Surface treatment solution, and surface treatment method and bonding method using the same

Abstract

The coupling agent further improves the adhesion of the treated object. [Solution] The surface treatment liquid disclosed herein is a surface treatment liquid for further surface treatment of an object that has been treated with a coupling agent. The object is one or more selected from the group consisting of inorganic materials and resin materials. The surface treatment liquid contains Component A: a triazole compound having an amino group and Component B: a tetrazole compound having an amino group.

Description

[Technical Field]

[0001] The present invention relates to a surface treatment liquid. The present invention also relates to a surface treatment method and a bonding method using the surface treatment liquid. [Background technology]

[0002] Conventionally, in the manufacture of printed wiring boards, a technique of treating a metal surface or a resin surface with a surface treatment solution has been known to improve the adhesion between a metal circuit such as copper and a resin. Examples of components contained in such surface treatment solutions include triazole compounds and tetrazole compounds (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2018-145475 [Patent Document 2] Patent Publication No. 2008-274311 Summary of the Invention [Problem to be solved by the invention]

[0004] Through independent research, the present inventors have found that a surface treatment solution containing a combination of a triazole compound having an amino group and a tetrazole compound having an amino group can further improve the adhesion of an object treated with a coupling agent.

[0005] One aspect of the present invention aims to further improve the adhesiveness of an object treated with a coupling agent. [Means for solving the problem]

[0006] A surface treatment liquid according to one aspect of the present invention is a surface treatment liquid for further surface treatment of an object that has been treated with a coupling agent, The target is one or more selected from the group consisting of inorganic materials and resin materials, The surface treatment solution contains the following components A and B: Component A: a triazole compound having an amino group; Component B: A tetrazole compound having an amino group.

[0007] A surface treatment method according to one embodiment of the present invention includes the following steps in this order: Step 1: contacting a first material with a coupling agent; Step 2: bringing the first material into contact with a surface treatment liquid; where: the first material includes one or more selected from the group consisting of an inorganic material and a resin material, The surface treatment solution contains the following components A and B: Component A: a triazole compound having an amino group; Component B: A tetrazole compound having an amino group.

[0008] A bonding method according to one embodiment of the present invention includes the following steps in this order: Step 1: contacting a first material with a coupling agent; Step 2: bringing the first material into contact with a surface treatment liquid; Step 3: contacting the first material with a second material; where: the first material includes one of an inorganic material or a resin material, the second material includes the other of an inorganic material and a resin material, The surface treatment solution contains the following components A and B: Component A: a triazole compound having an amino group; Component B: A tetrazole compound having an amino group. [Effects of the Invention]

[0009] According to one aspect of the present invention, the adhesiveness of an object treated with a coupling agent can be further improved. DETAILED DESCRIPTION OF THE INVENTION

[0010] An embodiment of the present invention will be described below. However, the present invention is not limited to the configurations described below. The present invention can be modified in various ways within the scope of the claims. The technical scope of the present invention also extends to embodiments or examples obtained by appropriately combining multiple technical means disclosed in this specification. In this case, multiple technical means may be disclosed across multiple embodiments or examples.

[0011] Unless otherwise specified in this specification, the expression "A to B" representing a range of numerical values ​​means "greater than or equal to A and less than or equal to B."

[0012] [1. Surface treatment liquid] 1.1. Ingredients and Composition A surface treatment liquid according to one aspect of the present invention contains Component A: a triazole compound having an amino group and Component B: a tetrazole compound having an amino group. In one embodiment, the surface treatment liquid contains Component A: a triazole compound having an amino group, Component B: a tetrazole compound having an amino group, and a solvent. The surface treatment liquid may contain other components such as additives. Each of these components may be contained alone or in combination of two or more. Each component will be described in detail below.

[0013] [1.1.1. Component A] Component A is a triazole compound having an amino group. A triazole compound is a compound having a triazole ring. A triazole ring is a five-membered ring having a nitrogen atom, and of the elements constituting this five-membered ring, three are nitrogen atoms and two are carbon atoms. Component A may have only one triazole ring in its structure, or may have two or more triazole rings. In one embodiment, component A has only one triazole ring in its structure.

[0014] The triazole ring has isomers that differ in the position of the nitrogen atom, namely, 1,2,3-triazole and 1,2,4-triazole. Component A may contain one or both of these isomers in its structure. In one embodiment, component A contains only 1,2,4-triazole in its structure.

[0015] The number of amino groups possessed by Component A is not particularly limited. The upper limit of the number of amino groups may be, for example, 5 or less, 4 or less, 3 or less, or 2 or less. The lower limit of the number of amino groups is 1. In one embodiment, the number of amino groups possessed by Component A is 1 or 2.

[0016] The position of the amino group in Component A is not particularly limited. The amino group may be directly bonded to the triazole ring, may be bonded via a linker such as an alkylene, or may be a combination thereof. In one embodiment, the amino group is directly bonded to the triazole ring.

[0017] Specific examples of Component A include 4-amino-1,2,3-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 4,5-diamino-1,2,3-triazole, and 3,5-diamino-1,2,4-triazole. In one embodiment, Component A comprises or consists solely of one or more compounds selected from these compounds. In one embodiment, Component A comprises or consists solely of one or more compounds selected from the group consisting of 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole.

[0018] The lower limit of the content of component A may be 0.01 wt % or more, 0.03 wt % or more, or 0.05 wt % or more, relative to 100 wt % of the weight of the surface treatment solution. The upper limit of the content of component A may be 1 wt % or less, 0.8 wt % or less, 0.5 wt % or less, or 0.3 wt % or less, relative to 100 wt % of the weight of the surface treatment solution.

[0019] [1.1.2.Component B] Component B is a tetrazole compound having an amino group. The tetrazole compound is a compound having a tetrazole ring. The tetrazole ring is a five-membered ring having a nitrogen atom, and of the elements constituting this five-membered ring, four are nitrogen atoms and one is a carbon atom. Component B may have only one tetrazole ring in its structure, or may have two or more tetrazole rings. In one embodiment, component B has only one tetrazole ring in its structure.

[0020] The number of amino groups possessed by Component B is not particularly limited. The upper limit of the number of amino groups may be, for example, 5 or less, 4 or less, 3 or less, or 2 or less. The lower limit of the number of amino groups is 1. In one embodiment, the number of amino groups possessed by Component B is 1.

[0021] The position of the amino group in Component B is not particularly limited. The amino group may be directly bonded to the tetrazole ring, may be bonded via a linker such as alkylene, or may be a combination thereof. In one embodiment, the amino group is directly bonded to the tetrazole ring.

[0022] Specific examples of component B include 1-amino-tetrazole, 2-amino-tetrazole, and 5-amino-tetrazole. In one embodiment, component B comprises or consists solely of one or more compounds selected from these compounds. In one embodiment, component B comprises or consists solely of 5-amino-tetrazole.

[0023] The lower limit of the content of component B may be 0.01 wt % or more, 0.03 wt % or more, or 0.05 wt % or more, relative to 100 wt % of the weight of the surface treatment solution. The upper limit of the content of component B may be 1 wt % or less, 0.8 wt % or less, 0.5 wt % or less, or 0.3 wt % or less, relative to 100 wt % of the weight of the surface treatment solution.

[0024] 1.1.3. Solvent The surface treatment solution may contain a solvent. An example of the solvent is water, preferably pure water. Examples of pure water include ion-exchanged water and distilled water.

[0025] [1.1.4. Other ingredients] The surface treatment agent may contain other components in addition to component A and component B. The other components will be described below by way of example. Each of the components described below may be used alone or in combination of two or more.

[0026] (solubilizer) The surface treatment solution may contain a solubilizer. The incorporation of the solubilizer promotes the dissolution of components A and B in the solvent. The solubilizer can also be used in place of the solvent. Examples of solubilizers include acids, bases, and organic solvents.

[0027] Examples of acids include inorganic acids and organic acids, and examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, 2-ethylbutyric acid, valeric acid, caproic acid, heptanoic 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, glycine, isobutyric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, iodoacetic acid, methoxyacetic acid, ethoxyacetic acid, propoxyacetic acid, butoxyacetic acid, 2-(2-methoxyethoxy)acetic acid, 2-[2-(2-ethoxyethoxy)ethoxy]acetic acid, 2-{2-[2-(2-ethoxyethoxy)ethoxy]ethoxy}acetic acid, 3-methoxypropionic acid, 3-ethoxy ... Examples of suitable carboxylic acids include propionic acid, 3-propoxypropionic acid, 3-butoxypropionic acid, glyoxylic acid, pyruvic acid, acetoacetic acid, acrylic acid, crotonic acid, p-nitrobenzoic acid, salicylic acid, malonic acid, succinic acid, levulinic acid, benzoic acid, oxalic acid, tartaric acid, phthalic acid, malic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, propane-1,2,3-tricarboxylic acid, citric 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, amino acids, and picric acid.

[0028] Examples of bases include alkali metal or alkaline earth metal hydrides, hydroxides, and alkoxides, carbonates, and amines. Examples of alkali metal or alkaline earth metal hydrides, hydroxides, and alkoxides include lithium hydride, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium alkoxide, and potassium alkoxide. Examples of carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, ammonium carbonate, and sodium sesquicarbonate.Examples of amines include 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, and 3-amino-1-propanol. , N,N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine, pyridine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, benzethonium chloride, benzalkonium chloride, cetylpyridinium chloride, and the like.

[0029] Examples of organic solvents include methanol, ethanol, 1-propanol, 2-propanol, butanol, tert-butyl alcohol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 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, and propylene glycol monobutyl ether. Examples of the solvent include tetrahydrofurfuryl alcohol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, acetone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, formamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, ethylene carbonate, N-methylpyrrolidone, γ-butyrolactone, and 1,3-dimethyl-2-imidazolidinone.

[0030] The lower limit of the solubilizing agent content may be 0.1 wt % or more, 0.5 wt % or more, or 1 wt % or more, based on 100 wt % of the surface treatment solution, and the upper limit of the solubilizing agent content may be 99 wt % or less, based on 100 wt % of the surface treatment solution.

[0031] (Halide ions or substances that generate them) The surface treatment solution may contain halide ions or a substance that generates halide ions. By adding halide ions, the chemical conversion film formed by the surface treatment solution can be formed uniformly.

[0032] Examples of halide ions include fluoride ions, chloride ions, bromide ions, and iodide ions.

[0033] Examples of substances that generate halide ions include lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, magnesium iodide, calcium iodide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, etc. Alternatively, halide ions may be contained as impurities in a substance that does not contain halide ions as a major component.

[0034] The lower limit of the halide ion content may be more than 0 mol / L, where the weight of the surface treatment solution is taken as 100 wt %, and the upper limit of the halide ion content may be 0.10 mol / L or less, 0.050 mol / L or less, 0.020 mol / L or less, or 0.010 mol / L or less, where the weight of the surface treatment solution is taken as 100 wt %.

[0035] (Metal ions or substances that generate them) The surface treatment solution may contain metal ions or substances that generate metal ions. Adding metal ions can improve the stability of the surface treatment solution and the uniformity of the chemical conversion coating formed by the surface treatment solution.

[0036] Examples of metal ions include copper ions, iron ions, and zinc ions. In one embodiment, the metal ions are copper ions. The copper ions form a complex with Component A and / or Component B, which can increase the strength of the conversion coating film formed by the surface treatment solution and increase the adhesive strength between the inorganic material (such as a metal) and the resin. The valence of the copper ions may be monovalent or divalent.

