Compound-attached metal, and compound

Abstract

The present invention addresses the problem of providing a compound-attached metal that is unlikely to corrode. A compound-attached metal according to the present invention includes a metal and at least one specific compound that is attached to the metal and is selected from the group consisting of compounds represented by formula (1A) and compounds represented by formula (1B).

Description

Compound metals, compounds

[0001] The present invention relates to a compound-bearing metal and a compound.

[0002] Metal materials are used in a variety of applications, including touch panels, solar cells, and electroluminescence (EL) elements. For example, they are used in the above applications as conductive materials, such as metal films and conductive wiring (thin wire-like wiring that exhibits conductivity), and the environments in which they are used and the performance requirements are becoming more diverse. Metals may corrode depending on the environment in which they are used, and may no longer be able to perform their desired functions. For example, corrosion of metals used as conductive materials can cause defects such as increased resistance, discoloration, and migration, so it is necessary to impart corrosion-inhibiting properties to metal materials.

[0003] As an example of such conductive wiring, Patent Document 1 describes a transparent electrode including a conductive layer and an intermediate layer provided adjacent to the conductive layer, wherein the transparent electrode has a light transmittance of 50% or more at a wavelength of 550 nm and a sheet resistance of 20 Ω / □ or less, the intermediate layer contains an organic compound having both a covalent bonding moiety capable of covalently bonding with silver and a coordinate bonding moiety capable of coordinate bonding with silver within the molecule, and the conductive layer contains silver as a main component.

[0004] Patent No. 6241193

[0005] The present inventors have investigated metal materials using the organic compounds described in the above documents as corrosion inhibitors for metals, and have found that the corrosion inhibition ability is insufficient and there is room for further improvement.

[0006] Therefore, an object of the present invention is to provide a metal with a compound that is resistant to corrosion. Another object of the present invention is to provide a compound that can inhibit metal corrosion.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A compound-attached metal comprising a metal and, attached to the metal, at least one specific compound selected from the group consisting of a compound represented by formula (1A) described later and a compound represented by formula (1B) described later. [2] The compound-attached metal according to [1], wherein r is an integer of 1 or more and s is an integer of 2 or more. [3] E １ ~E ６ [4] The compound-containing metal according to [1] or [2], wherein X in the formula (1A) is a single bond or —NH—. １ ~X ４ At least one of １ is a group represented by the above formula (2), which is a hydroxyl group or a sulfonamide group; １ and Z ２ At least one of １ is a group represented by formula (2) above, which is a hydroxyl group or a sulfonamide group. [5] The compound-attached metal according to any one of [1] to [4], wherein the specific compound has an aliphatic hydrocarbon group content of 20.0% or less. [6] The compound-attached metal according to any one of [1] to [5], wherein the specific compound has a heteroatom content of 15.0% or more. [7] The compound-attached metal according to any one of [1] to [6], wherein the specific compound has a molecular weight of 700.0 or more. [8] The compound-attached metal according to any one of [1] to [7], wherein the specific compound has an aliphatic hydrocarbon group content of 10.0% or less, a heteroatom content of 20.0% or more, and a molecular weight of 700.0 or more. [9] The compound-attached metal according to any one of [1] to [8], wherein the metal is copper, silver, or iron.

[10] The compound-containing metal according to any one of [1] to [9], wherein the metal is copper or silver.

[11] A compound represented by the formula (1A) or the formula (1B) described later.

[12] E １ ~E ６

[13] The compound according to

[11] , wherein Q and Y are a single bond or —NH—. １are each independently a hydroxyl group or a sulfonamide group.

[14] The compound according to any one of

[11] to

[13] , wherein p is 0.

[0009] According to the present invention, it is possible to provide a metal with a compound that is resistant to corrosion. Also, according to the present invention, it is possible to provide a compound that can inhibit the corrosion of metal.

[0010] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0012] In this specification, the bonding direction of a divalent group (e.g., -CO-O-, etc.) is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "X-Y-Z," the compound may be either "X-O-CO-Z" or "X-CO-O-Z." In this specification, unless otherwise specified, * in a formula represents a bonding position.

[0013] In this specification, when a formula showing a chemical structure contains a plurality of identical symbols indicating the type or number of groups, the contents of the plurality of identical symbols are independent of each other, and the contents of the plurality of identical symbols may be the same or different, unless otherwise specified. In this specification, when a formula showing a chemical structure contains a plurality of groups of the same type (e.g., alkyl groups, etc.), the specific contents of the plurality of groups of the same type are independent of each other, and the specific contents of the plurality of groups of the same type may be the same or different, unless otherwise specified.

[0014] In this specification, the term "aliphatic hydrocarbon group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from an aliphatic hydrocarbon. In this specification, the term "aromatic ring group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic ring. In this specification, the term "aromatic hydrocarbon ring group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic hydrocarbon ring, and in this specification, the term "aromatic heterocyclic group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic heterocycle. In this specification, the term "aliphatic ring group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from a ring corresponding to an aliphatic ring (e.g., an aliphatic hydrocarbon ring and an aliphatic heterocycle). In this specification, the term "x-valent group" refers to a group obtained by removing x hydrogen atoms from the structure constituting the group. For example, an x-valent aromatic ring group is a group obtained by removing x hydrogen atoms from an aromatic ring that constitutes the aromatic ring group.

[0015] Furthermore, in the present specification, when it is stated that a compound "may have a substituent", the type, position, and number of the substituent are not particularly limited. The number of substituents may be, for example, one or two or more, and is often one to three. Examples of the substituent include monovalent non-metallic atomic groups excluding hydrogen atoms, which can be selected, for example, from the following substituent group Y. In the present specification, examples of halogen atoms include chlorine atoms, fluorine atoms, bromine atoms, and iodine atoms.

[0016] Substituent group Y: halogen atoms (such as -F, -Br, -Cl, and -I), hydroxyl groups, amino groups, carboxylic acid groups and their conjugate base groups, carboxylic anhydride groups, cyanate ester groups, unsaturated polymerizable groups, epoxy groups, oxetanyl groups, aziridinyl groups, thiol groups, isocyanate groups, thioisocyanate groups, aldehyde groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, N-alkylamino groups, N,N-dialkylamino groups, N-arylamino groups, N,N-diarylamino groups, N-alkyl-N-aryl an arylamino group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N,N-dialkylcarbamoyloxy group, an N,N-diarylcarbamoyloxy group, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group, an acylthio group, an acylamino group, an N-alkylacylamino group, an N-arylacylamino group, a ureido group, an N'-alkylureido group, an N',N'-dialkylureido group, an N'-arylureido group, an N' , N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N',N'-dialkyl-N-alkylureido group, N',N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N',N'-diaryl-N-alkylureido group, N',N'-diaryl-N-arylureido group, N'-aryl an alkyl-N'-aryl-N-alkylureido group, an N'-alkyl-N'-aryl-N-arylureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, an N-aryl-N-aryloxycarbonylamino group, a formyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyl group (—SO, ３ H) and their conjugate base groups, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N,N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N,N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and their conjugate base groups, N-alkylsulfonylsulfamoyl group (—SO ２ NHSO ２ (alkyl)) and its conjugate base group, N-arylsulfonylsulfamoyl group (—SO ２ NHSO ２ (aryl)) and its conjugate base group, N-alkylsulfonylcarbamoyl group (—CONHSO ２ (alkyl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (-CONHSO ２ (aryl)) and its conjugate base group, alkoxysilyl group (—Si(Oalkyl) ３ ), an aryloxysilyl group (—Si(Oaryl) ３ ), hydroxysilyl group (—Si(OH) ３ ) and its conjugate base group, phosphono group (-PO ３ H ２ ) and its conjugate base group, dialkylphosphono group (-PO ３ (alkyl) ２ ), diarylphosphono group (-PO ３ (aryl) ２ ), alkylarylphosphono group (—PO ３ (alkyl)(aryl)), monoalkylphosphono group (-PO ３H(alkyl)) and its conjugate base group, monoarylphosphono group (-PO ３ H(aryl)) and its conjugate base group, phosphonooxy group (-OPO ３ H ２ ) and its conjugate base group, dialkylphosphonooxy group (-OPO ３ (alkyl) ２ ), diarylphosphonooxy group (—OPO ３ (aryl) ２ ), alkylarylphosphonooxy group (—OPO ３ (alkyl)(aryl)), monoalkylphosphonooxy group (-OPO ３ H(alkyl)) and its conjugate base group, monoarylphosphonooxy group (-OPO ３ H(aryl)) and its conjugate base group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group, and alkyl group. If possible, these substituents may or may not be bonded to each other or to the group they substitute to form a ring.

