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

Abstract

The present invention addresses the problem of providing: a novel triazole compound; a method for synthesizing the triazole compound; and a coupling agent. A triazole compound according to the present invention is represented by chemical formula (I). The definition of each substituent in chemical formula (I) is as described in the description.

Description

[Technical Field]

[0001] This invention relates to novel triazole compounds, methods for synthesizing said triazole compounds, coupling agents, and their uses. [Background technology]

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

[0003] For example, coupling agents (silane coupling agents) that use compounds composed of organic matter and silicon are known, and these silane coupling agents function as intermediaries that link organic and inorganic materials that would not normally mix.

[0004] Furthermore, because triazole compounds have the function of preventing metal corrosion and curing epoxy resins and urethane resins, various coupling agents using triazole compounds have been proposed.

[0005] As a triazole compound that can be used as a coupling agent, for example, Patent Document 1 proposes a triazolesilane compound in which an alkoxysilyl group is introduced to a specific triazole ring. Also, Patent Document 2 has two specific triazole rings and a disulfide bond (-SS-), and the triazole ring has -CO-NH-(CH2) m Triazole silane compounds with -Si(OR)3 introduced have been proposed. [Prior art documents] [Patent Documents]

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

Summary of the Invention

Problems to be Solved by the Invention

[0007] In recent years, in the field of electric and electronic materials, in order to cope with miniaturization, thinning, precision, high-speed propagation, etc., it has been required to enhance the adhesion between materials. Although triazole compounds as disclosed in Patent Documents 1 and 2 can also exhibit excellent adhesion, compounds that can exhibit further higher adhesion have been demanded.

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

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that in a triazole compound having two triazole rings, the above problems can be solved by connecting these triazole rings with a specific linking group, and have completed the present invention.

[0010] That is, the present invention is as follows in [1] to

[20] below. [1] A triazole compound represented by the following chemical formula (I).

[0011]

Chem.

[0012] (In formula (I), R1 and R2 are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an amino group, a hydroxyl group or an alkylthio group having 1 to 6 carbon atoms. R3 and R4 are the same or different and each represents a hydrogen atom or -(CH2) m-Si(OR)3 represents a group, where R represents a methyl or ethyl group, and m represents an integer from 1 to 18, except when R3 and R4 are both hydrogen atoms. X is a phenylene group, -NH- or -(CH2) n The base is represented by -, where n is an integer between 0 and 12. [2] A method for synthesizing the triazole compound described in [1] above, comprising reacting a triazole compound represented by the following chemical formula (II) with a compound represented by the following chemical formula (III).

[0013] [ka]

[0014] (In equation (II), R1, R2, and X are as described above.)

[0015] [ka]

[0016] (In formula (III), R and m are as described 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).

[0017] [ka]

[0018] (In formula (IV), R1 and R2 are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkylthio group having 1 to 6 carbon atoms. R5 and R6 are either the same or different hydrogen atoms or -(CH2) m -Si(OR) 3-p (OH) prepresents a group represented by, where R represents a methyl group or an ethyl group, m represents an integer from 1 to 18, and p represents an integer from 0 to 3. X represents a phenylene group, -NH- or -(CH2) n represents a group represented by -, 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).

[0019] [Chemical formula]

[0020] (In formula (IV), R1 and R2 are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an amino group, a hydroxyl group or an alkylthio group having 1 to 6 carbon atoms. R5 and R6 are the same or different and represent a hydrogen atom or -(CH2) m -Si(OR) 3-p (OH) p represents a group represented by, where R represents a methyl group or an ethyl group, m represents an integer from 1 to 18, and p represents an integer from 0 to 3. X represents a phenylene group, -NH- or -(CH2) n represents a group represented by -, where n represents an integer from 0 to 12. )

[0021] [5] The surface treatment liquid according to [4] above, used for treating at least one surface selected from the group consisting of metals, inorganic materials and resin materials. [6] The surface treatment liquid according to [4] above, used for bonding two materials selected from the group consisting of metals, inorganic materials and resin materials. [7] The surface treatment liquid according to [5] or [​​​[8] A surface treatment method comprising bringing the surface treatment liquid described in [4] into contact with at least one surface selected from the group consisting of metal, inorganic material, and resin material. [9] The surface treatment method according to [8], wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold and alloys thereof.

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

[11] The surface treatment method according to

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

[12] The surface treatment method according to

[10] or

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

[13] A bonding method comprising contacting the surface treatment liquid described in [4] above with at least one selected from the group consisting of metal, inorganic material and resin material to form a chemical conversion film on at least one of the materials, and bonding them to each other via the chemical conversion film.

[14] A method for bonding a metal and a resin material, wherein the surface treatment liquid described in [4] is brought into contact with at least one of the metal and the resin material to form a chemical conversion film on the at least one, and the metal and the resin material are bonded to each other via the chemical conversion film.

[0023]

[15] A printed circuit board in which two materials selected from the group consisting of metals, inorganic materials, and resin materials are bonded together via a chemical conversion coating formed with the surface treatment liquid described in [4].

[16] A semiconductor wafer in which two materials selected from the group consisting of metals, inorganic materials and resin materials are bonded together via a chemical conversion film formed with the surface treatment liquid described in [4].

[17] An insulating composition containing the coupling agent described in [3] above and a resin material or an inorganic material.

[18] An insulating material containing the insulating composition described in

[17] above.

[19] A printed circuit board having an insulating layer obtained from the insulating composition described in

[17] above.

[20] A semiconductor wafer having an insulating layer obtained from the insulating composition described in

[17] above. [Effects of the Invention]

[0024] The triazole compound of the present invention is a compound in which two triazole rings are bonded, and therefore can enhance interaction with metals, resin materials, etc. Furthermore, the two triazole rings are bonded together by a phenylene group, -NH- and -(CH2) n Because it is bonded by a linking group selected from the group consisting of groups represented by -, it is resistant to decomposition by heat and alkali. Furthermore, since the coupling agent of the present invention comprises a triazole compound in which two triazole rings are linked by the aforementioned linking group, it can improve adhesion between materials with different properties. A surface treatment solution containing this triazole compound can improve adhesion between two materials of different materials, namely metal and inorganic material, metal and resin material, and inorganic material and resin material. [Modes for carrying out the invention]

[0025] The present invention will be described in detail below. However, the present invention is not limited to the embodiments described below.

[0026] (Triazole compounds) The triazole compound of the present invention is represented by the following chemical formula (I) (hereinafter sometimes referred to as triazole compound (I)).

[0027] [ka]

[0028] (In formula (I), R1 and R2 are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkylthio group having 1 to 6 carbon atoms. R3 and R4 are either the same or different hydrogen atoms or -(CH2) m -Si(OR)3 represents a group, where R represents a methyl or ethyl group, and m represents an integer from 1 to 18, except when R3 and R4 are both hydrogen atoms. X is a phenylene group, -NH- or -(CH2) n The base is represented by -, where n is an integer between 0 and 12.

[0029] In formula (I), R1 and R2 are a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkylthio group having 1 to 6 carbon atoms. R1 and R2 may be the same or different.

[0030] Examples of linear alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups. Examples of branched alkyl groups having 1 to 6 carbon atoms include branched alkyl groups having 3 to 6 carbon atoms, specifically isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, s-pentyl, t-pentyl, isohexyl, s-hexyl, and t-hexyl groups. Examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, trimethylphenyl, tetramethylphenyl, 1-naphthyl, and 2-naphthyl groups. Examples of aralkyl groups include benzyl, phenylethyl, phenylpropyl, and methylbenzyl groups. Examples of alkylthio groups having 1 to 6 carbon atoms include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, and hexylthio group.

[0031] R1 and R2 are more preferably the same or different hydrogen atom, an amino group, or an alkylthio group having 1 to 6 carbon atoms.

[0032] R3 and R4 are hydrogen atoms or -(CH2) m This is a group represented by -Si(OR)3 (where R represents a methyl or ethyl group, and m is an integer from 1 to 18). R3 and R4 may be the same or different, but R3 and R4 cannot be hydrogen atoms at the same time.

[0033] -(CH2) m The group represented by -Si(OR)3 is preferably an integer m between 2 and 12, more preferably an integer m between 3 and 10, and even more preferably an integer m between 3 and 8.

[0034] X is a phenylene group, -NH- or -(CH2) n This represents a base represented by -(n is an integer between 0 and 12). X is -(CH2) n It is preferable that the base is represented by -, more preferably that n is an integer between 0 and 10, even more preferably an integer between 0 and 8, and particularly preferably between 0 and 6.

[0035] In the compound represented by chemical formula (I) (triazole compound (I)), R3 and R4 are preferably bonded to the N atom at position 1 or 2 of the triazole ring.