[0037] 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, copper benzoate, etc.

[0038] The copper ions contained in the surface treatment solution may be derived from the object to be surface treated, for example, copper ions eluted from metallic copper or copper oxide contained in the copper circuit.

[0039] The lower limit of the copper ion content may be more than 0 mol / L, where the weight of the surface treatment solution is taken as 100 wt %, and the upper limit of the copper content may be 1.00 mol / L or less, 0.50 mol / L or less, 0.10 mol / L or less, or 0.010 mol / L or less, where the weight of the surface treatment solution is taken as 100 wt %.

[0040] (Alkylamine derivatives) The surface treatment solution may or may not contain an alkylamine derivative. In one embodiment, the surface treatment solution does not contain an alkylamine derivative.

[0041] An alkylamine derivative is a compound in which a part of the alkyl chain of an alkylamine is substituted with a heteroatom-containing group. The heteroatom may be one or more selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). Examples of the heteroatom-containing group include a hydroxy group, a carboxy group, a carbonyl group, and a polyoxyethylene group.

[0042] The lower limit of the number of carbon atoms in the alkyl chain contained in the alkylamine derivative may be 1 or more, 2 or more, 3 or more, or 4 or more, and the upper limit of the number of carbon atoms in the alkyl chain may be 20 or less, 19 or less, or 18 or less.

[0043] Specific examples of the alkylamine derivative include lauric acid diethanolamide, polyoxyethylene oleylamide, polyoxyethylene stearylamine, and N,N-bis(2-hydroxyethyl)-N-cyclohexylamine. In one embodiment, the alkylamine derivative is N,N-bis(2-hydroxyethyl)-N-cyclohexylamine.

[0044] [1.2. Characteristics of surface treatment solution] The pH of the surface treatment liquid is preferably weakly acidic to basic, and more preferably neutral to basic. By adjusting the pH of the surface treatment liquid, the effect of improving the adhesion between the inorganic material and the resin material can be further enhanced. Specifically, the lower limit of the pH of the surface treatment liquid can be 5.0 or more, 5.3 or more, 5.5 or more, 6.0 or more, 6.5 or more, or 7.0 or more. The upper limit of the pH of the surface treatment liquid can be 12.0 or less, 11.0 or less, 10.0 or less, or 9.0 or less.

[0045] In one embodiment, the surface treatment solution may contain an acid or a base for adjusting the pH. The acid or base may be any of the acids or bases exemplified above as solubilizing agents, or may be any other acid or base.

[0046] [1.3. Method for producing surface treatment solution] The surface treatment liquid can be produced by mixing the above-mentioned component A, component B, and other optional components with a solvent (such as water).

[0047] The surface treatment liquid can also be produced by mixing the above-mentioned component A, component B, and other optional components (excluding the solubilizer) with the solubilizer.

[0048] The order in which these components are mixed is not particularly limited. For example, when the surface treatment liquid contains a solubilizer, the surface treatment liquid may be produced by any of the following procedures. Add the solubilizer to the mixture of components A and B and water. Add the mixture of water and solubilizer to components A and B. Add water to the mixture of components A and B and the solubilizer. Add the solubilizer to components A and B.

[0049] [1.4. Uses of surface treatment liquid] The surface treatment liquid is used to further treat the surface of the object that has been treated with the coupling agent. The method of treatment with the coupling agent will be described later in Section [2], and in this section, the object and the coupling agent will be described in detail.

[0050] [1.4.1. Objects to be treated with surface treatment solution] The object to be treated with the surface treatment liquid is one or more selected from the group consisting of inorganic materials and resin materials. Examples of inorganic materials include metals and inorganic materials other than metals.

[0051] Examples of metals include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. Specific examples of the target include plates, foils, plated films, etc. that contain (or consist of) the above-mentioned metals.

[0052] Examples of alloys include copper alloys, aluminum alloys, nickel alloys, and iron alloys. The copper alloy is not particularly limited as long as it contains copper. Examples of copper alloys include Cu-Ag alloys, Cu-Te alloys, Cu-Mg alloys, Cu-Sn alloys, Cu-Si alloys, Cu-Mn alloys, Cu-Be-Co alloys, Cu-Ti alloys, Cu-Ni-Si alloys, Cu-Zn-Ni alloys, Cu-Cr alloys, Cu-Zr alloys, Cu-Fe alloys, Cu-Al alloys, Cu-Zn alloys, and Cu-Co alloys. Examples of aluminum alloys include Al-Si alloys. Examples of nickel alloys include Ni-Cr alloys. Examples of iron alloys include Fe-Ni alloys, stainless steel, and steel.

[0053] Among these metals, one or more selected from the group consisting of copper and copper alloys are preferred.

[0054] Examples of inorganic materials other than metals include silicon, ceramics, inorganic materials used as fillers, and glass.

[0055] More specific examples include silicon compounds (silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminosilicate, mica, etc.); oxides (alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, etc.); hydroxides (magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, etc.); carbonates (calcium carbonate, zinc carbonate, hydrotalcite, magnesium carbonate, etc.); sulfates (barium sulfate, gypsum, etc.); titanates (barium titanate, etc.); nitrides (aluminum nitride, silicon nitride, etc.); carbon fibers, etc.

[0056] Among these inorganic materials, one or more selected from the group consisting of silicon, ceramics (alumina, silicon carbide, aluminum nitride, silicon nitride, barium titanate, etc.), and glass are preferred.

[0057] Examples of resin materials include nylon, acrylate resin, epoxy resin, polybenzoxazole resin, silicone resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, polybutadiene resin, olefin resin, fluorine-containing resin, polyetherimide resin, polyether ether ketone resin, liquid crystal resin, etc. Mixtures and modified resins of these resins are also included in the examples of resin materials.

[0058] Among these resin materials, one or more selected from the group consisting of polyphenylene ether resin, polyphenylene oxide resin, liquid crystal resin, acrylate resin, epoxy resin, olefin resin, polybenzoxazole resin, silicone resin and polyimide resin are preferred.

[0059] The shape of the target is not particularly limited, and examples of the shape include needle-like, fibrous, woven, plate-like, foil-like, and amorphous.

[0060] In one embodiment, when the target is copper or a copper alloy used in a printed wiring board or the like, it is preferable that the surface of the target is not roughened or is subjected to a low-roughening treatment. Such targets generally have a low surface roughness. When the target is a copper foil, the upper and lower limits of various surface roughnesses may be within the following ranges. Ra (arithmetic mean roughness): The upper limit may be 0.26 μm or less, 0.24 μm or less, or 0.22 μm or less. The lower limit may be 0.01 μm or more. Rz (maximum height roughness): The upper limit may be 2.0 μm or less, 1.8 μm or less, or 1.6 μm or less. The lower limit may be 0.01 μm or more. Sa (arithmetic mean height): The upper limit may be 0.26 μm or less, 0.24 μm or less, or 0.22 μm or less. The lower limit may be 0.01 μm or more. Sq (root mean square height): The upper limit can be 0.40 μm or less or 0.30 μm or less. The lower limit can be 0.01 μm or more. Sz (maximum height): The upper limit can be 2.0 μm or less, 1.8 μm or less, or 1.6 μm or less. The lower limit can be 0.01 μm or more. Sdr (interface developed area ratio): The upper limit can be 0.10 or less or 0.05 or less. The lower limit can be 0.0001 or more. Spd (peak density (counts peaks higher than 5% of the maximum amplitude)): upper limit is 10 x 10 6 / mm 2 Below, 8 x 10 6 / mm 2 or less or 5×10 6 / mm 2 The lower limit is 0.5×10 6 / mm 2 It could be more than that.

[0061] [1.4.2. Coupling Agents] The object to be surface-treated with the surface treatment liquid is an object that has been treated with a coupling agent.

[0062] Examples of coupling agents include silane coupling agents, aluminum-based coupling agents, titanium-based coupling agents, and zirconium-based coupling agents. In one embodiment, the coupling agent is a silane coupling agent. A silane coupling agent is an organic silane compound having a silyl group. The silyl group has one or more hydroxyl and / or alkoxy groups.

[0063] Examples of the silane coupling agent include silane compounds 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. Specific examples thereof include mercaptosilane compounds (3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, etc.); vinylsilane compounds (vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, etc.); styrylsilane compounds (p-styryltrimethoxysilane, etc.); epoxysilane compounds (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.); acryloxysilane compounds (3-acryloxypropyltrimethoxysilane, etc.); methacryloxysilane compounds (3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.). aminosilane 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, etc.); ureidosilane compounds (3-ureidopropyltriethoxysilane, etc.); chloropropylsilane compounds (3-chloropropyltrimethoxysilane, etc.); sulfide silane compounds (bis(triethoxysilylpropyl)tetrasulfide, etc.); isocyanatosilane compounds (3-isocyanatopropyltriethoxysilane, etc.).

[0064] In one embodiment, the silane coupling agent has a nitrogen atom in the molecule, and such a silane coupling agent is expected to improve adhesion between inorganic materials and resin materials (particularly adhesion between metals and organic coatings), chemical resistance, and storage stability.

[0065] The nitrogen atom of the silane coupling agent may be contained in a substituent, may be contained in a heterocyclic skeleton, or may be contained in both. From the viewpoint of improving the adhesion between the inorganic material and the resin material, the nitrogen atom is preferably contained in the heterocyclic skeleton, and more preferably contained in both the substituent and the heterocyclic skeleton. That is, in one embodiment, the coupling agent is a silane compound having a nitrogen-containing heterocycle in the molecule. In one embodiment, the coupling agent is a silane compound having a nitrogen-containing heterocycle and a nitrogen-containing substituent in the molecule.

[0066] Examples of the substituent having a nitrogen atom include an amino group, an amido group, a cyano group, a nitro group, an azo group, a diazo group, a carbamide group, a ureido group, an azide group, and a guanidino group. Examples of the amino group include an unsubstituted amino group, a monosubstituted amino group, and a disubstituted amino group. An example of the unsubstituted amino group is -NH2. Examples of the monosubstituted amino group include a methylamino group, an ethylamino group, an n-propylamino group, an n-aminohexylamino group, a 2-aminoethylamino group, and a phenylamino group. Examples of the disubstituted amino group include a dimethylamino group, a diethylamino group, an ethylmethylamino group, and a diphenylamino group. From the viewpoint of further improving the adhesion between the inorganic material and the resin material, the substituent is preferably an amino group, more preferably an unsubstituted amino group or a monosubstituted amino group, and even more preferably an unsubstituted amino group.

[0067] Examples of heterocyclic skeletons having a nitrogen atom include monocyclic skeletons (pyrrole, pyrazole, diazole (imidazole), triazole, tetrazole, oxazole, oxadiazole, isoxazole, thiazole, isothiazole, furazan, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, pentazine, azepine, diazepine, triazepine, etc.); fused bicyclic skeletons (indole, isoindole, thienoindole, indazole, purine, quinoline, isoquinoline, benzodiazole, benzotriazole, etc.); and fused tricyclic skeletons (carbazole, acridine, β-carboline, acridone, perimidine, phenazine, phenanthridine, phenothiazine, phenoxazine, phenanthroline, etc.). The heterocyclic skeleton is preferably an aromatic ring. Among these heterocyclic skeletons, diazole, triazole, tetrazole, benzotriazole, or triazine is more preferred, triazole, benzotriazole, or tetrazole is even more preferred, and triazole or tetrazole is particularly preferred.

[0068] Examples of silane coupling agents having nitrogen atoms only in the substituents include 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(triethoxysilyl)propyl]amine.