[0017] [Compound-Attached Metal] The compound-attached metal of the present invention is described in detail below. The compound-attached metal of the present invention comprises a metal and, attached to the metal, at least one specific compound selected from the group consisting of a compound represented by formula (1A) described below and a compound represented by formula (1B) described below.

[0018] Although the reason why the compound-attached metal having the above-described structure can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The specific compound has a predetermined specific functional group that interacts with the metal. Furthermore, the specific compound has a predetermined triazine skeleton and one or more aromatic rings, and has numerous hydrogen bonding sites and π-π interaction sites. Due to the above structure, the specific compound easily adheres to the metal surface and is capable of stacking with other specific compounds. As a result, it is speculated that a dense corrosion-preventing film of the specific compound is formed on the metal, thereby inhibiting metal corrosion. Hereinafter, the fact that corrosion of the compound-attached metal is better inhibited will also be simply referred to as "the effect of the present invention being better."

[0019] [Specific Compound] The compound-attached metal contains at least one specific compound selected from the group consisting of compounds represented by formula (1A) and compounds represented by formula (1B).

[0020]

[0021] In formula (1A) and formula (1B), E １ ~E ６ each independently represents a single bond, —O—, —S—, —NH—, or —NR—. R represents a substituent. B １ , B ２ , B ３ , and B ４ represent k+1-valent, l+1-valent, m+1-valent, and n+1-valent organic groups, respectively. １ , B ２ , B ３ , and B ４ At least one of B represents a k+1-valent, l+1-valent, m+1-valent, or n+1-valent aromatic ring group, １ and B ２At least one of the groups represents a (k+1)-valent or (l+1)-valent aromatic ring group. k, l, m, and n each independently represent an integer of 0 or greater. However, in formula (1A), the sum of k, l, m, and n is 2 or greater, and in formula (1B), the sum of k and l is 2 or greater. X １ ~X ４ and Z １ ~Z ２ Each independently represents a group represented by formula (2). Each L independently represents a divalent organic group. r represents an integer of 0 or more. T represents an s-valent organic group. s represents an integer of 1 or more. In formula (2), * represents a bonding position. D １ each independently represents a single bond or a divalent linking group. １ each independently represents an aromatic ring group which may have a substituent, or an aliphatic ring group which may have a substituent. １ each independently represents a specific functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxylic acid group, a sulfonic acid group, an amide group, a sulfonamide group, and an alkoxy group. Each p independently represents an integer of 0 or more. Each q independently represents an integer of 0 to 2.

[0022] In formula (1A) and formula (1B), E １ ~E ６ each independently represents a single bond, -O-, -S-, -NH-, or -NR-. R represents a substituent. Examples of the substituent represented by R include substituents selected from the above-mentioned substituent group Y, and a linear or branched alkyl group having 1 to 5 carbon atoms is preferred. When there are multiple Rs, the multiple Rs may be the same or different. E １ ~E ６ As the alkyl group, a single bond, —S—, or —NH— is preferred, a single bond or —NH— is more preferred, and —NH— is even more preferred, in terms of achieving better effects of the present invention.

[0023] E １ , E ２ , E ３ , E ４ , E ５ , E ６If there are multiple E １ , E ２ , E ３ , E ４ , E ５ , or E ６ may be the same or different from each other.

[0024] In formula (1A) and formula (1B), B １ , B ２ , B ３ , and B ４ represent k+1, l+1, m+1, and n+1 valent organic groups, respectively. １ ~B ４Examples of organic groups represented by the formula (I) include j-valent hydrocarbon groups having 1 to 20 carbon atoms and optionally having a heteroatom, which may have a substituent. Here, j refers to k+1, l+1, m+1, or n+1. Examples of the hydrocarbon groups having 1 to 20 carbon atoms and optionally having a heteroatom include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, aliphatic heterocyclic groups having 3 to 20 carbon atoms, and aromatic ring groups having 3 to 20 carbon atoms. Examples of aliphatic hydrocarbons constituting the aliphatic hydrocarbon groups having 1 to 20 carbon atoms (preferably 1 to 7 carbon atoms) include linear or branched aliphatic hydrocarbons such as methane, ethane, propane, butane, pentane, hexane, and heptane, as well as aliphatic hydrocarbon rings such as a cyclohexane ring, a cycloheptane ring, a norbornane ring, and an adamantane ring. Examples of the aliphatic heterocycle constituting the aliphatic heterocyclic group having 3 to 20 carbon atoms (preferably 3 to 10 carbon atoms) include a piperidine ring, a tetrahydropyran ring, and a piperazine ring. Examples of the aromatic ring constituting the aromatic ring group having 3 to 20 carbon atoms include an aromatic hydrocarbon ring having 6 to 20 carbon atoms and an aromatic heterocycle having 3 to 20 carbon atoms. Examples of the aromatic hydrocarbon ring having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the aromatic heterocycle having 3 to 20 carbon atoms (preferably 3 to 10 carbon atoms) include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, a carbazole ring, an indole ring, and a benzothiazole ring. Examples of the substituent that the hydrocarbon having 1 to 20 carbon atoms and optionally having a heteroatom may have include substituents selected from the above-mentioned group Y of substituents other than the specific functional groups, and a linear or branched alkyl group having 1 to 5 carbon atoms is preferred. １ ~B ４ The j-valent organic group represented by the formula (1A) is preferably a j-valent aromatic ring group having 3 to 10 carbon atoms which may have a substituent, or a j-valent aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and more preferably a j-valent benzene ring group which may have a substituent. １ , B ２ , B３ , and B ４ At least one of B represents an aromatic ring group having a valence of k+1, l+1, m+1, or n+1, which may have a substituent; １ and B ２ At least one of the groups represents an optionally substituted aromatic ring group having a valence of k+1 or 1+1.

