solution consisting of 12.0 g (92 mmol) of 3-amino-5-methylthio-1H-1,2,4-triazole and 37 mL of N,N-dimethylformamide was heated to 70°C, 31.4 g (92 mmol) of a 20% sodium ethoxide ethanol solution was added, and the mixture was stirred for 1 hour. The mixture was then cooled to 40°C and the ethanol was distilled off under reduced pressure. Next, 14.6 g (92 mmol) of 4-vinylbenzyl chloride was added, and the mixture was stirred at 60°C for 21 hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a brown viscous product. Subsequently, 120 mL of water was added, and the mixture was stirred at room temperature for 1 hour, after which the solid was collected by filtration. Further, 80 mL of n-hexane was added, and the mixture was stirred at room temperature for 1 hour. The solid was then collected by filtration, washed with n-hexane, and dried to obtain 18.5 g (75.1 mmol, yield 81.5%) of a brown solid.

[0210] The resulting brown solid １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３ ) δ: 2.52 (s, 1.8H), 2.61 (s, 1.2HH), 4.52 (br, 2H), 5.03 (s, 0.8H), 5.06 (s , 1.2H), 5.26 (m, 1H), 5.75 (m, 1H), 6.69 (m, 1H), 7.19 (m, 2H), 7.38 (m, 2H). this １ From the H-NMR spectrum data, the obtained brown solid was identified as the title azole compounds represented by chemical formula (I-1-2) and chemical formula (I-1-3).

[0211]

[0212] Example 3 Synthesis of 3,5-dimethyl-1-(4-vinylbenzyl)-1H-1,2,4-triazole A solution consisting of 5.1 g (52 mmol) of 3,5-dimethyl-1H-1,2,4-triazole and 20 mL of N,N-dimethylformamide was heated to 70°C, and 17.8 g (52 mmol) of a 20% sodium ethoxide ethanol solution was added. After stirring for 1 hour, the mixture was cooled to 40°C and the ethanol was distilled off under reduced pressure. Next, 8.3 g (52 mmol) of 4-vinylbenzyl chloride was added, and the mixture was stirred at 60°C for 20 hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a brown liquid. Subsequently, 80 mL of water was added, and the mixture was stirred at room temperature for 1 hour, after which the aqueous layer was removed. Furthermore, 40 mL of n-hexane was added, and the mixture was stirred at room temperature for 1 hour. The hexane layer was removed, and the mixture was concentrated under reduced pressure to obtain 6.2 g (29.1 mmol, yield 55.4%) of a brown liquid.

[0213] The resulting brown liquid １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３ ) δ: 2.35 (s, 6H), 5.19 (s, 2H), 5.27 (d, 1H), 5.74 (d, 1H), 6.69 (dd, 1H), 7.12 (d, 2H), 7.38 (d, 2H). １ From the H-NMR spectrum data, the obtained brown liquid was identified as the title azole compound represented by chemical formula (I-1-4).

[0214]

[0215] Example 4 Synthesis of a Mixture of 3-chloro-1-(4-vinylbenzyl)-1H-1,2,4-triazole and 5-chloro-1-(4-vinylbenzyl)-1H-1,2,4-triazole A solution consisting of 5.0 g (48 mmol) of 3-chloro-1H-1,2,4-triazole and 17 mL of N,N-dimethylformamide was heated to 70°C, and 16.4 g (48 mmol) of a 20% sodium ethoxide ethanol solution was added. After stirring for 1 hour, the mixture was cooled to 40°C and the ethanol was distilled off under reduced pressure. Next, 7.6 g (48 mmol) of 4-vinylbenzyl chloride was added and stirred at 60°C for 20 hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a brown viscous product. Subsequently, 80 mL of water was added, and the mixture was stirred at room temperature for 1 hour, after which the aqueous layer was removed. Further, 40 mL of n-hexane was added, and the mixture was stirred at room temperature for 1 hour, after which the hexane layer was removed and the mixture was concentrated under reduced pressure to obtain 9.2 g (41.9 mmol, yield 86.9%) of a brown viscous product.

[0216] The obtained brown viscous material １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３ ) δ: 5.25 (s, 1.6H), 5.29 (s, 0.4H), 5.32 (m, 1H), 5.80 (m, 1H), 6.71 (m, 1H), 7.25 (m, 2H), 7.43 (m, 2H), 7.86 (s, 0.2H), 7.91 (s, 0.8H). １ From the H-NMR spectrum data, the obtained brown viscous substance was identified as the title azole compounds represented by chemical formula (I-1-5) and chemical formula (I-1-6).