[0069] Examples of silane coupling agents having a nitrogen atom in the heterocyclic skeleton include azole silane coupling agents and triazine silane coupling agents (these coupling agents may have a nitrogen atom in the substituent). From the viewpoint of further improving the adhesion between the inorganic material and the resin material, chemical resistance, and storage stability, the silane coupling agent preferably contains an azole silane coupling agent. The azole silane coupling agent preferably contains one or more compounds selected from the group consisting of triazole silane compounds and tetrazole silane compounds, and more preferably contains a triazole silane compound.

[0070] Examples of the silane coupling agent having nitrogen atoms in both the substituent and the heterocyclic skeleton include amino group-containing azole silane coupling agents and amino group-containing triazine silane coupling agents.

[0071] [1.4.2.1. Azole silane coupling agents] The azole silane coupling agent contains one or more azole silane compounds selected from the group consisting of monoazole silane compounds, diazole silane compounds, triazole silane compounds, and tetrazole silane compounds. Each compound is described in detail below.

[0072] (Triazole silane compound) The triazole silane compound is a compound having a triazole ring and a silyl group-containing alkyl group. The triazole ring is a five-membered ring containing a nitrogen atom, and of the elements constituting this five-membered ring, three are nitrogen atoms and two are carbon atoms. The triazole silane compound may have only one triazole ring or two or more. The triazole ring may be a 1,2,4-triazole ring or a 1,2,3-triazole ring. From the viewpoint of further improving the adhesion between inorganic materials and resin materials, chemical resistance, and storage stability, a 1,2,4-triazole ring is preferred.

[0073] The number of silyl group-containing alkyl groups in the triazole silane compound may be one or more. The silyl group-containing alkyl group may be bonded to an atom constituting the triazole ring. From the viewpoint of further improving the adhesion between the inorganic material and the resin material, chemical resistance, and storage stability, it is preferable that the silyl group-containing alkyl group be bonded to a nitrogen atom of the triazole ring.

[0074] Examples of the triazole silane compound include the triazole silane compound (Ia) and the triazole silane compound (Ib) shown by the following general formula.

[0075] [ka]

[0076] In formula (Ia), X 1 and X 2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a phenyl group, a benzyl group, an amino group, or an alkylthio group having 1 to 6 carbon atoms. Examples of alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group. Examples of alkylthio groups include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, an n-pentylthio group, and an n-hexylthio group. X 1 and X 2 may be the same or different, and are preferably the same.

[0077] Preferably, X 1 and X 2are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms (particularly a linear or branched alkyl group having 1 to 8 carbon atoms), a phenyl group, or an amino group. 1 and X 2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or an amino group. 1 and X 2 is an amino group. 1 and X 2 With such a structure, the adhesiveness between the inorganic material and the resin material, the chemical resistance and the storage stability can be further improved.

[0078] In formula (Ia), m represents an integer of 1 to 12. The lower limit of m is preferably 1 or more, or 2 or more. The upper limit of m is preferably 10 or less, or 6 or less. When m is within the above range, the solubility of the compound, the adhesion between the inorganic material and the resin material, the chemical resistance, and the storage stability can be further improved.

[0079] In formula (Ia), n represents an integer of 0 to 3.

[0080] In formula (Ia), R represents a methyl group or an ethyl group. Preferably, R is an ethyl group. When R is an ethyl group, the working environment can be improved.

[0081] In formula (Ia), X 1 or X 2 The triazole silane compound (Ia) in which at least one of the groups is an amino group corresponds to an amino group-containing azole silane coupling agent.

[0082] [ka]

[0083] In formula (Ib), X 1 , X 2 , m, n and R are the same as defined in formula (Ia).

[0084] In formula (Ib), preferably, X 1 and X 2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms (particularly a linear or branched alkyl group having 1 to 8 carbon atoms), a phenyl group, or an amino group. 1 and X 2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or an amino group. 1 and X 2 is an amino group. 1 and X 2 With such a structure, the adhesiveness between the inorganic material and the resin material, the chemical resistance and the storage stability can be further improved.

[0085] In formula (Ib), X 1 and X 2 If both X and X are alkyl groups, 1 and X 2 may be bonded to each other to form a carbocyclic ring having 6 to 10 carbon atoms that is fused with the triazole ring in formula (Ib) (the number of carbon atoms in the carbocyclic ring includes the number of carbon atoms shared with the triazole ring that is fused with the carbocyclic ring). The carbocyclic ring that is fused with the triazole ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

[0086] In formula (Ib), the lower limit of m is preferably 1 or more, or 2 or more. The upper limit of m is preferably 10 or less, or 6 or less. When m is within the above range, the solubility of the compound, the adhesiveness between the inorganic material and the resin material, the chemical resistance, and the storage stability can be further improved.

[0087] In formula (Ib), n represents an integer of 0 to 3.

[0088] In formula (Ib), R represents a methyl group or an ethyl group. Preferably, R is an ethyl group. When R is an ethyl group, the working environment can be improved.

[0089] In formula (Ib), the silyl group-containing alkyl group is depicted as being bonded to the nitrogen atom at position 1. However, the silyl group-containing alkyl group may be bonded to the nitrogen atom at position 2. That is, the triazole silane compound (Ib) also includes compounds in which the bonding position of the silyl group-containing alkyl group in general formula (Ib) is changed to the nitrogen atom at position 2.

[0090] In this specification, triazole silane compounds (Ib) in which a silyl group-containing alkyl group is bonded to the nitrogen atom at position 1 are referred to as "triazole silane compound (Ib) 1-position bonded compound." Triazole silane compounds (Ib) in which a silyl group-containing alkyl group is bonded to the nitrogen atom at position 2 are referred to as "triazole silane compound (Ib) 2-position bonded compound."

[0091] In formula (Ib), X 1 or X 2 The triazole silane compound (Ib) in which at least one of the groups is an amino group corresponds to an amino group-containing azole silane coupling agent.

[0092] Specific examples of the triazole silane compound (Ia) include the triazole silane compound (Ia-1), the triazole silane compound (Ia-2), the triazole silane compound (Ia-3), and the triazole silane compound (Ia-4) represented by the following general formulas.

[0093] [ka]

[0094] In formulas (Ia-1) to (Ia-4), X 1 , X 2 , m, and R are the same as those defined in formula (Ia). In addition, the preferred embodiments of each symbol are the same as those in formula (Ia).

[0095] In formulas (Ia-1) to (Ia-4), X 1 or X 2A compound in which at least one of the above groups is an amino group corresponds to an amino group-containing azole silane coupling agent.

[0096] The triazole silane compound (Ia-1) is a compound (trialkoxy compound) in which n is 0 in the triazole silane compound (Ia). The triazole silane compound (Ia-2) is a compound in which n is 1 in the triazole silane compound (Ia). The triazole silane compound (Ia-3) is a compound in which n is 2 in the triazole silane compound (Ia). The triazole silane compound (Ia-4) is a compound in which n is 3 in the triazole silane compound (Ia).

[0097] Specific examples of the triazole silane compound (Ia) include the following compounds. All of these compounds fall under the category of triazole silane compound (Ia-1). Among the following compounds, compounds in which one to three alkoxy groups (e.g., methoxy groups, ethoxy groups) have been converted to hydroxy groups fall under the category of triazole silane compound (Ia-2), triazole silane compound (Ia-3), or triazole silane compound (Ia-4). Therefore, it should be understood that the list below also includes examples of the corresponding triazole silane compound (Ia-2), triazole silane compound (Ia-3), or triazole silane compound (Ia-4).

[0098] 1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 3-Methyl-1-[2-(triethoxysilyl)ethyl]-1,2,4-triazole 5-Methyl-1-[4-(trimethoxysilyl)butyl]-1,2,4-triazole 3-Ethyl-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3-Propyl-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3-Isopropyl-1-[10-(trimethoxysilyl)decyl]-1,2,4-triazole 3-Butyl-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3-Hexyl-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 5-Methyl-3-octyl-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3-Dodecyl-1-[6-(triethoxysilyl)hexyl]-1,2,4-triazole 3,5-Dimethyl-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3,5-Diisopropyl-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 3-Phenyl-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3-Methyl-5-phenyl-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3-Ethyl-5-phenyl-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3,5-Diphenyl-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 3-Benzyl-1-[4-(triethoxysilyl)butyl]-1,2,4-triazole 3-Benzyl-5-phenyl-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 3-Hexylthio-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 3-Benzyl-5-propyl-1-[6-(triethoxysilyl)hexyl]-1,2,4-triazole 3-Amino-1-(triethoxysilyl)methyl-1,2,4-triazole 3-Amino-1-[2-(trimethoxysilyl)ethyl]-1,2,4-triazole 3-Amino-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 5-Amino-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 5-Amino-3-ethyl-1-[6-(trimethoxysilyl)hexyl]-1,2,4-triazole 3-Amino-5-phenyl-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 3-Amino-5-benzyl-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 3-Amino-1-[6-(trimethoxysilyl)hexyl]-1,2,4-triazole 3-Amino-1-[6-(triethoxysilyl)hexyl]-1,2,4-triazole 3-Amino-1-[12-(trimethoxysilyl)dodecyl]-1,2,4-triazole 3,5-Diamino-1-[1-(trimethoxysilyl)methyl]-1,2,4-triazole 3,5-Diamino-1-[1-(triethoxysilyl)methyl]-1,2,4-triazole 3,5-Diamino-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3,5-Diamino-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 3,5-Diamino-1-[6-(trimethoxysilyl)hexyl]-1,2,4-triazole 3,5-Diamino-1-[12-(trimethoxysilyl)dodecyl]-1,2,4-triazole 3-Methylthio-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3-Isopropylthio-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3-Hexylthio-1-[10-(triethoxysilyl)decyl]-1,2,4-triazole 3-Ethylthio-5-isopropyl-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 3,5-Bis(methylthio)-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 5-Hexylthio-3-methylthio-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 3-Amino-5-methylthio-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 5-Amino-3-methylthio-1-[3-(trimethoxysilyl)propyl]-1,2,4-triazole 5-Amino-3-methylthio-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole 5-Amino-3-isopropylthio-1-[6-(triethoxysilyl)hexyl]-1,2,4-triazole 3-Amino-5-hexylthio-1-[3-(triethoxysilyl)propyl]-1,2,4-triazole The triazole silane compound (Ia) may be a mixture of any combination of the triazole silane compounds (Ia-1) to (Ia-4).

[0099] The triazole silane compound (Ia-1) can be synthesized in accordance with WO 2018 / 186476, U.S. Patent Application Publication No. 2012 / 0021232, and WO 2019 / 058773. Specifically, as shown in Scheme 1 below, the compound can be synthesized by reacting a triazole compound (Ia-x) with a halogenated alkyl silane compound (Ia-y). The synthesis conditions may be appropriately set in the presence of a dehydrohalogenating agent, a reaction solvent, a reaction temperature, and a reaction time.

[0100] [ka]

[0101] In Scheme 1, X 1 , X 2, m and R are each defined as in formula (Ia). Hal represents a halogen atom.

[0102] The triazole silane compounds (Ia-2) to (Ia-4) can be synthesized by bringing the trialkoxy triazole silane compound (Ia-1) into contact with an appropriate amount of water to hydrolyze it.

[0103] Specific examples of the triazole silane compound (Ib) include triazole silane compound (Ib-1), triazole silane compound (Ib-2), triazole silane compound (Ib-3), and triazole silane compound (Ib-4), which are represented by the following general formulas.