[0025] B １ , B ２ , and B ３ If there are multiple B １ , B ２ , or B ３ may be the same or different from each other.

[0026] In formula (1A) and formula (1B), k, l, m, and n each independently represent an integer of 0 or greater. k, l, m, and n are preferably integers of 0 to 5, more preferably integers of 1 to 5, and even more preferably 1 or 2. However, in formula (1A), the total of k, l, m, and n is 2 or greater, preferably an integer of 2 to 12, and more preferably an integer of 4 to 8. In other words, the value of k + l + r × m + n is 2 or greater, preferably 2 to 12, and more preferably 4 to 8. Furthermore, in formula (1B), the total of k and l is 2 or greater, preferably an integer of 2 to 12, and more preferably an integer of 4 to 8. In other words, the value of s × k + s × l is 2 or greater, preferably 2 to 12, and more preferably 4 to 8.

[0027] When there are multiple k's, the multiple k's may be the same or different, when there are multiple l's, the multiple l's may be the same or different, and when there are multiple m's, the multiple m's may be the same or different.

[0028] In formula (1A), L represents a divalent organic group. Examples of the organic group include a divalent aromatic ring group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, a divalent aliphatic heterocyclic group which may have a substituent, -N(R Ｎ)-, -CO-, and groups formed by combining these groups. ２ and at least one selected from the group consisting of R Ｎ represents an organic group. Ｎ Examples of the organic group represented by the formula (I) include linear or branched alkyl groups having 1 to 5 carbon atoms.

[0029] The aromatic ring group may be either monocyclic or polycyclic, with monocyclic being preferred. Examples of divalent aromatic ring groups include groups in which two hydrogen atoms have been removed from an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon rings having 6 to 20 carbon atoms and aromatic heterocyclic rings having 3 to 20 carbon atoms. Examples of aromatic hydrocarbon rings having 6 to 20 carbon atoms include monocyclic aromatic rings such as a benzene ring; and polycyclic aromatic rings such as a naphthalene ring, an anthracene ring, and a fluorene ring. Examples of aromatic heterocyclic rings having 3 to 20 carbon atoms include monocyclic aromatic rings such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, and a thiazole ring; and polycyclic aromatic rings such as a benzothiazole ring, a carbazole ring, and an indole ring. As the divalent aromatic ring group, a divalent aromatic hydrocarbon ring group having 6 to 20 carbon atoms is preferable, a divalent benzene ring group, a divalent naphthalene ring group, or a divalent fluorene ring group is more preferable, and a divalent benzene ring group (phenylene group) is even more preferable.

[0030] The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 1 to 3 carbon atoms. Examples of the divalent aliphatic hydrocarbon group include linear or branched alkylene groups having 1 to 12 carbon atoms, specifically methylene, ethylene, propylene, butylene, pentylene, hexylene, methylhexylene, and heptylene. Examples of the divalent aliphatic hydrocarbon group include divalent aliphatic hydrocarbon ring groups. Examples of the divalent aliphatic hydrocarbon ring group include groups in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring. The aliphatic hydrocarbon ring may be either monocyclic or polycyclic, and examples thereof include a cyclohexane ring, a cycloheptane ring, a norbornane ring, and an adamantane ring.

[0031] The divalent aliphatic heterocyclic group may be either monocyclic or polycyclic. Examples of the divalent aliphatic heterocyclic group include groups in which two hydrogen atoms have been removed from an aliphatic heterocycle. Examples of the aliphatic heterocycle include a piperazine ring, a tetrahydrofuran ring, and a piperidine ring.

[0032] Examples of the substituent that the aromatic ring group, the aliphatic hydrocarbon group, and the aliphatic heterocyclic group may have include groups selected from the above-mentioned substituent group Y other than the specific functional groups, and a linear or branched alkyl group having 1 to 5 carbon atoms is preferred.

[0033] The group formed by combining the groups exemplified as the organic group represented by L may be a group formed by combining two or more types of groups, or may be a group in which two or more groups of the same type (e.g., aromatic ring groups) are linked via a single bond.

[0034] L is E ３ and a group represented by E ４It is preferable that the atom bonded to the group represented by the formula (I) is a carbon atom. The carbon atom may be a ring atom. L is preferably a group containing at least one group selected from the group consisting of a divalent aromatic ring group which may have a substituent, a divalent aliphatic ring group which may have a substituent, and a linear or branched alkylene group, and more preferably a group containing a divalent aromatic ring group which may have a substituent. Among them, L is preferably *-Ar-*, *-Cy-*, *-Ar-(L １ -Ar) ｎｌ -*, *-Ar-L １ -Ar-Ar-L １ -Ar-*, *-Ar-Ar-*, *-Ar-Ar-Ar-*, *-L １ -Cy-L １ -* or *-Cy-L １ -Cy-* is preferred, and *-Ar-* and *-Ar-(L １ -Ar) ｎｌ -*, *-Ar-L １ -Ar-Ar-L １ -Ar-* or *-Ar-Ar-* is more preferred. Ar's each independently represent a divalent aromatic ring group which may have a substituent, preferably a divalent aromatic hydrocarbon ring group having 6 to 20 carbon atoms which may have a substituent, and more preferably a phenylene group which may have a substituent. L １ each independently represents —O—, —NH—, —S—, or —SO ２ -, -N(R Ｎ )-, -C(=O)-, or a linear or branched alkylene group having 1 to 3 carbon atoms; ２ -, or a linear or branched alkylene group having 1 to 3 carbon atoms is preferred. nl represents an integer of 1 to 5, preferably an integer of 1 to 3. Each Cy independently represents a divalent aliphatic hydrocarbon ring group or a divalent aliphatic heterocyclic group which may have a substituent, preferably a divalent aliphatic hydrocarbon group which may have a substituent, more preferably a divalent cyclohexane ring group which may have a substituent. * represents a bonding position.

[0035] When a plurality of L's are present, the plurality of L's may be the same or different.

[0036] In formula (1A), r represents an integer of 0 or more. r is preferably an integer of 1 or more. The upper limit is preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less.

[0037] In formula (1B), T represents an s-valent organic group. Examples of the organic group include an aromatic ring group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, -N(R Ｎ )-, -CO-, and groups formed by combining these groups. ２ and at least one selected from the group consisting of R Ｎ is as described above.

[0038] The aromatic ring group may be either monocyclic or polycyclic. Examples of the aromatic ring constituting the aromatic ring group include the aromatic rings exemplified as the aromatic ring constituting the aromatic ring group represented by L. Among these, the aromatic ring group is preferably an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, more preferably a benzene ring group or a naphthalene ring group, and even more preferably a benzene ring group. When T is an s-valent aromatic ring group, examples include groups in which s hydrogen atoms have been removed from the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle.

[0039] Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups having 1 to 12 carbon atoms and aliphatic hydrocarbon ring groups having 3 to 12 carbon atoms, and linear or branched aliphatic hydrocarbon groups having 1 to 6 carbon atoms are preferred.

[0040] The aliphatic heterocyclic group may be either monocyclic or polycyclic. Examples of the aliphatic heterocyclic ring constituting the aliphatic heterocyclic group include the aliphatic heterocycles exemplified as the aliphatic heterocycle constituting the aliphatic heterocyclic group represented by L. When T is an s-valent aliphatic heterocyclic group, examples include groups in which s hydrogen atoms have been removed from the above-mentioned aliphatic heterocycle.

