Triazole compounds, methods for synthesizing such triazole compounds, coupling agents, and their uses

Abstract

The object of this invention is to provide novel triazole compounds, methods for their synthesis, and coupling agents. The triazole compounds of this invention are shown in chemical formula (I). The definitions of each substituent in chemical formula (I) are as defined in the specification. [Chem. 1]

Description

[Technical Field]

[0001] This invention relates to novel triazole compounds, methods for synthesizing the triazole compounds, coupling agents, and their uses. [Previous Technology]

[0002] Coupling agents are known to be used to combine organic and inorganic materials with different properties, and are used in fields such as electronic materials, coatings, primers, and adhesives. Therefore, coupling agents are indispensable agents in the development or production of composite materials.

[0003] For example, there are known coupling agents (silane coupling agents) that use compounds composed of organic matter and silicon. These silane coupling agents typically function as intermediaries to combine non-fused organic and inorganic materials.

[0004] Furthermore, since triazole compounds have the functions of preventing metal corrosion and curing epoxy resins or ethyl carbamate resins, various coupling agents using triazole compounds have been proposed.

[0005] Triazole compounds that can be used as coupling agents include, for example, a triazole silane compound proposed in Patent Document 1, in which a specific triazole ring has an alkoxysilane group introduced into it. Patent Document 2 proposes a triazole silane compound having two specific triazole rings and a disulfide bond (-SS-), and in which a -CO-NH-(CH2)m-Si(OR)3 group is introduced into the triazole ring. [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] International Patent Publication No. 2018 / 186476 [Patent Document 2] International Patent Publication No. 2015 / 002158 [Summary of the Invention]

[0007] (The problem that the invention aims to solve)

[0008] In recent years, in the field of electrical and electronic materials, there has been a demand for improved adhesion between materials in response to miniaturization, thinning, precision, and high-speed transmission. Although the triazole compounds disclosed in Patent Documents 1 and 2 can also exhibit excellent adhesion, there is still a need for compounds that can exhibit even higher adhesion.

[0009] This invention was made in view of the above-mentioned problems, and its objective is to provide novel triazole compounds, methods for synthesizing the same, and coupling agents. (Technical means to solve the problem)

[0010] The inventors of this invention have conducted in-depth research in order to solve the above-mentioned problems and have found that by bonding the triazole rings in a triazole compound having two triazole rings with a specific bonding group, the above-mentioned problems can be solved, and thus the present invention was completed.

[0011] That is, the present invention is as follows [1]~

[20] . [1] A triazole compound, which is shown in the following chemical formula (I);

[0012] [Chemical 1]

[0013] (In formula (I), R1 and R2 may be the same or different, representing hydrogen atoms, straight-chain or branched-chain alkyl, aryl, aralkyl, amino, hydroxyl or alkylthio with 1 to 6 carbon atoms; R3 and R4 may be the same or different, representing hydrogen atoms or the group shown in -(CH2)m-Si(OR)3, where R represents methyl or ethyl, and m represents an integer from 1 to 18; where R3 and R4 are both hydrogen atoms, the case of R3 and R4 being hydrogen atoms is excluded; X represents the group shown in -phenyl, -NH- or -(CH2)n-, where n represents an integer from 0 to 12). [2] A method for synthesizing a triazole compound is the method for synthesizing the triazole compound of the above [1], which is to react the triazole compound shown in the following chemical formula (II) with the compound shown in the following chemical formula (III).

[0014] [Chemical 2]

[0015] (In formula (II), R1, R2 and X are the same as above)

[0016] [Chemical 3]

[0017] (In formula (III), R and m are the same as above; Hal represents a chlorine atom, a bromine atom or an iodine atom). [3] A coupling agent, which is composed of a triazole compound as shown in the following chemical formula (IV);

[0018] [Chemical 4]

[0019] (In formula (IV), R1 and R2 may be the same or different, representing hydrogen atoms, straight-chain or branched-chain alkyl, aryl, aralkyl, amino, hydroxyl or alkylthio group with 1 to 6 carbon atoms; R5 and R6 may be the same or different, representing hydrogen atoms or the group shown in -(CH2)m-Si(OR)3-p(OH)p, where R represents methyl or ethyl, m represents an integer from 1 to 18, and p represents an integer from 0 to 3; X represents the group shown in -phenyl, -NH- or -(CH2)n-, where n represents an integer from 0 to 12). [4] A surface treatment liquid containing a triazole compound shown in the following chemical formula (IV);

[0020] [Chemical 5]

[0021] (In formula (IV), R1 and R2 may be the same or different, representing hydrogen atoms, straight-chain or branched-chain alkyl, aryl, aralkyl, amino, hydroxyl or alkathioyl groups having 1 to 6 carbon atoms; R5 and R6 may be the same or different, representing hydrogen atoms or groups represented by -(CH2)m-Si(OR)3-p(OH)p, where R represents methyl or ethyl, m represents an integer from 1 to 18, and p represents an integer from 0 to 3; X represents a group represented by phenyl, -NH- or -(CH2)n-, where n represents an integer from 0 to 12).

[0022] [5] The surface treatment liquid of [4] is used to treat the surface of at least one of the group consisting of metals, inorganic materials and resin materials. [6] The surface treatment liquid of [4] is used to bond two materials consisting of the group consisting of metals, inorganic materials and resin materials. [7] The surface treatment liquid of [5] or [6], wherein the metal is selected from at least one of the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold and alloys thereof.

[0023] [8] A surface treatment method wherein the surface treatment liquid of the above [4] is brought into contact with a surface selected from at least one of the group consisting of metals, inorganic materials and resin materials. [9] The surface treatment method of [8] wherein the metal is selected from at least one of the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold and alloys thereof.

[10] The surface treatment method of [9] wherein the metal is copper or a copper alloy.

[11] The surface treatment method of

[10] wherein, before bringing the surface treatment liquid into contact with the surface of copper or copper alloy, an aqueous solution containing copper ions is brought into contact with the surface of copper or copper alloy.

[12] The surface treatment method of

[10] or

[11] wherein, after bringing the surface treatment liquid into contact with the surface of copper or copper alloy, an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the surface of copper or copper alloy.

[13] A bonding method in which the surface treatment liquid of [4] is brought into contact with at least one of a group consisting of a metal, an inorganic material and a resin material, and a chemically formed film is formed on the at least one of them, and the chemically formed film is used to bond the metal and the resin material to each other.

[14] A bonding method is a method for bonding a metal and a resin material, in which the surface treatment liquid of [4] is brought into contact with at least one of a metal and a resin material, and a chemically formed film is formed on the at least one of them, and the metal and the resin material are used to bond the metal and the resin material to each other through the chemically formed film.

[0024]

[15] A printed wiring board is formed by bonding two materials selected from the group consisting of metal, inorganic material and resin material, separated by a formation film formed by the surface treatment liquid of the above [4].

[16] A semiconductor wafer is formed by bonding two materials selected from the group consisting of metal, inorganic material and resin material, separated by a formation film formed by the surface treatment liquid of the above [4].

[17] An insulating composition contains the coupling agent of the above [3] and a resin material or an inorganic material.

[18] An insulating material contains the insulating composition of the above

[17] .

[19] A printed wiring board has an insulating layer obtained from the insulating composition of the above

[17] .

[20] A semiconductor wafer has an insulating layer obtained from the insulating composition of the above

[17] . (Effects compared to the prior art)

[0025] The triazole compound of the present invention, being a compound formed by two triazole rings, can improve its interaction with metals or resin materials. Furthermore, since the two triazole rings are bonded by bonding groups selected from the group consisting of phenyl, -NH-, and -(CH2)n- groups, it is less prone to decomposition due to heat or alkali. Moreover, the coupling agent of the present invention, being composed of a triazole compound formed by two triazole rings bonded by the aforementioned bonding groups, can improve the adhesion between materials with different properties. According to the surface treatment liquid containing this triazole compound, the adhesion between two materials with different materials, namely metal and inorganic materials, metal and resin materials, and inorganic and resin materials, can be improved.

Implementation Method

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

[0027] (Triazole compound) The triazole compound of the present invention is represented by the following chemical formula (I) (hereinafter also referred to as triazole compound (I)).

[0028] [Chemical 6]

[0029] (In formula (I), R1 and R2 may be the same or different, representing hydrogen atoms, straight-chain or branched-chain alkyl, aryl, aralkyl, amino, hydroxyl or alkathioyl groups with 1 to 6 carbon atoms; R3 and R4 may be the same or different, representing hydrogen atoms or groups represented by -(CH2)m-Si(OR)3, where R represents methyl or ethyl, and m represents an integer from 1 to 18; excluding the case where R3 and R4 are both hydrogen atoms; X represents a group represented by phenyl, -NH- or -(CH2)n-, where n represents an integer from 0 to 12).

[0030] In formula (I), R1 and R2 are hydrogen atoms, straight-chain or branched-chain alkyl, aryl, aralkyl, amino, hydroxyl, or alkylthio group having 1 to 6 carbon atoms. R1 and R2 may be the same or different.

[0031] Examples of straight-chain alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. Examples of branched-chain alkyl groups having 1 to 6 carbon atoms, specifically those having 3 to 6 carbon atoms, include isopropyl, isobutyl, dibutyl, tributyl, isopentyl, dipentyl, tripentyl, isohexyl, dihexyl, and trihexyl. Examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, trimethylphenyl, tetramethylphenyl, 1-naphthyl, and 2-naphthyl. Examples of aralkyl groups include benzyl, phenylethyl, phenylpropyl, and methylbenzyl. Examples of alkylthio groups having 1 to 6 carbon atoms include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, dibutylthio, tributylthio, pentylthio, and hexylthio.

[0032] R1 and R2 may be the same or different, and are more preferably hydrogen atoms, amino groups or alkylthio groups with 1 to 6 carbon atoms.

[0033] R3 and R4 represent hydrogen atoms or the radical shown in -(CH2)m-Si(OR)3 (R represents methyl or ethyl, m represents an integer from 1 to 18). R3 and R4 may be the same or different, but R3 and R4 may not both be hydrogen atoms.

[0034] -(CH 2) m-Si(OR) 3 The preferred system m is an integer from 2 to 12, the more preferred system m is an integer from 3 to 10, and the even more preferred system m is an integer from 3 to 8.

[0035] X represents a group consisting of -phenyl, -NH- or -(CH2)n- (n represents an integer from 0 to 12). X is preferably a group consisting of -(CH2)n-, and more preferably n is an integer from 0 to 10, even more preferably an integer from 0 to 8, and most preferably an integer from 0 to 6.

[0036] In the compound shown in chemical formula (I) (triazole compound (I)), R3 and R4 are preferably bonded to the N atom at the 1st or 2nd position of the triazole ring.

[0037] As a triazole compound (I), examples include triazole compounds shown in chemical formulas (I-1) to (I-8).

