Tetrazole compound as well as synthesis method and application thereof

Abstract

The invention provides a novel tetrazole compound, a synthesis method thereof, and a coupling agent. The tetrazole compound of the present invention is represented by chemical formula (I). In chemical formula (I), R1 and R2 may be the same or different and each represents a hydrogen atom or a group represented by-(CH2) m-Si (OR) 3-p (OH) p (where R represents a methyl group or an ethyl group, m represents an integer of 1-18, and p represents an integer of 0-3). X represents a group represented by phenylene,-NH-or-(CH2) n-, and n represents an integer of 0-12. Wherein the condition that R1 and R2 are hydrogen atoms at the same time is excluded.

Description

TECHNICAL FIELD

[0001] The present application relates to a novel tetrazole compound, a method for synthesizing the tetrazole compound, and applications thereof. BACKGROUND

[0002] In the past, coupling agents have been used in order to combine materials having different properties from each other, like organic materials and inorganic materials, in the fields of electronic materials, paints, primers, adhesives, and the like. Therefore, coupling agents are indispensable reagents in the development and production of composite materials.

[0003] For example, a coupling agent (silane coupling agent) composed of an organic substance and silicon, which generally functions as an intermediary that connects organic materials and inorganic materials that are difficult to be compatible, is known to be used.

[0004] In addition, azole compounds such as tetrazole compounds have a function of rust-proofing metals and a function of curing epoxy resins and polyurethane resins, and thus various coupling agents using azole compounds have been proposed.

[0005] As a coupling agent, for example, a triazole silane compound in which an alkoxysilyl group is introduced to a specific triazole ring is proposed in Patent Literature 1. In addition, a triazole silane compound having a specific two triazole rings and a disulfide bond (-S-S-) with a -CO-NH-(CH2) m -Si(OR)3.

[0006] Prior Art Documents

[0007] Patent Literature

[0008] Patent Literature 1: International Publication No. 2018 / 186476

[0009] Patent Literature 2: International Publication No. 2015 / 002158 SUMMARY

[0010] Problems to be Solved by the Invention

[0011] In recent years, in the field of electrical and electronic materials, in order to cope with miniaturization, thinning, precision, and high-speed transmission, it is required to improve the adhesion between materials. Although the azole compounds disclosed in Patent Literatures 1 and 2 can also exhibit excellent adhesion, compounds capable of exhibiting higher adhesion are required.

[0012] The present application was made in view of the above problems, and aims to provide a novel tetrazole compound and a method for synthesizing the same, and a coupling agent.

[0013] Means for Solving the Problems

[0014] The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that a tetrazole compound obtained by reacting a certain tetrazole compound with a certain halogenated alkylsilane compound can solve the above problems, thereby completing the present invention.

[0015] That is, the first invention is a tetrazole compound represented by Chemical Formula (I).

[0016]

[0017] In Chemical Formula (I), R 1 and R 2 represent a hydrogen atom or a -(CH2) m -Si(OR) 3-p (OH) p group, wherein R represents a methyl group or an ethyl group, m represents an integer of 1 to 18, and p represents an integer of 0 to 3. X represents a phenylene group, -NH- or a -(CH2) n group, and n represents an integer of 0 to 12. Among them, the case where R 1 and R 2 are both hydrogen atoms is excluded.

[0018] The second invention is a synthesis method of the tetrazole compound of the first invention, wherein a tetrazole compound represented by Chemical Formula (II) is reacted with a halogenated alkylsilane compound represented by Chemical Formula (III).

[0019]

[0020] In Chemical Formula (II), X is the same as described above.

[0021]

[0022] In Chemical Formula (III), R, m and p are the same as described above. Hal represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0023] The third invention is a coupling agent containing the tetrazole compound of the first invention.

[0024] The fourth invention is a surface treatment liquid containing the tetrazole compound of the first invention.

[0025] The fifth invention is the surface treatment liquid of the fourth invention, which is used for treating a surface of at least one selected from the group consisting of a metal, an inorganic material and a resin material.

[0026] The sixth invention is the surface treatment liquid of the fourth invention, which is used for bonding two materials selected from the group consisting of a metal, an inorganic material and a resin material.

[0027] The seventh invention is the surface treatment liquid described in the fifth or sixth invention, wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold and alloys thereof.

[0028] The eighth invention is a surface treatment method in which a surface treatment liquid, as described in any one of the fourth to seventh inventions, is brought into contact with a surface selected from the group consisting of metals, inorganic materials and resin materials.

[0029] The ninth invention is the surface treatment method described in the eighth invention, wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold and alloys thereof.

[0030] The tenth invention is the surface treatment method described in the eighth or ninth invention, wherein the metal is copper or a copper alloy.

[0031] The eleventh invention is a surface treatment method according to any one of the eighth to tenth inventions, wherein, before the surface treatment liquid is brought into contact with the surface of copper or copper alloy, an aqueous solution containing copper ions is brought into contact with the surface of copper or copper alloy.

[0032] The twelfth invention is a surface treatment method according to any one of the eighth to eleventh inventions, wherein, after the surface treatment liquid is brought into contact with the surface of copper or copper alloy, an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the surface of copper or copper alloy.

[0033] The thirteenth invention is an adhesive method in which a surface treatment liquid, as described in any one of the fourth to seventh inventions, is brought into contact with at least one selected from the group consisting of metals, inorganic materials and resin materials to form a chemical conversion coating on the at least one material, and the chemical conversion coatings are then bonded together.

[0034] The fourteenth invention is a method for bonding a metal and a resin material, wherein a surface treatment liquid, as described in any one of the fourth to seventh inventions, is brought into contact with at least one of the metal and the resin material to form a chemical conversion coating on the at least one, and the metal and the resin material are bonded to each other via the chemical conversion coating.

[0035] The fifteenth invention is a printed wiring board, which is formed by bonding two materials selected from the group consisting of metal, inorganic materials and resin materials through a chemical conversion coating formed by any one of the surface treatment liquids of the fourth to seventh inventions.

[0036] The sixteenth invention is a semiconductor wafer in which two materials selected from the group consisting of metals, inorganic materials and resin materials are bonded together by a chemical conversion coating formed by a surface treatment liquid of the fourth to seventh inventions.

[0037] The seventeenth invention is an insulating composition containing...

[0038] The coupling agent of the third invention, and

[0039] Resin materials or inorganic materials.

[0040] The eighteenth invention is an insulating material containing the insulating composition of the seventeenth invention.

[0041] The nineteenth invention is a printed wiring board having an insulating layer obtained from the insulating composition of the seventeenth invention.

[0042] The twentieth invention is a semiconductor wafer having an insulating layer obtained from the insulating composition of the seventeenth invention.

[0043] Invention Effects

[0044] The tetrazolium compound of the present invention is a compound formed by combining two tetrazolium rings, thus improving its interaction with metals, resin materials, etc. In addition, it utilizes the selection of phenylene, -NH- and -(CH2) groups. n - The linking group in the group shown in the figure combines two tetrazolium rings, so it is not easily decomposed even when exposed to heat or alkali.

[0045] Furthermore, the coupling agent of the present invention is composed of a tetrazolium compound obtained by linking two tetrazolium rings using the aforementioned linking group, thus improving the adhesion between materials with different properties. According to the surface treatment liquid containing this tetrazolium compound, the adhesion between two materials of different materials, namely metal and inorganic materials, metal and resin materials, and inorganic materials and resin materials, can be improved. Detailed Implementation

[0046] The present invention will now be described in detail. It should be noted that the present invention is not limited to the embodiments described below.

[0047] (Tetraazole compounds)

[0048] The tetrazolium compound of the present invention is represented by the following chemical formula (I) (hereinafter, sometimes referred to as the tetrazolium compound of the present invention).

[0049]

[0050] In equation (I), R 1 and R 2 Same or different, indicating hydrogen atoms or -(CH2). m -Si(OR) 3-p (OH) pThe indicated groups are: R represents methyl or ethyl, m represents an integer from 1 to 18, and p represents an integer from 0 to 3. X represents phenylene, -NH-, or -(CH2). n - The group shown, n represents an integer from 0 to 12. Excluding R 1 and R 2 The case where it is both a hydrogen atom.

[0051] -(CH2) m -Si(OR) 3-p (OH) p The group shown is preferably m is an integer from 2 to 12, more preferably m is an integer from 3 to 10, and even more preferably m is an integer from 3 to 8.