[0041] Examples of the substituent that the aromatic ring group, the aliphatic hydrocarbon group, and the aliphatic heterocyclic group may have include groups selected from the above-mentioned substituent group Y other than the specific functional groups, and the specific functional groups described below or linear or branched alkyl groups having 1 to 5 carbon atoms are preferred.

[0042] The group formed by combining the groups exemplified as the organic group represented by T may be a group formed by combining two or more types of groups, or may be a group in which two or more groups of the same type (e.g., aromatic ring groups) are linked via a single bond.

[0043] T is E ３ is a group other than a single bond, E ３ It is preferable that the atom bonded to the group represented by the formula (I) is a carbon atom. The carbon atom may be a ring atom. ３ is a single bond, E ３ It is preferable that the atom bonded to the group represented by the formula: is a nitrogen atom.

[0044] T preferably contains at least one group selected from the group consisting of an aromatic ring group which may have a substituent, and a linear or branched aliphatic hydrocarbon group. T is preferably an s-valent aromatic hydrocarbon ring group having 6 to 20 carbon atoms which may have a substituent, and more preferably an s-valent benzene ring group which may have a substituent. T also preferably contains -N<, -NH-, -N(R Ｎ A group formed by combining at least one group selected from the group consisting of -, -O-, and -CO- with an aliphatic hydrocarbon group is also preferred. T is also preferably *-Ar-*, *-Cy-*, *-Ar-(L １ -Ar) ｎｌ -*, *-Ar-L １ -Ar-Ar-L １ -Ar-*, *-Ar-Ar-*, *-Ar-Ar-Ar-*, *-L １ -Cy-L １ -* or *-Cy-L １ -Cy-* is also preferred. １ , nl, and Cy are as described above.

[0045] Examples of the compound represented by formula (1B) include a compound represented by formula (1B-1) and a compound represented by formula (1B-2).

[0046]

[0047] In formula (1B-1), W １ each independently represents a group represented by formula (W). １ ~E ３ , B １ , B ２ , Z １ , Z ２ , k, and l are the same as the respective groups in formula (1B). * represents the bonding position.

[0048] In formula (1B-1), L Ｂ１ each independently represents a single bond or a divalent organic group. Examples of the divalent organic group include the groups exemplified as the divalent organic group represented by L above, and is preferably a linear or branched alkylene group having 1 to 12 carbon atoms, more preferably a linear or branched alkylene group having 1 to 4 carbon atoms.

[0049] In formula (1B-1), L Ｂ２ each independently represents a divalent organic group. Examples of the divalent organic group include the groups exemplified as the divalent organic group represented by L above, and are preferably linear or branched alkylene groups having 1 to 12 carbon atoms, more preferably linear or branched alkylene groups having 1 to 4 carbon atoms.

[0050] In formula (1B-1), b1 represents an integer of 0 to 3, and is preferably 0 or 1.

[0051] Multiple Ws １ may be the same or different, and multiple L Ｂ１ may be the same or different. Ｂ２ If there are multiple L Ｂ２ may be the same or different from each other.

[0052] In formula (1B-2), W １each independently represents a group represented by formula (W), where formula (W) is as defined above.

[0053] In formula (1B-2), L Ｂ３ each independently represents a single bond or a divalent organic group. Examples of the divalent organic group include the groups exemplified as the divalent organic group represented by L above, and include a divalent aliphatic hydrocarbon group, or a combination of a divalent aliphatic hydrocarbon group and —N(R Ｎ )-, -CO-, -O-, -NH-, -S-, and -SO ２ and at least one selected from the group consisting of - are preferred. Ｂ３ Among them, *-Al-L Ｂ４ -Al-* or *-Al-* is preferred. Each Al independently represents a linear or branched alkylene group having 1 to 12 carbon atoms, and a linear or branched alkylene group having 1 to 4 carbon atoms is preferred. Ｂ４ is -N(R Ｎ )-, -CO-, -O-, -NH-, -S-, -SO ２ - or a group formed by combining these, and -CO-, -O- or a group formed by combining these is more preferred. * indicates the bonding position.

[0054] In formula (1B-2), R Ｂ each independently represents a hydrogen atom or a substituent. Examples of the substituent include those selected from the above-mentioned substituent group Y, and a linear or branched alkyl group having 1 to 5 carbon atoms is preferred.

[0055] In formula (1B-2), b2 represents 3 or 4, with 3 being preferred.

[0056] Multiple Ws １ may be the same or different, and multiple L Ｂ２ may be the same or different. Ｂ If there are multiple R Ｂ may be the same or different from each other.

[0057] In formula (1B), s represents an integer of 1 or greater. s is preferably an integer of 2 or greater, and more preferably an integer of 3 or greater. The upper limit of s is preferably 12 or less, and more preferably 6 or less.

[0058] In formula (1A) and formula (1B), X １ ~X ４ and Z １ ~Z ２ each independently represents a group represented by formula (2).

[0059]

[0060] In formula (2), * represents a bonding position.

[0061] In formula (2), D １ each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include —O—, —S—, —CO—, and —NR Ｎ -, -SO ２ -, an alkylene group, and a group formed by a combination thereof. Ｎ As the alkylene group, a linear or branched alkylene group having 1 to 8 carbon atoms is preferred. １ is preferably a group consisting of a combination of groups selected from the group consisting of —O—, —CO—, and alkylene groups, or a single bond, and Ａ -Alkylene group -O-CO-* Ｂ , * Ａ -CO-O-alkylene group-* Ｂ , * Ａ -O-alkylene group -O-* Ｂ , * Ａ -CO-O-alkylene group -O-CO-* Ｂ , * Ａ —CO—O-alkylene group —O—* Ｂ , or * Ａ -O-alkylene group -O-CO-* Ｂ is more preferable. Ａ A １ is the binding position opposite to * Ｂ A １ This is the bonding position with

[0062] In formula (2), A １ each independently represents an aromatic ring group which may have a substituent, or an aliphatic ring group which may have a substituent.

[0063] The aromatic ring group may be either a monocyclic or polycyclic ring. The number of ring members in the aromatic ring is preferably 5 to 20, more preferably 5 to 16, and even more preferably 5 to 10. The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The number of heteroatoms in the aromatic heterocyclic group is preferably 1 to 5. Examples of heteroatoms include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a nitrogen atom, a sulfur atom, or an oxygen atom being preferred. Examples of the aromatic ring group include a benzene ring group, a naphthalene ring group, an anthracene ring group, a benzothiazole ring group, a carbazole ring group, and an indole ring group.

[0064] The aliphatic cyclic group may be either monocyclic or polycyclic. The number of ring members in the aliphatic cyclic group is preferably 5 to 20, more preferably 5 to 16, and even more preferably 5 to 10. The aliphatic cyclic group may be either an aliphatic hydrocarbon cyclic group or an aliphatic heterocyclic group. Examples of the aliphatic cyclic group include a cyclohexane cyclic group, a cycloheptane cyclic group, a norbornane cyclic group, and an adamantane cyclic group.