[0104] [ka]

[0105] In formulas (Ib-1) to (Ib-4), X 1 , X 2 , m, and R are the same as those in formula (Ib). In addition, the preferred embodiments of each symbol are the same as those in formula (Ib).

[0106] In formulas (Ib-1) to (Ib-4), the silyl group-containing alkyl group is depicted as being bonded to the nitrogen atom at position 1. However, the silyl group-containing alkyl group may be bonded to the nitrogen atom at position 2. In other words, the triazole silane compounds (Ib-1) to (Ib-4) also include compounds in which the bonding position of the silyl group-containing alkyl group in general formulas (Ib-1) to (Ib-4) has been changed to the nitrogen atom at position 2.

[0107] In formulas (Ib-1) to (Ib-4), X 1 or X 2 A compound in which at least one of the above groups is an amino group corresponds to an amino group-containing azole silane coupling agent.

[0108] The triazole silane compound (Ib-1) is a compound (trialkoxy compound) in which n is 0 in the triazole silane compound (Ib). The triazole silane compound (Ib-2) is a compound in which n is 1 in the triazole silane compound (Ib). The triazole silane compound (Ib-3) is a compound in which n is 2 in the triazole silane compound (Ib). The triazole silane compound (Ib-4) is a compound in which n is 3 in the triazole silane compound (Ib).

[0109] Specific examples of the triazole silane compound (Ib) include the following compounds. All of these compounds fall under the category of triazole silane compound (Ib-1). Among the following compounds, compounds in which one to three alkoxy groups (e.g., methoxy groups, ethoxy groups) have been converted to hydroxy groups fall under the category of triazole silane compound (Ib-2), triazole silane compound (Ib-3), or triazole silane compound (Ib-4). Therefore, it should be understood that the list below also includes examples of the corresponding triazole silane compound (Ib-2), triazole silane compound (Ib-3), or triazole silane compound (Ib-4).

[0110] 1-[3-(trimethoxysilyl)propyl]-1,2,3-triazole 1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Methyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Ethyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Propyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Isopropyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Butyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Hexyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Dodecyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4,5-Dimethyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Benzyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Phenyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4,5-Diphenyl-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Amino-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Methylthio-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Isopropylthio-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Hexylthio-1-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Methyl-2-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Hexyl-2-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Methylthio-2-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Amino-2-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Methyl-3-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Hexyl-3-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Methylthio-3-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Amino-3-[3-(triethoxysilyl)propyl]-1,2,3-triazole 4-Propyl-1-[3-(trimethoxysilyl)propyl]-1,2,3-triazole 4-Amino-1-[3-(trimethoxysilyl)propyl]-1,2,3-triazole 4-Amino-1-[6-(triethoxysilyl)hexyl]-1,2,3-triazole 4-Amino-1-[10-(triethoxysilyl)decyl]-1,2,3-triazole 4-Amino-1-[12-(triethoxysilyl)dodecyl]-1,2,3-triazole 1-[3-(trimethoxysilyl)propyl]-1H-benzotriazole 1-[3-(triethoxysilyl)propyl]-1H-benzotriazole 2-[3-(trimethoxysilyl)propyl]-2H-benzotriazole 2-[3-(triethoxysilyl)propyl]-2H-benzotriazole

[0111] The triazole silane compound (Ib) may be a mixture of any combination of the triazole silane compounds (Ib-1) to (Ib-4). The triazole silane compound (Ib) may be a mixture of a 1-position bonded triazole silane compound (Ib) and a 2-position bonded triazole silane compound (Ib). The mixing ratio of the 1-position bonded triazole silane compound (Ib) to the 2-position bonded triazole silane compound (Ib) may be (10:90) to (90:10) in terms of molar ratio, preferably (20:80) to (80:20), and more preferably (30:70) to (70:30).

[0112] The triazole silane compound (Ib-1) can be synthesized by a method similar to that shown in Scheme 1. Specifically, the triazole compound (Ia-x) in Scheme 1 can be replaced with the following triazole compound (Ib-x). [ka] In formula (Ib-x), X 1 and X 2is the same as defined in formula (Ib).

[0113] The triazole silane compounds (Ib-2) to (Ib-4) can be synthesized by bringing the trialkoxy triazole silane compound (Ib-1) into contact with an appropriate amount of water to hydrolyze it.

[0114] (Monoazole silane compound) The monoazole silane compound is a compound having a monoazole ring and a silyl group-containing alkyl group. The monoazole ring is a five-membered ring having a nitrogen atom, and among the elements constituting this five-membered ring, one is a nitrogen atom and four are carbon atoms. The monoazole silane compound may have only one monoazole ring, or may have two or more monoazole rings.

[0115] The number of silyl group-containing alkyl groups in the monoazole silane compound may be one or more. The silyl group-containing alkyl group may be bonded to an atom constituting the monoazole ring. From the viewpoint of further improving the adhesion between the inorganic material and the resin material, chemical resistance, and storage stability, it is preferable that the silyl group-containing alkyl group be bonded to the nitrogen atom of the monoazole ring.

[0116] The monoazole silane compound may have a substituent on the monoazole ring in addition to the silyl group-containing alkyl group. Examples of the substituent include X in general formula (Ia). 1 and X 2 A monoazole silane compound in which one or more of the substituents is an amino group corresponds to an amino group-containing azole silane coupling agent.

[0117] (Diazole silane compound) The diazole silane compound is a compound having a diazole ring and a silyl group-containing alkyl group. The diazole ring is a five-membered ring having a nitrogen atom, and of the elements constituting this five-membered ring, two are nitrogen atoms and three are carbon atoms. The diazole silane compound may have only one diazole ring or may have two or more diazole rings.

[0118] The number of silyl group-containing alkyl groups in the diazole silane compound may be one or more. The silyl group-containing alkyl group may be bonded to an atom constituting the diazole ring. From the viewpoint of further improving the adhesion between the inorganic material and the resin material, chemical resistance, and storage stability, it is preferable that the silyl group-containing alkyl group be bonded to a nitrogen atom of the diazole ring.

[0119] The diazole silane compound may have a substituent on the diazole ring in addition to the silyl group-containing alkyl group. Examples of the substituent include X in general formula (Ia). 1 and X 2 Diazole silane compounds in which one or more of the substituents is an amino group are classified as amino group-containing azole silane coupling agents.

[0120] (Tetrazole silane compound) The tetrazole silane compound is a compound having a tetrazole ring and a silyl group-containing alkyl group. The tetrazole ring is a five-membered ring having a nitrogen atom, and among the elements constituting this five-membered ring, four are nitrogen atoms and one is a carbon atom. The tetrazole silane compound may have only one tetrazole ring or may have two or more tetrazole rings.

[0121] The number of silyl group-containing alkyl groups in the tetrazole silane compound may be one or more. The silyl group-containing alkyl group may be bonded to an atom constituting the tetrazole ring. From the viewpoint of further improving the adhesion between the inorganic material and the resin material, chemical resistance, and storage stability, it is preferable that the silyl group-containing alkyl group be bonded to a nitrogen atom of the tetrazole ring.

[0122] The tetrazole silane compound may have a substituent on the tetrazole ring in addition to the silyl group-containing alkyl group. Examples of the substituent include X in general formula (Ia). 1 From the viewpoint of further improving the adhesiveness between the inorganic material and the resin material, the chemical resistance, and the storage stability, the substituent is preferably bonded to a carbon atom of the tetrazole ring.

[0123] An example of the tetrazole silane compound is the tetrazole silane compound (Ic) shown by the following general formula.

[0124] [ka]

[0125] In formula (Ic), X 1 , m, n and R are the same as defined in formula (Ia).

[0126] In formula (Ic), preferably, X 1 is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms (particularly a linear or branched alkyl group having 1 to 8 carbon atoms), a phenyl group, or an amino group. 1 is a phenyl group or an amino group. More preferably, X 1 is an amino group. 1 With such a structure, the adhesiveness between the inorganic material and the resin material, the chemical resistance and the storage stability can be further improved.

[0127] In formula (Ic), the lower limit of m is preferably 1 or more, or 2 or more. The upper limit of m is preferably 10 or less, or 6 or less. If m is within the above range, the solubility of the compound can be further improved.

[0128] In formula (Ic), n represents an integer of 0 to 3.

[0129] In formula (Ic), R represents a methyl group or an ethyl group. Preferably, R is an ethyl group. When R is an ethyl group, the working environment can be improved.

[0130] In formula (Ic), the silyl group-containing alkyl group is depicted as being bonded to the nitrogen atom at position 2. However, the silyl group-containing alkyl group may be bonded to the nitrogen atom at position 1. That is, the tetrazolesilane compound (Ic) also includes compounds in which the bonding position of the silyl group-containing alkyl group in general formula (Ic) is changed to the nitrogen atom at position 1.

[0131] In this specification, tetrazolesilane compounds (Ic) in which a silyl group-containing alkyl group is bonded to the nitrogen atom at position 1 are referred to as "tetrazolesilane compound (Ic) 1-position bonded compound." Tetrazolesilane compounds (Ic) in which a silyl group-containing alkyl group is bonded to the nitrogen atom at position 2 are referred to as "tetrazolesilane compound (Ic) 2-position bonded compound."

[0132] In formula (Ic), X 1 The tetrazole silane compound in which R is an amino group corresponds to an amino group-containing azole silane coupling agent.

[0133] Specific examples of the triazole silane compound (Ic) include tetrazole silane compound (Ic-1), tetrazole silane compound (Ic-2), tetrazole silane compound (Ic-3), and tetrazole silane compound (Ic-4), which are represented by the general formulas below.

[0134] [ka]

[0135] In formulas (Ic-1) to (Ic-4), X 1 , m, and R are the same as those in formula (Ia). In addition, the preferred embodiments of each symbol are the same as those in formula (Ic).

[0136] In formulas (Ic-1) to (Ic-4), the silyl group-containing alkyl group is depicted as being bonded to the nitrogen atom at position 2. However, the silyl group-containing alkyl group may be bonded to the nitrogen atom at position 1. In other words, the tetrazolesilane compounds (Ic-1) to (Ic-4) also include compounds in which the bonding position of the silyl group-containing alkyl group in general formulas (Ic-1) to (Ic-4) has been changed to the nitrogen atom at position 1.

[0137] In formulas (Ic-1) to (Ic-4), X 1 The compound in which is an amino group corresponds to an amino group-containing azole silane coupling agent.

[0138] The tetrazole silane compound (Ic-1) is a compound (trialkoxy compound) in which n is 0 in the tetrazole silane compound (Ic). The tetrazole silane compound (Ic-2) is a compound in which n is 1 in the tetrazole silane compound (Ic). The tetrazole silane compound (Ic-3) is a compound in which n is 2 in the tetrazole silane compound (Ic). The tetrazole silane compound (Ic-4) is a compound in which n is 3 in the tetrazole silane compound (Ic).

[0139] Specific examples of the tetrazole silane compound (Ic) include the following compounds. All of these compounds fall under the category of tetrazole silane compound (Ic-1). Among the following compounds, compounds in which one to three alkoxy groups (e.g., methoxy groups, ethoxy groups) have been converted to hydroxy groups fall under the category of tetrazole silane compound (Ic-2), tetrazole silane compound (Ic-3), or tetrazole silane compound (Ic-4). Therefore, it should be understood that the list below also includes examples of the corresponding tetrazole silane compound (Ic-2), tetrazole silane compound (Ic-3), or tetrazole silane compound (Ic-4).