[0052] X is preferably -(CH2) n -The group shown, in addition, n is more preferably an integer from 0 to 10, further preferably an integer from 0 to 8, and particularly preferably 0 to 6.

[0053] In the tetrazolium compound of the present invention, R 1 and R 2 The N atom is preferably bonded to the 1st or 2nd position of the tetrazolium ring.

[0054] Examples of tetrazolium compounds of the present invention include those represented by chemical formulas (I-1) to (I-8).

[0055]

[0056] In equations (I-1) to (I-8), X, m, p, and R are the same as those described above.

[0057] As the tetrazolium compound of the present invention, as R 1 -(CH2) m -Si(OR) 3-p (OH) p The groups shown, R 2 For hydrogen, R 1 and R 2 Specific examples of the N-position bonded to the tetrazolium ring (compounds represented by chemical formula (I-1)) can be cited as follows: 1-(trimethoxysilyl)methyl-5,5'-(1,4-phenylene)bis(1,2,3,4-tetraazole), 1-[2-(triethoxysilyl)ethyl]-5,5'-(1,2-phenylene)bis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-(1,3-phenylene)bis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-(1,4-phenylene)bis(1,2,3,4-tetraazole), 1-[6-(triethoxysilyl)hexyl]-5,5'-(1,4-phenylene)bis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-iminobis(1,2,3,4-tetraazole), 1-[8-(trimethoxysilyl)octyl]-5,5'-iminobis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-bi(1,2,3,4-tetraazole), 1-[10-(triethoxysilyl)decyl]-5,5'-bi(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-methylenebis(1,2,3,4-tetraazole), 1-[6-(trimethoxysilyl)hexyl]-5,5'-methylenebis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-ethylenebis(1,2,3,4-tetraazole), 1-[12-(triethoxysilyl)dodecyl]-5,5'-ethylenebis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-tetramethylenebis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-pentamethylenebis(1,2,3,4-tetraazole), 1-[4-(triethoxysilyl)butyl]-5,5'-pentamethylenebis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-hexamethylenebis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-octamethylenebis(1,2,3,4-tetraazole), 1-[2-(trimethoxysilyl)ethyl]-5,5'-nonamethylenebis(1,2,3,4-tetraazole), 1-[2-(trimethoxysilyl)ethyl]-5,5'-decamethylbis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-undecylmethylenebis(1,2,3,4-tetraazole), 1-[3-(triethoxysilyl)propyl]-5,5'-dodecylmethylenebis(1,2,3,4-tetraazole), etc.

[0058] As the tetrazolium compound of the present invention, as R 1 and R 2 Same or different and of the type -(CH2) m -Si(OR) 3-p (OH) p The indicated groups, and R 1 and R 2 Specific examples of the N-position bonded to the tetrazolium ring (compounds shown in formula (I-5)) can be cited, for example: 5,5'-(1,4-phenylene)bis[1-(trimethoxysilyl)methyl-1,2,3,4-tetraazole], 5,5'-(1,2-phenylene)bis{1-[2-(triethoxysilyl)ethyl]-1,2,3,4-tetraazole}, 5,5'-(1,3-phenylene)bis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-(1,4-phenylene)bis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-(1,4-phenylene)bis{1-[6-(triethoxysilyl)hexyl]-1,2,3,4-tetraazole}, 5,5'-Iminebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-Iminebis{1-[8-(trimethoxysilyl)octyl]-1,2,3,4-tetraazole}, 5,5'-Bi{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-Bi{1-[10-(triethoxysilyl)decyl]-1,2,3,4-tetraazole}, 5,5'-Methylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-Methylenebis{1-[6-(trimethoxysilyl)hexyl]-1,2,3,4-tetraazole}, 5,5'-Ethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-Ethylenebis{1-[12-(triethoxysilyl)dodecyl]-1,2,3,4-tetraazole}, 5,5'-Tetramethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-Pentamethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-Pentamethylenebis{1-[4-(triethoxysilyl)butyl]-1,2,3,4-tetraazole}, 5,5'-Hexamethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-Octamethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-Nonamethylenebis{1-[2-(trimethoxysilyl)ethyl]-1,2,3,4-tetraazole}, 5,5'-Decamethylbis{1-[2-(trimethoxysilyl)ethyl]-1,2,3,4-tetraazole}, 5,5'-Undecylmethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole}, 5,5'-Dodecylmethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetraazole} etc.

[0059] When the tetrazolium compounds of the present invention are used as coupling agents or components of surface treatment liquids described later, different types of tetrazolium compounds can be used in combination.

[0060] Alternatively, a mixture of isomers of a tetrazolium compound, such as a 1H-tetrazole compound (e.g., the compound shown in chemical formula (I-1)) and a 2H-tetrazole compound (e.g., the compound shown in chemical formula (I-3)), can be obtained and used by reacting the halogenated alkylsilane compound shown in chemical formula (III) below. From a manufacturing cost perspective, the mixing ratio (molar ratio) of the 1H-tetrazole compound to the 2H-tetrazole compound is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

[0061] The tetrazolium compound of the present invention is obtained by reacting the tetrazolium compound of chemical formula (II) with the haloalkylsilane compound of chemical formula (III).

[0062]

[0063] In equation (II), X is the same as above.

[0064]

[0065] In formula (III), R, m, and p are the same as above. Hal represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0066] In the tetrazolium compound represented by chemical formula (II), X is the same as that shown in the tetrazolium compound of the present invention, and preferably in the same manner.

[0067] In the alkyl halogenated silane compounds represented by chemical formula (III), R, m, and p are the same as those shown in the tetrazolium compounds of the present invention, and preferably the same as those shown in the present invention.

[0068] Furthermore, in the halogenated alkylsilane compound represented by chemical formula (III), Hal is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. From the viewpoint of reactivity and ease of obtaining raw materials, a chlorine atom or a bromine atom is preferred.

[0069] Examples of tetrazolium compounds represented by chemical formula (II) include: 5,5'-(1,4-phenylene)bis(1,2,3,4-tetrazole), 5,5'-(1,2-phenylene)bis(1,2,3,4-tetrazole), 5,5'-(1,3-phenylene)bis(1,2,3,4-tetrazole), 5,5'-Iminebis(1,2,3,4-tetraazole), 5,5'-Bis(1,2,3,4-tetraazole), 5,5'-Methylenebis(1,2,3,4-tetrazole), 5,5'-Ethylenebis(1,2,3,4-tetraazole), 5,5'-Trimethylenebis(1,2,3,4-tetrazol), 5,5'-Tetramethylenebis(1,2,3,4-tetraazole), 5,5'-Pentamethylenebis(1,2,3,4-Tetrazolium), 5,5'-Hexamethylenebis(1,2,3,4-tetraazole), 5,5'-Heptamethylbis(1,2,3,4-tetraazole), 5,5'-Octamethylenebis(1,2,3,4-Tetrazolium), 5,5'-Nonamethylenebis(1,2,3,4-tetraazole), 5,5'-Decamethylbis(1,2,3,4-tetraazole), 5,5'-Undecymethylenebis(1,2,3,4-tetraazole), 5,5'-dodecylmethylenebis(1,2,3,4-tetraazole), etc.

[0070] These exemplified tetrazolium compounds can be synthesized, for example, according to the synthetic method described in International Publication No. 2015 / 084830.

[0071] In addition, these tetrazolium compounds can also be used in the form of salts with suitable bases. Examples of such bases include ammonia, lithium hydroxide, sodium hydroxide, and potassium hydroxide, which can be used as ammonium salts, Li salts, Na salts, and K salts.

[0072] Examples of haloalkylsilane compounds represented by chemical formula (III) include: chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 2-Chloroethyltrimethoxysilane, 2-Chloroethyltriethoxysilane, 3-Chloropropyltrimethoxysilane, 3-Chloropropyltriethoxysilane, 3-Bromopropyltrimethoxysilane, 3-Bromopropyltriethoxysilane, 3-Iodopropyltrimethoxysilane, 3-Iodopropyltriethoxysilane, 4-Bromobutyltrimethoxysilane, 4-Bromobutyltriethoxysilane, 5-Bromopentyltrimethoxysilane, 5-Bromopentyltriethoxysilane, 6-Bromohexyltrimethoxysilane, 6-Bromohexyltriethoxysilane, 8-Bromooctyltrimethoxysilane, 8-Bromooctyltriethoxysilane, 10-Bromodecyltrimethoxysilane, 10-Bromodecyltriethoxysilane, 12-Bromododecyltrimethoxysilane, 12-Bromododecyltriethoxysilane, etc.