[0065] In formula (2), Q and Y １ are each independently a hydroxyl group (—OH), an amino group (—N(R Ｅ ) ２ ), carboxylic acid group (—COOH), sulfonic acid group (—SO ３ H ２ ), an amide group (-CONH ２ ), sulfonamide group (—SO ２ NH ２ ), and an alkoxy group (—OR Ａ R represents a specific functional group selected from the group consisting of Ｅ R each independently represents a hydrogen atom or an alkyl group. Ａrepresents an alkyl group (preferably having 1 to 6 carbon atoms). The specific functional group is a group that interacts with a metal, and the presence of the specific functional group enables the specific compound to adhere firmly to the metal surface. Examples of the interaction include a coordinate bond, a covalent bond, and an acid-base interaction, and the specific functional group is typically a coordinate bond. As the specific functional group, a hydroxyl group or a sulfonamide group is preferred in terms of achieving better effects of the present invention.

[0066] In formula (2), p represents an integer of 0 or more. p is preferably an integer of 0 to 5, more preferably 0 or 1, and even more preferably 0. When p is 0, X １ ~X ４ or Z １ ~Z ２ But Y １ represents a specific functional group represented by the formula:

[0067] In formula (2), q represents an integer of 0 to 2. q is preferably 0 or 1.

[0068] A １ , D １ , Q, Y １ , p and , q are each, if there are multiple, A １ , D １ , Q, Y １ , p, or q may be the same or different from each other.

[0069] In order to achieve the effects of the present invention more effectively, in formula (1A), X １ ~X ４ At least one of １ is preferably a group represented by formula (2) in which X is a hydroxyl group or a sulfonamide group, １ ~X ４ But Y １ is more preferably a group represented by formula (2) in which X is a hydroxyl group or a sulfonamide group. １ ~X ４ is Q and Y １ In addition, in terms of the effects of the present invention being more excellent, it is also preferable that the group represented by formula (2) is a group represented by formula (1B) in which at least one of Z １ and Z ２At least one of １ is preferably a group represented by formula (2) in which R is a hydroxyl group or a sulfonamide group.

[0070] X １ , X ２ , X ３ , X ４ , Z １ , and Z ２ If there are multiple Xs, １ , X ２ , X ３ , X ４ , Z １ , or Z ２ may be the same or different from each other.

[0071] The specific compound has low light absorption in the visible light region, and coloring of the compound-attached metal can be suppressed. １ ~B ４ When the groups represented by L and T contain a divalent conjugated group, the number of π electrons contained in the divalent conjugated group is preferably 13 or less. Examples of the divalent conjugated group include aromatic ring groups, alkenylene groups, alkynylene groups, and divalent conjugated groups formed by linking these groups. Specifically, for example, the number of π electrons of a phenylene group is 6, and the number of π electrons of a divalent conjugated group represented by -Ph-CH=CH-Ph- (Ph represents a phenylene group) is 14.

[0072] The content of the aliphatic hydrocarbon group in the specific compound is preferably 30.0% or less, more preferably 20.0% or less, and even more preferably 10.0% or less, in terms of achieving better effects of the present invention. The lower limit may be 0%. The content of the aliphatic hydrocarbon group is the percentage of the total atomic weight of all atoms constituting the aliphatic hydrocarbon group in the specific compound relative to the molecular weight of the specific compound. The aliphatic hydrocarbon group is an aliphatic group consisting of carbon atoms and hydrogen atoms, containing at least one carbon atom and one hydrogen atom. The carbon atom in the aliphatic hydrocarbon group may be primary, secondary, tertiary, or quaternary. The aliphatic hydrocarbon group may be a monovalent group (e.g., a methyl group, an ethyl group, a t-butyl group, etc.) or a divalent or higher valent group (e.g., -CH ２ -, >CH-CH２ -, and >CH-CH<).

[0073] The heteroatom content of the specific compound is preferably 15.0% or more, more preferably 20.0% or more, even more preferably 25.0% or more, and particularly preferably 35.0% or more, in order to obtain better effects of the present invention. The upper limit is preferably 65.0% or less, more preferably 55.0% or less. The heteroatom content is the percentage of the total atomic weight of all heteroatoms contained in the specific compound relative to the molecular weight of the specific compound.

[0074] The molecular weight of the specific compound is preferably 350.0 or more, more preferably 700.0 or more, and more preferably 1000.0 or more, in terms of achieving better effects of the present invention. The upper limit is preferably 50000.0 or less, and more preferably 10000.0 or less.

[0075] Specific examples of the compound represented by formula (1A) include compounds in which each group in formula (1A) is selected from the groups shown below. １ ~E ６ : Single bond, -S-, -NH-, -N(CH ３ )-B １ ~B ４ : B-1 to B-6 below k, l, m, n: 0, 1 r: 0, 1, 2, 3 X １ ~X ４ : Hydroxyl group, sulfonamide group, methoxy group L: L-1 to L-17 below

[0076]

[0077]

[0078] Specific examples of the compound represented by formula (1B) include compounds in which each group in formula (1B) is selected from the groups shown below. １ ~E ３ : Single bond, -S-, -NH-, -N(CH ３ )-B １ , B ２ : Above B-1 to B-6 k, l: 0, 1 s: 1, 2, 3, 4 X １ ~X ４: Hydroxyl group, sulfonamide group, methoxy group T: T-1 to T-27 below

[0079]

[0080] In the compound-attached metal of the present invention, the specific compound is attached to the metal. The manner of attachment is not particularly limited, and the specific compound may be physically adsorbed to the metal or bonded to the metal. Examples of bonds between the metal and the specific compound include hydrogen bonds, acid-base interactions, ionic bonds, coordinate bonds, and covalent bonds. In terms of achieving better effects of the present invention, it is preferable for the metal and the specific compound to form an ionic bond or a covalent bond.

[0081] The specific compound is preferably attached to the metal in a planar manner, and more preferably forms a coating of the specific compound. When the specific compound forms a coating, the thickness of the coating is not particularly limited, but is often 1 to 100 nm, and preferably 3 to 20 nm.

[0082] [Metal] The metal in the compound-attached metal preferably contains at least one selected from the group consisting of copper, silver, iron, gold, cobalt, nickel, tungsten, molybdenum, ruthenium, titanium, tantalum, germanium, zirconium, aluminum, tin, palladium, indium, zinc, and platinum, more preferably contains copper, silver, or iron, more preferably contains copper or silver, and even more preferably contains silver. The metal may be either a simple metal or an alloy, and a simple metal is preferred. Among these, the metal is preferably copper, silver, or iron, more preferably copper or silver, and even more preferably silver.

[0083] [Manufacturing Method] Known methods can be used to manufacture the compound-coated metal of the present invention, including contacting a metal with a composition containing a specific compound. The composition containing the specific compound is preferably a specific compound solution containing a solvent and the specific compound. The solvent is not particularly limited as long as it can dissolve the specific compound, but examples include water, organic solvents, and mixtures of two or more of these. Examples of the organic solvent include alcohol-based solvents such as ethanol, 2-propanol, and ethylene glycol monoethyl ether; ether-based solvents such as tetrahydrofuran; ester-based solvents such as ethyl acetate; ketone-based solvents such as cyclopentanone, cyclohexanone, and 2-butanone; amide-based solvents such as N,N-dimethylacetamide; chlorine-based solvents such as dichloromethane; and hydrocarbon-based solvents. The concentration of the specific compound in the specific compound solution is preferably 0.05 to 10 wt %, more preferably 0.1 to 5 wt %.