[0036] Examples of triazole compounds (I) include the triazole compounds represented by chemical formulas (I-1) to (I-8).

[0037] [ka]

[0038] (In equations (I-1) to (I-8), R1, R2, m, R, and X are the same as described above.)

[0039] A specific example of a triazole compound (I) where R3 is hydrogen and R4 is bonded to the nitrogen at position 1 of the triazole ring (the compound shown by formula (I-3)) is, for example, 1-(trimethoxysilyl)methyl-3,3′-(1,4-phenylene)bis(1,2,4-triazole), 1-[2-(triethoxysilyl)ethyl]-3,3′-(1,2-phenylene)bis(5-methyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3′-(1,3-phenylene)bis(5-butyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3′-(1,4-phenylene)bis(5-amino-1,2,4-triazole), 1-[6-(triethoxysilyl)hexyl]-3,3′-(1,4-phenylene)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′-bi-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′-ethylenebis(5-ethyl-1,2,4-triazole), 1-[3-(triethoxysilyl)propyl]-3,3′-ethylenebis(5-amino-1,2,4-triazole), 1-[12-(triethoxysilyl)dodecyl]-3,3′-ethylenebis(5-amino-1,2,4-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′-nonameethylenebis(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′-undecamethylenebis(5-amino-1,2,4-triazole), Examples include 1-[3-(triethoxysilyl)propyl]-3,3′-dodecamethylenebis(5-amino-1,2,4-triazole).

[0040] As triazole compound (I), R3 and R4 are the same or different, -(CH2) m A specific example of a group represented by -Si(OR)3, where R3 and R4 are bonded to the nitrogen at position 1 of the triazole ring (compounds represented by formula (I-5)), is, for example, 3,3′-(1,4-phenylene)bis[1-(trimethoxysilyl)methyl-1,2,4-triazole], 3,3′-(1,2-phenylene)bis{1-[2-(triethoxysilyl)ethyl]-5-methyl-1,2,4-triazole}, 3,3′-(1,3-phenylene)bis{1-[3-(triethoxysilyl)propyl]-5-butyl-1,2,4-triazole}, 3,3′-(1,4-phenylene)bis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3′-(1,4-phenylene)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′-Iminobis{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[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′-Ethylenebis{1-[3-(triethoxysilyl)propyl]-5-ethyl-1,2,4-triazole}, 3,3′-Ethylenebis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 3,3′-Ethylenebis{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′-Nonameethylenebis{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′-Undecamethylenebis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, Examples include 3,3′-dodecamethylenebis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}.

[0041] Triazole compound (I) is obtained by reacting a triazole compound represented by chemical formula (II) (hereinafter sometimes referred to as triazole compound (II)) with an alkylsilane halide compound represented by chemical formula (III) (hereinafter sometimes referred to as alkylsilane halide compound (III)).

[0042] [ka]

[0043] (In equation (II), R1, R2, and X are as described above.)

[0044] [ka]

[0045] (In formula (III), R and m are as described above. Hal represents a chlorine atom, a bromine atom, or an iodine atom.)

[0046] In equation (II), R1, R2, and X are the same as those shown in equation (I), and the preferred values ​​are also the same. In equation (III), R and m are the same as those shown in equation (I), and the preferred values ​​are also the same. In formula (III), Hal is a chlorine atom, a bromine atom, or an iodine atom, and from the viewpoint of reactivity and availability of raw materials, a chlorine atom or a bromine atom is preferred.

[0047] Examples of triazole compounds (II) include, 3,3′-(1,4-phenylene)bis(1,2,4-triazole), 3,3′-(1,4-phenylene)bis(5-methyl-1,2,4-triazole), 3,3′-(1,2-phenylene)bis(5-ethyl-1,2,4-triazole), 3,3′-(1,4-phenylene)bis(5-isopropyl-1,2,4-triazole), 3,3′-(1,3-phenylene)bis(5-butyl-1,2,4-triazole), 3,3′-(1,4-phenylene)bis(5-phenyl-1,2,4-triazole), 3,3′-(1,4-phenylene)bis(5-amino-1,2,4-triazole), 3,3′-(1,4-phenylene)bis(5-hydroxy-1,2,4-triazole), 3,3′-(1,4-phenylene)bis(5-ethylthio-1,2,4-triazole), 5-amino-3,3′-(1,4-phenylene)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′-Iminobis(5-hydroxy-1,2,4-triazole), 3,3′-Iminobis(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-Phenethyl-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), 5-amino-5′-ethyl-3,3′-methylenebis(1,2,4-triazole), 3,3′-Ethylenebis(1,2,4-triazole), 3,3′-Ethylenebis(5-propyl-1,2,4-triazole), 3,3′-Ethylenebis(5-hexyl-1,2,4-triazole), 3,3′-Ethylenebis(5-m-tolyl-1,2,4-triazole), 3,3′-Ethylenebis(5-amino-1,2,4-triazole), 3,3′-Ethylenebis(5-hydroxy-1,2,4-triazole), 3,3′-Ethylenebis(5-isopropylthio-1,2,4-triazole), 5-amino-3,3′-ethylenebis(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-pentylthio-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′-heptamethylenebis(1,2,4-triazole), 3,3′-heptamethylenebis(5-tert-butyl-1,2,4-triazole), 3,3′-heptamethylenebis(5-phenyl-1,2,4-triazole), 3,3′-heptamethylenebis(5-amino-1,2,4-triazole), 5-amino-5′-hydroxy-3,3′-heptamethylenebis(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′-nonameethylenebis(1,2,4-triazole), 3,3′-Nonameethylenebis(5-Isopentyl-1,2,4-Triazole), 5-phenyl-3,3′-nonameethylenebis(1,2,4-triazole), 3,3′-Nonameethylenebis(5-amino-1,2,4-triazole), 3,3′-Nonameethylenebis(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′-Undecamethylenebis(1,2,4-triazole), 3,3′-Undecamethylenebis(5-propyl-1,2,4-triazole), 3,3′-Undecamethylenebis(5-amino-1,2,4-triazole), 3,3′-Undecamethylenebis(5-methylthio-1,2,4-triazole), 3,3′-Dodecamethylenebis(1,2,4-triazole), 3,3′-Dodecamethylenebis(5-ethyl-1,2,4-triazole), 3,3′-Dodecamethylenebis(5-amino-1,2,4-triazole), Examples include 3,3′-undecamethylenebis(5-hydroxy-1,2,4-triazole).

[0048] These exemplified triazole compounds (II) can be synthesized, for example, in accordance with the synthesis methods described in Chem. Eur. J., 18, 16742 (2012), J. Applied. Chem., 82, 276 (2009), and U.S. Patent No. 2,744,116.

[0049] Examples of the alkylsilane halogen compound (III) mentioned above 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 Examples include 12-bromoddecyltriethoxysilane.

[0050] The triazole compound (I) of the present invention can be synthesized in generally high yield by, for example, reacting the triazole compound (II) and the alkylsilane halide compound (III) in an appropriate amount of reaction solvent in the presence of a dehydrohalogenating agent at an appropriate reaction temperature and reaction time. In the following reaction scheme (A), R3 is a hydrogen atom and R4 is -(CH2) m The reaction scheme for obtaining triazole compound (I), which has a group represented by -Si(OR)3, is shown.

[0051] [ka]

[0052] (In the formula, R1, R2, X, R, Hal, and m are as described above.)

[0053] The reaction solvent is not particularly limited as long as it is inert to the triazole compound (II) and the alkylsilane halide compound (III), for example, Hydrocarbon solvents such as hexane, toluene, and xylene; Ether-based solvents such as diethyl ether, tetrahydrofuran, dioxane, and cyclopentyl methyl ether; Ester solvents such as ethyl acetate and butyl acetate; Alcohol-based solvents such as methanol and ethanol; Amide 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; Examples include acetonitrile, dimethyl sulfoxide, and hexamethylphosphoramide.

[0054] Examples of the aforementioned dehalogenating agent include, Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, and potassium t-butoxide; Alkali carbonates such as sodium carbonate and potassium carbonate; Examples include organic bases such as triethylamine and diazabicycloundecene, and sodium hydride.

[0055] The reaction between the triazole compound (II) and the alkylsilane halide compound (III) proceeds stoichiometrically as shown in the reaction scheme (A) above. However, the amount of alkylsilane halide compound (III) used relative to the amount of triazole compound (II) should be adjusted considering factors such as reaction temperature, reaction time, the type of raw materials and reaction solvent used, and the reaction scale. Preferably, 0.8 to 1.2 equivalents of alkylsilane halide compound (III) should be used for each -NH of the triazole ring that serves as the reaction site. If the amount of alkylsilane halide compound (III) charged per reaction site (-NH) is greater than 1.2 equivalents, there is a risk that the compound will polymerize and gel. If the amount is less than 0.8 equivalents, there is a risk that the purity of the product will decrease or that the separation procedure for the product will become complicated. Furthermore, since the dehydrohalogenating agent is used to neutralize the hydrogen halides produced as a by-product of the reaction between the triazole compound (II) and the alkylsilane halide compound (III), the amount used (charged amount) should be equal to or greater than the amount of alkylsilane halide compound (III) used.