[0073] These exemplified alkyl halogenated silane compounds can be synthesized not only using commercially available reagents, but also according to synthetic methods described in, for example, Chem. Eur. J., 18, 16742 (2012), J. Applied. Chem., 82, 276 (2009), and U.S. Patent No. 2744116.

[0074] The tetrazolium compound of the present invention can be synthesized, for example, by reacting a tetrazolium compound of formula (II) with a haloalkylsilane compound of formula (III) in the presence of a dehydrohalogenating agent in an appropriate amount of reaction solvent at a suitable reaction temperature and time. Scheme (A) below shows the yield of R. 1 For hydrogen atoms, R 2 -(CH2) m -Si(OR) 3-p (OH) p The reaction scheme for the tetrazolium compound (Ia) of the present invention with the indicated group.

[0075]

[0076] In equations (II), (III), and (Ia), X, R, Hal, m, and p are the same as those described above.

[0077] As the reaction solvent described above, there are no particular limitations as long as the solvent is inert to the tetrazolium compound represented by chemical formula (II) and the alkyl halogenated silane compound represented by chemical formula (III). Examples include: Hexane, toluene, xylene, and other hydrocarbon solvents; Diethyl ether, tetrahydrofuran, dioxane, cyclopentyl methyl ether and other ether-based solvents; Ester solvents such as ethyl acetate and butyl acetate; Methanol, ethanol and other alcohol-based solvents; 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; Acetonitrile, dimethyl sulfoxide, hexamethylphosphoric triamine, etc.

[0078] Examples of dehydrohalogenating agents mentioned above include: Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, and potassium tert-butoxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Organic bases such as triethylamine, diazabicycloundecene, and sodium hydride.

[0079] The reaction between the tetrazolium compound represented by chemical formula (II) and the haloalkylsilane compound represented by chemical formula (III) is carried out according to the above scheme (A) on a stoichiometric basis. However, the amount of haloalkylsilane compound represented by chemical formula (III) used relative to the amount of tetrazolium compound represented by chemical formula (II) is determined by factors such as reaction temperature, reaction time, the type of raw materials used, the type of reaction solvent, and the scale of the reaction, in addition to the reaction temperature and reaction time. It is preferable to use 0.8 to 1.2 equivalents of haloalkylsilane compound represented by chemical formula (III) relative to each -NH of the tetrazolium ring that becomes the reaction site.

[0080] When the amount of the haloalkylsilane compound represented by chemical formula (III) at each reaction point (-NH) is more than 1.2 equivalents, the compound may polymerize and gel; when it is less than 0.8 equivalents, the purity of the product may decrease, or the separation of the product may become cumbersome.

[0081] In addition, the dehydrohalogenating agent is used to neutralize hydrogen halide produced by the reaction of the tetrazolium compound shown in chemical formula (II) with the alkyl halogenated silane compound shown in chemical formula (III), so its amount used (input amount) can be equimolar or more relative to the amount of the alkyl halogenated silane compound shown in chemical formula (III).

[0082] The reaction temperature is not particularly limited as long as it is the temperature range of the reaction between the -NH of the tetrazolium ring of the tetrazolium compound represented by chemical formula (II) and the haloalkylsilane compound represented by chemical formula (III). It is preferably in the range of 0 to 150°C, and more preferably in the range of 5 to 100°C.

[0083] The reaction time can be appropriately determined according to the set reaction temperature, preferably in the range of 30 minutes to 48 hours, and more preferably in the range of 1 to 24 hours.

[0084] (Coupled agent)

[0085] The coupling agent of the present invention is composed of a tetrazolium compound represented by the above chemical formula (I).

[0086] When using the coupling agent of the present invention, the same surface treatment method as that used for conventional coupling agents can be employed.

[0087] Examples of such surface treatment methods include: (a) spraying a treatment solution prepared by diluting an appropriate amount of coupling agent with an organic solvent onto a substrate; (b) spraying a treatment solution prepared by diluting the coupling agent with a water-organic solvent onto a substrate; (c) spraying a treatment solution prepared by diluting the coupling agent with water onto a substrate; (d) immersing a substrate in a treatment solution prepared by diluting the coupling agent with an organic solvent; (e) immersing a substrate in a treatment solution prepared by diluting the coupling agent with a water-organic solvent; and (f) immersing a substrate in a treatment solution prepared by diluting the coupling agent with water.

[0088] Examples of organic solvents mentioned above 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; Diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and other ether-based solvents; Methanol, ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol, diethylene glycol, propylene glycol and other alcohol-based solvents.

[0089] Examples of substrates used in this invention include granular, needle-like, fibrous, woven, plate-like, foil-like, and amorphous substrates formed from metals, inorganic materials, resin materials, etc.

[0090] Examples of the aforementioned metals include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and their alloys. Plates, foils, coatings, etc., containing these metals can be used as substrates.

[0091] As specific examples of the aforementioned alloys, there are no particular limitations on copper alloys as long as they contain copper. Examples include alloys of the following systems: 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.

[0092] Other alloys that can be cited include: aluminum alloys (Al-Si alloys), nickel alloys (Ni-Cr alloys), and iron alloys (Fe-Ni alloys, stainless steel, steel), etc.

[0093] Among these metals, copper and copper alloys are preferred.

[0094] Examples of such inorganic materials include silicon, ceramics, inorganic materials used as fillers, and glass.

[0095] Specifically, examples include: silicon compounds such as silicon, silicon carbide, silicon dioxide, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminosilicates, and mica; oxides such as aluminum oxide, 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.

[0096] Among these inorganic materials, silicon, ceramics (alumina, silicon carbide, aluminum nitride, silicon nitride, and barium titanate, etc.) and glass are preferred.

[0097] Examples of resin materials mentioned above include: nylon, acrylate resin, epoxy resin, polybenzoxazole resin, silicone resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate ester resin, polyphenylene ether resin, polyphenylene oxide resin, polybutadiene resin, olefin resin, fluorinated resin, polyetherimide resin, polyetheretherketone resin, liquid crystal resin, etc., which can be mixed or modified together.

[0098] Among these resin materials, polyphenylene ether resin, polyphenylene oxide resin, liquid crystal resin, acrylate resin, epoxy resin, olefin resin, polybenzoxazole resin, silicone resin and polyimide resin are preferred.

[0099] By subjecting the substrate to surface treatment with a treatment solution containing the coupling agent of the present invention, the oleophilicity of the substrate surface is improved, thereby enhancing its affinity (adhesion, adhesion) to resins and the like.

[0100] It should be noted that, in order to further enhance the effect of this treatment, the surface-treated substrate can be further subjected to heat treatment.

[0101] (Surface treatment liquid)

[0102] <Surface treatment solution containing a tetrazolium compound represented by chemical formula (I)>

[0103] The surface treatment liquid of the present invention contains a tetrazolium compound (hereinafter, sometimes referred to as tetrazolium compound (I)) as shown in the above chemical formula (I). In this tetrazolium compound (I), R 1 and / or R 2 -(CH2) m -Si(OR) 3-p(OH) p The compounds with p-values ​​of integers 1 to 3 shown are substances generated by hydrolyzing a compound with p-value 0 in a surface treatment solution. These are all suitable as components of the surface treatment solution. In addition, the tetrazolium compound (I) with p-values ​​of integers 1 to 3 can be extracted from the surface treatment solution for example by removing volatile components from the surface treatment solution containing the tetrazolium compound (I) with p-value 0.

[0104] In the implementation of this invention, a compound with p=0, i.e., R, is preferably used as a raw material for preparing the surface treatment liquid. 1 and R 2 At least one of them is -(CH2). m Tetraazole compound (I) with the group represented by -Si(OR)3.

[0105] The surface treatment liquid of the present invention is prepared by mixing a tetrazolium compound (I) with water.

[0106] The water used in the preparation of the surface treatment solution is preferably pure water such as ion-exchanged water or distilled water.