[0084] Examples of methods for contacting a metal with the composition containing the specific compound include applying (e.g., spin coating) or spraying the composition containing the specific compound onto the metal, and immersing the metal in the composition containing the specific compound. The temperature of the composition containing the specific compound when contacting the metal with the composition containing the specific compound is not particularly limited, but is preferably 0 to 50°C, and more preferably 10 to 30°C.

[0085] It is also preferable to carry out a cleaning treatment after contacting the metal with the specific compound or a composition containing the specific compound. The cleaning treatment can remove excess specific compound and / or impurities from the compound-containing metal. The cleaning method is not particularly limited, and examples include a method of contacting the compound-containing metal with a cleaning liquid. As the contact method, the same method as the method of contacting the substrate with a composition containing the specific compound can be used. The temperature of the cleaning liquid during contact is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. Water or an organic solvent can be used as the cleaning liquid. As the organic solvent, for example, the solvents mentioned above can be used.

[0086] [Uses] The compound-attached metal is suitably used as a member for which metal corrosion inhibition is required. The form of corrosion is not particularly limited, but typical examples include oxidation of copper, iron, and the like, and sulfidation of copper, iron, and silver, and the like. The compound-attached metal of the present invention is preferably used, for example, as a conductive material. Specific examples of conductive materials include conductive films and conductive wiring, and the compound-attached metal is preferably used for a conductive substrate in which the conductive film or conductive wiring is formed on a substrate.

[0087] [Compound] The present invention includes the invention of a compound. The compound of the present invention can adhere to a metal and inhibit corrosion of the metal. The compound of the present invention is the specific compound described above, and among them, the following compound is preferable.

[0088]

[0089] In formula (1A) and formula (1B), E １ ~E ６ each independently represents a single bond, —O—, —S—, —NH—, or —NR—. R represents a substituent. B １ , B ２ , B ３ , and B ４ represent k+1, l+1, m+1, and n+1 valent organic groups, respectively. １ , B ２ , B ３ , and B ４ At least one of B represents a k+1-valent, l+1-valent, m+1-valent, or n+1-valent aromatic ring group, １ and B ２ At least one of represents a k+1 or l+1 valent aromatic ring group. k, l, m, and n each independently represent an integer of 0 or more. In formula (1A), the sum of k, l, m, and n is 2 or more, and in formula (1B), the sum of k and l is 2 or more. L each independently represents a divalent organic group. r represents an integer of 1 or more. T represents an s-valent organic group. s represents an integer of 3 or more. X １ ~X ４ and Z １ ~Z ２each independently represents a group represented by the above formula (2), provided that in formula (1A), X １ ~X ４ is Q and Y １ represents a group represented by formula (2), in which at least one of B is a sulfonamide group. １ ~B ４ When the groups represented by L and T contain a divalent conjugated group, the number of π electrons contained in the divalent conjugated group is 13 or less.

[0090] In addition, Q and Y １ The group represented by formula (2) in which at least one of the groups is a sulfonamide group is, in other words, a group represented by formula (2) having at least a sulfonamide group.

[0091] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0092] [Preparation of Compound-Attached Metal] <Specific Compounds and Comparative Compounds> The specific compounds used in the examples and the comparative compounds used in the comparative examples are as shown in the table below. Compounds A-1 to A-32 are specific compounds, and B-1 and B-2 are comparative compounds.

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] (Synthesis of Compound A-1) Compound A-1 was synthesized according to the following procedure.

[0099]

[0100] A mixture of cyanuric chloride (15.5 g, 0.083 mol) and 2-butanone (75 ml) was ice-cooled, and 5-amino-o-cresol (0.168 mol) was added in small portions. Subsequently, an aqueous solution of sodium acetate trihydrate (22.8 g, 0.168 mol) dissolved in water (32 ml) was added to the mixture. The mixture was stirred at 40°C for 2 hours, after which 3-aminophenol (0.092 mol) was added, and the mixture was stirred at 80°C for 2 hours. After cooling to room temperature, an aqueous solution of sodium carbonate (21.3 g, 0.20 mol) dissolved in water (134 ml) was added dropwise to the mixture, and the mixture was stirred for 30 minutes. The mixture was allowed to stand, and the aqueous layer was removed. The organic layer was then filtered through Celite, and 34 ml of ethanol was added. Water (435 ml) was added dropwise to the resulting organic layer while stirring, and after stirring for 2 hours, the precipitated crystals were collected by filtration and dried to obtain A-1.

[0101] (Synthesis of Compound A-2) Compound A-2 was synthesized according to the following procedure.

[0102]

[0103] A mixture of cyanuric chloride (74.7 g, 0.41 mol) and 2-butanone (400 ml) was ice-cooled, and 3-aminophenol (1.26 mol) was added in small portions. Subsequently, an aqueous solution of sodium acetate trihydrate (110.2 g, 0.81 mol) dissolved in water (165 ml) was added to the mixture. The mixture was stirred at 80°C for 2 hours, cooled to room temperature, and an aqueous solution of sodium carbonate (103 g, 0.97 mol) dissolved in water (596 ml) was added dropwise to the mixture and stirred for 30 minutes. The mixture was allowed to stand and the aqueous layer was removed, and the organic layer was filtered through Celite, and 150 ml of ethanol was added. Water (1.91 L) was added dropwise to the resulting organic layer while stirring, and after stirring for 2 hours, the precipitated crystals were collected by filtration and dried to obtain A-2.

[0104] (Method of Synthesizing A-3) A-3 was synthesized in the same manner as A-1, except that 3-aminophenol was changed to sulfanilamide.

[0105] (Method for Synthesizing A-4) Compound A-4 was synthesized according to the following procedure.

[0106]

[0107] A mixture of cyanuric chloride (87.6 g, 0.475 mol) and 2-butanone (620 ml) was ice-cooled, and 3-aminophenol (0.95 mol) was added in small portions. Subsequently, an aqueous solution of sodium acetate trihydrate (135.8 g, 0.998 mol) dissolved in water (193 ml) was added to the mixture. The mixture was stirred at 45°C for 2 hours, cooled to room temperature, and an aqueous solution of sodium carbonate (80.6 g, 0.76 mol) dissolved in water (700 ml) was added dropwise to the mixture and stirred for 30 minutes. The mixture was allowed to stand and the aqueous layer was removed, and the organic layer was filtered through Celite, and 210 ml of ethanol was added. Water (1.75 L) was added dropwise to the resulting organic layer while stirring, and after stirring for 2 hours, the precipitated crystals were collected by filtration and dried to obtain intermediate A-4. The diamine compound (0.175 mol) was added to a mixture of A-4 intermediate (0.35 mol) and 2-butanone (410 ml). Water (170 ml) was added to the mixture, and the mixture was stirred at 80°C for 2 hours and then cooled to room temperature. An aqueous solution of sodium carbonate (29.8 g, 0.28 mol) dissolved in water (620 ml) was added dropwise to the mixture and stirred for 30 minutes. The mixture was allowed to stand and the aqueous layer was removed, and the organic layer was then filtered through Celite. The solvent in the resulting organic layer was removed using an evaporator, and the organic layer was dissolved in 2-propanol (195 ml). The resulting solution was added dropwise to water (2.25 L), and the mixture was stirred for 2 hours. The precipitated crystals were then collected by filtration and dried to obtain A-4.