[0038] [Chemical 7]

[0039] (In formulas (I-1) to (I-8), R1, R2, m, R and X are the same as above.)

[0040] Specific examples of triazole compounds (I) where R3 is hydrogen and R4 is N bonded to the 1-position of the triazole ring (compounds shown in formula (I-3)) include, for example, 1-(trimethoxysilyl)methyl-3,3'-(1,4-epenylphenyl)bis(1,2,4-triazole), 1-[2-(triethoxysilyl)ethyl]-3,3'-(1,2-epenylphenyl)bis(5-methyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-(1,3-epenylphenyl)bis(5-butyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-(1,4-epenylphenyl)bis(5-amino-1,2,4-triazole). 1-[6-(triethoxysilyl)hexyl]-3,3'-(1,4-epenylphenyl)bis(5-ethylthio-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-iminobis(5-ethyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-iminobis(5-p-tolyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-iminobis(5-amino-1,2,4-triazole), 1-[8-(trimethoxysilyl)octyl]-3,3'-iminobis(5-isopropyl-1,2,4-triazole) 1-[3-(triethoxysilyl)propyl]-3,3'-bis(5-methyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-bis(5-pentyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-bis(5-amino-1,2,4-triazole), 1-[10-(triethoxysilyl)decyl]-3,3'-bis(5-phenyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-5-amino-5'-methyl-3,3'-bis(1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-methylenebis(5-isobutyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-methylenebis(5-hydroxy-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-methylenebis(5-amino-1,2,4-triazole), 1-[6-(trimethoxysilyl)hexyl]-3,3'-methylenebis(5-amino-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-ethylbis(5-ethyl-1,2,4-triazole) 1-[3-(triethoxysilyl)propyl]-3,3'-epenylethylbis(5-amino-1,2,4-triazole), 1-[12-(triethoxysilyl)decyl]-3,3'-epenylethylbis(5-amino-1,2,4-triazole)4-Triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-tetramethylenebis(5-benzyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-tetramethylenebis(5-butylthio-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-tetramethylenebis(5-amino-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-pentamethylenebis(1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-pentamethylenebis(5-amino-1,2,4-triazole), 1-[4-(triethoxysilyl)butyl]-3,3'-pentamethylenebis(5-amino-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-hexamethylenebis(5-amino-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-octamethylenebis(5-amino-1,2,4-triazole), 1-[2-(trimethoxysilyl)ethyl]-3,3'-nonamethylenebis(5-amino-1,2,4-triazole), 1-[2-(trimethoxysilyl)ethyl]-3,3'-decamethylenebis(5-amino-1,2,4-triazole) 1-[3-(triethoxysilyl)propyl]-3,3'-undecylmethylenebis(5-amino-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3'-dodecylmethylenebis(5-amino-1,2,4-triazole), etc.

[0041] As a triazole compound (I), R3 and R4 may be the same or different. Specific examples of compounds with the group represented by -(CH2)m-Si(OR)3 and R3 and R4 bonded to the N at the 1-position of the triazole ring (compounds shown in formula (I-5)) include 3,3'-(1,4-epenylphenyl)bis[1-(trimethoxysilyl)methyl-1,2,4-triazole], 3,3'-(1,2-epenylphenyl)bis{1-[2-(triethoxysilyl)ethyl]-5-methyl-1,2,4-triazole}, and 3,3'-(1,3-epenylphenyl)bis{1-[3-(triethoxysilyl)propyl]-5-butyl-1,2,4-triazole}. 3,3'-(1,4-Phenylphenyl)bis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3'-(1,4-Phenylphenyl)bis{1-[6-(triethoxysilyl)hexyl]-5-ethylthio-1,2,4-triazole}, 3,3'-iminobis{1-[3-(triethoxysilyl)propyl]-5-ethyl-1,2,4-triazole}, 3,3'-iminobis{1-[3-(triethoxysilyl)propyl]-5-p-tolyl-1,2,4-triazole}, 3,3'-iminobis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3'-Iminebis{1-[8-(trimethoxysilyl)octyl]-5-isopropyl-1,2,4-triazole}, 3,3'-bis{1-[3-(triethoxysilyl)propyl]-5-pentyl-1,2,4-triazole}, 3,3'-bis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3'-bis{1-[10-(triethoxysilyl)decyl]-5-phenyl-1,2,4-triazole}, 1,1'-bis{1-[3-(triethoxysilyl)propyl]-5-amino-5'-methyl-3,3'-bi-1,2,4-triazole}, 3,3'-Methylenebis{1-[3-(triethoxysilyl)propyl]-5-isobutyl-1,2,4-triazole}, 3,3'-Methylenebis{1-[3-(triethoxysilyl)propyl]-5-hydroxy-1,2,4-triazole}, 3,3'-Methylenebis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3'-Methylenebis{1-[6-(trimethoxysilyl)hexyl]-5-amino-1,2,4-triazole}, 3,3'-Ethylbis{1-[3-(triethoxysilyl)propyl]-5-ethyl-1,2,4-triazole}, 3,3'-Ethylbis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3'-Ethylbis{1-[12-(triethoxysilyl)dodecyl]-5-amino-1,2,4-triazole}, 3,3'-Tetramethylenebis{1-[3-(triethoxysilyl)propyl]-5-benzyl-1,2,4-triazole}, 3,3'-Tetramethylenebis{1-[3-(triethoxysilyl)propyl]-5-butylthio-1,2,4-triazole}, 3,3'-Tetramethylenebis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3'-Pentamethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,4-triazole}, 3,3'-Pentamethylenebis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3'-Pentamethylenebis{1-[4-(triethoxysilyl)butyl]-5-amino-1,2,4-triazole}, 3,3'-Hexamethylenebis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3'-Octamethylenebis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3'-Nonamethylenebis{1-[2-(trimethoxysilyl)ethyl]-5-amino-1,2,4-triazole}, 3,3'-Decamethylenebis{1-[2-(trimethoxysilyl)ethyl]-5-amino-1,2,4-triazole}, 3,3'-Undecylmethylenebis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3'-Dodecylmethylenebis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, etc.

[0042] Triazole compound (I) is obtained by reacting a triazole compound of chemical formula (II) (hereinafter sometimes referred to as triazole compound (II)) with a haloalkylsilane compound of chemical formula (III) (hereinafter sometimes referred to as haloalkylsilane compound (III)).

[0043] [Chemical 8]

[0044] (In formula (II), R1, R2 and X are the same as above.)

[0045] [Chemical 9]

[0046] (In formula (III), R and m are the same as above. Hal represents a chlorine atom, a bromine atom, or an iodine atom.)

[0047] In formula (II), R1, R2, and X are the same as those shown in formula (I), and preferably also the same. In formula (III), R and m are the same as those shown in formula (I), and preferably also the same. In formula (III), Hal represents a chlorine atom, a bromine atom, or an iodine atom. From the viewpoint of reactivity and ease of obtaining raw materials, a chlorine atom or a bromine atom is preferred.

[0048] Examples of triazole compounds (II) include 3,3'-(1,4-epenylphenyl)bis(1,2,4-triazole), 3,3'-(1,4-epenylphenyl)bis(5-methyl-1,2,4-triazole), 3,3'-(1,2-epenylphenyl)bis(5-ethyl-1,2,4-triazole), 3,3'-(1,4-epenylphenyl)bis(5-isopropyl-1,2,4-triazole), 3,3'-(1,3-epenylphenyl)bis(5-butyl-1,2,4-triazole), 3,3'-(1,4-epenylphenyl)bis(5-phenyl-1,2,4-triazole), and 3,3'-(1,4-epenylphenyl)bis(5-amino-1,2,4-triazole). 3,3'-(1,4-epenylphenyl)bis(5-hydroxy-1,2,4-triazole), 3,3'-(1,4-epenylphenyl)bis(5-ethylthio-1,2,4-triazole), 5-amino-3,3'-(1,4-epenylphenyl)bis(1,2,4-triazole), 3,3'-iminobis(1,2,4-triazole), 3,3'-iminobis(5-methyl-1,2,4-triazole), 3,3'-iminobis(5-hexyl-1,2,4-triazole), 3,3'-iminobis(5-phenyl-1,2,4-triazole), 3,3'-iminobis(5-benzyl-1,2,4-triazole), 3,3'-iminobis(5-amino-1,2,4-triazole) 3,3'-Iminebis(5-hydroxy-1,2,4-triazole), 3,3'-Iminebis(5-methylthio-1,2,4-triazole), 5-amino-3,3'-iminobis(1,2,4-triazole), 3,3'-bi-1,2,4-triazole, 3,3'-bis(5-methyl-1,2,4-triazole), 3,3'-bis(5-ethyl-1,2,4-triazole), 3,3'-bis(5-pentyl-1,2,4-triazole), 3,3'-bis(5-p-tolyl-1,2,4-triazole), 3,3'-bis(5-benzyl-1,2,4-triazole), 3,3'-bis(5-amino-1,2,4-triazole), 3,3'-bis(5-hydroxy-1,2,4-triazole) 3,3'-Bis(5-hexylthio-1,2,4-triazole), 5-amino-5'-methyl-3,3'-bi-1,2,4-triazole, 3,3'-methylenebis(1,2,4-triazole), 3,3'-methylenebis(5-methyl-1,2,4-triazole), 3,3'-methylenebis(5-isobutyl-1,2,4-triazole), 3,3'-methylenebis(5-phenyl-1,2,4-triazole), 3,3'-methylenebis(5-phenylethyl-1,2,4-triazole), 3,3'-methylenebis(5-amino-1,2,4-triazole), 3,3'-methylenebis(5-hydroxy-1,2,4-triazole), 3,3'-methylenebis(5-methylthio-1,2,4-triazole),4-Triazole), 5-amino-5'-ethyl-3,3'-methylenebis(1,2,4-triazole), 3,3'-epoxyethylbis(1,2,4-triazole), 3,3'-epoxyethylbis(5-propyl-1,2,4-triazole), 3,3'-epoxyethylbis(5-hexyl-1,2,4-triazole), 3,3'-epoxyethylbis(5-m-tolyl-1,2,4-triazole), 3,3'-epoxyethylbis(5-amino-1,2,4-triazole), 3,3'-epoxyethylbis(5-hydroxy-1,2,4-triazole), 3,3'-epoxyethylbis(5-isopropylthio-1,2,4-triazole), 5-amino-3,3'-epoxyethylbis(1,2,4-triazole), 3,3'-trimethylenebis(1,2,4-triazole) 5-Methyl-3,3'-trimethylenebis(1,2,4-triazole), 3,3'-trimethylenebis(5-butyl-1,2,4-triazole), 3,3'-trimethylenebis(5-phenyl-1,2,4-triazole), 3,3'-trimethylenebis(5-amino-1,2,4-triazole), 3,3'-trimethylenebis(5-propylthio-1,2,4-triazole), 5-amino-5'-benzyl-3,3'-trimethylenebis(1,2,4-triazole), 3,3'-tetramethylenebis(1,2,4-triazole), 3,3'-tetramethylenebis(5-ethyl-1,2,4-triazole), 3,3'-tetramethylenebis(5-hexyl-1,2,4-triazole) 3,3'-Tetramethylenebis(5-benzyl-1,2,4-triazole), 3,3'-tetramethylenebis(5-amino-1,2,4-triazole), 3,3'-tetramethylenebis(5-hydroxy-1,2,4-triazole), 3,3'-tetramethylenebis(5-butylthio-1,2,4-triazole), 5-amino-3,3'-tetramethylenebis(1,2,4-triazole), 3,3'-pentamethylenebis(1,2,4-triazole), 3,3'-pentamethylenebis(5-propyl-1,2,4-triazole), 3,3'-pentamethylenebis(5-amino-1,2,4-triazole), 3,3'-pentamethylenebis(5-hydroxy-1,2,4-triazole), 3,3'-pentamethylenebis(5-pentathio-1,2,4-triazole) 5-Amino-5'-phenyl-3,3'-pentamethylenebis(1,2,4-triazole), 3,3'-hexamethylenebis(1,2,4-triazole), 3,3'-hexamethylenebis(5-pentyl-1,2,4-triazole), 3,3'-hexamethylenebis(5-amino-1,2,4-triazole), 5-hydroxy-3,3'-hexamethylenebis(1,2,4-triazole), 5-phenyl-3,3'-hexamethylenebis(1,2,4-triazole), 5-amino-5'-methylthio-3,3'-hexamethylenebis(1,2,4-triazole), 3,3'-heptamethylbis(1,2,4-triazole), 3,3'-Hepamethylenebis(5-tert-butyl-1,2,4-triazole), 3,3'-Hepamethylenebis(5-phenyl-1,2,4-triazole), 3,3'-Hepamethylenebis(5-amino-1,2,4-triazole), 5-amino-5'-hydroxy-3,3'-Hepamethylenebis(1,2,4-triazole), 3,3'-Octamethylenebis(1,2,4-triazole), 3,3'-Octamethylenebis(5-isobutyl-1,2,4-triazole), 3,3'-Octamethylenebis(5-amino-1,2,4-triazole), 3,3'-Octamethylenebis(5-hydroxy-1,2,4-triazole), 5-propylthio-3,3'-Octamethylenebis(1,2,4-triazole), 3,3'-Nonamethylenebis(1,2,4-triazole) 3,3'-Nonamethylenebis(5-isopentyl-1,2,4-triazole), 5-phenyl-3,3'-nonamethylenebis(1,2,4-triazole), 3,3'-nonamethylenebis(5-amino-1,2,4-triazole), 3,3'-nonamethylenebis(5-methylthio-1,2,4-triazole), 3,3'-decamethylenebis(1,2,4-triazole), 3,3'-decamethylenebis(5-methyl-1,2,4-triazole), 3,3'-decamethylenebis(5-amino-1,2,4-triazole), 5-ethyl-3,3'-decamethylenebis(1,2,4-triazole), 3,3'-undecylmethylenebis(1,2,4-triazole), 3,3'-undecylmethylenebis(5-propyl-1,2,4-triazole) 3,3'-Undecylmethylenebis(5-amino-1,2,4-triazole), 3,3'-Undecylmethylenebis(5-methylthio-1,2,4-triazole), 3,3'-Dodecylmethylenebis(1,2,4-triazole), 3,3'-Dodecylmethylenebis(5-ethyl-1,2,4-triazole), 3,3'-Dodecylmethylenebis(5-amino-1,2,4-triazole), 3,3'-Undecylmethylenebis(5-hydroxy-1,2,4-triazole), etc.