[0107] Furthermore, in the surface treatment solution of the present invention, a solubilizer is preferably used to promote the dissolution (aqueous solution formation) of the tetrazolium compound (I). Examples of solubilizers include acids, bases, and organic solvents. One of these solubilizers may be used alone, or two or more may be used in combination.

[0108] It should be noted that, regarding the preparation method of the surface treatment solution using a solubilizer and water, the solubilizer can be added after mixing the tetrazolium compound with water, or the tetrazolium compound can be mixed with a mixture of water and solubilizer, or the tetrazolium compound can be mixed with a solubilizer and then water can be added.

[0109] Examples of acids mentioned above include: inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, 2-ethylbutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, heptadecanic acid, oleic acid, stearic acid, glycolic acid, lactic acid, gluconic acid, glyceric acid, malonic acid, succinic acid, levulinic acid, benzoic acid, oxalic acid, tartaric acid, malic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, 5-sulfosalicylic acid, 4-hydroxybenzenesulfonic acid, 3-methyl-4-hydroxybenzenesulfonic acid, 4-aminobenzenesulfonic acid, camphorsulfonic acid, benzenedisulfonic acid, benzenetrisulfonic acid, aminosulfonic acid, and amino acids. These acids can be used alone or in combination of two or more.

[0110] Examples of the aforementioned bases include: hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol, N,N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine, pyridine, and other amines. These bases can be used alone or in combination of two or more.

[0111] Examples of organic solvents mentioned above include: methanol, ethanol, 1-propanol, 2-propanol, butanol, tert-butanol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol dimethyl ether. Diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl 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-imidazolium ketone, etc. These organic solvents can be used alone or in combination of two or more.

[0112] The content of the solubilizer in the surface treatment liquid is preferably 0.1% to 99% by weight, more preferably 0.5% to 99% by weight, and even more preferably 1% to 99% by weight.

[0113] <Hydrolysis of tetrazolium compound (I)>

[0114] Tetraazole compound (I) has a tetraazole ring in its molecule, so the tetraazole ring interacts with the surface of the above-mentioned substrate (metal, resin material, inorganic material) to form a chemical bond, thus improving the adhesion between different materials.

[0115] The hydrolysis mechanism of tetrazolium compound (I) is illustrated in scheme (B). Scheme (B) illustrates the R-phase of tetrazolium compound (I). 1 and R 2 At least one of them is -(CH2). m -Si(OR) 3-p (OH) p The situation of the groups shown.

[0116] In scheme (B), the alkoxysilyl group of the above-mentioned tetrazolium compound (I) is shown to be hydrolyzed in a manner in which the trialkoxysilyl group is gradually transformed into dialkoxyhydroxysilyl, dihydroxyalkoxysilyl, and trihydroxysilyl.

[0117]

[0118] Substances containing alkoxysilyl groups in their molecules are generally known to function as silane coupling agents.

[0119] For example, taking the bonding of copper and resin materials as an example, in the implementation of the present invention, the tetrazolium compound (I) has an alkoxysilyl group in its molecule. The tetrazolium ring interacts with the resin and copper to form a chemical bond. The alkoxysilyl group (-Si-OR) is hydrolyzed to be converted into a hydroxysilyl group (-Si-OH). The hydroxysilyl group chemically bonds with the copper oxides dispersed on the copper surface.

[0120] Therefore, by contacting copper with a surface treatment liquid, a chemical conversion coating derived from a tetrazolium compound (I) is formed on the copper surface through the combination of a tetrazolium ring and a hydroxysilyl group. A resin layer containing resin material is formed on the surface of the chemical conversion coating. In this case, compared with the case where a resin layer is formed directly on the copper surface, the adhesion between copper and resin material can be improved.

[0121] In the implementation of the present invention, the concentration of tetrazolium compound (I) in the surface treatment liquid is converted to the concentration of the trialkoxy tetrazolium compound, preferably 0.0001 mol / L to 1 mol / L, more preferably 0.001 mol / L to 0.5 mol / L, and even more preferably 0.01 mol / L to 0.1 mol / L.

[0122] However, the tetrazolium compound (I) with hydroxysilyl groups generated in the surface treatment solution gradually reacts with each other and undergoes dehydration condensation. The hydroxysilyl groups form siloxane bonds (Si-O-Si) (see scheme (B)), transforming into a silane oligomer that is poorly soluble in water (the tetrazolium compound with the group shown in chemical formula (e) in scheme (B)). It should be noted that X in the group shown in chemical formula (e) is an integer representing the number of repeating units.

[0123] When the amount of silane oligomers generated in the surface treatment solution increases, they do not dissolve and precipitate out (causing the treatment solution to become cloudy). They adhere to the treatment tank, the piping connected to the treatment tank, and sensors immersed in the treatment solution used to detect the temperature and level of the treatment solution, which may hinder the smooth progress of surface treatment.

[0124] To avoid this situation, in the preparation of the surface treatment solution, the aforementioned organic solvent is preferably included as a solubilizer for the water-insoluble silane oligomer. Furthermore, in the preparation of the surface treatment solution, in order to promote the dissolution of the tetrazolium compound (I), the aforementioned solubilizer (acid, base, organic solvent) is preferably included. It should be noted that organic solvents also function as solubilizers for silane oligomers; therefore, in the surface treatment solution of the present invention, at least one selected from the group consisting of acid, base, and organic solvent is preferably included as a solubilizer.

[0125] Similarly, in order to improve the stability of the surface treatment solution and the uniformity of the chemical conversion coating, substances that generate halide ions such as fluoride ions, chloride ions, bromide ions, and iodide ions, as well as metal ions such as copper ions, iron ions, and zinc ions, can also be used.

[0126] Halogen ions exhibit the effect of uniformly forming flat portions of the chemical conversion coating. Examples of substances that generate halide ions include: lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, magnesium iodide, calcium iodide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, cuprous chloride, cuprous chloride, cuprous bromide, and cuprous bromide. Halogen compounds may also be present as impurities in other components.

[0127] The content of halide ions in the surface treatment solution is not particularly limited, but is preferably 0.1 mol / L or less (especially 0 to 0.1 mol / L), more preferably 0.05 mol / L or less (especially 0 to 0.05 mol / L), even more preferably 0.02 mol / L or less (especially 0 to 0.02 mol / L), and particularly preferably 0.01 mol / L or less (especially 0 to 0.01 mol / L).

[0128] Copper ions form complexes with tetrazolium compounds (I), which can improve the strength of chemical conversion coatings or the adhesion strength between metals and resins. Copper ions can be monovalent or divalent. Examples of substances that can generate copper ions include: metallic copper, copper sulfates (and their hydrates (especially pentahydrates)), copper formates (and their hydrates (especially tetrahydrates)), copper nitrates, cuprous chloride, copper chloride, copper acetates (and their hydrates (especially monohydrates)), copper hydroxides, copper oxides, copper sulfides, copper carbonates, cuprous bromide, copper bromide, copper phosphates, and copper benzoates.

[0129] In addition, the copper ions in the surface treatment solution may also include copper ions dissolved from the metallic copper and copper oxide contained in the copper circuit when the copper circuit is treated with the surface treatment solution.

[0130] The content of copper ions in the surface treatment solution is not particularly limited, but is preferably 1 mol / L or less (especially 0 mol / L or more and 1 mol / L or less), more preferably 0.5 mol / L or less (especially 0 mol / L or more and 0.5 mol / L or less), further preferably 0.1 mol / L or less (especially 0 mol / L or more and 0.1 mol / L or less), and particularly preferably 0.01 mol / L or less (especially 0 mol / L or more and 0.01 mol / L or less).

[0131] Furthermore, known coupling agents may also be used in combination without impairing the effects of the present invention. Examples of known coupling agents include silane-based coupling agents (silane coupling agents) having thiol (mercapto) groups, vinyl groups, epoxy groups, (meth)acryloyl groups, amino groups, chloropropyl groups, etc.