[0108] (Synthesis method of A-5 to A-8, 10 to A-14, 16 to A-17, and A-31) A-5 to A-8, 10 to A-14, 16 to A-17, and A-31 were obtained in the same manner as A-4, except that the diamine compound reacted with the A-4 intermediate was changed so as to obtain the target compound.

[0109] (Method for Synthesizing A-9) A-9 was synthesized in the same manner as A-2, except that 3-aminophenol was changed to 5-aminonaphthalen-2-ol.

[0110] (Method for Synthesizing A-15) Compound A-15 was synthesized according to the following procedure.

[0111]

[0112] Intermediate A-4 was obtained according to the synthesis method for A-4. The above triamine compound (0.117 mol) was added dropwise to a mixture of intermediate A-4 (0.35 mol) and N,N-dimethylacetamide (410 ml). N-Ethyldiisopropylamine (0.42 mol) was added dropwise to the mixture, which was stirred at 120°C for 2 hours and then cooled to room temperature. Ethyl acetate (200 ml) / tetrahydrofuran (600 ml), 2N aqueous hydrochloric acid (200 ml), and 10% saline (200 ml) were added to the mixture, and the target product was extracted. The resulting organic layer was washed with 1N aqueous hydrochloric acid, 5% aqueous sodium bicarbonate, and 5% saline, in that order. The organic layer was dried over magnesium sulfate and then filtered through Celite. The solvent was removed from the resulting organic layer using an evaporator, and the resulting organic layer was dissolved in 2-propanol (195 ml). The resulting solution was added dropwise to water (2.25 L) and stirred for 2 hours, and then the precipitated crystals were collected by filtration and dried to obtain A-15.

[0113] (Method for synthesizing A-18 to 20, A-24, and 25) A-18 to 20, A-24, and 25 were obtained in the same manner as A-4, except that 3-aminophenol was changed to 3-aminobenzenesulfonamide and the diamine compound was changed to a diamine compound that would yield the target compound.

[0114] (Method for synthesizing A-21) A-21 was synthesized in the same manner as A-15, except that 3-aminophenol was changed to 3-aminobenzenesulfonamide.

[0115] (Method of Synthesizing A-22) A-22 was synthesized in the same manner as A-4, except that 3-aminophenol was changed to m-anisidine and the above diamine compound was changed to a diamine compound that would give the target compound.

[0116] (Method for Synthesizing A-23) A-23 was synthesized according to the following scheme.

[0117]

[0118] A mixture of cyanuric chloride (87.6 g, 0.475 mol) and 2-butanone (620 ml) was ice-cooled, and aminoethanol (0.475 mol) and N-ethyldiisopropylamine (0.475 mol) were added dropwise in this order. After stirring for 1 hour under ice-cooling, 3-aminobenzenesulfonamide (0.475 mol) and N-ethyldiisopropylamine (0.475 mol) were added in this order, and the mixture was stirred at 40°C for 2 hours. After cooling to room temperature, water (1000 ml) was added dropwise to the mixture and stirred for 30 minutes. The precipitated crystals were collected by filtration and dried to obtain intermediate A-23. A-23 was synthesized in the same manner as A-4, except that the A-4 intermediate was changed to A-23 intermediate and the diamine compound was changed to m-tolidine.

[0119] (Method for Synthesizing A-26) A-26 was synthesized according to the following scheme.

[0120]

[0121] A mixture of cyanuric chloride (87.6 g, 0.475 mol) and 2-butanone (620 ml) was ice-cooled, and 3-aminophenol (0.475 mol) was added in small portions. Subsequently, an aqueous solution of sodium acetate trihydrate (0.523 mol) dissolved in water (193 ml) was added dropwise to the mixture. After stirring the mixture at room temperature for 2 hours, an aqueous solution of sodium carbonate (0.38 mol) dissolved in water (700 ml) was added dropwise and stirred for 30 minutes. The mixture was allowed to stand and the aqueous layer was removed, and the organic layer was filtered through Celite, and 210 ml of ethanol was added. Water (1.75 L) was added dropwise to the resulting organic layer with stirring, and after stirring for 2 hours, the precipitated crystals were collected by filtration and dried to obtain intermediate A-26. To a mixture of A-26 intermediate (7.55 mmol), A-4 intermediate (7.55 mmol), N,N-dimethylacetamide (25 ml), and 2-butanone (25 ml), bis(3-aminophenyl)sulfone (10.7 mmol) was added and stirred at 100°C for 2 hours, followed by cooling to room temperature. The mixture was added dropwise to water (300 ml), and the precipitated solid was collected by filtration. The obtained solid was dissolved in ethyl acetate (25 ml) / tetrahydrofuran (75 ml) and washed with 5% aqueous sodium bicarbonate and 5% saline, successively. The organic layer was dried over magnesium sulfate and then filtered through Celite. The solvent was removed from the obtained organic layer using an evaporator, and the organic layer was dissolved in 2-propanol (25 ml). The resulting solution was added dropwise to water (300 ml) and stirred for 2 hours. The precipitated crystals were collected by filtration and dried to obtain A-26. The average r of A-26 was 3.

[0122] (Method for synthesizing A-27) A-27 was synthesized in the same manner as A-26, except that the A-26 intermediate (7.55 mmol) and A-4 intermediate (7.55 mmol) were replaced with the A-26 intermediate (5.52 mmol), the A-4 intermediate (12.0 mmol), and bis(3-aminophenyl)sulfone (10.4 mmol). The average r of A-27 was 2.

[0123] (Synthesis Method of A-28, 29, 30) A-28, 29, 30 were synthesized in the same manner as the synthesis method of A-15, except that the above triamine compound was changed to a triamine compound, a tetramine compound, or a trithiol compound that would yield the target compound.

[0124] (Method of Synthesizing A-32) A-32 was synthesized in the same manner as A-23, except that the amine compound and diamine compound were changed to amine compounds and diamine compounds that would give the target compound.

[0125] [Evaluation] The corrosion resistance of the compound-attached metals was evaluated by the following methods, in terms of sulfurization resistance of the compound-attached silver and oxidation resistance of the compound-attached copper.

[0126] <Silver sulfurization test> Each specific compound or comparative compound was dissolved in a 50 / 50 (mass ratio) mixed solvent of ethylene glycol monoethyl ether and water to a concentration of 0.5 wt % to prepare 30 ml of a solution. A 3 cm square silver foil with a polished surface was prepared and immersed in the solution at room temperature for 60 seconds. After immersion, the silver foil was immersed in 30 ml of pure water to wash, and then dried at 70°C for 1 minute to obtain a silver foil with the compound.

[0127] The obtained silver foil with the compound was placed in a desiccator together with sulfur powder, and the desiccator was placed in a thermostatic bath at 70°C and heated. The silver foil was checked every 30 minutes for 5 hours from the start of heating, and the time until the silver foil turned black was measured. The longer the time until the silver foil turned black, the more corrosion was suppressed, which is preferable.