[0049] The triazole compounds (II) illustrated herein can be synthesized according to, for example, the synthetic methods described in Chem. Eur. J., 18, 16742 (2012), J. Applied. Chem., 82, 276 (2009), and U.S. Patent No. 2744116.

[0050] Examples of the above-mentioned alkyl halogenated silane compound (III) include chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 3-iodopropyltrimethoxysilane, 3-iodopropyltriethoxysilane, 4-bromobutyltrimethoxysilane, 4-bromobutyltriethoxysilane, 5-bromopentyltrimethoxysilane, 5-bromopentyltriethoxysilane, 6-bromohexyltrimethoxysilane, 6-bromohexyltriethoxysilane. 8-Bromooctyltrimethoxysilane, 8-Bromooctyltriethoxysilane, 10-Bromodecyltrimethoxysilane, 10-Bromodecyltriethoxysilane, 12-Bromododecyltrimethoxysilane, and 12-Bromododecyltriethoxysilane, etc.

[0051] The triazole compound (I) of the present invention is synthesized, for example, by reacting a triazole compound (II) with a haloalkylsilane compound (III) in the presence of a dehydrohalogenating agent in an appropriate amount of reaction solvent at a suitable reaction temperature and reaction time, thereby achieving a substantially high yield. The following reaction flow (A) illustrates the reaction flow for obtaining a triazole compound (I) with R3 being a hydrogen atom and R4 being a group represented by -(CH2)m-Si(OR)3.

[0052] [Chemical 10]

[0053] (In the formula, R1, R2, X, R, Hal and m are the same as above.)

[0054] As the reaction solvent, there are no particular limitations on the solvent that is inert to the triazole compound (II) and the haloalkylsilane compound (III). Examples include hydrocarbon solvents such as hexane, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, dimethyl ether, and cyclopentyl methyl ether; ester solvents such as ethyl acetate and butyl acetate; alcohol solvents such as methanol and ethanol; acetamine solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and acetonitrile, dimethyl sulfoxide, or hexamethylphosphatamine, etc.

[0055] As the above-mentioned dehalogenating agents, examples include alkane oxides of alkali metals such as sodium methoxide, sodium ethoxide, potassium methoxide, and potassium tributoxide; carbonate salts such as sodium carbonate and potassium carbonate; organic bases such as triethylamine or diazabicycloundecene, or sodium hydride.

[0056] The reaction of triazole compound (II) with haloalkylsilane compound (III) is carried out stoichiometrically as described in the above reaction procedure (A). The amount of haloalkylsilane compound (III) used (filling amount) is determined relative to the amount of triazole compound (II), taking into account factors such as reaction temperature or reaction time, the type of raw materials or reaction solvent used, and the scale of the reaction. Preferably, 0.8 to 1.2 equivalents of haloalkylsilane compound (III) are used relative to each -NH group of the triazole ring that becomes a reaction point. If the filling amount of haloalkylsilane compound (III) relative to each reaction point (-NH) is greater than 1.2 equivalents, there is a risk that the compound will polymerize and gel; if it is less than 0.8 equivalents, there is a risk that the purity of the product will decrease and the separation operation of the product will become more complicated. Furthermore, since the dehydrohalogenating agent is used to neutralize the hydrogen halide produced by the reaction of triazole compound (II) and alkyl halogenated silica compound (III), its usage (filling amount) should be at least 1 mole relative to the amount of alkyl halogenated silica compound (III).

[0057] The above reaction temperature is not particularly limited to the temperature range in which the -NH of the triazole ring of the triazole compound (II) reacts with the haloalkylsilane compound (III), but is preferably in the range of 0 to 150°C, and more preferably in the range of 5 to 100°C.

[0058] The above reaction time is appropriately determined in conjunction with the set reaction temperature, preferably in the range of 30 minutes to 24 hours, and more preferably in the range of 1 to 8 hours.

[0059] (Coupling agent) The coupling agent of the present invention is composed of a triazole compound (hereinafter also referred to as triazole compound (IV)) as shown in the following chemical formula (IV).

[0060] [Chemical 11]

[0061] (In formula (IV), R1 and R2 may be the same or different, representing hydrogen atoms, straight-chain or branched-chain alkyl, aryl, aralkyl, amino, hydroxyl or alkathioyl groups having 1 to 6 carbon atoms; R5 and R6 may be the same or different, representing hydrogen atoms or groups represented by -(CH2)m-Si(OR)3-p(OH)p, where R represents methyl or ethyl, m represents an integer from 1 to 18, and p represents an integer from 0 to 3; X represents a group represented by phenyl, -NH- or -(CH2)n-, where n represents an integer from 0 to 12).

[0062] In formula (IV), R1 and R2 are hydrogen atoms, straight-chain or branched-chain alkyl, aryl, aralkyl, amino, hydroxyl, or alkylthio group having 1 to 6 carbon atoms. R1 and R2 may be the same or different.

[0063] Examples of straight-chain alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. Examples of branched-chain alkyl groups having 1 to 6 carbon atoms, specifically those having 3 to 6 carbon atoms, include isopropyl, isobutyl, dibutyl, tributyl, isopentyl, dipentyl, tripentyl, isohexyl, dihexyl, and trihexyl. Examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, trimethylphenyl, tetramethylphenyl, 1-naphthyl, and 2-naphthyl. Examples of aralkyl groups include benzyl, phenylethyl, phenylpropyl, and methylbenzyl. Examples of alkylthio groups having 1 to 6 carbon atoms include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, dibutylthio, tributylthio, pentylthio, and hexylthio.

[0064] R1 and R2 may be the same or different, and are more preferably hydrogen atoms, amino groups or alkylthio groups with 1 to 6 carbon atoms.

[0065] R5 and R6 represent hydrogen atoms or radicals as shown in -(CH2)m-Si(OR)3-p(OH)p (R represents methyl or ethyl, m represents an integer from 1 to 18, and p represents an integer from 0 to 3). R5 and R6 may be the same or different.

[0066] At least one of R5 and R6 is a group represented by -(CH2)m-Si(OR)3-p(OH)p. Furthermore, in the group represented by -(CH2)m-Si(OR)3-p(OH)p, m is preferably an integer from 2 to 12, more preferably an integer from 3 to 10, and even more preferably an integer from 3 to 8.

[0067] X represents a group consisting of -phenyl, -NH- or -(CH2)n- (n represents an integer from 0 to 12). X is preferably a group consisting of -(CH2)n-, and more preferably n is an integer from 0 to 10, even more preferably an integer from 0 to 8, and most preferably an integer from 0 to 6.

[0068] The compound shown in chemical formula (IV) (triazole compound (IV)) comprises the above-mentioned triazole compound (I), the hydrolysate of the above-mentioned triazole compound (I), and the above-mentioned triazole compound (II). In this triazole compound (IV), compounds in which the p-number of the -(CH2)m-Si(OR)3-p(OH)p group of R5 and / or R6 is an integer from 1 to 3 are those generated by hydrolyzing a triazole compound (I) with p=0. These are all suitable as components of coupling agents. Furthermore, in the triazole compound (IV), compounds in which p is an integer from 1 to 3 can be, for example, those obtained by hydrolyzing a triazole compound (I) with p=0 and removing the volatile components.