[0132] Examples of such silane coupling agents include: 3-Mercaptopropyltrimethoxysilane, 3-Mercaptopropylmethyldimethoxysilane and other mercaptosilane compounds; Vinyltrichlorosilane, Vinyltrimethoxysilane, Vinylsilane compounds such as vinyltriethoxysilane; Styrene-based silane compounds such as styrene-trimethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-Epoxypropoxypropyltrimethoxysilane, 3-Epoxypropoxypropylmethyldiethoxysilane, Epoxysilane compounds such as 3-epoxypropoxypropyltriethoxysilane; Acryloyloxypropyltrimethoxysilane and other acryloxysilane compounds; 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropylmethyldiethoxysilane, 3-Methacryloxypropyltriethoxysilane and other methacryloxysilane compounds; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-Phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane and other aminosilane compounds; 3-Uretopropyltriethoxysilane and other ureosilane compounds; 3-Chloropropyltrimethoxysilane and other chloropropylsilane compounds; Sulfide silane compounds such as bis(triethoxysilylpropyl)tetrasulfide; and Isocyanate-based silane compounds such as 3-isocyanate-propyltriethoxysilane.

[0133] In addition, aluminum-based coupling agents, titanium-based coupling agents, zirconium-based coupling agents, etc. can also be cited.

[0134] The surface treatment solution of the present invention can generally be adjusted at a pH of -1 to 12. The surface treatment solution of the present invention preferably has a pH of 3 to 11.5. Furthermore, in acidic regions, a pH of 3 to 7 is more preferred, and in alkaline regions, a pH of 8 to 11.5 is more preferred, and a pH of 8.5 to 9.5 is even more preferred.

[0135] (Handling method)

[0136] 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. Similar to the case of the coupling agent described above, spraying, impregnation, coating, or other means can be used.

[0137] Regarding the contact time between the surface treatment liquid and the substrate (processing time), it is preferably 1 second to 10 minutes, more preferably 5 seconds to 3 minutes. When the processing time is less than 1 second, the thickness of the chemical conversion coating formed on the substrate surface becomes thinner, making it difficult to obtain sufficient adhesion between materials of different materials. On the other hand, even if the processing time is greater than 10 minutes, the thickness of the chemical conversion coating does not vary significantly. Therefore, from a productivity point of view, it is preferable to perform the processing within 10 minutes.

[0138] In addition, the temperature of the treatment liquid when it comes into contact with the substrate surface is preferably set to 5 to 50°C, but it can be appropriately set in relation to the treatment time mentioned above.

[0139] After the surface treatment liquid of the present invention comes into contact with the substrate, it can be dried after washing with water, or it can be dried without washing with water.

[0140] The drying process is preferably set at a temperature of room temperature to 150°C.

[0141] It should be noted that the water used for washing is preferably pure water such as ion-exchanged water or distilled water. There are no particular restrictions on the washing method or time; it can be based on spraying, immersion, or other appropriate methods for an appropriate duration.

[0142] It should be noted that the thickness of the chemical conversion coating is preferably 0.5 nm to 1000 nm, more preferably 1 to 200 nm, and even more preferably 1 to 100 nm. When the film thickness is above 0.5 nm, the adhesion between materials is sufficiently improved, and when it is below 1000 nm, the chemical resistance of the chemical conversion coating can be maintained.

[0143] In this invention, the dried chemical conversion coating can be treated with plasma, laser, ion beam, ozone, heating, humidification, etc., to modify the surface of the chemical conversion coating. Alternatively, mechanical grinding methods such as plasma, laser, ion beam, pumice brush, and drill bits can be used to clean the metal surface to remove resin and ion residues.

[0144] Before bringing the surface treatment liquid of the present invention into contact with the surface of copper or copper alloy (hereinafter, both are sometimes referred to as copper), the surface of the copper may be subjected to at least one pretreatment selected from pickling, alkali treatment, roughening treatment, heat treatment, rust prevention treatment or chemical conversion treatment.

[0145] The pickling process described above is performed to remove grease and grease adhering to the copper surface and to remove the oxide coating on the copper surface. 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 in this pickling process.

[0146] The aforementioned alkaline treatment is performed to remove grease adhering to the copper surface and to remove residues from previous processes (e.g., dry film resists used in copper circuit formation). This alkaline treatment can be performed using solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amines such as ammonia, ethanolamine, monopropanolamine, and tetramethylammonium hydroxide, as well as aqueous solutions and organic solvents 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.

[0147] The roughening treatment described above is performed to improve the adhesion between copper and resin based on the anchoring effect. By giving the copper surface an uneven shape, the adhesion between the copper and resin materials can be improved. This roughening treatment can be performed using methods such as micro-etching, electroplating, chemical plating, oxidation (black oxide, brown oxide), redox, brush polishing, and jet washing.

[0148] In micro-etching, various etchants can be used, such as those based on organic acids-divalent copper ions, sulfuric acid-hydrogen peroxide, persulfate, copper chloride, and iron chloride. In electroplating, fine copper particles are deposited on the copper surface to create an uneven surface.

[0149] In the above heat-resistant treatment, a coating selected from nickel, nickel-phosphorus, zinc, zinc-nickel, copper-zinc, copper-nickel, copper-nickel-cobalt, or nickel-cobalt is formed on the copper surface. The coating can be formed using a known electroplating method, but is not limited to electroplating; vapor deposition or other means may also be used.

[0150] The aforementioned rust prevention treatment is carried out to prevent oxidation and corrosion of the copper surface. This can be achieved by forming a zinc or zinc alloy coating on the copper surface, or by electrolytic chromate coating. Alternatively, a treatment solution containing organic compound rust inhibitors such as benzotriazole can be brought into contact with the copper surface.

[0151] In the above chemical conversion process, methods for forming a passive coating of tin or a passive coating of copper oxide can be used.

[0152] 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 improving the film-forming properties of the chemical conversion coating formed on the copper surface and ensuring uniform thickness of the chemical conversion coating formed on the copper surface. The valence of the copper ions is not particularly limited; they may be monovalent or divalent copper ions.

[0153] As a copper ion source for aqueous solutions containing copper ions, there are no particular limitations as long as the copper salt is soluble in water; examples include copper sulfate, copper nitrate, copper chloride, copper formate, and copper acetate. Ammonia or hydrochloric acid can also be added to dissolve the copper salt in water.

[0154] Before and / or after contacting the surface treatment solution of the present invention with the copper surface, an acidic or alkaline aqueous solution may be applied to the copper surface. This acidic or alkaline aqueous solution, like the aforementioned aqueous solution containing copper ions, also has the function of ensuring uniform thickness of the chemical conversion coating formed on the copper surface.

[0155] There are no particular limitations on acidic and alkaline aqueous solutions. Examples of acidic aqueous solutions include: aqueous solutions containing inorganic 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: hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; amines such as ammonia, ethanolamine, monopropanolamine, and tetramethylammonium hydroxide; and aqueous solutions of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium acetate, potassium acetate, sodium phosphate, disodium hydrogen phosphate, potassium phosphate, and dipotassium hydrogen phosphate.

[0156] Before and / or after contacting the surface treatment liquid of the present invention with the copper surface, an aqueous solution containing a known coupling agent may be contacted with the copper surface.

[0157] Before and / or after contacting the surface treatment agent of the present invention with the copper surface, an impregnation solution containing an azole compound may be contacted with the copper surface. This impregnation solution has the function of improving the strength of the chemical conversion coating formed on the copper surface.

[0158] There are no particular limitations on azole compounds; examples include commercially available imidazole compounds, triazole compounds, and tetraazole compounds. Examples of these azole compounds include: imidazole, 2-methylimidazolium, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4-triazole, 5-methyltetrazole, 5-aminotetrazole, and 5-phenyltetrazole.

[0159] The impregnation solution contains water and / or a solubilizer in addition to the azole compound. Examples of solubilizers include the aforementioned acids, bases, and organic solvents.

[0160] The impregnation solution may further contain additives. Examples of additives include copper compounds, halogen compounds, and other additives (such as ammonium salts like ammonium sulfate, ammonium formate, ammonium acetate, ammonium chloride, ammonium carbonate, and ammonium nitrate).

[0161] After the surface treatment liquid of the present invention comes into contact with the copper surface, it can be contacted with a treatment liquid containing, for example, a known organic compound rust inhibitor such as a benzotriazole rust inhibitor.

[0162] 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 using the surface treatment liquid of the present invention to treat the surface of the substrate, a chemical conversion coating can be formed on the substrate surface, improving adhesion to other materials.

