Tetrazole compound, method for synthesizing said tetrazole compound, and use thereof

Abstract

The present invention provides a novel tetrazole compound, a method for synthesizing the same, and a coupling agent. A tetrazole compound according to the present invention is represented by chemical formula (I). In chemical formula (I), R1 and R2 are the same or different and represent 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 phenylene group, -NH-, or -(CH2)n-, and n represents an integer of 0-12. However, R1 and R2 are not simultaneously hydrogen atoms.

Description

Tetrazole compounds, synthesis methods for said tetrazole compounds and uses thereof

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

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

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

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

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

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

[0007] In recent years, in the field of electric and electronic materials, there has been a demand for improved adhesion between materials in response to trends toward smaller size, thinner size, higher precision, faster propagation speeds, etc. Although azole compounds such as those disclosed in Patent Documents 1 and 2 can exhibit excellent adhesion, compounds that can exhibit even higher adhesion have been desired.

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

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

[0010]

[0011] (In formula (I), R １ and R ２ are the same or different and represent a hydrogen atom or -(CH ２ ) ｍ -Si(OR) ３－ｐ (OH) ｐ where 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 —(CH ２ ) ｎ -, and n represents an integer of 0 to 12. １ and R ２ Except when is also a hydrogen atom.)

[0012] The second invention is a method for synthesizing the tetrazole compound of the first invention, which comprises reacting a tetrazole compound represented by chemical formula (II) with a halogenated alkylsilane compound represented by chemical formula (III).

[0013]

[0014] (In formula (II), X is the same as defined above.)

[0015]

[0016] (In formula (III), R, m, and p are the same as defined above. Hal represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)

[0017] The third invention is a coupling agent containing the tetrazole compound of the first invention. The fourth invention is a surface treatment liquid containing the tetrazole compound of the first invention. The fifth invention is the surface treatment liquid of the fourth invention used to treat at least one surface selected from the group consisting of metals, inorganic materials, and resin materials. The sixth invention is the surface treatment liquid of the fourth invention used to bond two materials selected from the group consisting of metals, inorganic materials, and resin materials. The seventh invention is the surface treatment liquid according to the fifth or sixth invention, in which the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. The eighth invention is a surface treatment method in which the surface treatment liquid according to any one of the fourth to seventh inventions is brought into contact with at least one surface selected from the group consisting of metals, inorganic materials, and resin materials. A ninth invention is the surface treatment method according to the eighth invention, wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. A tenth invention is the surface treatment method according to the eighth or ninth invention, wherein the metal is copper or a copper alloy. An eleventh invention is the surface treatment method according to any one of the eighth to tenth inventions, wherein an aqueous solution containing copper ions is brought into contact with the copper or copper alloy surface before the surface treatment liquid is brought into contact with the copper or copper alloy surface. A twelfth invention is the surface treatment method according to any one of the eighth to eleventh inventions, wherein an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the copper or copper alloy surface after the surface treatment liquid has been brought into contact with the copper or copper alloy surface. A thirteenth invention is a bonding method comprising contacting the surface treatment liquid according to any one of the fourth to seventh inventions with at least one material selected from the group consisting of a metal, an inorganic material, and a resin material to form a chemical conversion coating on at least one of the materials, and bonding the materials together via the chemical conversion coating.The fourteenth invention is a method for bonding metal and resin materials, which comprises contacting at least one of the metal and resin material with the surface treatment liquid according to any one of the fourth to seventh inventions to form a chemical conversion film on at least one of the metal and resin material, and bonding the metal and resin material to each other via the chemical conversion film. The fifteenth invention is a printed wiring board in which two materials selected from the group consisting of metals, inorganic materials, and resin materials are bonded via a chemical conversion film formed using the surface treatment liquid according to any one of the fourth to seventh inventions. The sixteenth invention is a semiconductor wafer in which two materials selected from the group consisting of metals, inorganic materials, and resin materials are bonded via a chemical conversion film formed using the surface treatment liquid according to any one of the fourth to seventh inventions. The seventeenth invention is an insulating composition containing the coupling agent according to the third invention and a resin material or an inorganic material. The eighteenth invention is an insulating material containing the insulating composition according to the seventeenth invention. A nineteenth invention is a printed wiring board having an insulating layer obtained from the insulating composition of the seventeenth invention. A twentieth invention is a semiconductor wafer having an insulating layer obtained from the insulating composition of the seventeenth invention.

[0018] The tetrazole compound of the present invention is a compound in which two tetrazole rings are bonded, and therefore can enhance the interaction with metals, resin materials, etc., and the two tetrazole rings can be bonded to each other by a phenylene group, -NH-, and -(CH ２ ) ｎ Since the bond is formed via a linking group selected from the group consisting of groups represented by -, it is resistant to decomposition by heat or alkali. Furthermore, since the coupling agent of the present invention contains a tetrazole compound in which two tetrazole rings are linked via the linking group, it can improve adhesion between materials with different properties. A surface treatment liquid containing this tetrazole compound can improve adhesion between two materials of different properties, i.e., between a metal and an inorganic material, a metal and a resin material, and an inorganic material and a resin material.

[0019] The present invention will be described in detail below. However, the present invention is not limited to the embodiments described below.

[0020] (Tetrazole Compound) The tetrazole compound of the present invention is represented by the following chemical formula (I) (hereinafter, sometimes referred to as the tetrazole compound of the present invention).

[0021]

[0022] (In formula (I), R １ and R ２ are the same or different and represent a hydrogen atom or -(CH ２ ) ｍ -Si(OR) ３－ｐ (OH) ｐ where 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 —(CH ２ ) ｎ -, and n represents an integer of 0 to 12. １ and R ２ Except when is also a hydrogen atom.)

[0023] - (CH ２ ) ｍ -Si(OR) ３－ｐ (OH) ｐ In the group represented by the formula: m is preferably an integer of 2 to 12, more preferably an integer of 3 to 10, and even more preferably an integer of 3 to 8.

[0024] X is -(CH ２ ) ｎ Preferably, n is a group represented by -, and more preferably, n is an integer of 0 to 10, even more preferably an integer of 0 to 8, and particularly preferably an integer of 0 to 6.

[0025] In the tetrazole compound of the present invention, R １ and R ２ is preferably bonded to the N atom at position 1 or 2 of the tetrazole ring.

[0026] The tetrazole compound of the present invention includes tetrazole compounds represented by chemical formulas (I-1) to (I-8).

[0027]

[0028] (In formulas (I-1) to (I-8), X, m, p, and R are the same as defined above.)

[0029] The tetrazole compound of the present invention is R １ Ga-(CH ２ ) ｍ -Si(OR) ３－ｐ (OH) ｐ is a group represented by R ２ is hydrogen and R １ and R ２is bonded to N at the 1-position of the tetrazole ring (compounds represented by chemical formula (I-1)), specific examples thereof include 1-(trimethoxysilyl)methyl-5,5'-(1,4-phenylene)bis(1,2,3,4-tetrazole), 1-[2-(triethoxysilyl)ethyl]-5,5'-(1,2-phenylene)bis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-(1,3-phenylene)bis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-(1,4-phenylene)bis(1,2,3,4-tetrazole), 1-[6-(triethoxysilyl)hexyl]-5,5'-(1,4-phenylene)bis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-iminobis(1,2,3,4-tetrazole), 1-[8-(trimethoxysilyl)octyl]-5,5'-iminobis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-bi(1,2,3,4-tetrazole), 1-[10-(triethoxysilyl)decyl]-5,5'-bi(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-methylenebis(1,2,3,4-tetrazole), 1-[6-(trimethoxysilyl)hexyl]-5,5'-methylenebis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-ethylenebis(1,2,3,4-tetrazole), 1-[12-(triethoxysilyl)dodecyl]-5,5'-ethylenebis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-tetramethylenebis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-pentamethylenebis(1,2,3,4-tetrazole), 1-[4-(triethoxysilyl)butyl]-5,5'-pentamethylenebis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-hexamethylenebis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-octamethylenebis(1,2,3,4-tetrazole), 1-[2-(trimethoxysilyl)ethyl]-5,5'-nonamethylenebis(1,2,3,4-tetrazole), 1-[2-(trimethoxysilyl)ethyl]-5,5'-decamethylenebis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-undecamethylenebis(1,2,3,4-tetrazole), 1-[3-(triethoxysilyl)propyl]-5,5'-dodecamethylenebis(1,2,3,4-tetrazole), and the like.