[0069] When using the coupling agent of the present invention, the same surface treatment method as that used for conventional coupling agents can be employed. Examples of such surface treatment methods include (a) spraying an appropriate amount of coupling agent onto a substrate using a treatment solution diluted with an organic solvent; (b) spraying the same coupling agent onto a substrate using a treatment solution diluted with a water-organic solvent; (c) spraying the same coupling agent onto a substrate using a treatment solution diluted with water; (d) impregnating a substrate with the same coupling agent diluted with an organic solvent; (e) impregnating a substrate with the same coupling agent diluted with a water-organic solvent; and (f) impregnating a substrate with the same coupling agent diluted with water.

[0070] Examples of the above-mentioned organic solvents 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, dimethyl ether, ethylene glycol monomethyl ether (methyl ceroxythione), ethylene glycol monoethyl ether (ethyl ceroxythione), ethylene glycol monobutyl ether, and diethylene glycol monobutyl ether; and alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, tributanol, ethylene glycol, diethylene glycol, and propylene glycol.

[0071] As the substrate used in this invention, examples include substrates formed from metals, inorganic materials, resin materials, etc., in the form of granules, needles, fibers, fabrics, plates, foils, amorphous materials, etc.

[0072] Examples of the aforementioned metals include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof; plates, foils, or coatings made of such metals can be used as substrates. As specific examples of the aforementioned alloys, there are no particular limitations on copper alloys if 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, steel). Among these metals, copper and copper alloys are preferred.

[0073] Examples of the aforementioned inorganic materials include silicon, ceramics, or inorganic materials and glass used as fillers. Specific examples include silicon compounds such as silicon carbide, silicon dioxide, 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, and barium titanate, etc.) and glass are preferred.

[0074] Examples of the aforementioned resin materials include nylon, acrylate resin, epoxy resin, polybenzoxazole resin, polysiloxane resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate ester resin, polyphenylene ether resin, polyoxymethylene resin, polybutadiene resin, olefin resin, fluorinated resin, polyetherimide resin, polyetheretherketone resin, liquid crystal resin, etc., and combinations of these resins by mixing or modifying each other are also possible. Among these resin materials, polyphenylene ether resin, polyoxymethylene resin, liquid crystal resin, acrylate resin, epoxy resin, olefin resin, polybenzoxazole resin, polysiloxane resin, and polyimide resin are preferred.

[0075] By performing surface treatment on the substrate using a treatment solution containing the coupling agent of the present invention, the oleophilicity of the substrate surface can be improved, thereby enhancing its affinity (adhesion, adhesion) to resins and the like. Furthermore, to further enhance the effects of this treatment, the surface-treated substrate can be further subjected to heat treatment.

[0076] (Surface Treatment Liquid) <Surface Treatment Liquid Containing Triazole Compounds with Chemical Formula (IV)> The surface treatment liquid of the present invention contains triazole compounds (triazole compounds (IV)) with the aforementioned chemical formula (IV). In this triazole compound (IV), compounds in which the p-number of the -(CH2)m-Si(OR)3-p(OH)p group of R5 and / or R6 is an integer from 1 to 3 are generated by hydrolyzing a compound with p=0 in the surface treatment liquid. These are all suitable as components of the surface treatment liquid. Furthermore, compounds in triazole compound (IV) with p=1 to 3 can, for example, have their volatile components removed by a surface treatment liquid containing triazole compound (I) with p=0, thereby being extracted and used.

[0077] In the implementation of the present invention, it is preferable to use a compound with p=0 as a raw material when preparing the surface treatment liquid. When p=0, that is, when at least one of R5 and R6 is a group represented by -(CH2)m-Si(OR)3, it can be the same compound as the above-mentioned triazole compound (I), and preferably the same compound.

[0078] The surface treatment solution of the present invention is prepared by mixing a triazole compound (IV) with water. The water used for preparing the surface treatment solution is preferably pure water such as ion-exchanged water or distilled water. Furthermore, in order to promote the dissolution (aqueous solution preparation) of the triazole compound (IV) in the surface treatment solution of the present invention, a solubilizing agent is preferably used. Examples of solubilizing agents include acids, alkalis, and organic solvents. One such solubilizing agent may be used alone, or two or more may be used in combination. Moreover, regarding the preparation method of the surface treatment solution using a solubilizing agent and water, the triazole compound may be mixed with water and then the solubilizing agent may be added; alternatively, the triazole compound may be mixed with a mixture of water and the solubilizing agent; or the triazole compound may be mixed with the solubilizing agent and then water may be added.

[0079] Examples of the aforementioned acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, as well as organic acids such as formic acid, acetic acid, propionic acid, butyric acid, 2-ethylbutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, heptadecanic acid, oleic acid, stearic acid, glycolic acid, lactic acid, gluconic acid, glyceric acid, malonic acid, succinic acid, acetopropionic acid, benzoic acid, oxalic acid, tartaric acid, malic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, 5-sulfosalicylic acid, 4-hydroxybenzenesulfonic acid, 3-methyl-4-hydroxybenzenesulfonic acid, 4-aminobenzenesulfonic acid, camphorsulfonic acid, benzenedisulfonic acid, benzenetrisulfonic acid, aminosulfonic acid, and amino acids. One of these acids may be used alone, or two or more may be used in combination.

[0080] Examples of the above-mentioned bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptaylamine, 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, piperidine, and pyridine. One of these bases may be used alone, or two or more may be used in combination.

[0081] Examples of the above-mentioned organic solvents include methanol, ethanol, 1-propanol, 2-propanol, butanol, tributanol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerol, 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, diethylene glycol monomethyl ether, and diethylene glycol dimethyl ether. Ethers, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, acetone, tetrahydrofuran, dimethyl ether, acetonitrile, 2-pyrrolidone, methylamine, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, cyclobutane, dimethyl carbonate, ethyl carbonate, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolinone, etc. These organic solvents can be used alone or in combination of two or more.

[0082] 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.

[0083] <Hydrolysis of Triazole Compounds> The triazole compound (IV) of the present invention has a triazole ring in its molecule, so the triazole ring interacts with the surface of the above-mentioned substrate (metal, resin material, inorganic material) to form a chemical bond, thereby improving the adhesion between different materials.

[0084] The hydrolysis state of the triazole compound (IV) is shown in process (B). Process (B) illustrates the case where at least one of R5 and R6 of the triazole compound (IV) is a group represented by -(CH2)m-Si(OR)3-p(OH)p. In this process (B), the hydrolysis state of the alkoxysilyl group of the above-mentioned triazole compound (IV) is shown, that is, the trialkoxysilyl group gradually changes to a dialkoxyhydroxysilyl group, a dihydroxyalkoxysilyl group, and a trihydroxysilyl group.

[0085] [Chemical 12] Process (B)

[0086] It is generally known that substances containing alkoxysilyl groups in their molecules act as silane coupling agents. For example, taking the bonding of copper and resin materials as an example, the triazole compound used in this embodiment of the invention contains alkoxysilyl groups in its molecules. The triazole ring interacts with the resin and copper to form chemical bonds. The alkoxysilyl group (-Si-OR) is hydrolyzed to convert into a hydroxysilyl group (-Si-OH), which then forms a chemical bond with copper oxide dots present on the copper surface. Thus, by contacting the copper with the surface treatment liquid, a formation film from the triazole compound (IV) is formed on the surface of the copper through the bonds between the triazole ring or the hydroxysilyl group. Compared to the case where a resin layer is formed directly on the copper surface, the formation of a resin layer composed of resin material on the surface of this formation film improves the adhesion between the copper and the resin material.

[0087] In the embodiments of the present invention, the concentration of the triazole compound (IV) in the surface treatment solution is converted to the concentration of the trialkoxytriazole compound, preferably 0.0001~1.0000 mol / L, more preferably 0.0010~0.5000 mol / L, and even more preferably 0.0100~0.1000 mol / L.

[0088] However, the triazole compound (IV) having hydroxysilicone groups generated in the surface treatment solution undergoes gradual mutual reaction and dehydration condensation, with the hydroxysilicone groups forming siloxane bonds (Si-O-Si) (refer to process (B)), converting into a water-insoluble silane oligomer (a triazole silane compound having the group shown in chemical formula (e) in process (B)). Furthermore, the X in the group shown in chemical formula (e) is an integer representing the number of repeating units.

[0089] If the amount of silane oligomers generated in the surface treatment solution increases, insoluble components will precipitate out (making the treatment solution cloudy), adhering to the treatment tank or piping connected to the treatment tank, and sensors immersed in the treatment solution for detecting the temperature or level of the treatment solution, potentially hindering smooth surface treatment. To avoid this, when preparing the surface treatment solution, it is preferable to include the aforementioned organic solvent as a solubilizer for silane oligomers that are poorly soluble in water. Furthermore, in preparing the surface treatment solution, it is preferable to include the aforementioned solubilizer (acid, alkali, organic solvent) to promote the dissolution of triazole compounds. Since organic solvents also function as solubilizers for silane oligomers, the surface treatment solution of the present invention preferably contains at least one selected from the group consisting of acids, alkalis, and organic solvents as a solubilizer.

[0090] Similarly, in order to improve the stability of the surface treatment solution or the uniformity of the formed film, substances that generate halide ions such as chloride ions, bromide ions, and iodide ions, or metal ions such as copper ions, iron ions, and zinc ions can also be used.

[0091] Halogen ions exhibit the effect of uniformly forming a flat portion of the chemically formed film. 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, cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, etc. Halogen compounds may also be present as impurities in other components.

[0092] The content of halide ions in the surface treatment solution is not particularly limited, but is preferably 0.10 mol / L or less (especially 0 to 0.10 mol / L), more preferably 0.050 mol / L or less (especially 0 to 0.050 mol / L), even more preferably 0.020 mol / L or less (especially 0 to 0.020 mol / L), and most preferably 0.010 mol / L or less (especially 0 to 0.010 mol / L).

[0093] Copper ions form complexes with triazole compounds, which can improve the strength of the formed film or the adhesion strength between the metal and the resin. The valence of copper ions can be monovalent or divalent. Examples of substances that generate copper ions include metallic copper, copper sulfate (and its hydrates (especially pentahydrate)), copper formate (and its hydrates (especially tetrahydrate)), copper nitrate, copper chloride, cuprous chloride, copper acetate (and its hydrates (especially monohydrate)), copper hydroxide, copper oxide, copper sulfide, copper carbonate, copper bromide, cuprous bromide, copper phosphate, and copper benzoate. Furthermore, the copper ions in the surface treatment solution may also be copper ions dissolved from metallic copper or copper oxide contained in the copper circuit during the copper circuit treatment process using the surface treatment solution.