[0217]

[0218] Example 5 Synthesis of a Mixture of 5-amino-1-(4-vinylbenzyl)-1H-tetrazole and 5-amino-2-(4-vinylbenzyl)-2H-tetrazole A solution consisting of 13.4 g (158 mmol) of 5-amino-1H-tetrazole and 50 mL of N,N-dimethylacetamide was heated to 70°C, 54.1 g (159 mol) of a 20% sodium ethoxide ethanol solution was added, and the mixture was stirred for 1 hour. The mixture was then cooled to 50°C and the ethanol was distilled off under reduced pressure. Next, 25.1 g (158 mmol) of 4-vinylbenzyl chloride was added, and the mixture was stirred at 50°C for 20 hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a solid. Subsequently, 120 mL of water was added, and the mixture was stirred at room temperature for 1 hour. The solid was then filtered, washed with water, and dried to obtain 28.6 g (142.1 mmol, 90.0% yield) of a pale pink powder.

[0219] The resulting pale pink powder １ The H-NMR spectrum data was as follows: １ H-NMR (DMSO-d ６ ) δ: 5.25 (dd, 0.45H), 5.28 (dd, 0.55H), 5.36 (s, 0.90H), 5.60 (s, 1.10H), 5.81 (dd, 0.45H), 5.85 (dd, 0.55H), 6.04 (s, 0.90 H), 6.70 (dd, 0.55H), 6.72 (dd, 0.45H), 6.86 (s, 1.10H), 7.22 (d, 1.10H), 7.29 (d, 0.90H), 7.46 (d, 1.10H), 7.48 (d, 0.90H). this １ From the H-NMR spectrum data, the obtained pale pink powder was identified as a mixture of the title azole compounds represented by chemical formula (I-2-1) and chemical formula (I-3-1).

[0220]

[0221] Example 6 Synthesis of a Mixture of 5-ethylthio-1-(4-vinylbenzyl)-1H-tetrazole and 5-ethylthio-2-(4-vinylbenzyl)-2H-tetrazole A solution consisting of 10.0 g (77 mmol) of 5-ethylthio-1H-tetrazole and 37 mL of N,N-dimethylformamide was heated to 70°C, 26.3 g (77 mol) of a 20% sodium ethoxide ethanol solution was added, and the mixture was stirred for 1 hour. The mixture was then cooled to 40°C and the ethanol was distilled off under reduced pressure. Next, 12.2 g (77 mmol) of 4-vinylbenzyl chloride was added, and the mixture was stirred at 55°C for 20 hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a brown liquid. Subsequently, 100 mL of water was added, and the mixture was stirred at room temperature for 1 hour, after which the aqueous layer was removed. Further, 60 mL of n-hexane was added, and the mixture was stirred at room temperature for 1 hour, after which the hexane layer was removed and the mixture was concentrated under reduced pressure to obtain 17.1 g (69.4 mmol, yield 90.2%) of a brown liquid.

[0222] The resulting brown liquid １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３ ) δ: 1.41 (m, 3H), 3.18 (q, 1.2H), 3.32 (q, 0.8H), 5.28 (d, 1H), 5.39 (s, 0.8H), 5.68 (s, 1.2H), 5.78 (d, 1H), 6.69 (m, 1H), 7.33 (m, 4H). this １ From the H-NMR spectrum data, the obtained brown liquid was identified as the title azole compounds represented by chemical formula (I-2-2) and chemical formula (I-3-2).

[0223]

[0224] Example 7 Synthesis of a Mixture of 5-phenyl-1-(4-vinylbenzyl)-1H-tetrazole and 5-phenyl-2-(4-vinylbenzyl)-2H-tetrazole A solution consisting of 12.0 g (82 mmol) of 5-phenyl-1H-tetrazole and 37 mL of N,N-dimethylformamide was heated to 70°C, 28.0 g (82 mol) of a 20% sodium ethoxide ethanol solution was added, and the mixture was stirred for 1 hour. The mixture was then cooled to 40°C and the ethanol was distilled off under reduced pressure. Next, 13.0 g (82 mmol) of 4-vinylbenzyl chloride was added, and the mixture was stirred at 55°C for 20 hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a reddish-brown viscous product. Subsequently, 120 mL of water was added, and the mixture was stirred at room temperature for 1 hour, after which the aqueous layer was removed. Further, 40 mL of n-hexane was added, and the mixture was stirred at room temperature for 1 hour, after which the hexane layer was removed and the mixture was concentrated under reduced pressure to obtain 20.3 g (77.4 mmol, yield 94.4%) of a reddish-brown viscous product.

[0225] The obtained reddish-brown viscous material １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３ ) δ: 5.27 (m, 1H), 5.75 (d, 1H), 5.78 (s, 2H), 6.69 (m, 1H), 7.48 (m, 7H), 8.13 (m, 2H). １ From the H-NMR spectrum data, the obtained reddish-brown viscous substance was identified as the title azole compounds represented by chemical formula (I-2-3) and chemical formula (I-3-3).