[0056] The reaction temperature is not particularly limited as long as it is within the temperature range in which the -NH of the triazole ring of triazole compound (II) reacts with alkylsilane halide compound (III), but is preferably in the range of 0 to 150°C, and more preferably in the range of 5 to 100°C.

[0057] The reaction time is determined appropriately according to the set reaction temperature, but is preferably in the range of 30 minutes to 24 hours, and more preferably in the range of 1 to 8 hours.

[0058] (Coupling agent) The coupling agent of the present invention comprises a triazole compound represented by the following chemical formula (IV) (hereinafter sometimes referred to as triazole compound (IV)).

[0059] [ka]

[0060] (In formula (IV), R1 and R2 are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkylthio group having 1 to 6 carbon atoms. R5 and R6 are either the same or different hydrogen atoms or -(CH2) m -Si(OR) 3-p (OH) pThe group is represented by , where R represents a methyl group or an ethyl group, m represents an integer from 1 to 18, and p represents an integer from 0 to 3. X is a phenylene group, -NH- or -(CH2) n The base is represented by -, where n is an integer between 0 and 12.

[0061] In formula (IV), R1 and R2 are a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkylthio group having 1 to 6 carbon atoms. R1 and R2 may be the same or different.

[0062] Examples of linear alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups. Examples of branched alkyl groups having 1 to 6 carbon atoms include branched alkyl groups having 3 to 6 carbon atoms, specifically isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, s-pentyl, t-pentyl, isohexyl, s-hexyl, and t-hexyl groups. Examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, trimethylphenyl, tetramethylphenyl, 1-naphthyl, and 2-naphthyl groups. Examples of aralkyl groups include benzyl, phenylethyl, phenylpropyl, and methylbenzyl groups. Examples of alkylthio groups having 1 to 6 carbon atoms include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, and hexylthio group.

[0063] R1 and R2 are more preferably the same or different hydrogen atom, an amino group, or an alkylthio group having 1 to 6 carbon atoms.

[0064] R5 and R6 are hydrogen atoms or -(CH2) m -Si(OR)3-p (OH) p The group is represented by (where R is a methyl or ethyl group, m is an integer from 1 to 18, and p is an integer from 0 to 3). R5 and R6 may be the same or different.

[0065] R5 and R6 are at least one of -(CH2) m -Si(OR) 3-p (OH) p It is preferable that the group is represented by [the symbol shown]. Also, -(CH2) m -Si(OR) 3-p (OH) p The base represented by is preferably an integer m between 2 and 12, more preferably an integer m between 3 and 10, and even more preferably an integer m between 3 and 8.

[0066] X is a phenylene group, -NH- or -(CH2) n This represents a base represented by -(n is an integer between 0 and 12). X is -(CH2) n It is preferable that the base is represented by -, and more preferably that n is an integer between 0 and 10, even more preferably an integer between 0 and 8, and particularly preferably an integer between 0 and 6.

[0067] The compound represented by chemical formula (IV) (triazole compound (IV)) includes the triazole compound (I), the hydrolysate of the triazole compound (I), and the triazole compound (II). In this triazole compound (IV), R5 and / or R6 -(CH2) m -Si(OR) 3-p (OH) p Compounds in which the p of the group indicated by is an integer from 1 to 3 are species produced by hydrolysis of triazole compound (I) in which p is 0. All of these are suitable as components of coupling agents. Furthermore, in triazole compound (IV), a compound in which the p of 1 to 3 is an integer can be obtained, for example, by hydrolyzing triazole compound (I) in which p is 0 and then removing the volatile components.

[0068] When using the coupling agent of the present invention, the same surface treatment method as in the case of conventional coupling agents can be employed. Examples of this surface treatment method include (a) spraying a treatment solution obtained by diluting an appropriate amount of coupling agent with an organic solvent onto the substrate, (b) spraying a treatment solution obtained by diluting the coupling agent with water and an organic solvent onto the substrate, (c) spraying a treatment solution obtained by diluting the coupling agent with water onto the substrate, (d) immersing the substrate in a treatment solution obtained by diluting the coupling agent with an organic solvent, (e) immersing the substrate in a treatment solution obtained by diluting the coupling agent with water and an organic solvent, and (f) immersing the substrate in a treatment solution obtained by diluting the coupling agent with water.

[0069] Examples of the aforementioned 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-based solvents such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether, and diethylene glycol monobutyl ether; Examples of alcohol-based solvents include methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, 2-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, and propylene glycol.

[0070] Examples of substrates used in the present invention include granular, needle-shaped, fibrous, woven, plate-shaped, foil-shaped, and amorphous substrates formed from metals, inorganic materials, resin materials, etc.

[0071] Examples of the aforementioned metals include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. Plates, foils, or plated films made of these metals can be used as substrates. Specific examples of the aforementioned alloys include copper alloys, which are not particularly limited as long as they contain copper, such as 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, etc.). Among these metals, copper and copper alloys are preferred.

[0072] Examples of the aforementioned inorganic materials include silicon, ceramics, inorganic materials used as fillers, and glass. Specifically, examples include silicon compounds such as silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminosilicate, 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.

[0073] Examples of the aforementioned resin materials include nylon, acrylate resin, epoxy resin, polybenzoxazole resin, silicone resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, polybutadiene resin, olefin resin, fluorine-containing resin, polyetherimide resin, polyetheretherketone resin, and liquid crystal resin. These may be mixed or modified and combined. Among these resin materials, polyphenylene ether resins, polyphenylene oxide resins, liquid crystal resins, acrylate resins, epoxy resins, olefin resins, polybenzoxazole resins, silicone resins, and polyimide resins are preferred.

[0074] By applying a surface treatment to a substrate with a treatment solution containing the coupling agent of the present invention, the lipophilicity of the substrate surface is increased, thereby improving its affinity (adhesion, adhesion) to resins and the like. Furthermore, to enhance the effects of this treatment, the surface-treated substrate may be further heat-treated.

[0075] (Surface treatment liquid) <Surface treatment solution containing a triazole compound represented by chemical formula (IV)> The surface treatment solution of the present invention contains a triazole compound represented by the above chemical formula (IV) (triazole compound (IV)). In this triazole compound (IV), R5 and / or R6 -(CH2) m -Si(OR) 3-p (OH) p Compounds in which the group represented by has p as an integer from 1 to 3 are species produced by the hydrolysis of compounds with p of 0 in the surface treatment solution. All of these are suitable as components of the surface treatment solution. Furthermore, in triazole compound (IV), compounds with p as an integer from 1 to 3 can be extracted from the surface treatment solution by removing volatile components from the surface treatment solution containing triazole compound (I) with p of 0, for example.

[0076] In carrying out the present invention, it is preferable to use a compound with p = 0 as a raw material when preparing the surface treatment solution. When p = 0, that is, at least one of R5 and R6 is -(CH2) m If the group is represented by -Si(OR)3, it can be the same compound as the triazole compound (I) described above, and the preferred compound is also the same.

[0077] The surface treatment solution of the present invention is prepared by mixing a triazole compound (IV) with water. For preparing the surface treatment solution, pure water such as ion-exchanged water or distilled water is preferred. Furthermore, it is preferable to use a solubilizer in the surface treatment solution of the present invention to promote the dissolution (aqueous solution formation) of the triazole compound (IV). Examples of solubilizers include acids, alkalis, and organic solvents. These solubilizers may be used individually or in combination of two or more. Regarding the preparation method of the surface treatment solution when using a solubilizer and water, the solubilizer may be added after mixing the triazole compound and water, or the triazole compound may be mixed with a mixture of water and a solubilizer, or the water may be added after mixing the triazole compound and the solubilizer.

[0078] 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, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, oleic acid, stearic acid, glycolic acid, lactic acid, gluconic acid, glyceric acid, malonic acid, succinic acid, levulinic acid, benzoic acid, oxalic acid, tartaric acid, malic acid, benzenesulfonic acid, tosylic acid, methanesulfonic acid, 5-sulfosalicylic acid, 4-hydroxybenzenesulfonic acid, 3-methyl-4-hydroxybenzenesulfonic acid, 4-aminobenzenesulfonic acid, camphorsulfonic acid, benzenedisulfonic acid, benzenetrisulfonic acid, sulfamic acid, and amino acids. These acids may be used individually or in combination of two or more.