[0030] The tetrazole compound of the present invention is R １ and R ２ are the same or different and -(CH ２ ) ｍ -Si(OR) ３－ｐ (OH) ｐ is a group represented by R １ and R ２is bonded to N at the 1-position of the tetrazole ring (compounds represented by chemical formula (I-5)), specific examples include 5,5'-(1,4-phenylene)bis[1-(trimethoxysilyl)methyl-1,2,3,4-tetrazole], 5,5'-(1,2-phenylene)bis{1-[2-(triethoxysilyl)ethyl]-1,2,3,4-tetrazole}, 5,5'-(1,3-phenylene)bis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-(1,4-phenylene)bis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-(1,4-phenylene)bis{1-[6-(triethoxysilyl)hexyl]-1,2,3,4-tetrazole}, 5,5'-iminobis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-iminobis{1-[8-(trimethoxysilyl)octyl]-1,2,3,4-tetrazole}, 5,5'-bi{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-bi{1-[10-(triethoxysilyl)decyl]-1,2,3,4-tetrazole}, 5,5'-methylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-methylenebis{1-[6-(trimethoxysilyl)hexyl]-1,2,3,4-tetrazole}, 5,5'-ethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-ethylenebis{1-[12-(triethoxysilyl)dodecyl]-1,2,3,4-tetrazole}, 5,5'-tetramethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-pentamethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-pentamethylenebis{1-[4-(triethoxysilyl)butyl]-1,2,3,4-tetrazole}, 5,5'-hexamethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-octamethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-nonamethylenebis{1-[2-(trimethoxysilyl)ethyl]-1,2,3,4-tetrazole}, 5,5'-decamethylenebis{1-[2-(trimethoxysilyl)ethyl]-1,2,3,4-tetrazole}, 5,5'-undecamethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, 5,5'-dodecamethylenebis{1-[3-(triethoxysilyl)propyl]-1,2,3,4-tetrazole}, and the like.

[0031] When the tetrazole compound of the present invention is used as a coupling agent or a component of a surface treatment solution, as described below, different types of tetrazole compounds may be used in combination. Furthermore, by reacting a halogenated alkylsilane compound represented by the following chemical formula (III), a tetrazole compound in the form of a mixture of isomers, such as a 1H-tetrazole compound (e.g., a compound represented by chemical formula (I-1)) and a 2H-tetrazole compound (e.g., a compound represented by chemical formula (I-3)), may be obtained and used. From the viewpoint of production cost, the mixing ratio (molar ratio) of the 1H-tetrazole compound and the 2H-tetrazole compound is preferably 5:95 to 95:5, and more preferably 20:80 to 80:20.

[0032] The tetrazole compound of the present invention can be obtained by reacting a tetrazole compound represented by the chemical formula (II) with a halogenated alkylsilane compound represented by the chemical formula (III).

[0033]

[0034] (In formula (II), X is the same as defined above.)

[0035]

[0036] (In formula (III), R, m, and p are the same as defined above. Hal represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)

[0037] In the tetrazole compound represented by chemical formula (II), X is the same as that shown in the tetrazole compound of the present invention, and the preferred examples are also the same. In the halogenated alkylsilane compound represented by chemical formula (III), R, m, and p are the same as those shown in the tetrazole compound of the present invention, and the preferred examples are also the same. Furthermore, Hal in the halogenated alkylsilane compound represented by chemical formula (III) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and from the viewpoints of reactivity and easy availability of raw materials, a chlorine atom or a bromine atom is preferred.

[0038] Examples of the tetrazole compound 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'-iminobis(1,2,3,4-tetrazole), 5,5'-bi(1,2,3,4-tetrazole), 5,5'-methylenebis(1,2,3,4-tetrazole), 5,5'-ethylenebis(1,2,3,4-tetrazole), 5,5'-trimethylenebis(1,2,3,4-tetrazole), 5,5'-tetramethylenebis(1,2,3,4-tetrazole), Examples of the tetrazole include 5,5'-pentamethylenebis(1,2,3,4-tetrazole), 5,5'-hexamethylenebis(1,2,3,4-tetrazole), 5,5'-heptamethylenebis(1,2,3,4-tetrazole), 5,5'-octamethylenebis(1,2,3,4-tetrazole), 5,5'-nonamethylenebis(1,2,3,4-tetrazole), 5,5'-decamethylenebis(1,2,3,4-tetrazole), 5,5'-undecamethylenebis(1,2,3,4-tetrazole), and 5,5'-dodecamethylenebis(1,2,3,4-tetrazole).

[0039] These exemplified tetrazole compounds can be synthesized, for example, according to the synthesis method described in WO 2015 / 084830. These tetrazole compounds can also be used in the form of salts with an appropriate base. Examples of the base include ammonia, lithium hydroxide, sodium hydroxide, and potassium hydroxide, and these compounds can be used as ammonium salts, Li salts, Na salts, or K salts.

[0040] Examples of the halogenated alkylsilane compound 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, Examples thereof include 10-bromodecyltrimethoxysilane, 10-bromodecyltriethoxysilane, 12-bromododecyltrimethoxysilane, and 12-bromododecyltriethoxysilane.

[0041] These exemplified halogenated alkylsilane compounds can be purchased as commercially available reagents and used, or can be synthesized in accordance with the synthesis methods described in, for example, Chem. Eur. J., 18, 16742 (2012), J. Applied. Chem., 82, 276 (2009), and U.S. Pat. No. 2,744,116.

[0042] The tetraazole compound of the present invention can be synthesized, for example, by reacting a tetrazole compound represented by chemical formula (II) with a halogenated alkylsilane compound represented by chemical formula (III) in the presence of a dehydrohalogenating agent in an appropriate amount of reaction solvent at an appropriate reaction temperature and reaction time. １ is a hydrogen atom, and R ２ Ga-(CH ２ ) ｍ -Si(OR) ３－ｐ (OH) ｐ The reaction scheme for obtaining the tetrazole compound (Ia) of the present invention, which is a group represented by the formula:

[0043]

[0044] (In formulas (II), (III) and (Ia), X, R, Hal, m and p are the same as defined above.)

[0045] The reaction solvent is not particularly limited as long as it is a solvent inert to the tetrazole compound represented by chemical formula (II) and the halogenated alkylsilane compound represented by chemical formula (III), and examples thereof include hydrocarbon solvents such as hexane, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, and cyclopentyl methyl ether; ester solvents such as ethyl acetate and butyl acetate; alcohol solvents such as methanol and ethanol; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and acetonitrile, dimethyl sulfoxide, and hexamethylphosphoramide.

[0046] Examples of the dehydrohalogenating agent include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, and potassium t-butoxide; alkali carbonates such as sodium carbonate and potassium carbonate; organic bases such as triethylamine and diazabicycloundecene; and sodium hydride.