[0226]

[0227] Example 8 Synthesis of a Mixture of 5-benzyl-1-(4-vinylbenzyl)-1H-tetrazole and 5-benzyl-2-(4-vinylbenzyl)-2H-tetrazole A solution consisting of 12.0 g (75 mmol) of 5-benzyl-1H-tetrazole and 37 mL of N,N-dimethylformamide was heated to 70°C, 25.5 g (75 mol) of a 20% sodium ethoxide ethanol solution was added, and the mixture was stirred for 1 hour. The mixture was then cooled to 40°C and the ethanol was distilled off under reduced pressure. Next, 11.9 g (75 mmol) of 4-vinylbenzyl chloride was added, and the mixture was stirred at 55°C for 20 hours. After cooling the reaction solution to room temperature, insoluble matter was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a brown liquid. Subsequently, 120 mL of water was added, and the mixture was stirred at room temperature for 1 hour, after which the aqueous layer was removed. Further, 60 mL of n-hexane was added, and the mixture was stirred at room temperature for 1 hour, after which the hexane layer was removed and the mixture was concentrated under reduced pressure to obtain 20.1 g (72.7 mmol, yield 97.0%) of a brown liquid.

[0228] The resulting brown liquid １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３ ) δ: 4.15 (s, 1H), 4.21 (s, 1H), 5.28 (m, 1H), 5.29 (s, 1H), 5.68 (s, 1H), 5.75 (d, 1H), 6.68 (m, 1H), 6.95 (m, 1H), 7.05 (m, 1H), 7.30 (m, 7H). this １ From the H-NMR spectrum data, the obtained brown liquid was identified as the title azole compounds represented by chemical formula (I-2-4) and chemical formula (I-3-4).

[0229]

[0230] <Adhesion Test> The surface treatment solutions prepared in Examples 9 to 11 and Comparative Examples 2 and 3 below were evaluated for adhesion as follows.

[0231] [Adhesion Evaluation Test] (1) Metal Electrolytic copper foil (thickness: 35 μm) was used as the metal. (2) Surface Treatment of Metal The copper foil was treated according to the following steps a to b: a. Acid cleaning (potassium persulfate-based soft etching agent / 30 seconds (30°C)), water rinsing b. Brush application of surface treatment solution, drying / 1 minute (100°C) (3) Adhesion of Metal and Resin A dry film type solder resist (SR1-A (manufactured by Taiyo Ink Mfg. Co., Ltd., thickness 15 μm)) was laminated / flat pressed onto the S-side of the treated copper foil, followed by UV exposure and post-curing (160°C / 60 minutes) to produce a copper-clad laminate with an insulating resin layer. (4) Evaluation of Adhesion After reflow heating twice (peak temperature 260°C, atmosphere), a 10 mm wide test piece was prepared from this copper clad laminate in accordance with JIS C6481 (1996) and the peel strength (kN / m) of the copper foil was measured.

[0232] Example 9 99 g of methanol was added to 1 g of the azole compound obtained in Example 2 as a coupling agent component, and the mixture was stirred at room temperature for 1 hour to prepare a surface treatment liquid.

[0233] [Examples 10 and 11] A surface treatment liquid was prepared in the same manner as in Example 9, except that the azole compound obtained in Example 5 or the azole compound obtained in Example 6 was used instead of the azole compound obtained in Example 2.

[0234] Comparative Example 1 An adhesiveness evaluation test was carried out on a copper foil that had been subjected to only step (2)a of the adhesiveness evaluation test.

[0235] Comparative Examples 2 and 3 Surface treatment solutions were prepared in the same manner as in Example 9, except that the azole compound obtained in Example 2 was replaced with the azole compound represented by the chemical formula (41) and a mixture of the azole compound represented by the chemical formula (42) and the azole compound represented by the chemical formula (43).

[0236] The surface treatment solutions prepared above were each subjected to an evaluation test for adhesiveness. The test results are shown in Table 1.

[0237]

[0238] The results in Table 1 show that the surface treatment solutions of the present invention (surface treatment solutions of Examples 9 to 11) have higher peel strength than Comparative Examples 1 to 3 and are excellent in adhesion (adhesion) between metal and resin.

[0239] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-088281) filed on May 30, 2023, the contents of which are incorporated herein by reference.

[0240] The azole compound of the present invention can be used as a coupling agent that combines the metal rust prevention function, which is a characteristic of azole compounds, with the function of curing resins such as epoxy resins and urethane resins, and is therefore expected to be used in composite materials such as printed wiring boards, which are manufactured by combining many different materials.In addition, according to the present invention, it is expected that the adhesiveness (adhesion) of metals, inorganic materials, and resin materials can be improved, so that the surface of the substrate can be maintained in a smooth state without roughening.Therefore, the present invention can greatly contribute to the realization of multilayer printed wiring boards that are smaller, thinner, have higher frequency, and have higher density, and therefore has great industrial applicability.