[0079] Examples of the alkalis mentioned above include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, trippropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol, N,N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine, and pyridine. These alkalis may be used individually or in combination of two or more.

[0080] Examples of the aforementioned organic solvents include methanol, ethanol, 1-propanol, 2-propanol, butanol, tert-butyl alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and diethylene glycol monomethyl ether. Examples include ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, acetone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, formamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, ethylene carbonate, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, etc. These organic solvents may be used individually or in combination of two or more.

[0081] The solubilizer content is preferably 0.1 to 99% by weight in the surface treatment solution, more preferably 0.5 to 99% by weight, and even more preferably 1 to 99% by weight.

[0082] <Hydrolysis of triazole compounds> Since the triazole compound (IV) of the present invention has a triazole ring in its molecule, the triazole ring interacts with the surface of the substrate (metal, resin material, inorganic material) to form a chemical bond, thereby improving the adhesion between different materials.

[0083] The mode of hydrolysis of triazole compound (IV) is shown in scheme (B). In scheme (B), at least one of R5 and R6 of triazole compound (IV) is -(CH2) m -Si(OR) 3-p (OH) p This illustrates the case where the group is represented by [the symbol]. In this scheme (B), the alkoxysilyl group of the triazole compound (IV) is hydrolyzed, that is, the trialkoxysilyl group is gradually changed to a dialkoxyhydroxysilyl group, a dihydroxyalkoxysilyl group, and a trihydroxysilyl group.

[0084] [ka]

[0085] In general, substances containing alkoxysilyl groups in their molecules are known to act as silane coupling agents. For example, in the case of bonding copper to a resin material, if the triazole compound used in the implementation of the present invention has an alkoxysilyl group in its molecule, the triazole ring interacts with the resin and copper to form a chemical bond, the alkoxysilyl group (-Si-OR) is hydrolyzed and converted to a hydroxysilyl group (-Si-OH), and this hydroxysilyl group chemically bonds with copper oxide scattered on the surface of the copper. Therefore, by bringing copper into contact with a surface treatment solution, a chemical conversion film derived from triazole compound (IV) is formed on the surface of the copper through bonding with triazole rings and hydroxysilyl groups. When a resin layer made of a resin material is formed on the surface of this chemical conversion film, the adhesion between the copper and the resin material can be improved compared to when the resin layer is formed directly on the surface of the copper.

[0086] In carrying out the present invention, the concentration of the triazole compound (IV) in the surface treatment solution is preferably 0.0001 to 1.0000 mol / L, more preferably 0.0010 to 0.5000 mol / L, and even more preferably 0.0100 to 0.1000 mol / L, when converted to the concentration of the trialkoxy triazole compound.

[0087] Incidentally, the triazolesilane compound (IV) having a hydroxysilyl group, which is generated in the surface treatment solution, gradually reacts with each other and undergoes dehydration condensation, causing the hydroxysilyl group to form a siloxane bond (Si-O-Si) (see scheme (B)), and is converted into a water-insoluble silane oligomer (a triazolesilane compound having the group shown in chemical formula (e) in scheme (B)). Note that X in the group shown in chemical formula (e) is an integer representing the number of repeating units.

[0088] If the amount of silane oligomers generated in the surface treatment solution increases, insoluble components may precipitate (causing the treatment solution to become cloudy), and these may adhere to the treatment tank, the piping connected to the treatment tank, and sensors immersed in the treatment solution to detect the temperature and level of the solution, potentially hindering smooth surface treatment. To avoid this, it is preferable to include the aforementioned organic solvent in the surface treatment solution as a solubilizer for silane oligomers, which are poorly soluble in water, when preparing the surface treatment solution. Furthermore, it is preferable to include the aforementioned solubilizer (acid, alkali, or organic solvent) in the preparation of the surface treatment solution in order to promote the dissolution of the triazole compound. Since organic solvents also function as solubilizers for silane oligomers, it is preferable to include at least one selected from the group consisting of acids, alkalis, and organic solvents as a solubilizer in the surface treatment solution of the present invention.

[0089] Similarly, to improve the stability of the surface treatment solution and the uniformity of the chemical conversion 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.

[0090] Halide ions have the effect of uniformly forming flat surfaces in the conversion coating. Examples of substances that generate halide ions include lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, magnesium iodide, calcium iodide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, etc. Halogen compounds may also be present as impurities in other components.

[0091] The content of halide ions in the surface treatment solution is not particularly limited, but is preferably 0.10 mol / L or less (particularly 0 to 0.10 mol / L), more preferably 0.050 mol / L or less (particularly 0 to 0.050 mol / L), even more preferably 0.020 mol / L or less (particularly 0 to 0.020 mol / L), and particularly preferably 0.010 mol / L or less (particularly 0 to 0.010 mol / L).

[0092] Copper ions can form complexes with triazole compounds, thereby increasing the strength of the chemical conversion film or enhancing the adhesion strength between the metal and the resin. The valence of the copper ions can be either 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, cuprous chloride, cupric chloride, copper acetate (and its hydrates, especially monohydrate), copper hydroxide, copper oxide, copper sulfide, copper carbonate, cuprous bromide, cupric bromide, copper phosphate, and copper benzoate. Furthermore, the copper ions in the surface treatment solution may include copper ions that have eluted from metallic copper or copper oxide contained in the copper circuit during the treatment of the copper circuit with the surface treatment solution.

[0093] The copper ion content in the surface treatment solution is not particularly limited, but is preferably 1.00 mol / L or less (particularly 0 mol / L to 1.00 mol / L), more preferably 0.50 mol / L or less (particularly 0 mol / L to 0.50 mol / L), even more preferably 0.10 mol / L or less (particularly 0 mol / L to 0.10 mol / L), and particularly preferably 0.010 mol / L or less (particularly 0 mol / L to 0.010 mol / L).

[0094] Furthermore, known coupling agents may be used in combination, to the extent that they do not impair the effects of the present invention. Examples of known coupling agents include silane-based coupling agents (silane coupling agents) having thiol groups (mercapto groups), vinyl groups, epoxy groups, (meth)acrylic groups, amino groups, chloropropyl groups, etc.

[0095] Examples of such silane-based coupling agents include, for example, 3-mercaptopropyltrimethoxysilane, Mercaptosilane compounds such as 3-mercaptopropylmethyldimethoxysilane, Vinyltrichlorosilane, Vinyltrimethoxysilane, Vinyl silane compounds such as vinyltriethoxysilane, Styrylsilane compounds such as p-styryltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldiethoxysilane, Epoxysilane compounds such as 3-glycidoxypropyltriethoxysilane, Acryloxysilane compounds such as 3-acryloxypropyltrimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropylmethyldiethoxysilane, Methacryloxysilane compounds such as 3-methacryloxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-Triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, Aminosilane compounds such as N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, Ureidosilane compounds such as 3-ureidopropyltriethoxysilane, Chloropropylsilane compounds such as 3-chloropropyltrimethoxysilane, Sulfidosilane compounds such as bis(triethoxysilylpropyl)tetrasulfide, and Examples include isocyanatosilane compounds such as 3-isocyanatopropyltriethoxysilane. Other examples include aluminum-based coupling agents, titanium-based coupling agents, and zirconium-based coupling agents.

[0096] (Processing method) There are no particular limitations on the method for bringing the surface treatment liquid of the present invention into contact with the surface of the substrate, and means such as spraying, dipping, or coating can be used, as in the case of the coupling agent described above. The contact time between the surface treatment liquid and the substrate (treatment time) is preferably 1 second to 10 minutes, and more preferably 5 seconds to 3 minutes. If the treatment time is less than 1 second, the thickness of the chemical conversion film formed on the substrate surface will be thin, making it difficult to obtain sufficient adhesion between materials of different materials. On the other hand, even if the treatment time is longer than 10 minutes, there is no significant difference in the thickness of the chemical conversion film. Therefore, from the viewpoint of productivity, it is preferable to treat within 10 minutes. Furthermore, while it is preferable that the temperature of the treatment solution be 5 to 50°C when it is brought into contact with the substrate surface, it may be set appropriately in relation to the aforementioned treatment time.

[0097] After the surface treatment liquid of the present invention comes into contact with the substrate, it may be washed with water and then dried, or it may be dried without washing with water. Drying is preferably carried out at a temperature between room temperature and 150°C. While pure water such as deionized water or distilled water is preferred for rinsing, there are no particular restrictions on the rinsing method or duration; any appropriate duration using methods such as spraying or immersion is acceptable.

[0098] The thickness of the chemical conversion coating is preferably 0.5 to 1,000 nm, more preferably 1 to 200 nm, and even more preferably 1 to 100 nm. A thickness of 0.5 nm or more ensures sufficient adhesion between materials, while a thickness of 1,000 nm or less maintains the chemical resistance of the chemical conversion coating.