[0047] The reaction between the tetrazole compound represented by chemical formula (II) and the halogenated alkylsilane compound represented by chemical formula (III) proceeds stoichiometrically as shown in Scheme (A) above, but the amount of the halogenated alkylsilane compound represented by chemical formula (III) used (charge amount) relative to the amount of the tetrazole compound represented by chemical formula (II) used (charge amount) should be determined taking into consideration factors such as the reaction temperature and reaction time, as well as the types of raw materials and reaction solvent used, and the reaction scale. It is preferable to use 0.8 to 1.2 equivalents of the halogenated alkylsilane compound represented by chemical formula (III) per —NH on the tetrazole ring, which serves as a reaction site. If the amount of the halogenated alkylsilane compound represented by chemical formula (III) charged per reaction site (—NH) is more than 1.2 equivalents, the compound may polymerize and gel, whereas if it is less than 0.8 equivalents, the purity of the product may decrease or the product separation process may become complicated. The dehydrohalogenating agent is used to neutralize hydrogen halide produced as a by-product in the reaction between the tetrazole compound represented by chemical formula (II) and the halogenated alkylsilane compound represented by chemical formula (III). Therefore, the amount used (charged amount) of the dehydrohalogenating agent may be at least equimolar to the amount of the halogenated alkylsilane compound represented by chemical formula (III).

[0048] The reaction temperature is not particularly limited as long as it is within a temperature range in which —NH of the tetrazole ring of the tetrazole compound represented by chemical formula (II) reacts with the halogenated alkylsilane compound represented by chemical formula (III). The reaction temperature is preferably in the range of 0 to 150° C., and more preferably in the range of 5 to 100° C.

[0049] The reaction time is appropriately determined depending on the reaction temperature, but is preferably in the range of 30 minutes to 48 hours, more preferably in the range of 1 to 24 hours.

[0050] (Coupling Agent) The coupling agent of the present invention contains the tetrazole compound represented by the above chemical formula (I) as a component.

[0051] When using the coupling agent of the present invention, the same surface treatment methods as those used for conventional coupling agents can be employed. Examples of such surface treatment methods include (a) spraying a substrate with a treatment liquid prepared by diluting an appropriate amount of the coupling agent with an organic solvent, (b) spraying a substrate with a treatment liquid prepared by diluting the coupling agent with water and an organic solvent, (c) spraying a substrate with a treatment liquid prepared by diluting the coupling agent with water, (d) immersing a substrate in a treatment liquid prepared by diluting the coupling agent with an organic solvent, (e) immersing a substrate in a treatment liquid prepared by diluting the coupling agent with water and an organic solvent, and (f) immersing a substrate in a treatment liquid prepared by diluting the coupling agent with water.

[0052] Examples of the organic solvent include hydrocarbon solvents such as benzene, toluene, xylene, heptane, hexane, cyclohexane, and n-octane; halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, carbon tetrachloride, chloroform, chlorobenzene, dichlorobenzene, and trichlorobenzene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether, and diethylene glycol monobutyl ether; and alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, 2-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, and propylene glycol.

[0053] Examples of the substrate used in the present invention include granular, needle-like, fibrous, woven, plate-like, foil-like, amorphous, and other substrates formed from metals, inorganic materials, resin materials, and the like.

[0054] Examples of the metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. Plates, foils, and plating films made of these metals can be used as the substrate. Specific examples of the alloy include copper alloys, and are not particularly limited as long as they contain copper. Examples include Cu-Ag, Cu-Te, Cu-Mg, Cu-Sn, Cu-Si, Cu-Mn, Cu-Be-Co, Cu-Ti, Cu-Ni-Si, Cu-Zn-Ni, Cu-Cr, Cu-Zr, Cu-Fe, Cu-Al, Cu-Zn, and Cu-Co alloys. Other alloys include aluminum alloys (Al-Si alloys), nickel alloys (Ni-Cr alloys), and iron alloys (Fe-Ni alloys, stainless steel, and steel). Among these metals, copper and copper alloys are preferred.

[0055] Examples of the inorganic material include silicon, ceramics, inorganic materials used as fillers, and glass. Specific examples include silicon compounds such as silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminosilicates, and mica; oxides such as alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide; hydroxides such as magnesium hydroxide, aluminum hydroxide, and basic magnesium carbonate; carbonates such as calcium carbonate, zinc carbonate, hydrotalcite, and magnesium carbonate; sulfates such as barium sulfate and gypsum; titanates such as barium titanate; nitrides such as aluminum nitride and silicon nitride; and carbon fibers. Among these inorganic materials, silicon, ceramics (alumina, silicon carbide, aluminum nitride, silicon nitride, barium titanate, etc.), and glass are preferred.

[0056] Examples of the resin material include nylon, acrylate resin, epoxy resin, polybenzoxazole resin, silicone resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, polybutadiene resin, olefin resin, fluorine-containing resin, polyetherimide resin, polyether ether ketone resin, liquid crystal resin, etc., and these may be mixed or modified and combined. Among these resin materials, polyphenylene ether resin, polyphenylene oxide resin, liquid crystal resin, acrylate resin, epoxy resin, olefin resin, polybenzoxazole resin, silicone resin, and polyimide resin are preferred.

[0057] By subjecting a substrate to surface treatment with a treatment liquid containing the coupling agent of the present invention, the lipophilicity of the substrate surface is increased, and the affinity (adhesion and adhesion) for resins, etc. may be improved. In order to further enhance the effects of this treatment, the surface-treated substrate may be further subjected to a heat treatment.

[0058] (Surface Treatment Solution) <Surface Treatment Solution Containing a Tetrazole Compound Represented by Chemical Formula (I)> The surface treatment solution of the present invention contains a tetrazole compound represented by the above-mentioned chemical formula (I) (hereinafter, sometimes referred to as tetrazole compound (I)). In this tetrazole compound (I), R １ and / or R ２ No-(CH ２ ) ｍ -Si(OR) ３－ｐ (OH) ｐ where p is an integer of 1 to 3, is a species produced by hydrolysis of a compound where p is 0 in a surface treatment solution. All of these are suitable as components of the surface treatment solution. Furthermore, the tetrazole compound (I) where p is an integer of 1 to 3 can be used by extracting it from a surface treatment solution containing the tetrazole compound (I) where p is 0 by removing volatile components.

[0059] In the practice of the present invention, a compound in which p is 0, i.e., R １ and R ２ At least one of the following is -(CH ２ ) ｍ -Si(OR) ３ It is preferable to use a tetrazole compound (I) which is a group represented by the following formula:

[0060] The surface treatment solution of the present invention is prepared by mixing the tetrazole compound (I) with water. The water used in preparing the surface treatment solution is preferably pure water, such as ion-exchanged water or distilled water. Furthermore, a solubilizing agent is preferably used in the surface treatment solution of the present invention to promote dissolution (formation of an aqueous solution) of the tetrazole compound (I). Examples of the solubilizing agent include acids, alkalis, and organic solvents. These solubilizing agents may be used alone or in combination of two or more. Regarding the method for preparing the surface treatment solution using a solubilizing agent and water, the tetrazole compound may be mixed with water and then the solubilizing agent is added; the tetrazole compound may be mixed with a mixture of water and the solubilizing agent; or the tetrazole compound may be mixed with the solubilizing agent and then water is added.

[0061] Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, 2-ethylbutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, oleic acid, stearic acid, glycolic acid, lactic acid, gluconic acid, glyceric acid, malonic acid, succinic acid, levulinic acid, benzoic acid, oxalic acid, tartaric acid, malic acid, benzenesulfonic acid, tosylic acid, methanesulfonic acid, 5-sulfosalicylic acid, 4-hydroxybenzenesulfonic acid, 3-methyl-4-hydroxybenzenesulfonic acid, 4-aminobenzenesulfonic acid, camphorsulfonic acid, benzenedisulfonic acid, benzenetrisulfonic acid, sulfamic acid, and amino acids. These acids may be used alone or in combination of two or more.