[0128] <Copper Oxidation Test> Each specific compound or comparative compound was dissolved in a mixed solvent of ethylene glycol monoethyl ether / water = 50 / 50 (mass ratio) to prepare 30 ml of a solution at a concentration of 0.5 wt %. ２ SO ４ A 3 cm square copper foil, which had been immersed in an aqueous solution (liquid temperature: 30° C.) for 10 minutes to remove the oxide film from the surface, was prepared and immersed in the solution at room temperature for 60 seconds. After immersion, the copper foil was immersed in 30 ml of pure water for washing and then dried at 70° C. for 1 minute to obtain a compound-coated copper foil.

[0129] The obtained copper foil with the compound was placed in a thermostatic chamber at 60°C and 90% RH and heated. The foil was checked every half day for 5 days from the start of heating, and the number of days until the copper foil turned black was measured. The longer the time until the foil turned black, the more inhibited corrosion is, which is preferable.

[0130] [Results] The following table shows the structure of the compound and the evaluation results. In the table, "≧5h" in the "silver sulfide" column means that no discoloration was observed even after 5 hours, and "≧5d" in the "copper oxidation" column means that no discoloration was observed even after 5 days.

[0131]

[0132] From the results shown in the above table, it was confirmed that the metal with the compound of the present invention was inhibited from corrosion.

[0133] Comparison of Examples 1 to 13 and 23 to 29, etc., confirmed that the effects of the present invention are better when the molecular weight of the specific compound is 700.0 or more, and even better when it is 1000.0 or more. Comparison of Examples 14, 22, and 32 with other Examples, and comparison of Examples 17 to 21, confirmed that the effects of the present invention are better when the heteroatom content of the specific compound is 20.0% or more, and even better when it is 35.0% or more. Comparison of Example 31 with other Examples confirmed that the effects of the present invention are better when the aliphatic hydrocarbon group content of the specific compound is 20.0% or less. Comparison of Example 22 with other Examples confirmed that the effects of the present invention are better when the specific functional group is a hydroxyl group or a sulfonamide group. Comparison of Example 30 with other Examples confirmed that E １ ~E ６ It was confirmed that the effects of the present invention are more excellent when s is —NH—. From the comparison of Examples 1 to 3, 9, 21, and 28 to 29, it was confirmed that the effects of the present invention are more excellent when the specific compound represented by formula (1B) has s of 2 or more.

Claims

1. A compound-attached metal comprising a metal and, attached to the metal, at least one specific compound selected from the group consisting of a compound represented by formula (1A) and a compound represented by formula (1B): In formula (1A) and formula (1B), E １ ~E ６ each independently represents a single bond, —O—, —S—, —NH—, or —NR—. R represents a substituent. B １ , B ２ , B ３ , and B ４ represent k+1, l+1, m+1, and n+1 valent organic groups, respectively. １ , B ２ , B ３ , and B ４ At least one of B represents an aromatic ring group having a valence of k+1, l+1, m+1, or n+1, which may have a substituent; １ and B ２ At least one of represents a k+1 or l+1 valent aromatic ring group which may have a substituent. k, l, m, and n each independently represent an integer of 0 or more. However, in the formula (1A), the sum of k, l, m, and n is 2 or more, and in the formula (1B), the sum of k and l is 2 or more. L each independently represents a divalent organic group. r represents an integer of 0 or more. T represents an s-valent organic group. s represents an integer of 1 or more. X １ ~X ４ and Z １ ~Z ２ each independently represents a group represented by formula (2). In formula (2), * represents a bonding position. １ each independently represents a single bond or a divalent linking group. １ each independently represents an aromatic ring group which may have a substituent, or an aliphatic ring group which may have a substituent. １ each independently represents a specific functional group selected from the group consisting of a hydroxyl group, an amino group, a thiol group, a carboxylic acid group, a sulfonic acid group, an amide group, a sulfonamide group, and an alkoxy group. Each p independently represents an integer of 0 or more. Each q independently represents an integer of 0 to 2.

2. The compound-containing metal according to claim 1, wherein r is an integer of 1 or more and s is an integer of 2 or more.

3. E １ ~E ６ The compound-containing metal according to claim 1, wherein is a single bond or -NH-.

4. In the formula (1A), X １ ~X ４ At least one of １ is a group represented by the formula (2) which is a hydroxyl group or a sulfonamide group, and in the formula (1B), Z １ and Z ２ At least one of １ The compound-containing metal according to claim 1 , wherein is a group represented by formula (2) which is a hydroxyl group or a sulfonamide group.

5. The compound-containing metal according to any one of claims 1 to 4, wherein the specific compound has an aliphatic hydrocarbon group content of 20.0% or less.

6. The compound-containing metal according to any one of claims 1 to 4, wherein the heteroatom content of the specific compound is 15.0% or more.

7. The compound-containing metal according to any one of claims 1 to 4, wherein the molecular weight of the specific compound is 700.0 or more.

8. The compound-containing metal according to any one of claims 1 to 4, wherein the specific compound has an aliphatic hydrocarbon group content of 10.0% or less, a heteroatom content of 20.0% or more, and a molecular weight of 700.0 or more.

9. The compound-containing metal according to any one of claims 1 to 4, wherein the metal is copper, silver, or iron.

10. The compound-containing metal according to any one of claims 1 to 4, wherein the metal is copper or silver.

11. A compound represented by formula (1A) or formula (1B). In formula (1A) and formula (1B), E １ ~E ６ each independently represents a single bond, —O—, —S—, —NH—, or —NR—. R represents a substituent. B １ , B ２ , B ３ , and B ４ represent k+1, l+1, m+1, and n+1 valent organic groups, respectively. １ , B ２ , B ３ , and B ４ At least one of B represents an aromatic ring group having a valence of k+1, l+1, m+1, or n+1, which may have a substituent; １ and B ２ At least one of represents a k+1 or l+1 valent aromatic ring group which may have a substituent. k, l, m, and n each independently represent an integer of 0 or more. However, in the formula (1A), the sum of k, l, m, and n is 2 or more, and in the formula (1B), the sum of k and l is 2 or more. L each independently represents a divalent organic group. r represents an integer of 1 or more. T represents an s-valent organic group. s represents an integer of 3 or more. X １ ~X ４ and Z １ ~Z ２ each independently represents a group represented by formula (2). In formula (2), * represents a bonding position. １ each independently represents a single bond or a divalent linking group. １ each independently represents an aromatic ring group which may have a substituent, or an aliphatic ring group which may have a substituent. １ each independently represents a specific functional group selected from the group consisting of a hydroxyl group, an amino group, a thiol group, a carboxylic acid group, a sulfonic acid group, an amide group, a sulfonamide group, and an alkoxy group. p represents an integer of 0 or more. q represents an integer of 0 to 2. However, in the formula (1A), X １ ~X ４ is Q and Y １ represents a group represented by the formula (2) in which at least one of B is a sulfonamide group. １ ~B ４ When the groups represented by L and T contain a divalent conjugated group, the number of π electrons contained in the divalent conjugated group is 13 or less.

12. E １ ~E ６ The compound according to claim 11, wherein is a single bond or -NH-.

13. Q and Y １ and each independently represent a hydroxyl group or a sulfonamide group.

14. The compound of claim 11 or 12, wherein p is 0.

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