[0099] In the present invention, the surface of the chemical conversion coating may be modified by treating the dried coating with plasma, laser, ion beam, ozone, heating, humidification, etc. Alternatively, cleaning may be performed on the metal surface for the purpose of removing resin and ion residue using plasma, laser, ion beam, mechanical polishing such as permis brush, or processing methods such as drilling.

[0100] Before bringing the surface treatment solution of the present invention into contact with the surface of copper or a copper alloy (hereinafter, both may be referred to simply as copper), the copper surface may be subjected to at least one pretreatment selected from pickling, alkali treatment, roughening treatment, heat-resistant treatment, rust-preventive treatment, or chemical conversion treatment.

[0101] The aforementioned pickling treatment is performed to remove oily components adhering to the surface of copper and to remove the oxide film on the surface of copper. Solutions such as hydrochloric acid-based solutions, sulfuric acid-based solutions, nitric acid-based solutions, sulfuric acid-hydrogen peroxide-based solutions, organic acid-based solutions, inorganic acid-organic solvent-based solutions, and organic acid-organic solvent-based solutions can be used for this pickling treatment.

[0102] The aforementioned alkaline treatment is performed to remove oily components adhering to the copper surface or to remove residues from the previous process (for example, dry film resist for copper circuit formation). For this alkaline treatment, solutions such as aqueous solutions or organic solvent-based solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amines such as ammonia, ethanolamine, monopropanolamine, and tetramethylammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium acetate, potassium acetate, sodium phosphate, disodium hydrogen phosphate, potassium phosphate, and dipotassium hydrogen phosphate can be used.

[0103] The aforementioned roughening treatment is performed to improve the adhesion between copper and resin through an anchoring effect. This process imparts an uneven surface to the copper, thereby enhancing the adhesion between the copper and the resin material. Methods such as micro-etching, electroplating, electroless plating, oxidation (black oxide, brown oxide), oxidation-reduction, brush polishing, and jet scrubbing can be employed for this roughening treatment.

[0104] In the micro-etching method, for example, organic acid-cupric ion systems, sulfuric acid-hydrogen peroxide systems, persulfate systems, copper chloride systems, and iron chloride systems can be used as etching agents. In the electroplating method, fine copper particles are deposited on the surface of the copper, thereby creating irregularities on the copper surface.

[0105] In the aforementioned heat-resistant treatment, at least one film selected from nickel, nickel-phosphorus, zinc, zinc-nickel, copper-zinc, copper-nickel, copper-nickel-cobalt, or nickel-cobalt is formed on the surface of the copper. This film can be formed by known electroplating methods, but is not limited to electroplating; vapor deposition or other means may also be used.

[0106] The aforementioned rust prevention treatment is performed to prevent the surface of copper from oxidizing and corroding. This can involve forming a plating film of zinc or a zinc alloy composition, or an electrolytic chromate plating film, on the surface of the copper. Alternatively, a treatment solution containing an organic compound-based rust inhibitor, such as a benzotriazole-based rust inhibitor, may be brought into contact with the surface of the copper.

[0107] In the aforementioned chemical conversion treatment, a method for forming a tin passivation film or a method for forming a copper oxide passivation film can be employed.

[0108] Before and / or after contacting the surface treatment solution of the present invention with the copper surface, an aqueous solution containing copper ions may be brought into contact with the copper surface. This aqueous solution containing copper ions has the function of enhancing the film-forming properties of the chemical conversion film formed on the copper surface and the function of making the thickness of the chemical conversion film formed on the copper surface uniform. The valency of the copper ions is not particularly limited and can be monovalent or divalent copper ions. The copper ion source for an aqueous solution containing copper ions is not particularly limited as long as it is a copper salt that dissolves in water, and examples include copper sulfate, copper nitrate, copper chloride, copper formate, and copper acetate. Ammonia or hydrochloric acid may be added to solubilize the copper salt in water.

[0109] An acidic aqueous solution or an alkaline aqueous solution may be brought into contact with the copper surface before and / or after bringing the surface treatment solution of the present invention into contact with the copper surface. This acidic aqueous solution or alkaline aqueous solution, like the aqueous solution containing copper ions described above, has the function of making the thickness of the conversion film formed on the copper surface uniform. Acidic and alkaline aqueous solutions are not particularly limited, but examples of acidic aqueous solutions include aqueous solutions containing mineral acids such as sulfuric acid, nitric acid, and hydrochloric acid, and aqueous solutions containing organic acids such as formic acid, acetic acid, lactic acid, glycolic acid, and amino acids. Examples of alkaline aqueous solutions include aqueous solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amines such as ammonia, ethanolamine, monopropanolamine, and tetramethylammonium hydroxide, and 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.

[0110] Before bringing the surface treatment solution of the present invention into contact with the copper surface, an aqueous solution containing a known coupling agent may be brought into contact with the copper surface.

[0111] After bringing the surface treatment solution of the present invention into contact with the copper surface, an aqueous solution containing a known coupling agent may be brought into contact with the copper surface.

[0112] After bringing the surface treatment solution of the present invention into contact with the copper surface, a treatment solution containing a known organic compound-based rust inhibitor, such as a benzotriazole-based rust inhibitor, may be brought into contact with the copper surface.

[0113] 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 a substrate with the surface treatment liquid of the present invention, a chemical conversion film can be formed on the substrate surface, thereby improving adhesion with other materials.

[0114] In the present invention, two materials selected from the group consisting of metals, inorganic materials, and resin materials can be bonded together using the surface treatment solution of the present invention. By bonding the two materials through a layer of chemical conversion film formed by the surface treatment solution of the present invention, the affinity between them can be improved, allowing for stronger bonding even between materials of different materials.

[0115] (Adhesion method) The two materials can be bonded together by known methods. These methods include contacting the surface treatment solution of the present invention with the surface of a substrate made of metal, inorganic material, or resin material to form a chemical conversion film, and then applying, pressing, mixing, or otherwise bonding a part or all of the formed chemical conversion film with the other substrate, or using an adhesive, adhesive sheet (film), or a combination of these methods. Furthermore, 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 to form a chemical conversion film on each of the two substrates, and the two substrates are bonded together by means such as coating, pressing, or mixing, or by using an adhesive, adhesive sheet (film), or a combination of these means.

[0116] By using the surface treatment liquid of the present invention, it is possible to bond two materials, particularly two materials of different materials, as described above, and therefore it can be suitably used for various electrical and electronic components, semiconductor wafers, printed circuit boards, and other electronic devices.

[0117] Furthermore, in the present invention, the surface treatment liquid of the present invention can be suitably used on substrates formed from metals, particularly copper or copper alloys. For example, it is suitable for surface treatment of copper or copper alloys aimed at improving the adhesion between copper circuits (copper wiring layers) and semi-cured or cured prepregs, solder resists, or semi-cured or cured dry film resists (insulating resin layers). In printed circuit boards having an insulating resin layer in contact with a copper wiring layer, the adhesion between the copper wiring layer and the insulating resin layer can be improved.

[0118] In applications involving semiconductor wafers, this technology is suitable for surface treatment of semiconductor circuits aimed at improving adhesion between the semiconductor circuit formed on the semiconductor wafer and a protective film (for example, photosensitive positive type, photosensitive negative type, non-photosensitive buffer coat, bump protective film, or other insulating protective film). Furthermore, it is suitable for surface treatment of copper circuit redistribution layers in package substrates (WL-CSP, FO-WLP, PLP) and 2.5D or 3D interposer substrates, where a redistribution layer is formed on a semiconductor wafer, with the aim of improving the adhesion between the copper circuit redistribution layer and the insulating material. Examples of the protective film and insulating material mentioned above include polyimide resin, polybenzoxazole resin, and silicone resin.

[0119] The aforementioned printed circuit board can be manufactured by bringing the surface treatment liquid of the present invention into contact with the surface of the copper wiring, then washing and drying it, and finally forming an insulating resin layer on the surface of the copper wiring. As for the method of contact, as described above, immersion of the copper wiring in the surface treatment liquid or spraying the copper wiring with the treatment liquid is simple, reliable, and preferred. Furthermore, there are no particular restrictions on the method of washing, but immersing the copper wiring in the washing water or spraying the surface of the copper wiring with washing water is simple, reliable, and preferable. For forming the aforementioned insulating resin layer, known methods can be employed, such as a method of attaching a semi-cured resin material or a means of applying a liquid resin material containing a solvent. Next, via holes are formed to allow electrical conductivity between the upper and lower wiring. By repeating this process, a multilayer printed circuit board can be manufactured.