[0062] Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol, N,N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine, and pyridine. These alkalis may be used alone or in combination of two or more.

[0063] Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, butanol, tert-butyl alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and diethylene glycol monomethyl ether. Examples of the organic solvent include tetrahydrofurfuryl alcohol, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, acetone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, formamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, ethylene carbonate, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, etc. These organic solvents may be used alone or in combination of two or more.

[0064] 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.

[0065] <Hydrolysis of Tetrazole Compound (I)> Since the tetrazole compound (I) has a tetrazole ring in the molecule, the tetrazole ring interacts with the surface of the substrate (metal, resin material, inorganic material) to form a chemical bond, thereby improving the adhesion between different materials.

[0066] The hydrolysis of the tetrazole compound (I) is shown in scheme (B). In scheme (B), R of the tetrazole compound (I) １ and R２ At least one of the following is -(CH ２ ) ｍ -Si(OR) ３－ｐ (OH) ｐ Scheme (B) illustrates an example in which the alkoxysilyl group in the tetrazole compound (I) is hydrolyzed, i.e., the trialkoxysilyl group is gradually converted into a dialkoxyhydroxysilyl group, a dihydroxyalkoxysilyl group, and a trihydroxysilyl group.

[0067]

[0068] In general, substances having alkoxysilyl groups in their molecules are known to function as silane coupling agents. For example, in the case of bonding copper to a resin material, if the tetrazole compound (I) used in the present invention has an alkoxysilyl group in its molecule, the tetrazole ring interacts with the resin and copper to form a chemical bond, and the alkoxysilyl group (—Si—OR) undergoes hydrolysis and is converted to a hydroxysilyl group (—Si—OH), which chemically bonds with copper oxide scattered on the copper surface. Therefore, by contacting copper with a surface treatment solution, a chemical conversion coating derived from the tetrazole compound (I) is formed on the copper surface through bonding with the tetrazole ring and the hydroxysilyl group. Forming a resin layer made of a resin material on the surface of this chemical conversion coating can improve adhesion between the copper and the resin material compared to forming a resin layer directly on the copper surface.

[0069] In carrying out the present invention, the concentration of the tetrazole compound (I) in the surface treatment solution is preferably 0.0001 to 1 mol / L, more preferably 0.001 to 0.5 mol / L, and even more preferably 0.01 to 0.1 mol / L, calculated as the concentration of the trialkoxy tetrazole compound.

[0070] The tetrazole compounds (I) having hydroxysilyl groups produced in the surface treatment solution gradually react with each other and undergo dehydration condensation, with the hydroxysilyl groups forming siloxane bonds (Si—O—Si) (see Scheme (B)), and are converted into silane oligomers (tetrazole compounds having groups represented by chemical formula (e) in Scheme (B)) that are poorly soluble in water. Note that X in the group represented by chemical formula (e) is an integer representing the number of repeating units.

[0071] If the amount of silane oligomer produced in the surface treatment solution increases, insoluble components may precipitate (the treatment solution may become cloudy) and adhere to the treatment tank, the piping connected to the treatment tank, and sensors immersed in the treatment solution for detecting the temperature and liquid level of the treatment solution, potentially hindering smooth surface treatment. To avoid this, it is preferable to add the aforementioned organic solvent to the surface treatment solution as a solubilizer for the silane oligomer, which is poorly soluble in water. Furthermore, it is preferable to add the aforementioned solubilizer (acid, alkali, organic solvent) to the surface treatment solution in order to promote the dissolution of the tetrazole compound (I). Since the organic solvent also functions as a solubilizer for the silane oligomer, it is preferable to add at least one solubilizer selected from the group consisting of acids, alkalis, and organic solvents to the surface treatment solution of the present invention.

[0072] Similarly, in order to improve the stability of the surface treatment solution and the uniformity of the chemical conversion coating, it is also possible to use a substance that generates halide ions such as fluoride ions, chloride ions, bromide ions, and iodide ions, or metal ions such as copper ions, iron ions, and zinc ions.

[0073] Halide ions are effective in forming uniform flat portions of the chemical conversion coating. Examples of substances that generate halide ions include lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, magnesium iodide, calcium iodide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. Halogen compounds may be contained as impurities in other components.

[0074] The content of halide ions in the surface treatment solution is not particularly limited, and is, for example, preferably 0.1 mol / L or less (particularly 0 to 0.1 mol / L), more preferably 0.05 mol / L or less (particularly 0 to 0.05 mol / L), further preferably 0.02 mol / L or less (particularly 0 to 0.02 mol / L), and particularly preferably 0.01 mol / L or less (particularly 0 to 0.01 mol / L).

[0075] Copper ions form complexes with the tetrazole compound (I) to enhance the strength of the conversion coating or the adhesive strength between the metal and the resin. The valence of the copper ions may be monovalent or divalent. Examples of substances that generate copper ions include metallic copper, copper sulfate (and its hydrates (particularly the pentahydrate)), copper formate (and its hydrates (particularly the tetrahydrate)), copper nitrate, cuprous chloride, cupric chloride, copper acetate (and its hydrates (particularly the monohydrate)), copper hydroxide, copper oxide, copper sulfide, copper carbonate, cuprous bromide, cupric bromide, copper phosphate, and copper benzoate. The copper ions in the surface treatment solution may also include copper ions eluted from metallic copper or copper oxide contained in the copper circuit during treatment of the copper circuit with the surface treatment solution.

[0076] The content of copper ions in the surface treatment solution is not particularly limited, and is, for example, preferably 1 mol / L or less (particularly 0 mol / L or more and 1 mol / L or less), more preferably 0.5 mol / L or less (particularly 0 mol / L or more and 0.5 mol / L or less), even more preferably 0.1 mol / L or less (particularly 0 mol / L or more and 0.1 mol / L or less), and particularly preferably 0.01 mol / L or less (particularly 0 mol / L or more and 0.01 mol / L or less).

[0077] A known coupling agent may be used in combination as long as it does not impair the effects of the present invention. Examples of known coupling agents include silane coupling agents (silane coupling agents) having a thiol group (mercapto group), a vinyl group, an epoxy group, a (meth)acrylic group, an amino group, a chloropropyl group, or the like.

[0078] Examples of such silane coupling agents include mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, vinylsilane compounds such as vinyltrichlorosilane, vinyltrimethoxysilane and vinyltriethoxysilane, styrylsilane compounds such as p-styryltrimethoxysilane, epoxysilane compounds such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, acryloxysilane compounds such as 3-acryloxypropyltrimethoxysilane, methacryloxysilane compounds such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane, Examples of the silane compound include aminosilane compounds such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; ureidosilane compounds such as 3-ureidopropyltriethoxysilane; chloropropylsilane compounds such as 3-chloropropyltrimethoxysilane; sulfide silane compounds such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanatosilane compounds such as 3-isocyanatopropyltriethoxysilane. Other examples include aluminum-based coupling agents, titanium-based coupling agents, and zirconium-based coupling agents.

[0079] The surface treatment solution of the present invention can usually be adjusted to a pH of −1 to 12. The surface treatment solution of the present invention preferably has a pH of 3 to 11.5. If it is in the acidic range, it more preferably has a pH of 3 to 7, and if it is in the basic range, it more preferably has a pH of 8 to 11.5, and even more preferably has a pH of 8.5 to 9.5.