[0094] The content of copper ions in the surface treatment solution is not particularly limited, but is preferably 1.00 mol / L or less (especially 0 mol / L or more and 1.00 mol / L or less), more preferably 0.50 mol / L or less (especially 0 mol / L or more and 0.50 mol / L or less), even more preferably 0.10 mol / L or less (especially 0 mol / L or more and 0.10 mol / L or less), and particularly preferably 0.010 mol / L or less (especially 0 mol / L or more and 0.010 mol / L or less).

[0095] Furthermore, known coupling agents may also be used without impairing the effects of the present invention. Examples of known coupling agents include silane-based coupling agents (silane coupling agents) having thiol (mercapto) groups, vinyl groups, epoxy groups, (meth)acrylate groups, amino groups, chloropropyl groups, etc.

[0096] Examples of such silane coupling agents include, for example, mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and other vinylsilane compounds; styrylsilane compounds such as p-styryltrimethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; 3-epoxypropoxypropyltrimethoxysilane; 3-epoxypropoxypropylmethyldiethoxysilane; 3-epoxypropoxypropyltriethoxysilane, and other epoxysilane compounds; 3-propenoxypropyltrimethoxysilane, and other propenoxysilane compounds; 3-methylpropenoxypropylmethyldimethoxysilane; 3-Methylpropoxypropyltrimethoxysilane, 3-methpropoxypropylmethyldiethoxysilane, 3-methpropoxypropyltriethoxysilane, and other methpropoxysilanes; 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-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, and other aminosilane compounds. Urea silane compounds such as 3-ureapropyltriethoxysilane, chloropropyl silane compounds such as 3-chloropropyltrimethoxysilane, thiosilane compounds such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanate silane compounds such as 3-isocyanopropyltriethoxysilane. Other examples include aluminum-based coupling agents, titanium-based coupling agents, and zirconium-based coupling agents.

[0097] (Processing Method) There are no particular limitations on the method for bringing the surface treatment liquid of the present invention into contact with the substrate surface. Spraying, dipping, or coating can be used, similar to the method for the coupling agent described above. Regarding the contact time between the surface treatment liquid and the substrate (processing time), it is preferably set to 1 second to 10 minutes, more preferably 5 seconds to 3 minutes. If the processing time is less than 1 second, the thickness of the formed film on the substrate surface becomes thinner, making it difficult to obtain sufficient adhesion between materials of different materials. On the other hand, even if it is longer than 10 minutes, since the thickness of the formed film does not differ significantly, from a production point of view, it is preferable to process within 10 minutes. Furthermore, regarding the temperature of the treatment liquid when bringing the surface treatment liquid into contact with the substrate surface, it is preferably 5 to 50°C, but can be appropriately set in relation to the aforementioned processing time.

[0098] After the surface treatment liquid of the present invention comes into contact with the substrate, it can be dried after washing with water, or it can be dried without washing with water. The drying temperature is preferably set at room temperature to 150°C. Furthermore, the water used for washing is preferably pure water such as ion-exchanged water or distilled water. There are no particular limitations on the method or time of washing, and it can be carried out for an appropriate time by means of spraying or immersion.

[0099] Furthermore, the thickness of the formed film is preferably 0.5~1,000 nm, more preferably 1~200 nm, and even more preferably 1~100 nm. If the film thickness is 0.5 nm or more, the adhesion between materials is sufficiently improved; if it is less than 1,000 nm, the chemical resistance of the formed film can be maintained.

[0100] In this invention, the dried formed film can also be treated with plasma, laser, ion beam, ozone, heating, humidification, etc., to modify the surface of the formed film. Alternatively, mechanical grinding or drilling methods such as plasma, laser, ion beam, pumice brush, etc., can be used to clean the metal surface for the purpose of removing resin and ion residues.

[0101] Before the surface treatment liquid of the present invention comes into contact with the surface of copper or copper alloy (hereinafter both, or copper alone), the surface of the copper may be subjected to at least one pretreatment selected from pickling, alkali treatment, roughening treatment, heat resistance treatment, rust prevention treatment or chemical formation treatment.

[0102] The above-mentioned pickling treatment refers to the process performed to remove grease and grease adhering to the copper surface and to remove oxide film from the copper surface. For this pickling treatment, 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 can be used.

[0103] The above-mentioned alkaline treatment refers to the treatment performed to remove grease adhering to the copper surface and to remove residues from previous steps (such as dry thin-film resists used in copper circuit formation). For this alkaline treatment, solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amines such as ammonia, ethanolamine, monopropanolamine, and tetramethylammonium hydroxide, or aqueous solutions or organic solvent solutions of 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.

[0104] The above-mentioned roughening treatment refers to the process performed to improve the adhesion between copper and resin caused by the anchoring effect. This roughening treatment can be achieved by giving the copper surface an uneven shape, thereby improving the adhesion between the copper and resin materials. Methods such as micro-etching, electroplating, electroless electroplating, oxidation (black oxide, brown oxide), oxidation-reduction, brush polishing, and spray washing can be used for this roughening treatment.

[0105] In the micro-etching method, various etchants such as organic acid-cuprous ion system, sulfuric acid-hydrogen peroxide system, persulfate system, copper chloride system, or ferric chloride system can be used. In the electroplating method, the surface of copper is formed by the precipitation of fine copper particles.

[0106] In the above heat-resistant treatment, a film selected from nickel, nickel-phosphorus, zinc, zinc-nickel, copper-zinc, copper-nickel, copper-nickel-cobalt, or nickel-cobalt is formed on the copper surface. The formation of this film can be carried out by a known electroplating method, but is not limited to electroplating; other means such as vapor deposition can also be used.

[0107] The above-mentioned rust prevention treatment refers to the treatment carried out to prevent oxidation and corrosion of the copper surface. It can be carried out by forming a zinc or zinc alloy coating film or an electrolytic chromate coating film on the copper surface. Alternatively, a treatment solution containing an organic compound such as a benzotriazole rust inhibitor can be brought into contact with the copper surface.

[0108] In the above formation process, a method for forming a non-dynamic film of tin or a method for forming a non-dynamic film of copper oxide can be used.

[0109] Before and / or after the surface treatment solution of the present invention is brought into contact with the copper surface, an aqueous solution containing copper ions may also be brought into contact with the copper surface. This aqueous solution containing copper ions has the function of improving the film-forming properties of the formed film on the copper surface, or making the thickness of the formed film on the copper surface uniform. The valence of the copper ions is not particularly limited, and can be monovalent or divalent copper ions. As the copper ion source for the aqueous solution containing copper ions, there is no particular limitation if it is a copper salt that is soluble in water, such as copper sulfate, copper nitrate, copper chloride, copper formate, copper acetate, etc. Ammonia or hydrochloric acid may also be added to make the copper salt soluble in water.

[0110] Before and / or after the surface treatment solution of the present invention is brought into contact with the copper surface, an acidic aqueous solution or an alkaline aqueous solution may also be brought into contact with the copper surface. This acidic or alkaline aqueous solution, like the aqueous solution containing copper ions, also has the function of making the thickness of the deposited film formed on the copper surface uniform. There are no particular limitations on the acidic or alkaline aqueous solution. Examples of acidic aqueous solutions include aqueous solutions containing inorganic acids such as sulfuric acid, nitric acid, and hydrochloric acid, or aqueous solutions containing organic acids such as formic acid, acetic acid, lactic acid, glycolic acid, and amino acids. Examples of alkaline aqueous solutions include, for example, aqueous solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amines such as ammonia, ethanolamine, monopropanolamine, and tetramethylammonium hydroxide, as well as aqueous solutions containing 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.

[0111] Before the surface treatment liquid of the present invention comes into contact with the copper surface, an aqueous solution containing a known coupling agent may also come into contact with the copper surface.

[0112] After the surface treatment liquid of the present invention is brought into contact with the copper surface, an aqueous solution containing a known coupling agent may also be brought into contact with the copper surface.

[0113] After the surface treatment liquid of the present invention is brought into contact with the copper surface, a treatment liquid containing a known organic compound rust inhibitor, such as a benzotriazole-based rust inhibitor, may also be brought into contact with it.

[0114] 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 chemically formed film can be formed on the surface of the substrate, thereby improving the adhesion between the substrate and other materials.

[0115] In this invention, the surface treatment liquid of this invention can be used to bond two materials selected from the group consisting of metals, inorganic materials and resin materials. By bonding the two materials through a layer of chemically formed film with the surface treatment liquid of this invention, the affinity between them can be improved, so even materials of different materials can be bonded more firmly.

[0116] (Bonding Method) The bonding method for the two materials can be carried out using known methods. For example, the surface treatment liquid of the present invention is brought into contact with the surface of a substrate made of metal, inorganic material, or resin material to form a formed film. Other substrates are then bonded to a portion or all of the formed formed film by means of coating, pressing, mixing, or using an adhesive, bonding sheet (film), or a combination of these means. Alternatively, the surface treatment liquid of the present invention is brought into contact with the surfaces of two substrates selected from metal, inorganic material, and resin material, forming formed films on the surfaces of each substrate. The two substrates are then bonded by means of coating, pressing, mixing, or using an adhesive, bonding sheet (film), or a combination of these means.

[0117] By using the surface treatment liquid of the present invention, two materials, especially two materials of different materials, can be bonded together as described above, so it is suitable for use in various electrical and electronic components or electronic devices such as semiconductor wafers and printed wiring boards.

[0118] Furthermore, in this invention, the surface treatment liquid of this invention is suitable for use on metals, especially substrates formed of copper or copper alloys. For example, it is suitable for surface treatment of copper or copper alloys for the purpose of improving the adhesion (tightness) between copper circuits (copper wiring layers) and semi-cured or cured prepregs or solder resists, semi-cured or cured dry film resists (insulating resin layers). In printed wiring boards that contact the copper wiring layers and have insulating resin layers, the adhesion between the copper wiring layers and the insulating resin layers can be improved.

[0119] In the example of using a semiconductor wafer, a surface treatment is suitable for improving the adhesion (close bonding) between the semiconductor circuit formed on the semiconductor wafer and the protective film (e.g., an insulating protective film such as a photosensitive positive coating, a photosensitive negative coating, a non-photosensitive buffer coating, or an impact protective film). Furthermore, a surface treatment is suitable for improving the adhesion (close bonding) between the copper circuit redistribution layer and the insulating material in a packaging substrate (WL-CSP, FO-WLP, PLP) or a 2.5D or 3D interposer substrate on which a redistribution layer is formed on a semiconductor wafer. Examples of the aforementioned protective film or insulating material include, for instance, polyimide resin, polybenzoxazole resin, and polysiloxane resin.