[0120] An example of a semi-additive method using the surface treatment liquid of the present invention in the circuit formation method for printed circuit boards described above is shown below. (a) A step of preparing an insulating substrate having an insulating substrate or an insulating substrate having through-holes and via holes, the first surface and the second surface opposite to the first surface, and the inner walls of the through-holes and via holes, (b) A step of forming a photocrosslinkable resin layer and a mask layer on the first and second surfaces, and covering the first conductive layer on the first and second surfaces and the inner walls of the through-holes and via holes with the photocrosslinkable resin layer and the mask layer. (c) A step of pattern exposure of the first and second surfaces and the photocrosslinkable resin layer around the through-holes and via holes, (d) A step of removing the mask layer from the first and second surfaces and around the through-holes and via holes, (e) Using a photocrosslinkable resin layer removal solution, develop and remove the uncured photocrosslinkable resin layer on the first and second surfaces, as well as around the through-holes and via holes, to expose the first conductive layer on the first surface, the first conductive layer on the second surface, and the first conductive layer around the through-holes and via holes; (f) Form a second conductive layer on the first conductive layer exposed on the first and second surfaces, as well as on the inner walls of the through-holes and via holes, by electroplating; (g) A step of removing the cured photocrosslinkable resin layer on the first and second surfaces and around the through-holes and via holes to expose the first and second conductive layers on the first and second surfaces and the inner walls of the through-holes and via holes. (h) A step of flash etching to remove the exposed first conductive layer, (i) A step of forming a third conductive layer on the first and second surfaces and on the first and second conductive layers of the through-holes and via holes by electroless plating and electrolytic plating treatment, (j) A step of laminating insulating resin layers on the first surface and the second surface, and on the first, second, and third conductive layers on the through-holes and via holes and inner walls. In a method for manufacturing a circuit board comprising at least one of the following, the surface treatment liquid of the present invention is brought into contact with at least one of the metal layers or resist layers among the first, second, and third conductive layers on the first surface and the first, second, and third conductive layers on the through-holes and via holes, the insulating resin substrate, the photocrosslinkable resin layer used for the etching resist layer and the plating resist layer, and the insulating resin layer, in order to manufacture a printed wiring board.

[0121] Furthermore, an example of a subtractive method using the surface treatment liquid of the present invention in the circuit formation method of the printed wiring board described above is shown below. (a) A step of preparing an insulating substrate having an insulating substrate or an insulating substrate having through-holes and via holes, the first surface and the second surface opposite to the first surface, and the inner walls of the through-holes and via holes, (b) A step of forming a photocrosslinkable resin layer and a mask layer on the first and second surfaces, and covering the first conductive layer on the first and second surfaces and the inner walls of the through-holes and via holes with the photocrosslinkable resin layer and the mask layer. (c) A step of pattern exposure of the first and second surfaces and the photocrosslinkable resin layer around the through-holes and via holes, (d) A step of removing the mask layer from the first and second surfaces and around the through-holes and via holes, (e) Using a photocrosslinkable resin layer removal solution, develop and remove the uncured photocrosslinkable resin layer on the first and second surfaces, as well as around the through-holes and via holes, to expose the first conductive layer on the first surface, the first conductive layer on the second surface, and the first conductive layer around the through-holes and via holes; (f) Etch and remove the first conductive layer exposed on the first and second surfaces, as well as on the inner walls of the through-holes and via holes. (g) A step of removing the cured photocrosslinkable resin layer on the first and second surfaces and around the through-holes and via holes to expose the first and second conductive layers on the first and second surfaces and the inner walls of the through-holes and via holes. (h) A step of forming a third conductive layer on the first and second surfaces and on the first and second conductive layers of the through-holes and via holes by electroless plating and electrolytic plating treatment. (i) A step of laminating insulating resin layers on the first surface and the second surface, and on the first, second, and third conductive layers of the through-holes and via holes, In a method for manufacturing a circuit board comprising at least one of the following, the surface treatment liquid of the present invention is brought into contact with at least one of the metal layers or resist layers among the first, second, and third conductive layers on the first surface and the first, second, and third conductive layers on the through-holes and via holes, the insulating resin substrate, the photocrosslinkable resin layer used for the etching resist layer and the plating resist layer, and the insulating resin layer, in order to manufacture a printed wiring board.

[0122] The aforementioned copper wiring and conductive layers may be manufactured using any method, such as electroless plating, electrolytic plating, vapor deposition, sputtering, or damascene, and may include inner via holes, through holes, and connection terminals.

[0123] 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) used in electronic devices such as printed circuit boards and lead frames, decorative items, building materials, etc., as well as plating films (electroless copper plating films, electrolytic copper plating films), thin films formed by vapor deposition, sputtering, damascene, etc., and copper used in applications and forms such as grains, needles, fibers, wires, rods, tubes, and plates. In the case of copper wiring through which high-frequency electrical signals flow, it is preferable that the surface of the copper be a smooth surface with an average roughness of 0.1 μm or less. The surface of the copper may be plated with nickel, zinc, chromium, tin, etc., as a pretreatment.

[0124] Furthermore, for example, in the case of use in lead frames during wire bonding mounting, the surface treatment liquid of the present invention is suitable for surface treatment of lead frames with the aim of improving adhesion (tightness) with sealing resin and adhesive used when mounting semiconductor chips on the metal surface during the lead frame fabrication process, the frame metal surface after mounting semiconductor chips (before and after die bonding and pre-baking processes), the frame metal surface after wire bonding mounting, and the frame metal surface during the process up to resin sealing (before and after resin molding and baking processes).

[0125] Furthermore, for example, in the case of use on lead frames when flip-chip mounting, the surface treatment liquid of the present invention is suitable for surface treatment of lead frames with the aim of improving adhesion (tightness) with sealing resin and adhesives used when mounting semiconductor chips, on the metal surface of the lead frame during the lead frame fabrication process, the metal surface of the lead frame after temporarily placing bonding materials (solder, Au plating, Sn plating, etc.), the metal surface of the frame after mounting semiconductor chips (before and after alignment, chip mounting and baking processes), the metal surface of the lead frame after full curing (before and after processes such as reflow heating, thermocompression bonding, ultrasonic, plasma, etc.), and the metal surface of the lead frame during the process up to resin sealing.

[0126] Furthermore, for example, in the case of use in fine wiring substrates with enhanced integration technology for placing semiconductor chips in close proximity, the surface treatment liquid of the present invention is also suitable for surface treatment of copper circuit wiring layers in 2.1-dimensional (2.1D) organic substrates or glass substrates, component embedded substrates (EPS substrates) with semiconductors embedded in the substrate, and coreless substrates, with the aim of improving the adhesion between the copper circuit wiring layer and the insulating material. Furthermore, for example, the metal surface treatment liquid of the present invention is suitable for surface treatment of copper circuit wiring layers with the aim of improving adhesion (tightness) between the copper circuit wiring layer and insulating material, in cases where pattern wiring is incorporated and the upper and lower layers are laser via processed and via-fill plating is performed, or when using a circuit embedded substrate (ETS substrate) using MIS, in which copper pillars formed by plating are used for conductivity between the upper and lower layers and molded resin is used for the insulating layer.

[0127] Furthermore, the carrier-attached copper foil treated with the surface treatment solution of the present invention is an ultrathin electrolytic copper foil used in a printed wiring board that includes a step of forming a circuit by any of the following methods: semi-additive, subtractive, partly additive, or modified semi-additive, and comprises a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer. The surface of the copper may be subjected to at least one pretreatment selected from the group consisting of pickling, roughening, heat-resistant treatment, rust prevention treatment, or chemical conversion treatment.

[0128] (Insulating composition) The coupling agent of the present invention can be incorporated into a resin material or an inorganic material to create an insulating composition. Furthermore, an insulating composition can be obtained by dissolving triazole compound (IV) in an organic solvent or the like and mixing it with a resin material or an inorganic material.

[0129] The content of triazole compound (IV) in the insulating composition is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight. When the content of triazole compound (IV) in the insulating composition is 0.001% by weight or more, a sufficient improvement in adhesion is obtained, and when this concentration exceeds 10% by weight, the improvement in adhesion almost plateaus, so from an economic standpoint, it is preferable to keep the content of triazole compound (IV) at 10% by weight or less. The insulating composition can be prepared by known methods. For example, an insulating composition can be prepared by dissolving a triazole compound (IV) in an organic solvent and mixing it with a solid or liquid resin material. Alternatively, an insulating composition may be prepared by directly adding and mixing a triazole compound (IV) with a liquid resin material.

[0130] The insulating composition of the present invention provides an insulating material with high adhesive strength, and can therefore be suitably used in various electrical and electronic components and electronic devices such as printed circuit boards.