[0080] (Treatment Method) The method for contacting the surface treatment solution of the present invention with the surface of a substrate is not particularly limited, and, as with the coupling agent described above, methods such as spraying, immersion, and coating can be used. The time for contacting the surface treatment solution with the substrate (treatment time) is preferably 1 second to 10 minutes, and more preferably 5 seconds to 3 minutes. If the treatment time is less than 1 second, the thickness of the chemical conversion coating formed on the substrate surface will be thin, making it difficult to obtain sufficient adhesion between different materials. On the other hand, even if the treatment time is longer than 10 minutes, there will be no significant difference in the thickness of the chemical conversion coating. Therefore, from the viewpoint of productivity, treatment for 10 minutes or less is preferred. Furthermore, the temperature of the treatment solution when contacting the surface treatment solution with the substrate surface is preferably 5 to 50°C, but this may be set appropriately in relation to the treatment time described above.

[0081] After contacting the substrate with the surface treatment solution of the present invention, the substrate may be washed with water and then dried, or may be dried without being washed with water. Drying is preferably carried out at a temperature of room temperature to 150° C. The water used for washing is preferably pure water such as ion-exchanged water or distilled water, but there are no particular restrictions on the method or duration of washing, and it may be washed for an appropriate period of time by means of spraying, immersion, or the like.

[0082] The thickness of the chemical conversion coating is preferably 0.5 to 1000 nm, more preferably 1 to 200 nm, and even more preferably 1 to 100 nm. A thickness of 0.5 nm or more sufficiently improves adhesion between materials, while a thickness of 1000 nm or less allows the chemical resistance of the chemical conversion coating to be maintained.

[0083] In the present invention, the surface of the dried chemical conversion coating may be modified by treatment with plasma, laser, ion beam, ozone, heating, humidification, etc. Alternatively, the metal surface may be cleaned using mechanical polishing such as plasma, laser, ion beam, or pumice brush, or processing methods such as drilling, in order to remove resin and ion residues from the metal surface.

[0084] Before contacting the surface of copper or a copper alloy (hereinafter, both may be referred to simply as copper) with the surface treatment liquid of the present invention, the copper surface may be subjected to at least one pretreatment selected from pickling treatment, alkali treatment, roughening treatment, heat-resistant treatment, rust-proofing treatment, and chemical conversion treatment.

[0085] The pickling treatment is carried out to remove oil and fat components adhering to the copper surface and to remove an oxide film from the copper surface, and can be carried out using solutions such as hydrochloric acid solutions, sulfuric acid solutions, nitric acid solutions, sulfuric acid-hydrogen peroxide solutions, organic acid solutions, inorganic acid-organic solvent solutions, and organic acid-organic solvent solutions.

[0086] The alkali treatment is carried out to remove oil and fat components adhering to the copper surface and to remove residues from previous processes (e.g., dry film resist for forming copper circuits). For this alkali treatment, solutions such as aqueous solutions or organic solvent-based solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amines such as ammonia, ethanolamine, monopropanolamine, and tetramethylammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium acetate, potassium acetate, sodium phosphate, disodium hydrogen phosphate, potassium phosphate, and dipotassium hydrogen phosphate can be used.

[0087] The roughening treatment is carried out to enhance adhesion between copper and resin through the anchor effect, and imparts an irregular shape to the copper surface, thereby enhancing adhesion between copper and resin materials. Methods that can be used for this roughening treatment include microetching, electroplating, electroless plating, oxidation (black oxide, brown oxide), oxidation-reduction, brush polishing, and jet scrubbing.

[0088] In the microetching method, for example, etching agents such as organic acid-cupric ion system, sulfuric acid-hydrogen peroxide system, persulfate system, copper chloride system, and iron chloride system can be used. In the electroplating method, minute copper particles are deposited on the copper surface to form irregularities on the copper surface.

[0089] In the heat-resistant treatment, a coating of at least one material selected from nickel, nickel-phosphorus, zinc, zinc-nickel, copper-zinc, copper-nickel, copper-nickel-cobalt, and nickel-cobalt is formed on the surface of the copper. This coating can be formed by a known electroplating method, but is not limited to electroplating, and vapor deposition or other means may also be used.

[0090] The rust prevention treatment is carried out to prevent oxidation corrosion of the copper surface, and can be carried out by forming a zinc or zinc alloy plating film or an electrolytic chromate plating film on the copper surface. Alternatively, a treatment solution containing an organic compound-based rust inhibitor such as a benzotriazole-based rust inhibitor may be brought into contact with the copper surface.

[0091] In the chemical conversion treatment, a method of forming a passivation film of tin or a method of forming a passivation film of copper oxide can be employed.

[0092] Before and / or after contacting the copper surface with the surface treatment solution of the present invention, an aqueous solution containing copper ions may be brought into contact with the copper surface. This aqueous solution containing copper ions has the functions of improving the film-forming properties of the chemical conversion coating formed on the copper surface and uniforming the thickness of the chemical conversion coating formed on the copper surface. The valence of the copper ions is not particularly limited, and they are monovalent or divalent copper ions. The copper ion source for the aqueous solution containing copper ions is not particularly limited as long as it is a copper salt that dissolves in water, and examples of copper salts include copper sulfate, copper nitrate, copper chloride, copper formate, and copper acetate. Ammonia, hydrochloric acid, or the like may be added to solubilize the copper salt in water.

[0093] An acidic or alkaline aqueous solution may be contacted with the copper surface before and / or after contacting the copper surface with the surface treatment solution of the present invention. Like the copper ion-containing aqueous solution, this acidic or alkaline aqueous solution also functions to uniformize the thickness of the chemical conversion coating formed on the copper surface. While the acidic and alkaline aqueous solutions are not particularly limited, examples of the acidic aqueous solution include aqueous solutions containing mineral acids such as sulfuric acid, nitric acid, and hydrochloric acid, and aqueous solutions containing organic acids such as formic acid, acetic acid, lactic acid, glycolic acid, and amino acids. Examples of alkaline aqueous solutions include aqueous solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amines such as ammonia, ethanolamine, monopropanolamine, and tetramethylammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium acetate, potassium acetate, sodium phosphate, disodium hydrogenphosphate, potassium phosphate, and dipotassium hydrogenphosphate.

[0094] Before and / or after contacting the copper surface with the surface treatment liquid of the present invention, an aqueous solution containing a known coupling agent may be brought into contact with the copper surface.

[0095] Before and / or after contacting the copper surface with the surface treatment agent of the present invention, a dipping solution containing an azole compound may be contacted with the copper surface. This dipping solution functions to enhance the strength of the chemical conversion coating formed on the copper surface. The azole compound is not particularly limited, and examples thereof include commercially available imidazole compounds, triazole compounds, and tetrazole compounds. Examples of these azole compounds include imidazole, 2-methylimidazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4-triazole, 5-methyltetrazole, 5-aminotetrazole, and 5-phenyltetrazole. In addition to the azole compound, the dipping solution contains water and / or a solubilizing agent. Examples of solubilizing agents include the solubilizing agents described above (acid, alkali, organic solvent). The dipping solution may further contain additives. Examples of the additives include copper compounds, halogen compounds, and other additives (for example, ammonium salts such as ammonium sulfate, ammonium formate, ammonium acetate, ammonium chloride, ammonium carbonate, and ammonium nitrate).

[0096] After the surface treatment solution of the present invention has been brought into contact with the copper surface, the copper surface may be contacted with a treatment solution containing a known organic compound-based rust inhibitor, such as a benzotriazole-based rust inhibitor.

[0097] The surface treatment liquid of the present invention can be used to treat the surface of at least one substrate selected from the group consisting of metals, inorganic materials, and resin materials. By treating the surface of the substrate with the surface treatment liquid of the present invention, a chemical conversion film can be formed on the surface of the substrate, thereby improving adhesion to other materials.