[0120] The above-described printed wiring board can be manufactured by contacting the surface treatment liquid of the present invention with the surface of the copper wiring, followed by washing and drying, to form an insulating resin layer on the surface of the copper wiring. Regarding this contact method, as described above, immersing the copper wiring in the surface treatment liquid or spraying the copper wiring with the treatment liquid is simple and reliable, and therefore preferred. Furthermore, the above-described washing method is not particularly limited; immersing the copper wiring in washing water or spraying the surface of the copper wiring with washing water is simple and reliable, and therefore preferred. When forming the above-described insulating resin layer, known methods can be used, such as a method of attaching a semi-cured resin material, or a method of coating a liquid resin material containing a solvent. Next, through-holes are formed to allow the upper and lower wirings to conduct. By repeating this process, a multilayer printed wiring board can be manufactured.

[0121] In the above-described method for forming a circuit of a printed wiring board, the semi-additive process using the surface treatment liquid of the present invention is illustrated below. The method comprises the following steps: (a) preparing an insulating substrate having a first conductive layer on a first surface and a second surface opposite to the first surface, and on the inner wall of the through-holes and vias, on an insulating substrate or an insulating substrate having through-holes and vias; (b) forming a photocrosslinked resin layer and a masking layer on the first surface and the second surface, thereby covering the first conductive layer on the first surface and the second surface and on the inner wall of the through-holes and vias with the photocrosslinked resin layer and the masking layer; (c) patterning the photocrosslinked resin layer on the first surface and the second surface and around the through-holes and vias; (d) removing the masking layer on the first surface and the second surface and around the through-holes and vias; (e) developing and removing the uncured photocrosslinked resin layer on the first surface and the second surface and around the through-holes and vias using a photocrosslinked resin layer removal liquid, thereby exposing the first conductive layer on the first surface and the first conductive layer on the second surface and around the through-holes and vias. (f) A step of forming a second conductive layer on the first conductive layer exposed on the first surface, the second surface, and the inner walls of the through holes and vias by electroplating; (g) A step of removing the hardened photocrosslinking resin layer on the first surface, the second surface, and around the through holes and vias to expose the first conductive layer and the second conductive layer on the first surface, the second surface, and the inner walls of the through holes and vias; (h) A step of removing the exposed first conductive layer by flash etching; (i) A step of forming a third conductive layer on the first and second conductive layers on the first surface, the second surface, and the inner walls of the through holes and vias by electroless electroplating and electroplating; (j) A step of depositing an insulating resin layer on the first surface, the second surface, and the inner walls of the through holes and vias; In a method for manufacturing at least one circuit board, the surface treatment liquid of the present invention is brought into contact with at least one of the following: the first, second, and third conductive layers, the insulating resin substrate, the photocrosslinking resin layer, the insulating resin layer, or the anti-etching layer used on the first and second surfaces and the inner walls of the through holes; to manufacture a printed wiring board.

[0122] Furthermore, in the above-described method for forming a circuit of a printed wiring board, the method of removing surface treatment liquid of the present invention is illustrated below. The method comprises the following steps: (a) preparing an insulating substrate having a first conductive layer on a first surface and a second surface opposite to the first surface, and on the inner wall of the through-holes and vias, on an insulating substrate or an insulating substrate having through-holes and vias; (b) forming a photocrosslinked resin layer and a masking layer on the first surface and the second surface, thereby covering the first conductive layer on the first surface and the second surface and on the inner wall of the through-holes and vias with the photocrosslinked resin layer and the masking layer; (c) patterning the photocrosslinked resin layer on the first surface and the second surface and around the through-holes and vias; (d) removing the masking layer on the first surface and the second surface and around the through-holes and vias; (e) developing and removing the uncured photocrosslinked resin layer on the first surface and the second surface and around the through-holes and vias using a photocrosslinked resin layer removal liquid, thereby exposing the first conductive layer on the first surface and the first conductive layer on the second surface and around the through-holes and vias. (f) Etching away the first conductive layer exposed on the first surface, the second surface, and the inner walls of the through holes and vias; (g) Removing the hardened photocrosslinking resin layer on the first surface, the second surface, and around the through holes and vias, exposing the first and second conductive layers on the first surface, the second surface, and the inner walls of the through holes and vias; (h) Forming a third conductive layer on the first and second conductive layers on the first surface, the second surface, and the inner walls of the through holes and vias by electroless electroplating and electroplating treatment; (i) Depositing an insulating resin layer on the first surface, the second surface, and the inner walls of the through holes and vias; In a method for manufacturing at least one circuit board, the surface treatment liquid of the present invention is brought into contact with at least one of the following: the first, second, and third conductive layers, the insulating resin substrate, the photocrosslinking resin layer, the insulating resin layer, or the anti-etching layer used on the first and second surfaces and the inner walls of the through holes; to manufacture a printed wiring board.

[0123] The copper wiring or conductive layer mentioned above can be made by any of the following methods: electroless plating, electroplating, vapor deposition, sputtering, or inlay. It can also include internal through holes, through holes, and connecting terminals.

[0124] Furthermore, the term "copper" in this 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) and films (electroless copper film, electroplated copper film) used in electronic devices, decorative items, building materials, etc., formed by methods such as vapor deposition, sputtering, and inlay, and used in various applications and forms such as thin films, particles, needles, fibers, wires, rods, tubes, and plates. Moreover, in the case of copper wiring for transmitting high-frequency electrical signals in recent years, a smooth surface with an average roughness of 0.1 μm or less is preferred. For the copper surface, plating with nickel, zinc, chromium, tin, etc., can also be performed as a pretreatment.

[0125] Furthermore, for example, in the application example of lead frames during wiring bonding installation, the surface treatment liquid system of the present invention is suitable for lead frame surface treatment for the purpose of improving the adhesion (tight adhesion) between the metal surface of the lead frame during the lead frame manufacturing step, or the metal surface of the frame after the semiconductor wafer is mounted (before and after the die bonding and pre-baking steps), the metal surface of the frame after wiring bonding installation, and the metal surface of the frame up to the resin sealing step (before and after the resin molding and baking steps) and the adhesive used during semiconductor wafer mounting.

[0126] Furthermore, in the example of application in lead frames during flip-chip bonding, the surface treatment liquid system of the present invention is suitable for improving the adhesion (tight adhesion) between the metal surface of the lead frame during the lead frame manufacturing process, or the metal surface of the lead frame after temporary bonding materials (soldering, Au plating, Sn plating, etc.), the metal surface of the lead frame after semiconductor wafer mounting (alignment, wafer mounting, baking steps), the metal surface of the lead frame after formal hardening (before and after steps such as reflow heating, hot pressing, ultrasonic, plasma, etc.), the metal surface of the lead frame during the resin sealing process, and the adhesive used during semiconductor wafer mounting.

[0127] Furthermore, for example, in applications that improve the use of micro-wiring substrates for integrated technology of close-proximity configuration of semiconductor wafers, the surface treatment liquid system of the present invention is suitable for surface treatment of copper wiring layers for the purpose of improving adhesion (close bonding) between copper wiring layers and insulating materials in 2.1D organic substrates or glass substrates, component embedded substrates (EPS substrates) in which semiconductors are embedded in the substrate, and coreless substrates. Furthermore, for example, when embedded pattern wiring is used and laser vias are processed and via-filling plating is performed on the upper and lower layers, or when the upper and lower layers use copper pillars formed by plating for conduction and the insulating layer is a MIS using molding resin (ETS substrate), the metal surface treatment liquid system of the present invention is suitable for surface treatment of copper wiring layers for the purpose of improving adhesion (close bonding) between copper wiring layers and insulating materials.

[0128] Furthermore, the carrier copper foil treated by the surface treatment liquid of the present invention is an extremely thin electroplated copper foil used in a printed wiring board that includes the step of forming a circuit by any of the methods of semi-addition, subtraction, partial addition, or modified semi-addition. It comprises a copper foil carrier, a release layer deposited on the copper foil carrier, and an extremely thin copper layer deposited on the release layer. For the copper surface, at least one pretreatment selected from the group consisting of pickling, roughening, heat treatment, rust prevention, or chemical formation can also be performed.

[0129] (Insulating Composition) An insulating composition can be made by incorporating the coupling agent of the present invention into a resin material or an inorganic material. Alternatively, an insulating composition can also be obtained by dissolving a triazole compound (IV) in an organic solvent or the like and mixing it with a resin material or an inorganic material.

[0130] The content of triazole compound (IV) in the insulating composition is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight. If the content of triazole compound (IV) in the insulating composition is 0.001% by weight or more, the adhesion-enhancing effect can be sufficiently obtained. When this concentration exceeds 10% by weight, the adhesion-enhancing effect is almost saturated. Therefore, from an economic point of view, the content of triazole compound (IV) is preferably set to 10% by weight or less. The above-mentioned insulating composition can be prepared by known methods. For example, the triazole compound (IV) can be dissolved in an organic solvent and mixed into a solid or liquid resin material to prepare an insulating composition. Alternatively, the triazole compound (IV) can be directly added to or mixed into a liquid resin material to prepare an insulating composition.

[0131] The insulating composition of the present invention is made into an insulating material with high bonding strength, and is therefore suitable for use in various electrical and electronic components, or electronic devices such as printed wiring boards.

[0132] However, Japanese Patent Application Publication No. 2009-19266 discloses an invention concerning a method for forming a silane coupling agent film, characterized by comprising: a step of coating a metal surface with a liquid containing a silane coupling agent; a step of drying the metal surface coated with the liquid at a temperature of 25-150°C for no more than 5 minutes; and a step of washing the dried metal surface with water. Furthermore, a pre-surface treatment can also be performed on the aforementioned metal surface by forming an adhesive metal layer such as tin using an immersion plating solution. The surface treatment solution of the present invention can be used as a liquid containing the aforementioned silane coupling agent. Furthermore, the matters described in this patent publication are incorporated herein by reference. [Examples]

[0133] The present invention will be specifically described below by way of examples (synthesis experiments, evaluation experiments), but the present invention is not limited thereto. Furthermore, in the following chemical formulas, OEt represents ethoxy.

[0134] The triazole compounds and haloalkylsilane compounds used in the synthesis experiments are as follows. [Triazole compounds] ‧The triazole compound (3,3'-bis(5-amino-1,2,4-triazole)) shown in formula (11) was synthesized according to the method described in "Chem. Eur. J.", Vol. 18, p. 16742 (2012). ‧The triazole compound (3,3'-methylenebis(5-amino-1,2,4-triazole)) shown in formula (12) was synthesized according to the method described in "Russ. J. Applied. Chem.", Vol. 82, p. 276 (2009). ‧The triazole compound (3,3'-tetramethylenebis(5-amino-1,2,4-triazole)) shown in formula (13) was synthesized according to the method described in U.S. Patent No. 2744116. • The triazole compound (3,3'-bis(5-methyl-1,2,4-triazole)) shown in formula (14) was synthesized according to the method described in Indian J. Chem., Vol. 44B, p. 568 (2005).