[0131] Incidentally, Japanese Patent Publication No. 2009-19266 describes an invention for forming a silane coupling agent film, characterized by comprising the steps of: applying a liquid containing a silane coupling agent to a metal surface; drying the metal surface to which the liquid has been applied at a temperature of 25 to 150°C for no more than 5 minutes; and washing the dried metal surface with water. Furthermore, the metal surface may be pre-treated by forming an adhesive metal layer, such as tin, using an immersion plating solution. The surface treatment liquid of the present invention can be used as a liquid containing the silane coupling agent described above. The matters described in this patent publication shall be incorporated herein by reference. [Examples]

[0132] The present invention will be specifically described below with reference to examples (synthesis tests, evaluation tests), but the present invention is not limited to these. In the chemical formulas shown below, OEt represents the ethoxy group.

[0133] The triazole and alkylsilane compounds used as raw materials in the synthesis test are as follows: [Triazole compounds] The triazole compound represented by formula (11) below (3,3′-bis(5-amino-1,2,4-triazole)) was synthesized according to the method described in "Chem. Eur. J.", Vol. 18, p. 16742 (2012). The triazole compound represented by formula (12) below (3,3′-methylenebis(5-amino-1,2,4-triazole)) was synthesized according to the method described in "Russ. J. Applied. Chem.", Vol. 82, p. 276 (2009). • The triazole compound represented by the following formula (13) (3,3′-tetramethylenebis(5-amino-1,2,4-triazole)): synthesized in accordance with the method described in U.S. Patent No. 2,744,116. The triazole compound represented by formula (14) below (3,3′-bis(5-methyl-1,2,4-triazole)) was synthesized according to the method described in "Indian J. Chem.", Vol. 44B, p. 568 (2005).

[0134] [ka]

[0135] [Halogenated alkylsilane compounds] • 3-chloropropyltriethoxysilane: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0136] The triazole compounds used in Comparative Example 1 (evaluation test) are as follows: [Triazole compounds] • The triazole compound represented by the following formula (21) (3-amino-5-methyl-1,2,4-triazole): synthesized in accordance with the method described in U.S. Patent No. 4,734,413. ·Triazole compound (3-amino-5-methyl-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole) represented by the following formula (22): Synthesized according to the method described in International Publication No. 2018 / 186476.

[0137] [Chemical formula]

[0138] [Synthesis of triazole compound (I)] The triazole compounds of Examples 1 to 5 below were synthesized.

[0139] [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)] A compound (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)) represented by the following formula (1) was synthesized. <00,00898>A suspension consisting of 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, 16.20 g (47.6 mmol) of a 20% sodium ethoxide ethanol solution was added, the temperature was raised to 100 °C and stirred for 1 hour. Then, after cooling to 70 °C, 11.40 g (47.3 mmol) of 3-chloropropyltriethoxysilane was added and stirred for 1 hour. Subsequently, the temperature was raised to 100 °C and stirred for 16.5 hours. After cooling the reaction solution to 60 °C, the insoluble matter was filtered off, and the filtrate was distilled off under reduced pressure to obtain 15.81 g (46.9 mmol, yield 91.0%) of a brown viscous substance.

[0140] The 1 1H-NMR spectral data of the obtained brown viscous substance was as follows. 1 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). From this 1 1H-NMR spectrum data, the obtained brown paste-like substance was identified as the title triazole compound represented by Chemical Formula (1).

[0141] [Chemical Formula]

[0142] [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)] A compound represented by the following formula (2) (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)) was synthesized. A suspension consisting of 6.08 g (33.8 mol) 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 mol) of a 20% sodium ethoxide ethanol solution was added, and after stirring for 2 hours, 8.30 g (34.5 mol) of 3-chloropropyltriethoxysilane was added and stirred for 30 minutes, and then stirred at 100 °C for 20 hours. After cooling the reaction solution to 70 °C, the insoluble matter was filtered off, and the filtrate was distilled off under reduced pressure to obtain 10.50 g (27.3 mol, yield 80.8%) of a light brown solid.

[0143] The obtained light brown solid 1 1H-NMR spectrum data was 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). this 1 Based on the 1H-NMR spectral data, the obtained light brown solid was identified as the triazole compound shown in the title, represented by chemical formula (2).

[0144] [ka]

[0145] [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)> A compound represented by the following formula (3) (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)) was synthesized. A suspension consisting of 8.20 g (36.9 mol) 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 mol) of 20% sodium ethoxide ethanol solution was added. The temperature was then raised to 100°C and the mixture was stirred for 1 hour. Next, the temperature was reduced to 70°C, and 9.04 g (37.5 mol) of 3-chloropropyltriethoxysilane was added and the mixture was stirred for 1 hour. Subsequently, the temperature was raised to 100°C and the mixture was stirred for 16 hours. After cooling the reaction mixture to 60°C, insoluble matter was filtered off, and the filtrate was removed by reduced pressure distillation to obtain 13.8 g (32.3 mol, yield 87.7%) of a light brown, amber-like substance.

[0146] The obtained light brown amber substance 1The H-NMR spectral data were as follows: 1 H-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). this 1 Based on the 1H-NMR spectral data, the obtained light brown, amber-like substance was identified as the triazole compound shown in the title, represented by chemical formula (3).

[0147] [ka]

[0148] [Example 4] Synthesis of a mixture of 3,3′-bis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 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)> A compound represented by the following formula (4) (a mixture of 3,3′-bis{1-[3-(triethoxysilyl)propyl]-5-amino-1,2,4-triazole}, 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. A suspension consisting of 1.50 g (9.0 mmol) of 3,3′-bis(5-amino-1,2,4-triazole) and 5.60 g of water was mixed with 1.50 g (18.0 mmol) of 48% sodium hydroxide aqueous solution and stirred at room temperature for 30 minutes. The water was then removed by distillation under reduced pressure, followed by the addition of 5.6 g of ethanol and stirring at room temperature for 1 hour. The solid was then filtered, washed with ethanol, and dried to obtain 2.1 g of a white powder. To 2.1 g of the obtained white powder, 30 g of dimethyl sulfoxide was added, 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. Then, the mixture was stirred at 100 °C for 16 hours. After the reaction solution was cooled to room temperature, insoluble matters were filtered off. After the filtrate was distilled off under reduced pressure, 30 g of isopropyl acetate was added, and the mixture was stirred at room temperature for 1 hour. Subsequently, the solid was collected by filtration, washed with isopropyl acetate, and dried to obtain 4.67 g (8.1 mmol, yield 90.0%) of a yellowish-brown powder.

[0149] Of the obtained yellowish-brown powder 1 The 1H-NMR spectral data was as follows. 1 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). From this 1 1H-NMR spectral data, the obtained yellowish-brown powder was identified as the title triazole compound represented by Chemical Formula (4).

[0150] [Chemical formula]

[0151] [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)] A compound represented by the following formula (5) (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)) was synthesized. A suspension consisting of 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, and the mixture was stirred for 1 hour. Next, 4.80 g (20.0 mmol) of 3-chloropropyltriethoxysilane was added, and the mixture was stirred for 30 minutes. Subsequently, the temperature was raised to 100°C and the mixture was stirred for 19 hours. After the reaction mixture was cooled to room temperature, insoluble matter was filtered off, and the filtrate was removed by reduced pressure distillation. Then, 30 g of isopropyl acetate was added, and the mixture was stirred at room temperature for 1 hour. Subsequently, the solid was filtered off, washed with isopropyl acetate, and dried to obtain 3.39 g (9.2 mmol, yield 46.0%) of a light brown powder.

[0152] The obtained light brown powder 1 The H-NMR spectral data were as follows: 1 H-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). this 1 Based on the 1H-NMR spectral data, the obtained light brown powder was identified as the triazole compound shown in the title, represented by chemical formula (5).

[0153] [ka]

[0154] <Adhesion Test 1> The surface treatment solutions prepared in Examples 6-9 and Comparative Examples 2-3 were evaluated for their adhesion as described below.

[0155] [Adhesion evaluation test (i)] (1) Metal Electrolytic copper foil (thickness: 35 μm) was used as the metal. (2) Surface treatment of metals The copper foil was processed according to the following steps a to b. a. Acid cleaning (5% sulfuric acid solution) / 1 minute (room temperature), rinse with water b. Apply the surface treatment solution with a brush and let it dry for 1 minute (at 100°C). (3) Bonding of metal and resin A copper-clad laminate was fabricated by laminating a glass cloth epoxy resin-impregnated prepreg (MEGTRON7 (manufactured by Panasonic)) onto the S-side of a treated copper foil using a pressing process, and then bonding the copper foil and prepreg together. (4) Evaluation of adhesion For this copper-clad laminate, after one reflow heating cycle (peak temperature 260°C, air), a 10 mm wide test specimen was prepared according to "JIS C6481 (1996)" and the peel strength (kN / m) of the copper foil was measured.