Claims

1. An azole compound represented by chemical formula (I): 【Chemistry 1】 (In formula (I), A represents a group represented by formulas (1) to (3).) 【Chemistry 2】 (In formula (1), R １ and R ２ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a group represented by formula (11), or a group represented by formula (12). ３ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a trimethylphenyl group, a tetramethylphenyl group, a 1-naphthyl group, a 2-naphthyl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 2 to 6 carbon atoms, a group represented by formula (21), or a group represented by formula (31). １ and R ２ are simultaneously hydrogen atoms, R １ and R ２ is simultaneously a group represented by formula (11), R １ and R ２ is simultaneously a group represented by formula (12), R １ and R ２ is a group represented by formula (11) or formula (12). 【Transformation 3】 (In formula (11) and formula (12), R ４ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, or an alkylthio group having 1 to 6 carbon atoms. １１ represents a hydrogen atom or a group represented by formula (4), and Y represents a phenylene group, —NH—, or —(CH ２ ) ｎ -, where n is an integer of 0 to 12. 【Chemistry 4】

2. 2. A method for synthesizing an azole compound according to claim 1, which comprises reacting a styryl compound represented by chemical formula (II) with a triazole compound represented by chemical formula (III) or a tetrazole compound represented by chemical formula (IV). 【Transformation 5】 (In formula (II), X represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.) 【Transformation 6】 (In formula (III), R ２１ and R ２２ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a group represented by formula (13), or a group represented by formula (14). ２３ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a trimethylphenyl group, a tetramethylphenyl group, a 1-naphthyl group, a 2-naphthyl group, an aralkyl group, an amino group which may be substituted, a hydroxyl group, a cyano group, a halogen atom, an alkylthio group having 2 to 6 carbon atoms, a group represented by formula (22), or a group represented by formula (32). ２１ and R ２２ are simultaneously hydrogen atoms, R ２１ and R ２２ is simultaneously a group represented by formula (13), R ２１ and R ２２ is simultaneously a group represented by formula (14), R ２１ and R ２２ is a group represented by formula (13) or formula (14). 【Transformation 7】 (R in formula (13) and formula (14) ４ and Y in formulas (13), (14), (22) and (32) are the same as defined above.

3. A coupling agent comprising the azole compound according to claim 1 as a component.

4. A surface treatment liquid containing the azole compound according to claim 1.

5. The surface treatment solution according to claim 4, which is used to treat the surface of at least one material selected from the group consisting of metals, inorganic materials, and resin materials.

6. The surface treatment liquid according to claim 4, which is used to bond two materials selected from the group consisting of metals, inorganic materials, and resin materials.

7. 7. The surface treatment solution according to claim 5, wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof.

8. A surface treatment method comprising contacting the surface treatment liquid according to claim 4 with at least one surface selected from the group consisting of metals, inorganic materials, and resin materials.

9. 9. The surface treatment method according to claim 8, wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof.

10. The surface treatment method according to claim 9, wherein the metal is copper or a copper alloy.

11. 11. The surface treatment method according to claim 10, wherein an aqueous solution containing copper ions is brought into contact with the surface of the copper or copper alloy before the surface treatment liquid is brought into contact with the surface of the copper or copper alloy.

12. 12. The surface treatment method according to claim 10, wherein after the surface treatment liquid is brought into contact with the surface of copper or a copper alloy, an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the surface of the copper or copper alloy.

13. A bonding method comprising contacting the surface treatment liquid according to claim 4 with at least one material selected from the group consisting of a metal, an inorganic material, and a resin material to form a chemical conversion coating on at least one of the materials, and bonding the materials to each other via the chemical conversion coating.

14. A method for bonding metal and resin materials, comprising:

5. A method for bonding a metal and a resin material, comprising contacting the surface treatment liquid according to claim 4 with at least one of a metal and a resin material to form a chemical conversion coating on the at least one of the metal and the resin material, and bonding the metal and the resin material to each other via the chemical conversion coating.

15. A printed wiring board in which two materials selected from the group consisting of metals, inorganic materials, and resin materials are bonded via a chemical conversion coating formed by the surface treatment liquid according to claim 4.

16. A semiconductor wafer having two materials selected from the group consisting of metals, inorganic materials, and resin materials bonded together via a chemical conversion film formed using the surface treatment liquid according to claim 4.

17. An insulating composition comprising the coupling agent according to claim 3 and a resin material or an inorganic material.

18. An insulating material comprising the insulating composition according to claim 17.

19. A printed wiring board having an insulating layer obtained from the insulating composition according to claim 17.

20. A semiconductor wafer having an insulating layer obtained from the insulating composition of claim 17.

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