[0098] In the present invention, two materials selected from the group consisting of metals, inorganic materials, and resin materials can be bonded using the surface treatment liquid of the present invention. By bonding the two materials via a chemical conversion coating layer formed by the surface treatment liquid of the present invention, the affinity between the two materials can be improved, and therefore, even materials of different properties can be bonded more firmly.

[0099] (Bonding Method) The bonding of two materials can be carried out by known methods. Examples include a method in which the surface treatment liquid of the present invention is brought into contact with the surface of a substrate made of a metal, inorganic material, or resin material to form a chemical conversion coating, and then another substrate is applied to part or all of the formed chemical conversion coating by means of coating, pressing, mixing, etc., or by using an adhesive or an adhesive sheet (film), or by combining these methods. Another example includes a method in which the surface treatment liquid of the present invention is brought into contact with the surfaces of two substrates selected from a metal, inorganic material, or resin material to form chemical conversion coatings on the surfaces of the two substrates, and then the two substrates are bonded by means of coating, pressing, mixing, etc., or by using an adhesive or an adhesive sheet (film), or by combining these methods.

[0100] By using the surface treatment liquid of the present invention, two materials, particularly two materials of different properties, can be bonded together as described above, and therefore the surface treatment liquid of the present invention can be suitably used for various electric and electronic components and electronic devices such as semiconductor wafers and printed wiring boards.

[0101] In the present invention, the surface treatment liquid of the present invention can be suitably used for substrates made of metal, particularly copper or copper alloy. For example, it is suitable for surface treatment of copper or copper alloys for the purpose of improving the adhesion (adhesion) between a copper circuit (copper wiring layer) and a semi-cured or cured prepreg or solder resist, or a semi-cured or cured dry film resist (insulating resin layer), and can improve the adhesion between the copper wiring layer and the insulating resin layer in a printed wiring board having an insulating resin layer in contact with the copper wiring layer.

[0102] In an example of use in semiconductor wafers, the present invention is suitable for surface treatment of semiconductor circuits with the aim of increasing the adhesion (tightness) between a semiconductor circuit formed on a semiconductor wafer and a protective film (e.g., an insulating protective film such as a photosensitive positive type, a photosensitive negative type, or a non-photosensitive buffer coat or bump protective film). Furthermore, the present invention is suitable for surface treatment of a copper circuit rewiring layer in a package substrate (WL-CSP, FO-WLP, PLP) or a 2.5-dimensional (2.5D) or three-dimensional (3D) interposer substrate in which a rewiring layer is formed on a semiconductor wafer, with the aim of increasing the adhesion (tightness) between the copper circuit rewiring layer and an insulating material. Examples of the protective film and insulating material include polyimide resin, polybenzoxazole resin, and silicone resin.

[0103] The printed wiring board can be produced by contacting the surface of a copper wiring with the surface treatment solution of the present invention, followed by rinsing and drying, and then forming an insulating resin layer on the copper wiring surface. The contact method is as described above. Immersing the copper wiring in the surface treatment solution or spraying the copper wiring with the treatment solution is simple and reliable, and is preferred. The water-washing method is not particularly limited, but immersing the copper wiring in cleaning water or spraying the copper wiring surface with cleaning water is simple and reliable, and is preferred. The insulating resin layer can be formed by known methods, such as applying a semi-cured resin material or applying a liquid resin material containing a solvent. Next, via holes are formed to connect the upper and lower wirings. Repeating this process can produce a multilayer printed wiring board.

[0104] In the above-mentioned method for forming a circuit on a printed wiring board, an example of a semi-additive process using the surface treatment liquid of the present invention will be described below. (a) preparing an insulating substrate or an insulating substrate having through-holes and via holes, the insulating substrate having a first conductive layer on a first surface and a second surface opposite to the first surface, and on the inner walls of the through-holes and via holes; (b) forming a photocrosslinkable resin layer and a mask layer on the first surface and the second surface, and covering the first conductive layer on the first surface and the second surface and on the inner walls of the through-holes and via holes with the photocrosslinkable resin layer and the mask layer; (c) pattern-exposing the photocrosslinkable resin layer on the first surface and the second surface and around the through-holes and via holes; (d) removing the mask layer on the first surface and the second surface and around the through-holes and via holes; (e) developing and removing the uncured photocrosslinkable resin layer on the first surface and the second surface and around the through-holes and via holes using a photocrosslinkable resin layer removal liquid, thereby exposing the first conductive layer on the first surface, the first conductive layer on the second surface, and the first conductive layer around the through-holes and via holes; (f) forming a second conductive layer by electrolytic plating on the first conductive layer exposed on the first and second surfaces and on the inner walls of the through-holes and via holes; (g) removing the cured photocrosslinkable resin layer on the first and second surfaces and around the through-holes and via holes to expose the first and second conductive layers on the first and second surfaces and on the inner walls of the through-holes and via holes; (h) removing the exposed first conductive layer by flash etching; (i) forming a third conductive layer by electroless plating and electrolytic plating on the first and second conductive layers on the first and second surfaces and on the inner walls of the through-holes and via holes; (j) laminating an insulating resin layer on the first, second, and third conductive layers on the first and second surfaces and on the inner walls of the through-holes and via holes; In the method for manufacturing a circuit board, a printed wiring board is manufactured by bringing the surface treatment liquid of the present invention into contact with at least one metal layer or resist layer selected from the first, second, and third conductive layers on the first surface, the second surface, and the inner walls of the through-holes and via holes, the insulating resin substrate, the photo-crosslinkable resin layer used for the etching resist layer or the plating resist layer, and the insulating resin layer.

[0105] Furthermore, in the above-mentioned method for forming a circuit on a printed wiring board, an example of a subtractive process using the surface treatment liquid of the present invention will be described below. (a) preparing an insulating substrate or an insulating substrate having through-holes and via holes, the insulating substrate having a first conductive layer on a first surface and a second surface opposite to the first surface, and on the inner walls of the through-holes and via holes; (b) forming a photocrosslinkable resin layer and a mask layer on the first surface and the second surface, and covering the first conductive layer on the first surface and the second surface and on the inner walls of the through-holes and via holes with the photocrosslinkable resin layer and the mask layer; (c) pattern-exposing the photocrosslinkable resin layer on the first surface and the second surface and around the through-holes and via holes; (d) removing the mask layer on the first surface and the second surface and around the through-holes and via holes; (e) developing and removing the uncured photocrosslinkable resin layer on the first surface and the second surface and around the through-holes and via holes using a photocrosslinkable resin layer removal liquid, thereby exposing the first conductive layer on the first surface, the first conductive layer on the second surface, and the first conductive layer around the through-holes and via holes; (f) etching and removing the first conductive layer exposed on the first and second surfaces and on the inner walls of the through-holes and via holes; (g) removing the cured photocrosslinkable resin layer on the first and second surfaces and around the through-holes and via holes to expose the first conductive layer on the first and second surfaces and on the inner walls of the through-holes and via holes; (h) forming a second conductive layer on the first conductive layer on the first and second surfaces and on the inner walls of the through-holes and via holes by electroless plating and electrolytic plating; (i) laminating an insulating resin layer on the first and second conductive layers on the first and second surfaces and on the inner walls of the through-holes and via holes; In the method for manufacturing a circuit board comprising at least one of the above, the surface treatment liquid of the present invention is brought into contact with at least one metal layer or resist layer selected from the group consisting of first and second conductive layers on the first surface, second surface, and inner walls of through-holes and via holes, an insulating resin substrate, a photo-crosslinkable resin layer used for an etching resist layer or a plating resist layer, and an insulating resin layer, to manufacture a printed wiring board.

[0106] The copper wiring and conductive layer may be produced by any method such as electroless plating, electrolytic plating, vapor deposition, sputtering, or damascene, and may include inner via holes, through holes, connection terminals, etc.