[0140] 5-Amino-2-[(trimethoxysilyl)methyl]-2H-tetrazole 5-Amino-1-[(trimethoxysilyl)methyl]-1H-tetrazole 5-Amino-2-[(triethoxysilyl)methyl]-2H-tetrazole 5-Amino-1-[(triethoxysilyl)methyl]-1H-tetrazole 5-Amino-2-[3-(trimethoxysilyl)propyl]-2H-tetrazole 5-Amino-1-[3-(trimethoxysilyl)propyl]-1H-tetrazole 5-Amino-2-[3-(triethoxysilyl)propyl]-2H-tetrazole 5-Amino-1-[3-(triethoxysilyl)propyl]-1H-tetrazole 5-Amino-2-[6-(trimethoxysilyl)hexyl]-2H-tetrazole 5-Amino-1-[6-(trimethoxysilyl)hexyl]-1H-tetrazole 5-Amino-2-[6-(triethoxysilyl)hexyl]-2H-tetrazole 5-Amino-1-[6-(triethoxysilyl)hexyl]-1H-tetrazole 5-phenyl-2-[3-(trimethoxysilyl)propyl]-2H-tetrazole 5-phenyl-1-[3-(trimethoxysilyl)propyl]-1H-tetrazole 5-phenyl-2-[3-(triethoxysilyl)propyl]-2H-tetrazole 5-phenyl-1-[3-(triethoxysilyl)propyl]-1H-tetrazole

[0141] The tetrazole silane compound (Ic) may be a mixture of any combination of the tetrazole silane compounds (Ic-1) to (Ic-4). The tetrazole silane compound (Ic) may be a mixture of a 1-position bonded tetrazole silane compound (Ic) and a 2-position bonded tetrazole silane compound (Ic). The mixing ratio of the 1-position bonded tetrazole silane compound (Ic) to the 2-position bonded tetrazole silane compound (Ic) may be (10:90) to (90:10) in terms of molar ratio, preferably (20:80) to (80:20), more preferably (30:70) to (70:30), and even more preferably (35:65) to (45:55). When the mixing ratio is within the above range, the adhesion, chemical resistance, and storage stability between the inorganic material and the resin material can be further improved.

[0142] The tetrazole silane compound (Ic-1) can be synthesized by a method similar to that shown in Scheme 1. Specifically, it can be synthesized by changing the triazole compound (Ia-x) in Scheme 1 to the following tetrazole compound (Ic-x).

[0143] [ka]

[0144] In the formula (Ic-x), X 1 is the same as defined in formula (Ia).

[0145] The tetrazolesilane compounds (Ic-2) to (Ic-4) can be synthesized by bringing the trialkoxy tetrazolesilane compound (Ic-1) into contact with an appropriate amount of water to hydrolyze it.

[0146] (Condensation product of azole silane compound) The azole silane coupling agent may contain a condensate of the above-mentioned azole silane compound. The alkoxysilyl group contained in the azole silane compound may be hydrolyzed upon contact with water to form a hydroxysilyl group. The hydroxysilyl group may undergo dehydration condensation to form a siloxane bond. The above reactions are summarized in Scheme 2 below.

[0147] [ka]

[0148] In Scheme 2, (a) is a trialkoxysilyl group, (b) is a dialkoxyhydroxysilyl group, (c) is a dihydroxyalkoxysilyl group, and (d) is a trihydroxysilyl group. The alkoxysilyl groups are hydrolyzed stepwise in the order of (a) to (d). Furthermore, (e) is a siloxane bond, which is formed by dehydration condensation between hydroxysilyl groups (x is the repeating number).

[0149] Some of the azole silane compounds having a hydroxysilyl group may undergo dehydration condensation with each other to form a condensate as shown in (e) of Scheme 2. Examples of the azole silane compound having a hydroxysilyl group include triazole silane compounds (Ia-2) to (Ia-4), triazole silane compounds (Ib-2) to (Ib-4), and tetrazole silane compounds (Ic-2) to (Ic-4).

[0150] However, since such condensates have low solubility, if the content of the condensates in the coupling agent is high, they will precipitate as insoluble components. Such coupling agents are cloudy and may contaminate the treated product. Therefore, it is preferable to reduce the content of the condensates in the coupling agent to obtain a transparent solution.

[0151] [1.4.2.2. Triazine silane coupling agents] The triazine silane coupling agent contains a triazine silane compound. The triazine silane compound is a compound having a triazine ring and a silyl group-containing amino group. The triazine ring is a six-membered ring having a nitrogen atom, and of the elements constituting this six-membered ring, three are nitrogen atoms and three are carbon atoms. The triazine silane compound may have only one triazine ring or two or more triazine rings. The triazine ring may be a 1,2,3-triazine ring, a 1,2,4-triazine ring, or a 1,3,5-triazine ring. Among these, the 1,3,5-triazine ring is preferred.

[0152] The number of silyl group-containing amino groups in the triazine silane compound may be one or more. The silyl group-containing amino group may be bonded to an atom constituting the triazine ring. Preferably, the silyl group-containing amino group is bonded to a carbon atom constituting the triazine ring.

[0153] An example of the structure of a silyl group-containing amino group is -NH-(CH2) m -Si(OR) 3-n (OH) n In the formula, m, n, and R are the same as defined in formula (Ia).

[0154] The triazine silane compound may have a substituent on the triazine ring in addition to the silyl group-containing amino group. Examples of the substituent include X in general formula (Ia). 1 The substituent is preferably bonded to a carbon atom of the triazine ring. A triazine silane compound having an amino group as a substituent corresponds to an amino group-containing triazine silane coupling agent.

[0155] Specific examples of the triazine silane compound include the following compounds:

[0156] N-trimethoxysilanylmethyl-[1,3,5]triazine-2,4,6-triamine N-(2-trimethoxysilanyl-ethyl)-[1,3,5]triazine-2,4,6-triamine N-(3-trimethoxysilanyl-propyl)-[1,3,5]triazine-2,4,6-triamine N-(4-trimethoxysilanyl-butyl)-[1,3,5]triazine-2,4,6-triamine N-(6-trimethoxysilanyl-hexyl)-[1,3,5]triazine-2,4,6-triamine N-(8-trimethoxysilanyl-octyl)-[1,3,5]triazine-2,4,6-triamine N-(10-trimethoxysilanyl-decyl)-[1,3,5]triazine-2,4,6-triamine N-(12-trimethoxysilanyl-dodecyl)-[1,3,5]triazine-2,4,6-triamine N-triethoxysilanylmethyl-[1,3,5]triazine-2,4,6-triamine N-(2-triethoxysilanyl-ethyl)-[1,3,5]triazine-2,4,6-triamine N-(3-triethoxysilanyl-propyl)-[1,3,5]triazine-2,4,6-triamine N-(4-triethoxysilanyl-butyl)-[1,3,5]triazine-2,4,6-triamine N-(6-triethoxysilanyl-hexyl)-[1,3,5]triazine-2,4,6-triamine N-(8-triethoxysilanyl-octyl)-[1,3,5]triazine-2,4,6-triamine N-(10-triethoxysilanyl-decyl)-[1,3,5]triazine-2,4,6-triamine N-(12-triethoxysilanyl-dodecyl)-[1,3,5]triazine-2,4,6-triamine

[0157] [2. Surface treatment method and adhesion method] A surface treatment method according to one embodiment of the present invention involves carrying out the following steps 1 and 2 in this order. An adhesion method according to one embodiment of the present invention involves carrying out the following steps 1 to 3 in this order. In other words, if step 3 is carried out after completing the surface treatment method, it becomes an adhesion method. The order of steps 1 and 2 is important to improve the adhesion between the first material and the second material. In other words, it is necessary to carry out the surface treatment liquid treatment after carrying out the coupling agent treatment (see Example 3 for details). Step 1: A step of bringing the coupling agent into contact with the first material Step 2: A step of contacting the first material with a surface treatment liquid Step 3: contacting the first material with the second material

[0158] The surface treatment liquid used in the above method is the surface treatment liquid described in Section [1], and contains component A and component B.

[0159] The first material includes one of an inorganic material or a resin material, and the second material includes the other of an inorganic material or a resin material. Thus, if the first material includes an inorganic material, the second material includes a resin material. If the first material includes a resin material, the second material includes an inorganic material. In one embodiment, the inorganic material includes or consists of a metal. In one embodiment, the metal includes or consists of copper or a copper alloy.

[0160] In relation to the above description, the percentage of the area of ​​the surface of the first material that comes into contact with the coupling agent that is occupied by the inorganic material or resin material may be 30 area% or more, 50 area% or more, 70 area% or more, 90 area% or more, or 100 area%. Also, the percentage of the area of ​​the surface of the second material that comes into contact with the first material that is occupied by the inorganic material or resin material may be 30 area% or more, 50 area% or more, 70 area% or more, 90 area% or more, or 100 area%.

[0161] The inorganic material, resin material and coupling agent are as explained in Section [1].

[0162] The details of each step will be explained below.

[0163] [2.1.Process 1] In step 1, the first material is brought into contact with a coupling agent, thereby treating the first material with the coupling agent.

[0164] The coupling agent treatment can be carried out by a conventionally known method, for example, the following method. · Spray the coupling agent diluted with organic solvent onto the first material. Spray the coupling agent diluted with water and organic solvent onto the first material. Spray the coupling agent diluted with water onto the first material. · Immerse the first material in coupling agent diluted with organic solvent. · Immerse the first material in coupling agent diluted with water and organic solvent. · Immerse the first material in the coupling agent diluted with water.

[0165] Examples of organic solvents that can be used in the above method include hydrocarbon solvents (benzene, toluene, xylene, heptane, hexane, cyclohexane, n-octane, etc.); halogenated hydrocarbon solvents (dichloromethane, dichloroethane, carbon tetrachloride, chloroform, chlorobenzene, dichlorobenzene, trichlorobenzene, etc.); ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); ether solvents (diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.); and alcohol solvents (methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, 2-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, etc.).

[0166] Diluting the coupling agent with an organic solvent is preferred because it can reduce the formation of coupling agent condensates. As explained in relation to Scheme 2 in Section [1], condensates formed from the silane coupling agent may contaminate the treated product, so a low content is preferred. Organic solvents can act as solubilizers for such condensates. Similarly, acids and bases can also act as solubilizers. Examples of acids and bases include the acids and bases exemplified in Section [1] as solubilizers that can be included in the surface treatment solution.

[0167] The lower limit of the concentration of the coupling agent (e.g., silane coupling agent) in the coupling agent treatment liquid (a coupling agent diluted with water and / or an organic solvent) may be 0.001 mol / L, preferably 0.005 mol / L or more, and more preferably 0.020 mol / L or more. The upper limit of the coupling agent concentration may be 1.000 mol / L or less, preferably 0.500 mol / L or less, more preferably 0.100 mol / L, and even more preferably 0.030 mol / L or less. If the content is within the above range, the adhesion, chemical resistance, and storage stability between the inorganic material and the resin material can be further improved. When two or more types of coupling agents are used, it is preferable that the total content be within the above range.

[0168] [2.1.1. Possible mechanism of action of silane coupling agents containing nitrogen atoms] Silane coupling agents having nitrogen atoms in the molecule are presumed to exhibit the following effects. However, the mechanism explained below is provided to aid in understanding the invention and is not intended to limit the scope of the invention.