[0135] [Chemistry 13]

[0136] [Halogenated Alkyl Silicate Compounds] ‧3-Chloropropyltriethoxysilane: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0137] The triazole compound used in Comparative Example 1 (evaluation test) is as follows. [Triazole compound] ‧The triazole compound (3-amino-5-methyl-1,2,4-triazole) shown in formula (21) was synthesized according to the method described in U.S. Patent No. 4,734,413. ‧The triazole compound (3-amino-5-methyl-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole) shown in formula (22) was synthesized according to the method described in International Patent Publication No. 2018 / 186476.

[0138] [Chemical 14]

[0139] <Synthesis of Triazole Compound (I)> The triazole compounds of Examples 1 to 5 below were synthesized.

[0140] [Example 1] <Synthesis of a mixture of 1-[3-(triethoxysilyl)propyl]-3,3'-bis(5-amino-1,2,4-triazole) and 2-[3-(triethoxysilyl)propyl]-3,3'-bis(5-amino-1,2,4-triazole)> Synthesize the compound shown in formula (1) (a mixture of 1-[3-(triethoxysilyl)propyl]-3,3'-bis(5-amino-1,2,4-triazole) and 2-[3-(triethoxysilyl)propyl]-3,3'-bis(5-amino-1,2,4-triazole)). A suspension containing 7.80 g (46.9 mmol) of 3,3'-bis(5-amino-1,2,4-triazole) and 200 mL of N,N-dimethylacetamide was heated to 80 °C, and 16.20 g (47.6 mmol) of 20% sodium ethoxyethanol solution was added. The mixture was then heated to 100 °C and stirred for 1 hour. Next, the mixture was cooled to 70 °C, and 11.40 g (47.3 mmol) of 3-chloropropyltriethoxysilane was added and stirred for 1 hour. The mixture was then heated to 100 °C and stirred for 16.5 hours. The reaction mixture was cooled to 60 °C, and insoluble matter was filtered off. The filtrate was then distilled under reduced pressure to give 15.81 g (46.9 mmol, yield 91.0%) of a brown maltose precipitate.

[0141] The 1H-NMR spectral data of the obtained brown maltose are as follows. 1H-NMR (DMSO-d6) δ: 0.55 (m, 2H), 1.14 (m, 9H), 1.75 (m, 2H), 3.34 (m, 2H), 3.73 (m, 6H), 5.23 (s, 2H), 6.41 (s, 2H). Based on this 1H-NMR spectral data, the obtained brown maltose is identified as a triazole compound with the title shown in formula (1).

[0142] [Chemistry 15]

[0143] [Example 2] <Synthesis of a mixture of 1-[3-(triethoxysilyl)propyl]-3,3'-methylenebis(5-amino-1,2,4-triazole) and 2-[3-(triethoxysilyl)propyl]-3,3'-methylenebis(5-amino-1,2,4-triazole)> Synthesize the compound shown in formula (2) below (a mixture of 1-[3-(triethoxysilyl)propyl]-3,3'-methylenebis(5-amino-1,2,4-triazole) and 2-[3-(triethoxysilyl)propyl]-3,3'-methylenebis(5-amino-1,2,4-triazole)). A suspension containing 6.08 g (33.8 mmol) of 3,3'-methylenebis(5-amino-1,2,4-triazole) and 150 mL of N,N-dimethylacetamide was heated to 80 °C. 11.72 g (34.4 mmol) of 20% sodium ethoxyethanol solution was added, and the mixture was stirred for 2 hours. Then, 8.30 g (34.5 mmol) of 3-chloropropyltriethoxysilane was added, and the mixture was stirred for 30 minutes. The mixture was then stirred at 100 °C for 20 hours. After cooling the reaction mixture to 70 °C, insoluble matter was filtered off, and the filtrate was distilled off under reduced pressure to give 10.50 g (27.3 mmol, yield 80.8%) of a light brown solid.

[0144] The 1H-NMR spectral data of the obtained light brown solid are as follows. 1H-NMR (DMSO-d6) δ: 0.57 (m, 2H), 1.15 (m, 9H), 1.53 (m, 2H), 2.94 (s, 2H), 3.45 (m, 2H), 3.73 (m, 6H), 5.04 (s, 2H), 5.98 (s, 2H). Based on this 1H-NMR spectral data, the obtained light brown solid system is identified as the triazole compound with the title shown in chemical formula (2).

[0145] [Chemical 16]

[0146] [Example 3] <Synthesis of a mixture of 1-[3-(triethoxysilyl)propyl]-3,3'-tetramethylenebis(5-amino-1,2,4-triazole) and 2-[3-(triethoxysilyl)propyl]-3,3'-tetramethylenebis(5-amino-1,2,4-triazole)> Synthesize the compound shown in formula (3) below (a mixture of 1-[3-(triethoxysilyl)propyl]-3,3'-tetramethylenebis(5-amino-1,2,4-triazole) and 2-[3-(triethoxysilyl)propyl]-3,3'-tetramethylenebis(5-amino-1,2,4-triazole)). A suspension containing 8.20 g (36.9 mmol) of 3,3'-tetramethylenebis(5-amino-1,2,4-triazole) and 200 mL of N,N-dimethylacetamide was heated to 80 °C, and 12.70 g (37.3 mmol) of 20% sodium ethoxyethanol solution was added. The mixture was then heated to 100 °C and stirred for 1 hour. Next, the mixture was cooled to 70 °C, and 9.04 g (37.5 mmol) of 3-chloropropyltriethoxysilane was added and stirred for 1 hour. The mixture was then heated to 100 °C and stirred for 16 hours. The reaction mixture was cooled to 60 °C, and insoluble matter was filtered off. The filtrate was then distilled under reduced pressure to give 13.8 g (32.3 mmol, yield 87.7%) of a light brown maltose precipitate.

[0147] The 1H-NMR spectral data of the obtained light brown maltose are as follows. 1H-NMR (DMSO-d6) δ: 0.50 (m, 2H), 1.13 (t, 9H), 1.61 (m, 4H), 2.09 (m, 2H), 2.42 (m, 4H), 3.34 (m, 2H), 3.73 (m, 6H), 5.06 (s, 2H), 5.96 (s, 2H). Based on this 1H-NMR spectral data, the obtained light brown maltose is identified as the triazole compound with the title shown in formula (3).

[0148] [Chemistry 17]

[0149] [Example 4] <Synthesis of a mixture of 3,3'-bis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole} and 3,3'-bis{2-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole} and 1-[3-(triethoxysilyl)propyl]-2'-[3-(triethoxysilyl)propyl]-3,3'-bis(5-amino-1,2,4-triazole)> The compound shown in formula (4) (a mixture of 3,3'-bis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole} and 3,3'-bis{2-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole} and 1-[3-(triethoxysilyl)propyl]-2'-[3-(triethoxysilyl)propyl]-3,3'-bis(5-amino-1,2,4-triazole)) was synthesized by adding 1.50 g (18.0 mmol) of 48% sodium hydroxide aqueous solution to a suspension containing 1.50 g (9.0 mmol) of 3,3'-bis(5-amino-1,2,4-triazole) and 5.60 g of water, and stirring at room temperature for 30 minutes. Then, after removing water by vacuum distillation, 5.6 g of ethanol was added, and stirring at room temperature for 1 hour. The solid was then filtered, washed with ethanol, and dried to obtain 2.1 g of white powder. 30 g of dimethyl sulfoxide was added to the 2.1 g of white powder, and the mixture was heated to 70 °C. 4.80 g (20.0 mmol) of 3-chloropropyltriethoxysilane was added, and the mixture was stirred for 1 hour, followed by stirring at 100 °C for 16 hours. The reaction mixture was cooled to room temperature, and insoluble matter was filtered off. The filtrate was then distilled under reduced pressure, and 30 g of isopropyl acetate was added. The mixture was stirred at room temperature for 1 hour. The solid was then filtered, washed with isopropyl acetate, and dried to obtain 4.67 g (8.1 mmol, yield 90.0%) of yellowish-brown powder.

[0150] The 1H-NMR spectral data of the obtained yellowish-brown powder are as follows. 1H-NMR (DMSO-d6) δ: 0.54 (m, 4H), 1.11 (m, 18H), 1.74 (m, 4H), 3.69 (m, 12H), 3.93 (m, 4H), 5.22 (s, 2H), 6.44 (s, 2H). Based on this 1H-NMR spectral data, the obtained yellowish-brown powder system is identified as the triazole compound with the title shown in chemical formula (4).

[0151] [Chemical 18]

[0152] [Example 5] <Synthesis of a mixture of 1-[3-(triethoxysilyl)propyl]-3,3'-bis(5-methyl-1,2,4-triazole) and 2-[3-(triethoxysilyl)propyl]-3,3'-bis(5-methyl-1,2,4-triazole)> Synthesize the compound shown in formula (5) below (a mixture of 1-[3-(triethoxysilyl)propyl]-3,3'-bis(5-methyl-1,2,4-triazole) and 2-[3-(triethoxysilyl)propyl]-3,3'-bis(5-methyl-1,2,4-triazole)). A suspension containing 3.30 g (20.0 mmol) of 3,3'-bis(5-methyl-1,2,4-triazole) and 30 g of dimethyl sulfoxide was heated to 70 °C, and 6.80 g (20.0 mmol) of 20% sodium ethoxide ethanol solution was added, followed by stirring for 1 hour. Then, 4.80 g (20.0 mmol) of 3-chloropropyltriethoxysilane was added and stirred for 30 minutes. The temperature was then raised to 100 °C and stirred for 19 hours. After cooling the reaction solution to room temperature, insoluble matter was filtered off, and the filtrate was subjected to vacuum distillation. 30 g of isopropyl acetate was added, and the mixture was stirred at room temperature for 1 hour. The solid was then filtered off, washed with isopropyl acetate, and dried to obtain 3.39 g (9.2 mmol, yield 46.0%) of a light brown powder.

[0153] The 1H-NMR spectral data of the obtained light brown powder are as follows. 1H-NMR (DMSO-d6) δ: 0.55 (m, 2H), 1.14 (t, 9H), 1.75 (m, 2H), 2.30 (s, 6H), 3.43 (q, 6H), 3.51 (m, 2H). Based on this 1H-NMR spectral data, the obtained light brown powder system is identified as the triazole compound with the title shown in chemical formula (5).

[0154] [Chemical 19]

[0155] <Adhesion Test 1> The adhesion of the surface treatment liquids prepared in Examples 6 to 9 and Comparative Examples 2 to 3 was evaluated as follows.