[0107] Furthermore, "copper" in the present invention refers to foils (electrolytic copper foil, rolled copper foil, resin-coated copper foil, carrier-coated copper foil, electroless copper foil, sputtered copper foil, thin copper foil) used in electronic devices such as printed wiring boards and lead frames, decorative items, building materials, etc., plated films (electroless copper plating film, electrolytic copper plating film), thin films formed by vapor deposition, sputtering, damascene method, etc., and particles, needles, fibers, wires, rods, tubes, plates, etc. In the case of copper wiring through which recent high-frequency electrical signals flow, it is preferable that the copper surface be smooth with an average roughness of 0.1 μm or less. The copper surface may be plated with nickel, zinc, chromium, tin, etc. as a pretreatment.

[0108] Furthermore, for example, in the case of use in lead frames during wire bonding mounting, the surface treatment liquid of the present invention is suitable for surface treatment of lead frames aimed at increasing the adhesiveness (adhesion) of the metal surface during the lead frame manufacturing process, the metal frame surface after mounting a semiconductor chip (before or after the die bonding and pre-baking processes), the metal frame surface after mounting by wire bonding, and the metal frame surface during processes up to resin sealing (before or after the resin molding and baking processes) with an adhesive when mounting a semiconductor chip.

[0109] Furthermore, for example, in an application example to a lead frame during flip-chip mounting, the surface treatment liquid of the present invention is suitable for surface treatment of the lead frame for the purpose of increasing the adhesiveness (adhesion) with the sealing resin or adhesive used during semiconductor chip mounting on the metal surface during the lead frame production process, the metal surface of the lead frame after a bonding material (solder, Au plating, Sn plating, etc.) has been temporarily placed, the metal surface of the frame after a semiconductor chip has been mounted (before or after alignment, chip mounting, and baking processes), the metal surface of the lead frame after main curing (before or after processes such as reflow heating, thermocompression bonding, ultrasonic waves, and plasma), and the metal surface of the lead frame during processes up to resin sealing.

[0110] For example, in the case of a microwiring substrate using advanced integration technology for closely arranging semiconductor chips, the surface treatment solution of the present invention is also suitable for surface treatment of a copper circuit wiring layer on a 2.5-dimensional (2.5D) organic substrate or glass substrate, a component-embedded substrate (EPS substrate) having a semiconductor embedded in the substrate, or a coreless substrate, with the aim of improving the adhesion (adhesion) between the copper circuit wiring layer and the insulating material. Furthermore, for example, the metal surface treatment solution of the present invention is suitable for surface treatment of a copper circuit wiring layer on a substrate having an embedded pattern wiring, in which upper and lower layers are subjected to laser via processing and via fill plating, or in the case of a circuit-embedded substrate (ETS substrate) using MIS in which copper pillars formed by plating are used for electrical continuity between the upper and lower layers and a molded resin is used for the insulating layer, with the aim of improving the adhesion (adhesion) between the copper circuit wiring layer and the insulating material.

[0111] The carrier-attached copper foil to be treated with the surface treatment solution of the present invention is an ultrathin electrolytic copper foil used for printed wiring boards that include a process for forming a circuit by any one of a semi-additive process, a subtractive process, a partly additive process, or a modified semi-additive process, and is provided with a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer. The copper surface may be subjected to at least one pretreatment selected from the group consisting of pickling treatment, roughening treatment, heat-resistant treatment, rust-proofing treatment, and chemical conversion treatment.

[0112] (Insulating composition) The coupling agent of the present invention can be incorporated into a resin material or an inorganic material to form an insulating composition. Alternatively, the insulating composition can be obtained by dissolving the tetrazole compound (I) in an organic solvent or the like and mixing the solution with a resin material or an inorganic material.

[0113] The content of the tetrazole compound (I) in the insulating composition is preferably 0.001 to 10 wt %, more preferably 0.01 to 5 wt %. When the content of the tetrazole compound (I) in the insulating composition is 0.001 wt % or more, the adhesiveness is sufficiently improved. However, when this concentration exceeds 10 wt %, the adhesiveness improvement effect almost reaches a plateau. Therefore, from an economical viewpoint, the content of the tetrazole compound (I) is preferably 10 wt % or less. The insulating composition can be prepared by a known method. For example, the tetrazole compound (I) can be prepared by dissolving the tetrazole compound (I) in an organic solvent and mixing it with a solid or liquid resin material. Alternatively, the insulating composition can be prepared by directly adding the tetrazole compound (I) to a liquid resin material and mixing it.

[0114] The insulating composition of the present invention provides an insulating material having high adhesive strength, and can therefore be suitably used in various electric and electronic parts and electronic devices such as printed wiring boards.

[0115] Japanese Patent Publication No. 2009-19266 describes a method for forming a silane coupling agent film, which comprises the steps of applying a liquid containing a silane coupling agent to a metal surface, drying the applied metal surface at a temperature of 25 to 150°C for 5 minutes or less, and rinsing the dried metal surface with water. It also states that the metal surface may be pre-treated by forming an adhesive metal layer of tin or the like using an immersion plating solution. The surface treatment liquid of the present invention can be used as the liquid containing the silane coupling agent. The contents of this patent publication are incorporated herein by reference.

[0116] The present invention will be specifically explained below with reference to examples (synthesis tests and evaluation tests), but the present invention is not limited thereto. In the chemical formula shown below, OEt represents an ethoxy group.

[0117] The raw material tetrazole compound and halogenated alkylsilane compound used in the synthesis test are as follows: [Tetrazole Compound] - Tetrazole compound (5,5'-bi(1,2,3,4-tetrazole)diammonium salt) represented by the following chemical formula (11): Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. - Tetrazole compound (5,5'-ethylenebis(1,2,3,4-tetrazole)) represented by the following chemical formula (12): Synthesized in accordance with the method described in WO 2015 / 084830.

[0118]

[0119] [Halogenated alkylsilane compound] 3-chloropropyltriethoxysilane: manufactured by Tokyo Chemical Industry Co., Ltd.

[0120] <Synthesis of Tetrazole Compound (I)> The following tetrazole compounds of Examples 1 and 2 were synthesized.

[0121] Example 1 Synthesis of a Mixture of 1-[3-(triethoxysilyl)propyl]-5,5'-bi(1,2,3,4-tetrazole) and 2-[3-(triethoxysilyl)propyl]-5,5'-bi(1,2,3,4-tetrazole) A compound represented by the following chemical formula (1) (a mixture of 1-[3-(triethoxysilyl)propyl]-5,5'-bi(1,2,3,4-tetrazole) and 2-[3-(triethoxysilyl)propyl]-5,5'-bi(1,2,3,4-tetrazole)) was synthesized. A suspension consisting of 17.0 g (98.7 mmol) of 5,5'-bi(1,2,3,4-tetrazole)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. After cooling to 70°C, 23.8 g (98.8 mmol) of 3-chloropropyltriethoxysilane was added and stirred for 10 minutes. The mixture was then heated to 100°C and stirred for 20 hours. After cooling the reaction mixture to room temperature, insoluble matter was removed by filtration, and the filtrate was evaporated under reduced pressure. Furthermore, 455 mL of isopropyl acetate was added, and the mixture was stirred at room temperature for 1 hour. The insoluble matter was then removed by filtration, and the filtrate was evaporated under reduced pressure, yielding 30.7 g (89.7 mmol, 91% yield) of a light brown liquid.

[0122] The resulting light brown liquid １ The H-NMR spectrum data was as follows: １ H-NMR (DMSO-d ６ ) δ: 0.50 (m, 2H), 1.13 (m, 9H), 2.00 (m, 2H), 3.73 (m, 6H), 4.84 (m, 2H). this １ From the H-NMR spectrum data, the obtained light brown liquid was identified as the title tetrazole compound represented by chemical formula (1).