[0163] In this invention, the surface treatment liquid of this invention can be used to bond two materials selected from the group consisting of metals, inorganic materials, and resin materials. By bonding the two materials through a chemical conversion coating layer formed by the surface treatment liquid of this invention, their affinity can be improved, thus enabling even materials of different materials to be bonded more firmly.

[0164] (Adhesion method)

[0165] As a method for bonding two materials, known methods can be used. Examples include: contacting the surface treatment liquid of the present invention with the surface of a substrate containing a metal, inorganic material or resin material to form a chemical conversion coating; coating, pressing, mixing or otherwise applying other substrates to part or all of the formed chemical conversion coating; using adhesives, adhesive sheets (films); or a combination of these methods to perform bonding.

[0166] Alternatively, the following methods can be used: contacting the surface treatment liquid of the present invention with the surfaces of two substrates selected from metal, inorganic materials, and resin materials, forming chemical conversion coatings on the surfaces of the two substrates respectively, coating, pressing, mixing, etc. on the two substrates; using adhesives, adhesive sheets (films); or combining these methods to bond.

[0167] By using the surface treatment liquid of the present invention, as described above, two materials, especially two materials of different materials, can be bonded together, thus making it applicable to various electrical and electronic components, semiconductor wafers, printed wiring boards and other electronic devices.

[0168] It should be noted that, in this invention, the surface treatment liquid of this invention is preferably used for substrates formed of metal, particularly copper or copper alloys. For example, it is suitable for surface treatment of copper or copper alloys aimed at improving the adhesion (bonding) 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 wiring boards having an insulating resin layer in contact with the copper wiring layer, the adhesion between the copper wiring layer and the insulating resin layer can be improved.

[0169] In applications involving semiconductor wafers, this is suitable for surface treatment of semiconductor circuits aimed at improving the adhesion (seamlessness) between semiconductor circuits formed on semiconductor wafers and protective films (such as photosensitive positive, photosensitive negative, non-photosensitive buffer coatings, bump protective films, and other insulating protective films).

[0170] In addition, in packaging substrates (WL-CSP, FO-WLP, PLP), 2.5D or 3D interposer substrates on which redistribution layers are formed on semiconductor wafers, surface treatment of copper circuit redistribution layers is suitable for improving the adhesion (tightness) of copper circuit redistribution layers to insulating materials.

[0171] Examples of protective films and insulating materials include polyimide resins, polybenzoxazole resins, and silicone resins.

[0172] The aforementioned printed wiring board can be manufactured by contacting the surface treatment liquid of the present invention with the surface of the copper wiring, followed by washing with water and drying to form an insulating resin layer on the surface of the copper wiring. Regarding the contact method, as described above, immersing the copper wiring in the surface treatment liquid or spraying the copper wiring with the treatment liquid are simple and reliable preferred methods.

[0173] In addition, there are no particular limitations to the above-mentioned water washing method. Immersing the copper wiring in cleaning water or spraying the surface of the copper wiring with cleaning water is a simple and reliable preferred method.

[0174] In forming the aforementioned insulating resin layer, known methods can be employed, such as bonding a semi-cured resin material or coating a liquid resin material containing a solvent. Next, vias are formed to allow the wiring above and below to conduct. By repeating this process, a multilayer printed circuit board can be fabricated.

[0175] The following shows an example of the semi-additive method of using the surface treatment liquid of the present invention in the circuit formation method of the above-described printed wiring board.

[0176] A method for manufacturing a circuit board includes at least one of the following steps: (a) Step: Prepare an insulating substrate, wherein the insulating substrate has a first conductive layer on a first surface of the insulating substrate or an insulating substrate having through holes and vias, a second surface opposite to the first surface, and the inner wall of the through holes and vias. (b) Step, forming a photocrosslinked resin layer and a mask layer on the first and second surfaces, and using the photocrosslinked resin layer and mask layer to cover the first and second surfaces as well as the first conductive layer on the inner wall of the through hole and via. (c) Process, patterning exposure is performed on the first and second surfaces, as well as the photocrosslinked resin layer around the through holes and vias; (d) Process: Remove the mask layer around the first and second surfaces, as well as the through holes and vias; (e) Step: Using a photocrosslinking resin layer removal liquid, the uncured photocrosslinking resin layer on the first surface and the second surface, as well as around the through holes and vias, is developed and removed to expose the first conductive layer on the first surface and the first conductive layer on the second surface, as well as the first conductive layer around the through holes and vias. (f) A second conductive layer is formed on the first conductive layer exposed on the first and second surfaces and on the inner walls of the through holes and vias by electroplating. (g) Step: Remove the cured photocrosslinking resin layer on the first surface and the second surface, as well as around the through hole and via, so that the first and second conductive layers on the first surface and the second surface, as well as the inner wall of the through hole and via, are exposed. (h) process, the exposed first conductive layer is flash-etched away; (i) A third conductive layer is formed on the first and second surfaces and on the first and second conductive layers of the through hole and the inner wall of the via by chemical plating and electroplating. (j) In the process of laminating an insulating resin layer on the first surface, the second surface, and the first, second, and third conductive layers on the inner walls of the through holes and vias, an insulating resin layer is laminated. The surface treatment liquid of the present invention is brought into contact with at least one of the following: a first, second, and third conductive layer, an insulating resin substrate, a photocrosslinking resin layer used in etching a resist layer, a resist plating layer, and an insulating resin layer, to manufacture a printed wiring board.

[0177] Furthermore, the following example illustrates the subtractive method of using the surface treatment liquid of the present invention in the circuit formation method of the above-described printed wiring board.

[0178] A method for manufacturing a circuit board includes at least one of the following steps: (a) Step: Prepare an insulating substrate, wherein the insulating substrate has a first conductive layer on a first surface of the insulating substrate or an insulating substrate having through holes and vias, a second surface opposite to the first surface, and the inner wall of the through holes and vias. (b) Step, forming a photocrosslinked resin layer and a mask layer on the first and second surfaces, and using the photocrosslinked resin layer and mask layer to cover the first and second surfaces as well as the first conductive layer on the inner wall of the through hole and via. (c) Process, patterning exposure is performed on the first and second surfaces, as well as the photocrosslinked resin layer around the through holes and vias; (d) Process: Remove the mask layer around the first and second surfaces, as well as the through holes and vias; (e) Step: Using a photocrosslinking resin layer removal liquid, the uncured photocrosslinking resin layer on the first surface and the second surface, as well as around the through holes and vias, is developed and removed to expose the first conductive layer on the first surface and the first conductive layer on the second surface, as well as the first conductive layer around the through holes and vias. (f) The first conductive layer exposed on the first and second surfaces, as well as on the inner walls of the through holes and vias, is etched away. (g) Step: Remove the cured photocrosslinking resin layer on the first surface and the second surface, as well as around the through hole and via, so that the first conductive layer on the first surface and the second surface, as well as the inner wall of the through hole and via, is exposed. (h) step, through chemical plating and electroplating, a second conductive layer is formed on the first and second surfaces and on the first conductive layer of the through hole and the inner wall of the via. (i) An insulating resin layer is laminated on the first and second conductive layers on the first and second surfaces, as well as on the inner walls of the through holes and vias. The printed wiring board is manufactured by contacting the surface treatment liquid of the present invention with at least one of the following: first and second conductive layers, insulating resin substrate, photocrosslinking resin layer used in etching resist layer, plating resist layer, insulating resin layer, etc., on the first and second surfaces and the inner walls of through holes and vias.

[0179] The aforementioned copper wiring and conductive layer can be fabricated using any method such as chemical plating, electroplating, vapor deposition, sputtering, or inlay, and may also include internal vias, through holes, and connecting terminals.

[0180] Furthermore, the "copper" involved in this invention refers to copper used in various applications and forms, including foils (electrolytic copper foil, rolled copper foil, resin-coated copper foil, carrier-coated copper foil, electroless copper foil, sputtered copper foil, thin copper foil), films (electroless copper film, electroplated copper film), thin films formed by vapor deposition, sputtering, inlay methods, etc., in electronic devices, decorations, and building materials such as printed wiring boards and lead frames, as well as in granules, needles, fibers, wires, rods, tubes, and plates. It should be noted that, in the case of copper wiring with high-frequency electrical signal flow in recent years, the copper surface is preferably a smooth surface with an average roughness of 0.1 μm or less. As a pretreatment, nickel, zinc, chromium, tin, etc., can be plated onto the copper surface.