[0169] Take the adhesion between metals such as copper and resin materials as an example. The nitrogen atoms contained in the silane coupling agent (e.g., nitrogen atoms contained in amino groups, azole rings, or triazine rings) interact with the metal to form chemical bonds. Meanwhile, the alkoxysilyl groups contained in the silane coupling agent are hydrolyzed to form hydroxysilyl groups. The hydroxysilyl groups chemically bond with metal oxides scattered on the metal surface.

[0170] When a metal is brought into contact with a silane coupling agent having a nitrogen atom, an organic film derived from the silane coupling agent is formed on the surface of the metal through bonding with the nitrogen atom or the hydroxysilyl group. Bonding a metal to a resin material via this organic film provides greater adhesion than bonding a resin material directly to the metal surface.

[0171] [2.2.Process 2] In step 2, the first material is brought into contact with the surface treatment liquid. Since step 2 is downstream of step 1, the coating formed by the coupling agent is treated with the surface treatment liquid, and a chemical conversion coating is formed by the surface treatment liquid.

[0172] The method for bringing the surface treatment solution into contact with the first material is not particularly limited, and examples include spraying, immersion, and coating.

[0173] The lower limit of the treatment time with the surface treatment liquid is preferably 1 second or more, more preferably 5 seconds or more. The upper limit of the treatment time is preferably 10 minutes or less, more preferably 3 minutes or less. If the treatment time is 1 second or more, a chemical conversion coating formed from the surface treatment liquid will have a sufficient thickness, and adhesion tends to be improved. If the treatment time is 10 minutes or less, the thickness of the chemical conversion coating formed from the surface treatment liquid increases depending on the treatment time, which is preferable from the viewpoint of productivity.

[0174] The treatment temperature with the surface treatment solution can be appropriately set in relation to the treatment time, and is, for example, 5 to 50°C.

[0175] The lower limit of the film thickness of the chemical conversion coating formed by the surface treatment liquid in step 2 is preferably 0.5 nm or more, more preferably 1 nm or more. The upper limit of the film thickness of the chemical conversion coating formed by the surface treatment liquid is preferably 1,000 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. If the film thickness is 0.5 nm or more, the adhesion between materials can be sufficiently improved. If the film thickness is 1,000 nm or less, the chemical resistance of the chemical conversion coating formed by the surface treatment liquid can be maintained.

[0176] [2.2.1. Processing before and after Step 1 and Step 2] Various treatments may be performed on the first material before step 1, between step 1 and step 2, or between step 2 and step 3. An example of such treatments is described below.

[0177] (Processing before step 1) In particular, when the first material is a metal such as copper or a copper alloy, a pretreatment may be performed before step 1. Examples of the pretreatment include cleaning treatment, pickling treatment, alkali treatment, roughening treatment, heat-resistant treatment, rust-proofing treatment, and chemical conversion treatment.

[0178] Pickling can remove oily or grease components or oxide films from metal surfaces. Examples of solutions that can be used for pickling include 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.

[0179] Alkaline treatment can remove oil and fat components from the metal surface or residues from previous processes (such as residues of dry film resists for forming metal circuits). Examples of solutes in the solution used in alkaline treatment include alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.); amines (ammonia, ethanolamine, monopropanolamine, tetramethylammonium hydroxide, etc.); 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. Examples of solvents in the solution used in alkaline treatment include water and organic solvents.

[0180] Roughening treatment creates an uneven surface on the metal, which has an anchoring effect that improves adhesion between the metal and resin material. Examples of methods that can be used for roughening treatment include microetching, electroplating, electroless plating, oxidation (black oxide, brown oxide), oxidation-reduction, brush polishing, and jet scrubbing.

[0181] Examples of etching agents that can be used in roughening treatment by microetching include organic acid-cupric ion systems, sulfuric acid-hydrogen peroxide systems, persulfate systems, copper chloride systems, and iron chloride systems. In roughening treatment by electroplating, minute metal particles are deposited on the metal surface to form irregularities on the metal surface.

[0182] In the heat-resistant treatment, one or more coatings selected from nickel, nickel-phosphorus, zinc, zinc-nickel, copper-zinc, copper-nickel, copper-nickel-cobalt, and nickel-cobalt are formed on the surface of the metal. Examples of methods for forming the coating include electroplating and vapor deposition.

[0183] Anti-rust treatment prevents oxidation corrosion of metal surfaces. Anti-rust treatment may involve forming a coating such as zinc plating, zinc alloy plating, or electrolytic chromate plating. Alternatively, an organic compound-based anti-rust agent (such as a benzotriazole-based anti-rust agent) may be brought into contact with the metal surface.

[0184] In the chemical conversion treatment, a passivation film of tin or copper oxide may be formed.

[0185] (Processing after step 2 and before step 3) The first material may be dried after step 2. The drying temperature is preferably 20 to 150°C.

[0186] Prior to drying, the first material may be washed with water. The water used for washing is preferably pure water (ion-exchanged water, distilled water, etc.). Examples of the washing method include spraying and immersion. The washing time can be set appropriately.

[0187] After drying the chemical conversion coating formed by the surface treatment solution, the surface may be modified by, for example, plasma, laser, ion beam, ozone, heating, or humidification.

[0188] After step 2, the first material may be brought into contact with an organic compound-based rust inhibitor (such as a benzotriazole-based rust inhibitor).

[0189] (Processing before and after step 1 and / or step 2) A certain type of treatment may be carried out at any one or more of before step 1, between step 1 and step 2, and between step 2 and step 3. For example, when the first material is copper or a copper alloy, the first material may be contacted with one or more selected from the group consisting of an aqueous solution containing copper ions, an acidic aqueous solution, and a basic aqueous solution.

[0190] By contacting the first material with an aqueous solution containing copper ions, the film-forming properties of the organic film and / or chemical conversion film formed on the surface of copper or a copper alloy are improved, and the uniformity of the organic film and / or chemical conversion film is also improved. The valence of the copper ions may be monovalent or divalent. Here, the "organic film" refers to the film formed by the coupling agent treatment in step 1. The "chemical conversion film" refers to the film formed by the surface treatment solution treatment in step 2.

[0191] Examples of substances contained in aqueous solutions containing copper ions include copper sulfate, copper nitrate, copper chloride, copper formate, and copper acetate. Ammonia or hydrochloric acid may be added to dissolve copper salts in water.

[0192] By contacting the first material with an acidic aqueous solution and / or a basic aqueous solution, the uniformity of the organic film and / or chemical conversion film formed on the copper surface is improved.

[0193] Examples of solutes for acidic aqueous solutions include inorganic acids (sulfuric acid, nitric acid, hydrochloric acid, etc.) and organic acids (formic acid, acetic acid, lactic acid, glycolic acid, amino acids, etc.). Examples of solutes for basic aqueous solutions include alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.), amines (ammonia, ethanolamine, monopropanolamine, tetramethylammonium hydroxide, etc.), 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.

[0194] [2.3.Process 3] In step 3, the second material is brought into contact with the first material, thereby bonding the first material and the second material together via the organic coating and / or chemical conversion coating formed in step 2.

[0195] The method for bringing the first material and the second material into contact is not particularly limited. For example, the second material may be bonded by applying, pressing, or mixing the second material onto part or all of the organic coating and / or chemical conversion coating formed on the first material. Alternatively, the second material may be bonded to part or all of the organic coating and / or chemical conversion coating formed on the first material using an adhesive, adhesive sheet, adhesive film, or the like. Alternatively, the first material and the second material may be bonded together by combining the above-mentioned methods.

[0196] In one embodiment, step 1 and / or step 2 are also performed on the second material. In this bonding method, the coating on the surface of the first material and the coating on the surface of the second material are brought into contact with each other and bonded together. Examples of methods for bringing the coatings into contact with each other include the methods exemplified above.

[0197] [3. Use of surface treatment liquid] The surface treatment liquid according to one aspect of the present invention can be used to effectively bond inorganic materials and resin materials, and therefore can be suitably used for various electric and electronic components, semiconductor wafers, printed wiring boards, and other electronic devices.

[0198] Preferably, a surface treatment solution can be used with a metal such as copper or a copper alloy as the first material. For example, by further treating a copper circuit (copper wiring layer) that has been treated with a coupling agent with a surface treatment solution, the adhesion to prepreg, solder resist, dry film resist (resin insulating layer), etc. can be improved (the prepreg, solder resist, and dry film resist may be in a cured or semi-cured state). In this way, the adhesion between the copper wiring layer and the insulating resin layer in the printed wiring board is improved.

[0199] For example, in the case of semiconductor wafers, surface treatment is used to improve adhesion between the semiconductor circuit formed on the semiconductor wafer and a protective film, such as a buffer coat (which can be a photosensitive positive type, a photosensitive negative type, or a non-photosensitive type) or a bump protective film.

[0200] Another application example in semiconductor wafers is surface treatment of copper circuit redistribution layers to improve adhesion between the copper circuit redistribution layers and insulating materials in substrates where redistribution layers are formed on semiconductor wafers. Examples of such substrates include package substrates (WL-CSP, FO-WLP, PLP), 2.5-dimensional (2.5D) interposer substrates, and three-dimensional (3D) interposer substrates.

[0201] Examples of the protective film or insulating material include polyimide resin, polybenzoxazole resin, and silicone resin.

[0202] A multilayer printed wiring board can be produced, for example, by repeating the following steps. 1. Contact the copper wiring surface with a coupling agent. 2. Bring the surface treatment liquid into contact with the copper wiring surface. 3. Rinse and dry the copper wiring. 4. An insulating resin layer is formed on the surface of the copper wiring. 5. Form via holes to connect the upper and lower wiring.

[0203] The method for contacting the copper wiring with the surface treatment solution is as described above. Specific examples include a method of immersing the copper wiring in the surface treatment solution and a method of spraying the surface treatment solution onto the copper wiring, which are simple, reliable, and preferable.

[0204] The method for washing the copper wiring with water is not particularly limited. Specific examples include a method of immersing the copper wiring in washing water and a method of spraying washing water onto the surface of the copper wiring, which are simple, reliable, and preferable.

[0205] The insulating resin layer can be formed by a known method, for example, by applying a semi-cured resin material or by applying a liquid resin material containing a solvent.

[0206] This paper describes a method for using a surface treatment solution in a circuit formation method for a printed wiring board using a semi-additive process. This circuit formation method includes one or more of the following steps. An insulating substrate is prepared. The insulating substrate has a first surface and a second surface facing each other. The insulating substrate may be provided with a through-hole and a via hole. A first conductive layer is provided on the first surface, the second surface, the inner wall of the through-hole, and the inner wall of the via hole. A photo-crosslinkable resin layer and a mask layer are formed on the first and second surfaces, thereby covering the first conductive layer on the first and second surfaces, the inner walls of the through-holes, and the inner walls of the via holes with the photo-crosslinkable resin layer and the mask layer. The photo-crosslinkable resin layer on the first surface, the second surface, the periphery of the through-holes, and the periphery of the via holes is exposed to pattern light. The mask layer on the first surface, the second surface, around the through-holes, and around the via holes is removed. The uncured photo-crosslinkable resin layer remaining on the first surface, the second surface, around the through-holes, and around the via holes is developed and removed using a photo-crosslinkable resin layer remover. This exposes the first conductive layer on the first surface, the second surface, around the through-holes, and around the via holes. The first conductive layer exposed on the first surface, the second surface, the inner wall of the through hole, and the inner wall of the via hole is subjected to electrolytic plating to form a second conductive layer. The cured photocrosslinkable resin layer is removed from the first surface, the second surface, around the through-holes, and around the via holes, thereby exposing the first and second conductive layers on the first surface, the second surface, the inner walls of the through-holes, and the inner walls of the via holes. The exposed first conductive layer is removed by flash etching. The first and second conductive layers on the first and second surfaces, the inner walls of the through holes, and the inner walls of the via holes are subjected to electroless plating and electrolytic plating, respectively, to form a third conductive layer. An insulating resin layer is laminated on the first conductive layer, the second conductive layer, and the third conductive layer on the first surface, the second surface, the inner wall of the through hole, and the inner wall of the via hole.