[0123]

[0124] Example 2 Synthesis of a mixture of 1-[3-(triethoxysilyl)propyl]-5,5'-ethylenebis(1,2,3,4-tetrazole) and 2-[3-(triethoxysilyl)propyl]-5,5'-ethylenebis(1,2,3,4-tetrazole) A compound represented by the following chemical formula (2) (a mixture of 1-[3-(triethoxysilyl)propyl]-5,5'-ethylenebis(1,2,3,4-tetrazole) and 2-[3-(triethoxysilyl)propyl]-5,5'-ethylenebis(1,2,3,4-tetrazole)) was synthesized. A suspension consisting of 9.5 g (57.2 mmol) of 5,5'-ethylenebis(1,2,3,4-tetrazole) and 62 mL of N,N-dimethylacetamide was heated to 50°C, 20.0 g (58.8 mmol) of a 20% sodium ethoxide ethanol solution was added, and the mixture was heated to 70°C and stirred for 1 hour. Next, 13.8 g (57.3 mmol) of 3-chloropropyltriethoxysilane was added and stirred for 10 minutes. The mixture was then heated to 100°C and stirred for 20 hours. The reaction solution was cooled to 60°C, and the filtrate was evaporated under reduced pressure. Next, 120 mL of isopropyl acetate was added, and the mixture was stirred at room temperature for 1 hour. After that, insoluble matter was removed by filtration, and the filtrate was evaporated under reduced pressure to obtain 18.4 g (49.7 mmol, 87% yield) of a light brown liquid.

[0125] The resulting light brown liquid １ The H-NMR spectrum data was as follows: １ H-NMR (DMSO-d ６ ) 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). this １ From the H-NMR spectrum data, the obtained light brown liquid was identified as the title tetrazole compound represented by chemical formula (2).

[0126]

[0127] <Adhesion Test 1> The surface treatment solutions prepared in Examples 3 and 4 below were evaluated for adhesion as follows.

[0128] [Adhesion Evaluation Test (i)] (1) Metal: Electrolytic copper foil (thickness: 35 μm) was used as the metal. (2) Metal Surface Treatment: The copper foil was treated according to the following steps a to b: a. Acid cleaning (5% sulfuric acid aqueous solution) for 1 minute (room temperature), water rinsing; b. Brush application of the surface treatment solution, followed by drying for 1 minute (100°C). (3) Metal and Resin Adhesion: A glass cloth epoxy resin-impregnated prepreg (MEGTRON7 (manufactured by Panasonic)) was laminated and pressed onto the S-side of the treated copper foil, and the copper foil and prepreg were bonded to produce a copper-clad laminate. (4) Adhesion Evaluation: After one reflow heating (peak temperature 288°C, atmosphere), a 10 mm wide test piece was prepared from this copper-clad laminate according to JIS C6481 (1996) and the copper foil peel strength (kN / m) was measured.

[0129] [Example 3] A surface treatment liquid was prepared by adding 99.5 g of a mixed liquid (weight ratio) of acetic acid: ion-exchanged water: methanol = 1:8:90.5 to 0.5 g of the tetrazole compound represented by the chemical formula (1) as a coupling agent component, and stirring the mixture at room temperature for 1 hour.

[0130] Example 4 A surface treatment liquid was prepared in the same manner as in Example 3, except that the tetrazole compound represented by the chemical formula (2) was used instead of the tetrazole compound represented by the chemical formula (1).

[0131] The surface treatment solutions prepared above were each subjected to an adhesiveness evaluation test (i). The test results are shown in Table 1.

[0132] Comparative Example 1 The copper foil subjected to only the step (2)a of the adhesiveness evaluation test (i) was subjected to the adhesiveness evaluation test (i). The obtained test results are shown in Table 1.

[0133]

[0134] The results in Table 1 show that the surface treatment solutions of the present invention (surface treatment solutions of Examples 3 and 4) have higher peel strength than Comparative Example 1 and are superior in adhesion between metal and resin.

[0135] <Adhesion Test 2> The surface treatment liquid prepared in Example 5 below was evaluated for adhesion as follows.

[0136] [Adhesion Evaluation Test (ii)] (1) Metal Electrolytic copper foil (thickness: 35 μm) was used as the metal. (2) Surface Treatment of Metal The copper foil was treated according to the following steps a to b: a. Acid cleaning (5% hydrochloric acid aqueous solution) / 1 minute (room temperature), water rinsing b. Immersion in surface treatment solution / 2 minutes (30 °C), water rinsing, drying / 1 minute (100 °C) (3) Adhesion of Metal and Resin Polyimide varnish (manufactured by UBE, product name "U-Varnish A") was applied to the S side of the treated copper foil using a bar coater to a thickness of 100 μm, and then cured in a nitrogen atmosphere (120 °C / 30 minutes, 150 °C / 10 minutes, 200 °C / 10 minutes, 250 °C / 10 minutes) to produce a copper-clad laminate. (4) Evaluation of Adhesion The copper-clad laminate was subjected to HTS treatment in an oven at 150° C. under an air atmosphere for 250 hours. Then, a 10 mm wide test piece was prepared according to JIS C6481 (1996), and the peel strength (kN / m) of the copper foil was measured.

[0137] [Example 5] As a coupling agent component, 99.5 g of a mixed solution of acetic acid: ion-exchanged water = 5:95 (weight ratio) was added to 0.5 g of the tetrazole compound represented by the above chemical formula (2), and then the pH was adjusted to 7.1 with ammonia water and stirred at room temperature for 1 hour to prepare a surface treatment solution.

[0138] The surface treatment solution prepared above was subjected to an adhesiveness evaluation test (ii). The test results are shown in Table 2.

[0139] Comparative Example 2 The copper foil that had been subjected to only the step (2)a of the adhesiveness evaluation test (ii) was subjected to the adhesiveness evaluation test (ii). The obtained test results are shown in Table 2.

[0140]

[0141] The results in Table 2 show that the surface treatment solution of the present invention (surface treatment solution of Example 5) has higher peel strength than Comparative Example 2 and is excellent in adhesion between metal and resin.

[0142] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-138677) filed on August 29, 2023, the contents of which are incorporated herein by reference.

[0143] The tetrazole compound of the present invention can be used as a coupling agent that combines the metal rust prevention function, which is a characteristic of tetrazole compounds, with the function of curing epoxy resins and urethane resins, and is therefore expected to be used in composite materials such as printed wiring boards, which are manufactured by combining many different materials. Furthermore, according to the present invention, the adhesiveness (adhesion) of metals, inorganic materials, and resin materials can be improved, so the surface of the substrate can be maintained in a smooth state without roughening. Therefore, the present invention can greatly contribute to the realization of multilayer printed wiring boards that are smaller, thinner, have higher frequency, and have higher density, and therefore has great industrial applicability.

Claims

1. A tetrazole compound represented by chemical formula (I): (In formula (I), R １ and R ２ are the same or different and each represents a hydrogen atom or -(CH ２ ) ｍ -Si(OR) ３－ｐ (OH) ｐ where 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 -(CH ２ ) ｎ -, and n represents an integer of 0 to 12. １ and R ２ is also a hydrogen atom.) 2. A method for synthesizing the tetrazole compound according to claim 1, which comprises reacting a tetrazole compound represented by the chemical formula (II) with a halogenated alkylsilane compound represented by the chemical formula (III). (In formula (II), X is the same as defined above.) (In formula (III), R, m and p are the same as defined above. Hal represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.) 3. A coupling agent comprising the tetrazole compound according to claim 1 as a component.

4. A surface treatment solution containing the tetrazole compound according to claim 1.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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