[0181] Additionally, for example, in the application of lead frames during wire bonding, the surface treatment liquid of the present invention is suitable for surface treatment of lead frames aimed at improving adhesion (adhesion) to sealing resin and adhesives used in the process of lead frame fabrication, or on the metal surface of the lead frame after mounting semiconductor chips (before and after the bare wafer bonding and pre-baking processes), the metal surface of the lead frame after wire bonding, or the metal surface of the lead frame up to the process of resin sealing (before and after the resin molding and baking processes).

[0182] Additionally, for example, in applications involving lead frames during flip chip mounting, the surface treatment liquid of the present invention is suitable for surface treatment of lead frames aimed at improving adhesion (sealing) with sealing resin and adhesives used during semiconductor chip mounting, in the following ways: on the metal surface during lead frame fabrication, after temporary placement of bonding materials (solder, Au plating, Sn plating, etc.), on the metal surface of the lead frame after mounting semiconductor chips (before and after alignment, chip mounting, baking processes), on the metal surface of the lead frame after formal curing (before and after reflow heating, hot pressing, ultrasonic, plasma, etc. processes), and on the metal surface of the lead frame during resin sealing processes.

[0183] Additionally, for example, in applications that improve the use of micro-wiring substrates for integrating 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 2.5D organic substrates or glass substrates, component-embedded substrates (EPS substrates) in which semiconductors are embedded, and coreless substrates, for the purpose of improving the adhesion (tightness) of copper circuit wiring layers to insulating materials.

[0184] In addition, for example, the metal surface treatment liquid of the present invention is suitable for surface treatment of copper circuit wiring layers with the purpose of improving the adhesion (adhesion) between copper circuit wiring layers and insulating materials in cases where through-hole filling plating is performed by laser through-hole processing of upper and lower layers with built-in pattern wiring, and in cases where copper pillars formed by plating are used for conduction of upper and lower layers and molding resin is used for insulating layers.

[0185] Furthermore, the carrier copper foil treated by the surface treatment liquid of the present invention refers to an extremely thin electrolytic copper foil used in a printed wiring board that includes a process of forming a circuit using any one of the methods of semi-addition, subtraction, partial addition, or modified semi-addition, and has a copper foil carrier, a release layer laminated on the copper foil carrier, and an extremely thin copper layer laminated on the release layer. At least one pretreatment selected from the group consisting of pickling, roughening, heat treatment, rust prevention, or chemical conversion treatment can be applied to the copper surface.

[0186] (Insulating composition)

[0187] By incorporating the coupling agent of the present invention into resin or inorganic materials, insulating compositions can be prepared.

[0188] Alternatively, a tetrazolium compound (I) can be dissolved in an organic solvent or the like and mixed with a resin material or an inorganic material to obtain an insulating composition.

[0189] The content of tetrazolium compound (I) in the insulating composition is preferably 0.001 wt% to 10 wt%, more preferably 0.01 wt% to 5 wt%. When the content of tetrazolium compound (I) in the insulating composition is 0.001 wt% or more, the effect of improving adhesion can be sufficiently obtained. When the concentration exceeds 10 wt%, the effect of improving adhesion is almost saturated. Therefore, from an economic point of view, the content of tetrazolium compound (I) is preferably 10 wt% or less.

[0190] The above-mentioned insulating composition can be prepared by known methods. For example, an insulating composition can be prepared by dissolving a tetrazolium compound (I) in an organic solvent and mixing it with a solid or liquid resin material. Alternatively, an insulating composition can be prepared by directly adding the tetrazolium compound (I) to a liquid resin material and mixing it.

[0191] The insulating composition of the present invention provides an insulating material with high adhesive strength, and is therefore suitable for use in various electrical and electronic components, electronic devices such as printed wiring boards.

[0192] Furthermore, Japanese Patent Application Publication No. 2009-19266 discloses an invention relating to a method for forming a silane coupling agent coating, characterized by comprising: a step of coating a metal surface with a liquid containing a silane coupling agent; a step of drying the metal surface coated with the liquid at a temperature of 25 to 150°C for no more than 5 minutes; and a step of washing the dried metal surface with water.

[0193] In addition, as a pre-surface treatment, an adhesive metal layer such as tin can be formed on the metal surface using an immersion plating solution.

[0194] The surface treatment liquid of the present invention can be used as the aforementioned liquid containing a silane coupling agent. It should be noted that the matters described in this patent publication constitute a part of this specification by reference.

[0195] Example

[0196] The present invention will be specifically described below through examples (synthesis experiments and evaluation experiments), but the present invention is not limited thereto.

[0197] It should be noted that OEt in the chemical formula shown below represents ethoxy.

[0198] The starting materials used in the synthesis experiment, including tetrazolium compounds and halogenated alkylsilane compounds, are shown below.

[0199] [Tetraazole compounds]

[0200] • The tetrazolium compound (5,5'-bi(1,2,3,4-tetrazolium) diammonium salt) shown in the following chemical formula (11): manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd.

[0201] • The tetrazolium compound (5,5'-ethylenebis(1,2,3,4-tetrazolium)) shown in the following chemical formula (12) was synthesized according to the method described in International Publication No. 2015 / 084830.

[0202]

[0203] [Halogenated alkylsilane compounds]

[0204] ·3-Chloropropyltriethoxysilane: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0205] <Synthesis of Tetrazolium Compound (I)>

[0206] The tetrazolium compounds of Examples 1 and 2 below were synthesized.

[0207] [Example 1]

[0208] Synthesis of a mixture of 1-[3-(triethoxysilyl)propyl]-5,5'-bi(1,2,3,4-tetrazolium) and 2-[3-(triethoxysilyl)propyl]-5,5'-bi(1,2,3,4-tetrazolium)>

[0209] Synthesize the compound shown in chemical formula (1) below (a mixture of 1-[3-(triethoxysilyl)propyl]-5,5'-bi(1,2,3,4-tetrazolium) and 2-[3-(triethoxysilyl)propyl]-5,5'-bi(1,2,3,4-tetrazolium)).

[0210] A suspension consisting of 17.0 g (98.7 mmol) of 5,5'-bi(1,2,3,4-tetraazole)diammonium salt and 182 mL of dimethyl sulfoxide was heated to 70 °C, and 33.6 g (98.7 mmol) of 20% sodium ethoxide ethanol solution was added. The mixture was then heated to 100 °C and stirred for 1 hour. Next, after cooling to 70 °C, 23.8 g (98.8 mmol) of 3-chloropropyltriethoxysilane was added, and the mixture was stirred for 10 minutes. The mixture was then heated to 100 °C and stirred for 20 hours. After cooling to room temperature, the insoluble matter was filtered off, and the filtrate was removed by vacuum distillation. 455 mL of isopropyl acetate was further added, and the mixture was stirred at room temperature for 1 hour. The insoluble matter was then filtered off, and the filtrate was removed by vacuum distillation to give 30.7 g (89.7 mmol, 91% yield) of a light brown liquid.

[0211] The resulting light brown liquid 1 The H-NMR spectral data are as follows.

[0212] 1 H-NMR(DMSO-d6)δ:0.50(m,2H),1.13(m,9H),2.00(m,2H),3.73(m,6H),4.84(m,2H).

[0213] By this 1 The light brown liquid obtained by H-NMR spectral data was identified as the target tetrazolium compound represented by chemical formula (1).

[0214]

[0215] [Example 2]

[0216] Synthesis of a mixture of 1-[3-(triethoxysilyl)propyl]-5,5'-ethylenebis(1,2,3,4-tetrazolium) and 2-[3-(triethoxysilyl)propyl]-5,5'-ethylenebis(1,2,3,4-tetrazolium)

[0217] Synthesize the compound shown in chemical formula (2) below (a mixture of 1-[3-(triethoxysilyl)propyl]-5,5'-ethylenebis(1,2,3,4-tetrazolium) and 2-[3-(triethoxysilyl)propyl]-5,5'-ethylenebis(1,2,3,4-tetrazolium)).