[0207] One or more of the metal layers or resist layers used in the above manufacturing method may be treated with a surface treatment solution. Specifically, one or more of the first conductive layer, the second conductive layer, the third conductive layer, the insulating resin substrate, the photo-crosslinkable resin layer, and the insulating resin layer may be treated with a surface treatment solution.

[0208] The method for forming a circuit on a printed wiring board using a subtractive process is described below. This circuit forming method includes one or more of the following steps. An insulating substrate is prepared. The insulating substrate has a first surface and a second surface facing each other. The insulating substrate may be provided with a through-hole and a via hole. A first conductive layer is provided on the first surface, the second surface, the inner wall of the through-hole, and the inner wall of the via hole. A photo-crosslinkable resin layer and a mask layer are formed on the first and second surfaces, thereby covering the first conductive layer on the first and second surfaces, the inner walls of the through-holes, and the inner walls of the via holes with the photo-crosslinkable resin layer and the mask layer. The photo-crosslinkable resin layer on the first surface, the second surface, the periphery of the through-holes, and the periphery of the via holes is exposed to pattern light. The mask layer on the first surface, the second surface, around the through-holes, and around the via holes is removed. The uncured photo-crosslinkable resin layer remaining on the first surface, the second surface, around the through-holes, and around the via holes is developed and removed using a photo-crosslinkable resin layer remover. This exposes the first conductive layer on the first surface, the second surface, around the through-holes, and around the via holes. The first conductive layer exposed on the first surface, the second surface, the inner wall of the through hole, and the inner wall of the via hole is removed by etching. The cured photocrosslinkable resin layer is removed from the first surface, the second surface, around the through-holes, and around the via holes, thereby exposing the first conductive layer on the first surface, the second surface, the inner walls of the through-holes, and the inner walls of the via holes. The first conductive layer on the first surface, the second surface, the inner wall of the through hole, and the inner wall of the via hole is subjected to electroless plating and electrolytic plating, thereby forming a third conductive layer. An insulating resin layer is laminated on the first and second conductive layers on the first and second surfaces, the inner walls of the through holes, and the inner walls of the via holes.

[0209] One or more of the metal layers or resist layers used in the above manufacturing method may be treated with a surface treatment solution. Specifically, one or more of the first conductive layer, the second conductive layer, the third conductive layer, the insulating resin substrate, the photo-crosslinkable resin layer, and the insulating resin layer may be treated with a surface treatment solution.

[0210] The method for producing the copper wiring and conductive layer is not particularly limited. Specific examples include electroless plating, electrolytic plating, vapor deposition, sputtering, and damascene. The copper wiring and conductive layer may include inner via holes, through holes, connection terminals, etc.

[0211] The form of copper to be treated with the surface treatment solution is not particularly limited. In one example, the copper is copper foil (electrolytic copper foil, rolled copper foil, resin-coated copper foil, carrier-coated copper foil, electroless copper foil, sputtered copper foil, thin copper foil, etc.). Copper foil can be used for electronic devices (printed wiring boards, lead frames, etc.), decorative items, building materials, etc. In one example, the copper is a plated film (electroless copper plating film, electrolytic copper plating film, etc.). In one example, the copper is a thin film. Thin copper can be formed by vapor deposition, sputtering, damascene, etc. In addition, the copper may be in the form of particles, needles, fibers, wires, rods, tubes, plates, etc. The surface of the copper may be plated with nickel, zinc, chromium, tin, etc.

[0212] For lead frames mounted by wire bonding, surface treatment solutions can be used to improve adhesion between the metal surface and resin. Examples of metal surfaces include the metal surface during the lead frame manufacturing process, the frame metal surface after mounting a semiconductor chip (before or after the die bonding and pre-baking processes), the frame metal surface after mounting by wire bonding, and the frame metal surface during processes up to resin encapsulation (before or after the resin molding and baking processes). Examples of resins include encapsulation resins and adhesives used when mounting semiconductor chips.

[0213] Surface treatment solutions can be used to improve the adhesion between metal surfaces and resins on lead frames used in flip-chip mounting. Examples of metal surfaces include those during the lead frame manufacturing process, those after temporary placement of bonding materials (solder, gold plating, tin plating, etc.), those after semiconductor chip mounting (before and after alignment, chip mounting, and baking processes), those after final curing (before and after processes such as reflow heating, thermocompression bonding, ultrasonic waves, and plasma), and those before and after resin encapsulation. Examples of resins include encapsulation resins and adhesives used when mounting semiconductor chips.

[0214] In micro-wiring boards, which utilize advanced integration technology to closely align semiconductor chips, surface treatment solutions can be used to improve adhesion between the copper circuit wiring layer and insulating materials. The copper circuit wiring layer can be included in 2.5-dimensional (2.5D) organic substrates, glass substrates, component-embedded substrates (EPS substrates) with semiconductors embedded in the substrate, coreless substrates, etc.

[0215] Surface treatment solutions can also be used to improve adhesion between copper circuit wiring layers and insulating materials. One example of a use case is when incorporating pattern wiring, performing laser via processing on the upper and lower layers, and then via fill plating. Another example is when using an embedded circuit board (ETS board) using MIS, where copper pillars formed by plating are used to connect the upper and lower layers, and mold resin is used for the insulating layer.

[0216] In one embodiment, a carrier-attached copper foil is treated with a surface treatment solution. The carrier-attached copper foil is an ultra-thin electrolytic copper foil used in printed wiring boards, and includes a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer. Examples of methods for forming a circuit on the carrier-attached copper foil include the semi-additive method, the subtractive method, the partly additive method, and the modified semi-additive method. The copper surface may be subjected to one or more pretreatments selected from the group consisting of pickling treatment, roughening treatment, heat-resistant treatment, rust-proofing treatment, and chemical conversion treatment.

[0217] [4. Summary] <1> A surface treatment liquid for further surface treatment of an object treated with a coupling agent, The target is one or more selected from the group consisting of inorganic materials and resin materials, The surface treatment liquid contains the following component A and component B: Component A: a triazole compound having an amino group; Component B: A tetrazole compound having an amino group. <2> the component A includes one or more selected from the group consisting of 4-amino-1,2,3-triazole, 4-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 4,5-diamino-1,2,3-triazole, and 3,5-diamino-1,2,4-triazole; The component B contains one or more selected from the group consisting of 5-amino-tetrazole, 2-amino-tetrazole, and 1-amino-tetrazole. <1> The surface treatment solution according to claim 1. <3> The coupling agent is a silane compound having a nitrogen-containing heterocycle in the molecule. <1> or <2> The surface treatment solution according to claim 1. <4> The pH of the surface treatment solution is 5 to 12. <1> ~ <3> 1. The surface treatment solution according to claim 1 , <5> The inorganic material is one or more selected from the group consisting of copper and copper alloys. <1> ~ <4> 1. The surface treatment solution according to claim 1 , <6> A surface treatment method comprising the following steps in this order: Step 1: contacting a first material with a coupling agent; Step 2: bringing the first material into contact with a surface treatment liquid; where: the first material includes one or more selected from the group consisting of an inorganic material and a resin material, The surface treatment solution contains the following components A and B: Component A: a triazole compound having an amino group; Component B: A tetrazole compound having an amino group. <7> The inorganic material contains one or more selected from the group consisting of copper and copper alloys. <6> The surface treatment method according to claim 1. <8> The adhesive method involves the following steps in this order: Step 1: contacting a first material with a coupling agent; Step 2: bringing the first material into contact with a surface treatment liquid; Step 3: contacting the first material with a second material; where: the first material includes one of an inorganic material or a resin material, the second material includes the other of an inorganic material and a resin material, The surface treatment solution contains the following components A and B: Component A: a triazole compound having an amino group; Component B: A tetrazole compound having an amino group. [Example]

[0218] [Materials used] The main materials used in the examples and comparative examples are described below. Ingredient A 3-Amino-1,2,4-triazole (abbreviated as "3ATZ." See formula (1) below for the structure. Tokyo Chemical Industry Co., Ltd.) 4-amino-1,2,4-triazole (abbreviated as "4ATZ." See formula (2) below for the structure. Tokyo Chemical Industry Co., Ltd.) 3,5-diamino-1,2,4-triazole (abbreviated as "3,5ATZ". See formula (3) below for the structure. Tokyo Chemical Industry Co., Ltd.) Triazole compounds that are not component A 1,2,4-triazole (abbreviated as "124TZ". See formula (4) below for the structure. Tokyo Chemical Industry Co., Ltd.) 1,2,3-triazole (abbreviated as "123TZ". See formula (5) below for the structure. Tokyo Chemical Industry Co., Ltd.) ●Ingredient B 5-amino-tetrazole (abbreviated as "5AT". See formula (6) below for the structure. Tokyo Chemical Industry Co., Ltd.) Tetrazole compounds that are not component B 5-Methyl-tetrazole (abbreviated as "5MT". See formula (7) below for the structure. Tokyo Chemical Industry Co., Ltd.)

[0219] [ka]

[0220] [Adhesion evaluation test 1] In Examples 1 to 4, unless otherwise specified, the adhesiveness was evaluated according to the following procedure. 1. As an inorganic material, electrolytic copper foil (thickness: 35 μm) was prepared. 2. The copper foil was acid-washed. Specifically, the copper foil was treated with a potassium persulfate-based soft etching agent at 30°C for 30 seconds. The copper foil was then rinsed with water. On the S-side of the treated copper foil, the Ra (arithmetic mean roughness) was 0.22 μm and the Rz (maximum height roughness) was 1.50 μm. These roughnesses were measured using a laser microscope VK-8710 (Keyence Corporation). 3. The copper foil was treated with a coupling agent. Specifically, the copper foil was treated with GliCAP GC-750AP (Shikoku Chemicals Corporation) at 30°C for 40 seconds, and then washed with water. 4. The copper foil was treated with a surface treatment solution. Specifically, the copper foil was treated with the surface treatment solution according to the example or comparative example at 25° C. for 30 seconds, and then washed with water. 5. The copper foil was dried at 100°C for 1 minute. 6. A glass cloth epoxy resin-impregnated prepreg (MEGTRON7, Panasonic Industries Co., Ltd.) was laminated and pressed onto the S-side of the copper foil to form a copper-clad laminate. 7. Test pieces (width: 10 mm) were prepared from the copper clad laminate, and the initial peel strength (kN / m) of the copper foil was measured in accordance with JIS C6481 (1996). 8. The copper-clad laminate was subjected to reflow heating five times (peak temperature: 288°C, in air). Test pieces (width: 10 mm) were then prepared from the copper-clad laminate, and the peel strength (kN / m) of the copper foil after reflow heating was measured. This measurement was carried out in accordance with JIS C6481 (1996).