[0156] [Adhesion Evaluation Test (i)] (1) The metal used is electroplated copper foil (thickness: 35μm). (2) The surface treatment of the metal is carried out according to the following steps a~b, the copper foil is treated as described above. a. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. The surface treatment solution is brushed and dried / 1 minute (100°C) (3) Metal and resin bonding On the S-side of the treated copper foil, a glass cloth impregnated with epoxy resin prepreg (MEGTRON7 (manufactured by Panasonic)) is laminated and bonded to the copper foil and the prepreg to produce a copper foil laminate. (4) Adhesion evaluation For this copper foil laminate, after one reflow heating (wave peak temperature 260°C, atmospheric), a 10mm wide test piece is made according to "JIS C6481 (1996)" to determine the tensile strength (peel strength (kN / m)) of the copper foil.

[0157] [Example 6] 1g of the compound shown in formula (1) above, which is a coupling agent component, was mixed with 99g of a 4:96 mixture of 25% ammonia and methanol (by weight), and stirred at room temperature for 1 hour to prepare a surface treatment solution.

[0158] [Examples 7~9] Except for replacing the compound shown in Formula (1) above, using the compound shown in Formula (2), the compound shown in Formula (3) above, or the compound shown in Formula (11) above, the surface treatment liquid was prepared in the same manner as in Example 6.

[0159] [Comparative Example 1] For copper foil that only undergoes the adhesion evaluation test (i) step (2)a, the adhesion evaluation test (i) is performed.

[0160] [Comparative Examples 2-3] Except for replacing the compound shown in Formula (1) above, the surface treatment liquid was prepared in the same manner as in Example 6 using the compound shown in Formula (21) above and the compound shown in Formula (22) above.

[0161] Various adhesion evaluation tests (i) were conducted on the surface treatment liquid prepared above. The test results are shown in Table 1.

[0162] [Table 1] Coupling agent Peel strength (kN / m) Example 6 Triazole compound (1) 0.40 7 Triazole compound (2) 0.33 8 Triazole compounds (3) 0.28 9 Triazole compounds (11) 0.13 Comparative example 1 none 0.01 2 Triazole compounds (21) 0.04 3 Triazole compounds (22) 0.03

[0163] As can be seen from the results in Table 1, the surface treatment liquid of the present invention (the surface treatment liquid of Examples 6 to 9) has a higher peel strength than Comparative Examples 1 to 3, and the adhesion between the metal and the resin is superior.

[0164] <Adhesion Test 2> The adhesion of the surface treatment liquids prepared in Examples 10-11 and Comparative Examples 5-6 was evaluated as follows.

[0165] [Example 10] 1g of the compound shown in formula (1) above, which is a coupling agent, was added to 99g of a 1:9 mixture of 10% acetic acid water and methanol (by weight), and stirred at room temperature for 1 hour to prepare a surface treatment solution.

[0166] [Example 11] Except for replacing the compound shown in formula (1) above with the compound shown in formula (11) above, the surface treatment liquid was prepared in the same manner as in Example 10.

[0167] [Comparative Example 4] For copper foil that only underwent the adhesion evaluation test (i) step (2)a, the adhesion evaluation test (i) was performed. Also, Comparative Example 4 is the same as Comparative Example 1.

[0168] [Comparative Examples 5-6] Except for replacing the compound shown in Formula (1) above, the surface treatment liquid was prepared in the same manner as in Example 10, using the compound shown in Formula (21) above and the compound shown in Formula (22) above.

[0169] Various adhesion evaluation tests (i) were conducted on the surface treatment liquid prepared above. The test results are shown in Table 2.

[0170] [Table 2] Coupling agent Peel strength (kN / m) Example 10 Triazole compound (1) 0.35 11 Triazole compounds (11) 0.20 Comparative example 4 none 0.01 5 Triazole compounds (21) 0.06 6 Triazole compounds (22) 0.03

[0171] As can be seen from the results in Table 2, even when a mixture of acetic acid and methanol is used as a solvent, the surface treatment solution of the present invention (the surface treatment solution of Examples 10-11) has a higher peel strength than Comparative Examples 4-6.

[0172] <Adhesion Test 3> The following adhesion evaluation test was conducted on the surface treatment liquid prepared in Example 12 and Comparative Example 7.

[0173] [Adhesion Evaluation Test (ii)] (1) The metal used is electroplated copper foil (thickness: 35μm). (2) The surface treatment of the metal is carried out according to the following steps a~b, the copper foil is treated as described above. a. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. The surface treatment solution is brushed and dried / 1 minute (100°C) (3) The metal and resin are bonded to the S surface of the treated copper foil, and a copper foil laminate is made by laminating and bonding the laminate with a resin for adding wiring boards (GX-T31 (manufactured by Ajinomoto Fine-Techno)). (4) Adhesion evaluation For this copper foil laminate, after one reflow heating (wave peak temperature 250°C, atmospheric), a 10mm wide test piece is made according to "JIS C6481 (1996)" and the peel strength (peel strength (kN / m)) of the copper foil is measured.

[0174] [Example 12] 1g of the compound shown in formula (1) above, which is a coupling agent component, was added to 99g of a 9:90 mixture of 11% acetic acid water and methanol (by weight), and stirred at room temperature for 1 hour to prepare a surface treatment solution.

[0175] [Comparative Example 7] For copper foil that only undergoes the adhesion evaluation test (ii) step (2)a, the adhesion evaluation test (ii) is performed.

[0176] Various adhesion evaluation tests (ii) were conducted on the surface treatment liquid prepared above. The test results are shown in Table 3.

[0177] [Table 3] Coupling agent Peel strength (kN / m) Example 12 Triazole compound (1) 1.05 Comparative example 7 none 0.54

[0178] As can be seen from the results in Table 3, the surface treatment liquid of the present invention (the surface treatment liquid of Example 12) has a higher peel strength than that of Comparative Example 7 and superior adhesion between metal and resin.

[0179] The present invention has been described above with reference to detailed and specific embodiments; however, it will be understood by those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the invention. This application is incorporated herein by reference to Japanese Patent Application No. 2022-054330, filed March 29, 2022. (Industrial Applicability)

[0180] The triazole compound of the present invention can exert the metal rust-preventive function characteristic of triazole compounds, and can also be used as a coupling agent that adds the function of curing epoxy resin or urethane resin. Therefore, it is expected to be used in composite materials such as printed wiring boards manufactured by combining multiple different materials. Furthermore, according to the present invention, since the adhesion (tightness) of metal, inorganic materials and resin materials can be improved, it is not necessary to roughen the surface of the substrate and can maintain a smooth state. Therefore, the present invention makes a significant contribution to the realization of miniaturization, thinning, high frequency, and high density of multilayer printed wiring boards, and thus has great industrial applicability.

Claims

1. A triazole compound, as shown in the following chemical formula (I); [Chemical 1] (in formula (I), R1 and R2 may be the same or different, representing a hydrogen atom, a straight-chain or branched-chain alkyl, aryl, aralkyl, amino, hydroxyl, or an alkylthio group having 1 to 6 carbon atoms; R3 and R4 may be the same or different, representing a hydrogen atom or a group represented by -(CH2)m-Si(OR)3, where R represents methyl or ethyl, and m represents an integer from 1 to 18; wherein, Excluding the case where R3 and R4 are both hydrogen atoms; X represents the radical represented by -NH- or -(CH2)n-, where n represents an integer from 0 to 12).

2. A method for synthesizing a triazole compound, which is the method for synthesizing the triazole compound of claim 1, wherein the triazole compound shown in chemical formula (II) below is reacted with the compound shown in chemical formula (III) below; [Chemical 2] (in formula (II), R1, R2 and X are the same as above) [Chemical 3] (in formula (III), R and m are the same as above; Hal represents a chlorine atom, a bromine atom or an iodine atom).

3. A coupling agent comprising a triazole compound represented by the following chemical formula (IV); [Chemical 4] (in formula (IV), R1 and R2 may be the same or different, representing a hydrogen atom, a straight-chain or branched alkyl, aryl, aralkyl, amino, hydroxyl, or an alkylthio group having 1 to 6 carbon atoms; R5 and R6 may be the same or different, representing a hydrogen atom or a group represented by -(CH2)m-Si(OR)3-p(OH)p, where R represents methyl or ethyl, m represents an integer from 1 to 18, and p represents an integer from 0 to 3; X represents a group represented by phenyl, -NH-, or -(CH2)n-, where n represents an integer from 0 to 12).

4. A surface treatment liquid containing a triazole compound represented by the following chemical formula (IV); [Chemical 5] (in formula (IV), R1 and R2 may be the same or different, representing a hydrogen atom, a straight-chain or branched-chain alkyl, aryl, aralkyl, amino, hydroxyl, or an alkylthio group having 1 to 6 carbon atoms; R5 and R6 may be the same or different, representing a hydrogen atom or a group represented by -(CH2)m-Si(OR)3-p(OH)p, and at least one of R5 and R6 is a group represented by -(CH2)m-Si(OR)3-p(OH)p; here, R represents methyl or ethyl, m represents an integer from 1 to 18, and p represents an integer from 0 to 3; X represents a group represented by phenyl, -NH-, or -(CH2)n-, where n represents an integer from 0 to 12).

5. The surface treatment liquid of claim 4 is used to treat the surface of at least one of the group consisting of metals, inorganic materials and resin materials.

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

7. The surface treatment liquid as described in claim 5 or 6, wherein, The aforementioned metals are selected from at least one of the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof.

8. A surface treatment method comprising bringing the surface treatment liquid of claim 4 into contact with a surface selected from at least one of the group consisting of metal, inorganic material and resin material.

9. The surface treatment method as described in request item 8, wherein, The aforementioned metals are selected from at least one of the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof.

10. The surface treatment method as described in claim 9, wherein, The metal mentioned above is copper or a copper alloy.

11. The surface treatment method as described in claim 10, wherein, Before the surface treatment solution is brought into contact with the surface of copper or copper alloy, an aqueous solution containing copper ions is brought into contact with the surface of copper or copper alloy.

12. The surface treatment method as described in request item 10 or 11, wherein, After the surface treatment solution is brought into contact with the surface of copper or copper alloy, an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the surface of copper or copper alloy.

13. A bonding method comprising contacting the surface treatment liquid of claim 4 with at least one of a group consisting of metals, inorganic materials and resin materials, and forming a chemically formed film on the at least one of the chemically formed films, thereby bonding the chemically formed films together.

14. A bonding method for bonding a metal and a resin material, wherein the surface treatment liquid of claim 4 is brought into contact with at least one of the metal and the resin material, and a chemical coating is formed on the at least one of them, and the metal and the resin material are bonded to each other through the chemical coating.

15. A printed wiring board comprising two materials selected from the group consisting of metal, inorganic material and resin material, separated by an oxidation film formed by the surface treatment liquid of claim 4.

16. A semiconductor wafer comprising two materials selected from a group consisting of a metal, an inorganic material, and a resin material, bonded together by a formation film formed by a surface treatment liquid of claim 4.

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

18. An insulating material comprising the insulating composition of claim 17.

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

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