[0218] A suspension consisting of 9.5 g (57.2 mmol) of 5,5'-ethylenebis(1,2,3,4-tetraazole) and 62 mL of N,N-dimethylacetamide was heated to 50 °C, and 20.0 g (58.8 mmol) of 20% sodium ethoxide ethanol solution was added. The mixture was then heated to 70 °C and stirred for 1 hour. Next, 13.8 g (57.3 mmol) of 3-chloropropyltriethoxysilane was added, and the mixture was stirred for 10 minutes. The mixture was then heated to 100 °C and stirred for 20 hours. The reaction mixture was cooled to 60 °C, and the filtrate was removed by vacuum distillation. Next, 120 mL of isopropyl acetate was added, and the mixture was stirred at room temperature for 1 hour. The insoluble matter was filtered off, and the filtrate was removed by vacuum distillation to give 18.4 g (49.7 mmol, 87% yield) of a light brown liquid.

[0219] The resulting light brown liquid 1 The H-NMR spectral data are as follows.

[0220] 1 H-NMR(DMSO-d6)δ:0.51(m,1.5H),0.58(m,0.5H),1.12(m,9H),1.92(m,2H),3.35(m,4H),3.74(m,6H),4.33(m,0.5H),4.57(m,1.5H).

[0221] By this 1 The light brown liquid obtained by H-NMR spectral data was identified as the target tetrazolium compound represented by chemical formula (2).

[0222]

[0223] <Adhesion Test 1>

[0224] The adhesive properties of the surface treatment liquids prepared in Examples 3-4 were evaluated as follows.

[0225] [Evaluation test of adhesion (i)]

[0226] (1) Metal

[0227] Electrolytic copper foil (thickness: 35μm) is used as the metal.

[0228] (2) Surface treatment of metals

[0229] The copper foil above shall be processed according to the following steps a to b.

[0230] a. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water rinsing

[0231] b. Apply surface treatment liquid by brushing, and dry for 1 minute (100℃).

[0232] (3) Bonding of metal and resin

[0233] A glass cloth epoxy resin impregnated prepreg (MEGTRON7 (manufactured by Panasonic)) is laminated onto the S-surface of the treated copper foil, and the copper foil and prepreg are bonded together to produce a copper-clad laminate.

[0234] (4) Evaluation of adhesiveness

[0235] For this copper-clad laminate, after reflow heating once (peak temperature 288℃, atmospheric), a test piece with a width of 10mm was made according to "JIS C6481(1996)" to determine the peel strength (peel force (kN / m)) of the copper foil.

[0236] [Example 3]

[0237] Add 99.5g of a mixture of acetic acid, ion-exchanged water and methanol in a ratio of 1:8:90.5 (by weight) to 0.5g of the tetrazolium compound represented by the above chemical formula (1) as a coupling agent, and stir at room temperature for 1 hour to prepare a surface treatment solution.

[0238] [Example 4]

[0239] The surface treatment solution was prepared in the same manner as in Example 3, except that the tetrazolium compound represented by the above chemical formula (2) was used instead of the tetrazolium compound represented by the above chemical formula (1).

[0240] For the surface treatment liquids prepared above, an adhesion evaluation test (i) was conducted. The test results are shown in Table 1.

[0241] [Comparative Example 1]

[0242] For the copper foil in process (2)a., which only underwent the adhesion evaluation test (i), the adhesion evaluation test (i) was performed. The test results are shown in Table 1.

[0243]

[0244] As can be seen from the results in Table 1, the surface treatment liquid of the present invention (the surface treatment liquid of Examples 3 to 4) has higher peel strength and better adhesion between metal and resin compared with Comparative Example 1.

[0245] <Adhesion Test 2>

[0246] The adhesive properties of the surface treatment liquid prepared in Example 5 were evaluated as follows.

[0247] [Evaluation of Adhesion Test (ii)]

[0248] (1) Metal

[0249] Electrolytic copper foil (thickness: 35μm) is used as the metal.

[0250] (2) Surface treatment of metals

[0251] The copper foil above shall be processed according to the following steps a to b.

[0252] a. Acid cleaning (5% hydrochloric acid aqueous solution) / 1 minute (room temperature), water rinsing

[0253] b. Immerse in surface treatment solution for 2 minutes (30°C), rinse with water, and dry for 1 minute (100°C).

[0254] (3) Bonding of metal and resin

[0255] After applying a polyimide varnish (manufactured by UBE Corporation, trade name "U-Varnish A") to the S-side of the treated copper foil to a thickness of 100 μm using a bar coater, the copper-clad laminate is cured under a nitrogen atmosphere (120℃ / 30 min, 150℃ / 10 min, 200℃ / 10 min, 250℃ / 10 min) to produce a copper-clad laminate.

[0256] (4) Evaluation of adhesiveness

[0257] For this copper-clad laminate, it was kept in an oven at 150°C under atmospheric conditions for 250 hours (HTS treatment). Then, according to "JIS C6481 (1996)", test pieces with a width of 10 mm were made, and the peel strength of the copper foil (peel force (kN / m)) was determined.

[0258] [Example 5]

[0259] Add 99.5g of a mixture of acetic acid and ion-exchanged water (weight ratio) of 5:95 to 0.5g of the tetrazolium compound shown in the above chemical formula (2) as a coupling agent, adjust the pH to 7.1 with ammonia water, and stir for 1 hour at room temperature to prepare a surface treatment solution.

[0260] The surface treatment liquid prepared above was subjected to an adhesion evaluation test (ii). The test results are shown in Table 2.

[0261] [Comparative Example 2]

[0262] For the copper foil in process (2)a, which only underwent the adhesion evaluation test (ii), an adhesion evaluation test (ii) was performed. The test results are shown in Table 2.

[0263]

[0264] As can be seen from the results in Table 2, the surface treatment liquid of the present invention (the surface treatment liquid of Example 5) has higher peel strength and better adhesion between metal and resin compared with Comparative Example 2.

[0265] Although the present invention has been described in detail 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. 2023-138677, filed on August 29, 2023, the contents of which are incorporated herein by reference.

[0266] Industrial practicality

[0267] The tetrazolium compound of the present invention can be formulated into a coupling agent with the added functions of preventing metal corrosion and curing epoxy resin and polyurethane resin, which are characteristic of tetrazolium compounds. Therefore, it is expected to be used in composite materials such as printed wiring boards made by combining a variety of different kinds of materials.

[0268] Furthermore, according to the present invention, the adhesion (bonding) of metals, inorganic materials, and resin materials can be improved, thus maintaining a smooth state without roughening the substrate surface. Therefore, the present invention can make a significant contribution to the miniaturization, thinning, high-frequency operation, and high-density of multilayer printed wiring boards, and thus has great industrial applicability.

Claims

1. A tetrazolium compound represented by chemical formula (I), In equation (I), R 1 and R 2 Same or different, indicating hydrogen atoms or -(CH2). m -Si(OR) 3-p (OH) p The groups shown, wherein, R represents methyl or ethyl, m represents an integer from 1 to 18, p represents an integer from 0 to 3, and X represents phenylene, -NH-, or -(CH2). n - The group shown, n represents an integer from 0 to 12, where R is excluded. 1 and R 2 The case where it is both a hydrogen atom.

2. The method for synthesizing the tetrazolium compound according to claim 1, wherein, The tetrazolium compound represented by chemical formula (II) is reacted with the haloalkylsilane compound represented by chemical formula (III). In equation (II), X is the same as above. In formula (III), R, m, and p are the same as above, and Hal represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

3. A coupling agent comprising the tetrazolium compound of claim 1.

4. A surface treatment liquid containing the tetrazolium compound of claim 1.

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

6. The 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, wherein, The surface treatment liquid of claim 4 is brought into contact with the surface of at least one 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, Before the surface treatment liquid is brought into contact with the surface of copper or copper alloy, an aqueous solution containing copper ions is brought into contact with the surface of copper or copper alloy.

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

13. An adhesive method comprising contacting the surface treatment liquid of claim 4 with at least one selected from the group consisting of metals, inorganic materials and resin materials to form a chemical conversion coating on the at least one, and bonding the chemical conversion coatings together.

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

15. A printed wiring board is formed by bonding two materials selected from the group consisting of metals, inorganic materials and resin materials via a chemical conversion coating formed by the surface treatment liquid of claim 4.

16. A semiconductor wafer formed by bonding two materials selected from the group consisting of metals, inorganic materials and resin materials via a chemical conversion coating formed by the surface treatment liquid of claim 4.

17. An insulating composition comprising The coupling agent according to claim 3, and Resin materials or inorganic materials.

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

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

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

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