[0221] [Adhesion evaluation test 2] In Example 5, the adhesion was evaluated by the following procedure. In Adhesion Evaluation Test 2, the type of coupling agent and the type of substrate were changed from those in Adhesion Evaluation Test 1. 1. As an inorganic material, electrolytic copper foil (thickness: 35 μm) was prepared. 2. The copper foil was acid-washed. Specifically, the copper foil was treated with a potassium persulfate-based soft etching agent at 30°C for 30 seconds. The copper foil was then rinsed with water. On the S-side of the treated copper foil, the Ra (arithmetic mean roughness) was 0.22 μm and the Rz (maximum height roughness) was 1.50 μm. These roughnesses were measured using a laser microscope VK-8710 (Keyence Corporation). 3. The copper foil was treated with a coupling agent. Specifically, the copper foil was treated with GliCAP GC-821AP (Shikoku Chemicals Corporation) at 30°C for 40 seconds, and then washed with water. 4. The copper foil was treated with a surface treatment solution. Specifically, the copper foil was treated with the surface treatment solution according to the example at 30° C. for 60 seconds, and then washed with water. 5. The copper foil was dried at 100°C for 1 minute. 6. A build-up wiring board resin (GX-T31, Ajinomoto Fine-Techno Co., Ltd.) and an FR-4 substrate (thickness: 1 mm) were laminated in this order on the S-side of the copper foil. The board was then heated in air at 100°C for 30 minutes, and then at 180°C for 30 minutes to produce a copper-clad laminate. 7. Test pieces (width: 10 mm) were prepared from the copper clad laminate, and the peel strength (kN / m) of the copper foil was measured in accordance with JIS C6481 (1996).

[0222] Example 1 The effect of the composition of the surface treatment solution used in step 4 of Adhesion Evaluation Test 1 on the peel strength of the copper foil was examined.

[0223] [Examples 1-1 to 1-7] The surface treatment solution was prepared according to the following procedure. 1. The components listed in Table 1 were dissolved in ion-exchanged water. The amounts of each component were adjusted so that the final concentrations were as listed in Table 1. 2. A 48% by weight aqueous solution of sodium hydroxide was added to adjust the pH to 8.5.

[0224] [Comparative Example 1-1] A copper-clad laminate was produced without treatment with a surface treatment solution, i.e., step 4 in the procedure of Adhesion Evaluation Test 1 was omitted.

[0225] [Comparative Examples 1-2 to 1-6] A surface treatment liquid was prepared in the same manner as in Example 1-1.

[0226] [result] The results are shown in Table 1. [Table 1]

[0227] Comparative Example 1-1 shows the peel strength of the copper foil in a copper-clad laminate that was not treated with a surface treatment solution. As can be seen from Table 1, the surface treatment solutions of Examples 1-1 to 1-7 contained both Component A and Component B. The copper-clad laminates of Examples 1-1 to 1-7 had improved copper foil peel strength compared to Comparative Example 1-1. On the other hand, the surface treatment solutions of Comparative Examples 1-2 to 1-6 did not contain either or both of Component A and Component B. The copper-clad laminates of Comparative Examples 1-2 to 1-6 had copper foil peel strengths that were comparable to or lower than that of Comparative Example 1-1.

[0228] The above results suggest that a surface treatment solution containing a combination of component A and component B can improve the adhesion between inorganic materials and resin materials.

[0229] Example 2 The effect of the pH of the surface treatment solution used in step 4 of Adhesion Evaluation Test 1 on the peel strength of the copper foil was examined.

[0230] [Examples 2-1 to 2-4] The surface treatment solution was prepared according to the following procedure. 1. 3,5-Diamino-1,2,4-triazole was dissolved in ion-exchanged water as component A, and 5-amino-tetrazole was dissolved in ion-exchanged water as component B. The amount of each component was adjusted so that the final concentration was 0.1% by weight. 2. A 48 wt % aqueous solution of sodium hydroxide was added to adjust the pH to the value shown in Table 2. However, in Example 2-1, no aqueous solution of sodium hydroxide was added.

[0231] [result] The results are shown in Table 2. For reference, the results of Example 1-4 and Comparative Example 1-1 are also shown. [Table 2]

[0232] Comparative Example 1-1 shows the peel strength of the copper foil in a copper-clad laminate that was not treated with a surface treatment solution. As can be seen from Table 2, the peel strength improvement effect was consistently observed even when the pH of the surface treatment solution was changed. When comparing the examples, the copper-clad laminates of the other examples had much greater peel strength than the copper-clad laminate of Example 2-1.

[0233] These results suggest that in order to enhance the adhesiveness-improving effect, it is preferable that the pH of the surface treatment solution be somewhat higher. For example, the pH of the surface treatment solution may be 6.0 or higher, 6.5 or higher, or 7.0 or higher.

[0234] Example 3 The effect of the order of surface treatment solutions on the peel strength of copper foil was investigated. Specifically, the order of steps 3 and 4 in Adhesion Evaluation Test 1 was changed to examine the effect on the peel strength of copper foil.

[0235] [Comparative Examples 3-1 to 3-4] The surface treatment solution was prepared according to the following procedure. 1. The components listed in Table 3 were dissolved in a coupling agent. The amounts of each component were adjusted so that the final concentrations were as listed in Table 3. 2. A copper-clad laminate was produced without treatment with a coupling agent. That is, step 3 was omitted from the procedure of Adhesion Evaluation Test 1.

[0236] [Comparative Examples 3-5 to 3-8] The surface treatment solution was prepared according to the following procedure. 1. The components listed in Table 3 were dissolved in ion-exchanged water. The amounts of each component were adjusted so that the final concentrations were as listed in Table 3. 2. A 48% by weight aqueous solution of sodium hydroxide was added to adjust the pH to 8.5. 3. A copper-clad laminate was produced by switching the order of steps 3 and 4 of Adhesion Evaluation Test 1.

[0237] [result] The results are shown in Table 3. For reference, the results of Examples 1-4, 1-7 and Comparative Example 1-1 are also shown. [Table 3]

[0238] Comparative Example 1-1 shows the peel strength of the copper foil in a copper-clad laminate that was not treated with a surface treatment solution. As can be seen from Table 3, the copper-clad laminates of Comparative Examples 3-1 to 3-4 were subjected to a surface treatment solution treatment with a surface treatment solution prepared by dissolving a triazole compound and / or a tetrazole compound in a coupling agent after acid cleaning. The copper-clad laminates of Comparative Examples 3-5 to 3-8 were subjected to a surface treatment solution treatment before the coupling agent treatment. The copper-clad laminates of Comparative Examples 3-1 to 3-8 had lower copper foil peel strength than Comparative Example 1-1.

[0239] The above results suggest that even a surface treatment solution containing a combination of Components A and B cannot improve the adhesion between inorganic materials and resin materials unless it is used after treatment with a coupling agent.

[0240] Example 4 The influence of the type of prepreg used in step 6 of Adhesion Evaluation Test 1 on the peel strength of the copper foil was examined.

[0241] [Examples 4-1 to 4-3] The same surface treatment solution as in Examples 1-4 was prepared. That is, component A was 3,5-diamino-1,2,4-triazole (final concentration: 0.1 wt%), component B was 5-amino-tetrazole (final concentration: 0.1 wt%), and the pH was 8.5. This surface treatment solution was used in this example.

[0242] In step 6 of Adhesion Evaluation Test 1, the glass cloth epoxy resin-impregnated prepreg used was changed as follows. Otherwise, a copper-clad laminate was produced in the same manner as in Adhesion Evaluation Test 1, and the peel strength of the copper foil was measured. Prepreg A: DS-7409DV(N) (Doosan Corporation) Prepreg B: TU-883P (Taiwan Union Technology Corporation) Prepreg C: EM-892BK (Elite Material Co., Ltd.)

[0243] [Comparative Examples 4-1 to 4-3] In Examples 4-1 to 4-3, copper-clad laminates were produced without treatment with a surface treatment liquid. That is, in the procedure of Adhesion Evaluation Test 1, step 4 was omitted and the prepreg used in step 6 was changed.

[0244] [result] The results are shown in Table 4. [Table 4]

[0245] Comparative Examples 4-1 to 4-3 show the peel strength of the copper foil in copper-clad laminates that were not treated with a surface treatment solution. As can be seen from Table 4, the copper-clad laminates of Examples 4-1 to 4-3 had improved peel strength of the copper foil compared to Comparative Examples 4-1 to 4-3, which used the same prepreg.

[0246] The above results suggest that by using a surface treatment liquid that combines Component A and Component B, it is possible to improve the adhesion between inorganic materials and resin materials in various resin materials (prepregs).

[0247] Example 5 The peel strength of the copper foil was measured in Adhesion Evaluation Test 2, and the effect of the surface treatment solution treatment was examined.

[0248] [Example 5-1] A surface treatment solution was prepared in the same manner as in Example 1. That is, component A was 3-amino-1,2,4-triazole (final concentration: 0.1 wt%), component B was 5-amino-tetrazole (final concentration: 0.1 wt%), and the pH was 8.5. A copper-clad laminate was produced using this surface treatment solution.

[0249] [Comparative Example 5-1] A copper-clad laminate was produced without treatment with a surface treatment solution, i.e., step 4 in the procedure of Adhesion Evaluation Test 2 was omitted.

[0250] [result] The results are shown in Table 5. [Table 5]

[0251] Comparative Example 5-1 is the peel strength of the copper foil in a copper-clad laminate that was not treated with a surface treatment solution. As can be seen from Table 5, the copper-clad laminate of Example 5-1 had an improved peel strength of the copper foil compared to Comparative Example 5-1.

[0252] This example showed that the use of a surface treatment liquid combining Components A and B can improve the adhesion between inorganic materials and resin materials, even when the types of coupling agent and resin material are changed. Taking into account the results of Example 4, it is suggested that the use of a surface treatment liquid combining Components A and B can improve the adhesion between objects treated with various coupling agents and inorganic materials or resin materials. [Industrial Applicability]

[0253] The present invention can be used in the manufacture of printed wiring boards, etc.

Claims

1. A surface treatment liquid for further surface treatment of an object treated with a coupling agent, The target is one or more selected from the group consisting of copper and copper alloys, The surface treatment liquid contains the following component A and component B: Component A: a triazole compound having an amino group; Component B: A tetrazole compound having an amino group.

2. Component A includes one or more selected from the group consisting of 4-amino-1,2,3-triazole, 4-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 4,5-diamino-1,2,3-triazole, and 3,5-diamino-1,2,4-triazole; The component B contains one or more selected from the group consisting of 5-amino-tetrazole, 2-amino-tetrazole, and 1-amino-tetrazole. The surface treatment solution according to claim 1 .

3. The coupling agent is a silane compound having a nitrogen-containing heterocycle in the molecule. The surface treatment solution according to claim 1 .

4. The pH of the surface treatment solution is 5 to 12. The surface treatment solution according to claim 1 .

5. A surface treatment method comprising carrying out the following steps 1 and 2 in this order: Step 1: contacting a first material with a coupling agent; Step 2: bringing the first material into contact with a surface treatment liquid; where: The first material includes one or more selected from the group consisting of copper and copper alloys, The surface treatment solution contains the following components A and B: Component A: a triazole compound having an amino group; Component B: A tetrazole compound having an amino group.

6. A bonding method comprising the following steps in this order: Step 1: contacting a first material with a coupling agent; Step 2: bringing the first material into contact with a surface treatment liquid; Step 3: contacting the first material with the second material; where: The first material includes one or more selected from the group consisting of copper and copper alloys, The second material includes a resin material, The surface treatment solution contains the following components A and B: Component A: a triazole compound having an amino group; Component B: A tetrazole compound having an amino group.

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