[0156] [Example 6] As a coupling agent component, 1 g of the compound represented by formula (1) was added to 99 g of a 4:96 mixture (by weight) of 25% aqueous ammonia and methanol, and the mixture was stirred at room temperature for 1 hour to prepare a surface treatment solution.

[0157] [Examples 7-9] A surface treatment solution was prepared in the same manner as in Example 6, except that the compound represented by formula (2), the compound represented by formula (3), or the compound represented by formula (11) was used instead of the compound represented by formula (1).

[0158] [Comparative Example 1] Adhesion evaluation test (i) was performed on copper foil that had undergone only step (2)a. of adhesion evaluation test (i).

[0159] [Comparative Examples 2-3] A surface treatment solution was prepared in the same manner as in Example 6, except that the compound represented by formula (21) and the compound represented by formula (22) were used instead of the compound represented by formula (1).

[0160] Each of the surface treatment solutions prepared as described above underwent an adhesion evaluation test (i). The test results are shown in Table 1.

[0161] [Table 1]

[0162] The results in Table 1 show that the surface treatment liquid of the present invention (surface treatment liquids of Examples 6-9) has higher peel strength and superior adhesion between metal and resin compared to Comparative Examples 1-3.

[0163] <Adhesion Test 2> The surface treatment solutions prepared in Examples 10-11 and Comparative Examples 5-6 were evaluated for their adhesion as described below.

[0164] [Example 10] As a coupling agent component, 1 g of the compound represented by formula (1) was added to 99 g of a 1:9 mixture (by weight) of 10% aqueous acetate and methanol, and the mixture was stirred at room temperature for 1 hour to prepare a surface treatment solution.

[0165] [Example 11] A surface treatment solution was prepared in the same manner as in Example 10, except that the compound represented by formula (11) was used instead of the compound represented by formula (1).

[0166] [Comparative Example 4] The adhesive evaluation test (i) was performed on copper foil that had undergone only step (2)a. of the adhesive evaluation test (i). Comparative Example 4 is the same as Comparative Example 1.

[0167] [Comparative Examples 5-6] A surface treatment solution was prepared in the same manner as in Example 10, except that the compound represented by formula (21) and the compound represented by formula (22) were used instead of the compound represented by formula (1).

[0168] Each of the surface treatment solutions prepared as described above underwent an adhesion evaluation test (i). The test results are shown in Table 2.

[0169] [Table 2]

[0170] As shown in Table 2, even when a mixture of acetic acid and methanol was used as a solubilizer, the surface treatment solution of the present invention (surface treatment solutions of Examples 10-11) exhibited higher peel strength compared to Comparative Examples 4-6.

[0171] <Adhesion Test 3> The surface treatment solutions prepared in Example 12 and Comparative Example 7 were evaluated for their adhesion as described below.

[0172] [Adhesion evaluation test (ii)] (1) Metal Electrolytic copper foil (thickness: 35 μm) was used as the metal. (2) Surface treatment of metals The copper foil was processed according to the following steps a to b. a. Acid cleaning (5% sulfuric acid solution) / 1 minute (room temperature), rinse with water b. Apply the surface treatment solution with a brush and let it dry for 1 minute (at 100°C). (3) Bonding of metal and resin A copper-clad laminate was fabricated by laminating and pressing a build-up wiring board resin (GX-T31, manufactured by Ajinomoto Fine Techno Co., Ltd.) onto the S-side of the processed copper foil. (4) Evaluation of adhesion For this copper-clad laminate, after one reflow heating cycle (peak temperature 250°C, air), a 10 mm wide test specimen was prepared according to "JIS C6481 (1996)", and the peel strength (kN / m) of the copper foil was measured.

[0173] [Example 12] As a coupling agent component, 1 g of the compound represented by formula (1) was added to 99 g of a 9:90 mixture (by weight) of 11% aqueous acetic acid and methanol, and the mixture was stirred at room temperature for 1 hour to prepare a surface treatment solution.

[0174] [Comparative Example 7] For copper foil that underwent only step (2)a. of the adhesion evaluation test (ii), the adhesion evaluation test (ii) was performed.

[0175] Each of the surface treatment solutions prepared as described above underwent an adhesion evaluation test (ii). The test results are shown in Table 3.

[0176] [Table 3]

[0177] The results in Table 3 show that the surface treatment solution of the present invention (surface treatment solution of Example 12) has higher peel strength and superior adhesion between metal and resin compared to Comparative Example 7.

[0178] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2022-054330, filed on 29 March 2022, the contents of which are incorporated herein by reference. [Industrial applicability]

[0179] The triazole compound of the present invention can be used as a coupling agent that combines the characteristic metal corrosion prevention function of triazole compounds with the function of curing epoxy resins and urethane resins. Therefore, it is expected to be used in composite materials such as printed circuit boards, which are manufactured by combining many different types of materials. Furthermore, according to the present invention, the adhesion (bonding) of metals, inorganic materials, and resin materials can be improved, so the surface of the substrate can be kept smooth without roughening. Therefore, the present invention can greatly contribute to the miniaturization, thinning, high-frequency and high-density realization of multilayer printed circuit boards, and thus has great industrial applicability.

Claims

1. A triazole compound represented by the following chemical formula (I). 【Chemistry 1】 (In formula (I), R １ and R ２ This represents an amino group. R ３ and R ４ are the same or different and each represents a hydrogen atom or a group represented by -(CH ２ ) ｍ -Si(OR) ３ where R represents a methyl group or an ethyl group and m represents an integer of 1 to 18, provided that the case where R ３ and R ４ are simultaneously hydrogen atoms is excluded. X is -NH- or -(CH ２ ) ｎ The base indicated by the dash is represented, where n is an integer from 0 to 12.

2. A method for synthesizing a triazole compound according to claim 1, comprising reacting a triazole compound represented by the following chemical formula (II) with a compound represented by the following chemical formula (III). 【Chemistry 2】 (In formula (II), R １ , R ２ (And X is the same as described above.) 【Transformation 3】 (In formula (III), R and m are as described above. Haal 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). 【Chemistry 4】 (In formula (IV), R １ and R ２ This represents an amino group. R ５ and R ６ These are identical or different hydrogen atoms or -(CH ２ ) ｍ -Si (OR) ３－ｐ (OH) ｐ The group is represented by , where R represents a methyl group or an ethyl group, m represents an integer from 1 to 18, and p represents an integer from 0 to 3. However, at least one of R5 and R6 is a group represented by -(CH2)m-Si(OR)3-p(OH)p. X is -NH- or -(CH ２ ) ｎ The base indicated by the dash is represented, where n is an integer from 0 to 12.

4. A surface treatment solution containing a triazole compound represented by the following chemical formula (IV). 【Transformation 5】 (In formula (IV), R １ and R ２ This represents an amino group. R ５ and R ６ These are identical or different hydrogen atoms or -(CH ２ ) ｍ -Si (OR) ３－ｐ (OH) ｐ The group is represented by , where R represents a methyl group or an ethyl group, m represents an integer from 1 to 18, and p represents an integer from 0 to 3. However, at least one of R5 and R6 is a group represented by -(CH2)m-Si(OR)3-p(OH)p. X is -NH- or -(CH ２ ) ｎ The base indicated by the dash is represented, where n is an integer from 0 to 12.

5. A surface treatment liquid according to claim 4, used for treating at least one surface selected from the group consisting of metals, inorganic materials, and resin materials.

6. A surface treatment liquid according to claim 4, used for bonding two materials selected from the group consisting of metals, inorganic materials, and resin materials.

7. The surface treatment liquid according to claim 5 or 6, wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof.

8. A surface treatment method comprising bringing the surface treatment liquid described in claim 4 into contact with at least one surface selected from the group consisting of metals, inorganic materials, and resin materials.

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

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

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

12. The surface treatment method according to claim 10 or claim 11, wherein the surface treatment liquid is brought into contact with the surface of copper or a copper alloy, and then an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the surface of the copper or copper alloy.

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

14. A method for bonding metal and resin materials, A method for bonding a metal and a resin material, comprising bringing the surface treatment liquid described in claim 4 into contact with at least one of a metal and a resin material to form a chemical conversion film on the at least one, and bonding the metal and the resin material to each other via the chemical conversion film.

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

16. A semiconductor wafer in which two materials selected from the group consisting of metals, inorganic materials, and resin materials are bonded together via a chemical conversion film formed with the surface treatment liquid described in claim 4.

17. An insulating composition containing the coupling agent described in claim 3 and a resin material or an inorganic material.

18. An insulating material containing the insulating composition described in claim 17.

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

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

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